An Analytic Solution for Surface Source Sigma Z Calculations.

DTIC Science & Technology

1981-01-01

diabatic influence function , dimensionless temperature gradient 20. continued. - urbulence as a function of stability for inversion conditions. The...diabatic influence function (f). The unstable u = u,(In(z/zo) - )/k (4) regime diabatic influence function as defined by Paulson (1970) is presented in

Diabatization for Time-Dependent Density Functional Theory: Exciton Transfers and Related Conical Intersections.

PubMed

Tamura, Hiroyuki

2016-11-23

Intermolecular exciton transfers and related conical intersections are analyzed by diabatization for time-dependent density functional theory. The diabatic states are expressed as a linear combination of the adiabatic states so as to emulate the well-defined reference states. The singlet exciton coupling calculated by the diabatization scheme includes contributions from the Coulomb (Förster) and electron exchange (Dexter) couplings. For triplet exciton transfers, the Dexter coupling, charge transfer integral, and diabatic potentials of stacked molecules are calculated for analyzing direct and superexchange pathways. We discuss some topologies of molecular aggregates that induce conical intersections on the vanishing points of the exciton coupling, namely boundary of H- and J-aggregates and T-shape aggregates, as well as canceled exciton coupling to the bright state of H-aggregate, i.e., selective exciton transfer to the dark state. The diabatization scheme automatically accounts for the Berry phase by fixing the signs of reference states while scanning the coordinates.

Electron-vibration entanglement in the Born-Oppenheimer description of chemical reactions and spectroscopy.

PubMed

McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S; Reimers, Jeffrey R

2015-10-14

Entanglement is sometimes regarded as the quintessential measure of the quantum nature of a system and its significance for the understanding of coupled electronic and vibrational motions in molecules has been conjectured. Previously, we considered the entanglement developed in a spatially localized diabatic basis representation of the electronic states, considering design rules for qubits in a low-temperature chemical quantum computer. We extend this to consider the entanglement developed during high-energy processes. We also consider the entanglement developed using adiabatic electronic basis, providing a novel way for interpreting effects of the breakdown of the Born-Oppenheimer (BO) approximation. We consider: (i) BO entanglement in the ground-state wavefunction relevant to equilibrium thermodynamics, (ii) BO entanglement associated with low-energy wavefunctions relevant to infrared and tunneling spectroscopies, (iii) BO entanglement in high-energy eigenfunctions relevant to chemical reaction processes, and (iv) BO entanglement developed during reactive wavepacket dynamics. A two-state single-mode diabatic model descriptive of a wide range of chemical phenomena is used for this purpose. The entanglement developed by BO breakdown correlates simply with the diameter of the cusp introduced by the BO approximation, and a hierarchy appears between the various BO-breakdown correction terms, with the first-derivative correction being more important than the second-derivative correction which is more important than the diagonal correction. This simplicity is in contrast to the complexity of BO-breakdown effects on thermodynamic, spectroscopic, and kinetic properties. Further, processes poorly treated at the BO level that appear adequately treated using the Born-Huang adiabatic approximation are found to have properties that can only be described using a non-adiabatic description. For the entanglement developed between diabatic electronic states and the nuclear motion, qualitatively differently behavior is found compared to traditional properties of the density matrix and hence entanglement provides new information about system properties. For chemical reactions, this type of entanglement simply builds up as the transition-state region is crossed. It is robust to small changes in parameter values and is therefore more attractive for making quantum qubits than is the related fragile ground-state entanglement, provided that coherent motion at the transition state can be sustained.

Quantum dynamics intervened by repeated nonselective measurements

NASA Astrophysics Data System (ADS)

Filippov, Sergey N.

We derive the theory of open quantum system dynamics intervened by a series of nonselective measurements. We analyze the cases of time-independent and time-dependent Hamiltonian dynamics between the measurements and find the approximate master equation in the stroboscopic limit. We also consider a situation, in which the measurement basis changes in time, and illustrate it by nonselective measurements in the basis of diabatic states of the Landau-Zener model.

Avoided crossings: A study of the nonadiabatic transition probabilities

NASA Astrophysics Data System (ADS)

Desouter-Lecomte, M.; Leyh-Nihant, B.; Praet, M. T.; Lorquet, J. C.

1987-06-01

An approximate solution to the problem of constructing a pair of diabatic states exists only if certain requirements are fulfilled, for example, when the nonadiabatic coupling results from an interaction between two electronic configurations which are doubly excited with respect to one another. It is then possible to build up a model in which the series expansion of the elements of the Hamiltonian matrix is truncated after the first nonzero term. This leads to several conclusions concerning the nonadiabatic transition probability which differentiate conical intersections from avoided crossings. For the latter, the nonadiabatic coupling matrix elements (which are Lorentzians with an area equal to π/2) reach their maximum at the nuclear geometry for which ΔE (the energy gap between adiabatic surfaces) is a minimum. The loci along which the angle θ of the orthogonal transformation which relates adiabatic and diabatic wave functions keeps a constant value are a set of parallel straight lines which coincides with the loci along which ΔE remains constant. This reference direction in the configuration space corresponds to nuclear trajectories which are unable to bring about a nonadiabatic transition. In the case of avoided crossings, there exists only one nuclear degree of freedom which gives rise to surface hopping. Conical intersections, on the other hand, have two such active degrees of freedom. This creates a qualitative difference between the two cases which makes conical intersections more efficient as funnels than avoided crossings. A two-dimensional extension of the Landau-Zener formula is derived for avoided crossings. It contains a factor of anisotropy. It is possible, at least in favorable cases, to extract approximate diabatic quantities from ab initio calculations and to compare them with the predictions of these models. This has been done for two 2A1 electronic states of the CH+2 ion. The results are found to agree with the predictions of the model, at least in a restricted range of internuclear distances.

The best of both Reps—Diabatized Gaussians on adiabatic surfaces

NASA Astrophysics Data System (ADS)

Meek, Garrett A.; Levine, Benjamin G.

2016-11-01

When simulating nonadiabatic molecular dynamics, choosing an electronic representation requires consideration of well-known trade-offs. The uniqueness and spatially local couplings of the adiabatic representation come at the expense of an electronic wave function that changes discontinuously with nuclear motion and associated singularities in the nonadiabatic coupling matrix elements. The quasi-diabatic representation offers a smoothly varying wave function and finite couplings, but identification of a globally well-behaved quasi-diabatic representation is a system-specific challenge. In this work, we introduce the diabatized Gaussians on adiabatic surfaces (DGAS) approximation, a variant of the ab initio multiple spawning (AIMS) method that preserves the advantages of both electronic representations while avoiding their respective pitfalls. The DGAS wave function is expanded in a basis of vibronic functions that are continuous in both electronic and nuclear coordinates, but potentially discontinuous in time. Because the time-dependent Schrödinger equation contains only first-order derivatives with respect to time, singularities in the second-derivative nonadiabatic coupling terms (i.e., diagonal Born-Oppenheimer correction; DBOC) at conical intersections are rigorously absent, though singular time-derivative couplings remain. Interpolation of the electronic wave function allows the accurate prediction of population transfer probabilities even in the presence of the remaining singularities. We compare DGAS calculations of the dynamics of photoexcited ethene to AIMS calculations performed in the adiabatic representation, including the DBOC. The 28 fs excited state lifetime observed in DGAS simulations is considerably shorter than the 50 fs lifetime observed in the adiabatic simulations. The slower decay in the adiabatic representation is attributable to the large, repulsive DBOC in the neighborhood of conical intersections. These repulsive DBOC terms are artifacts of the discontinuities in the individual adiabatic vibronic basis functions and therefore cannot reflect the behavior of the exact molecular wave function, which must be continuous.

Diagnostic calculations of the circulation in the Martian atmosphere

NASA Technical Reports Server (NTRS)

Santee, Michelle L.; Crisp, David

1995-01-01

The circulation of the Martian atmosphere during late southern summer is derived from atmospheric temperature and dust distributions retrieved from a subset of the Mariner 9 infrared interferometer spectrometer (IRIS) thermal emission spectra (L(sub s) = 343-348 deg). Zonal-mean zonal winds are calculated by assuming gradient wind balance and zero surface zonal wind. Both hemispheres have intense midlatitude westerly jets with velocities of 80-90 m/s near 50 km; in the southern tropics the winds are easterly with velocities of 40 m/s near 50 km. The net effect of the zonal mean meridional circulation and large-scale waves can be approximated by the diabatic circulation, which is defined from the atmospheric thermal structure and net radiative heating rates. The radiative transfer model described by Crisp (1990) and Santee (1993) is used to compute solar heating and thermal cooling rates from diurnal averages of the retrieved IRIS temperature and dust distributions. At pressures below 4 mbar, there are large net radiative heating rates (up to 5 K/d) in the equatorial region and large net radiative cooling rates (up to 12 K/d) in the polar regions. These net radiative heating rates are used in a diagnostic stream function model which solves for the meridional and vertical components of the diabatic circulation simultaneously. We find a two-cell circulation, with rising motion over the equator, poleward flow in both hemispheres, sinking motion over both polar regions, and return flow in the lowest atmospheric levels. The maximum poleward velocity is 3 m/s in the tropics at approx. 55 km altitude, and the maximum vertical velocity is 2.5 cm/s downward over the north pole at approx. 60 km altitude. If these large transport rates are sustained for an entire season, the Martian atmosphere above the 1-mbar level is overturned in about 38 days. This diabatic circulation is qualitatively similar to the terrestrial diabatic circulation at the comparable season, but is more vigorous.

Understanding the Global Distribution of Monsoon Depressions

DTIC Science & Technology

2013-09-30

1.0 PVU interval) is shown for reference. Top left panel shows the Eulerian rate of change of PV, top right shows the diabatic PV tendency, bottom...left shows the horizontal advective tendency, and bottom right shows the sum of the diabatic and total advective tendencies. The vertical advective tendency is not plotted, but is of similar amplitude to the diabatic tendency.

Construction of diabatic energy surfaces for LiFH with artificial neural networks

NASA Astrophysics Data System (ADS)

Guan, Yafu; Fu, Bina; Zhang, Dong H.

2017-12-01

A new set of diabatic potential energy surfaces (PESs) for LiFH is constructed with artificial neural networks (NNs). The adiabatic PESs of the ground state and the first excited state are directly fitted with NNs. Meanwhile, the adiabatic-to-diabatic transformation (ADT) angles (mixing angles) are obtained by simultaneously fitting energy difference and interstate coupling gradients. No prior assumptions of the functional form of ADT angles are used before fitting, and the ab initio data including energy difference and interstate coupling gradients are well reproduced. Converged dynamical results show remarkable differences between adiabatic and diabatic PESs, which suggests the significance of non-adiabatic processes.

Diabatic processes and the evolution of two contrasting extratropical cyclones

NASA Astrophysics Data System (ADS)

Martinez-Alvarado, Oscar; Gray, Suzanne; Methven, John

2016-04-01

Two contrasting extratropical cyclones were observed over the United Kingdom during the summer 2012 field campaign of the DIAMET (DIAbatic influences on Mesoscale structures in ExtraTropical storms) project. The first cyclone, observed in July, was a shallow system typical of summer over west Europe while the second cyclone, observed in August, was a much deeper system which developed a potential vorticity (PV) tower. The evolution of these two cyclones was analysed and compared in terms of diabatic effects with respect to two aspects. The first aspect is the amount and distribution of heat produced during the development of each cyclone, measured by the cross-isentropic motion around the cyclone centre. The second aspect is the modification to the circulation around the cyclones' centres, measured by area-averaged isentropic vorticity. The contributions from individual diabatic processes, such as convection, cloud microphysics and radiation, to these two aspects is also considered. The cyclones were analysed via hindcast simulations with a research version of the Met Office Unified Model, enhanced with on-line tracers of diabatic changes of potential temperature and PV. A new methodology for the interpretation of these tracers was also implemented and used. The hindcast simulations were compared with the available dropsonde observations from the field campaign as well as operational analyses and radar rainfall rates. It is shown that, while boundary layer and turbulent mixing processes and cloud microphysics processes contributed to the development of both cyclones, the main differences between the cyclones in terms of diabatic effects could be attributed to differences in convective activity. It is also shown that the contribution from all these diabatic processes to changes in the circulation was modulated by the characteristics of advection around each cyclone in a highly nonlinear fashion. This research establishes a new framework for a systematic comparison of diabatic processes and their importance for the evolution of extratropical cyclones.

Improving Tropical Cyclone Intensity Forecasting with Theoretically-Based Statistical

DTIC Science & Technology

2013-01-03

solely by diabatic heating. The sense of the circulation is counterclockwise for the dashed lines and clockwise for the solid lines. The four panels...indicates the region of diabatic heating. Colored contours indicate  , the vertical pressure velocity, which is related to w by  = −gw, with...equation (GTE) and determine the associated tangential wind tendency for a variety of initial tangential wind profiles and annular rings of diabatic

The Effect of Atmospheric Diabatic Heating on Low-Frequency Oscillations.

NASA Astrophysics Data System (ADS)

Yen, Ming-Cheng

1990-01-01

A diagnostic scheme is devised to illustrate a chain relationship between diabatic heating and planetary -scale divergent and rotational circulations. The scheme consists of the velocity-potential (chi) maintenance equation, which relates diabatic heating and velocity potential, and the streamfunction (psi ) budget equation, which depicts the streamfunction tendency caused by the imbalance between streamfunction tendencies induced by vorticity advection and source. The proposed scheme is employed to examine the effect of tropical diabatic heating on the annual variation of subtropical jet streams. Furthermore, the chi -maintenance analysis is used to examine how the 30-60 day oscillation of planetary-scale divergent circulation is maintained; and the psi-budget analysis is performed to illustrate how the 30-60 day velocity potential (~{chi}) mode interacts with the upper-level monsoon flow to induce the 30-60 day oscillation of the tropical easterly jet. It was found that annual variations of both tropical diabatic heating and planetary-scale divergent circulation exhibit an annual in-phase seesaw oscillation between the winter and summer hemispheres. The annual variation of subtropical jet streams is caused by the adjustment of atmospheric rotational flow through planetary-scale divergent circulation in response to the annual cycle of tropical diabatic heating. The chi-maintenance equation is expressed as chi = chi _sp{rm Q}{.} - chi_{rm HA} , where chi_sp{rm Q}{.} and chi_ {rm HA} are the effects of vertical differential diabatic and adiabatic heating, respectively. The 30-60 day chi oscillation is shown to be primarily maintained by the differential diabatic heating effect, which can be inferred from the H _{rm VD} anomalies, the Laplician of the filtered chi_sp{rm Q}{.} anomalies. The resemblance of the H_{rm VD} and OLR anomalies in terms of the geographic distributions indicates that the differential diabatic heating effect maintaining the 30-60 day chi oscillation is attributable to the latent heat released by cumulus convection. The synoptic relationship among (~ {chi}, nabla~ {chi}) (200 mb), OLR and ~{psi} (200 mb) makes clear the synchronization of the 30-60 day oscillation of the tropical easterly jet and the Somali jet. The significant outcome of the psi-budget analysis demonstrates that the 30-60 day oscillation of the southern part of the tropical easterly jet is a response of the upper-level monsoon circulation to the eastward propagating ~{chi} mode.

Are Eyewall Replacement Cycles Governed Largely by Axisymmetric Balance Dynamics?

DTIC Science & Technology

2015-01-01

this viewpoint, the inward contraction of an eyewall is a mechanism driven by differential diabatic heating, and friction plays an un- important role...shows the azimuthally averaged kinematic and thermodynamical structure of the RAMS simulation, along with the corresponding averaged diabatic heating rate...structure of the storm, with the 360-K isotherm sloping upward from 9 to 13.5km between the center of the storm and 150-km radius. The mean diabatic heating

Proton-coupled electron transfer versus hydrogen atom transfer: generation of charge-localized diabatic states.

PubMed

Sirjoosingh, Andrew; Hammes-Schiffer, Sharon

2011-03-24

The distinction between proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) mechanisms is important for the characterization of many chemical and biological processes. PCET and HAT mechanisms can be differentiated in terms of electronically nonadiabatic and adiabatic proton transfer, respectively. In this paper, quantitative diagnostics to evaluate the degree of electron-proton nonadiabaticity are presented. Moreover, the connection between the degree of electron-proton nonadiabaticity and the physical characteristics distinguishing PCET from HAT, namely, the extent of electronic charge redistribution, is clarified. In addition, a rigorous diabatization scheme for transforming the adiabatic electronic states into charge-localized diabatic states for PCET reactions is presented. These diabatic states are constructed to ensure that the first-order nonadiabatic couplings with respect to the one-dimensional transferring hydrogen coordinate vanish exactly. Application of these approaches to the phenoxyl-phenol and benzyl-toluene systems characterizes the former as PCET and the latter as HAT. The diabatic states generated for the phenoxyl-phenol system possess physically meaningful, localized electronic charge distributions that are relatively invariant along the hydrogen coordinate. These diabatic electronic states can be combined with the associated proton vibrational states to generate the reactant and product electron-proton vibronic states that form the basis of nonadiabatic PCET theories. Furthermore, these vibronic states and the corresponding vibronic couplings may be used to calculate rate constants and kinetic isotope effects of PCET reactions.

Photodissociation dynamics in the first absorption band of pyrrole. II. Photofragment distributions for the 1A2(π σ* ) ←X˜ 1A1(π π ) transition

NASA Astrophysics Data System (ADS)

Picconi, David; Grebenshchikov, Sergy Yu.

2018-03-01

The analysis of the total kinetic energy release (TKER) of the photofragments pyrrolyl + H-atom formed in the photodissociation of pyrrole in the low-lying state 1A2(πσ*) is presented. The TKER distributions contain complementary and often more precise information on the fragmentation process than the broad diffuse absorption spectra. The distributions are calculated quantum mechanically for the diabatic state 1A2(πσ*) either isolated or coupled to the ground electronic state at an exit channel conical intersection. The calculations use the novel ab initio quasi-diabatic potential energy matrix constructed in the work of Picconi and Grebenshchikov [J. Chem. Phys. 148, 104103 (2018)]. The approximate overlap integral-based adiabatic mapping approach is introduced with which the quantum mechanical TKER distributions can be efficiently and accurately reproduced. Finally, the calculated TKERs are compared with the experimental results. The main features of the measured vibrationally resolved distributions are reproduced, and the spectral peaks are assigned and interpreted in detail.

Origin of the Energy Barrier to Chemical Reactions of O2 on Al(111): Evidence for Charge Transfer, Not Spin Selection

DTIC Science & Technology

2012-11-08

change of O2 spin, at the barrier [Fig. 3]; i.e., the corresponding diabatic surfaces cross. Far from the Al surface, the triplet state is...previous theoretical models, in particular nonadiabatic [17] or diabatic [16] approaches, which also find an energy barrier consistent with experiment...crossings of different diabatic O2 spin configuration sur- faces are accommodated by small spin fluctuations within the metal surface. For parallel

Leveraging the MJO for Predicting Envelopes of Tropical Wave and Synoptic Activity at Multi-Week Lead Times

DTIC Science & Technology

2013-09-30

GEWEX GASS MJO Diabatic Heating Experiment, 2) Intraseasonal Variability Hindcast Experiment (ISVHE) C. Conduct more comprehensive analysis on the...since her Ph.D. study. Key partners include M. Zhao (GFDL) and J. Ridout (NRL). Both Zhao and Ridout are contributors to the MJO multi-model diabatic ...a paper and submitted to the Journal of the Atmospheric Sciences (Guo et al. 2013). We have also begun acquiring model data from the MJO Diabatic

Predictability of the North Atlantic Oscillation on Intraseasonal Time Scales

DTIC Science & Technology

2013-09-30

skill when realistic MJO-related tropical diabatic heating is added to the models. (4) To diagnose the dynamical mechanisms by which the tropical...was added to each of the 50 simulations, has also been completed. Figure 1 shows the 50-member ensemble mean of the 500 hPa diabatic heating (averaged...contour interval of 2 oC/day. Separately, the added MJO diabatic heating is shown in black contours in the left panel with a contour interval of 0.5 oC

Constructing diabatic states from adiabatic states: Extending generalized Mulliken-Hush to multiple charge centers with Boys localization

NASA Astrophysics Data System (ADS)

Subotnik, Joseph E.; Yeganeh, Sina; Cave, Robert J.; Ratner, Mark A.

2008-12-01

This article shows that, although Boys localization is usually applied to single-electron orbitals, the Boys method itself can be applied to many electron molecular states. For the two-state charge-transfer problem, we show analytically that Boys localization yields the same charge-localized diabatic states as those found by generalized Mulliken-Hush theory. We suggest that for future work in electron transfer, where systems have more than two charge centers, one may benefit by using a variant of Boys localization to construct diabatic potential energy surfaces and extract electronic coupling matrix elements. We discuss two chemical examples of Boys localization and propose a generalization of the Boys algorithm for creating diabatic states with localized spin density that should be useful for Dexter triplet-triplet energy transfer.

Constructing diabatic states from adiabatic states: extending generalized Mulliken-Hush to multiple charge centers with boys localization.

PubMed

Subotnik, Joseph E; Yeganeh, Sina; Cave, Robert J; Ratner, Mark A

2008-12-28

This article shows that, although Boys localization is usually applied to single-electron orbitals, the Boys method itself can be applied to many electron molecular states. For the two-state charge-transfer problem, we show analytically that Boys localization yields the same charge-localized diabatic states as those found by generalized Mulliken-Hush theory. We suggest that for future work in electron transfer, where systems have more than two charge centers, one may benefit by using a variant of Boys localization to construct diabatic potential energy surfaces and extract electronic coupling matrix elements. We discuss two chemical examples of Boys localization and propose a generalization of the Boys algorithm for creating diabatic states with localized spin density that should be useful for Dexter triplet-triplet energy transfer.

Optimal Diabatic Dynamics of Majoarana-based Topological Qubits

NASA Astrophysics Data System (ADS)

Seradjeh, Babak; Rahmani, Armin; Franz, Marcel

In topological quantum computing, unitary operations on qubits are performed by adiabatic braiding of non-Abelian quasiparticles such as Majorana zero modes and are protected from local environmental perturbations. This scheme requires slow operations. By using the Pontryagin's maximum principle, here we show the same quantum gates can be implemented in much shorter times through optimal diabatic pulses. While our fast diabatic gates no not enjoy topological protection, they provide significant practical advantages due to their optimal speed and remarkable robustness to calibration errors and noise. NSERC, CIfAR, NSF DMR- 1350663, BSF 2014345.

The Effect of Enhanced Diabatic Heating on Stratospheric Circulation. Degree awarded by Michigan University, 1997.

NASA Technical Reports Server (NTRS)

Kleb, Mary M.

1997-01-01

The objective of this research focuses on the stratospheric dynamical response to the increase in aerosol loading and subsequent enhanced diabatic heating resulting from the eruption of Mt. Pinatubo. The Langley research Center three dimensional general circulation model and modifications made to that model for this study are described (addition of hydrogen fluoride tracer and diabatic heating enhancement). Unperturbed hydrogen fluoride distribution is compared to the hydrogen fluoride distribution measured by HALOE. A comparison of control and perturbed model runs is presented.

Localized diabatization applied to excitons in molecular crystals

NASA Astrophysics Data System (ADS)

Jin, Zuxin; Subotnik, Joseph E.

2017-06-01

Traditional ab initio electronic structure calculations of periodic systems yield delocalized eigenstates that should be understood as adiabatic states. For example, excitons are bands of extended states which superimpose localized excitations on every lattice site. However, in general, in order to study the effects of nuclear motion on exciton transport, it is standard to work with a localized description of excitons, especially in a hopping regime; even in a band regime, a localized description can be helpful. To extract localized excitons from a band requires essentially a diabatization procedure. In this paper, three distinct methods are proposed for such localized diabatization: (i) a simple projection method, (ii) a more general Pipek-Mezey localization scheme, and (iii) a variant of Boys diabatization. Approaches (i) and (ii) require localized, single-particle Wannier orbitals, while approach (iii) has no such dependence. These methods should be very useful for studying energy transfer through solids with ab initio calculations.

Effects of diabatic heating on the ageostrophic circulation of an upper tropospheric jet streak

NASA Technical Reports Server (NTRS)

Keyser, D. A.; Johnson, D. R.

1982-01-01

Interaction between the mass circulation within a mesoscale convective complex (MCC) and a direct mass circulation in the entrance region of an upper tropospheric polar jet streak was examined within the isentropic structure to investigate mechanisms responsible for linking these two scales of motion. The results establish that latent heating in the MCC modifies the direct mass circulation in the jet streak entrance region through the diabatically induced components of ageostrophic motion analyzed within isentropic coordinates. Within the strong mesoscale mass circulation of each MCC, strong horizontal mass flux convergence into the MCC at low levels is balanced by strong horizontal mass flux divergence away from the convergence at upper levels. Locations of large diabatic heating rates correspond well to the MCC position for each case; diabatic heating forces the upward vertical branch for the mesoscale mass circulation.

Global diabatic heating during FGGE SOP-1 and SOP-2

NASA Technical Reports Server (NTRS)

Chen, Tsing-Chang; Baker, Wayman E.

1986-01-01

With the increase in the observational data provided by FGGE and the use of global circulation models with full physics for the data assimilation, it is now becoming feasible to attempt to estimate globally the atmospheric diabatic heating. The thermodynamic equation in isobaric coordinates and the data generated by the FGGE III-b analysis of the Goddard Laboratory for Atmospheres (GLA) are employed to serve this purpose. The results of the present study generally agree with other previous investigations. However, some important differences are also revealed. (1) The diabatic heating obtained in the tropics in the present study is larger than that obtained elsewhere; (2) the relatively large heating over the mountainous areas shown in other studies does not appear; (3) no significant negative values of diabatic heating are found in the polar regions; and (4) unlike other studies, cooling is noted over parts of Eurasia in the summer.

Forecast model applications of retrieved three dimensional liquid water fields

NASA Technical Reports Server (NTRS)

Raymond, William H.; Olson, William S.

1990-01-01

Forecasts are made for tropical storm Emily using heating rates derived from the SSM/I physical retrievals described in chapters 2 and 3. Average values of the latent heating rates from the convective and stratiform cloud simulations, used in the physical retrieval, are obtained for individual 1.1 km thick vertical layers. Then, the layer-mean latent heating rates are regressed against the slant path-integrated liquid and ice precipitation water contents to determine the best fit two parameter regression coefficients for each layer. The regression formulae and retrieved precipitation water contents are utilized to infer the vertical distribution of heating rates for forecast model applications. In the forecast model, diabatic temperature contributions are calculated and used in a diabatic initialization, or in a diabatic initialization combined with a diabatic forcing procedure. Our forecasts show that the time needed to spin-up precipitation processes in tropical storm Emily is greatly accelerated through the application of the data.

Nonlinear optical detection of electron transfer adiabaticity in metal polypyridyl complexes.

PubMed

Miller, Stephen A; Moran, Andrew M

2010-02-11

Nonlinear optical signatures of electron transfer (ET) adiabaticity are investigated in a prototypical metal polypyridyl system, Os(II)(bpy)(3), known to possess large interligand couplings. Together with a theoretical model, transient absorption anisotropy (TAA) experiments show that field-matter interactions occur with diabatic basis states despite these large couplings. In addition, activated and activationless interligand ET mechanisms are distinguished with a series of TAA experiments in which the pump pulse frequency is tuned over a wide range. At lower pump frequencies, activated interligand ET, which occurs with a time constant of approximately 600 fs, is the dominant mechanism. However, an activationless mechanism becomes most prominent when the pump pulse is tuned by only 800 cm(-1) to higher frequency. This sensitivity of the ET mechanism to the pump frequency agrees with earlier experimental work that estimated an activation energy barrier of 875 cm(-1). The premise of signal interpretation in this paper is that the basis states appropriate for modeling nonradiative relaxation also govern the optical response. Model calculations suggest that optical nonlinearities corresponding to diabatic and adiabatic bases are readily distinguished with TAA experiments. In the diabatic basis, field-matter interaction sequences are restricted to terms in which the pump and probe pulses interact with the same transition dipoles, whereas the adiabatic basis imposes no such restriction and supports a class of coherent cross terms in the nonlinear response function. It is suggested that TAA should be preferred to alternative methods of studying ET adiabaticity that vary solvents and/or temperature. Altering the solvent, for example, generally also impacts solvent reorganization energies and the free energies of the donor and acceptor states. Parallels are discussed between the present work and research aimed at understanding energy transfer mechanisms in molecular aggregates.

Diabatic processes and the evolution of two contrasting extratropical cyclones

NASA Astrophysics Data System (ADS)

Methven, John; Martinez-Alvarado, Oscar; Gray, Suzanne

2017-04-01

Extratropical cyclones are typically weaker and less frequent in summer as a result of differences in the background state flow and diabatic processes with respect to other seasons. Two extratropical cyclones were observed in summer 2012 with a research aircraft during the DIAMET (DIAbatic influences on Mesoscale structure in ExTratropical storms) field campaign. The first cyclone deepened only down to 995 hPa; the second cyclone deepened down to 978 hPa and formed a potential vorticity (PV) tower, a frequent signature of intense cyclones. The cyclones were analyzed through numerical simulations incorporating tracers for the effects of diabatic processes on potential temperature and PV. It was found that the observed maximum vapor flux in the stronger cyclone was twice as strong as in the weaker cyclone; the water vapor mass flow along the warm conveyor belt of the stronger cyclone was over half that typical in winter even though the flow was weaker. Did the greater water transport and latent heat release associated with condensation result in the greater circulation in the PV tower case? A cyclone-centred integral framework is introduced relating the tracers with cross-isentropic mass transport and circulation around the cyclone. It is shown that the circulation increases much more slowly than the amplitude of the diabatically-generated PV tower at its centre. This effect is explained using the PV impermeability theorem and the influence of diabatic heating on circulation around a cyclone is shown to scale with Rossby number. The implication is that the stronger a cyclone becomes (larger Rossby number), the stronger the influence of latent heating on circulation.

Preliminary evaluation of diabatic heating distribution from FGGE level 3b analysis data

NASA Technical Reports Server (NTRS)

Kasahara, A.; Mizzi, A. P.

1985-01-01

A method is presented for calculating the global distribution of diabatic heating rate. Preliminary results of global heating rate evaluated from the European center for Medium Range Weather Forecasts Level IIIb analysis data is also presented.

Communication: Standard surface hopping predicts incorrect scaling for Marcus' golden-rule rate: The decoherence problem cannot be ignored

NASA Astrophysics Data System (ADS)

Landry, Brian R.; Subotnik, Joseph E.

2011-11-01

We evaluate the accuracy of Tully's surface hopping algorithm for the spin-boson model for the case of a small diabatic coupling parameter (V). We calculate the transition rates between diabatic surfaces, and we compare our results to the expected Marcus rates. We show that standard surface hopping yields an incorrect scaling with diabatic coupling (linear in V), which we demonstrate is due to an incorrect treatment of decoherence. By modifying standard surface hopping to include decoherence events, we recover the correct scaling (˜V2).

Diabatic forcing and intialization with assimilation of cloud water and rainwater in a forecast model

NASA Technical Reports Server (NTRS)

Raymond, William H.; Olson, William S.; Callan, Geary

1995-01-01

In this study, diabatic forcing, and liquid water assimilation techniques are tested in a semi-implicit hydrostatic regional forecast model containing explicit representations of grid-scale cloud water and rainwater. Diabatic forcing, in conjunction with diabatic contributions in the initialization, is found to help the forecast retain the diabatic signal found in the liquid water or heating rate data, consequently reducing the spinup time associated with grid-scale precipitation processes. Both observational Special Sensor Microwave/Imager (SSM/I) and model-generated data are used. A physical retrieval method incorporating SSM/I radiance data is utilized to estimate the 3D distribution of precipitating storms. In the retrieval method the relationship between precipitation distributions and upwelling microwave radiances is parameterized, based upon cloud ensemble-radiative model simulations. Regression formulae relating vertically integrated liquid and ice-phase precipitation amounts to latent heating rates are also derived from the cloud ensemble simulations. Thus, retrieved SSM/I precipitation structures can be used in conjunction with the regression-formulas to infer the 3D distribution of latent heating rates. These heating rates are used directly in the forecast model to help initiate Tropical Storm Emily (21 September 1987). The 14-h forecast of Emily's development yields atmospheric precipitation water contents that compare favorably with coincident SSM/I estimates.

Relationships between outgoing longwave radiation and diabatic heating in reanalyses

NASA Astrophysics Data System (ADS)

Zhang, Kai; Randel, William J.; Fu, Rong

2017-10-01

This study investigates relationships between daily variability in National Oceanographic and Atmospheric Administration (NOAA) outgoing longwave radiation (OLR), as a proxy for deep convection, and the global diabatic heat budget derived from reanalysis data sets. Results are evaluated based on data from ECMWF Reanalysis (ERA-Interim), Japanese 55-year Reanalysis (JRA-55) and Modern-Era Retrospective Analysis for Research and Applications (MERRA2). The diabatic heating is separated into components linked to `physics' (mainly latent heat fluxes), plus longwave (LW) and shortwave (SW) radiative tendencies. Transient variability in deep convection is highly correlated with diabatic heating throughout the troposphere and stratosphere. Correlation patterns and composite analyses show that enhanced deep convection (lower OLR) is linked to amplified heating in the tropical troposphere and in the mid-latitude storm tracks, tied to latent heat release. Enhanced convection is also linked to radiative cooling in the lower stratosphere, due to weaker upwelling LW from lower altitudes. Enhanced transient deep convection increases LW and decreases SW radiation in the lower troposphere, with opposite effects in the mid to upper troposphere. The compensating effects in LW and SW radiation are largely linked to variations in cloud fraction and water content (vapor, liquid and ice). These radiative balances in reanalyses are in agreement with idealized calculations using a column radiative transfer model. The overall relationships between OLR and diabatic heating are robust among the different reanalyses, although there are differences in radiative tendencies in the tropics due to large differences of cloud water and ice content among the reanalyses. These calculations provide a simple statistical method to quantify variations in diabatic heating linked to transient deep convection in the climate system.

Physics Parameterization for Seasonal Prediction

DTIC Science & Technology

2013-09-30

particularly the Madden Julian Oscillation (MJO). We are continuing our participation in the project “Vertical Structure and Diabatic Processes of...Results are shown for: a) TRMM rainfall, b) NAVGEM 20-year run submitted for the YOTC/GEWEX project “Vertical Structure and Diabatic Processes of the MJO

Localized diabatization applied to excitons in molecular crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, Zuxin; Subotnik, Joseph E.

Traditional ab initio electronic structure calculations of periodic systems yield delocalized eigenstates that should be understood as adiabatic states. For example, excitons are bands of extended states which superimpose localized excitations on every lattice site. However, in general, in order to study the effects of nuclear motion on exciton transport, it is standard to work with a localized description of excitons, especially in a hopping regime; even in a band regime, a localized description can be helpful. To extract localized excitons from a band requires essentially a diabatization procedure. In this paper, three distinct methods are proposed for such localizedmore » diabatization: (i) a simple projection method, (ii) a more general Pipek-Mezey localization scheme, and (iii) a variant of Boys diabatization. Approaches (i) and (ii) require localized, single-particle Wannier orbitals, while approach (iii) has no such dependence. Lastly, these methods should be very useful for studying energy transfer through solids with ab initio calculations.« less

Localized diabatization applied to excitons in molecular crystals

DOE PAGES

Jin, Zuxin; Subotnik, Joseph E.

2017-06-28

Traditional ab initio electronic structure calculations of periodic systems yield delocalized eigenstates that should be understood as adiabatic states. For example, excitons are bands of extended states which superimpose localized excitations on every lattice site. However, in general, in order to study the effects of nuclear motion on exciton transport, it is standard to work with a localized description of excitons, especially in a hopping regime; even in a band regime, a localized description can be helpful. To extract localized excitons from a band requires essentially a diabatization procedure. In this paper, three distinct methods are proposed for such localizedmore » diabatization: (i) a simple projection method, (ii) a more general Pipek-Mezey localization scheme, and (iii) a variant of Boys diabatization. Approaches (i) and (ii) require localized, single-particle Wannier orbitals, while approach (iii) has no such dependence. Lastly, these methods should be very useful for studying energy transfer through solids with ab initio calculations.« less

Impact of diabatic processes on the tropopause inversion layer formation in baroclinic life cycles

NASA Astrophysics Data System (ADS)

Kunkel, Daniel; Hoor, Peter; Wirth, Volkmar

2015-04-01

Observations of temperature profiles in the extratropical upper troposphere/lower stratosphere (UTLS) show the presence of an inversion layer just above the thermal tropopause, i.e., the tropopause inversion layer (TIL). In recent studies both diabatic and adiabatic processes have been identified to contribute to the formation of this layer. In particular, adiabatic simulations indicate a TIL formation without the explicit simulation of diabatic, i.e. radiative or humidity related, processes after wave breaking during baroclinic life cycles. One goal of this study is to assess the additional contribution of diabatic processes to the formation and strength of the TIL in such life cycles. Moreover, since irreversible stratosphere-troposphere exchange (STE) is another inherent feature of baroclinic life cycles and a consequence of diabatic processes, we study whether there is a relationship between STE and TIL. We use the non-hydrostatic model COSMO in an idealized mid-latitude channel configuration to simulate baroclinic life cycles. In a first step contributions of individual diabatic processes from turbulence, radiation, and cloud microphysics to the formation of the TIL are analyzed. These results are compared to those from adiabatic simulations of baroclinic life cycles in which the TIL forms during the life cycle with the limitation of being less sharp than in observations. In a second step the combined effects of several diabatic processes are studied to further include interactions between these processes as well as to advance towards a more realistic model setup. The results suggest a much more vigorous development of the TIL due to microphysics and the release of latent heat. Moreover, radiative effects can foster an increase in static stability above the thermal tropopause when large gradients of either water vapor or cloud ice are present at the level of the tropopause. By additionally adding sub-grid scale turbulence, a co-location of high static stability and increased turbulent kinetic energy is found in the vicinity of cirrus clouds at the tropopause level. The potential relation between STE and high static stability is further discussed based on results from trajectory calculations and the distribution of passive tracers of tropospheric and stratospheric origin.

The charger transfer electronic coupling in diabatic perspective: A multi-state density functional theory study

NASA Astrophysics Data System (ADS)

Guo, Xinwei; Qu, Zexing; Gao, Jiali

2018-01-01

The multi-state density functional theory (MSDFT) provides a convenient way to estimate electronic coupling of charge transfer processes based on a diabatic representation. Its performance has been benchmarked against the HAB11 database with a mean unsigned error (MUE) of 17 meV between MSDFT and ab initio methods. The small difference may be attributed to different representations, diabatic from MSDFT and adiabatic from ab initio calculations. In this discussion, we conclude that MSDFT provides a general and efficient way to estimate the electronic coupling for charge-transfer rate calculations based on the Marcus-Hush model.

Path integral molecular dynamics for exact quantum statistics of multi-electronic-state systems.

PubMed

Liu, Xinzijian; Liu, Jian

2018-03-14

An exact approach to compute physical properties for general multi-electronic-state (MES) systems in thermal equilibrium is presented. The approach is extended from our recent progress on path integral molecular dynamics (PIMD), Liu et al. [J. Chem. Phys. 145, 024103 (2016)] and Zhang et al. [J. Chem. Phys. 147, 034109 (2017)], for quantum statistical mechanics when a single potential energy surface is involved. We first define an effective potential function that is numerically favorable for MES-PIMD and then derive corresponding estimators in MES-PIMD for evaluating various physical properties. Its application to several representative one-dimensional and multi-dimensional models demonstrates that MES-PIMD in principle offers a practical tool in either of the diabatic and adiabatic representations for studying exact quantum statistics of complex/large MES systems when the Born-Oppenheimer approximation, Condon approximation, and harmonic bath approximation are broken.

Path integral molecular dynamics for exact quantum statistics of multi-electronic-state systems

NASA Astrophysics Data System (ADS)

Liu, Xinzijian; Liu, Jian

2018-03-01

An exact approach to compute physical properties for general multi-electronic-state (MES) systems in thermal equilibrium is presented. The approach is extended from our recent progress on path integral molecular dynamics (PIMD), Liu et al. [J. Chem. Phys. 145, 024103 (2016)] and Zhang et al. [J. Chem. Phys. 147, 034109 (2017)], for quantum statistical mechanics when a single potential energy surface is involved. We first define an effective potential function that is numerically favorable for MES-PIMD and then derive corresponding estimators in MES-PIMD for evaluating various physical properties. Its application to several representative one-dimensional and multi-dimensional models demonstrates that MES-PIMD in principle offers a practical tool in either of the diabatic and adiabatic representations for studying exact quantum statistics of complex/large MES systems when the Born-Oppenheimer approximation, Condon approximation, and harmonic bath approximation are broken.

The Influence of Atmosphere-Ocean Interaction on MJO Development and Propagation

DTIC Science & Technology

2013-09-30

MJO initiation. Figure 3. Time-height cross section of COAMPS grid 3 domain-averaged (a) diabatic heating, (b) perturbation mixing ratio...moist phase. The diurnal variability of 7 precipitation and diabatic heating that can be seen in Figs. 2 and 3 is not observed in the simulation with

Minimizing losses by variational counter-diabatic driving

NASA Astrophysics Data System (ADS)

Sels, Dries; Polkovnikov, Anatoli

Despite the time-reversal symmetry of the microscopic dynamics of isolated systems, losses are ubiquitous in any process that tries to manipulate them. Whether it's the heat produced in a car engine or the decoherence of a qubit, all losses arise from our lack of control on the microscopic degrees of freedom of the system. Counter-diabatic driving protocols were proposed as a means to do fast changes in the Hamiltonian without exciting transitions. Such driving in principle allows one to realize arbitrarily fast annealing protocols or implement fast dissipationless driving, circumventing standard adiabatic limitations requiring infinitesimally slow rates. These ideas were tested and used both experimentally and theoretically in small systems, but in larger chaotic systems it is known that exact counter-diabatic protocols do not exist. Here we will present a simple variational approach allowing one to find best physical counter-diabatic protocols. We will show that, while they do not get rid of all transitions, the variational protocols are able to significantly reduce the induced fluctuations in the system. D.S. acknowledges support by the FWO.

Ultrafast Electronic Relaxation through a Conical Intersection: Nonadiabatic Dynamics Disentangled through an Oscillator Strength-Based Diabatization Framework

DOE PAGES

Medders, Gregory R.; Alguire, Ethan C.; Jain, Amber; ...

2017-01-18

Here, we employ surface hopping trajectories to model the short-time dynamics of gas-phase and partially solvated 4-(N,N-dimethylamino)benzonitrile (DMABN), a dual fluorescent molecule that is known to undergo a nonadiabatic transition through a conical intersection. To compare theory vs time-resolved fluorescence measurements, we calculate the mixed quantum–classical density matrix and the ensemble averaged transition dipole moment. We introduce a diabatization scheme based on the oscillator strength to convert the TDDFT adiabatic states into diabatic states of L a and L b character. Somewhat surprisingly, we find that the rate of relaxation reported by emission to the ground state is almost 50%more » slower than the adiabatic population relaxation. Although our calculated adiabatic rates are largely consistent with previous theoretical calculations and no obvious effects of decoherence are seen, the diabatization procedure introduced here enables an explicit picture of dynamics in the branching plane, raising tantalizing questions about geometric phase effects in systems with dozens of atoms.« less

Nonadiabatic Coupling

NASA Astrophysics Data System (ADS)

Kryachko, Eugene S.

The general features of the nonadiabatic coupling and its relation to molecular properties are surveyed. Some consequences of the [`]equation of motion', formally expressing a [`]smoothness' of a given molecular property within the diabatic basis, are demonstrated. A particular emphasis is made on the relation between a [`]smoothness' of the electronic dipole moment and the generalized Mulliken-Hush formula for the diabatic electronic coupling.

Constrained subsystem density functional theory.

PubMed

Ramos, Pablo; Pavanello, Michele

2016-08-03

Constrained Subsystem Density Functional Theory (CSDFT) allows to compute diabatic states for charge transfer reactions using the machinery of the constrained DFT method, and at the same time is able to embed such diabatic states in a molecular environment via a subsystem DFT scheme. The CSDFT acronym is chosen to reflect the fact that on top of the subsystem DFT approach, a constraining potential is applied to each subsystem. We show that CSDFT can successfully tackle systems as complex as single stranded DNA complete of its backbone, and generate diabatic states as exotic as a hole localized on a phosphate group as well as on the nucleobases. CSDFT will be useful to investigators needing to evaluate the environmental effect on charge transfer couplings for systems in condensed phase environments.

Predicting Accurate Electronic Excitation Transfer Rates via Marcus Theory with Boys or Edmiston-Ruedenberg Localized Diabatization †

DOE Office of Scientific and Technical Information (OSTI.GOV)

Subotnik, Joseph E.; Vura-Weis, Josh; Sodt, Alex J.

We model the triplet-triplet energy-transfer experiments from the Closs group [Closs, G. L.; et al. J. Am. Chem. Soc. 1988, 110, 2652.] using a combination of Marcus theory and either Boys or Edmiston-Ruedenberg localized diabatization, and we show that relative and absolute rates of electronic excitation transfer may be computed successfully. For the case where both the donor and acceptor occupy equatorial positions on a rigid cyclohexane bridge, we find βcalc = 2.8 per C-C bond, compared with the experimental value βexp = 2.6. This work highlights the power of using localized diabatization methods as a tool for modeling nonequilibriummore » processes.« less

Predicting Accurate Electronic Excitation Transfer Rates via Marcus Theory with Boys or Edmiston-Ruedenberg Localized Diabatization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Subotnik, Joseph E.; Vura-Weis, Josh; Sodt, Alex J.

We model the triplet-triplet energy-transfer experiments from the Closs group [Closs, G. L.; et al. J. Am. Chem. Soc. 1988, 110, 2652.] using a combination of Marcus theory and either Boys or Edmiston-Ruedenberg localized diabatization, and we show that relative and absolute rates of electronic excitation transfer may be computed successfully. For the case where both the donor and acceptor occupy equatorial positions on a rigid cyclohexane bridge, we find β calc = 2.8 per C-C bond, compared with the experimental value β exp = 2.6. This work highlights the power of using localized diabatization methods as a tool formore » modeling nonequilibrium processes.« less

Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table.

PubMed

Aquilante, Francesco; Autschbach, Jochen; Carlson, Rebecca K; Chibotaru, Liviu F; Delcey, Mickaël G; De Vico, Luca; Fdez Galván, Ignacio; Ferré, Nicolas; Frutos, Luis Manuel; Gagliardi, Laura; Garavelli, Marco; Giussani, Angelo; Hoyer, Chad E; Li Manni, Giovanni; Lischka, Hans; Ma, Dongxia; Malmqvist, Per Åke; Müller, Thomas; Nenov, Artur; Olivucci, Massimo; Pedersen, Thomas Bondo; Peng, Daoling; Plasser, Felix; Pritchard, Ben; Reiher, Markus; Rivalta, Ivan; Schapiro, Igor; Segarra-Martí, Javier; Stenrup, Michael; Truhlar, Donald G; Ungur, Liviu; Valentini, Alessio; Vancoillie, Steven; Veryazov, Valera; Vysotskiy, Victor P; Weingart, Oliver; Zapata, Felipe; Lindh, Roland

2016-02-15

In this report, we summarize and describe the recent unique updates and additions to the Molcas quantum chemistry program suite as contained in release version 8. These updates include natural and spin orbitals for studies of magnetic properties, local and linear scaling methods for the Douglas-Kroll-Hess transformation, the generalized active space concept in MCSCF methods, a combination of multiconfigurational wave functions with density functional theory in the MC-PDFT method, additional methods for computation of magnetic properties, methods for diabatization, analytical gradients of state average complete active space SCF in association with density fitting, methods for constrained fragment optimization, large-scale parallel multireference configuration interaction including analytic gradients via the interface to the Columbus package, and approximations of the CASPT2 method to be used for computations of large systems. In addition, the report includes the description of a computational machinery for nonlinear optical spectroscopy through an interface to the QM/MM package Cobramm. Further, a module to run molecular dynamics simulations is added, two surface hopping algorithms are included to enable nonadiabatic calculations, and the DQ method for diabatization is added. Finally, we report on the subject of improvements with respects to alternative file options and parallelization. © 2015 Wiley Periodicals, Inc.

Quasi-Geostrophic Diagnosis of Mixed-Layer Dynamics Embedded in a Mesoscale Turbulent Field

NASA Astrophysics Data System (ADS)

Chavanne, C. P.; Klein, P.

2016-02-01

A new quasi-geostrophic model has been developed to diagnose the three-dimensional circulation, including the vertical velocity, in the upper ocean from high-resolution observations of sea surface height and buoyancy. The formulation for the adiabatic component departs from the classical surface quasi-geostrophic framework considered before since it takes into account the stratification within the surface mixed-layer that is usually much weaker than that in the ocean interior. To achieve this, the model approximates the ocean with two constant-stratification layers : a finite-thickness surface layer (or the mixed-layer) and an infinitely-deep interior layer. It is shown that the leading-order adiabatic circulation is entirely determined if both the surface streamfunction and buoyancy anomalies are considered. The surface layer further includes a diabatic dynamical contribution. Parameterization of diabatic vertical velocities is based on their restoring impacts of the thermal-wind balance that is perturbed by turbulent vertical mixing of momentum and buoyancy. The model skill in reproducing the three-dimensional circulation in the upper ocean from surface data is checked against the output of a high-resolution primitive-equation numerical simulation. Correlation between simulated and diagnosed vertical velocities are significantly improved in the mixed-layer for the new model compared to the classical surface quasi-geostrophic model, reaching 0.9 near the surface.

On the adiabatic representation of Meyer-Miller electronic-nuclear dynamics

NASA Astrophysics Data System (ADS)

Cotton, Stephen J.; Liang, Ruibin; Miller, William H.

2017-08-01

The Meyer-Miller (MM) classical vibronic (electronic + nuclear) Hamiltonian for electronically non-adiabatic dynamics—as used, for example, with the recently developed symmetrical quasiclassical (SQC) windowing model—can be written in either a diabatic or an adiabatic representation of the electronic degrees of freedom, the two being a canonical transformation of each other, thus giving the same dynamics. Although most recent applications of this SQC/MM approach have been carried out in the diabatic representation—because most of the benchmark model problems that have exact quantum results available for comparison are typically defined in a diabatic representation—it will typically be much more convenient to work in the adiabatic representation, e.g., when using Born-Oppenheimer potential energy surfaces (PESs) and derivative couplings that come from electronic structure calculations. The canonical equations of motion (EOMs) (i.e., Hamilton's equations) that come from the adiabatic MM Hamiltonian, however, in addition to the common first-derivative couplings, also involve second-derivative non-adiabatic coupling terms (as does the quantum Schrödinger equation), and the latter are considerably more difficult to calculate. This paper thus revisits the adiabatic version of the MM Hamiltonian and describes a modification of the classical adiabatic EOMs that are entirely equivalent to Hamilton's equations but that do not involve the second-derivative couplings. The second-derivative coupling terms have not been neglected; they simply do not appear in these modified adiabatic EOMs. This means that SQC/MM calculations can be carried out in the adiabatic representation, without approximation, needing only the PESs and the first-derivative coupling elements. The results of example SQC/MM calculations are presented, which illustrate this point, and also the fact that simply neglecting the second-derivative couplings in Hamilton's equations (and presumably also in the Schrödinger equation) can cause very significant errors.

Report of the 1988 2-D Intercomparison Workshop, chapter 3

NASA Technical Reports Server (NTRS)

Jackman, Charles H.; Brasseur, Guy; Soloman, Susan; Guthrie, Paul D.; Garcia, Rolando; Yung, Yuk L.; Gray, Lesley J.; Tung, K. K.; Ko, Malcolm K. W.; Isaken, Ivar

1989-01-01

Several factors contribute to the errors encountered. With the exception of the line-by-line model, all of the models employ simplifying assumptions that place fundamental limits on their accuracy and range of validity. For example, all 2-D modeling groups use the diffusivity factor approximation. This approximation produces little error in tropospheric H2O and CO2 cooling rates, but can produce significant errors in CO2 and O3 cooling rates at the stratopause. All models suffer from fundamental uncertainties in shapes and strengths of spectral lines. Thermal flux algorithms being used in 2-D tracer tranport models produce cooling rates that differ by as much as 40 percent for the same input model atmosphere. Disagreements of this magnitude are important since the thermal cooling rates must be subtracted from the almost-equal solar heating rates to derive the net radiative heating rates and the 2-D model diabatic circulation. For much of the annual cycle, the net radiative heating rates are comparable in magnitude to the cooling rate differences described. Many of the models underestimate the cooling rates in the middle and lower stratosphere. The consequences of these errors for the net heating rates and the diabatic circulation will depend on their meridional structure, which was not tested here. Other models underestimate the cooling near 1 mbar. Suchs errors pose potential problems for future interactive ozone assessment studies, since they could produce artificially-high temperatures and increased O3 destruction at these levels. These concerns suggest that a great deal of work is needed to improve the performance of thermal cooling rate algorithms used in the 2-D tracer transport models.

A unified diabatic description for electron transfer reactions, isomerization reactions, proton transfer reactions, and aromaticity.

PubMed

Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S

2015-10-14

While diabatic approaches are ubiquitous for the understanding of electron-transfer reactions and have been mooted as being of general relevance, alternate applications have not been able to unify the same wide range of observed spectroscopic and kinetic properties. The cause of this is identified as the fundamentally different orbital configurations involved: charge-transfer phenomena involve typically either 1 or 3 electrons in two orbitals whereas most reactions are typically closed shell. As a result, two vibrationally coupled electronic states depict charge-transfer scenarios whereas three coupled states arise for closed-shell reactions of non-degenerate molecules and seven states for the reactions implicated in the aromaticity of benzene. Previous diabatic treatments of closed-shell processes have considered only two arbitrarily chosen states as being critical, mapping these states to those for electron transfer. We show that such effective two-state diabatic models are feasible but involve renormalized electronic coupling and vibrational coupling parameters, with this renormalization being property dependent. With this caveat, diabatic models are shown to provide excellent descriptions of the spectroscopy and kinetics of the ammonia inversion reaction, proton transfer in N2H7(+), and aromaticity in benzene. This allows for the development of a single simple theory that can semi-quantitatively describe all of these chemical phenomena, as well as of course electron-transfer reactions. It forms a basis for understanding many technologically relevant aspects of chemical reactions, condensed-matter physics, chemical quantum entanglement, nanotechnology, and natural or artificial solar energy capture and conversion.

Observed large-scale structures and diabatic heating and drying profiles during TWP-ICE

DOE PAGES

Xie, Shaocheng; Hume, Timothy; Jakob, Christian; ...

2010-01-01

This study documents the characteristics of the large-scale structures and diabatic heating and drying profiles observed during the Tropical Warm Pool–International Cloud Experiment (TWP-ICE), which was conducted in January–February 2006 in Darwin during the northern Australian monsoon season. The examined profiles exhibit significant variations between four distinct synoptic regimes that were observed during the experiment. The active monsoon period is characterized by strong upward motion and large advective cooling and moistening throughout the entire troposphere, while the suppressed and clear periods are dominated by moderate midlevel subsidence and significant low- to midlevel drying through horizontal advection. The midlevel subsidence andmore » horizontal dry advection are largely responsible for the dry midtroposphere observed during the suppressed period and limit the growth of clouds to low levels. During the break period, upward motion and advective cooling and moistening located primarily at midlevels dominate together with weak advective warming and drying (mainly from horizontal advection) at low levels. The variations of the diabatic heating and drying profiles with the different regimes are closely associated with differences in the large-scale structures, cloud types, and rainfall rates between the regimes. Strong diabatic heating and drying are seen throughout the troposphere during the active monsoon period while they are moderate and only occur above 700 hPa during the break period. The diabatic heating and drying tend to have their maxima at low levels during the suppressed periods. Furthermore, the diurnal variations of these structures between monsoon systems, continental/coastal, and tropical inland-initiated convective systems are also examined.« less

The Role of “Vortical” Hot Towers in the Formation of Tropical Cyclone Diana (1984).

NASA Astrophysics Data System (ADS)

Hendricks, Eric A.; Montgomery, Michael T.; Davis, Christopher A.

2004-06-01

A high-resolution (3-km horizontal grid spacing) near-cloud-resolving numerical simulation of the formation of Hurricane Diana (1984) is used to examine the contribution of deep convective processes to tropical cyclone formation. This study is focused on the 3-km horizontal grid spacing simulation because this simulation was previously found to furnish an accurate forecast of the later stages of the observed storm life cycle. The numerical simulation reveals the presence of vortical hot towers, or cores of deep cumulonimbus convection possessing strong vertical vorticity, that arise from buoyancy-induced stretching of local absolute vertical vorticity in a vorticity-rich prehurricane environment.At near-cloud-resolving scales, these vortical hot towers are the preferred mode of convection. They are demonstrated to be the most important influence to the formation of the tropical storm via a two-stage evolutionary process: (i) preconditioning of the local environment via diabatic production of multiple small-scale lower-tropospheric cyclonic potential vorticity (PV) anomalies, and (ii) multiple mergers and axisymmetrization of these low-level PV anomalies. The local warm-core formation and tangential momentum spinup are shown to be dominated by the organizational process of the diabatically generated PV anomalies; the former process being accomplished by the strong vertical vorticity in the hot tower cores, which effectively traps the latent heat from moist convection. In addition to the organizational process of the PV anomalies, the cyclogenesis is enhanced by the aggregate diabatic heating associated with the vortical hot towers, which produces a net influx of low-level mean angular momentum throughout the genesis.Simpler models are examined to elucidate the underlying dynamics of tropical cyclogenesis in this case study. Using the Sawyer Eliassen balanced vortex model to diagnose the macroscale evolution, the cyclogenesis of Diana is demonstrated to proceed in approximate gradient and hydrostatic balance at many instances, where local radial and vertical accelerations are small. Using a shallow water primitive equation model, a characteristic “moist” (diabatic) vortex merger in the cloud-resolving numerical simulation is captured in a large part by the barotropic model. Since a moist merger results in a stronger vortex and occurs twice as fast as a dry merger, it is inferred (consistent with related work) that a net low-level convergence can accelerate and intensify the merger process in the real atmosphere.Although the findings reported herein are based on a sole case study and thus cannot yet be generalized, it is believed the results are sufficiently interesting to warrant further idealized simulations of this nature.

Vibrational relaxation and internal conversion in the overlapped optically-allowed 1Bu+ and optically-forbidden 1Bu- or 3Ag- vibronic levels of carotenoids: Effects of diabatic mixing as determined by Kerr-gate fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Kakitani, Yoshinori; Miki, Takeshi; Koyama, Yasushi; Nagae, Hiroyoshi; Nakamura, Ryosuke; Kanematsu, Yasuo

2009-07-01

The time constants of the vibrational relaxation, υ = 2 → υ = 1 and υ = 1 → υ = 0, in the 1Bu+ manifold and those of internal conversion from the 1Bu+(0) level, which is isoenergetic (so-called 'diabatic') with the 1Bu- vibronic levels in neurosporene and spheroidene and with the 3Ag- vibronic levels in lycopene and anhydrorhodovibrin, were determined by Kerr-gate fluorescence spectroscopy. The time constants of the vibrational relaxation were in the ˜1:2 ratio, and those of internal conversion agreed with the lifetimes of the diabatic counterparts, i.e., the 1Bu- and 3Ag- electronic states, respectively.

Evidence for Arctic Ozone Depletion in Late February and early March 1994

NASA Technical Reports Server (NTRS)

Manney, G. L.; Zurek, R. W.; Froidevaux, L.; Waters, J. W.

1995-01-01

Significant chemical ozone (O3 ) loss in the 1993-94 Arctic winter occurred mainly during an unusually late cold spell of approximately 10 days in late Feb/early Mar. Over the 30 d period studied (including the cold spell), observed vortex-averaged O3 at 465 K (approximately 40 hPa) decreased by approximately 10%. New three-dimensional, diabatic trajectory calculations show that this observed decrease represents only about half of the net chemical loss (approximately 20%) during the 30 day period. The resupply of lower stratospheric O3 by transport in Feb 1994 was considerably greater than in 1993, when transport masked only about a quarter of the chemical loss in Feb/Mar. The net estimated chemical loss over 30 days in 1994 was comparable to that over the same 30 days in 1993, but mainly occurred at a faster rate during the brief cold spell. These results highlight the impact of Arctic interannual variability on the relative roles of chemistry and dynamics in O3 evolution during recent Arctic winters.

Beyond Born-Oppenheimer theory for ab initio constructed diabatic potential energy surfaces of singlet H3+ to study reaction dynamics using coupled 3D time-dependent wave-packet approach.

PubMed

Ghosh, Sandip; Mukherjee, Saikat; Mukherjee, Bijit; Mandal, Souvik; Sharma, Rahul; Chaudhury, Pinaki; Adhikari, Satrajit

2017-08-21

The workability of beyond Born-Oppenheimer theory to construct diabatic potential energy surfaces (PESs) of a charge transfer atom-diatom collision process has been explored by performing scattering calculations to extract accurate integral cross sections (ICSs) and rate constants for comparison with most recent experimental quantities. We calculate non-adiabatic coupling terms among the lowest three singlet states of H 3 + system (1 1 A ' , 2 1 A ' , and 3 1 A ' ) using MRCI level of calculation and solve the adiabatic-diabatic transformation equation to formulate the diabatic Hamiltonian matrix of the same process [S. Mukherjee et al., J. Chem. Phys. 141, 204306 (2014)] for the entire region of nuclear configuration space. The nonadiabatic effects in the D + + H 2 reaction has been studied by implementing the coupled 3D time-dependent wave packet formalism in hyperspherical coordinates [S. Adhikari and A. J. C. Varandas, Comput. Phys. Commun. 184, 270 (2013)] with zero and non-zero total angular momentum (J) on such newly constructed accurate (ab initio) diabatic PESs of H 3 + . We have depicted the convergence profiles of reaction probabilities for the reactive non-charge transfer, non-reactive charge transfer, and reactive charge transfer processes for different collisional energies with respect to the helicity (K) and total angular momentum (J) quantum numbers. Finally, total and state-to-state ICSs are calculated as a function of collision energy for the initial rovibrational state (v = 0, j = 0) of the H 2 molecule, and consequently, those quantities are compared with previous theoretical and experimental results.

Diabatic forcing and initialization with assimilation of cloud and rain water in a forecast model: Methodology

NASA Technical Reports Server (NTRS)

Raymond, William H.; Olson, William S.; Callan, Geary

1990-01-01

The focus of this part of the investigation is to find one or more general modeling techniques that will help reduce the time taken by numerical forecast models to initiate or spin-up precipitation processes and enhance storm intensity. If the conventional data base could explain the atmospheric mesoscale flow in detail, then much of our problem would be eliminated. But the data base is primarily synoptic scale, requiring that a solution must be sought either in nonconventional data, in methods to initialize mesoscale circulations, or in ways of retaining between forecasts the model generated mesoscale dynamics and precipitation fields. All three methods are investigated. The initialization and assimilation of explicit cloud and rainwater quantities computed from conservation equations in a mesoscale regional model are examined. The physical processes include condensation, evaporation, autoconversion, accretion, and the removal of rainwater by fallout. The question of how to initialize the explicit liquid water calculations in numerical models and how to retain information about precipitation processes during the 4-D assimilation cycle are important issues that are addressed. The explicit cloud calculations were purposely kept simple so that different initialization techniques can be easily and economically tested. Precipitation spin-up processes associated with three different types of weather phenomena are examined. Our findings show that diabatic initialization, or diabatic initialization in combination with a new diabatic forcing procedure, work effectively to enhance the spin-up of precipitation in a mesoscale numerical weather prediction forecast. Also, the retention of cloud and rain water during the analysis phase of the 4-D data assimilation procedure is shown to be valuable. Without detailed observations, the vertical placement of the diabatic heating remains a critical problem.

The mesoscale forcing of a midlatitude upper-tropospheric jet streak by a simulated convective system. 1: Mass circulation and ageostrophic processes

NASA Technical Reports Server (NTRS)

Wolf, Bart J.; Johnson, D. R.

1995-01-01

The mutual forcing of a midlatitude upper-tropospheric jet streak by organized mesoscale adiabatic and diabatic processes within a simulated convective system (SCS) is investigated. Using isentropic diagnostics, results from a three-dimensional numerical simulation of an SCS are examined to study the isallobaric flow field, modes of dominant ageostrophic motion, and stability changes in relation to the mutual interdependence of adiabatic processes and latent heat release. Isentropic analysis affords an explicit isolation of a component of isallobaric flow associated with diabatic processes within the SCS. Prior to convective development within the simulations, atmospheric destabilization occurs through adiabatic ageostrophic mass adjustment and low-level convergence in association with the preexisting synoptic-scale upper-tropospheric jet streak. The SCS develops in a baroclinic zone and quickly initiates a vigorous mass circulation. By the mature stage, a pronounced vertical couplet of low-level convergence and upper-level mass divergence is established, linked by intense midtropospoheric diabatic heating. Significant divergence persists aloft for several hours subsequent to SCS decay. The dominant role of ageostrophic motion within which the low-level mass convergence develops is the adiabatic isallobaric component, while the mass divergence aloft develops principally through the diabatic isallobaric component. Both compnents are intrinsically linked to the convectively forced vertical mass transport. The inertial diabatic ageostrophic component is largest near the level of maximum heating and is responsible for the development of inertial instability to the north of SCS, resulting in this quadrant being preferred for outflow. The inertial advective component, the dominant term that produces the new downstream wind maximum, rapidly develops north of the SCS and through mutual adjustment creates the baroclinic support for the new jet streak.

A comparative study of methods for describing non-adiabatic coupling: diabatic representation of the 1Sigma +/1Pi HOH and HHO conical intersections

NASA Astrophysics Data System (ADS)

Dobbyn, Abigail J.; Knowles, Peter J.

A number of established techniques for obtaining diabatic electronic states in small molecules are critically compared for the example of the X and B states in the water molecule, which contribute to the two lowest-energy conical intersections. Integration of the coupling matrix elements and analysis of configuration mixing coefficients both produce reliable diabatic states globally. Methods relying on diagonalization of dipole moment and angular momentum operators are shown to fail in large regions of coordinate space. However, the use of transition angular momentum matrix elements involving the A state, which is degenerate with B at the conical intersections, is successful globally, provided that an appropriate choice of coordinates is made. Long range damping of non-adiabatic coupling to give correct asymptotic mixing angles also is investigated.

Laboratory simulations show diabatic heating drives cumulus-cloud evolution and entrainment

PubMed Central

Narasimha, Roddam; Diwan, Sourabh Suhas; Duvvuri, Subrahmanyam; Sreenivas, K. R.; Bhat, G. S.

2011-01-01

Clouds are the largest source of uncertainty in climate science, and remain a weak link in modeling tropical circulation. A major challenge is to establish connections between particulate microphysics and macroscale turbulent dynamics in cumulus clouds. Here we address the issue from the latter standpoint. First we show how to create bench-scale flows that reproduce a variety of cumulus-cloud forms (including two genera and three species), and track complete cloud life cycles—e.g., from a “cauliflower” congestus to a dissipating fractus. The flow model used is a transient plume with volumetric diabatic heating scaled dynamically to simulate latent-heat release from phase changes in clouds. Laser-based diagnostics of steady plumes reveal Riehl–Malkus type protected cores. They also show that, unlike the constancy implied by early self-similar plume models, the diabatic heating raises the Taylor entrainment coefficient just above cloud base, depressing it at higher levels. This behavior is consistent with cloud-dilution rates found in recent numerical simulations of steady deep convection, and with aircraft-based observations of homogeneous mixing in clouds. In-cloud diabatic heating thus emerges as the key driver in cloud development, and could well provide a major link between microphysics and cloud-scale dynamics. PMID:21918112

Precision Control and Randomized Benchmarking of a 12-us Class Superconducting Qubit

DTIC Science & Technology

2013-03-28

well potential profile. The  diabatic  ground state of the left (right) well corresponds to a persistent  current Iq with clockwise (counterclockwise...circulation. The two  diabatic  energy levels have an energy  separation  = 2 Iq fdc linear in the flux detuning fdc = fdc ‐  0/2. Higher‐excited states...is:  ⁄ ∆ . At detuning  fdc=0, the double‐well potential is symmetric and the  diabatic ‐state energies are degenerate. At this  ``degeneracy point

Simulation of heat storages and associated heat budgets in the Pacific Ocean: 2. Interdecadal timescale

NASA Astrophysics Data System (ADS)

Auad, Guillermo; Miller, Arthur J.; White, Warren B.

1998-11-01

We use a primitive equation isopycnal model of the Pacific Ocean to simulate and diagnose the anomalous heat balance on interdecadal timescales associated with heat storage changes observed from 1970-1988 in the expendable bathythermograph (XBT) data set. Given the smallness of the interdecadal signals compared to the El Niño-Southern Oscillation (ENSO) signal, the agreement between model and observations is remarkably good. The total anomalous heat balance is made up of two parts, the diabatic part (from the model temperature equation) and the adiabatic part (from the model mass conservation equation) due to thermocline heave. We therefore describe our analysis of both the total and diabatic anomalous heat balances in four areas of the tropical and subtropical North Pacific Ocean in the upper 400 m. The interdecadal total (diabatic plus adiabatic) heat balance in the North Pacific Ocean is characterized by a complicated interplay of different physical processes, especially revealed in basin-scale averages of the heat budget components that have comparable amounts of variance. In smaller subregions, simpler balances hold. For example, in the western equatorial Pacific (area 1) the total heat content tendency term is nearly zero, so that a simple balance exists between surface heat flux, vertical heat transport, and horizontal mixing. In the western subtropical Pacific the total heat content tendency balances the three-dimensional divergence of the heat flux. We speculate that this complexity is indicative of multiple physical mechanisms involved in the generation of North Pacific interdecadal variability. The diabatic heat balance north of 24°N, a region of special interest to The World Ocean Circulation Experiment (WOCE), can be simplified to a balance between the tendency term, surface heat flux, and meridional advection, the last term dominated by anomalous advection of mean temperature gradients. For the western equatorial region the diabatic heat content tendency is nearly zero and the steady balance involves simply horizontal advection and the surface heat flux, which at these latitudes has a damping role in the model. An important finding of this study is the identification of two interdecadal timescales, roughly 10 and 20 years, both similar to those reported by other investigators in recent years. [Tourre et al., 1998; Latif and Barnett, 1994; Robertson, 1995; White et al, 1997; Gu and Philander, 1997; Jacobs et al., 1994]. The 20-year timescale is only present in diabatic heat budget components, while the 10-year timescale is present in both diabatic and adiabatic components. The 10-year timescale can also be seen in the surface heat flux time series, but it occurs in the ocean adiabatic components which demonstrates the importance of oceanic adjustment through Rossby wave dynamics on decadal timescales.

Communication: GAIMS—Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Curchod, Basile F. E.; Martínez, Todd J., E-mail: toddjmartinez@gmail.com; SLAC National Accelerator Laboratory, Menlo Park, California 94025

2016-03-14

Full multiple spawning is a formally exact method to describe the excited-state dynamics of molecular systems beyond the Born-Oppenheimer approximation. However, it has been limited until now to the description of radiationless transitions taking place between electronic states with the same spin multiplicity. This Communication presents a generalization of the full and ab initio multiple spawning methods to both internal conversion (mediated by nonadiabatic coupling terms) and intersystem crossing events (triggered by spin-orbit coupling matrix elements) based on a spin-diabatic representation. The results of two numerical applications, a model system and the deactivation of thioformaldehyde, validate the presented formalism andmore » its implementation.« less

Communication: GAIMS—generalized ab initio multiple spawning for both internal conversion and intersystem crossing processes

DOE PAGES

Curchod, Basile F. E.; Rauer, Clemens; Marquetand, Philipp; ...

2016-03-11

Full Multiple Spawning is a formally exact method to describe the excited-state dynamics of molecular systems beyond the Born-Oppenheimer approximation. However, it has been limited until now to the description of radiationless transitions taking place between electronic states with the same spin multiplicity. This Communication presents a generalization of the full and ab initio Multiple Spawning methods to both internal conversion (mediated by nonadiabatic coupling terms) and intersystem crossing events (triggered by spin-orbit coupling matrix elements) based on a spin-diabatic representation. Lastly, the results of two numerical applications, a model system and the deactivation of thioformaldehyde, validate the presented formalismmore » and its implementation.« less

Infinite-order sudden approximation for collisions involving molecules in Pi electronic states: a new derivation and calculations of rotationally inelastic cross sections for NO(x superscript 2 Pi) + He and Ar

DOE Office of Scientific and Technical Information (OSTI.GOV)

Corey, G.C.; Alexander, M.H.

1986-11-15

A new derivation is presented of the infinite order sudden (IOS) approximation for rotationally inelastic collisions of a diatomic molecule in a Pi electronic state with a closed shell atom. This derivation clearly demonstrates the connection between the two sudden S functions for scattering off the adiabatic potential surface of A' and A symmetry, which would arise from an ab initio calculation on an atom + Pi-state molecule system, and the S matrix elements in diabatic basis, which are required in the quantum treatment of the collision dynamics. Coupled states and IOS calculations were carried out for collisions of NImore » X 2 Pi with helium and argon, based on a electron gas potential surface at total energies of 63, 150, and 300 meV. The IOS approximation is not reliable for collisions of NO with Ar, even at the highest collision energy considered here. However, for collisions with He at 150 and 300 meV, the IOS approximation is nearly quantitative for transitions both within and between the Omega = 1/2 and Omega = 3/2 manifolds.« less

The Integral Role of a Diabatic Rossby Vortex in a Heavy Snowfall Event

DTIC Science & Technology

2008-06-01

anomalies are identified: 1) a low-level anomaly to the east of the Appalachian Mountains associated with the incipient surface cyclone and 2) an upper-level...diagnostic eddy available potential energy ( APE ) equa- tion, one can gain insight into the relative importance of FIG. 4. As in Fig. 3, but at 0600 UTC 25...More specifically, the con- version ratio of the diabatic to baroclinic generation of eddy APE has been shown to be a useful diagnostic for

Global Distribution of Cloud Droplet Number Concentration, Autoconversion Rate, and Aerosol Indirect Effect Under Diabatic Droplet Activation

NASA Technical Reports Server (NTRS)

Barahona, Donifan; Sotiropoulou, Rafaella; Nenes, Athanasios

2011-01-01

This study presents a global assessment of the sensitivity of droplet number to diabatic activation (i.e., including effects from entrainment of dry air) and its first-order tendency on indirect forcing and autoconversion. Simulations were carried out with the NASA Global Modeling Initiative (GMI) atmospheric and transport model using climatological metereorological fields derived from the former NASA Data Assimilation Office (DAO), the NASA Finite volume GCM (FVGCM) and the Goddard Institute for Space Studies version II (GISS) GCM. Cloud droplet number concentration (CDNC) is calculated using a physically based prognostic parameterization that explicitly includes entrainment effects on droplet formation. Diabatic activation results in lower CDNC, compared to adiabatic treatment of the process. The largest decrease in CDNC (by up to 75 percent) was found in the tropics and in zones of moderate CCN concentration. This leads to a global mean effective radius increase between 0.2-0.5 micrometers (up to 3.5 micrometers over the tropics), a global mean autoconversion rate increase by a factor of 1.1 to 1.7 (up to a factor of 4 in the tropics), and a 0.2-0.4 W m(exp -2) decrease in indirect forcing. The spatial patterns of entrainment effects on droplet activation tend to reduce biases in effective radius (particularly in the tropics) when compared to satellite retrievals. Considering the diabatic nature of ambient clouds, entrainment effects on CDNC need to be considered in GCM studies of the aerosol indirect effect.

Diabatic modification of potential vorticity in extratropical cyclones

NASA Astrophysics Data System (ADS)

Chagnon, J.

2012-12-01

Representation of diabatic processes and their impact on extratropical cyclones is a likely source of skill degradation in operational numerical weather prediction systems. This investigation examines the source, structure, and magnitude of diabatic potential vorticity (PV) anomalies generated by small-scale and parameterized processes in both mesoscale and global model simulations of extratropical cyclones in the North Atlantic. Simulations of several cold season extratropical storms have been performed using the Met Office Unified Model. Several cases simulated were drawn from the DIAbatic influences on Mesoscale structures in ExTratropical cyclones (DIAMET) observational campaign during which the National Environmental Research Council (NERC) Facility for Airborne Atmospheric Measurement (FAAM) BAE-146 aircraft was deployed. The influence of specific modelled processes was quantified using a set of tracers, each of which represents a history of the PV contributed by a specific segment of the model (e.g., boundary-layer scheme, cloud microphysics, convection scheme , radiation, etc.). This presentation will highlight several differences and similarities in high and low resolution simulations. For example, in high resolution simulations, tropopause folds are sharpened by a tripolar PV anomaly arising from the convection, boundary-layer, and microphysics schemes; this structure is not present in coarser global model simulations. However, a dipole of PV straddling the tropopause is diagnosed in both coarse- and fine-resolution simulations. The PV dipole, which is strongly influenced by long-wave radiative cooling, increases the gradient of PV near the tropopause and therefore modifies the characteristics Rossby wave propagation and moist baroclinic wave growth.

Nonadiabatic dynamics on the two coupled electronic PESs: the H+ + O2 system.

PubMed

Xavier, F George D

2010-09-30

Multistate adiabatic and diabatic PESs were computed for the H+ + O2 collision system in Jacobi coordinates, (R,r,γ) using the cc-pVTZ basis set and the ic-MRCI level of theory. In addition, all possible interaction potentials and nonadiabatic coupling matrix elements among those different electronic states were also computed. Comparisons with earlier computed interaction potentials were made wherever possible, and the differences between them is attributed to the multistate diabatization and the chosen level of theory and basis set. Focusing our attention on the ground-state (GS) and the first excited-state (ES) PES, quantum dynamics were performed using the 2 × 2 diabatic potential submatrix obtained from the multistate (four) diabatic potential matrix within the VCC-RIOSA scheme at two experimentally reported collision energies, E(cm) = 9.5 and 23 eV. The scattering quantities were computed for two experimentally observed collision processes, namely, the inelastic vibrational excitation (IVE), H+ + O2 (X3Σg(−),v = 0) → H+ + O2 (X3Σg(−),v′), and the vibrational charge transfer (VCT), H+ + O2 (X3Σg(−),v = 0) → H (2S) + O (X2Πg,v′′). Comparisons were made with experimental results and found an overall improvement relative to the earlier computed results, and the discrepancies, if any, could be brought down to minimum by further modification in employed ab initio PESs and the interaction potential.

Tunneling and speedup in quantum optimization for permutation-symmetric problems

DOE PAGES

Muthukrishnan, Siddharth; Albash, Tameem; Lidar, Daniel A.

2016-07-21

Tunneling is often claimed to be the key mechanism underlying possible speedups in quantum optimization via quantum annealing (QA), especially for problems featuring a cost function with tall and thin barriers. We present and analyze several counterexamples from the class of perturbed Hamming weight optimization problems with qubit permutation symmetry. We first show that, for these problems, the adiabatic dynamics that make tunneling possible should be understood not in terms of the cost function but rather the semiclassical potential arising from the spin-coherent path-integral formalism. We then provide an example where the shape of the barrier in the final costmore » function is short and wide, which might suggest no quantum advantage for QA, yet where tunneling renders QA superior to simulated annealing in the adiabatic regime. However, the adiabatic dynamics turn out not be optimal. Instead, an evolution involving a sequence of diabatic transitions through many avoided-level crossings, involving no tunneling, is optimal and outperforms adiabatic QA. We show that this phenomenon of speedup by diabatic transitions is not unique to this example, and we provide an example where it provides an exponential speedup over adiabatic QA. In yet another twist, we show that a classical algorithm, spin-vector dynamics, is at least as efficient as diabatic QA. Lastly, in a different example with a convex cost function, the diabatic transitions result in a speedup relative to both adiabatic QA with tunneling and classical spin-vector dynamics.« less

Tunneling and speedup in quantum optimization for permutation-symmetric problems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muthukrishnan, Siddharth; Albash, Tameem; Lidar, Daniel A.

Tunneling is often claimed to be the key mechanism underlying possible speedups in quantum optimization via quantum annealing (QA), especially for problems featuring a cost function with tall and thin barriers. We present and analyze several counterexamples from the class of perturbed Hamming weight optimization problems with qubit permutation symmetry. We first show that, for these problems, the adiabatic dynamics that make tunneling possible should be understood not in terms of the cost function but rather the semiclassical potential arising from the spin-coherent path-integral formalism. We then provide an example where the shape of the barrier in the final costmore » function is short and wide, which might suggest no quantum advantage for QA, yet where tunneling renders QA superior to simulated annealing in the adiabatic regime. However, the adiabatic dynamics turn out not be optimal. Instead, an evolution involving a sequence of diabatic transitions through many avoided-level crossings, involving no tunneling, is optimal and outperforms adiabatic QA. We show that this phenomenon of speedup by diabatic transitions is not unique to this example, and we provide an example where it provides an exponential speedup over adiabatic QA. In yet another twist, we show that a classical algorithm, spin-vector dynamics, is at least as efficient as diabatic QA. Lastly, in a different example with a convex cost function, the diabatic transitions result in a speedup relative to both adiabatic QA with tunneling and classical spin-vector dynamics.« less

Seasonality and mechanisms of tropical intraseasonal oscillations

NASA Astrophysics Data System (ADS)

Hazra, Abheera; Krishnamurthy, V.

2018-01-01

This study has compared the monsoon intraseasonal oscillation (MISO) during the boreal summer and Madden Julian Oscillation (MJO) during the boreal winter. Based on MISO and MJO in high-resolution three-dimensional diabatic heating, the possible mechanisms are discussed through observational analyses of dynamical and thermodynamical variables. The MISO and MJO are extracted as nonlinear oscillations during boreal summer and winter, respectively, by applying multi-channel singular spectrum analysis on daily anomalies of diabatic heating over the Indo-Pacific region. Lead and lag relations among moisture, temperature and surface fields relative to diabatic heating are analyzed to compare the mechanisms of MISO and MJO. While both the oscillations show eastward propagation, MISO has a strong northward propagation and MJO has a weak southward propagation as well. The analysis shows that MJO and MISO are essentially driven by the same mechanisms but with some difference in the meridional propagation. The westerly shear leads the diabatic heating, while the vorticity has weak correlation. Large-scale circulation creates positive moisture preconditioning before convection and negative moisture preconditioning before suppressed conditions. A positive lower level horizontal advection of temperature and upper level temperature tendencies lead the convective state while a negative lower level horizontal advection of temperature and upper level temperature tendencies lead the suppressed state. There is positive feedback from the SST to atmosphere. The difference in the meridional propagation of MISO and MJO is hypothesized to be because of the different differential heating meridionally during the two seasons.

Nongeostrophic theory of zonally averaged circulation. I - Formulation

NASA Technical Reports Server (NTRS)

Tung, Ka Kit

1986-01-01

A nongeostrophic theory of zonally averaged circulation is formulated using the nonlinear primitive equations (mass conservation, thermodynamics, and zonal momentum) on a sphere. The relationship between the mean meridional circulation and diabatic heating rate is studied. Differences between results of nongeostropic theory and the geostrophic formulation concerning the role of eddy forcing of the diabatic circulation and the nonlinear nearly inviscid limit versus the geostrophic limit are discussed. Consideration is given to the Eliassen-Palm flux divergence, the Eliassen-Palm pseudodivergence, the nonacceleration theorem, and the nonlinear nongeostrophic Taylor relationship.

Nonadiabatic effects in C-Br bond scission in the photodissociation of bromoacetyl chloride

NASA Astrophysics Data System (ADS)

Valero, Rosendo; Truhlar, Donald G.

2006-11-01

Bromoacetyl chloride photodissociation has been interpreted as a paradigmatic example of a process in which nonadiabatic effects play a major role. In molecular beam experiments by Butler and co-workers [J. Chem. Phys. 95, 3848 (1991); J. Chem. Phys. 97, 355 (1992)], BrCH2C(O )Cl was prepared in its ground electronic state (S0) and excited with a laser at 248nm to its first excited singlet state (S1). The two main ensuing photoreactions are the ruptures of the C-Cl bond and of the C-Br bond. A nonadiabatic model was proposed in which the C-Br scission is strongly suppressed due to nonadiabatic recrossing at the barrier formed by the avoided crossing between the S1 and S2 states. Recent reduced-dimensional dynamical studies lend support to this model. However, another interpretation that has been given for the experimental results is that the reduced probability of C-Br scission is a consequence of incomplete intramolecular energy redistribution. To provide further insight into this problem, we have studied the energetically lowest six singlet electronic states of bromoacetyl chloride by using an ab initio multiconfigurational perturbative electronic structure method. Stationary points (minima and saddle points) and minimum energy paths have been characterized on the S0 and S1 potential energy surfaces. The fourfold way diabatization method has been applied to transform five adiabatic excited electronic states to a diabatic representation. The diabatic potential energy matrix of the first five excited singlet states has been constructed along several cuts of the potential energy hypersurfaces. The thermochemistry of the photodissociation reactions and a comparison with experimental translational energy distributions strongly suggest that nonadiabatic effects dominate the C-Br scission, but that the reaction proceeds along the energetically allowed diabatic pathway to excited-state products instead of being nonadiabatically suppressed. This conclusion is also supported by the low values of the diabatic couplings on the C-Br scission reaction path. The methodology established in the present study will be used for the construction of global potential energy surfaces suitable for multidimensional dynamics simulations to test these preliminary interpretations.

The mesoscale forcing of a midlatitude upper-tropospheric jet streak by a simulated convective system. 2: Kinetic energy and resolution analysis

NASA Technical Reports Server (NTRS)

Wolf, Bart J.; Johnson, D. R.

1995-01-01

A kinetic energy (KE) analysis of the forcing of a mesoscale upper-tropospheric jet streak by organized diabatic processes within the simulated convective system (SCS) that was discussed in Part 1 is presented in this study. The relative contributions of the ageostrophic components of motion to the generation of KE of the convectively generated jet streak are compared, along with the KE generation by the rotational (nondivergent) and irrotational (divergent) mass transport. The sensitivity of the numerical simulations of SCS development to resolution is also briefly examined. Analysis within isentropic coordinates provides for an explicit determination of the influence of the diabatic processes on the generation of KE. The upper-level production of specific KE is due predominatly to the inertial advective ageostrophic component (IAD), and as such represents the primary process through which the KE of the convectively generated jet streak is realized. A secondary contribution by the inertial diabatic (IDI) term is observed. Partitioning the KE generation into its rotational and irrotational components reveals that the latter, which is directly linked to the diabatic heating within the SCS through isentropic continuity requirements, is the ultimate source of KE generation as the global area integral of generation by the rotational component vanishes. Comparison with an identical dry simulation reveals that the net generation of KE must be attributed to latent heating. Both the IAD and IDI ageostrophic components play important roles in this regard. Examination of results from simulations conducted at several resolutions supports the previous findings in that the effects of diabatic processes and ageostrophic motion on KE generation remain consistent. Resolution does impact the location and timing of SCS development, a result that has important implications in forecasting the onset of convection that develops from evolution of the large-scale flow and moisture transport. Marked differences are observed in the momentum field aloft subsequent to the life cycle of the SCS in the 1 deg, 30-level base case (MP130) simulation discussed in Part 1 versus its 2 deg counterparts in that the MP130 simulation with higher spatial resolution contains from 14% to 30% more total KE.

Constructing polyatomic potential energy surfaces by interpolating diabatic Hamiltonian matrices with demonstration on green fluorescent protein chromophore

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Jae Woo; Rhee, Young Min, E-mail: ymrhee@postech.ac.kr; Department of Chemistry, Pohang University of Science and Technology

2014-04-28

Simulating molecular dynamics directly on quantum chemically obtained potential energy surfaces is generally time consuming. The cost becomes overwhelming especially when excited state dynamics is aimed with multiple electronic states. The interpolated potential has been suggested as a remedy for the cost issue in various simulation settings ranging from fast gas phase reactions of small molecules to relatively slow condensed phase dynamics with complex surrounding. Here, we present a scheme for interpolating multiple electronic surfaces of a relatively large molecule, with an intention of applying it to studying nonadiabatic behaviors. The scheme starts with adiabatic potential information and its diabaticmore » transformation, both of which can be readily obtained, in principle, with quantum chemical calculations. The adiabatic energies and their derivatives on each interpolation center are combined with the derivative coupling vectors to generate the corresponding diabatic Hamiltonian and its derivatives, and they are subsequently adopted in producing a globally defined diabatic Hamiltonian function. As a demonstration, we employ the scheme to build an interpolated Hamiltonian of a relatively large chromophore, para-hydroxybenzylidene imidazolinone, in reference to its all-atom analytical surface model. We show that the interpolation is indeed reliable enough to reproduce important features of the reference surface model, such as its adiabatic energies and derivative couplings. In addition, nonadiabatic surface hopping simulations with interpolation yield population transfer dynamics that is well in accord with the result generated with the reference analytic surface. With these, we conclude by suggesting that the interpolation of diabatic Hamiltonians will be applicable for studying nonadiabatic behaviors of sizeable molecules.« less

Numerical prediction of the Mid-Atlantic states cyclone of 18-19 February 1979

NASA Technical Reports Server (NTRS)

Atlas, R.; Rosenberg, R.

1982-01-01

A series of forecast experiments was conducted to assess the accuracy of the GLAS model, and to determine the importance of large scale dynamical processes and diabatic heating to the cyclogenesis. The GLAS model correctly predicted intense coastal cyclogenesis and heavy precipitation. Repeated without surface heat and moisture fluxes, the model failed to predict any cyclone development. An extended range forecast, a forecast from the NMC analysis interpolated to the GLAS grid, and a forecast from the GLAS analysis with the surface moisture flux excluded predicted weak coastal low development. Diabatic heating resulting from oceanic fluxes significantly contributed to the generation of low level cyclonic vorticity and the intensification and slow rate of movement of an upper level ridge over the western Atlantic. As an upper level short wave trough approached this ridge, diabatic heating associated with the release of latent heat intensified, and the gradient of vorticity, vorticity advection and upper level divergence in advance of the trough were greatly increased, providing strong large scale forcing for the surface cyclogenesis.

Composite Study Of Aerosol Long-Range Transport Events From East Asia And North America

NASA Astrophysics Data System (ADS)

Jiang, X.; Waliser, D. E.; Guan, B.; Xavier, P.; Petch, J.; Klingaman, N. P.; Woolnough, S.

2011-12-01

While the Madden-Julian Oscillation (MJO) exerts pronounced influences on global climate and weather systems, current general circulation models (GCMs) exhibit rather limited capability in representing this prominent tropical variability mode. Meanwhile, the fundamental physics of the MJO are still elusive. Given the central role of the diabatic heating for prevailing MJO theories and demands for reducing the model deficiencies in simulating the MJO, a global model inter-comparison project on diabatic processes and vertical heating structure associated with the MJO has been coordinated through a joint effort by the WCRP-WWRP/THORPEX YOTC MJO Task Force and GEWEX GASS Program. In this presentation, progress of this model inter-comparison project will be reported, with main focus on climate simulations from about 27 atmosphere-only and coupled GCMs. Vertical structures of heating and diabatic processes associated with the MJO based on multi-model simulations will be presented along with their reanalysis and satellite estimate counterparts. Key processes possibly responsible for a realistic simulation of the MJO, including moisture-convection interaction, gross moist stability, ocean coupling, and surface heat flux, will be discussed.

Theoretical calculation of reorganization energy for electron self-exchange reaction by constrained density functional theory and constrained equilibrium thermodynamics.

PubMed

Ren, Hai-Sheng; Ming, Mei-Jun; Ma, Jian-Yi; Li, Xiang-Yuan

2013-08-22

Within the framework of constrained density functional theory (CDFT), the diabatic or charge localized states of electron transfer (ET) have been constructed. Based on the diabatic states, inner reorganization energy λin has been directly calculated. For solvent reorganization energy λs, a novel and reasonable nonequilibrium solvation model is established by introducing a constrained equilibrium manipulation, and a new expression of λs has been formulated. It is found that λs is actually the cost of maintaining the residual polarization, which equilibrates with the extra electric field. On the basis of diabatic states constructed by CDFT, a numerical algorithm using the new formulations with the dielectric polarizable continuum model (D-PCM) has been implemented. As typical test cases, self-exchange ET reactions between tetracyanoethylene (TCNE) and tetrathiafulvalene (TTF) and their corresponding ionic radicals in acetonitrile are investigated. The calculated reorganization energies λ are 7293 cm(-1) for TCNE/TCNE(-) and 5939 cm(-1) for TTF/TTF(+) reactions, agreeing well with available experimental results of 7250 cm(-1) and 5810 cm(-1), respectively.

Global distribution of moisture, evaporation-precipitation, and diabatic heating rates

NASA Technical Reports Server (NTRS)

Christy, John R.

1989-01-01

Global archives were established for ECMWF 12-hour, multilevel analysis beginning 1 January 1985; day and night IR temperatures, and solar incoming and solar absorbed. Routines were written to access these data conveniently from NASA/MSFC MASSTOR facility for diagnostic analysis. Calculations of diabatic heating rates were performed from the ECMWF data using 4-day intervals. Calculations of precipitable water (W) from 1 May 1985 were carried out using the ECMWF data. Because a major operational change on 1 May 1985 had a significant impact on the moisture field, values prior to that date are incompatible with subsequent analyses.

Investigating the sensitivity of hurricane intensity and trajectory to sea surface temperatures using the regional model WRF

NASA Astrophysics Data System (ADS)

Kilic, Cevahir; Raible, Christoph C.

2015-04-01

It is well known that the sea surface temperature (SST) has an influence on the development and intensification of tropical cyclones (TCs). This influence has become even more important during the past decades, as TCs show an intensification, which goes along with an increase in SSTs. The influence of sea surface temperature (SST) anomalies on the hurricane characteristics are investigated in a set of sensitivity experiments employing the Weather Research and Forecasting (WRF) model. The idealised experiments are performed for the case of Hurricane Katrina in 2005. (Kilic and Raible, 2013) The first set of sensitivity experiments with basin-wide changes of the SST magnitude shows that the intensity goes along with changes in the SST, i.e., an increase in SST leads to an intensification of Katrina. Additionally, the trajectory is shifted to the west (east), with increasing (decreasing) SSTs. The main reason is a strengthening of the background flow. To gain further insights in the dynamics, the potential vorticity (PV) and its tendency (PVT) are analysed. A positive PVT is located to the moving direction relative to the TC centre. Splitting the PVT in the horizontal advection, vertical advection, and diabatic heating terms, we find that mainly the horizontal advection term contributes to this PVT maximum, due to a steering by strong environmental flow. The impact of the diabatic heating is of minor importance and, hence, the TC motion is dominated by horizontal advection. The amount of the horizontal advection as well as the amount of the diabatic heating rise with increasing SST due to the enhanced Carnot cycle. The second set of experiments investigates the influence of Loop Current eddies idealised by localised SST anomalies. The intensity of Hurricane Katrina is enhanced with increasing SSTs close to the core of a TC. Negative nearby SST anomalies reduce the intensity. The trajectory only changes if positive SST anomalies are located west or north of the hurricane centre. In this case the hurricane is attracted by the SST anomaly which causes an additional moisture source and increased vertical winds. This study confirm the linear relation between SST and TC intensity. However, in case of localised SST anomalies, the relative location to the TC core determes the gradient of the linear relation. The gradient decreases with increasing distance between SST anomaly and initialisation point. The anomalies located west and north of the initialisation point have a stronger impact than the ones located south and east, as they lie in the moving direction of the TC. Further, in terms of magnitude and pattern, the horizontal advection term of PVT does not strongly differ from the reference simulation. However, the pattern of diabatic heating term differs: A maximum of diabatic heating is still located in moving direction, but additionally the diabatic heating is found in the spiral rain bands. Thus, the vortex is drifted to the SST anomaly due to the asymmetry in the TC circulation induced by the diabatic heating term of the PVT. References Kilic, C., and C. C. Raible, Investigating the sensitivity of hurricane intensity and trajectory to sea surface temperatures using the regional model WRF, METEOROLOGISCHE ZEITSCHRIFT, 22(6), 685-698, 2013.

Extratropical Cyclones Leading to Extreme Weather Events over Central and Eastern North America

NASA Astrophysics Data System (ADS)

Bentley, Alicia M.

Cool-season extreme weather events (EWEs) occurring over central and eastern North America are typically associated with strong extratropical cyclones (ECs) that are governed by varying combinations of baroclinic, diabatic, and barotropic processes. This dissertation investigates the climatology, evolution, and predictability of ECs leading to EWEs over central and eastern North America, and provides a foundation on which to compare ECs leading to EWEs to ordinary ECs forming over and traversing the same regions. A climatology of ECs leading to EWEs over central and eastern North America during October-March 1979-2016 reveals that these ECs typically form 1) in the lee of the Rocky Mountains, 2) over the south central U.S., and 3) along the east coast of North America at latitudes equatorward of the typical genesis locations of ordinary ECs. ECs leading to EWEs included in the climatology form most frequently in November and March, when the seasonal alignment of baroclinic and convectively driven forcings occurs. Consistent with previous studies of North American ECs, the location and frequency of ECs leading to EWEs are partially determined by the states of the Pacific-North American pattern and the North Atlantic Oscillation. Metrics representing baroclinic, diabatic, and barotropic processes are formulated in this dissertation and are used to determine the combinations of baroclinic, diabatic, and barotropic processes associated with the formation and maintenance of ordinary ECs and ECs leading to EWEs. These metrics reveal that ECs leading to EWEs are associated with contributions from baroclinic, diabatic, and barotropic processes that are 1) similar to those associated with ordinary ECs at the time of formation (t0) and 2) considerably larger than those associated with ordinary ECs at the time of maximum intensity (tmax). Baroclinic processes typically contribute more than diabatic and barotropic processes throughout the evolution of ECs leading to EWEs. Diabatic processes typically contribute more during the intensification of ECs leading to EWEs than during their maintenance after tmax, whereas barotropic processes typically contribute more during the maintenance of ECs leading to EWEs after tmax than during their intensification. The relative contributions from baroclinic, diabatic, and barotropic processes during the evolution of ECs leading to EWEs are also shown to differ based on their genesis location. The 1.0° NOAA Global Ensemble Forecast System (GEFS) reforecast dataset is used in this dissertation to evaluate the forecast skill associated with ordinary ECs and ECs leading to EWEs at 0-192-h lead times. Ordinary ECs are consistently too slow and left of track in the GEFS, and are often too weak at longer lead times. ECs leading to EWEs are consistently too weak, fast, and right of track in the GEFS at longer lead times, and consistently too strong, slow, and left of track at shorter lead times. The positions of ordinary ECs are forecast with less skill and more spread than the positions of ECs leading to EWEs in the GEFS, whereas the intensities of ordinary ECs and ECs leading to EWEs are forecast with similar skill and spread. Locations over central and eastern North America where the positions and intensities of ordinary ECs and ECs leading to EWEs are frequently forecast with relatively low and high skill and spread in the GEFS are also identified.

A multi-state fragment charge difference approach for diabatic states in electron transfer: Extension and automation

NASA Astrophysics Data System (ADS)

Yang, Chou-Hsun; Hsu, Chao-Ping

2013-10-01

The electron transfer (ET) rate prediction requires the electronic coupling values. The Generalized Mulliken-Hush (GMH) and Fragment Charge Difference (FCD) schemes have been useful approaches to calculate ET coupling from an excited state calculation. In their typical form, both methods use two eigenstates in forming the target charge-localized diabatic states. For problems involve three or four states, a direct generalization is possible, but it is necessary to pick and assign the locally excited or charge-transfer states involved. In this work, we generalize the 3-state scheme for a multi-state FCD without the need of manual pick or assignment for the states. In this scheme, the diabatic states are obtained separately in the charge-transfer or neutral excited subspaces, defined by their eigenvalues in the fragment charge-difference matrix. In each subspace, the Hamiltonians are diagonalized, and there exist off-diagonal Hamiltonian matrix elements between different subspaces, particularly the charge-transfer and neutral excited diabatic states. The ET coupling values are obtained as the corresponding off-diagonal Hamiltonian matrix elements. A similar multi-state GMH scheme can also be developed. We test the new multi-state schemes for the performance in systems that have been studied using more than two states with FCD or GMH. We found that the multi-state approach yields much better charge-localized states in these systems. We further test for the dependence on the number of state included in the calculation of ET couplings. The final coupling values are converged when the number of state included is increased. In one system where experimental value is available, the multi-state FCD coupling value agrees better with the previous experimental result. We found that the multi-state GMH and FCD are useful when the original two-state approach fails.

Observational and Modeling Studies of Radiative, Chemical, and Dynamical Interactions in the Earth''s Atmosphere

NASA Technical Reports Server (NTRS)

Salby, Murry

1998-01-01

A 3-dimensional model was developed to support mechanistic studies. The model solves the global primitive equations in isentropic coordinates, which directly characterize diabatic processes forcing the Brewer-Dobson circulation of the middle atmosphere. It's numerical formulation is based on Hough harmonics, which partition horizontal motion into its rotational and divergent components. These computational features, along with others, enable 3D integrations to be performed practically on RISC computer architecture, on which they can be iterated to support mechanistic studies. The model conserves potential vorticity quite accurately under adiabatic conditions. Forced by observed tropospheric structure, in which integrations are anchored, the model generates a diabatic circulation that is consistent with satellite observations of tracer behavior and diabatic cooling rates. The model includes a basic but fairly complete treatment of gas-phase photochemistry that represents some 20 chemical species and 50 governing reactions with diurnally-varying shortwave absorption. The model thus provides a reliable framework to study transport and underlying diabatic processes, which can then be compared against chemical and dynamical structure observed and in GCM integrations. Integrations with the Langley GCM were performed to diagnose feedback between simulated convection and the tropical circulation. These were studied in relation to tropospheric properties controlling moisture convergence and environmental conditions supporting deep convection, for comparison against mechanistic integrations of wave CISK that successfully reproduce the Madden-Julian Oscillation (MJO) of the tropical circulation. These comparisons were aimed at identifying and ultimately improving aspects of the convective simulation, with the objective of recovering a successful simulation of the MJO in the Langley GCM, behavior that should be important to budgets of upper-tropospheric water vapor and chemical species.

Tropopause Inversion Layer and Stratosphere-Troposphere Exchange in Baroclinic Life Cycles: The Role of Diabatic Processes

NASA Astrophysics Data System (ADS)

Kunkel, D.; Hoor, P. M.; Wirth, V.

2014-12-01

Observations and model simulations of temperature and tracer profiles in the extratropical upper troposphere/lower stratosphere (UTLS) show the presence of an inversion layer just above the thermal tropopause, i.e., the tropopause inversion layer (TIL), which is situated in a region affected by stratosphere-troposphere exchange (STE). Moreover, from a dynamical perspective the extratropical UTLS is highly affected by baroclinic life cycles. Since both the TIL and STE emerge, amongst many other features, during simulated baroclinic life cycles, we study whether there is a relationship between the TIL and STE. We use the non-hydrostatic model COSMO in an idealized mid-latitude channel configuration to simulate baroclinic life cycles. In a first step contributions of individual diabatic processes from turbulence, radiation, and cloud microphysics to the formation of the TIL are analyzed. These results are compared to those from adiabatic simulations in which the TIL forms during the life cycles with the limitation of being less sharp than in observations. Furthermore, passive tropospheric and stratospheric tracers are used to identify STE. Regions of STE are then analyzed with respect to the temporal evolution of the static stability above the tropopause. The results suggest that radiative effects, especially from water vapor, have the largest additional contribution to the TIL formation, while additional individual effects of cloud microphysics are almost negligible. STE occurs in all diabatic simulations but its strength depends highly on how the underlying diabatic process can affect the thermal and dynamical structure in the tropopause region. Weak STE is found when considering cloud microphysics, while STE is stronger in case of using turbulence and radiation. Tropopause-based vertical profiles of the tropospheric tracers show in some cases similarities with observed tracer profiles of CO.

Vertical structure and physical processes of the Madden-Julian oscillation: Linking hindcast fidelity to simulated diabatic heating and moistening

DOE PAGES

Klingaman, Nicholas P.; Woolnough, Steven J.; Jiang, Xianan; ...

2015-04-10

Here, many theories for the Madden-Julian oscillation (MJO) focus on diabatic processes, particularly the evolution of vertical heating and moistening. Poor MJO performance in weather and climate models is often blamed on biases in these processes and their interactions with the large-scale circulation. We introduce one of the three components of a model evaluation project, which aims to connect MJO fidelity in models to their representations of several physical processes, focusing on diabatic heating and moistening. This component consists of 20 day hindcasts, initialized daily during two MJO events in winter 2009–2010. The 13 models exhibit a range of skill:more » several have accurate forecasts to 20 days lead, while others perform similarly to statistical models (8–11 days). Models that maintain the observed MJO amplitude accurately predict propagation, but not vice versa. We find no link between hindcast fidelity and the precipitation-moisture relationship, in contrast to other recent studies. There is also no relationship between models' performance and the evolution of their diabatic heating profiles with rain rate. A more robust association emerges between models' fidelity and net moistening: the highest-skill models show a clear transition from low-level moistening for light rainfall to midlevel moistening at moderate rainfall and upper level moistening for heavy rainfall. The midlevel moistening, arising from both dynamics and physics, may be most important. Accurately representing many processes may be necessary but not sufficient for capturing the MJO, which suggests that models fail to predict the MJO for a broad range of reasons and limits the possibility of finding a panacea.« less

Short-range precipitation forecasts using assimilation of simulated satellite water vapor profiles and column cloud liquid water amounts

NASA Technical Reports Server (NTRS)

Wu, Xiaohua; Diak, George R.; Hayden, Cristopher M.; Young, John A.

1995-01-01

These observing system simulation experiments investigate the assimilation of satellite-observed water vapor and cloud liquid water data in the initialization of a limited-area primitive equations model with the goal of improving short-range precipitation forecasts. The assimilation procedure presented includes two aspects: specification of an initial cloud liquid water vertical distribution and diabatic initialization. The satellite data is simulated for the next generation of polar-orbiting satellite instruments, the Advanced Microwave Sounding Unit (AMSU) and the High-Resolution Infrared Sounder (HIRS), which are scheduled to be launched on the NOAA-K satellite in the mid-1990s. Based on cloud-top height and total column cloud liquid water amounts simulated for satellite data a diagnostic method is used to specify an initial cloud water vertical distribution and to modify the initial moisture distribution in cloudy areas. Using a diabatic initialization procedure, the associated latent heating profiles are directly assimilated into the numerical model. The initial heating is estimated by time averaging the latent heat release from convective and large-scale condensation during the early forecast stage after insertion of satellite-observed temperature, water vapor, and cloud water formation. The assimilation of satellite-observed moisture and cloud water, together withy three-mode diabatic initialization, significantly alleviates the model precipitation spinup problem, especially in the first 3 h of the forecast. Experimental forecasts indicate that the impact of satellite-observed temperature and water vapor profiles and cloud water alone in the initialization procedure shortens the spinup time for precipitation rates by 1-2 h and for regeneration of the areal coverage by 3 h. The diabatic initialization further reduces the precipitation spinup time (compared to adiabatic initialization) by 1 h.

Quasi-biennial oscillations of ozone and diabatic circulation in the equatorial stratosphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hasebe, F.

1994-03-01

The quasi-biennial oscillation (QBO) in ozone in the equatorial stratosphere is obtained by analyzing the Stratospheric Aerosol and Gas Experiment (SAGE) data from 1984 to 1989. The phase of the ozone QBO in the lower stratosphere is found to precede the zonal wind QBO by several months as opposed to the theoretically expected in-phase relationship between the two. A mechanistic model is developed; to explore possible reasons for this disagreement. The model is capable of simulating the actual time evolution of the ozone QBO by introducing the observed zonal wind profile as input. The modeled results confirm the conventional viewmore » that the ozone QBO is generated by the vertical ozone advection that is driven to maintain the temperature structure against radiative damping. However, a series of experiments emphasizes the importance of the feedback of the ozone QBO to the diabatic heating through the absorption of solar radiation. Due to this effect, the phase of the ozone QBO shifts up to a quarter cycle ahead and approaches that of the temperature QBO. Because of this in-phase relationship, the feedback of the ozone QBO to the diabatic heating acts to compensate for the radiative damping of the temperature structure, thus reducing the magnitude of the induced diabatic circulation. Because the reduction of the magnitude of the vertical motion facilitates downward transport of easterly momentum by the mean flow, this feedback process can help to resolve the insufficiency of the easterly momentum in driving the dynamical QBO in GCMs. It should be emphasized that more sophisticated models that allow for full interaction between the chemical species and radiative and dynamical processes should be developed to improve the understanding of both dynamical and ozone QBOs. 48 refs., 13 figs., 2 tabs.« less

Quasi-biennial oscillations of ozone and diabatic circulation in the equatorial stratosphere

NASA Technical Reports Server (NTRS)

Hasebe, Fumio

1994-01-01

The quasi-biennial oscillation (QBO) in ozone in the equatorial stratosphere is obtained by analyzing the Stratospheric Aerosol and Gas Experiment (SAGE) data from 1984 to 1989. The phase of the ozone QBO in the lower stratosphere is found to precede the zonal wind QBO by several months as opposed to the theoretically expected in-phase relationship between the two. A mechanistic model is developed to explore possible reasons for this disagreement. The model is capable of simulating the actual time evolution of the ozone QBO by introducing the observed zonal wind profile as input. The modeled results confirm the conventional view that the ozone QBO is generated by the vertical ozone advection that is driven to maintain the temperature structure against radiative damping. However, a series of experiments emphasizes the importance of the feedback of the ozone QBO to the diabatic heating through the absorption of solar radiation. Due to this effect, the phase of the ozone QBO shifts up to a quarter cycle ahead and approaches that of the temperature QBO. Because of this inphase relationship, the feedback of the ozone QBO to the diabatic heating acts to compensate for the radiative damping of the temperature structure, thus reducing the magnitude of the induced diabatic circulation. Because the reduction of the magnitude of the vertical motion facilitates downward transport of easterly momentum by the mean flow, this feedback process can help to resolve the insufficiency of the easterly momentum in driving the dynamical QBO in general circulation models (GCMs). It should be emphasized that more sophisticated models that allow for full interaction between the chemical species and radiative and dynamical processes should be developed to improve our understanding of both dynamical and ozone QBOs.

Ultracold Heteronuclear Three-Body Systems: How Diabaticity Limits the Universality of Recombination into Shallow Dimers

NASA Astrophysics Data System (ADS)

Giannakeas, P.; Greene, Chris H.

2018-01-01

The mass-imbalanced three-body recombination process that forms a shallow dimer is shown to possess a rich Efimov-Stückelberg landscape, with corresponding spectra that differ fundamentally from the homonuclear case. A semianalytical treatment of the three-body recombination predicts unusual spectra with intertwined resonance peaks and minima and yields in-depth insight into the behavior of the corresponding Efimov spectra. In particular, the patterns of the Efimov-Stückelberg landscape are shown to depend inherently on the degree of diabaticity of the three-body collisions, which strongly affects the universality of the heteronuclear Efimov states.

An improved quasi-diabatic representation of the 1, 2, 3{sup 1}A coupled adiabatic potential energy surfaces of phenol in the full 33 internal coordinates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Xiaolei, E-mail: virtualzx@gmail.com; Malbon, Christopher L., E-mail: clmalbon@gmail.com; Yarkony, David R., E-mail: yarkony@jhu.edu

2016-03-28

In a recent work we constructed a quasi-diabatic representation, H{sup d}, of the 1, 2, 3{sup 1}A adiabatic states of phenol from high level multireference single and double excitation configuration interaction electronic structure data, energies, energy gradients, and derivative couplings. That H{sup d} accurately describes surface minima, saddle points, and also regions of strong nonadiabatic interactions, reproducing the locus of conical intersection seams and the coordinate dependence of the derivative couplings. The present work determines the accuracy of H{sup d} for describing phenol photodissociation. Additionally, we demonstrate that a modest energetic shift of two diabats yields a quantifiably more accuratemore » H{sup d} compared with experimental energetics. The analysis shows that in favorable circumstances it is possible to use single point energies obtained from the most reliable electronic structure methods available, including methods for which the energy gradients and derivative couplings are not available, to improve the quality of a global representation of several coupled potential energy surfaces. Our data suggest an alternative interpretation of kinetic energy release measurements near λ{sub phot} ∼ 248 nm.« less

Diabatic Definition of Geometric Phase Effects.

PubMed

Izmaylov, Artur F; Li, Jiaru; Joubert-Doriol, Loïc

2016-11-08

Electronic wave functions in the adiabatic representation acquire nontrivial geometric phases (GPs) when corresponding potential energy surfaces undergo conical intersection (CI). These GPs have profound effects on the nuclear quantum dynamics and cannot be eliminated in the adiabatic representation without changing the physics of the system. To define dynamical effects arising from the GP presence, the nuclear quantum dynamics of the CI containing system is compared with that of the system with artificially removed GP. We explore a new construction of the system with removed GP via a modification of the diabatic representation for the original CI containing system. Using an absolute value function of diabatic couplings, we remove the GP while preserving adiabatic potential energy surfaces and CI. We assess GP effects in dynamics of a two-dimensional linear vibronic coupling model both for ground and excited state dynamics. Results are compared with those obtained with a conventional removal of the GP by ignoring double-valued boundary conditions of the real electronic wave functions. Interestingly, GP effects appear similar in two approaches only for the low energy dynamics. In contrast with the conventional approach, the new approach does not have substantial GP effects in the ultrafast excited state dynamics.

Full-dimensional ground- and excited-state potential energy surfaces and state couplings for photodissociation of thioanisole

NASA Astrophysics Data System (ADS)

Li, Shaohong L.; Truhlar, Donald G.

2017-02-01

Analytic potential energy surfaces (PESs) and state couplings of the ground and two lowest singlet excited states of thioanisole (C6H5SCH3) are constructed in a diabatic representation based on electronic structure calculations including dynamic correlation. They cover all 42 internal degrees of freedom and a wide range of geometries including the Franck-Condon region and the reaction valley along the breaking S-CH3 bond with the full ranges of the torsion angles. The parameters in the PESs and couplings are fitted to the results of smooth diabatic electronic structure calculations including dynamic electron correlation by the extended multi-configurational quasi-degenerate perturbation theory method for the adiabatic state energies followed by diabatization by the fourfold way. The fit is accomplished by the anchor points reactive potential method with two reactive coordinates and 40 nonreactive degrees of freedom, where the anchor-point force fields are obtained with a locally modified version of the QuickFF package. The PESs and couplings are suitable for study of the topography of the trilayer potential energy landscape and for electronically nonadiabatic molecular dynamics simulations of the photodissociation of the S-CH3 bond.

HIRDLS Observations and Simulation of a Lower Stratospheric Intrusion of Tropical Air to High Latitudes

NASA Technical Reports Server (NTRS)

Olsen, Mark A.; Douglass, Anne R.; Newman, Paul A.; Gille, John C.; Nardi, Bruno; Yudin, Valery A.; Kinnison, Douglas E.; Khosravi, Rashid

2008-01-01

On 26 January 2006, the High Resolution Dynamic Limb Sounder (HIRDLS) observed low mixing ratios of ozone and nitric acid in an approximately 2 km vertical layer near 100 hPa extending from the subtropics to 55 degrees N over North America. The subsequent evolution of the layer is simulated with the Global Modeling Initiative (GMI) model and substantiated with HIRDLS observations. Air with low mixing ratios of ozone is transported poleward to 80 degrees N. Although there is evidence of mixing with extratropical air and diabatic descent, much of the tropical intrusion returns to the subtropics. This study demonstrates that HIRDLS and the GMI model are capable of resolving thin intrusion events. The observations combined with simulation are a first step towards development of a quantitative understanding of the lower stratospheric ozone budget.

Scale Dependend Investigations of the Dynamic State Index Concerning the QG-Theory

NASA Astrophysics Data System (ADS)

Mueller, Annette; Névir, Peter

2017-04-01

The Dynamic State Index (DSI) indicates local deviations of the atmospheric flow field from a steady wind solution based on the primitive equations under adiabatic and inviscid conditions. We represent generalizations of the DSI for reduced models given by the quasi-geostrophic theory and the Rossby-model. By applying a Fourier transformation to the circumpolar geopotential height field we demonstrate the characteristic dipole structure of the DSI-field related to atmospheric waves. Furthermore, by applying data of the COSMO-DE model of the German Weather Service (DWD), we compare the vertical profile of all three DSI-parameters concerning classes with and without precipitation. We work out that the relation to precipitation decreases with increasing approximation, but in all scales, it can be shown that the DSI is highly correlated to diabatic processes.

Tracer transport by the diabatic circulation deduced from satellite observations

NASA Technical Reports Server (NTRS)

Solomon, S.; Kiehl, J. T.; Garcia, R. R.; Grose, W.

1986-01-01

Nimbus-7 sensor data were used to track the diabatic circulation in the stratosphere to study the advective transport of CH4 and N2O as tracer species. Advective transport by the mean circulation was found to be a function of the temperature field and associated deviations from radiative equilibrium. A photochemical model was applied to account for the disappearance of the tracer species from the stratosphere. Comparisons between the SAMS data and modeling on the basis of the chemical loss rates of the tracers and the LIMS circulation data showed that the model predictions underestimated the resident abundances, although the global distributions and circulations exhibited a good match.

Speeding up adiabatic population transfer in a Josephson qutrit via counter-diabatic driving

NASA Astrophysics Data System (ADS)

Feng, Zhi-Bo; Lu, Xiao-Jing; Li, M.; Yan, Run-Ying; Zhou, Yun-Qing

2017-12-01

We propose a theoretical scheme to speed up adiabatic population transfer in a Josephson artificial qutrit by transitionless quantum driving. At a magic working point, an effective three-level subsystem can be chosen to constitute our qutrit. With Stokes and pump driving, adiabatic population transfer can be achieved in the qutrit by means of stimulated Raman adiabatic passage. Assisted by a counter-diabatic driving, the adiabatic population transfer can be sped up drastically with accessible parameters. Moreover, the accelerated operation is flexibly reversible and highly robust against decoherence effects. Thanks to these distinctive advantages, the present protocol could offer a promising avenue for optimal coherent operations in Josephson quantum circuits.

Extracting electron transfer coupling elements from constrained density functional theory

NASA Astrophysics Data System (ADS)

Wu, Qin; Van Voorhis, Troy

2006-10-01

Constrained density functional theory (DFT) is a useful tool for studying electron transfer (ET) reactions. It can straightforwardly construct the charge-localized diabatic states and give a direct measure of the inner-sphere reorganization energy. In this work, a method is presented for calculating the electronic coupling matrix element (Hab) based on constrained DFT. This method completely avoids the use of ground-state DFT energies because they are known to irrationally predict fractional electron transfer in many cases. Instead it makes use of the constrained DFT energies and the Kohn-Sham wave functions for the diabatic states in a careful way. Test calculations on the Zn2+ and the benzene-Cl atom systems show that the new prescription yields reasonable agreement with the standard generalized Mulliken-Hush method. We then proceed to produce the diabatic and adiabatic potential energy curves along the reaction pathway for intervalence ET in the tetrathiafulvalene-diquinone (Q-TTF-Q) anion. While the unconstrained DFT curve has no reaction barrier and gives Hab≈17kcal /mol, which qualitatively disagrees with experimental results, the Hab calculated from constrained DFT is about 3kcal /mol and the generated ground state has a barrier height of 1.70kcal/mol, successfully predicting (Q-TTF-Q)- to be a class II mixed-valence compound.

Optimal diabatic dynamics of Majorana-based quantum gates

NASA Astrophysics Data System (ADS)

Rahmani, Armin; Seradjeh, Babak; Franz, Marcel

2017-08-01

In topological quantum computing, unitary operations on qubits are performed by adiabatic braiding of non-Abelian quasiparticles, such as Majorana zero modes, and are protected from local environmental perturbations. In the adiabatic regime, with timescales set by the inverse gap of the system, the errors can be made arbitrarily small by performing the process more slowly. To enhance the performance of quantum information processing with Majorana zero modes, we apply the theory of optimal control to the diabatic dynamics of Majorana-based qubits. While we sacrifice complete topological protection, we impose constraints on the optimal protocol to take advantage of the nonlocal nature of topological information and increase the robustness of our gates. By using the Pontryagin's maximum principle, we show that robust equivalent gates to perfect adiabatic braiding can be implemented in finite times through optimal pulses. In our implementation, modifications to the device Hamiltonian are avoided. Focusing on thermally isolated systems, we study the effects of calibration errors and external white and 1 /f (pink) noise on Majorana-based gates. While a noise-induced antiadiabatic behavior, where a slower process creates more diabatic excitations, prohibits indefinite enhancement of the robustness of the adiabatic scheme, our fast optimal protocols exhibit remarkable stability to noise and have the potential to significantly enhance the practical performance of Majorana-based information processing.

Spin-Forbidden Reactions: Adiabatic Transition States Using Spin-Orbit Coupled Density Functional Theory.

PubMed

Gaggioli, Carlo Alberto; Belpassi, Leonardo; Tarantelli, Francesco; Harvey, Jeremy N; Belanzoni, Paola

2018-04-06

A spin-forbidden chemical reaction involves a change in the total electronic spin state from reactants to products. The mechanistic study is challenging because such a reaction does not occur on a single diabatic potential energy surface (PES), but rather on two (or multiple) spin diabatic PESs. One possible approach is to calculate the so-called "minimum energy crossing point" (MECP) between the diabatic PESs, which however is not a stationary point. Inclusion of spin-orbit coupling between spin states (SOC approach) allows the reaction to occur on a single adiabatic PES, in which a transition state (TS SOC) as well as activation free energy can be calculated. This Concept article summarizes a previously published application in which, for the first time, the SOC effects, using spin-orbit ZORA Hamiltonian within density functional theory (DFT) framework, are included and account for the mechanism of a spin-forbidden reaction in gold chemistry. The merits of the MECP and TS SOC approaches and the accuracy of the results are compared, considering both our recent calculations on molecular oxygen addition to gold(I)-hydride complexes and new calculations for the prototype spin-forbidden N 2 O and N 2 Se dissociation reactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spin-orbit coupled potential energy surfaces and properties using effective relativistic coupling by asymptotic representation.

PubMed

Ndome, Hameth; Eisfeld, Wolfgang

2012-08-14

A new method has been reported recently [H. Ndome, R. Welsch, and W. Eisfeld, J. Chem. Phys. 136, 034103 (2012)] that allows the efficient generation of fully coupled potential energy surfaces (PESs) including derivative and spin-orbit (SO) coupling. The method is based on the diabatic asymptotic representation of the molecular fine structure states and an effective relativistic coupling operator and therefore is called effective relativistic coupling by asymptotic representation (ERCAR). The resulting diabatic spin-orbit coupling matrix is constant and the geometry dependence of the coupling between the eigenstates is accounted for by the diabatization. This approach allows to generate an analytical model for the fully coupled PESs without performing any ab initio SO calculations (except perhaps for the atoms) and thus is very efficient. In the present work, we study the performance of this new method for the example of hydrogen iodide as a well-established test case. Details of the diabatization and the accuracy of the results are investigated in comparison to reference ab initio calculations. The energies of the adiabatic fine structure states are reproduced in excellent agreement with reference ab initio data. It is shown that the accuracy of the ERCAR approach mainly depends on the quality of the underlying ab initio data. This is also the case for dissociation and vibrational level energies, which are influenced by the SO coupling. A method is presented how one-electron operators and the corresponding properties can be evaluated in the framework of the ERCAR approach. This allows the computation of dipole and transition moments of the fine structure states in good agreement with ab initio data. The new method is shown to be very promising for the construction of fully coupled PESs for more complex polyatomic systems to be used in quantum dynamics studies.

The tropopause inversion layer in baroclinic life cycles experiments: the role of diabatic and mixing processes

NASA Astrophysics Data System (ADS)

Kunkel, D.; Hoor, P.; Wirth, V.

2015-08-01

Recent studies on the formation of a quasi-permanent layer of enhanced static stability above the thermal tropopause revealed the contributions of dynamical and radiative processes. Dry dynamics lead to the evolution of a tropopause inversion layer (TIL) which is, however, too weak compared to observations and thus diabatic contributions are required. In this study we aim to assess the importance of diabatic as well as mixing processes in the understanding of TIL formation at midlatitudes. The non-hydrostatic model COSMO is applied in an idealized mid-latitude channel configuration to simulate baroclinic life cycles. The effect of individual diabatic, i.e. related to humidity and radiation, and turbulent processes is studied first to estimate the additional contribution of these processes to dry dynamics. In a second step these processes are stepwise included in the model to increase the complexity and finally estimate the relative importance of each process. The results suggest that including turbulence leads to a weaker TIL than in a dry reference simulation. In contrast, the TIL evolves stronger when radiation is included but the temporal occurrence is still comparable to the reference. Using various cloud schemes in the model shows that latent heat release and consecutive increased vertical motions foster an earlier and stronger appearance of the TIL than in all other life cycles. Furthermore, updrafts moisten the upper troposphere and as such increase the radiative effect from water vapor. Particularly, this process becomes more relevant for maintaining the TIL during later stages of the life cycles. Increased convergence of the vertical wind induced by updrafts and by propagating and potentially dissipating inertia-gravity waves further contributes to the enhanced stability of the lower stratosphere. Furthermore, radiative feedback of ice clouds reaching up to the tropopause is identified to potentially further affect the strength of the TIL in the region of the cloud.

The tropopause inversion layer in baroclinic life-cycle experiments: the role of diabatic processes

NASA Astrophysics Data System (ADS)

Kunkel, D.; Hoor, P.; Wirth, V.

2016-01-01

Recent studies on the formation of a quasi-permanent layer of enhanced static stability above the thermal tropopause revealed the contributions of dynamical and radiative processes. Dry dynamics leads to the evolution of a tropopause inversion layer (TIL), which is, however, too weak compared to observations and thus diabatic contributions are required. In this study we aim to assess the importance of diabatic processes in the understanding of TIL formation at midlatitudes. The non-hydrostatic model COSMO (COnsortium for Small-scale MOdelling) is applied in an idealized midlatitude channel configuration to simulate baroclinic life cycles. The effect of individual diabatic processes related to humidity, radiation, and turbulence is studied first to estimate the contribution of each of these processes to the TIL formation in addition to dry dynamics. In a second step these processes are stepwise included in the model to increase the complexity and finally estimate the relative importance of each process. The results suggest that including turbulence leads to a weaker TIL than in a dry reference simulation. In contrast, the TIL evolves stronger when radiation is included but the temporal evolution is still comparable to the reference. Using various cloud schemes in the model shows that latent heat release and consecutive increased vertical motions foster an earlier and stronger appearance of the TIL than in all other life cycles. Furthermore, updrafts moisten the upper troposphere and as such increase the radiative effect from water vapor. Particularly, this process becomes more relevant for maintaining the TIL during later stages of the life cycles. Increased convergence of the vertical wind induced by updrafts and by propagating inertia-gravity waves, which potentially dissipate, further contributes to the enhanced stability of the lower stratosphere. Finally, radiative feedback of ice clouds reaching up to the tropopause is identified to potentially further affect the strength of the TIL in the region of the clouds.

The quantum dynamics of electronically nonadiabatic chemical reactions

NASA Technical Reports Server (NTRS)

Truhlar, Donald G.

1993-01-01

Considerable progress was achieved on the quantum mechanical treatment of electronically nonadiabatic collisions involving energy transfer and chemical reaction in the collision of an electronically excited atom with a molecule. In the first step, a new diabatic representation for the coupled potential energy surfaces was created. A two-state diabatic representation was developed which was designed to realistically reproduce the two lowest adiabatic states of the valence bond model and also to have the following three desirable features: (1) it is more economical to evaluate; (2) it is more portable; and (3) all spline fits are replaced by analytic functions. The new representation consists of a set of two coupled diabatic potential energy surfaces plus a coupling surface. It is suitable for dynamics calculations on both the electronic quenching and reaction processes in collisions of Na(3p2p) with H2. The new two-state representation was obtained by a three-step process from a modified eight-state diatomics-in-molecules (DIM) representation of Blais. The second step required the development of new dynamical methods. A formalism was developed for treating reactions with very general basis functions including electronically excited states. Our formalism is based on the generalized Newton, scattered wave, and outgoing wave variational principles that were used previously for reactive collisions on a single potential energy surface, and it incorporates three new features: (1) the basis functions include electronic degrees of freedom, as required to treat reactions involving electronic excitation and two or more coupled potential energy surfaces; (2) the primitive electronic basis is assumed to be diabatic, and it is not assumed that it diagonalizes the electronic Hamiltonian even asymptotically; and (3) contracted basis functions for vibrational-rotational-orbital degrees of freedom are included in a very general way, similar to previous prescriptions for locally adiabatic functions in various quantum scattering algorithms.

Canonical-ensemble state-averaged complete active space self-consistent field (SA-CASSCF) strategy for problems with more diabatic than adiabatic states: Charge-bond resonance in monomethine cyanines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Olsen, Seth, E-mail: seth.olsen@uq.edu.au

2015-01-28

This paper reviews basic results from a theory of the a priori classical probabilities (weights) in state-averaged complete active space self-consistent field (SA-CASSCF) models. It addresses how the classical probabilities limit the invariance of the self-consistency condition to transformations of the complete active space configuration interaction (CAS-CI) problem. Such transformations are of interest for choosing representations of the SA-CASSCF solution that are diabatic with respect to some interaction. I achieve the known result that a SA-CASSCF can be self-consistently transformed only within degenerate subspaces of the CAS-CI ensemble density matrix. For uniformly distributed (“microcanonical”) SA-CASSCF ensembles, self-consistency is invariant tomore » any unitary CAS-CI transformation that acts locally on the ensemble support. Most SA-CASSCF applications in current literature are microcanonical. A problem with microcanonical SA-CASSCF models for problems with “more diabatic than adiabatic” states is described. The problem is that not all diabatic energies and couplings are self-consistently resolvable. A canonical-ensemble SA-CASSCF strategy is proposed to solve the problem. For canonical-ensemble SA-CASSCF, the equilibrated ensemble is a Boltzmann density matrix parametrized by its own CAS-CI Hamiltonian and a Lagrange multiplier acting as an inverse “temperature,” unrelated to the physical temperature. Like the convergence criterion for microcanonical-ensemble SA-CASSCF, the equilibration condition for canonical-ensemble SA-CASSCF is invariant to transformations that act locally on the ensemble CAS-CI density matrix. The advantage of a canonical-ensemble description is that more adiabatic states can be included in the support of the ensemble without running into convergence problems. The constraint on the dimensionality of the problem is relieved by the introduction of an energy constraint. The method is illustrated with a complete active space valence-bond (CASVB) analysis of the charge/bond resonance electronic structure of a monomethine cyanine: Michler’s hydrol blue. The diabatic CASVB representation is shown to vary weakly for “temperatures” corresponding to visible photon energies. Canonical-ensemble SA-CASSCF enables the resolution of energies and couplings for all covalent and ionic CASVB structures contributing to the SA-CASSCF ensemble. The CASVB solution describes resonance of charge- and bond-localized electronic structures interacting via bridge resonance superexchange. The resonance couplings can be separated into channels associated with either covalent charge delocalization or chemical bonding interactions, with the latter significantly stronger than the former.« less

Canonical-ensemble state-averaged complete active space self-consistent field (SA-CASSCF) strategy for problems with more diabatic than adiabatic states: charge-bond resonance in monomethine cyanines.

PubMed

Olsen, Seth

2015-01-28

This paper reviews basic results from a theory of the a priori classical probabilities (weights) in state-averaged complete active space self-consistent field (SA-CASSCF) models. It addresses how the classical probabilities limit the invariance of the self-consistency condition to transformations of the complete active space configuration interaction (CAS-CI) problem. Such transformations are of interest for choosing representations of the SA-CASSCF solution that are diabatic with respect to some interaction. I achieve the known result that a SA-CASSCF can be self-consistently transformed only within degenerate subspaces of the CAS-CI ensemble density matrix. For uniformly distributed ("microcanonical") SA-CASSCF ensembles, self-consistency is invariant to any unitary CAS-CI transformation that acts locally on the ensemble support. Most SA-CASSCF applications in current literature are microcanonical. A problem with microcanonical SA-CASSCF models for problems with "more diabatic than adiabatic" states is described. The problem is that not all diabatic energies and couplings are self-consistently resolvable. A canonical-ensemble SA-CASSCF strategy is proposed to solve the problem. For canonical-ensemble SA-CASSCF, the equilibrated ensemble is a Boltzmann density matrix parametrized by its own CAS-CI Hamiltonian and a Lagrange multiplier acting as an inverse "temperature," unrelated to the physical temperature. Like the convergence criterion for microcanonical-ensemble SA-CASSCF, the equilibration condition for canonical-ensemble SA-CASSCF is invariant to transformations that act locally on the ensemble CAS-CI density matrix. The advantage of a canonical-ensemble description is that more adiabatic states can be included in the support of the ensemble without running into convergence problems. The constraint on the dimensionality of the problem is relieved by the introduction of an energy constraint. The method is illustrated with a complete active space valence-bond (CASVB) analysis of the charge/bond resonance electronic structure of a monomethine cyanine: Michler's hydrol blue. The diabatic CASVB representation is shown to vary weakly for "temperatures" corresponding to visible photon energies. Canonical-ensemble SA-CASSCF enables the resolution of energies and couplings for all covalent and ionic CASVB structures contributing to the SA-CASSCF ensemble. The CASVB solution describes resonance of charge- and bond-localized electronic structures interacting via bridge resonance superexchange. The resonance couplings can be separated into channels associated with either covalent charge delocalization or chemical bonding interactions, with the latter significantly stronger than the former.

Adiabatic/diabatic polarization beam splitter

DOEpatents

DeRose, Christopher; Cai, Hong

2017-09-12

The various presented herein relate to an on-chip polarization beam splitter (PBS), which is adiabatic for the transverse magnetic (TM) mode and diabatic for the transverse electric (TE) mode. The PBS comprises a through waveguide and a cross waveguide, wherein an electromagnetic beam comprising TE mode and TM mode components is applied to an input port of the through waveguide. The PBS can be utilized to separate the TE mode component from the TM mode component, wherein the TE mode component exits the PBS via an output port of the through waveguide, and the TM mode component exits the PBS via an output port of the cross waveguide. The PBS has a structure that is tolerant to manufacturing variations and exhibits high polarization extinction ratios over a wide bandwidth.

Diagonal Born-Oppenheimer correction for coupled-cluster wave-functions

NASA Astrophysics Data System (ADS)

Shamasundar, K. R.

2018-06-01

We examine how geometry-dependent normalisation freedom of electronic wave-functions affects extraction of a meaningful diagonal Born-Oppenheimer correction (DBOC) to the ground-state Born-Oppenheimer potential energy surface (PES). By viewing this freedom as a kind of gauge-freedom, it is shown that DBOC and the resulting associated mass-dependent adiabatic PES are gauge-invariant quantities. A sum-over-states (SOS) formula for DBOC which explicitly exhibits this invariance is derived. A biorthogonal formulation suitable for DBOC computations using standard unnormalised coupled-cluster (CC) wave-functions is presented. This is shown to lead to a biorthogonal version of SOS formula with similar properties. On this basis, different computational schemes for evaluating DBOC using approximate CC wave-functions are derived. One of this agrees with the formula used in the current literature. The connection to adiabatic-to-diabatic transformations in non-adiabatic dynamics is explored and complications arising from biorthogonal nature of CC theory are identified.

A rigorous approach to the formulation of extended Born-Oppenheimer equation for a three-state system

NASA Astrophysics Data System (ADS)

Sarkar, Biplab; Adhikari, Satrajit

If a coupled three-state electronic manifold forms a sub-Hilbert space, it is possible to express the non-adiabatic coupling (NAC) elements in terms of adiabatic-diabatic transformation (ADT) angles. Consequently, we demonstrate: (a) Those explicit forms of the NAC terms satisfy the Curl conditions with non-zero Divergences; (b) The formulation of extended Born-Oppenheimer (EBO) equation for any three-state BO system is possible only when there exists coordinate independent ratio of the gradients for each pair of ADT angles leading to zero Curls at and around the conical intersection(s). With these analytic advancements, we formulate a rigorous EBO equation and explore its validity as well as necessity with respect to the approximate one (Sarkar and Adhikari, J Chem Phys 2006, 124, 074101) by performing numerical calculations on two different models constructed with different chosen forms of the NAC elements.

Surface hopping simulation of vibrational predissociation of methanol dimer

NASA Astrophysics Data System (ADS)

Jiang, Ruomu; Sibert, Edwin L.

2012-06-01

The mixed quantum-classical surface hopping method is applied to the vibrational predissociation of methanol dimer, and the results are compared to more exact quantum calculations. Utilizing the vibrational SCF basis, the predissociation problem is cast into a curve crossing problem between dissociative and quasibound surfaces with different vibrational character. The varied features of the dissociative surfaces, arising from the large amplitude OH torsion, generate rich predissociation dynamics. The fewest switches surface hopping algorithm of Tully [J. Chem. Phys. 93, 1061 (1990), 10.1063/1.459170] is applied to both diabatic and adiabatic representations. The comparison affords new insight into the criterion for selecting the suitable representation. The adiabatic method's difficulty with low energy trajectories is highlighted. In the normal crossing case, the diabatic calculations yield good results, albeit showing its limitation in situations where tunneling is important. The quadratic scaling of the rates on coupling strength is confirmed. An interesting resonance behavior is identified and is dealt with using a simple decoherence scheme. For low lying dissociative surfaces that do not cross the quasibound surface, the diabatic method tends to overestimate the predissociation rate whereas the adiabatic method is qualitatively correct. Analysis reveals the major culprits involve Rabi-like oscillation, treatment of classically forbidden hops, and overcoherence. Improvements of the surface hopping results are achieved by adopting a few changes to the original surface hopping algorithms.

Extracting electron transfer coupling elements from constrained density functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu Qin; Van Voorhis, Troy

2006-10-28

Constrained density functional theory (DFT) is a useful tool for studying electron transfer (ET) reactions. It can straightforwardly construct the charge-localized diabatic states and give a direct measure of the inner-sphere reorganization energy. In this work, a method is presented for calculating the electronic coupling matrix element (H{sub ab}) based on constrained DFT. This method completely avoids the use of ground-state DFT energies because they are known to irrationally predict fractional electron transfer in many cases. Instead it makes use of the constrained DFT energies and the Kohn-Sham wave functions for the diabatic states in a careful way. Test calculationsmore » on the Zn{sub 2}{sup +} and the benzene-Cl atom systems show that the new prescription yields reasonable agreement with the standard generalized Mulliken-Hush method. We then proceed to produce the diabatic and adiabatic potential energy curves along the reaction pathway for intervalence ET in the tetrathiafulvalene-diquinone (Q-TTF-Q) anion. While the unconstrained DFT curve has no reaction barrier and gives H{sub ab}{approx_equal}17 kcal/mol, which qualitatively disagrees with experimental results, the H{sub ab} calculated from constrained DFT is about 3 kcal/mol and the generated ground state has a barrier height of 1.70 kcal/mol, successfully predicting (Q-TTF-Q){sup -} to be a class II mixed-valence compound.« less

Visualization and flow boiling heat transfer of hydrocarbons in a horizontal tube

NASA Astrophysics Data System (ADS)

Yang, Zhuqiang; Bi, Qincheng; Guo, Yong; Liu, Zhaohui; Yan, Jianguo

2013-07-01

Visualizations of a specific hydrocarbon fuel in a horizontal tube with 2.0 mm inside diameter were investigated. The experiments were conducted at mass velocity of 213.4, 426.5 and 640.2 kg/ (m2ṡs), diabatic lengths of 140, 240 and 420 mm under the pressure from 2.0-2.7 MPa. In the sub-pressure conditions, bubbly, intermittent, stratified-wave, churn and annular flow patterns were observed. The frictional pressure drops were also measured to distinguish the patterns. The development of flow patterns and frictional pressure drop were positively related to the mass velocity and the heat flux. However, the diabatic length of the tube takes an important part in the process. The residence time of the fluid does not only affect the transition of the patterns but influence the composition of the fuel manifested by the fuel color and carbon deposit. The special observational phenomenon was obtained for the supercritical pressure fluid. The flow in the tube became fuzzier and pressure drop changed sharply near the pseudocritical point. The flow boiling heat transfer characteristics of the hydrocarbons were also discussed respectively. The curve of critical heat flux about onset of nucleate boiling was plotted with different mass velocities and diabatic tube lengths. And heat transfer characteristics of supercritical fuel were proved to be better than that in subcritical conditions.

Precipitation and Diabatic Heating Distributions from TRMM/GPM

NASA Astrophysics Data System (ADS)

Olson, W. S.; Grecu, M.; Wu, D.; Tao, W. K.; L'Ecuyer, T.; Jiang, X.

2016-12-01

The initial focus of our research effort was the development of a physically-based methodology for estimating 3D precipitation distributions from a combination of spaceborne radar and passive microwave radiometer observations. This estimation methodology was originally developed for applications to Global Precipitation Measurement (GPM) mission sensor data, but it has recently been adapted to Tropical Rainfall Measuring Mission (TRMM) Precipitation Radar and Microwave Imager observations. Precipitation distributions derived from the TRMM sensors are interpreted using cloud-system resolving model simulations to infer atmospheric latent+eddy heating (Q1-QR) distributions in the tropics and subtropics. Further, the estimates of Q1-QR are combined with estimates of radiative heating (QR), derived from TRMM Microwave Imager and Visible and Infrared Scanner data as well as environmental properties from NCEP reanalyses, to yield estimates of the large-scale total diabatic heating (Q1). A thirteen-year database of precipitation and diabatic heating is constructed using TRMM observations from 1998-2010 as part of NASA's Energy and Water cycle Study program. State-dependent errors in precipitation and heating products are evaluated by propagating the potential errors of a priori modeling assumptions through the estimation method framework. Knowledge of these errors is critical for determining the "closure" of global water and energy budgets. Applications of the precipitation/heating products to climate studies will be presented at the conference.

The role of large-scale eddies in the climate equilibrium. Part 2: Variable static stability

NASA Technical Reports Server (NTRS)

Zhou, Shuntai; Stone, Peter H.

1993-01-01

Lorenz's two-level model on a sphere is used to investigate how the results of Part 1 are modified when the interaction of the vertical eddy heat flux and static stability is included. In general, the climate state does not depend very much on whether or not this interaction is included, because the poleward eddy heat transport dominates the eddy forcing of mean temperature and wind fields. However, the climatic sensitivity is significantly affected. Compared to two-level model results with fixed static stability, the poleward eddy heat flux is less sensitive to the meridional temperature gradient and the gradient is more sensitive to the forcing. For example, the logarithmic derivative of the eddy flux with respect to the gradient has a slope that is reduced from approximately 15 on a beta-plane with fixed static stability and approximately 6 on a sphere with fixed static stability, to approximately 3 to 4 in the present model. This last result is more in line with analyses from observations. The present model also has a stronger baroclinic adjustment than that in Part 1, more like that in two-level beta-plane models with fixed static stability, that is, the midlatitude isentropic slope is very insensitive to the forcing, the diabatic heating, and the friction, unless the forcing is very weak.

Effects of radiation and turbulence on the diabatic heating and water budget of the stratiform region of a tropical cloud cluster

NASA Technical Reports Server (NTRS)

Churchill, Dean D.; Houze, Robert A., Jr.

1991-01-01

A twi-dimensional kinematic model has been used to diagnose the thermodynamic, water vapor, and hydrometeor fields of the stratiform clouds associated with a mesoscale tropical cloud cluster. The model incorporates ice- and water-cloud microphysics, visible and infrared radiation, and convective adjustment. It is intended to determine the relative contributions of radiation, mycrophysics, and turbulence to diabatic heating, and the effects that radiation has on the water budget of the cluster in the absence of dynamical interactions. The model has been initialized with thermodynamic fields and wind velocities diagnosed from a GATE tropical squall line. It is found that radiation does not directly affect the water budget of the stratiform region, and any radiative effect on hydrometeors must involve interaction with dynamics.

Atmospheric Diabatic Heating in Different Weather States and the General Circulation

NASA Technical Reports Server (NTRS)

Rossow, William B.; Zhang, Yuanchong; Tselioudis, George

2016-01-01

Analysis of multiple global satellite products identifies distinctive weather states of the atmosphere from the mesoscale pattern of cloud properties and quantifies the associated diabatic heating/cooling by radiative flux divergence, precipitation, and surface sensible heat flux. The results show that the forcing for the atmospheric general circulation is a very dynamic process, varying strongly at weather space-time scales, comprising relatively infrequent, strong heating events by ''stormy'' weather and more nearly continuous, weak cooling by ''fair'' weather. Such behavior undercuts the value of analyses of time-averaged energy exchanges in observations or numerical models. It is proposed that an analysis of the joint time-related variations of the global weather states and the general circulation on weather space-time scales might be used to establish useful ''feedback like'' relationships between cloud processes and the large-scale circulation.

A theoretical study of the dissociative recombination of SH+ with electrons through the 2Π states of SH.

PubMed

Kashinski, D O; Talbi, D; Hickman, A P; Di Nallo, O E; Colboc, F; Chakrabarti, K; Schneider, I F; Mezei, J Zs

2017-05-28

A quantitative theoretical study of the dissociative recombination of SH + with electrons has been carried out. Multireference, configuration interaction calculations were used to determine accurate potential energy curves for SH + and SH. The block diagonalization method was used to disentangle strongly interacting SH valence and Rydberg states and to construct a diabatic Hamiltonian whose diagonal matrix elements provide the diabatic potential energy curves. The off-diagonal elements are related to the electronic valence-Rydberg couplings. Cross sections and rate coefficients for the dissociative recombination reaction were calculated with a stepwise version of the multichannel quantum defect theory, using the molecular data provided by the block diagonalization method. The calculated rates are compared with the most recent measurements performed on the ion Test Storage Ring (TSR) in Heidelberg, Germany.

Quantum entanglement and quantum information in biological systems (DNA)

NASA Astrophysics Data System (ADS)

Hubač, Ivan; Švec, Miloslav; Wilson, Stephen

2017-12-01

Recent studies of DNA show that the hydrogen bonds between given base pairs can be treated as diabatic systems with spin-orbit coupling. For solid state systems strong diabaticity and spin-orbit coupling the possibility of forming Majorana fermions has been discussed. We analyze the hydrogen bonds in the base pairs in DNA from this perspective. Our analysis is based on a quasiparticle supersymmetric transformation which couples electronic and vibrational motion and includes normal coordinates and the corresponding momenta. We define qubits formed by Majorana fermions in the hydrogen bonds and also discuss the entangled states in base pairs. Quantum information and quantum entropy are introduced. In addition to the well-known classical information connected with the DNA base pairs, we also consider quantum information and show that the classical and quantum information are closely connected.

Zonally averaged model of dynamics, chemistry and radiation for the atmosphere

NASA Technical Reports Server (NTRS)

Tung, K. K.

1985-01-01

A nongeostrophic theory of zonally averaged circulation is formulated using the nonlinear primitive equations on a sphere, taking advantage of the more direct relationship between the mean meridional circulation and diabatic heating rate which is available in isentropic coordinates. Possible differences between results of nongeostrophic theory and the commonly used geostrophic formulation are discussed concerning: (1) the role of eddy forcing of the diabatic circulation, and (2) the nonlinear nearly inviscid limit vs the geostrophic limit. Problems associated with the traditional Rossby number scaling in quasi-geostrophic formulations are pointed out and an alternate, more general scaling based on the smallness of mean meridional to zonal velocities for a rotating planet is suggested. Such a scaling recovers the geostrophic balanced wind relationship for the mean zonal flow but reveals that the mean meridional velocity is in general ageostrophic.

Generalized shortcuts to adiabaticity and enhanced robustness against decoherence

NASA Astrophysics Data System (ADS)

Santos, Alan C.; Sarandy, Marcelo S.

2018-01-01

Shortcuts to adiabaticity provide a general approach to mimic adiabatic quantum processes via arbitrarily fast evolutions in Hilbert space. For these counter-diabatic evolutions, higher speed comes at higher energy cost. Here, the counter-diabatic theory is employed as a minimal energy demanding scheme for speeding up adiabatic tasks. As a by-product, we show that this approach can be used to obtain infinite classes of transitionless models, including time-independent Hamiltonians under certain conditions over the eigenstates of the original Hamiltonian. We apply these results to investigate shortcuts to adiabaticity in decohering environments by introducing the requirement of a fixed energy resource. In this scenario, we show that generalized transitionless evolutions can be more robust against decoherence than their adiabatic counterparts. We illustrate this enhanced robustness both for the Landau-Zener model and for quantum gate Hamiltonians.

Numerical experiments with a general circulation model concerning the stratospheric distribution of ozone

NASA Technical Reports Server (NTRS)

Kurzeja, R. J.; Haggard, K. V.; Grose, W. L.

1981-01-01

Three experiments have been performed using a three-dimensional, spectral quasi-geostrophic model in order to investigate the sensitivity of ozone transport to tropospheric orographic and thermal effects and to the zonal wind distribution. In the first experiment, the ozone distribution averaged over the last 30 days of a 60 day transport simulation was determined; in the second experiment, the transport simulation was repeated, but nonzonal orographic and thermal forcing was omitted; and in the final experiment, the simulation was conducted with the intensity and position of the stratospheric jets altered by addition of a Newtonian cooling term to the zonal-mean diabatic heating rate. Results of the three experiments are summarized by comparing the zonal-mean ozone distribution, the amplitude of eddy geopotential height, the zonal winds, and zonal-mean diabatic heating.

Block-localized wavefunction (BLW) method at the density functional theory (DFT) level.

PubMed

Mo, Yirong; Song, Lingchun; Lin, Yuchun

2007-08-30

The block-localized wavefunction (BLW) approach is an ab initio valence bond (VB) method incorporating the efficiency of molecular orbital (MO) theory. It can generate the wavefunction for a resonance structure or diabatic state self-consistently by partitioning the overall electrons and primitive orbitals into several subgroups and expanding each block-localized molecular orbital in only one subspace. Although block-localized molecular orbitals in the same subspace are constrained to be orthogonal (a feature of MO theory), orbitals between different subspaces are generally nonorthogonal (a feature of VB theory). The BLW method is particularly useful in the quantification of the electron delocalization (resonance) effect within a molecule and the charge-transfer effect between molecules. In this paper, we extend the BLW method to the density functional theory (DFT) level and implement the BLW-DFT method to the quantum mechanical software GAMESS. Test applications to the pi conjugation in the planar allyl radical and ions with the basis sets of 6-31G(d), 6-31+G(d), 6-311+G(d,p), and cc-pVTZ show that the basis set dependency is insignificant. In addition, the BLW-DFT method can also be used to elucidate the nature of intermolecular interactions. Examples of pi-cation interactions and solute-solvent interactions will be presented and discussed. By expressing each diabatic state with one BLW, the BLW method can be further used to study chemical reactions and electron-transfer processes whose potential energy surfaces are typically described by two or more diabatic states.

"Adiabatic-hindered-rotor" treatment of the parahydrogen-water complex.

PubMed

Zeng, Tao; Li, Hui; Le Roy, Robert J; Roy, Pierre-Nicholas

2011-09-07

Inspired by a recent successful adiabatic-hindered-rotor treatment for parahydrogen pH(2) in CO(2)-H(2) complexes [H. Li, P.-N. Roy, and R. J. Le Roy, J. Chem. Phys. 133, 104305 (2010); H. Li, R. J. Le Roy, P.-N. Roy, and A. R. W. McKellar, Phys. Rev. Lett. 105, 133401 (2010)], we apply the same approximation to the more challenging H(2)O-H(2) system. This approximation reduces the dimension of the H(2)O-H(2) potential from 5D to 3D and greatly enhances the computational efficiency. The global minimum of the original 5D potential is missing from the adiabatic 3D potential for reasons based on solution of the hindered-rotor Schrödinger equation of the pH(2). Energies and wave functions of the discrete rovibrational levels of H(2)O-pH(2) complexes obtained from the adiabatic 3D potential are in good agreement with the results from calculations with the full 5D potential. This comparison validates our approximation, although it is a relatively cruder treatment for pH(2)-H(2)O than it is for pH(2)-CO(2). This adiabatic approximation makes large-scale simulations of H(2)O-pH(2) systems possible via a pairwise additive interaction model in which pH(2) is treated as a point-like particle. The poor performance of the diabatically spherical treatment of pH(2) rotation excludes the possibility of approximating pH(2) as a simple sphere in its interaction with H(2)O. © 2011 American Institute of Physics

Vibrational Properties of Hydrogen-Bonded Systems Using the Multireference Generalization to the "On-the-Fly" Electronic Structure within Quantum Wavepacket ab Initio Molecular Dynamics (QWAIMD).

PubMed

Li, Junjie; Li, Xiaohu; Iyengar, Srinivasan S

2014-06-10

We discuss a multiconfigurational treatment of the "on-the-fly" electronic structure within the quantum wavepacket ab initio molecular dynamics (QWAIMD) method for coupled treatment of quantum nuclear effects with electronic structural effects. Here, multiple single-particle electronic density matrices are simultaneously propagated with a quantum nuclear wavepacket and other classical nuclear degrees of freedom. The multiple density matrices are coupled through a nonorthogonal configuration interaction (NOCI) procedure to construct the instantaneous potential surface. An adaptive-mesh-guided set of basis functions composed of Gaussian primitives are used to simplify the electronic structure calculations. Specifically, with the replacement of the atom-centered basis functions positioned on the centers of the quantum-mechanically treated nuclei by a mesh-guided band of basis functions, the two-electron integrals used to compute the electronic structure potential surface become independent of the quantum nuclear variable and hence reusable along the entire Cartesian grid representing the quantum nuclear coordinates. This reduces the computational complexity involved in obtaining a potential surface and facilitates the interpretation of the individual density matrices as representative diabatic states. The parametric nuclear position dependence of the diabatic states is evaluated at the initial time-step using a Shannon-entropy-based sampling function that depends on an approximation to the quantum nuclear wavepacket and the potential surface. This development is meant as a precursor to an on-the-fly fully multireference electronic structure procedure embedded, on-the-fly, within a quantum nuclear dynamics formalism. We benchmark the current development by computing structural, dynamic, and spectroscopic features for a series of bihalide hydrogen-bonded systems: FHF(-), ClHCl(-), BrHBr(-), and BrHCl(-). We find that the donor-acceptor structural features are in good agreement with experiments. Spectroscopic features are computed using a unified velocity/flux autocorrelation function and include vibrational fundamentals and combination bands. These agree well with experiments and other theories.

Dynamics of Katabatic Winds in Colorado' Brush Creek Valley.

NASA Astrophysics Data System (ADS)

Vergeiner, I.; Dreiseitl, E.; Whiteman, C. David

1987-01-01

A method is proposed to evaluate the coupled mass, momentum and thermal energy budget equations for a deep valley under two-dimensional, steady-state flow conditions. The method requires the temperature, down- valley wind and valley width fields to be approximated by simple analytical functions. The vertical velocity field is calculated using the mass continuity equation. Advection terms in the momentum and energy equations are then calculated using finite differences computed on a vertical two-dimensional grid that runs down the valley's axis. The pressure gradient term in the momentum equation is calculated from the temperature field by means of the hydrostatic equation. The friction term is then calculated as a residual in the xmomentum equation, and the diabatic cooling term is calculated as a residual in the thermal energy budget equation.The method is applied to data from an 8-km-long segment of Colorado's; Brush Creek Valley on the night of 30-31 July 1982. Pressure decreased with distance down the peak on horizontal surfaces, with peak horizontal pressure gradients of 0.04 hPa km1. The valley mass budget indicated that subsidence was required in the valley to support calculated mean along-valley mass flux divergence. Peak subsidence rates on the order of 0.10 m s1 were calculated. Subsiding motions in the valley produced negative vertical down-valley momentum fluxes in the upper valley atmosphere, but produced positive down-valley momentum fluxes below the level of the jet. Friction, calculated as a residual in the x momentum equation, was negative, as expected on physical grounds. and attained reasonable quantitative values.The strong subsidence field in the stable valley atmosphere produced subsidence warming that was only partly counteracted by down-valley cold air advection. Strong diabatic cooling was therefore required in order to account for the weak net cooling of the valley atmosphere during the nighttime period when tethered balloon observations were made.

Diabatic models with transferrable parameters for generalized chemical reactions

NASA Astrophysics Data System (ADS)

Reimers, Jeffrey R.; McKemmish, Laura K.; McKenzie, Ross H.; Hush, Noel S.

2017-05-01

Diabatic models applied to adiabatic electron-transfer theory yield many equations involving just a few parameters that connect ground-state geometries and vibration frequencies to excited-state transition energies and vibration frequencies to the rate constants for electron-transfer reactions, utilizing properties of the conical-intersection seam linking the ground and excited states through the Pseudo Jahn-Teller effect. We review how such simplicity in basic understanding can also be obtained for general chemical reactions. The key feature that must be recognized is that electron-transfer (or hole transfer) processes typically involve one electron (hole) moving between two orbitals, whereas general reactions typically involve two electrons or even four electrons for processes in aromatic molecules. Each additional moving electron leads to new high-energy but interrelated conical-intersection seams that distort the shape of the critical lowest-energy seam. Recognizing this feature shows how conical-intersection descriptors can be transferred between systems, and how general chemical reactions can be compared using the same set of simple parameters. Mathematical relationships are presented depicting how different conical-intersection seams relate to each other, showing that complex problems can be reduced into an effective interaction between the ground-state and a critical excited state to provide the first semi-quantitative implementation of Shaik’s “twin state” concept. Applications are made (i) demonstrating why the chemistry of the first-row elements is qualitatively so different to that of the second and later rows, (ii) deducing the bond-length alternation in hypothetical cyclohexatriene from the observed UV spectroscopy of benzene, (iii) demonstrating that commonly used procedures for modelling surface hopping based on inclusion of only the first-derivative correction to the Born-Oppenheimer approximation are valid in no region of the chemical parameter space, and (iv), demonstrating the types of chemical reactions that may be suitable for exploitation as a chemical qubit in some quantum information processor.

An Analysis of Numerical Weather Prediction of the Diabatic Rossby Vortex

DTIC Science & Technology

2014-06-01

Forecast SLP Mean and Spread ...............................................................................................148   2.   DRV02 72 Hour...ECMWF Ensemble Forecast SLP Mean and Spread ...............................................................................................149   3...DRV03 72 Hour ECMWF Ensemble Forecast SLP Mean and Spread

Non-adiabatic molecular dynamics with complex quantum trajectories. I. The diabatic representation.

PubMed

Zamstein, Noa; Tannor, David J

2012-12-14

We extend a recently developed quantum trajectory method [Y. Goldfarb, I. Degani, and D. J. Tannor, J. Chem. Phys. 125, 231103 (2006)] to treat non-adiabatic transitions. Each trajectory evolves on a single surface according to Newton's laws with complex positions and momenta. The transfer of amplitude between surfaces stems naturally from the equations of motion, without the need for surface hopping. In this paper we derive the equations of motion and show results in the diabatic representation, which is rarely used in trajectory methods for calculating non-adiabatic dynamics. We apply our method to the first two benchmark models introduced by Tully [J. Chem. Phys. 93, 1061 (1990)]. Besides giving the probability branching ratios between the surfaces, the method also allows the reconstruction of the time-dependent wavepacket. Our results are in quantitative agreement with converged quantum mechanical calculations.

The Walker circulation, diabatic heating, and outgoing longwave radiation

NASA Astrophysics Data System (ADS)

Stechmann, S. N.; Ogrosky, H. R.

2014-12-01

For the tropical atmosphere on planetary scales, it is common to model the circulation using strong damping. Here, with new data analysis techniques, evidence suggests that damping can actually be neglected. Specifically, near the equator, the east--west overturning circulation is in agreement with the undamped wave response to atmospheric heating. To estimate the heating, satellite observations of outgoing longwave radiation (OLR) are used. Frequently OLR is used as a heuristic indicator of cloudiness. Here, the results further suggest that OLR variations are actually proportional to total diabatic heating variations, with a proportionality constant of 18 W m-2 (K/day)-1. While the agreement holds best over long time averages of years or decades, it also holds over shorter periods of one season or one month. Consequently, it is suggested that the strength of the Walker circulation -- and its evolution in time -- could be estimated using satellite data.

First-Principle Characterization for Singlet Fission Couplings.

PubMed

Yang, Chou-Hsun; Hsu, Chao-Ping

2015-05-21

The electronic coupling for singlet fission, an important parameter for determining the rate, has been found to be too small unless charge-transfer (CT) components were introduced in the diabatic states, mostly through perturbation or a model Hamiltonian. In the present work, the fragment spin difference (FSD) scheme was generalized to calculate the singlet fission coupling. The largest coupling strength obtained was 14.8 meV for two pentacenes in a crystal structure, or 33.7 meV for a transition-state structure, which yielded a singlet fission lifetime of 239 or 37 fs, generally consistent with experimental results (80 fs). Test results with other polyacene molecules are similar. We found that the charge on one fragment in the S1 diabatic state correlates well with FSD coupling, indicating the importance of the CT component. The FSD approach is a useful first-principle method for singlet fission coupling, without the need to include the CT component explicitly.

Three-dimensional evolution of water vapor distributions in the Northern Hemisphere stratosphere as observed by the MLS

NASA Technical Reports Server (NTRS)

Lahoz, W. A.; O'Neill, A.; Carr, E. S.; Harwood, R. S.; Froidevaux, L.; Read, W. G.; Waters, J. W.; Kumer, J. B.; Mergenthaler, J. L.; Roche, A. E.

1994-01-01

The three-dimensional evolution of stratospheric water vapor distributions observed by the Microwave Limb Sounder (MLS) during the period October 1991 - July 1992 is documented. The transport features inferred from the MLS water vapor distributions are corroborated using other dynamical fields, namely, nitrous oxide from the Cryogenic Limb Array Etalon Spectrometer instrument, analyzed winds from the U.K. Meteorological Office (UKMO), UKMO-derived potential vorticity, and the diabatic heating field. By taking a vortex-centered view and an along-track view, the authors observe in great detail the vertical and horizontal structure of the northern winter stratosphere. It is demonstrated that the water vapor distributions show clear signatures of the effects of diabatic descent through isentropic surfaces and quasi-horizontal transport along isentropic surfaces, and that the large-scale winter flow is organized by the interaction between the westerly polar vortex and the Aleutian high.

Laboratory Studies of Anomalous Entrainment in Cumulus Cloud Flows

NASA Astrophysics Data System (ADS)

Diwan, Sourabh S.; Narasimha, Roddam; Bhat, G. S.; Sreenivas, K. R.

2011-12-01

Entrainment in cumulus clouds has been a subject of investigation for the last sixty years, and continues to be a central issue in current research. The development of a laboratory facility that can simulate cumulus cloud evolution enables us to shed light on the problem. The apparatus for the purpose is based on a physical model of cloud flow as a plume with off-source diabatic heating that is dynamically similar to the effect of latent-heat release in natural clouds. We present a critical review of the experimental data so far obtained in such facilities on the variation of the entrainment coefficient in steady diabatic jets and plumes. Although there are some unexplained differences among different data sets, the dominant trend of the results compares favourably with recent numerical simulations on steady-state deep convection, and helps explain certain puzzles in the fluid dynamics of clouds.

Two-phase flow patterns in adiabatic and diabatic corrugated plate gaps

NASA Astrophysics Data System (ADS)

Polzin, A.-E.; Kabelac, S.; de Vries, B.

2016-09-01

Correlations for two-phase heat transfer and pressure drop can be improved considerably, when they are adapted to specific flow patterns. As plate heat exchangers find increasing application as evaporators and condensers, there is a need for flow pattern maps for corrugated plate gaps. This contribution presents experimental results on flow pattern investigations for such a plate heat exchanger background, using an adiabatic visualisation setup as well as a diabatic setup. Three characteristic flow patterns were observed in the considered range of two-phase flow: bubbly flow, film flow and slug flow. The occurrence of these flow patterns is a function of mass flux, void fraction, fluid properties and plate geometry. Two different plate geometries having a corrugation angle of 27° and 63°, respectively and two different fluids (water/air and R365mfc liquid/vapor) have been analysed. A flow pattern map using the momentum flux is presented.

Diabatic heating rate estimates from European Centre for Medium-Range Weather Forecasts analyses

NASA Technical Reports Server (NTRS)

Christy, John R.

1991-01-01

Vertically integrated diabatic heating rate estimates (H) calculated from 32 months of European Center for Medium-Range Weather Forecasts daily analyses (May 1985-December 1987) are determined as residuals of the thermodynamic equation in pressure coordinates. Values for global, hemispheric, zonal, and grid point H are given as they vary over the time period examined. The distribution of H is compared with previous results and with outgoing longwave radiation (OLR) measurements. The most significant negative correlations between H and OLR occur for (1) tropical and Northern-Hemisphere mid-latitude oceanic areas and (2) zonal and hemispheric mean values for periods less than 90 days. Largest positive correlations are seen in periods greater than 90 days for the Northern Hemispheric mean and continental areas of North Africa, North America, northern Asia, and Antarctica. The physical basis for these relationships is discussed. An interyear comparison between 1986 and 1987 reveals the ENSO signal.

The effect of physical parameterizations and initial data on the numerical prediction of the President's Day cyclone

NASA Technical Reports Server (NTRS)

Atlas, R.

1984-01-01

Results are presented from a series of forecast experiments which were conducted to assess the importance of large-scale dynamical processes, diabatic heating, and initial data to the prediction of the President's Day cyclone. The synoptic situation and NMC model forecasts for this case are summarized, and the analysis/forecast system and experiments are described. The GLAS Model forecast from the GLAS analysis at 0000 GMT 18 February is found to have correctly predicted intense coastal cyclogenesis and heavy precipitation. A forecast with surface heat and moisture fluxes eliminated failed to predict any cyclogenesis while a similar forecast with only the surface moisture flux excluded showed weak development. Diabatic heating resulting from oceanic fluxes significantly contributed to the generation of low-level cyclonic vorticity and the intensification and slow rate of movement of an upper level ridge over the western Atlantic.

Microwave (SSM/I) Estimates of the Precipitation Rate to Improve Numerical Atmospheric Model Forecasts

NASA Technical Reports Server (NTRS)

Raymond, William H.; Olson, William S.

1990-01-01

Delay in the spin-up of precipitation early in numerical atmospheric forecasts is a deficiency correctable by diabatic initialization combined with diabatic forcing. For either to be effective requires some knowledge of the magnitude and vertical placement of the latent heating fields. Until recently the best source of cloud and rain water data was the remotely sensed vertical integrated precipitation rate or liquid water content. Vertical placement of the condensation remains unknown. Some information about the vertical distribution of the heating rates and precipitating liquid water and ice can be obtained from retrieval techniques that use a physical model of precipitating clouds to refine and improve the interpretation of the remotely sensed data. A description of this procedure and an examination of its 3-D liquid water products, along with improved modeling methods that enhance or speed-up storm development is discussed.

Control of photodissociation and photoionization of the NaI molecule by dynamic Stark effect.

PubMed

Han, Yong-Chang; Yuan, Kai-Jun; Hu, Wen-Hui; Cong, Shu-Lin

2009-01-28

The diabatic photodissociation and photoionization processes of the NaI molecule are studied theoretically using the quantum wave packet method. A pump laser pulse is used to prepare a dissociation wave packet that propagates through both the ionic channel (NaI-->Na(+)+I(-)) and the covalent channel (NaI-->Na+I). A Stark pulse is used to control the diabatic dissociation dynamics and a probe pulse is employed to ionize the products from the two channels. Based on the first order nonresonant nonperturbative dynamic Stark effect, the dissociation probabilities and the branching ratio of the products from the two channels can be controlled. Moreover the final photoelectron kinetic energy distribution can also be affected by the Stark pulse. The influences of the delay time, intensity, frequency, and carrier-envelope phase of the Stark pulse on the dissociation and ionization dynamics of the NaI molecule are discussed in detail.

Multi-state trajectory approach to non-adiabatic dynamics: General formalism and the active state trajectory approximation

NASA Astrophysics Data System (ADS)

Tao, Guohua

2017-07-01

A general theoretical framework is derived for the recently developed multi-state trajectory (MST) approach from the time dependent Schrödinger equation, resulting in equations of motion for coupled nuclear-electronic dynamics equivalent to Hamilton dynamics or Heisenberg equation based on a new multistate Meyer-Miller (MM) model. The derived MST formalism incorporates both diabatic and adiabatic representations as limiting cases and reduces to Ehrenfest or Born-Oppenheimer dynamics in the mean-field or the single-state limits, respectively. In the general multistate formalism, nuclear dynamics is represented in terms of a set of individual state-specific trajectories, while in the active state trajectory (AST) approximation, only one single nuclear trajectory on the active state is propagated with its augmented images running on all other states. The AST approximation combines the advantages of consistent nuclear-coupled electronic dynamics in the MM model and the single nuclear trajectory in the trajectory surface hopping (TSH) treatment and therefore may provide a potential alternative to both Ehrenfest and TSH methods. The resulting algorithm features in a consistent description of coupled electronic-nuclear dynamics and excellent numerical stability. The implementation of the MST approach to several benchmark systems involving multiple nonadiabatic transitions and conical intersection shows reasonably good agreement with exact quantum calculations, and the results in both representations are similar in accuracy. The AST treatment also reproduces the exact results reasonably, sometimes even quantitatively well, with a better performance in the adiabatic representation.

Hydrostatic Adjustment in Vertically Stratified Atmospheres

NASA Technical Reports Server (NTRS)

Duffy, Dean G.

2000-01-01

Hydrostatic adjustment due to diabatic heat in two nonisothermal atmospheres is examined. In the first case the temperature stratification is continuous; in the second case the atmosphere is composed of a warm, isothermal troposphere and a colder, isothermal semi-infinitely deep stratosphere.In both cases hydrostatic adjustment, to a good approximation, follows the pattern found in the Lamb problem (semi-infinitely deep. isothermal atmosphere): Initially we have acoustic waves with the kinetic energy increasing or decreasing at the expense of available elastic energy. After this initial period the acoustic waves evolve into acoustic-gravity waves with the kinetic, available potential and available elastic energies interacting with each other. Relaxation to hydrostatic balance occurs within a few oscillations. Stratification in an atmosphere with a continuous temperature profile affects primarily the shape and amplitude of the disturbances. In the two-layer atmosphere, a certain amount of energy is trapped in the tropospheric waveguide as disturbances reflect off the tropopause and back into the troposphere. With each internal reflection a portion of this trapped energy escapes and radiates to infinity.

Diabatic Initialization of Mesoscale Models in the Southeastern United States: Can 0 to 12h Warm Season QPF be Improved?

NASA Technical Reports Server (NTRS)

Lapenta, William M.; Bradshaw, Tom; Burks, Jason; Darden, Chris; Dembek, Scott

2003-01-01

It is well known that numerical warm season quantitative precipitation forecasts lack significant skill for numerous reasons. Some are related to the model--it may lack physical processes required to realistically simulate convection or the numerical algorithms and dynamics employed may not be adequate. Others are related to initialization-mesoscale features play an important role in convective initialization and atmospheric observation systems are incapable of properly depicting the three-dimensional stability structure at the mesoscale. The purpose of this study is to determine if a mesoscale model initialized with a diabatic initialization scheme can improve short-term (0 to 12h) warm season quantitative precipitation forecasts in the Southeastern United States. The Local Analysis and Prediction System (LAPS) developed at the Forecast System Laboratory is used to diabatically initialize the Pennsylvania State University/National center for Atmospheric Research (PSUNCAR) Mesoscale Model version 5 (MM5). The SPORT Center runs LAPS operationally on an hourly cycle to produce analyses on a 15 km covering the eastern 2/3 of the United States. The 20 km National Centers for Environmental Prediction (NCEP) Rapid Update Cycle analyses are used for the background fields. Standard observational data are acquired from MADIS with GOES/CRAFT Nexrad data acquired from in-house feeds. The MM5 is configured on a 140 x 140 12 km grid centered on Huntsville Alabama. Preliminary results indicate that MM5 runs initialized with LAPS produce improved 6 and 12h QPF threat scores compared with those initialized with the NCEP RUC.

An Assessment of the Ozone Loss During the 1999-2000 SOLVE Campaign

NASA Technical Reports Server (NTRS)

Schoeberl, M. R.; Newman, P. A.; Lait, L. R.; McGee, T.; Burris, J.; Browell, E. V.; Richard, E.; VonderGathen, P.; Beveliaqua, R.; Mikkelsen, I. S.;

A TABULAR PRESENTATION OF THE SURFACE BOUNDARY LAYER MODELS OF WEBB, BUSINGER, AND PANOFSKY.

DTIC Science & Technology

methods. The models are presented in tabular form in terms of diabatic wind influence function , the gradient stability ratio and a universal function that corrects for thermal stratification in unstable air. (Author)

A Comparison of the Age-Spectra from Data Assimilation Models

NASA Technical Reports Server (NTRS)

Schoeberl, Mark R.; Douglass, Anne R.; Zhu, Zheng-Xin; Pawson, Steven; Einaudi, Franco (Technical Monitor)

2002-01-01

We use kinematic and diabatic back trajectory calculations, driven by winds from a general circulation model (GCM) and two different data assimilation systems (DAS), to compute the age spectrum at three latitudes in the lower stratosphere. The age-spectra are compared to chemical transport model (CTM) calculations, and the mean ages from all of these studies are compared to observations. The age spectra computed using the GCM winds show a reasonably well-isolated tropics in good agreement with observations; however, the age spectra determined from the DAS differ from the GCM spectra. For the diabatic trajectory calculations, the age spectrum is too broad as a result of too much exchange between the tropics and mid-latitudes. The age spectrum determined using the kinematic trajectory calculation is less broad and lacks an age offset; both of these features are due to excessive vertical dispersion of parcels. The tropical and mid-latitude mean age difference between the diabatically and kinematically determined age-spectra is about one year, the former being older. The CTM calculation of the age spectrum using the DAS winds shows the same dispersive characteristics of the kinematic trajectory calculation. These results suggest that the current DAS products will not give realistic trace gas distributions for long integrations; they also help explain why the mean ages determined in a number of previous DAS driven CTM's are too young compared with observations. Finally, we note trajectory-generated age spectra show significant age anomalies correlated with the seasonal cycles, and these anomalies can be linked to year-to-year variations in the tropical heating rate. These anomalies are suppressed in the CTM spectra suggesting that the CTM transport is too diffusive.

Interactions between cumulus convection and its environment as revealed by the MC3E sounding array

DOE PAGES

Xie, Shaocheng; Zhang, Yunyan; Giangrande, Scott E.; ...

2014-10-27

This study attempts to understand interactions between midlatitude convective systems and their environments through a heat and moisture budget analysis using the sounding data collected from the Midlatitude Continental Convective Clouds Experiment (MC3E) in central Oklahoma. Distinct large-scale structures and diabatic heating and drying profiles are presented for cases of weaker and elevated thunderstorms as well as intense squall line and supercell thunderstorm events during the campaign. The elevated cell events were nocturnal convective systems occurring in an environment having low convective available potential energy (CAPE) and a very dry boundary layer. In contrast, deeper convective events happened during themore » morning into early afternoon within an environment associated with large CAPE and a near-saturated boundary layer. As the systems reached maturity, the diagnosed diabatic heating in the latter deep convective cases was much stronger and of greater vertical extent than the former. Both groups showed considerable diabatic cooling in the lower troposphere, associated with the evaporation of precipitation and low-level clouds. The horizontal advection of moisture also played a dominant role in moistening the lower troposphere, particularly for the deeper convective events, wherein the near surface southeasterly flow allows persistent low-level moisture return from the Gulf of Mexico to support convection. The moisture convergence often was present before these systems develop, suggesting a strong correlation between the large-scale moisture convergence and convection. As a result, sensitivity tests indicated that the uncertainty in the surface precipitation and the size of analysis domain mainly affected the magnitude of these analyzed fields rather than their vertical structures.« less

Two-state model based on the block-localized wave function method

NASA Astrophysics Data System (ADS)

Mo, Yirong

2007-06-01

The block-localized wave function (BLW) method is a variant of ab initio valence bond method but retains the efficiency of molecular orbital methods. It can derive the wave function for a diabatic (resonance) state self-consistently and is available at the Hartree-Fock (HF) and density functional theory (DFT) levels. In this work we present a two-state model based on the BLW method. Although numerous empirical and semiempirical two-state models, such as the Marcus-Hush two-state model, have been proposed to describe a chemical reaction process, the advantage of this BLW-based two-state model is that no empirical parameter is required. Important quantities such as the electronic coupling energy, structural weights of two diabatic states, and excitation energy can be uniquely derived from the energies of two diabatic states and the adiabatic state at the same HF or DFT level. Two simple examples of formamide and thioformamide in the gas phase and aqueous solution were presented and discussed. The solvation of formamide and thioformamide was studied with the combined ab initio quantum mechanical and molecular mechanical Monte Carlo simulations, together with the BLW-DFT calculations and analyses. Due to the favorable solute-solvent electrostatic interaction, the contribution of the ionic resonance structure to the ground state of formamide and thioformamide significantly increases, and for thioformamide the ionic form is even more stable than the covalent form. Thus, thioformamide in aqueous solution is essentially ionic rather than covalent. Although our two-state model in general underestimates the electronic excitation energies, it can predict relative solvatochromic shifts well. For instance, the intense π →π* transition for formamide upon solvation undergoes a redshift of 0.3eV, compared with the experimental data (0.40-0.5eV).

The neglected Indo-Gangetic Plains low-level jet and its importance for moisture transport and precipitation during the peak summer monsoon

NASA Astrophysics Data System (ADS)

Acosta, R. P.; Huber, M.

2017-08-01

Accurately simulating the Indo-Asian monsoon (IAM) using atmospheric general circulation models (AGCMs) is challenging but crucial. This study uses reanalysis products European Centre of Medium-Range Forecast Interim reanalysis, Japanese Reanalysis year 55, and High Asia Reanalysis to highlight an easterly, low-level barrier jet along the Indo-Gangetic Plain (referred from here as IG LLJ), which we identify as the primary moisture transport mechanism for the northeastern branch of the IAM. We show that the NCAR family of AGCMs (Community Atmospheric Model (CAM)) does not capture this circulation until 1/2° or greater spatial horizontal resolution is used. The IG LLJ develops due to a persistent low-pressure system centered over the Ganges basin and is enhanced by the Himalayas. Using diabatic heating rates and the moist Froude number as diagnostics, we find that in CAM, this branch of the IAM displays two different dynamical regimes as a function of resolution. At low resolution, the atmosphere near the Himalayas is statically unstable, diabatic heating is strong, and the moisture flow is southwesterly from the Arabian Sea and moves over the terrain (unblocked). At high resolution, the moist static stability near the Himalayan Mountains is stable, diabatic heating is weak, and the flow primarily enters easterly from the Bay of Bengal and moves parallel to the terrain (blocked). During the summer season, the low-resolution CAM is locked into the unblocked mode, which has serious implications for interpreting topography-monsoon interactions. For a broader context, we demonstrate that more than half of the CMIP5 models do not capture the IG LLJ, which further highlights model-data mismatch across the IAM region.

An assessment of satellite temperature distributions used to derive the net diabatic transport for zonally averaged models of the middle atmosphere

NASA Technical Reports Server (NTRS)

Remsberg, Ellis E.; Bhatt, Praful P.; Miles, Thomas

1994-01-01

Determinations of the zonally averaged and diabatically derived residual mean circulation (RMC) are particularly sensitive to the assumed zonal mean temperature distribution used as input. Several different middle atmosphere satellite temperature distributions have been employed in models and are compared here: a 4-year (late 1978 to early 1982) National Meteorological Center (NMC) climatology, the Barnett and Corney (or BC) climatology, and the 7 months of Nimbus 7 limb infrared monitor of the stratosphere (LIMS) temperatures. All three climatologies are generally accurate below the 10 hPa level, but there are systematic differences between them of up to +/-5 K in the upper stratosphere and lower mesosphere. The NMC/LIMS differences are evaluated using time series of rocketsonde and reconstructed satellite temperatures at station locations. Much of those biases can be explained by the differing vertical resolutions for the satellite-derived temperatures; the time series of reconstructed LIMS profiles have higher resolution and are more accurate. Because the LIMS temperatures are limited to just two full seasons, one cannot obtain monthly RMCs from them for an annual model calculation. Two alternate monthly climatologies are examined briefly: the 4-year Nimbus 7 stratospheric and mesospheric sounder (SAMS) temperatures and for the mesosphere the distribution from the Solar Mesosphere Explorer (SME), both of which are limb viewers of medium vertical resolution. There are also differences of the order of +/-5 K for those data sets. It is concluded that a major source of error in the determination of diabatic RMCs is a persistent pattern of temperature bias whose characteristics vary according to the vertical resolution of each individual climatology.

Coupled potential energy surface for the F(2P)+CH4→HF+CH3 entrance channel and quantum dynamics of the CH4·F- photodetachment.

PubMed

Westermann, Till; Eisfeld, Wolfgang; Manthe, Uwe

2013-07-07

An approach to construct vibronically and spin-orbit coupled diabatic potential energy surfaces (PESs) which describe all three relevant electronic states in the entrance channels of the X(P) + CH4 →HX + CH3 reactions (with X=F((2)P), Cl((2)P), or O((3)P)) is introduced. The diabatization relies on the permutational symmetry present in the methane molecule and results in diabatic states which transform as the three p orbitals of the X atom. Spin-orbit coupling is easily and accurately included using the atomic spin-orbit coupling matrix of the isolated X atom. The method is applied to the F + CH4 system obtaining an accurate PES for the entrance channel based on ab initio multi-reference configuration interaction (MRCI) calculations. Comparing the resulting PESs with spin-orbit MRCI calculations, excellent agreement is found for the excited electronic states at all relevant geometries. The photodetachment spectrum of CH4·F(-) is investigated via full-dimensional (12D) quantum dynamics calculations on the coupled PESs using the multi-layer multi-configurational time-dependent Hartree approach. Extending previous work [J. Palma and U. Manthe, J. Chem. Phys. 137, 044306 (2012)], which was restricted to the dynamics on a single adiabatic PES, the contributions of the electronically excited states to the photodetachment spectrum are calculated and compared to experiment. Considering different experimental setups, good agreement between experiment and theory is found. Addressing questions raised in the previous work, the present dynamical calculations show that the main contribution to the second peak in the photodetachment spectrum results from electron detachment into the electronically excited states of the CH4F complex.

A case study of microphysical structures and hydrometeor phase in convection using radar Doppler spectra at Darwin, Australia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Riihimaki, Laura D.; Comstock, Jennifer M.; Luke, Edward

To understand the microphysical processes that impact diabatic heating and cloud lifetimes in convection, we need to characterize the spatial distribution of supercooled liquid water. To address this observational challenge, vertically pointing active sensors at the Darwin Atmospheric Radiation Measurement (ARM) site are used to classify cloud phase within a deep convective cloud in a shallow to deep convection transitional case. The cloud cannot be fully observed by a lidar due to signal attenuation. Thus we develop an objective method for identifying hydrometeor classes, including mixed-phase conditions, using k-means clustering on parameters that describe the shape of the Doppler spectramore » from vertically pointing Ka band cloud radar. This approach shows that multiple, overlapping mixed-phase layers exist within the cloud, rather than a single region of supercooled liquid, indicating complexity to how ice growth and diabatic heating occurs in the vertical structure of the cloud.« less

Evaluation of Boreal Summer Monsoon Intraseasonal Variability in the GASS-YOTC Multi-Model Physical Processes Experiment

NASA Astrophysics Data System (ADS)

Mani, N. J.; Waliser, D. E.; Jiang, X.

2014-12-01

While the boreal summer monsoon intraseasonal variability (BSISV) exerts profound influence on the south Asian monsoon, the capability of present day dynamical models in simulating and predicting the BSISV is still limited. The global model evaluation project on vertical structure and diabatic processes of the Madden Julian Oscillations (MJO) is a joint venture, coordinated by the Working Group on Numerical Experimentation (WGNE) MJO Task Force and GEWEX Atmospheric System Study (GASS) program, for assessing the model deficiencies in simulating the ISV and for improving our understanding of the underlying processes. In this study the simulation of the northward propagating BSISV is investigated in 26 climate models with special focus on the vertical diabatic heating structure and clouds. Following parallel lines of inquiry as the MJO Task Force has done with the eastward propagating MJO, we utilize previously proposed and newly developed model performance metrics and process diagnostics and apply them to the global climate model simulations of BSISV.

Boundary-layer diabatic processes, the virtual effect, and convective self-aggregation

NASA Astrophysics Data System (ADS)

Yang, D.

2017-12-01

The atmosphere can self-organize into long-lasting large-scale overturning circulations over an ocean surface with uniform temperature. This phenomenon is referred to as convective self-aggregation and has been argued to be important for tropical weather and climate systems. Here we use a 1D shallow water model and a 2D cloud-resolving model (CRM) to show that boundary-layer diabatic processes are essential for convective self-aggregation. We will show that boundary-layer radiative cooling, convective heating, and surface buoyancy flux help convection self-aggregate because they generate available potential energy (APE), which sustains the overturning circulation. We will also show that evaporative cooling in the boundary layer (cold pool) inhibits convective self-aggregation by reducing APE. Both the shallow water model and CRM results suggest that the enhanced virtual effect of water vapor can lead to convective self-aggregation, and this effect is mainly in the boundary layer. This study proposes new dynamical feedbacks for convective self-aggregation and complements current studies that focus on thermodynamic feedbacks.

Landau-Zener transitions and Dykhne formula in a simple continuum model

NASA Astrophysics Data System (ADS)

Dunham, Yujin; Garmon, Savannah

The Landau-Zener model describing the interaction between two linearly driven discrete levels is useful in describing many simple dynamical systems; however, no system is completely isolated from the surrounding environment. Here we examine a generalizations of the original Landau-Zener model to study simple environmental influences. We consider a model in which one of the discrete levels is replaced with a energy continuum, in which we find that the survival probability for the initially occupied diabatic level is unaffected by the presence of the continuum. This result can be predicted by assuming that each step in the evolution for the diabatic state evolves independently according to the Landau-Zener formula, even in the continuum limit. We also show that, at least for the simplest model, this result can also be predicted with the natural generalization of the Dykhne formula for open systems. We also observe dissipation as the non-escape probability from the discrete levels is no longer equal to one.

Stratospheric warmings during February and March 1993

NASA Technical Reports Server (NTRS)

Manney, G. L.; Zurek, R. W.; O'Neill, A.; Swinbank, R.; Kumer, J. B.; Mergenthaler, J. L.; Roche, A. E.

1994-01-01

Two stratospheric warmings during February and March 1993 are described using United Kingdom Meteorological Office (UKMO) analyses, calculated potential vorticity (PV) and diabetic heating, and N2O observed by the Cryogenic Limb Array Etalon Spectrometer (CLAES) instrument on the Upper Atmosphere Research Satellite (UARS). The first warming affected temperatures over a larger region, while the second produced a larger region of reversed zonal winds. Tilted baroclinic zones formed in the temperature field, and the polar vortex tilted westward with height. Narrow tongues of high PV and low N2O were drawn off the polar vortex, and irreversibly mixed. Tongues of material were drawn from low latitudes into the region between the polar vortex and the anticyclone; diabatic descent was also strongest in this region. Increased N2O over a broad region near the edge of the polar vortex indicates the importance of horizontal transport. N2O decreased in the vortex, consistent with enhanced diabatic descent during the warmings.

Large differences in the diabatic heat budget of the tropical UTLS in reanalyses

NASA Astrophysics Data System (ADS)

Wright, J. S.; Fueglistaler, S.

2013-04-01

We present the time mean heat budgets of the tropical upper troposphere (UT) and lower stratosphere (LS) as simulated by five reanalysis models: MERRA, ERA-Interim, CFSR, JRA-25/JCDAS, and NCEP/NCAR. The simulated diabatic heat budget in the tropical UTLS differs significantly from model to model, with substantial implications for representations of transport and mixing. Large differences are apparent both in the net heat budget and in all comparable individual components, including latent heating, heating due to radiative transfer, and heating due to parameterised vertical mixing. We describe and discuss the most pronounced differences. Although they may be expected given difficulties in representing moist convection in models, the discrepancies in latent heating are still disturbing. We pay particular attention to discrepancies in radiative heating (which may be surprising given the strength of observational constraints on temperature and tropospheric water vapour) and discrepancies in heating due to turbulent mixing (which have received comparatively little attention).

Isentropic Transport of Ozone Across the Tropopause on 345K

NASA Astrophysics Data System (ADS)

Jing, P.; Cunnold, D.

2002-05-01

Quantifying the transport of ozone from the stratosphere to the troposphere has been a challenge for many years. There are two types of cross-tropopause transport: the vertical diabatic transport and the quasi-horizontal isentropic transport. Because isentropic transport generally occurs more frequently than diabatic transport [Chen, 1995], it is a potentially important path for ozone to exchange between the stratosphere and the troposphere and to influence the chemistry in both regions. Based on the technique of contour advection, a method is developed to quantify the isentropic transport of ozone across the tropopause on the isentropic surface of 345K for the year 1990. This study employs the GSFC Data Assimilation Office assimilated products. It is shown that isentropic transport of ozone is a two-way process, but the annually integrated isentropic mass flux of ozone across the tropopause is directed from the stratosphere into the troposphere. The seasonality of the isentropic transport of ozone is also analyzed.

Signature of nonadiabatic coupling in excited-state vibrational modes.

PubMed

Soler, Miguel A; Nelson, Tammie; Roitberg, Adrian E; Tretiak, Sergei; Fernandez-Alberti, Sebastian

2014-11-13

Using analytical excited-state gradients, vibrational normal modes have been calculated at the minimum of the electronic excited-state potential energy surfaces for a set of extended conjugated molecules with different coupling between them. Molecular model systems composed of units of polyphenylene ethynylene (PPE), polyphenylenevinylene (PPV), and naphthacene/pentacene (NP) have been considered. In all cases except the NP model, the influence of the nonadiabatic coupling on the excited-state equilibrium normal modes is revealed as a unique highest frequency adiabatic vibrational mode that overlaps with the coupling vector. This feature is removed by using a locally diabatic representation in which the effect of NA interaction is removed. Comparison of the original adiabatic modes with a set of vibrational modes computed in the locally diabatic representation demonstrates that the effect of nonadiabaticity is confined to only a few modes. This suggests that the nonadiabatic character of a molecular system may be detected spectroscopically by identifying these unique state-specific high frequency vibrational modes.

Globally linearized control on diabatic continuous stirred tank reactor: a case study.

PubMed

Jana, Amiya Kumar; Samanta, Amar Nath; Ganguly, Saibal

2005-07-01

This paper focuses on the promise of globally linearized control (GLC) structure in the realm of strongly nonlinear reactor system control. The proposed nonlinear control strategy is comprised of: (i) an input-output linearizing state feedback law (transformer), (ii) a state observer, and (iii) an external linear controller. The synthesis of discrete-time GLC controller for single-input single-output diabatic continuous stirred tank reactor (DCSTR) has been studied first, followed by the synthesis of feedforward/feedback controller for the same reactor having dead time in process as well as in disturbance. Subsequently, the multivariable GLC structure has been designed and then applied on multi-input multi-output DCSTR system. The simulation study shows high quality performance of the derived nonlinear controllers. The better-performed GLC in conjunction with reduced-order observer has been compared with the conventional proportional integral controller on the example reactor and superior performance has been achieved by the proposed GLC control scheme.

Isentropic Analysis of Convective Motions

NASA Technical Reports Server (NTRS)

Pauluis, Olivier M.; Mrowiec, Agnieszka A.

2013-01-01

This paper analyzes the convective mass transport by sorting air parcels in terms of their equivalent potential temperature to determine an isentropic streamfunction. By averaging the vertical mass flux at a constant value of the equivalent potential temperature, one can compute an isentropic mass transport that filters out reversible oscillatory motions such as gravity waves. This novel approach emphasizes the fact that the vertical energy and entropy transports by convection are due to the combination of ascending air parcels with high energy and entropy and subsiding air parcels with lower energy and entropy. Such conditional averaging can be extended to other dynamic and thermodynamic variables such as vertical velocity, temperature, or relative humidity to obtain a comprehensive description of convective motions. It is also shown how this approach can be used to determine the mean diabatic tendencies from the three-dimensional dynamic and thermodynamic fields. A two-stream approximation that partitions the isentropic circulation into a mean updraft and a mean downdraft is also introduced. This offers a straightforward way to identify the mean properties of rising and subsiding air parcels. The results from the two-stream approximation are compared with two other definitions of the cloud mass flux. It is argued that the isentropic analysis offers a robust definition of the convective mass transport that is not tainted by the need to arbitrarily distinguish between convection and its environment, and that separates the irreversible convective overturning fromoscillations associated with gravity waves.

Bond angle variations in XH3 [X = N, P, As, Sb, Bi]: the critical role of Rydberg orbitals exposed using a diabatic state model.

PubMed

Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S

2015-10-14

Ammonia adopts sp(3) hybridization (HNH bond angle 108°) whereas the other members of the XH3 series PH3, AsH3, SbH3, and BiH3 instead prefer octahedral bond angles of 90-93°. We use a recently developed general diabatic description for closed-shell chemical reactions, expanded to include Rydberg states, to understand the geometry, spectroscopy and inversion reaction profile of these molecules, fitting its parameters to results from Equation of Motion Coupled-Cluster Singles and Doubles (EOM-CCSD) calculations using large basis sets. Bands observed in the one-photon absorption spectrum of NH3 at 18.3 eV, 30 eV, and 33 eV are reassigned from Rydberg (formally forbidden) double excitations to valence single-excitation resonances. Critical to the analysis is the inclusion of all three electronic states in which two electrons are placed in the lone-pair orbital n and/or the symmetric valence σ* antibonding orbital. An illustrative effective two-state diabatic model is also developed containing just three parameters: the resonance energy driving the high-symmetry planar structure, the reorganization energy opposing it, and HXH bond angle in the absence of resonance. The diabatic orbitals are identified as sp hybrids on X; for the radical cations XH3(+) for which only 2 electronic states and one conical intersection are involved, the principle of orbital following dictates that the bond angle in the absence of resonance is acos(-1/5) = 101.5°. The multiple states and associated multiple conical intersection seams controlling the ground-state structure of XH3 renormalize this to acos[3 sin(2)(2(1/2)atan(1/2))/2 - 1/2] = 86.7°. Depending on the ratio of the resonance energy to the reorganization energy, equilibrium angles can vary from these limiting values up to 120°, and the anomalously large bond angle in NH3 arises because the resonance energy is unexpectedly large. This occurs as the ordering of the lowest Rydberg orbital and the σ* orbital swap, allowing Rydbergization to compresses σ* to significantly increase the resonance energy. Failure of both the traditional and revised versions of the valence-shell electron-pair repulsion (VSEPR) theory to explain the ground-state structures in simple terms is attributed to exclusion of this key physical interaction.

Mechanistic exploration of the catalytic cycles for the CO oxidation by O2 over FeO(1-3) application of the energetic span model.

PubMed

Wang, Huan-Jiang; Wang, Yong-Cheng

2014-06-01

Carbon monoxide (CO) and oxygen (O2) catalyzed by small neutral iron oxide clusters (FeO(1-3)) was investigated at the density functional level of theory using the Becke-Perdew-Wang functional (BPW91). Three reaction pathways along with singlet, triplet and quintet states were calculated for ascertaining the presence of some spin inversion during the catalytic cycle. The catalytic cycle was found to be "two state reactivity" resulting from the crossing among the multistate energetic profiles. The Landau-Zener equation was used to calculate the thermally-averaged spin transition probabilities for the non-adiabatic surface crossing reaction. In order to predict the efficiency of catalyst the energetic span model developed by Kozuch was implemented, whereas this model is not suitable for handling the diabatic reaction, this feature we must take into consideration. To this end, a kinetic assessment is carried out with an expansion of the energetic span model, including the spin-crossing effects. This approximation enables one to measure the efficiency of catalytic cycle including spin-crossing effects by quantum mechanical computation.

Temperature dependence of dissociative electron attachment to bromo-chlorotoluene isomers: Competition between detachment of Cl- and Br-

NASA Astrophysics Data System (ADS)

Mahmoodi-Darian, Masoomeh; Huber, Stefan E.; Mauracher, Andreas; Probst, Michael; Denifl, Stephan; Scheier, Paul; Märk, Tilmann D.

2018-02-01

Dissociative electron attachment to three isomers of bromo-chlorotoluene was investigated in the electron energy range from 0 to 2 eV for gas temperatures in the range of 392-520 K using a crossed electron-molecular beam apparatus with a temperature regulated effusive molecular beam source. For all three molecules, both Cl- and Br- are formed. The ion yields of both halogenides show a pronounced temperature effect. In the case of Cl- and Br-, the influence of the gas temperature can be observed at the threshold peak close to 0 eV. The population of molecules that have some of their out-of-plane modes excited varies strongly in the temperature range investigated, indicating that such vibrations might play a role in the energy transfer towards bond breaking. Potential energy curves for the abstraction of Cl- and Br- were calculated and extrapolated into the metastable domain. The barriers in the diabatic curves approximated in this way agree well with the ones derived from the temperature dependence observed in the experiments.

Nonadiabatic dynamics of photo-induced proton-coupled electron transfer reactions via ring-polymer surface hopping

NASA Astrophysics Data System (ADS)

Shakib, Farnaz; Huo, Pengfei

Photo-induced proton-coupled electron transfer reactions (PCET) are at the heart of energy conversion reactions in photocatalysis. Here, we apply the recently developed ring-polymer surface-hopping (RPSH) approach to simulate the nonadiabatic dynamics of photo-induced PCET. The RPSH method incorporates ring-polymer (RP) quantization of the proton into the fewest-switches surface-hopping (FSSH) approach. Using two diabatic electronic states, corresponding to the electron donor and acceptor states, we model photo-induced PCET with the proton described by a classical isomorphism RP. From the RPSH method, we obtain numerical results that are comparable to those obtained when the proton is treated quantum mechanically. This accuracy stems from incorporating exact quantum statistics, such as proton tunnelling, into approximate quantum dynamics. Additionally, RPSH offers the numerical accuracy along with the computational efficiency. Namely, compared to the FSSH approach in vibronic representation, there is no need to calculate a massive number of vibronic states explicitly. This approach opens up the possibility to accurately and efficiently simulate photo-induced PCET with multiple transferring protons or electrons.

European Science Notes Information Bulletin Reports on Current European and Middle Eastern Science

DTIC Science & Technology

1993-01-01

Geophys. Res. diabatic effects of the midlatitude storm- 73, 487-492 (1968). track clouds on the climate system; 4. J. Testud , G. Breger, P. Amayenc...A. Clough and J. Testud , "The FRONTS- network will probably be to the northwest of Scot- 87 Experiment and Mesoscale Frontal Dy- land. Other

Low gravity two-phase flow with heat transfer

NASA Technical Reports Server (NTRS)

Antar, Basil N.

1991-01-01

A realistic model for the transfer line chilldown operation under low-gravity conditions is developed to provide a comprehensive predictive capability on the behavior of liquid vapor, two-phase diabatic flows in pipes. The tasks described involve the development of numerical code and the establishment of the necessary experimental data base for low-gravity simulation.

Potential energy and dipole moment surfaces of the triplet states of the O2(X3Σg-) - O2(X3Σg-,a1Δg,b1Σg+) complex

NASA Astrophysics Data System (ADS)

Karman, Tijs; van der Avoird, Ad; Groenenboom, Gerrit C.

2017-08-01

We compute four-dimensional diabatic potential energy surfaces and transition dipole moment surfaces of O2-O2, relevant for the theoretical description of collision-induced absorption in the forbidden X3Σg- → a1Δg and X3Σg- → b1Σg+ bands at 7883 cm-1 and 13 122 cm-1, respectively. We compute potentials at the multi-reference configuration interaction (MRCI) level and dipole surfaces at the MRCI and complete active space self-consistent field (CASSCF) levels of theory. Potentials and dipole surfaces are transformed to a diabatic basis using a recent multiple-property-based diabatization algorithm. We discuss the angular expansion of these surfaces, derive the symmetry constraints on the expansion coefficients, and present working equations for determining the expansion coefficients by numerical integration over the angles. We also present an interpolation scheme with exponential extrapolation to both short and large separations, which is used for representing the O2-O2 distance dependence of the angular expansion coefficients. For the triplet ground state of the complex, the potential energy surface is in reasonable agreement with previous calculations, whereas global excited state potentials are reported here for the first time. The transition dipole moment surfaces are strongly dependent on the level of theory at which they are calculated, as is also shown here by benchmark calculations at high symmetry geometries. Therefore, ab initio calculations of the collision-induced absorption spectra cannot become quantitatively predictive unless more accurate transition dipole surfaces can be computed. This is left as an open question for method development in electronic structure theory. The calculated potential energy and transition dipole moment surfaces are employed in quantum dynamical calculations of collision-induced absorption spectra reported in Paper II [T. Karman et al., J. Chem. Phys. 147, 084307 (2017)].

Three-dimensional constrained variational analysis: Approach and application to analysis of atmospheric diabatic heating and derivative fields during an ARM SGP intensive observational period

NASA Astrophysics Data System (ADS)

Tang, Shuaiqi; Zhang, Minghua

2015-08-01

Atmospheric vertical velocities and advective tendencies are essential large-scale forcing data to drive single-column models (SCMs), cloud-resolving models (CRMs), and large-eddy simulations (LESs). However, they cannot be directly measured from field measurements or easily calculated with great accuracy. In the Atmospheric Radiation Measurement Program (ARM), a constrained variational algorithm (1-D constrained variational analysis (1DCVA)) has been used to derive large-scale forcing data over a sounding network domain with the aid of flux measurements at the surface and top of the atmosphere (TOA). The 1DCVA algorithm is now extended into three dimensions (3DCVA) along with other improvements to calculate gridded large-scale forcing data, diabatic heating sources (Q1), and moisture sinks (Q2). Results are presented for a midlatitude cyclone case study on 3 March 2000 at the ARM Southern Great Plains site. These results are used to evaluate the diabatic heating fields in the available products such as Rapid Update Cycle, ERA-Interim, National Centers for Environmental Prediction Climate Forecast System Reanalysis, Modern-Era Retrospective Analysis for Research and Applications, Japanese 55-year Reanalysis, and North American Regional Reanalysis. We show that although the analysis/reanalysis generally captures the atmospheric state of the cyclone, their biases in the derivative terms (Q1 and Q2) at regional scale of a few hundred kilometers are large and all analyses/reanalyses tend to underestimate the subgrid-scale upward transport of moist static energy in the lower troposphere. The 3DCVA-gridded large-scale forcing data are physically consistent with the spatial distribution of surface and TOA measurements of radiation, precipitation, latent and sensible heat fluxes, and clouds that are better suited to force SCMs, CRMs, and LESs. Possible applications of the 3DCVA are discussed.

Potential energy and dipole moment surfaces of the triplet states of the O2(X3Σg-) - O2(X3Σg-,a1Δg,b1Σg+) complex.

PubMed

Karman, Tijs; van der Avoird, Ad; Groenenboom, Gerrit C

2017-08-28

We compute four-dimensional diabatic potential energy surfaces and transition dipole moment surfaces of O 2 -O 2 , relevant for the theoretical description of collision-induced absorption in the forbidden X 3 Σ g -  → a 1 Δ g and X 3 Σ g -  → b 1 Σ g + bands at 7883 cm -1 and 13 122 cm -1 , respectively. We compute potentials at the multi-reference configuration interaction (MRCI) level and dipole surfaces at the MRCI and complete active space self-consistent field (CASSCF) levels of theory. Potentials and dipole surfaces are transformed to a diabatic basis using a recent multiple-property-based diabatization algorithm. We discuss the angular expansion of these surfaces, derive the symmetry constraints on the expansion coefficients, and present working equations for determining the expansion coefficients by numerical integration over the angles. We also present an interpolation scheme with exponential extrapolation to both short and large separations, which is used for representing the O 2 -O 2 distance dependence of the angular expansion coefficients. For the triplet ground state of the complex, the potential energy surface is in reasonable agreement with previous calculations, whereas global excited state potentials are reported here for the first time. The transition dipole moment surfaces are strongly dependent on the level of theory at which they are calculated, as is also shown here by benchmark calculations at high symmetry geometries. Therefore, ab initio calculations of the collision-induced absorption spectra cannot become quantitatively predictive unless more accurate transition dipole surfaces can be computed. This is left as an open question for method development in electronic structure theory. The calculated potential energy and transition dipole moment surfaces are employed in quantum dynamical calculations of collision-induced absorption spectra reported in Paper II [T. Karman et al., J. Chem. Phys. 147, 084307 (2017)].

Fusing Multiple Satellite Datasets Toward Defining and Understanding Organized Convection

NASA Astrophysics Data System (ADS)

Elsaesser, G.; Del Genio, A. D.

2017-12-01

How do we differentiate unorganized from organized convection? We might think of organized convection as being long lasting (at least longer than the lifetime of any individual cumulus cell), clustered at larger spatial scales (>100 km), and responsible for substantial rainfall accumulation. Organized convection is sustained on such scales due to the arrangement of moist/dry and buoyant/non-buoyant mesoscale circulations. The nature of these circulations is tied to system diabatic heating profiles; in particular, the 2nd baroclinic (top-heavy), stratiform heating mode is thought to be important for organized convection maintenance/propagation. We investigate the extent to which these characteristics are jointly found in propagating convective systems. Lifecycle information comes from hi-res IR data. Diabatic heating profiles, convective fractions and rainfall are provided by GPM retrievals mapped to convective system tracks. Moisture is provided by AIRS/AMSU and passive microwave retrievals. Instead of compositing heating profile information along a system track, where information is smoothed out, we sort system heating profile structures according to their "top heaviness" and then analyze PDFs of system rainfall, system sizes, durations, convective/stratiform ratios, etc. as a function of diabatic heating structure. Perhaps contrary to expectation, we find only small differences in PDFs of rainfall rates, system sizes, and system duration for different heating profile structures. If organization is defined according to heating structures, then one possible interpretation of these results is that organization is independent of system size, duration, and many times, even lifecycle stage. Is it possible that most systems "hobble" along and exhibit varying degrees of organization, dependent on local environment moisture/buoyancy variations, unlike the archetypical MCS paradigm? This presentation will also discuss the questions posed above within the context of parameterizing organized convection in the GISS GCM. GCMs must make/sustain the right heating profile at the right time, which requires observations-based understanding of such distinctions. Such knowledge is important for simulating and understanding the deep convective contribution to cloud feedback in a changing climate.

Fully adaptive propagation of the quantum-classical Liouville equation

NASA Astrophysics Data System (ADS)

Horenko, Illia; Weiser, Martin; Schmidt, Burkhard; Schütte, Christof

2004-05-01

In mixed quantum-classical molecular dynamics few but important degrees of freedom of a dynamical system are modeled quantum-mechanically while the remaining ones are treated within the classical approximation. Rothe methods established in the theory of partial differential equations are used to control both temporal and spatial discretization errors on grounds of a global tolerance criterion. The TRAIL (trapezoidal rule for adaptive integration of Liouville dynamics) scheme [I. Horenko and M. Weiser, J. Comput. Chem. 24, 1921 (2003)] has been extended to account for nonadiabatic effects in molecular dynamics described by the quantum-classical Liouville equation. In the context of particle methods, the quality of the spatial approximation of the phase-space distributions is maximized while the numerical condition of the least-squares problem for the parameters of particles is minimized. The resulting dynamical scheme is based on a simultaneous propagation of moving particles (Gaussian and Dirac deltalike trajectories) in phase space employing a fully adaptive strategy to upgrade Dirac to Gaussian particles and, vice versa, downgrading Gaussians to Dirac-type trajectories. This allows for the combination of Monte-Carlo-based strategies for the sampling of densities and coherences in multidimensional problems with deterministic treatment of nonadiabatic effects. Numerical examples demonstrate the application of the method to spin-boson systems in different dimensionality. Nonadiabatic effects occurring at conical intersections are treated in the diabatic representation. By decreasing the global tolerance, the numerical solution obtained from the TRAIL scheme are shown to converge towards exact results.

Fully adaptive propagation of the quantum-classical Liouville equation.

PubMed

Horenko, Illia; Weiser, Martin; Schmidt, Burkhard; Schütte, Christof

2004-05-15

In mixed quantum-classical molecular dynamics few but important degrees of freedom of a dynamical system are modeled quantum-mechanically while the remaining ones are treated within the classical approximation. Rothe methods established in the theory of partial differential equations are used to control both temporal and spatial discretization errors on grounds of a global tolerance criterion. The TRAIL (trapezoidal rule for adaptive integration of Liouville dynamics) scheme [I. Horenko and M. Weiser, J. Comput. Chem. 24, 1921 (2003)] has been extended to account for nonadiabatic effects in molecular dynamics described by the quantum-classical Liouville equation. In the context of particle methods, the quality of the spatial approximation of the phase-space distributions is maximized while the numerical condition of the least-squares problem for the parameters of particles is minimized. The resulting dynamical scheme is based on a simultaneous propagation of moving particles (Gaussian and Dirac deltalike trajectories) in phase space employing a fully adaptive strategy to upgrade Dirac to Gaussian particles and, vice versa, downgrading Gaussians to Dirac-type trajectories. This allows for the combination of Monte-Carlo-based strategies for the sampling of densities and coherences in multidimensional problems with deterministic treatment of nonadiabatic effects. Numerical examples demonstrate the application of the method to spin-boson systems in different dimensionality. Nonadiabatic effects occurring at conical intersections are treated in the diabatic representation. By decreasing the global tolerance, the numerical solution obtained from the TRAIL scheme are shown to converge towards exact results.

Why Do Model Tropical Cyclones Grow Progressively in Size and Decay in Intensity after Reaching Maturity

DTIC Science & Technology

2015-08-17

the distribution of azimuthally-averaged diabatic heating rate derived from the MM5 output. The coefficients of this equation are deter- mined by the...contributions to the intensification of Hurricane Opal as diagnosed from a GFDL model forecast. Mon. Wea. Rev., 130, 1866–1881. Montgomery, M. T., M. E

The planetary distribution of heat sources and sinks during FGGE

NASA Technical Reports Server (NTRS)

Johnson, D. R.; Wei, M. Y.

1985-01-01

Heating distributions from analysis of the National Meteorological Center and European Center for Medium Range Weather Forecasts data sets; methods used and problems involved in the inference of diabatic heating; the relationship between differential heating and energy transport; and recommendations on the inference of heat soruces and heat sinks for the planetary show are discussed.

Assimilation of Long-Range Lightning Data over the Pacific

DTIC Science & Technology

2011-09-30

convective rainfall analyses over the Pacific, and (iii) to improve marine prediction of cyclogenesis of both tropical and extratropical cyclones through...data over the North Pacific Ocean, refine the relationships between lightning and storm hydrometeor characteristics, and assimilate lightning...unresolved storm -scale areas of deep convection over the data-sparse open oceans. Diabatic heating sources, especially latent heat release in deep

Identifying different mechanisms in the control of a nitrogen-vacancy center system

NASA Astrophysics Data System (ADS)

Li, Shouzhi; Yang, Ling; Cao, Dewen; Wang, Yaoxiong; Shuang, Feng; Gao, Fang

2017-10-01

The nitrogen-vacancy (NV) center system has shown great potential in quantum computing due to its long decoherence time at room temperature by encoding the qubit in dressed states [28]. The corresponding control mechanisms, which is expressed by the pathways linking the initial and target states, can be naturally investigated with the Hamiltonian-encoding and observable-decoding (HE-OD) method in the interaction adiabatic representation. This is proved by the fact that the mechanisms change slightly with different detunings, magnetic and driving field intensities, and the dominant pathway is always | g 〉 → | d 〉 → | g 〉 , with | g 〉 and | d 〉 as the first two lowest dressed states. Cases are different in the diabatic representation. The orders of dominant pathways increase the driving field intensities. Tendencies of quantum pathway amplitudes with driving fields, magnetic fields and detunings change at different conditions, which can be analyzed from the Dyson series. HE-OD analysis show that the two states | g 〉 and | d 〉 in the interaction adiabatic representation are preferable to be employed as a qubit than the state pair |0〉 and | - 1 〉 in the diabatic representation under the current Hamiltonian and parameters.

An efficient solution to the decoherence enhanced trivial crossing problem in surface hopping

NASA Astrophysics Data System (ADS)

Bai, Xin; Qiu, Jing; Wang, Linjun

2018-03-01

We provide an in-depth investigation of the time interval convergence when both trivial crossing and decoherence corrections are applied to Tully's fewest switches surface hopping (FSSH) algorithm. Using one force-based and one energy-based decoherence strategies as examples, we show decoherence corrections intrinsically enhance the trivial crossing problem. We propose a restricted decoherence (RD) strategy and incorporate it into the self-consistent (SC) fewest switches surface hopping algorithm [L. Wang and O. V. Prezhdo, J. Phys. Chem. Lett. 5, 713 (2014)]. The resulting SC-FSSH-RD approach is applied to general Hamiltonians with different electronic couplings and electron-phonon couplings to mimic charge transport in tens to hundreds of molecules. In all cases, SC-FSSH-RD allows us to use a large time interval of 0.1 fs for convergence and the simulation time is reduced by over one order of magnitude. Both the band and hopping mechanisms of charge transport have been captured perfectly. SC-FSSH-RD makes surface hops in the adiabatic representation and can be implemented in both diabatic and locally diabatic representations for wave function propagation. SC-FSSH-RD can potentially describe general nonadiabatic dynamics of electrons and excitons in organics and other materials.

Vertical variability and effect of stability on turbulence characteristics down to the floor of a pine forest

NASA Astrophysics Data System (ADS)

Launiainen, Samuli; Vesala, Timo; Mölder, Meelis; Mammarella, Ivan; Smolander, Sampo; Rannik, Üllar; Kolari, Pasi; Hari, Pertti; Lindroth, Anders; Katul, Gabriel G.

2007-11-01

Among the fundamental problems in canopy turbulence, particularly near the forest floor, remain the local diabatic effects and linkages between turbulent length scales and the canopy morphology. To progress on these problems, mean and higher order turbulence statistics are collected in a uniform pine forest across a wide range of atmospheric stability conditions using five 3-D anemometers in the subcanopy. The main novelties from this experiment are: (1) the agreement between second-order closure model results and measurements suggest that diabatic states in the layer above the canopy explain much of the modulations of the key velocity statistics inside the canopy except in the immediate vicinity of the trunk space and for very stable conditions. (2) The dimensionless turbulent kinetic energy in the trunk space is large due to a large longitudinal velocity variance but it is inactive and contributes little to momentum fluxes. (3) Near the floor layer, a logarithmic mean velocity profile is formed and vertical eddies are strongly suppressed modifying all power spectra. (4) A spectral peak in the vertical velocity near the ground commensurate with the trunk diameter emerged at a moderate element Reynolds number consistent with Strouhal instabilities describing wake production.

Evidence of Stratosphere-to-Troposphere Transport Within a Mesoscale Model and TOMS Total Ozone

NASA Technical Reports Server (NTRS)

Olsen, Mark A.; Stanford, John L.; Einaudi, Franco (Technical Monitor)

2001-01-01

We present evidence for stratospheric mass transport into, and remaining in, the troposphere in an intense midlatitude cyclone. Mesoscale forecast model analysis fields from the Mesoscale Analysis and Prediction System (MAPS) were compared with total ozone observations from the Total Ozone Measurement Spectrometer (TOMS). Coupled with parcel back-trajectory calculations, the analyses suggest two mechanisms contributed to the mass exchange: (1) A region of dynamical ly-induced exchange occurred on the cyclone's southern edge. Parcels originally in the stratosphere crossed the jet core and experienced dilution by turbulent mixing with tropospheric air. (2) Diabatic effects reduced parcel potential vorticity (PV) for trajectories traversing precipitation regions, resulting in a "PV-hole" signature in the cyclone center. Air with lower-stratospheric values of ozone and water vapor was left in the troposphere. The strength of the latter process may be atypical. These results, combined with other research, suggest that precipitation-induced diabatic effects can significantly modify, (either decreasing or increasing) parcel potential vorticity, depending on parcel trajectory configuration with respect to jet core and maximum heating regions. In addition, these results underscore the importance of using not only PV but also chemical constituents for diagnoses of stratosphere-troposphere exchange (STE).

Time-resolved photoelectron spectroscopy of IR-driven electron dynamics in a charge transfer model system.

PubMed

Falge, Mirjam; Fröbel, Friedrich Georg; Engel, Volker; Gräfe, Stefanie

2017-08-02

If the adiabatic approximation is valid, electrons smoothly adapt to molecular geometry changes. In contrast, as a characteristic of diabatic dynamics, the electron density does not follow the nuclear motion. Recently, we have shown that the asymmetry in time-resolved photoelectron spectra serves as a tool to distinguish between these dynamics [Falge et al., J. Phys. Chem. Lett., 2012, 3, 2617]. Here, we investigate the influence of an additional, moderately intense infrared (IR) laser field, as often applied in attosecond time-resolved experiments, on such asymmetries. This is done using a simple model for coupled electronic-nuclear motion. We calculate time-resolved photoelectron spectra and their asymmetries and demonstrate that the spectra directly map the bound electron-nuclear dynamics. From the asymmetries, we can trace the IR field-induced population transfer and both the field-driven and intrinsic (non-)adiabatic dynamics. This holds true when considering superposition states accompanied by electronic coherences. The latter are observable in the asymmetries for sufficiently short XUV pulses to coherently probe the coupled states. It is thus documented that the asymmetry is a measure for phases in bound electron wave packets and non-adiabatic dynamics.

All the nonadiabatic (J=0) bound states of NO{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Salzgeber, R.F.; Mandelshtam, V.A.; Schlier, C.

1999-02-01

We calculated all 3170 A{sub 1} and B{sub 2} (J=0) vibronic bound states of the coupled electronic ground ({tilde X}&hthinsp;{sup 2}A{sub 1}) and the first excited ({tilde A}&hthinsp;{sup 2}B{sub 2}) surfaces of NO{sub 2}, using a modification of the {ital ab initio} potentials of Leonardi {ital et al.} [J. Chem. Phys. {bold 105}, 9051 (1996)]. The calculation was performed by harmonic inversion of the Chebyshev correlation function generated from a DVR Hamiltonian in Radau coordinates. The rms error of the eigenenergies is about 2.5 cm{sup {minus}1}, corresponding to a relative error of 10{sup {minus}4} near the dissociation energy. The resultsmore » are compared with the adiabatic and diabatic levels calculated from the same surfaces, with experimental data, and with some approximations for the number of states function N(E). The experimental levels are reproduced fairly well up to an energy of 12&hthinsp;000 cm{sup {minus}1} above the potential minimum while the total number of bound levels agrees to within 2{percent} with that calculated from the phase space volume. {copyright} {ital 1999 American Institute of Physics.}« less

Vertical motions in the equatorial middle atmosphere

NASA Technical Reports Server (NTRS)

Weisman, M. L.

1979-01-01

A single station vertical velocity equation which considers ageostrophic and diabatic effects derived from the first law of thermodynamics and a generalized thermal wind relation is presented. An analysis and verification procedure which accounts for measurement and calculation errors as well as time and space continuity arguments and theoretical predictions are described. Vertical velocities are calculated at every kilometer between 25 and 60 km and for approximately every three hours for the above diurnal period at Kourou (French Guiana), Fort Sherman (Panama Canal Zone), Ascension Island, Antigua (British West Indies) and Natal (Brazil). The results, plotted as time series cross sections, suggest vertical motions ranging in magnitude from 1 or 2 cm/sec at 30 km to as much as 15 cm/sec at 60 km. Many of the general features of the results agree well with atmospheric tidal predictions but many particular features suggest that both smaller time scale gravity waves (periods less than 6 hours) and synoptic type waves (periods greater than 1 day) may be interacting significantly with the tidal fields. The results suggest that vertical motions can be calculated for the equatorial middle atmosphere and must be considered a significant part of the motion for time scales from 8 to 24 hours.

Progress and Challenges in Subseasonal Prediction

NASA Technical Reports Server (NTRS)

Schubert, Siegfried

2003-01-01

While substantial advances have occurred over the last few decades in both weather and seasonal prediction, progress in improving predictions on subseasonal time scales (approximately 2 weeks to 2 months) has been slow. In this talk I will highlight some of the recent progress that has been made to improve forecasts on subseasonal time scales and outline the challenges that we face both from an observational and modeling perspective. The talk will be based primarily on the results and conclusions of a recent NASA-sponsored workshop that focused on the subseasonal prediction problem. One of the key conclusions of that workshop was that there is compelling evidence for predictability at forecast lead times substantially longer than two weeks, and that much of that predictability is currently untapped. Tropical diabatic heating and soil wetness were singled out as particularly important processes affecting predictability on these time scales. Predictability was also linked to various low-frequency atmospheric phenomena such as the annular modes in high latitudes (including their connections to the stratosphere), the Pacific/North American pattern, and the Madden-Julian Oscillation. I will end the talk by summarizing the recommendations and plans that have been put forward for accelerating progress on the subseasonal prediction problem.

Large-Scale Atmosphere-Ocean Coupling.

DTIC Science & Technology

1984-05-01

connection. between Pacific tropical diabatic heating anomalies and extratropical circulation system over the North Pacific from East Asia to the...and G. J. Boer, 1972: REFERENCES The General Circulation of the Tropical Atmosphere and Interaction with Extratropical Latitudes. Vol. 1. MIT Press...implications for the development of severe convective storms . Mom. We& Rev.. Chang, C.-P., and K. M. Lau, 1980: Northeasterly cold surges 167, 682-703. and

An evaluation of the precipitation distribution associated with landfalling tropical systems

NASA Astrophysics Data System (ADS)

Atallah, Eyad H.

Several recent landfalling tropical cyclones (e.g. Dennis, Floyd, and Irene 1999) have highlighted a need for a refinement in the forecasting paradigms and techniques in the area of quantitative precipitation forecasting (QPF). Accordingly, several landfalling tropical storms were composited based on the precipitation distribution relative to the cyclone track (i.e. left of, right of, or along track), and cases from each composite were examined using a potential vorticity (PV) and quasi-geostrophic (QG) framework. Results indicate that a left of track precipitation distribution (e.g. Floyd 1999) is characteristic of tropical systems undergoing extratropical transition (ET). In these cases, a significant positively tilted mid-latitude trough approaches the cyclone from the northwest, shifting precipitation to the north-northwest of the cyclone. PV redistribution through diabatic heating then leads to enhanced ridging over and downstream of the tropical cyclone resulting in an increase in the cyclonic advection of vorticity by the thermal wind. Precipitation distribution is heaviest to the right of the track of the storm when downstream intensification of the ridge is important (e.g. David, 1979). Enhancement of the downstream ridge ahead of a weak mid-latitude trough accentuates the PV gradient between the tropical system and the downstream ridge. This, in combination with a slight acceleration in the movement of the tropical system, produces a region of enhanced positive PV advection (implied ascent) between the tropical system and the downstream ridge. Precipitation is heaviest along/very near the track of a storm when shear values are low and/or oriented along the track of the tropical cyclone (e.g. Fran 1996). Without large scale forcing for vertical motion associated with a midlatitude trough, most of the ascent remains concentrated near the storm core in the region of greatest diabatic heating and maximum wind speeds. In all cases, the diabatic enhancement of the downstream ridge is instrumental in the redistribution of precipitation about the tropical system. Unfortunately, this process is not well simulated in operational forecast models, leading to systematic errors in QPF.

Paradigms for Tropical-Cyclone Intensification

DTIC Science & Technology

2011-01-01

Hurricane Opal (1995) using the Geo- physical Fluid Dynamics Laboratory hurricane prediction model, Möller and Shapiro (2002) found unbalanced flow...al. (2008) calculations on an f -plane, described in section 6.1. A specific aim was to deter- mine the separate contributions of diabatic heating and... Opal as diagnosed from a GFDL model forecast. Mon. Wea. Rev., 130, 1866-1881. Marks FD Shay LK. 1998: Landfalling tropical cyclones: Forecast

The North Atlantic Waveguide and Downstream Impact Experiment (NAWDEX): First results

NASA Astrophysics Data System (ADS)

Craig, George; Schäfler, Andreas; Ament, Felix; Arbogast, Philippe; Crewell, Susanne; Doyle, James; Hirsch, Lutz; Mayer, Bernhard; McTaggart-Cowan, Ron; Methven, John; Rahm, Stephan; Rautenhaus, Marc; Reitebuch, Oliver; Rivière, Gwendal; Vaughan, Geraint; Wendisch, Manfred; Wernli, Heini; Wirth, Martin; Witschas, Benjamin

2017-04-01

First results will be presented from the NAWDEX experiment, an international field campaign with the overall goal of increasing the physical understanding and quantifying the effects of diabatic processes on disturbances to the jet stream over the North Atlantic, their influence on downstream propagation, and consequences for high-impact weather in Europe. The campaign took place from 19 September to 18 October 2016, and deployed a variety of remote-sensing and in-situ instruments that provided an extraordinarily detailed picture of the interacting dynamics and thermodynamics. Thirteen intensive observation periods took place over the course of the campaign, including moisture inflow and diabatic processes in warm conveyor belts, cloud and dynamical structure in outflow and ridge-building events, as well as other events This presentation will briefly review the weather events that were observed during NAWDEX and give a preliminary evaluation of how the observations contribute to new understanding of midlatitude weather systems. As an example, an analysis of the structure and evolution of ex-Tropical Storm Karl will be presented. This system was observed by a sequence of aircraft flights over a period of six days, as it moved from the subtropics into the midlatitudes off the coast of North America, reintensified explosively as a midlatitude cyclone south of Greenland, and eventually contributed to poor precipitation forecasts for Norway.

Theoretical Study of the Jahn-Teller effect in CH3CN+ (X2E) and CD3CN+ (X2E): multimode spin-vibronic energy level calculations.

PubMed

Zhang, Shiyang; Mo, Yuxiang

2009-10-15

The spin-vibronic energy levels for CH(3)CN(+)(X(2)E) and CD(3)CN(+)(X(2)E) have been calculated using a diabatic model including multimode vibronic couplings and spin-orbit interaction without adjusting any parameter. The diabatic potential energy surfaces are represented by the Taylor expansions including linear, quadratic and bilinear vibronic coupling terms. The normal coordinates used in the Taylor expansion were expressed by the mass-weighted Cartesian coordinates. The adiabatic potential energy surfaces for CH(3)CN(+) and CD(3)CN(+) were calculated at the level of CASPT2/cc-pvtz, and the spin-orbit coupling constant was calculated at the level of MRCI/CAS/cc-pvtz. The spin-orbit energy splittings for the ground vibrational states of CH(3)CN(+)(X(2)E) and CD(3)CN(+)(X(2)E) are 20 and 16 cm(-1), respectively, which are resulted from the quenching of the spin-orbit coupling strength of 51 cm(-1). The calculated spin-vibronic levels are in good agreement with the experimental data. The calculation results show that the Jahn-Teller effects in CH(3)CN(+)(X(2)E) and CD(3)CN(+)(X(2)E) are essential to understand their spin-vibronic energy structure.

Analysis of the Characteristics of Inertia-Gravity Waves during an Orographic Precipitation Event

NASA Astrophysics Data System (ADS)

Liu, Lu; Ran, Lingkun; Gao, Shouting

2018-05-01

A numerical experiment was performed using the Weather Research and Forecasting (WRF) model to analyze the generation and propagation of inertia-gravity waves during an orographic rainstorm that occurred in the Sichuan area on 17 August 2014. To examine the spatial and temporal structures of the inertia-gravity waves and identify the wave types, three wavenumber-frequency spectral analysis methods (Fourier analysis, cross-spectral analysis, and wavelet cross-spectrum analysis) were applied. During the storm, inertia-gravity waves appeared at heights of 10-14 km, with periods of 80-100 min and wavelengths of 40-50 km. These waves were generated over a mountain and propagated eastward at an average speed of 15-20 m s-1. Meanwhile, comparison between the reconstructed inertia-gravity waves and accumulated precipitation showed there was a mutual promotion process between them. The Richardson number and Scorer parameter were used to demonstrate that the eastward-moving inertia-gravity waves were trapped in an effective atmospheric ducting zone with favorable reflector and critical level conditions, which were the primary causes of the long lives of the waves. Finally, numerical experiments to test the sensitivity to terrain and diabatic heating were conducted, and the results suggested a cooperative effect of terrain and diabatic heating contributed to the propagation and enhancement of the waves.

The Yearly Variation in Fall-Winter Arctic Winter Vortex Descent

NASA Technical Reports Server (NTRS)

Schoeberl, Mark R.; Newman, Paul A.

1999-01-01

Using the change in HALOE methane profiles from early September to late March, we have estimated the minimum amount of diabatic descent within the polar which takes place during Arctic winter. The year to year variations are a result in the year to year variations in stratospheric wave activity which (1) modify the temperature of the vortex and thus the cooling rate; (2) reduce the apparent descent by mixing high amounts of methane into the vortex. The peak descent amounts from HALOE methane vary from l0km -14km near the arrival altitude of 25 km. Using a diabatic trajectory calculation, we compare forward and backward trajectories over the course of the winter using UKMO assimilated stratospheric data. The forward calculation agrees fairly well with the observed descent. The backward calculation appears to be unable to produce the observed amount of descent, but this is only an apparent effect due to the density decrease in parcels with altitude. Finally we show the results for unmixed descent experiments - where the parcels are fixed in latitude and longitude and allowed to descend based on the local cooling rate. Unmixed descent is found to always exceed mixed descent, because when normal parcel motion is included, the path average cooling is always less than the cooling at a fixed polar point.

Revisiting Gill's Circulation. Dynamic Response to Diabatic Heating of Different Horizontal Extents

NASA Astrophysics Data System (ADS)

Reboredo, B.; Bellon, G.

2017-12-01

The horizontal extent of diabatic heating associated with the MJO is thought to be crucial to its development, and the inability of GCMs to simulate the spatial, horizontal organization of clouds is considered a leading hypothesis to explain their limited capacity to simulate MJO events. This prevents the MJO large-circulation response from developing and feeding back on the development of clouds. We apply mid-tropospheric heating of different size in simple linear and non-linear models of the tropical atmosphere following Gill's seminal work on heat-induced tropical circulations. Results show that there is a scale for which the characteristic circulation {Γ c} for the vertical advection of moisture to produce the latent heat mean {Q} gives a rough estimate of the real world MJO scale. Overturning circulation flow rates above {Γ c} account for a circulation that transports more moisture than necessary to be maintained, and below {Γ c}, circulation would not transport enough moisture to maintain circulation. This dynamic scale might constrain the size of the spatially-organised convection necessary to the development of an MJO event. However, other effects are expected to modulate this scale, such as vertical advection of moisture anomalies, horizontal advection, evaporation, radiative heating, and sensible heat fluxes.

The influence of asymmetric convections on typhoon cyclonic deflection tracks across Taiwan

NASA Astrophysics Data System (ADS)

Hsu, L. H.; Su, S. H.

2016-12-01

This study focus on the mechanisms of typhoon cyclonic deflection tracks (CDT) approaching the east coast of Taiwan. We analyzed for 84 landfall typhoons which has 49 CDT cases, 18 cases are with very large deflection angles (DA) ( > 20°) and another 7 cases are with cyclonic looping tracks (CLT). Most of the large DA and CLT cases are with relatively slow translation speeds of 4 m s-1 and occurred near the east coast, north of 23 °N in Taiwan. The Weather Research and Forecasting (WRF) Model was used to simulate the typhoon CDT cases. We use the potential vorticity (PV) tendency diagnosis to analyze the typhoon movements, and decompose the wave number one component of PV tendencies into horizontal advection (HA), vertical advection (VA) and diabatic heating (DH) terms. The northern landfall storms have significant vorticity stretching and subsidence warming to the south of the storm. The subsidence warming suppresses convections and produces heating asymmetries for the typhoon structure. The vorticity stretching (VA effect) and diabatic heating asymmetries (DH effect) which lead the southwestward deflection storm motion. The HA effect in general does not contribute to the CDT. Our results highlight the effects of vorticity stretching and asymmetric convective heating in producing the CDT to north of 23 °N near the east coast of Taiwan.

Probing aerosol indirect effect on deep convection using idealized cloud-resolving simulations with parameterized large-scale dynamics.

NASA Astrophysics Data System (ADS)

Anber, U.; Wang, S.; Gentine, P.; Jensen, M. P.

2017-12-01

A framework is introduced to investigate the indirect impact of aerosol loading on tropical deep convection using 3-dimentional idealized cloud-system resolving simulations with coupled large-scale circulation. The large scale dynamics is parameterized using a spectral weak temperature gradient approximation that utilizes the dominant balance in the tropics between adiabatic cooling and diabatic heating. Aerosol loading effect is examined by varying the number concentration of nuclei (CCN) to form cloud droplets in the bulk microphysics scheme over a wide range from 30 to 5000 without including any radiative effect as the radiative cooling is prescribed at a constant rate, to isolate the microphysical effect. Increasing aerosol number concentration causes mean precipitation to decrease monotonically, despite the increase in cloud condensates. Such reduction in precipitation efficiency is attributed to reduction in the surface enthalpy fluxes, and not to the divergent circulation, as the gross moist stability remains unchanged. We drive a simple scaling argument based on the moist static energy budget, that enables a direct estimation of changes in precipitation given known changes in surfaces enthalpy fluxes and the constant gross moist stability. The impact on cloud hydrometers and microphysical properties is also examined and is consistent with the macro-physical picture.

Carbon Dioxide Convection in the Martian Polar Night and Its Implications for Polar Processes

NASA Technical Reports Server (NTRS)

Colaprete, A.; Haberle, R. M.

2003-01-01

Each Martian year nearly 30% of the atmosphere is exchanged with the polar ice caps. This exchange occurs through a combination of direct surface condensation and atmospheric precipitation of carbon dioxide. It has long been thought the amount of condensation within the polar night is maintained by a balance between diabatic processes such as radiative cooling and latent heating from condensing CO2. This assumption manifests itself in Mars General Circulation Models (GCM) in such a way as to never allow the atmospheric temperature to dip below the saturation temperature of CO2. However, observations from Mars Global Surveyor (MGS) Radio Science (RS) and the Thermal Emission Spectrometer (TES) have demonstrated this assumption to be, at best, approximate. Both RS and TES observations within the polar nights of both poles indicate substantial supersaturated regions with respect to CO2. The observed temperature profiles suggest conditionally unstable regions containing planetary significant amounts of potential convective energy. Presented here are estimates of the total planetary inventory of convective available potential energy (CAPE) and the potential convective energy flux (PCEF). The values for CAPE and PCEF are derived from RS temperature profiles and compared to Mars GCM results using a new convective CO2 cloud model that allows for the formation of CAPE.

The role of potential vorticity anomalies in the Somali Jet on Indian Summer Monsoon Intraseasonal Variability

NASA Astrophysics Data System (ADS)

Rai, P.; Joshi, M.; Dimri, A. P.; Turner, A. G.

2017-08-01

The climate of the Indian subcontinent is dominated by rainfall arising from the Indian summer monsoon (ISM) during June to September. Intraseasonal variability during the monsoon is characterized by periods of heavy rainfall interspersed by drier periods, known as active and break events respectively. Understanding and predicting such events is of vital importance for forecasting human impacts such as water resources. The Somali Jet is a key regional feature of the monsoon circulation. In the present study, we find that the spatial structure of Somali Jet potential vorticity (PV) anomalies varies considerably during active and break periods. Analysis of these anomalies shows a mechanism whereby sea surface temperature (SST) anomalies propagate north/northwestwards through the Arabian Sea, caused by a positive feedback loop joining anomalies in SST, convection, modification of PV by diabatic heating and mixing in the atmospheric boundary layer, wind-stress curl, and ocean upwelling processes. The feedback mechanism is consistent with observed variability in the coupled ocean-atmosphere system on timescales of approximately 20 days. This research suggests that better understanding and prediction of monsoon intraseasonal variability in the South Asian monsoon may be gained by analysis of the day-to-day dynamical evolution of PV in the Somali Jet.

The role of potential vorticity anomalies in the Somali Jet on Indian Summer Monsoon Intraseasonal Variability

NASA Astrophysics Data System (ADS)

Rai, P.; Joshi, M.; Dimri, A. P.; Turner, A. G.

2018-06-01

The climate of the Indian subcontinent is dominated by rainfall arising from the Indian summer monsoon (ISM) during June to September. Intraseasonal variability during the monsoon is characterized by periods of heavy rainfall interspersed by drier periods, known as active and break events respectively. Understanding and predicting such events is of vital importance for forecasting human impacts such as water resources. The Somali Jet is a key regional feature of the monsoon circulation. In the present study, we find that the spatial structure of Somali Jet potential vorticity (PV) anomalies varies considerably during active and break periods. Analysis of these anomalies shows a mechanism whereby sea surface temperature (SST) anomalies propagate north/northwestwards through the Arabian Sea, caused by a positive feedback loop joining anomalies in SST, convection, modification of PV by diabatic heating and mixing in the atmospheric boundary layer, wind-stress curl, and ocean upwelling processes. The feedback mechanism is consistent with observed variability in the coupled ocean-atmosphere system on timescales of approximately 20 days. This research suggests that better understanding and prediction of monsoon intraseasonal variability in the South Asian monsoon may be gained by analysis of the day-to-day dynamical evolution of PV in the Somali Jet.

Diagnostics of severe convection and subsynoptic scale ageostrophic circulations

NASA Technical Reports Server (NTRS)

1985-01-01

Diagnostics of severe convection and subsynoptic scale ageostrophic circulations are reported. Mesoscale circulations through forcing of ageostrophic motion by adiabatic, diabatic and frictional processes were studied. The development and application of a hybrid isentropic sigma coordinate numerical model was examined. The numerical model simulates mesoscale ageostrophic circulations associated with propagating jet streaks and severe convection. A complete list of publications and these completed through support of the NASA severe storms research project is included.

Electronic coupling matrix elements from charge constrained density functional theory calculations using a plane wave basis set

NASA Astrophysics Data System (ADS)

Oberhofer, Harald; Blumberger, Jochen

2010-12-01

We present a plane wave basis set implementation for the calculation of electronic coupling matrix elements of electron transfer reactions within the framework of constrained density functional theory (CDFT). Following the work of Wu and Van Voorhis [J. Chem. Phys. 125, 164105 (2006)], the diabatic wavefunctions are approximated by the Kohn-Sham determinants obtained from CDFT calculations, and the coupling matrix element calculated by an efficient integration scheme. Our results for intermolecular electron transfer in small systems agree very well with high-level ab initio calculations based on generalized Mulliken-Hush theory, and with previous local basis set CDFT calculations. The effect of thermal fluctuations on the coupling matrix element is demonstrated for intramolecular electron transfer in the tetrathiafulvalene-diquinone (Q-TTF-Q-) anion. Sampling the electronic coupling along density functional based molecular dynamics trajectories, we find that thermal fluctuations, in particular the slow bending motion of the molecule, can lead to changes in the instantaneous electron transfer rate by more than an order of magnitude. The thermal average, ( {< {| {H_ab } |^2 } > } )^{1/2} = 6.7 {mH}, is significantly higher than the value obtained for the minimum energy structure, | {H_ab } | = 3.8 {mH}. While CDFT in combination with generalized gradient approximation (GGA) functionals describes the intermolecular electron transfer in the studied systems well, exact exchange is required for Q-TTF-Q- in order to obtain coupling matrix elements in agreement with experiment (3.9 mH). The implementation presented opens up the possibility to compute electronic coupling matrix elements for extended systems where donor, acceptor, and the environment are treated at the quantum mechanical (QM) level.

Tropical Cyclogenesis in a Tropical Wave Critical Layer: Easterly Waves

NASA Technical Reports Server (NTRS)

Dunkerton, T. J.; Montgomery, M. T.; Wang, Z.

2009-01-01

The development of tropical depressions within tropical waves over the Atlantic and eastern Pacific is usually preceded by a "surface low along the wave" as if to suggest a hybrid wave-vortex structure in which flow streamlines not only undulate with the waves, but form a closed circulation in the lower troposphere surrounding the low. This structure, equatorward of the easterly jet axis, is identified herein as the familiar critical layer of waves in shear flow, a flow configuration which arguably provides the simplest conceptual framework for tropical cyclogenesis resulting from tropical waves, their interaction with the mean flow, and with diabatic processes associated with deep moist convection. The recirculating Kelvin cat's eye within the critical layer represents a sweet spot for tropical cyclogenesis in which a proto-vortex may form and grow within its parent wave. A common location for storm development is given by the intersection of the wave's critical latitude and trough axis at the center of the cat's eye, with analyzed vorticity centroid nearby. The wave and vortex live together for a time, and initially propagate at approximately the same speed. In most cases this coupled propagation continues for a few days after a tropical depression is identified. For easterly waves, as the name suggests, the propagation is westward. It is shown that in order to visualize optimally the associated Lagrangian motions, one should view the flow streamlines, or stream function, in a frame of reference translating horizontally with the phase propagation of the parent wave. In this co-moving frame, streamlines are approximately equivalent to particle trajectories. The closed circulation is quasi-stationary, and a dividing streamline separates air within the cat's eye from air outside.

Resummed memory kernels in generalized system-bath master equations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mavros, Michael G.; Van Voorhis, Troy, E-mail: tvan@mit.edu

2014-08-07

Generalized master equations provide a concise formalism for studying reduced population dynamics. Usually, these master equations require a perturbative expansion of the memory kernels governing the dynamics; in order to prevent divergences, these expansions must be resummed. Resummation techniques of perturbation series are ubiquitous in physics, but they have not been readily studied for the time-dependent memory kernels used in generalized master equations. In this paper, we present a comparison of different resummation techniques for such memory kernels up to fourth order. We study specifically the spin-boson Hamiltonian as a model system bath Hamiltonian, treating the diabatic coupling between themore » two states as a perturbation. A novel derivation of the fourth-order memory kernel for the spin-boson problem is presented; then, the second- and fourth-order kernels are evaluated numerically for a variety of spin-boson parameter regimes. We find that resumming the kernels through fourth order using a Padé approximant results in divergent populations in the strong electronic coupling regime due to a singularity introduced by the nature of the resummation, and thus recommend a non-divergent exponential resummation (the “Landau-Zener resummation” of previous work). The inclusion of fourth-order effects in a Landau-Zener-resummed kernel is shown to improve both the dephasing rate and the obedience of detailed balance over simpler prescriptions like the non-interacting blip approximation, showing a relatively quick convergence on the exact answer. The results suggest that including higher-order contributions to the memory kernel of a generalized master equation and performing an appropriate resummation can provide a numerically-exact solution to system-bath dynamics for a general spectral density, opening the way to a new class of methods for treating system-bath dynamics.« less

Non-adiabatic effects in thermochemistry, spectroscopy and kinetics: the general importance of all three Born-Oppenheimer breakdown corrections.

PubMed

Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S

2015-10-14

Using a simple model Hamiltonian, the three correction terms for Born-Oppenheimer (BO) breakdown, the adiabatic diagonal correction (DC), the first-derivative momentum non-adiabatic correction (FD), and the second-derivative kinetic-energy non-adiabatic correction (SD), are shown to all contribute to thermodynamic and spectroscopic properties as well as to thermal non-diabatic chemical reaction rates. While DC often accounts for >80% of thermodynamic and spectroscopic property changes, the commonly used practice of including only the FD correction in kinetics calculations is rarely found to be adequate. For electron-transfer reactions not in the inverted region, the common physical picture that diabatic processes occur because of surface hopping at the transition state is proven inadequate as the DC acts first to block access, increasing the transition state energy by (ℏω)(2)λ/16J(2) (where λ is the reorganization energy, J the electronic coupling and ω the vibration frequency). However, the rate constant in the weakly-coupled Golden-Rule limit is identified as being only inversely proportional to this change rather than exponentially damped, owing to the effects of tunneling and surface hopping. Such weakly-coupled long-range electron-transfer processes should therefore not be described as "non-adiabatic" processes as they are easily described by Born-Huang ground-state adiabatic surfaces made by adding the DC to the BO surfaces; instead, they should be called just "non-Born-Oppenheimer" processes. The model system studied consists of two diabatic harmonic potential-energy surfaces coupled linearly through a single vibration, the "two-site Holstein model". Analytical expressions are derived for the BO breakdown terms, and the model is solved over a large parameter space focusing on both the lowest-energy spectroscopic transitions and the quantum dynamics of coherent-state wavepackets. BO breakdown is investigated pertinent to: ammonia inversion, aromaticity in benzene, the Creutz-Taube ion, the bacterial photosynthetic reaction centre, BNB, the molecular conductor Alq3, and inverted-region charge recombination in a ferrocene-porphyrin-fullerene triad photosynthetic model compound. Throughout, the fundamental nature of BO breakdown is linked to the properties of the cusp catastrophe: the cusp diameter is shown to determine the magnitudes of all couplings, numerical basis-set and trajectory-integration requirements, and to determine the transmission coefficient κ used to understand deviations from transition-state theory.

Formation and Development of Diabatic Rossby Vortices in a 10-Year Climatology

DTIC Science & Technology

2012-06-01

subsequent low-level PV generation. 4. The “Perfect Storms ” Cordeira and Bosart (2011; hereafter CB11) noted there were two intense extratropical ...northeast. While more DRVs form during the warm season, a larger fraction of storms that explosively deepen occur during the cold season. Composite...preferentially over warm ocean currents. All DRVs track to the east northeast. While more DRVs form during the warm season, a larger fraction of storms that

The effects of couplings to symmetric and antisymmetric modes and minor asymmetry on the spectral properties of mixed-valence and related charge-transfer systems

NASA Astrophysics Data System (ADS)

Reimers, J. R.; Hush, N. S.

1996-08-01

The most common methods used to describe the energy levels of charge-transfer systems (including mixed-valence systems) are the linear response approach of Rice and co-workers and the essentially equivalent PKS model described initially by Piepho, Krausz, and Schatz. While these methods were quite successful, in their original form they omitted the effects of overall symmetric vibrations. As a consequence, in particular they were not capable of adequately describing the electronic band width in the strong-coupling limit: Hush and later Ondrechen et al. demonstrated that symmetric modes are essential in this case, and modern versions of these models now include them. Here, we explore the relationship between symmetric and antisymmetric modes, concentrating on how this is modified by the presence of weak (e.g., environmentally or substitutionally induced) asymmetry. For the symmetric case, we show that when the electronic Hamiltonian operators are transformed from their usual localized diabatic representation into a delocalized diabatic representation, the effects of the symmetric and antisymmetric modes are interchanged. The primary effect of weak asymmetry is to mix the properties of the various modes, and possible consequences of this for the spectroscopy of bacterial photosynthetic reaction centre and substituted Creutz—Taube cations are discussed. We also consider the problem from an adiabatic Bom—Oppenheimer perspective and examine the regions in which this approach is appropriate.

Sensitivity of the simulation of tropical cyclone size to microphysics schemes

NASA Astrophysics Data System (ADS)

Chan, Kelvin T. F.; Chan, Johnny C. L.

2016-09-01

The sensitivity of the simulation of tropical cyclone (TC) size to microphysics schemes is studied using the Advanced Hurricane Weather Research and Forecasting Model (WRF). Six TCs during the 2013 western North Pacific typhoon season and three mainstream microphysics schemes-Ferrier (FER), WRF Single-Moment 5-class (WSM5) and WRF Single-Moment 6-class (WSM6)-are investigated. The results consistently show that the simulated TC track is not sensitive to the choice of microphysics scheme in the early simulation, especially in the open ocean. However, the sensitivity is much greater for TC intensity and inner-core size. The TC intensity and size simulated using the WSM5 and WSM6 schemes are respectively higher and larger than those using the FER scheme in general, which likely results from more diabatic heating being generated outside the eyewall in rainbands. More diabatic heating in rainbands gives higher inflow in the lower troposphere and higher outflow in the upper troposphere, with higher upward motion outside the eyewall. The lower-tropospheric inflow would transport absolute angular momentum inward to spin up tangential wind predominantly near the eyewall, leading to the increment in TC intensity and size (the inner-core size, especially). In addition, the inclusion of graupel microphysics processes (as in WSM6) may not have a significant impact on the simulation of TC track, intensity and size.

The strength of the meridional overturning circulation of the stratosphere

PubMed Central

Linz, Marianna; Plumb, R. Alan; Gerber, Edwin P.; Haenel, Florian J.; Stiller, Gabriele; Kinnison, Douglas E.; Ming, Alison; Neu, Jessica L.

2017-01-01

The distribution of gases such as ozone and water vapour in the stratosphere — which affect surface climate — is influenced by the meridional overturning of mass in the stratosphere, the Brewer–Dobson circulation. However, observation-based estimates of its global strength are difficult to obtain. Here we present two calculations of the mean strength of the meridional overturning of the stratosphere. We analyze satellite data that document the global diabatic circulation between 2007– 2011, and compare these to three re-analysis data sets and to simulations with a state-of-the-art chemistry-climate model. Using measurements of sulfur hexafluoride (SF6) and nitrous oxide, we calculate the global mean diabatic overturning mass flux throughout the stratosphere. In the lower stratosphere, these two estimates agree, and at a potential temperature level of 460 K (about 20 km or 60 hPa in tropics), the global circulation strength is 6.3–7.6 × 109 kg/s. Higher in the atmosphere, only the SF6-based estimate is available, and it diverges from the re-analysis data and simulations. Interpretation of the SF6 data-based estimate is limited because of a mesospheric sink of SF6; however, the reanalyses also differ substantially from each other. We conclude that the uncertainty in the mean meridional overturning circulation strength at upper levels of the stratosphere amounts to at least 100 %. PMID:28966661

Pathways of upwelling deep waters to the surface of the Southern Ocean

NASA Astrophysics Data System (ADS)

Tamsitt, Veronica; Drake, Henri; Morrison, Adele; Talley, Lynne; Dufour, Carolina; Gray, Alison; Griffies, Stephen; Mazloff, Matthew; Sarmiento, Jorge; Wang, Jinbo; Weijer, Wilbert

2017-04-01

Upwelling of Atlantic, Indian and Pacific deep waters to the sea surface in the Southern Ocean closes the global overturning circulation and is fundamentally important for oceanic uptake of anthropogenic carbon and heat, nutrient resupply for sustaining oceanic biological production, and the melt rate of ice shelves. Here we go beyond the two-dimensional view of Southern Ocean upwelling, to show detailed Southern Ocean upwelling pathways in three dimensions, using hydrographic observations and particle tracking in high-resolution ocean and climate models. The northern deep waters enter the Antarctic Circumpolar Current (ACC) via narrow southward currents along the boundaries of the three ocean basins, before spiraling southeastward and upward through the ACC. Upwelling is greatly enhanced at five major topographic features, associated with vigorous mesoscale eddy activity. Deep water reaches the upper ocean predominantly south of the southern ACC boundary, with a spatially nonuniform distribution, regionalizing warm water supply to Antarctic ice shelves and the delivery of nutrient and carbon-rich water to the sea surface. The timescale for half of the deep water to upwell from 30°S to the mixed layer is on the order of 60-90 years, which has important implications for the timescale for signals to propagate through the deep ocean. In addition, we quantify the diabatic transformation along particle trajectories, to identify where diabatic processes are important along the upwelling pathways.

Lagrangian Transport Calculations Using UARS Data. Part 2; Ozone

NASA Technical Reports Server (NTRS)

Manney, Gloria L.; Zurek, R. W.; Froidevaux, L.; Waters, J. W.; ONeill, A.; Swinbank, R.

1995-01-01

Trajectory calculations are used to examine ozone transport in the polar winter stratosphere during periods of the Upper Atmosphere Research Satellite (UARS) observations. The value of these calculations for determining mass transport was demonstrated previously using UARS observations of long-lived tracers, In the middle stratosphere, the overall ozone behavior observed by the Microwave Limb Sounder in the polar vortex is reproduced by this purely dynamical model. Calculations show the evolution of ozone in the lower stratosphere during early winter to be dominated by dynamics in December 1992 in the Arctic. Calculations for June 1992 in the Antarctic show evidence of chemical ozone destruction and indicate that approx. 50% of the chemical destruction may be masked by dynamical effects, mainly diabatic descent, which bring higher ozone into the lower-stratospheric vortex. Estimating differences between calculated and observed fields suggests that dynamical changes masked approx. 20% - 35% of chemical ozone loss during late February and early March 1993 in the Arctic. In the Antarctic late winter, in late August and early September 1992, below approx. 520 K, the evolution of vortex-averaged ozone is entirely dominated by chemical effects; above this level, however, chemical ozone depletion can be partially or completely masked by dynamical effects. Our calculations for 1992 showed that chemical loss was nearly completely compensated by increases due to diabatic descent at 655 K.

On the sensitivities of idealized moist baroclinic waves to environmental temperature and moist convection

NASA Astrophysics Data System (ADS)

Kirshbaum, Daniel; Merlis, Timothy; Gyakum, John; McTaggart-Cowan, Ron

2017-04-01

The impact of cloud diabatic heating on baroclinic life cycles has been studied for decades, with the nearly universal finding that this heating enhances the system growth rate. However, few if any studies have systematically addressed the sensitivity of baroclinic waves to environmental temperature. For a given relative humidity, warmer atmospheres contain more moisture than colder atmospheres. They also are more prone to the development of deep moist convection, which is itself a major source of diabatic heating. Thus, it is reasonable to expect faster baroclinic wave growth in warmer systems. To address this question, this study performs idealized simulations of moist baroclinic waves in a periodic channel, using initial environments with identical relative humidities, dry stabilities, and dry available potential energies but varying environmental temperatures and moist instabilities. While the dry versions of these simulations exhibit virtually identical wave growth, the moist versions exhibit major differences in life cycle. Counter-intuitively, despite slightly faster initial wave growth, the warmer and moister waves ultimately develop into weaker baroclinic systems with an earlier onset of the decay phase. An energetics analysis reveals that the reduced wave amplitude in the warmer cases stems from a reduced transfer of available potential energy into eddy potential energy. This reduced energy transfer is associated with an unfavorable phasing of mid-to-upper-level thermal and vorticity anomalies, which limits the meridional heat flux.

Study of Topological Effects Concerning the Lowest A″ and the Three A' States for the CO2(+) Ion.

PubMed

Dhindhwal, Vikash; Baer, Michael; Sathyamurthy, N

2016-05-19

A study of the topological effects, viz., the Jahn-Teller (JT) and Renner-Teller (RT) effects, in CO2(+) has been carried out by calculating nonadiabatic coupling terms (NACTs) at the state-averaged CASSCF level using the cc-pVTZ basis set for the lowest three A' states and one A″ state along a circular contour. Using the NACTs, the privileged adiabatic-to-diabatic transformation (ADT) angles (γ12) for 1A' and 2A' states of CO2(+) have been calculated along various circular contours. Employing one of the oxygen atoms as the test particle exposed two conical intersections (ci) located on each side of the CO diatom. The main purpose of this study is to explore the possibility of forming reliable diabatic potential energy surfaces for this system. Success in achieving this goal is guaranteed by the ability to calculate quantized privileged ADT angles along closed contours covering large regions in configuration space (see, e.g., J. Phys. Chem. A 2014 , 118 , 6361 ). The calculations were carried out for two and three JT states. In most cases very nice quantization has been achieved although the calculations were frequently done, as required, for large regions in configuration space (sometimes ≥18 Å(2)). In one case, for which the quantization was not gratifying, the inclusion of the RT effect modified it considerably.

Solvable multistate model of Landau-Zener transitions in cavity QED

DOE PAGES

Sinitsyn, Nikolai; Li, Fuxiang

2016-06-29

We consider the model of a single optical cavity mode interacting with two-level systems (spins) driven by a linearly time-dependent field. When this field passes through values at which spin energy level splittings become comparable to spin coupling to the optical mode, a cascade of Landau-Zener (LZ) transitions leads to co-flips of spins in exchange for photons of the cavity. We derive exact transition probabilities between different diabatic states induced by such a sweep of the field.

Electronic coupling in long-range electron transfer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Newton, M.D.

1996-12-31

One of the quantities crucial in controlling electron transfer (et) kinetics is the donor/acceptor electronic coupling integral (HDA). Recent theoretical models for HDA will be presented, and the results of ab initio computational implementation will be reported and analyzed for several metal-to-metal ligand charge transfer processes in complex molecular aggregates. New procedures for defining diabatic states, including a generalization of the Mulliken-Hush model, allow applications to optical and excited state as well as ground state et in a many-state framework.

Estimates of tropical analysis differences in daily values produced by two operational centers

NASA Technical Reports Server (NTRS)

Kasahara, Akira; Mizzi, Arthur P.

1992-01-01

To assess the uncertainty of daily synoptic analyses for the atmospheric state, the intercomparison of three First GARP Global Experiment level IIIb datasets is performed. Daily values of divergence, vorticity, temperature, static stability, vertical motion, mixing ratio, and diagnosed diabatic heating rate are compared for the period of 26 January-11 February 1979. The spatial variance and mean, temporal mean and variance, 2D wavenumber power spectrum, anomaly correlation, and normalized square difference are employed for comparison.

Global water cycle

NASA Technical Reports Server (NTRS)

Robertson, Franklin R.; Christy, John R.; Goodman, Steven J.; Miller, Tim L.; Fitzjarrald, Dan; Lapenta, Bill; Wang, Shouping

1991-01-01

The primary objective is to determine the scope and interactions of the global water cycle with all components of the Earth system and to understand how it stimulates and regulates changes on both global and regional scales. The following subject areas are covered: (1) water vapor variability; (2) multi-phase water analysis; (3) diabatic heating; (4) MSU (Microwave Sounding Unit) temperature analysis; (5) Optimal precipitation and streamflow analysis; (6) CCM (Community Climate Model) hydrological cycle; (7) CCM1 climate sensitivity to lower boundary forcing; and (8) mesoscale modeling of atmosphere/surface interaction.

Mechanisms of Stratospheric Ozone Transport.

DTIC Science & Technology

1982-12-03

amounts orcur too fat south and about 1 month too late. 92 CHANGE IN (740) (PPM) DIABATIC. cos ( LAT ) 70 50 ~40 (D 30_ _ _ _ _ ) 1 5 Ŗ 2.5 Z. 20 10 0 D...AD-A122 609 MECHANISMS OF STRATOSPHERIC OZONE BRANSPOR(U) NAVAL RESEARCH LAB WASHINGTON DC R B ROOD ET AL 03 DEC 82 UNCLASSIFIED F/G 4/ 1 ...NLIEIIIIEIIII EIIIIIIIIIIIIl IIIEIIIIIEEEEE IIIIIIIIIIIIIl EIIIIIIIIIIIIl EIIIIIIIIIIIIl 1111.0 112 M *0 MIt ROCLt RLS’OLU7ION TLST CHART - - - ,T 1 m -N ;’ V

Idealized numerical modeling of polar mesocyclones dynamics diagnosed by energy budget

NASA Astrophysics Data System (ADS)

Sergeev, Dennis; Stepanenko, Victor

2014-05-01

Polar mesocyclones (MC) refer to a wide class of mesoscale vortices occuring poleward of the main polar front [1]. Their subtype - polar low - is commonly known for its intensity, that can result in windstorm damage of infrastructure in high latitudes. The observational data sparsity and the small size of polar MCs are major limitations for the clear understanding and numerical prediction of the evolution of these objects. The origin of polar MCs is still a matter of uncertainty, though the recent numerical investigations have exposed a strong dependence of the polar mesocyclone development upon the magnitude of baroclinicity and upon the water vapor concentration in the atmosphere. However, most of the previous studies focused on the individual polar low (the so-called case studies), with too many factors affecting it simultaneously and none of them being dominant in polar MC generation. This study focuses on the early stages of polar MC development within an idealized numerical experiments with mesoscale atmospheric model, where it is possible to look deeper into each single physical process. Our aim is to explain the role of such mechanisms as baroclinic instability or diabatic heating by comparing their contribution to the structure and dynamics of the vortex. The baroclinic instability, as reported by many researchers [2], can be a crucial factor in a MC's life cycle, especially in polar regions. Besides the baroclinic instability several diabatic processes can contribute to the energy generation that fuels a polar mesocyclone. One of the key energy sources in polar regions is surface heat fluxes. The other is the moisture content in the atmosphere that can affect the development of the disturbance by altering the latent heat release. To evaluate the relative importance of the diabatic and baroclinic energy sources for the development of the polar mesocyclone we apply energy diagnostics. In other words, we examine the rate of change of the kinetic energy (that can be interpreted as the growth rate of the vortex) and energy conversion in the diagnostic equations for kinetic and available potential energy (APE). The energy budget equations are implemented in two forms. The first approach follows the scheme developed by Lorenz (1955) in which KE and APE are broken into a mean component and an eddy component forming a well-known energy cycle. The second method is based on the energy equations that are strictly derived from the governing equations of the numerical mesoscale model used. The latter approach, hence, takes into account all the approximations and numerical features used in the model. Some conclusions based on the comparison of the described methods are presented in the study. A series of high-resolution experiments is carried out using three-dimensional non-hydrostatic limited-area sigma-coordinate numerical model ReMeDy (Research Mesoscale Dynamics), being developed at Lomonosov Moscow State University [3]. An idealized basic state condition is used for all simulations. It is composed of the zonally oriented baroclinic zone over the sea surface partly covered with ice. To realize a baroclinic channel environment zero-gradient boundary conditions at the meridional lateral oundaries are imposed, while the zonal boundary conditions are periodic. The initialization of the mesocyclone is achieved by creating a small axis-symmetric vortex in the center of the model domain. The baroclinicity and stratification of the basic state, as well as the surface parameters, are varied in the typically observed range. References 1. Heinemann G, Øyvind S. 2013. Workshop On Polar Lows. Bull. Amer. Meteor. Soc. 94: ES123-ES126. 2. Yanase W, Niino H. 2006. Dependence of Polar Low Development on Baroclinicity and Physical Processes: An Idealized High-Resolution Experiment, J. Atmos. Sci. 64: 3044-3067. 3. Chechin DG et al. 2013. Idealized dry quasi 2-D mesoscale simulations of cold-air outbreaks over the marginal sea ice zone with fine and coarse resolution. J. Geophys. Res. 118: 8787-8813.

An exact variational method to calculate rovibrational spectra of polyatomic molecules with large amplitude motion

NASA Astrophysics Data System (ADS)

Yu, Hua-Gen

2016-08-01

We report a new full-dimensional variational algorithm to calculate rovibrational spectra of polyatomic molecules using an exact quantum mechanical Hamiltonian. The rovibrational Hamiltonian of system is derived in a set of orthogonal polyspherical coordinates in the body-fixed frame. It is expressed in an explicitly Hermitian form. The Hamiltonian has a universal formulation regardless of the choice of orthogonal polyspherical coordinates and the number of atoms in molecule, which is suitable for developing a general program to study the spectra of many polyatomic systems. An efficient coupled-state approach is also proposed to solve the eigenvalue problem of the Hamiltonian using a multi-layer Lanczos iterative diagonalization approach via a set of direct product basis set in three coordinate groups: radial coordinates, angular variables, and overall rotational angles. A simple set of symmetric top rotational functions is used for the overall rotation whereas a potential-optimized discrete variable representation method is employed in radial coordinates. A set of contracted vibrationally diabatic basis functions is adopted in internal angular variables. Those diabatic functions are first computed using a neural network iterative diagonalization method based on a reduced-dimension Hamiltonian but only once. The final rovibrational energies are computed using a modified Lanczos method for a given total angular momentum J, which is usually fast. Two numerical applications to CH4 and H2CO are given, together with a comparison with previous results.

An exact variational method to calculate rovibrational spectra of polyatomic molecules with large amplitude motion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Hua-Gen, E-mail: hgy@bnl.gov

We report a new full-dimensional variational algorithm to calculate rovibrational spectra of polyatomic molecules using an exact quantum mechanical Hamiltonian. The rovibrational Hamiltonian of system is derived in a set of orthogonal polyspherical coordinates in the body-fixed frame. It is expressed in an explicitly Hermitian form. The Hamiltonian has a universal formulation regardless of the choice of orthogonal polyspherical coordinates and the number of atoms in molecule, which is suitable for developing a general program to study the spectra of many polyatomic systems. An efficient coupled-state approach is also proposed to solve the eigenvalue problem of the Hamiltonian using amore » multi-layer Lanczos iterative diagonalization approach via a set of direct product basis set in three coordinate groups: radial coordinates, angular variables, and overall rotational angles. A simple set of symmetric top rotational functions is used for the overall rotation whereas a potential-optimized discrete variable representation method is employed in radial coordinates. A set of contracted vibrationally diabatic basis functions is adopted in internal angular variables. Those diabatic functions are first computed using a neural network iterative diagonalization method based on a reduced-dimension Hamiltonian but only once. The final rovibrational energies are computed using a modified Lanczos method for a given total angular momentum J, which is usually fast. Two numerical applications to CH{sub 4} and H{sub 2}CO are given, together with a comparison with previous results.« less

Quantifying the Impact of the North American Monsoon and Deep Midlatitude Convection on the Subtropical Lowermost Stratosphere using in Situ Measurements

NASA Technical Reports Server (NTRS)

Weinstock, E. M.; Pittman, J. V.; Sayres, D. S.; Smith, J. B.; Anderson, J. G.; Wofsy, S. C.; Xueref, I.; Gerbig, C.; Daube, B. C.; Pfister, L.;

Response of eddy activities to localized diabatic heating in Held-Suarez simulations

NASA Astrophysics Data System (ADS)

Lin, Yanluan; Zhang, Jishi; Li, Xingrui; Deng, Yi

2018-01-01

Widespread air pollutions, such as black carbon over East Asia in recent years, could induce a localized diabatic heating, and thus lead to localized static stability and meridional temperature gradient (MTG) changes. Although effect of static stability and MTG on eddies has been addressed by the linear baroclinic instability theory, impacts of a localized heating on mid-latitude eddy activities have not been well explored and quantified. Via a series of idealized global Held-Suarez simulations with different magnitudes of localized heating at different altitudes and latitudes, responses of mid-latitude eddy activity and circulation to these temperature perturbations are systematically investigated. Climatologically, the localized heating in the lower atmosphere induces a wave-like response of eddy activity near the mid-latitude jet stream. Over the heating region, eddy activity tends to be weakening due to the increased static stability. However, there are cyclonic anomalies over the upstream and downstream of the heating region. The zonal mean eddy activity weakens along the baroclinic zone due to reduced MTG and increased static stability. Furthermore, the response of eddy activity increased as the heating magnitude is increased and moved to higher altitudes. The influence of the heating decreases as the heating is prescribed further away from the climatological mid-latitude jet. This implies that the localized heating is most effective over the region with the maximum baroclinicity. Besides, enhanced storm track downstream of the localized heating area found here suggests that increased aerosols over East Asia might strengthen the North Pacific storm track.

Understanding the West African Monsoon from the analysis of diabatic heating distributions as simulated by climate models

NASA Astrophysics Data System (ADS)

Martin, G. M.; Peyrillé, P.; Roehrig, R.; Rio, C.; Caian, M.; Bellon, G.; Codron, F.; Lafore, J.-P.; Poan, D. E.; Idelkadi, A.

2017-03-01

Vertical and horizontal distributions of diabatic heating in the West African monsoon (WAM) region as simulated by four model families are analyzed in order to assess the physical processes that affect the WAM circulation. For each model family, atmosphere-only runs of their CMIP5 configurations are compared with more recent configurations which are on the development path toward CMIP6. The various configurations of these models exhibit significant differences in their heating/moistening profiles, related to the different representation of physical processes such as boundary layer mixing, convection, large-scale condensation and radiative heating/cooling. There are also significant differences in the models' simulation of WAM rainfall patterns and circulations. The weaker the radiative cooling in the Saharan region, the larger the ascent in the rainband and the more intense the monsoon flow, while the latitude of the rainband is related to heating in the Gulf of Guinea region and on the northern side of the Saharan heat low. Overall, this work illustrates the difficulty experienced by current climate models in representing the characteristics of monsoon systems, but also that we can still use them to understand the interactions between local subgrid physical processes and the WAM circulation. Moreover, our conclusions regarding the relationship between errors in the large-scale circulation of the WAM and the structure of the heating by small-scale processes will motivate future studies and model development.

Large differences in reanalyses of diabatic heating in the tropical upper troposphere and lower stratosphere

NASA Astrophysics Data System (ADS)

Wright, J. S.; Fueglistaler, S.

2013-09-01

We present the time mean heat budgets of the tropical upper troposphere (UT) and lower stratosphere (LS) as simulated by five reanalysis models: the Modern-Era Retrospective Analysis for Research and Applications (MERRA), European Reanalysis (ERA-Interim), Climate Forecast System Reanalysis (CFSR), Japanese 25-yr Reanalysis and Japan Meteorological Agency Climate Data Assimilation System (JRA-25/JCDAS), and National Centers for Environmental Prediction/National Center for Atmospheric Research (NCEP/NCAR) Reanalysis 1. The simulated diabatic heat budget in the tropical UTLS differs significantly from model to model, with substantial implications for representations of transport and mixing. Large differences are apparent both in the net heat budget and in all comparable individual components, including latent heating, heating due to radiative transfer, and heating due to parameterised vertical mixing. We describe and discuss the most pronounced differences. Discrepancies in latent heating reflect continuing difficulties in representing moist convection in models. Although these discrepancies may be expected, their magnitude is still disturbing. We pay particular attention to discrepancies in radiative heating (which may be surprising given the strength of observational constraints on temperature and tropospheric water vapour) and discrepancies in heating due to turbulent mixing (which have received comparatively little attention). The largest differences in radiative heating in the tropical UTLS are attributable to differences in cloud radiative heating, but important systematic differences are present even in the absence of clouds. Local maxima in heating and cooling due to parameterised turbulent mixing occur in the vicinity of the tropical tropopause.

Exact transition probabilities in a 6-state Landau–Zener system with path interference

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sinitsyn, Nikolai A.

2015-04-23

In this paper, we identify a nontrivial multistate Landau–Zener (LZ) model for which transition probabilities between any pair of diabatic states can be determined analytically and exactly. In the semiclassical picture, this model features the possibility of interference of different trajectories that connect the same initial and final states. Hence, transition probabilities are generally not described by the incoherent successive application of the LZ formula. Finally, we discuss reasons for integrability of this system and provide numerical tests of the suggested expression for the transition probability matrix.

Opposed slant tube diabatic sorber

DOEpatents

Erickson, Donald C.

2004-01-20

A sorber comprised of at least three concentric coils of tubing contained in a shell with a flow path for liquid sorbent in one direction, a flow path for heat transfer fluid which is in counter-current heat exchange relationship with sorbent flow, a sorbate vapor port in communication with at least one of sorbent inlet or exit ports, wherein each coil is coiled in opposite direction to those coils adjoining it, whereby the opposed slant tube configuration is achieved, with structure for flow modification in the core space inside the innermost coil.

The quest for solvable multistate Landau-Zener models

DOE PAGES

Sinitsyn, Nikolai A.; Chernyak, Vladimir Y.

2017-05-24

Recently, integrability conditions (ICs) in mutistate Landau-Zener (MLZ) theory were proposed. They describe common properties of all known solved systems with linearly time-dependent Hamiltonians. Here we show that ICs enable efficient computer assisted search for new solvable MLZ models that span complexity range from several interacting states to mesoscopic systems with many-body dynamics and combinatorially large phase space. This diversity suggests that nontrivial solvable MLZ models are numerous. Additionally, we refine the formulation of ICs and extend the class of solvable systems to models with points of multiple diabatic level crossing.

Multistate Landau-Zener models with all levels crossing at one point

DOE PAGES

Li, Fuxiang; Sun, Chen; Chernyak, Vladimir Y.; ...

2017-08-04

Within this paper, we discuss common properties and reasons for integrability in the class of multistate Landau-Zener models with all diabatic levels crossing at one point. Exploring the Stokes phenomenon, we show that each previously solved model has a dual one, whose scattering matrix can be also obtained analytically. For applications, we demonstrate how our results can be used to study conversion of molecular into atomic Bose condensates during passage through the Feshbach resonance, and provide purely algebraic solutions of the bowtie and special cases of the driven Tavis-Cummings model.

European Geophysical Society (23rd) General Assembly, Annales Geophysicae, Part 3, Space & Planetary Sciences, Supplement 3 to Volume 16 Held in Nice, France on 20-24 April 1998

DTIC Science & Technology

1998-01-01

For the lower stratosphere diabatic heating sources and planetary wave activity will be discussed. Above 10 hPa observations are less frequent and...the observation durations being minutes-days; ~30 to 200 samples covering each source of the disturbances. The authors have been supported by STCU...the "classical" sinks. The observed stratospheric N20 mixing ratios will not be perturbed by the new source because of: (1) the inevitable loss

Coupling of Clouds and Moisture Transport in Extratropical Cyclonic Systems and the Associated Atmospheric Heating (Q1) and Moisture Sink (Q2)

NASA Astrophysics Data System (ADS)

Wong, S.; Naud, C. M.; Kahn, B. H.; Wu, L.; Fetzer, E. J.

2017-12-01

Different sectors in extratropical cyclonic systems (ETCs) exhibit various patterns in atmospheric moisture transport and provide an excellent test bed for studying coupling between cloud processes and large-scale circulation. Large-scale atmospheric moisture transport diagnosed from the Modern-Era Retrospective analysis for Research and Applications Version 2 and cloud properties (cloud top pressure and optical depth, cloud effective radii and thermodynamic phase) from both the Moderate Resolution Imaging Spectroradiometer (MODIS) and Atmospheric Infrared Sounder (AIRS) will be composited around Northern Hemispheric ETCs over ocean according to their stages of development. Atmospheric diabatic heating rates (Q1) and moisture sinks (Q2) are also inferred from the reanalysis winds, temperature, and specific humidity. Across the warm fronts, elevated convection in the pre-warm front regime is associated with frequent stratiform clouds with middle-to-upper tropospheric heating and lower tropospheric cooling, while upright convection in the warm front regime has frequent deep convective clouds with free-tropospheric heating and strong boundary layer cooling. Thinner stratiform and cirrus clouds are evident in the warm sector with top-heavy profiles of rising motion and diabatic heating. Moisture advection exhibits a sharp gradient across the cold fronts, with convection in the pre-cold front regime highly dependent on the stage of the ETC development. Heating in the boundary layers of the cold sector, polar-air intrusion, and pre-warm sector regimes depends on the amount of low-level clouds, which is again modulated by the stage of the ETC development.

Photodynamics of oxybenzone sunscreen: Nonadiabatic dynamics simulations.

PubMed

Li, Chun-Xiang; Guo, Wei-Wei; Xie, Bin-Bin; Cui, Ganglong

2016-08-21

Herein we have used combined static electronic structure calculations and "on-the-fly" global-switching trajectory surface-hopping dynamics simulations to explore the photochemical mechanism of oxybenzone sunscreen. We have first employed the multi-configurational CASSCF method to optimize minima, conical intersections, and minimum-energy reaction paths related to excited-state intramolecular proton transfer (ESIPT) and excited-state decays in the (1)ππ(∗), (1)nπ(∗), and S0 states (energies are refined at the higher MS-CASPT2 level). According to the mapped potential energy profiles, we have identified two ultrafast excited-state deactivation pathways for the initially populated (1)ππ(∗) system. The first is the diabatic ESIPT process along the (1)ππ(∗) potential energy profile. The generated (1)ππ(∗) keto species then decays to the S0 state via the keto (1)ππ(∗)/gs conical intersection. The second is internal conversion to the dark (1)nπ(∗) state near the (1)ππ(∗) /(1)nπ(∗) crossing point in the course of the diabatic (1)ππ(∗) ESIPT process. Our following dynamics simulations have shown that the ESIPT and (1)ππ(∗) → S0 internal conversion times are 104 and 286 fs, respectively. Finally, our present work demonstrates that in addition to the ESIPT process and the (1)ππ(∗) → S0 internal conversion in the keto region, the (1)ππ(∗) → (1)nπ(∗) internal conversion in the enol region plays as well an important role for the excited-state relaxation dynamics of oxybenzone.

Photodynamics of oxybenzone sunscreen: Nonadiabatic dynamics simulations

NASA Astrophysics Data System (ADS)

Li, Chun-Xiang; Guo, Wei-Wei; Xie, Bin-Bin; Cui, Ganglong

2016-08-01

Herein we have used combined static electronic structure calculations and "on-the-fly" global-switching trajectory surface-hopping dynamics simulations to explore the photochemical mechanism of oxybenzone sunscreen. We have first employed the multi-configurational CASSCF method to optimize minima, conical intersections, and minimum-energy reaction paths related to excited-state intramolecular proton transfer (ESIPT) and excited-state decays in the 1ππ∗, 1nπ∗, and S0 states (energies are refined at the higher MS-CASPT2 level). According to the mapped potential energy profiles, we have identified two ultrafast excited-state deactivation pathways for the initially populated 1ππ∗ system. The first is the diabatic ESIPT process along the 1ππ∗ potential energy profile. The generated 1ππ∗ keto species then decays to the S0 state via the keto 1ππ∗/gs conical intersection. The second is internal conversion to the dark 1nπ∗ state near the 1ππ∗ /1nπ∗ crossing point in the course of the diabatic 1ππ∗ ESIPT process. Our following dynamics simulations have shown that the ESIPT and 1ππ∗ → S0 internal conversion times are 104 and 286 fs, respectively. Finally, our present work demonstrates that in addition to the ESIPT process and the 1ππ∗ → S0 internal conversion in the keto region, the 1ππ∗ → 1nπ∗ internal conversion in the enol region plays as well an important role for the excited-state relaxation dynamics of oxybenzone.

Fragment-orbital tunneling currents and electronic couplings for analysis of molecular charge-transfer systems.

PubMed

Hwang, Sang-Yeon; Kim, Jaewook; Kim, Woo Youn

2018-04-04

In theoretical charge-transfer research, calculation of the electronic coupling element is crucial for examining the degree of the electronic donor-acceptor interaction. The tunneling current (TC), representing the magnitudes and directions of electron flow, provides a way of evaluating electronic couplings, along with the ability of visualizing how electrons flow in systems. Here, we applied the TC theory to π-conjugated organic dimer systems, in the form of our fragment-orbital tunneling current (FOTC) method, which uses the frontier molecular-orbitals of system fragments as diabatic states. For a comprehensive test of FOTC, we assessed how reasonable the computed electronic couplings and the corresponding TC densities are for the hole- and electron-transfer databases HAB11 and HAB7. FOTC gave 12.5% mean relative unsigned error with regard to the high-level ab initio reference. The shown performance is comparable with that of fragment-orbital density functional theory, which gave the same error by 20.6% or 13.9% depending on the formulation. In the test of a set of nucleobase π stacks, we showed that the original TC expression is also applicable to nondegenerate cases under the condition that the overlap between the charge distributions of diabatic states is small enough to offset the energy difference. Lastly, we carried out visual analysis on the FOTC densities of thiophene dimers with different intermolecular alignments. The result depicts an intimate topological connection between the system geometry and electron flow. Our work provides quantitative and qualitative grounds for FOTC, showing it to be a versatile tool in characterization of molecular charge-transfer systems.

The Influence of the 2006 Indonesian Biomass Burning Aerosols on Tropical Dynamics Studied with the GEOS-5 AGCM

NASA Technical Reports Server (NTRS)

Ott, Lesley; Duncan, Bryan; Pawson, Steven; Colarco, Peter; Chin, Mian; Randles, Cynthia; Diehl, Thomas; Nielsen, Eric

2009-01-01

The direct and semi-direct effects of aerosols produced by Indonesian biomass burning (BB) during August November 2006 on tropical dynamics have been examined using NASA's Goddard Earth Observing System, Version 5 (GEOS-5) atmospheric general circulation model (AGCM). The AGCM includes CO, which is transported by resolved and sub-grid processes and subject to a linearized chemical loss rate. Simulations were driven by two sets of aerosol forcing fields calculated offline, one that included Indonesian BB aerosol emissions and one that did not. In order to separate the influence of the aerosols from internal model variability, the means of two ten-member ensembles were compared. Diabatic heating from BB aerosols increased temperatures over Indonesia between 150 and 400 hPa. The higher temperatures resulted in strong increases in upward grid-scale vertical motion, which increased water vapor and CO over Indonesia. In October, the largest increases in water vapor were found in the mid-troposphere (25%) while the largest increases in CO occurred just below the tropopause (80 ppbv or 50%). Diabatic heating from the Indonesian BB aerosols caused CO to increase by 9% throughout the tropical tropopause layer in November and 5% in the lower stratosphere in December. The results demonstrate that aerosol heating plays an important role in the transport of BB pollution and troposphere-to-stratosphere transport. Changes in vertical motion and cloudiness induced by aerosol heating can also alter the transport and phase of water vapor in the upper troposphere/lower stratosphere.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhattacharyya, Swarnendu, E-mail: swarnendu.bhattacharyya@ch.tum.de; Domcke, Wolfgang, E-mail: wolfgang.domcke@ch.tum.de; Dai, Zuyang

A diabatic three-sheeted six-dimensional potential-energy surface has been constructed for the ground state and the lowest excited state of the PH{sub 3}{sup +} cation. Coupling terms of Jahn-Teller and pseudo-Jahn-Teller origin up to eighth order had to be included to describe the pronounced anharmonicity of the surface due to multiple conical intersections. The parameters of the diabatic Hamiltonian have been optimized by fitting the eigenvalues of the potential-energy matrix to ab initio data calculated at the CASSCF/MRCI level employing the correlation-consistent triple-ζ basis. The theoretical photoelectron spectrum of phosphine and the non-adiabatic nuclear dynamics of the phosphine cation have beenmore » computed by propagating nuclear wave packets with the multiconfiguration time-dependent Hartree method. The theoretical photoelectron bands obtained by Fourier transformation of the autocorrelation function agree well with the experimental results. It is shown that the ultrafast non-radiative decay dynamics of the first excited state of PH{sub 3}{sup +} is dominated by the exceptionally strong Jahn-Teller coupling of the asymmetric bending vibrational mode together with a hyperline of conical intersections with the electronic ground state induced by the umbrella mode. Time-dependent population probabilities have been computed for the three adiabatic electronic states. The non-adiabatic Jahn-Teller dynamics within the excited state takes place within ≈5 fs. Almost 80% of the excited-state population decay to the ground state within about 10 fs. The wave packets become highly complex and delocalized after 20 fs and no further significant transfer of electronic population seems to occur up to 100 fs propagation time.« less

Critical analysis of fragment-orbital DFT schemes for the calculation of electronic coupling values

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schober, Christoph; Reuter, Karsten; Oberhofer, Harald, E-mail: harald.oberhofer@ch.tum.de

2016-02-07

We present a critical analysis of the popular fragment-orbital density-functional theory (FO-DFT) scheme for the calculation of electronic coupling values. We discuss the characteristics of different possible formulations or “flavors” of the scheme which differ by the number of electrons in the calculation of the fragments and the construction of the Hamiltonian. In addition to two previously described variants based on neutral fragments, we present a third version taking a different route to the approximate diabatic state by explicitly considering charged fragments. In applying these FO-DFT flavors to the two molecular test sets HAB7 (electron transfer) and HAB11 (hole transfer),more » we find that our new scheme gives improved electronic couplings for HAB7 (−6.2% decrease in mean relative signed error) and greatly improved electronic couplings for HAB11 (−15.3% decrease in mean relative signed error). A systematic investigation of the influence of exact exchange on the electronic coupling values shows that the use of hybrid functionals in FO-DFT calculations improves the electronic couplings, giving values close to or even better than more sophisticated constrained DFT calculations. Comparing the accuracy and computational cost of each variant, we devise simple rules to choose the best possible flavor depending on the task. For accuracy, our new scheme with charged-fragment calculations performs best, while numerically more efficient at reasonable accuracy is the variant with neutral fragments.« less

Non-adiabatic pumping in an oscillating-piston model

NASA Astrophysics Data System (ADS)

Chuchem, Maya; Dittrich, Thomas; Cohen, Doron

2012-05-01

We consider the prototypical "piston pump" operating on a ring, where a circulating current is induced by means of an AC driving. This can be regarded as a generalized Fermi-Ulam model, incorporating a finite-height moving wall (piston) and non-trivial topology (ring). The amount of particles transported per cycle is determined by a layered structure of phase space. Each layer is characterized by a different drift velocity. We discuss the differences compared with the adiabatic and Boltzmann pictures, and highlight the significance of the "diabatic" contribution that might lead to a counter-stirring effect.

Recent examples of mesoscale numerical forecasts of severe weather events along the east coast

NASA Technical Reports Server (NTRS)

Kocin, P. J.; Uccellini, L. W.; Zack, J. W.; Kaplan, M. L.

1984-01-01

Mesoscale numerical forecasts utilizing the Mesoscale Atmospheric Simulation System (MASS) are documented for two East Coast severe weather events. The two events are the thunderstorm and heavy snow bursts in the Washington, D.C. - Baltimore, MD region on 8 March 1984 and the devastating tornado outbreak across North and South Carolina on 28 March 1984. The forecasts are presented to demonstrate the ability of the model to simulate dynamical interactions and diabatic processes and to note some of the problems encountered when using mesoscale models for day-to-day forecasting.

Performance of Frozen Density Embedding for Modeling Hole Transfer Reactions.

PubMed

Ramos, Pablo; Papadakis, Markos; Pavanello, Michele

2015-06-18

We have carried out a thorough benchmark of the frozen density-embedding (FDE) method for calculating hole transfer couplings. We have considered 10 exchange-correlation functionals, 3 nonadditive kinetic energy functionals, and 3 basis sets. Overall, we conclude that with a 7% mean relative unsigned error, the PBE and PW91 functionals coupled with the PW91k nonadditive kinetic energy functional and a TZP basis set constitute the most stable and accurate levels of theory for hole transfer coupling calculations. The FDE-ET method is found to be an excellent tool for computing diabatic couplings for hole transfer reactions.

Momentum flux measurements: Techniques and needs, part 4.5A

NASA Technical Reports Server (NTRS)

Fritts, D. C.

1984-01-01

The vertical flux of horizontal momentum by internal gravity waves is now recognized to play a significant role in the large-scale circulation and thermal structure of the middle atmosphere. This is because a divergence of momentum flux due to wave dissipation results in an acceleration of the local mean flow towards the phase speed of the gravity wave. Such mean flow acceleration are required to offset the large zonal accelerations driven by Coriolis torques acting on the diabatic meridional circulation. Techniques and observations regarding the momentum flux distribution in the middle atmosphere are discussed.

Assimilation of GOES-Derived Cloud Fields Into MM5

NASA Astrophysics Data System (ADS)

Biazar, A. P.; Doty, K. G.; McNider, R.

2007-12-01

This approach for the assimilation of GOES-derived cloud data into an atmospheric model (the Fifth-Generation Pennsylvania State University-National Center for Atmospheric Research Mesoscale Model, or MM5) was performed in two steps. In the first step, multiple linear regression equations were developed using a control MM5 simulation to develop relationships for several dependent variables in model columns that had one or more layers of clouds. In the second step, the regression equations were applied during an MM5 simulation with assimilation in which the hourly GOES satellite data were used to determine the cloud locations and some of the cloud properties, but with all the other variables being determined by the model data. The satellite-derived fields used were shortwave cloud albedo and cloud top pressure. Ten multiple linear regression equations were developed for the following dependent variables: total cloud depth, number of cloud layers, depth of the layer that contains the maximum vertical velocity, the maximum vertical velocity, the height of the maximum vertical velocity, the estimated 1-h stable (i.e., grid scale) precipitation rate, the estimated 1-h convective precipitation rate, the height of the level with the maximum positive diabatic heating, the magnitude of the maximum positive diabatic heating, and the largest continuous layer of upward motion. The horizontal components of the divergent wind were adjusted to be consistent with the regression estimate of the maximum vertical velocity. The new total horizontal wind field with these new divergent components was then used to nudge an ongoing MM5 model simulation towards the target vertical velocity. Other adjustments included diabatic heating and moistening at specified levels. Where the model simulation had clouds when the satellite data indicated clear conditions, procedures were taken to remove or diminish the errant clouds. The results for the period of 0000 UTC 28 June - 0000 UTC 16 July 1999 for both a continental 32-km grid and an 8-km grid over the Southeastern United States indicate a significant improvement in the cloud bias statistics. The main improvement was the reduction of high bias values that indicated times and locations in the control run when there were model clouds but when the satellite indicated clear conditions. The importance of this technique is that it has been able to assimilate the observed clouds in the model in a dynamically sustainable manner. Acknowledgments. This work was partially funded by the following grants: a GEWEX grant from NASA , the Cooperative Agreement between the University of Alabama in Huntsville and the Minerals Management Service on Gulf of Mexico Issues, a NASA applications grant, and a NSF grant.

Delving Into Dissipative Quantum Dynamics: From Approximate to Numerically Exact Approaches

NASA Astrophysics Data System (ADS)

Chen, Hsing-Ta

In this thesis, I explore dissipative quantum dynamics of several prototypical model systems via various approaches, ranging from approximate to numerically exact schemes. In particular, in the realm of the approximate I explore the accuracy of Pade-resummed master equations and the fewest switches surface hopping (FSSH) algorithm for the spin-boson model, and non-crossing approximations (NCA) for the Anderson-Holstein model. Next, I develop new and exact Monte Carlo approaches and test them on the spin-boson model. I propose well-defined criteria for assessing the accuracy of Pade-resummed quantum master equations, which correctly demarcate the regions of parameter space where the Pade approximation is reliable. I continue the investigation of spin-boson dynamics by benchmark comparisons of the semiclassical FSSH algorithm to exact dynamics over a wide range of parameters. Despite small deviations from golden-rule scaling in the Marcus regime, standard surface hopping algorithm is found to be accurate over a large portion of parameter space. The inclusion of decoherence corrections via the augmented FSSH algorithm improves the accuracy of dynamical behavior compared to exact simulations, but the effects are generally not dramatic for the cases I consider. Next, I introduce new methods for numerically exact real-time simulation based on real-time diagrammatic Quantum Monte Carlo (dQMC) and the inchworm algorithm. These methods optimally recycle Monte Carlo information from earlier times to greatly suppress the dynamical sign problem. In the context of the spin-boson model, I formulate the inchworm expansion in two distinct ways: the first with respect to an expansion in the system-bath coupling and the second as an expansion in the diabatic coupling. In addition, a cumulant version of the inchworm Monte Carlo method is motivated by the latter expansion, which allows for further suppression of the growth of the sign error. I provide a comprehensive comparison of the performance of the inchworm Monte Carlo algorithms to other exact methodologies as well as a discussion of the relative advantages and disadvantages of each. Finally, I investigate the dynamical interplay between the electron-electron interaction and the electron-phonon coupling within the Anderson-Holstein model via two complementary NCAs: the first is constructed around the weak-coupling limit and the second around the polaron limit. The influence of phonons on spectral and transport properties is explored in equilibrium, for non-equilibrium steady state and for transient dynamics after a quench. I find the two NCAs disagree in nontrivial ways, indicating that more reliable approaches to the problem are needed. The complementary frameworks used here pave the way for numerically exact methods based on inchworm dQMC algorithms capable of treating open systems simultaneously coupled to multiple fermionic and bosonic baths.

The Precipitation Response Over the Continental United States to Cold Tropical Pacific Sea Surface Temperatures

NASA Technical Reports Server (NTRS)

Wang, Hailan; Schubert, Siegfried D.

2013-01-01

The dominant pattern of annual mean SST variability in the Pacific (in its cold phase) produces pronounced precipitation deficits over the continental United States (U.S.) throughout the annual cycle. This study investigates the physical and dynamical processes through which the cold Pacific pattern affects the U.S. precipitation, particularly the causes for the peak dry impacts in fall, as well as the nature of the differences between the summer and fall responses. Results, based on observations and reanalyses, show that the peak precipitation deficit over the U.S. during fall is primarily due to reduced atmospheric moisture transport from the Gulf of Mexico into the central and eastern U.S., and secondarily due to a reduction in local evaporation from land-atmosphere feedback. The former is associated with a strong and systematic low-level northeasterly flow anomaly over the southeastern U.S. that counteracts the northwest branch of the climatological flow associated with the north Atlantic subtropical high. The above northeasterly anomaly is maintained by both diabatic heating anomalies in the nearby Intra-American Seas and diabatic cooling anomalies in the tropical Pacific. In contrast, the modest summertime precipitation deficit over the U.S. is mainly the result of local land-atmosphere feedback; the rather weak and disorganized atmospheric circulation anomalies over and to the south of the U.S. make little contribution. An evaluation of NSIPP-1 AGCM simulations shows it to be deficient in simulating the warm season tropical convection responses over the Intra-American Seas to the cold Pacific pattern and thereby the precipitation responses over the U.S., a problem that appears to be common to many AGCMs.

The link between Tibetan Plateau monsoon and Indian summer precipitation: a linear diagnostic perspective

NASA Astrophysics Data System (ADS)

Ge, Fei; Sielmann, Frank; Zhu, Xiuhua; Fraedrich, Klaus; Zhi, Xiefei; Peng, Ting; Wang, Lei

2017-12-01

The thermal forcing of the Tibetan Plateau (TP) is analyzed to investigate the formation and variability of Tibetan Plateau Summer Monsoon (TPSM), which affects the climates of the surrounding regions, in particular the Indian summer monsoon precipitation. Dynamic composites and statistical analyses indicate that the Indian summer monsoon precipitation is less/greater than normal during the strong/weak TPSM. Strong (weak) TPSM is associated with an anomalous near surface cyclone (anticyclone) over the western part of the Tibetan Plateau, enhancing (reducing) the westerly flow along its southern flank, suppressing (favoring) the meridional flow of warm and moist air from the Indian ocean and thus cutting (providing) moisture supply for the northern part of India and its monsoonal rainfall. These results are complemented by a dynamic and thermodynamic analysis: (i) A linear thermal vorticity forcing primarily describes the influence of the asymmetric heating of TP generating an anomalous stationary wave flux. Composite analysis of anomalous stationary wave flux activity (after Plumb in J Atmos Sci 42:217-229, 1985) strongly indicate that non-orographic effects (diabatic heating and/or interaction with transient eddies) of the Tibetan Plateau contribute to the generation of an anomalous cyclone (anti-cyclone) over the western TP. (ii) Anomalous TPSM generation shows that strong TPSM years are related to the positive surface sensible heating anomalies over the eastern TP favoring the strong diabatic heating in summer. While negative TPSM years are associated with the atmospheric circulation anomalies during the preceding spring, enhancing northerly dry-cold air intrusions into TP, which may weaken the condensational heat release in the middle and upper troposphere, leading to a weaker than normal summer monsoon over the TP in summer.

On the elimination of the electronic structure bottleneck in on the fly nonadiabatic dynamics for small to moderate sized (10-15 atom) molecules using fit diabatic representations based solely on ab initio electronic structure data: The photodissociation of phenol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Xiaolei, E-mail: virtualzx@gmail.com; Yarkony, David R., E-mail: yarkony@jhu.edu

2016-01-14

In this work, we demonstrate that for moderate sized systems, here a system with 13 atoms, global coupled potential energy surfaces defined for several electronic states over a wide energy range and for distinct regions of nuclear coordinate space characterized by distinct electron configurations, can be constructed with precise energetics and an excellent description of non-adiabatic interactions in all regions. This is accomplished using a recently reported algorithm for constructing quasi-diabatic representations, H{sup d}, of adiabatic electronic states coupled by conical intersections. In this work, the algorithm is used to construct an H{sup d} to describe the photodissociation of phenolmore » from its first and second excited electronic states. The representation treats all 33 internal degrees of freedom in an even handed manner. The ab initio adiabatic electronic structure data used to construct the fit are obtained exclusively from multireference configuration interaction with single and double excitation wave functions comprised of 88 × 10{sup 6} configuration state functions, at geometries determined by quasi-classical trajectories. Since the algorithm uses energy gradients and derivative couplings in addition to electronic energies to construct H{sup d}, data at only 7379 nuclear configurations are required to construct a representation, which describes all nuclear configurations involved in H atom photodissociation to produce the phenoxyl radical in its ground or first excited electronic state, with a mean unsigned energy error of 202.9 cm{sup −1} for electronic energies <60 000 cm{sup −1}.« less

Energetics, structure and photodissociation dynamics of the cluster Arter dot N sup + sub 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, H.; Bowers, M.T.

A mass selected ion beam of ArN{sup +}{sub 2} clusters is brought to a spatial focus and crossed with the polarized output of an argon ion laser. Photofragment ions are mass and energy analyzed using an electrostatic analyzer and detected using single ion counting methods. Photoproducts observed over the photon energy range of 2.1 to 3.5 eV are Ar{sup +}/N{sub 2} and N{sup +}{sub 2}/Ar with the former favored by about a factor of 3. Analysis of the data indicate the upper state is purely repulsive leading to strongly translationally and vibrationally excited products. The absolute cross section has anmore » onset at about 600 nm and smoothly increases to 357 nm. In order to reasonably interpret the data it is suggested the higher energy Ar{sup +}({sup 2}{ital P}{sub 3/2})/N{sub 2} asymptote diabatically correlates to the ground state of ArN{sup +}{sub 2} and the lower energy N{sup +}{sub 2}({ital X} {sup 2}{Sigma})/Ar asymptote diabatically correlates to the repulsive state accessed by the photon. Detailed dynamics in the region where the curves cross are responsible for the observed product distribution. Application of an impulsive model indicates the ground state of ArN{sup +}{sub 2} is linear. Finally, equilibrium measurements of the reaction (N{sub 2}){sup +}{sub 2}+Ar{leftrightarrow}ArN{sup +}{sub 2}+N{sub 2} indicate {Delta}{ital H}{sup 0}{sub 0}={minus}1.0{plus minus}0.3 kcal/mol and {Delta}{ital S}{sup 0}=1.5{plus minus}0.5 cal k{sup {minus}1} mol{sup {minus}1} in agreement with the result of Teng and Conway which had been disputed in the literature.« less

Three-Dimensional Ageostrophic Motion and Water Mass Subduction in the Southern Ocean

NASA Astrophysics Data System (ADS)

Buongiorno Nardelli, B.; Mulet, S.; Iudicone, D.

2018-02-01

Vertical velocities at the ocean mesoscale are several orders of magnitude smaller than corresponding horizontal flows, making their direct monitoring a still unsolved challenge. Vertical motion is generally retrieved indirectly by applying diagnostic equations to observation-based fields. The most common approach relies on the solution of an adiabatic version of the Omega equation, neglecting the ageostrophic secondary circulation driven by frictional effects and turbulent mixing in the boundary layers. Here we apply a diabatic semigeostrophic diagnostic model to two different 3-D reconstructions covering the Southern Ocean during the period 2010-2012. We incorporate the effect of vertical mixing through a modified K-profile parameterization and using ERA-interim data, and perform an indirect validation of the ageostrophic circulation with independent drifter observations. Even if horizontal gradients and associated vertical flow are likely underestimated at 1/4° × 1/4° resolution, the exercise provides an unprecedented relative quantification of the contribution of vertical mixing and adiabatic internal dynamics on the vertical exchanges along the Antarctic Circumpolar Current. Kinematic estimates of subduction rates show the destruction of poleward flowing waters lighter than 26.6 kg/m3 (14 ÷ 15 Sv) and two main positive bands associated with the Antarctic Intermediate Water (7 ÷ 11 Sv) and Sub-Antarctic Mode Waters (4 ÷ 7 Sv) formation, while Circumpolar Deep Water upwelling attains around 3 ÷ 6 Sv. Diabatic and adiabatic terms force distinct spatial responses and vertical velocity magnitudes along the water column and the restratifying effect of adiabatic internal dynamics due to mesoscale eddies is shown to at least partly compensate the contribution of wind-driven vertical exchanges to net subduction.

Propagation Dynamics of Successive, Circumnavigating MJO Events in MERRA2 Reanalysis

NASA Astrophysics Data System (ADS)

Powell, Scott

2017-04-01

Propagation speeds of strong circumnavigating successive MJO events are investigated in MERRA2 reanalysis. Coherent, statistically significant circumnavigating signals in parameterized latent heating and modeled adiabatic cooling associated with large-scale vertical motion are detected and tracked. The signals appear to be associated with propagation of a first baroclinic Kelvin wave, but they obviously moved at a rate much slower than the theoretical phase speed for a dry first baroclinic Kelvin wave. ( 45-50 m/s). The goal is to determine what factors primarily control the variable propagation speed of the MJO signal as a function of longitude. Following theory of Neelin and Held (1987) and Emanuel et al. (1994), the climatological offset (i.e. cancellation) between column integrated diabatic heating and adiabatic cooling in MERRA2 is used to the estimate the wave propagation speed if a reduction of "effective static stability" governed the phase speed. The offset is robust from year to year at all longitudes. A first baroclinic mode based on applying the theory to reanalysis output would propagate between 20-25 m/s over much of the Western Hemisphere, between 20-35 m/s over the eastern Atlantic and Africa, and between 5-20 m/s over the tropical warm pool. The theoretically predicted velocities closely match the propagation speed of the circumnavigating convective signal seen in reanalysis over regions of the tropics where the weak temperature gradient (WTG) approximation is apparently inapplicable (i.e. where deep convection is not prevalent and the offset between diabatic heating and adiabatic cooling is small enough to allow a non-negligible temperature tendency). However, in places where deep convection is prevalent and the offset is large (greater than about 0.9), such as over the warm pool, the theory greatly overestimates propagation speed of the MJO signal. Rather, the moisture wave theory of Adames and Kim (2016), which assumes a WTG, accurately predicts the speed of the MJO signal. Thus, two distinct dynamic regimes, one in which gravity waves dominate and another in which moisture wave dynamics are more applicable, govern MJO propagation depending on where the signal is located. In the East Pacific, the offset has seasonal dependence. It is small (about 0.7) during boreal winter, and a reduction of effective static stability adequately describes propagation of the MJO signal. During boreal summer, the offset approaches 0.9, meaning that the WTG dynamic regime is prevalent like over the warm pool. However, no known theory for MJO propagation can explain the propagation speed of the signal, 8-9 m/s. In the East Pacific, convection tends to have a second baroclinic vertical structure, and it is centered off the equator. This highlights the need for extension of moisture wave/moisture mode theories to incorporate the second convective vertical mode and convection that is not centered latitudinally at the equator.

Photodissociation of phenol via nonadiabatic tunneling: Comparison of two ab initio based potential energy surfaces

NASA Astrophysics Data System (ADS)

Xie, Changjian; Guo, Hua

2017-09-01

The nonadiabatic tunneling-facilitated photodissociation of phenol is investigated using a reduced-dimensional quantum model on two ab initio-based coupled potential energy surfaces (PESs). Although dynamics occurs largely on the lower adiabat, the proximity to a conical intersection between the S1 and S2 states requires the inclusion of both the geometric phase (GP) and diagonal Born-Oppenheimer correction (DBOC). The lifetime of the lowest-lying vibronic state is computed using the diabatic and various adiabatic models. The GP and DBOC terms are found to be essential on one set of PESs, but have a small impact on the other.

Programmable superpositions of Ising configurations

NASA Astrophysics Data System (ADS)

Sieberer, Lukas M.; Lechner, Wolfgang

2018-05-01

We present a framework to prepare superpositions of bit strings, i.e., many-body spin configurations, with deterministic programmable probabilities. The spin configurations are encoded in the degenerate ground states of the lattice-gauge representation of an all-to-all connected Ising spin glass. The ground-state manifold is invariant under variations of the gauge degrees of freedom, which take the form of four-body parity constraints. Our framework makes use of these degrees of freedom by individually tuning them to dynamically prepare programmable superpositions. The dynamics combines an adiabatic protocol with controlled diabatic transitions. We derive an effective model that allows one to determine the control parameters efficiently even for large system sizes.

The Amazon and climate

NASA Technical Reports Server (NTRS)

Nobre, C. A.

1984-01-01

The climatologies of cloudiness and precipitation for the Amazon, are reviewed and the physical causes of some of the observed features and those which are not well known are explained. The atmospheric circulation over the Amazon is discussed on the large scale tropical circulations forced by deep diabatic heating sources. Weather deforestation which leads to a reduction in evapotranspiration into the atmosphere, and a reduction in precipitation and its implicated for the gobal climate is discussed. It is indicated that a large scale clearing of tropical rainforests there would be a reduction in rainfall which would have global effects on climate and weather both in the tropical and extratropical regions.

The Dissociative Recombination of OH(+)

NASA Technical Reports Server (NTRS)

Guberman, Steven L.

1995-01-01

Theoretical quantum chemical calculations of the cross sections and rates for the dissociative recombination of the upsilon = 0 level of the ground state of OH(+) show that recombination occurs primarily along the 2 (2)Pi diabatic route. The products are 0((1)D) and a hot H atom with 6.1 eV kinetic energy. The coupling to the resonances is very small and the indirect recombination mechanism plays only a minor role. The recommended value for the rate coefficient is (6.3 +/- 0.7) x 10(exp -9)x (T(e)/1300)(exp -0.48) cu.cm/s for 10 less than T(e) less than 1000 K.

Determination of rainfall and condensational heating in the South Pacific convergence zone during FGGE SOP-1

NASA Technical Reports Server (NTRS)

Robertson, F. R.

1984-01-01

The role of cloud related diabatic processes in maintaining the structure of the South Pacific Convergence Zone is discussed. The method chosen to evaluate the condensational heating is a diagnostic cumulus mass flux technique which uses GOES digital IR data to characterize the cloud population. This method requires as input an estimate of time/area mean rainfall rate over the area in question. Since direct observation of rainfall in the South Pacific is not feasible, a technique using GOES IR data is being developed to estimate rainfall amounts for a 2.5 degree grid at 12h intervals.

Heat balance statistics derived from four-dimensional assimilations with a global circulation model

NASA Technical Reports Server (NTRS)

Schubert, S. D.; Herman, G. F.

1981-01-01

The reported investigation was conducted to develop a reliable procedure for obtaining the diabatic and vertical terms required for atmospheric heat balance studies. The method developed employs a four-dimensional assimilation mode in connection with the general circulation model of NASA's Goddard Laboratory for Atmospheric Sciences. The initial analysis was conducted with data obtained in connection with the 1976 Data Systems Test. On the basis of the results of the investigation, it appears possible to use the model's observationally constrained diagnostics to provide estimates of the global distribution of virtually all of the quantities which are needed to compute the atmosphere's heat and energy balance.

Ab initio study of H + + H 2 collisions: Elastic/inelastic and charge transfer processes

NASA Astrophysics Data System (ADS)

Saieswari, A.; Kumar, Sanjay

2007-12-01

An ab initio full configuration interaction study has been undertaken to obtain the global potential energy surfaces for the ground and the first excited electronic state of the H + + H 2 system employing Dunning's cc-pVQZ basis set. Using the ab initio approach the corresponding quasi-diabatic potential energy surfaces and coupling potentials have been obtained. A time-independent quantum mechanical study has been also undertaken for both the inelastic and charge transfer processes at the experimental collision energy Ec.m. = 20.0 eV and the preliminary results show better agreement with the experimental data as compared to the earlier available theoretical studies.

Direct Radiative Effects of Aerosols Over South Asia From Observations and Modeling

NASA Technical Reports Server (NTRS)

Nair, Vijayakumar S.; Babu, S. Suresh; Manoj, M. R.; Moorthy, Krishna K.; Chin, Mian

2016-01-01

Quantitative assessment of the seasonal variations in the direct radiative effect (DRE) of composite aerosols as well as the constituent species over the Indian sub continent has been carried out using a synergy of observations from a dense network of ground based aerosol observatories and modeling based on chemical transport model simulations. Seasonal variation of aerosol constituents depict significant influence of anthropogenic aerosol sources in winter and the dominance of natural sources in spring, even though the aerosol optical depth doesn't change significantly between these two seasons. A significant increase in the surface cooling and atmospheric warming has been observed as season changes from winter DRE(sub SUR) = -28 +/- 12 W m(exp -2) and DRE(sub ATM) = +19.6 +/- 9 W m(exp -2) to spring DRE(sub SUR) = -33.7 +/- 12 W m(exp -2) and DRE(sub ATM) = +27 +/- 9 W m(exp-2). Interestingly, springtime aerosols are more absorptive in nature compared to winter and consequently the aerosol induced diabatic heating of the atmosphere goes as high as approximately 1 K day(exp -1) during spring, especially over eastern India. The atmospheric DRE due to dust aerosols (+14 +/- 7 W m(exp 2) during spring overwhelms that of black carbon DRE (+11.8 +/- 6 W m(exp -2) during winter. The DRE at the top of the atmosphere is mostly governed by the anthropogenic aerosols during all the seasons. The columnar aerosol loading, its anthropogenic fraction and radiative effects shows a steady increase with latitude across Indian mainland leading to a larger aerosol-induced atmospheric warming during spring than in winter.

Goddard Cumulus Ensemble (GCE) Model: Application for Understanding Preciptation Processes

NASA Technical Reports Server (NTRS)

Tao, Wei-Kuo; Einaudi, Franco (Technical Monitor)

2000-01-01

The global hydrological cycle is central to climate system interactions and the key to understanding their behavior. Rainfall and its associated precipitation processes are a key link in the hydrologic cycle. Fresh water provided by tropical rainfall and its variability can exert a large impact upon the structure of the upper ocean layer. In addition, approximately two-thirds of the global rain falls in the Tropics, while the associated latent heat release accounts for about three-fourths of the total heat energy for the Earth's atmosphere. Precipitation from convective cloud systems comprises a large portion of tropical heating and rainfall. Furthermore, the vertical distribution of convective latent-heat releases modulates large-scale tropical circulations (e.g., the 30-60-day intraseasonal oscillation), which, in turn, impacts midlatitude weather through teleconnection patterns such as those associated with El Nino. Shifts in these global circulations can result in prolonged periods of droughts and floods, thereby exerting a tremendous impact upon the biosphere and human habitation. And yet, monthly rainfall over the tropical oceans is still not known within a factor of two over large (5 degrees latitude by 5 degrees longitude) areas. Hence, the Tropical Rainfall Measuring Mission (TRMM), a joint U.S./Japan space project, can provide a more accurate measurement of rainfall as well as estimate the four-dimensional structure of diabatic heating over the global tropics. The distributions of rainfall and inferred heating can be used to advance our understanding of the global energy and water cycle. In addition, this information can be used for global circulation and climate models for testing and improving their parameterizations.

Life Cycle of Midlatitude Deep Convective Systems in a Lagrangian Framework

NASA Technical Reports Server (NTRS)

Feng, Zhe; Dong, Xiquan; Xie, Baike; McFarlane, Sally A.; Kennedy, Aaron; Lin, Bing; Minnis, Patrick

2012-01-01

Deep Convective Systems (DCSs) consist of intense convective cores (CC), large stratiform rain (SR) regions, and extensive non-precipitating anvil clouds (AC). This study focuses on the evolution of these three components and the factors that affect convective AC production. An automated satellite tracking method is used in conjunction with a recently developed multi-sensor hybrid classification to analyze the evolution of DCS structure in a Lagrangian framework over the central United States. Composite analysis from 4221 tracked DCSs during two warm seasons (May-August, 2010-2011) shows that maximum system size correlates with lifetime, and longer-lived DCSs have more extensive SR and AC. Maximum SR and AC area lag behind peak convective intensity and the lag increases linearly from approximately 1-hour for short-lived systems to more than 3-hours for long-lived ones. The increased lag, which depends on the convective environment, suggests that changes in the overall diabatic heating structure associated with the transition from CC to SR and AC could prolong the system lifetime by sustaining stratiform cloud development. Longer-lasting systems are associated with up to 60% higher mid-tropospheric relative humidity and up to 40% stronger middle to upper tropospheric wind shear. Regression analysis shows that the areal coverage of thick AC is strongly correlated with the size of CC, updraft strength, and SR area. Ambient upper tropospheric wind speed and wind shear also play an important role for convective AC production where for systems with large AC (radius greater than 120-km) they are 24% and 20% higher, respectively, than those with small AC (radius=20 km).

Controls on the Climates of Tidally Locked Terrestrial Planets

NASA Astrophysics Data System (ADS)

Yang, J.; Cowan, N. B.; Abbot, D. S.

2013-12-01

Earth-size planets in the habitable zone of M-dwarf stars may be very common. Due to strong tidal forces, these planets in circulate orbits are expected to be tidally locked, with one hemisphere experiencing perpetual day and the other permanent night. Previous studies on the climates of tidally locked planets were primarily based on complex 3D general circulation models (GCMs). The central question to be answered in this work is: what is the minimum necessary physics needed to understand the climates simulated by GCMs? A two-column model, primarily based on the weak temperature gradient (WTG) approximation (Sobel et al. 2001) and the fixed anvil temperature (FAT) hypothesis (Hartmann and Larson 2002) for the tropical climate of Earth, is developed for understanding the climates of tidally locked planets. This highly idealized model well reproduces fundamental features of the climates obtained in complicated GCMs (Yang et al. 2013), including planetary albedo, longwave cloud forcing, outgoing longwave radiation (OLR), and atmospheric energy transport. This suggests that the WTG approximation and the FAT hypothesis may be good approximations for tidally locked habitable planets, which provides strong constraints on the large-scale circulations, diabatic processes, and cloud behaviour on these planets. Both the simple model and the GCMs predict that (i) convection and planetary albedo on the dayside increase as stellar flux is increased; (ii) longwave cloud radiative forcing increases as stellar flux is increased, due to the cloud top temperature remains nearly constant as the climate changes (FAT hypothesis); (iii) for planets at the inner regions of the habitable zone, the dayside--nightside OLR contrast becomes very weak or even reverses, due to the strong longwave absorption by water vapor and clouds on the dayside; (iv) the dayside--to--nightside atmospheric energy transport (AET) increases as stellar flux is increased, and decreases as oceanic energy transport (OET) is included, although the compensation between AET and OET is incomplete. To summarize, we are able to construct a realistic low-order model for the climate of tidally locked terrestrial planets, including the cloud behavior, using only the two constraints. This bodes well for the interpretation of complex GCMs and future observations of such planets using, for example, the James Webb Space Telescope. Cited papers: [1]. Sobel, A. H., J. Nilsson and L. M. Polvani: The weak temperature gradient approximation and balanced tropical moisture waves, J. Atmos. Sci., 58, 3650-65, 2001. [2]. Hartmann, D. L. and K. Larson, An important constraint on tropical cloud-climate feedback, Geophys. Res. Lett., 29, 1951-54, 2002. [3]. Yang, J., N. B. Cowan and D. S. Abbot: Stabilizing cloud feedback dramatically expands the habitable zone of tidally locked planets, ApJ. Lett., 771, L45, 2013.

Modelling charge transfer reactions with the frozen density embedding formalism.

PubMed

Pavanello, Michele; Neugebauer, Johannes

2011-12-21

The frozen density embedding (FDE) subsystem formulation of density-functional theory is a useful tool for studying charge transfer reactions. In this work charge-localized, diabatic states are generated directly with FDE and used to calculate electronic couplings of hole transfer reactions in two π-stacked nucleobase dimers of B-DNA: 5'-GG-3' and 5'-GT-3'. The calculations rely on two assumptions: the two-state model, and a small differential overlap between donor and acceptor subsystem densities. The resulting electronic couplings agree well with benchmark values for those exchange-correlation functionals that contain a high percentage of exact exchange. Instead, when semilocal GGA functionals are used the electronic couplings are grossly overestimated.

Quasi-geostrophic free mode models of long-lived Jovian eddies: Forcing mechanisms and crucial observational tests

NASA Technical Reports Server (NTRS)

Read, P. L.

1986-01-01

Observations of Jupiter and Saturn long-lived eddies, such as Jupiter's Great Red Spot and White Ovals, are presently compared with laboratory experiments and corresponding numerical simulations for free thermal convection in a rotating fluid that is subject to horizontal differential heating and cooling. Difficulties in determining the essential processes maintaining and dissipating stable eddies, on the basis of global energy budget studies, are discussed; such difficulties do not arise in considerations of the flow's potential vorticity budget. On Jupiter, diabatically forced and transient eddy-driven flows primarily differ in the implied role of transient eddies in transporting potential vorticity across closed geostrophic streamlines in the time mean.

[Clinically documented fungal infections].

PubMed

Kakeya, Hiroshi; Kohno, Shigeru

2008-12-01

Proven fungal infections are diagnosed by histological/microbiological evidence of fungi at the site of infection and positive blood culture (fungemia). However, invasive diagnosing examinations are not always applied for all of immunocompromised patients. Clinically documented invasive fungal infections are diagnosed by typical radiological findings such as halo sign on chest CT plus positive serological/molecular evidence of fungi. Serological tests of Aspergillus galactomannan antigen and beta-glucan for aspergillosis and cryptococcal glucuronoxylomannan antigen for cryptococcosis are useful. Hence, none of reliable serological tests for zygomycosis are available so far. In this article, risk factors, sign and symptoms, and diagnostic methods for clinically documented cases of invasive aspergillosis, pulmonary cryptococcosis, and zygomycosis with diabates, are reviewed.

Surface hopping trajectory simulations with spin-orbit and dynamical couplings

NASA Astrophysics Data System (ADS)

Granucci, Giovanni; Persico, Maurizio; Spighi, Gloria

2012-12-01

In this paper we consider the inclusion of the spin-orbit interaction in surface hopping molecular dynamics simulations to take into account spin forbidden transitions. Two alternative approaches are examined. The spin-diabatic one makes use of eigenstates of the spin-free electronic Hamiltonian and of hat{S}^2 and is commonly applied when the spin-orbit coupling is weak. We point out some inconsistencies of this approach, especially important when more than two spin multiplets are coupled. The spin-adiabatic approach is based on the eigenstates of the total electronic Hamiltonian including the spin-orbit coupling. Advantages and drawbacks of both strategies are discussed and illustrated with the help of two model systems.

Ab initio study of the diatomic fluorides FeF, CoF, NiF, and CuF.

PubMed

Koukounas, Constantine; Mavridis, Aristides

2008-11-06

The late-3d transition-metal diatomic fluorides MF = FeF, CoF, NiF, and CuF have been studied using variational multireference (MRCI) and coupled-cluster [RCCSD(T)] methods, combined with large to very large basis sets. We examined a total of 35 (2S+1)|Lambda| states, constructing as well 29 full potential energy curves through the MRCI method. All examined states are ionic, diabatically correlating to M(+)+F(-)((1)S). Notwithstanding the "eccentric" character of the 3d transition metals and the difficulties to accurately be described with all-electron ab initio methods, our results are, in general, in very good agreement with available experimental numbers.

Use of satellite data and modeling to asses the influence of stratospheric processes on the troposphere

NASA Technical Reports Server (NTRS)

Nathan, Terrence R.; Yarger, Douglas N.

1989-01-01

The research is comprised of the following tasks: use of simple analytical and numerical models of a coupled troposphere-stratosphere system to examine the effects of radiation and ozone on planetary wave dynamics and the tropospheric circulation; use of satellite data obtained from the Nimbus 7 Limb Infrared Monitor of the Stratosphere (LIMS) instrument and Solar Backscattered Ultraviolet (SBUV) experiment, in conjunction with National Meteorological Center (NMC) data, to determine the planetary wave vertical structures, dominant wave spectra, ozone spectra, and time variations in diabatic heating rate; and synthesis of the modeling and observational results to provide a better understanding of the effects that stratospheric processes have on tropospheric dynamics.

Non-adiabatic excited state molecular dynamics of phenylene ethynylene dendrimer using a multiconfigurational Ehrenfest approach

DOE PAGES

Fernandez-Alberti, Sebastian; Makhov, Dmitry V.; Tretiak, Sergei; ...

2016-03-10

Photoinduced dynamics of electronic and vibrational unidirectional energy transfer between meta-linked building blocks in a phenylene ethynylene dendrimer is simulated using a multiconfigurational Ehrenfest in time-dependent diabatic basis (MCE-TDDB) method, a new variant of the MCE approach developed by us for dynamics involving multiple electronic states with numerous abrupt crossings. Excited-state energies, gradients and non-adiabatic coupling terms needed for dynamics simulation are calculated on-the-fly using the Collective Electron Oscillator (CEO) approach. In conclusion, a comparative analysis of our results obtained using MCE-TDDB, the conventional Ehrenfest method and the surface-hopping approach with and without decoherence corrections is presented.

On the Magnitude of the Nonadiabatic Error for Highly Coupled Radicals

NASA Astrophysics Data System (ADS)

Stanton, J. F.

2009-06-01

A review is given of recent advances in the construction of (quasi)diabatic model Hamiltonians and their application to analyzing the spectroscopy of molecules with strong vibronic coupling. A numerical application to the vibronic levels of the BNB radical below 0.6 eV is presented, together with corresponding adiabatic (quantum chemistry) calculations. The agreement with the experimental levels is nearly quantitative with the model Hamiltonian, attesting to the power of the approach. On the contrary, it is also revealed that the magnitude of the nonadiabatic contributions to the zero-point energy and the lowest fundamental frequency of the coupling mode are considerably larger than expected, at least by your narrator.

Solvent-assisted multistage nonequilibrium electron transfer in rigid supramolecular systems: Diabatic free energy surfaces and algorithms for numerical simulations

NASA Astrophysics Data System (ADS)

Feskov, Serguei V.; Ivanov, Anatoly I.

2018-03-01

An approach to the construction of diabatic free energy surfaces (FESs) for ultrafast electron transfer (ET) in a supramolecule with an arbitrary number of electron localization centers (redox sites) is developed, supposing that the reorganization energies for the charge transfers and shifts between all these centers are known. Dimensionality of the coordinate space required for the description of multistage ET in this supramolecular system is shown to be equal to N - 1, where N is the number of the molecular centers involved in the reaction. The proposed algorithm of FES construction employs metric properties of the coordinate space, namely, relation between the solvent reorganization energy and the distance between the two FES minima. In this space, the ET reaction coordinate zn n' associated with electron transfer between the nth and n'th centers is calculated through the projection to the direction, connecting the FES minima. The energy-gap reaction coordinates zn n' corresponding to different ET processes are not in general orthogonal so that ET between two molecular centers can create nonequilibrium distribution, not only along its own reaction coordinate but along other reaction coordinates too. This results in the influence of the preceding ET steps on the kinetics of the ensuing ET. It is important for the ensuing reaction to be ultrafast to proceed in parallel with relaxation along the ET reaction coordinates. Efficient algorithms for numerical simulation of multistage ET within the stochastic point-transition model are developed. The algorithms are based on the Brownian simulation technique with the recrossing-event detection procedure. The main advantages of the numerical method are (i) its computational complexity is linear with respect to the number of electronic states involved and (ii) calculations can be naturally parallelized up to the level of individual trajectories. The efficiency of the proposed approach is demonstrated for a model supramolecular system involving four redox centers.

Non-adiabatic quantum reactive scattering in hyperspherical coordinates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kendrick, Brian K.

A new electronically non-adiabatic quantum reactive scattering methodology is presented based on a time-independent coupled channel formalism and the adiabatically adjusting principal axis hyperspherical coordinates of Pack and Parker [J. Chem. Phys. 87, 3888 (1987)]. The methodology computes the full state-to-state scattering matrix for A + B 2(v, j) ↔ AB(v', j') + B and A + AB(v, j) → A + AB(v', j') reactions that involve two coupled electronic states which exhibit a conical intersection. The methodology accurately treats all six degrees of freedom relative to the center-of-mass which includes non-zero total angular momentum J and identical particle exchangemore » symmetry. The new methodology is applied to the ultracold hydrogen exchange reaction for which large geometric phase effects have been recently reported [B. K. Kendrick et al., Phys. Rev. Lett. 115, 153201 (2015)]. Rate coefficients for the H/D + HD(v = 4, j = 0) → H/D + HD(v', j') reactions are reported for collision energies between 1 μK and 100 K (total energy ≈1.9 eV). A new diabatic potential energy matrix is developed based on the Boothroyd, Keogh, Martin, and Peterson (BKMP2) and double many body expansion plus single-polynomial (DSP) adiabatic potential energy surfaces for the ground and first excited electronic states of H 3, respectively. The rate coefficients computed using the new non-adiabatic methodology and diabatic potential matrix reproduce the recently reported rates that include the geometric phase and are computed using a single adiabatic ground electronic state potential energy surface (BKMP2). The dramatic enhancement and suppression of the ultracold rates due to the geometric phase are confirmed as well as its effects on several shape resonances near 1 K. In conclusion, the results reported here represent the first fully non-adiabatic quantum reactive scattering calculation for an ultracold reaction and validate the importance of the geometric phase on the Wigner threshold behavior.« less

Non-adiabatic quantum reactive scattering in hyperspherical coordinates

NASA Astrophysics Data System (ADS)

Kendrick, Brian K.

2018-01-01

A new electronically non-adiabatic quantum reactive scattering methodology is presented based on a time-independent coupled channel formalism and the adiabatically adjusting principal axis hyperspherical coordinates of Pack and Parker [J. Chem. Phys. 87, 3888 (1987)]. The methodology computes the full state-to-state scattering matrix for A + B2(v , j) ↔ AB(v ', j') + B and A + AB(v , j) → A + AB(v ', j') reactions that involve two coupled electronic states which exhibit a conical intersection. The methodology accurately treats all six degrees of freedom relative to the center-of-mass which includes non-zero total angular momentum J and identical particle exchange symmetry. The new methodology is applied to the ultracold hydrogen exchange reaction for which large geometric phase effects have been recently reported [B. K. Kendrick et al., Phys. Rev. Lett. 115, 153201 (2015)]. Rate coefficients for the H/D + HD(v = 4, j = 0) → H/D + HD(v ', j') reactions are reported for collision energies between 1 μK and 100 K (total energy ≈1.9 eV). A new diabatic potential energy matrix is developed based on the Boothroyd, Keogh, Martin, and Peterson (BKMP2) and double many body expansion plus single-polynomial (DSP) adiabatic potential energy surfaces for the ground and first excited electronic states of H3, respectively. The rate coefficients computed using the new non-adiabatic methodology and diabatic potential matrix reproduce the recently reported rates that include the geometric phase and are computed using a single adiabatic ground electronic state potential energy surface (BKMP2). The dramatic enhancement and suppression of the ultracold rates due to the geometric phase are confirmed as well as its effects on several shape resonances near 1 K. The results reported here represent the first fully non-adiabatic quantum reactive scattering calculation for an ultracold reaction and validate the importance of the geometric phase on the Wigner threshold behavior.

Anomalous Heat Budgets in the Interior Pacific Ocean on Seasonal- to -Timescales and Gyre Spacescales

NASA Technical Reports Server (NTRS)

White, Warren; Cayan, Daniel R.; Lindstrom, Eric (Technical Monitor)

2002-01-01

This study quantifies uncertainties in closing the seasonal cycle of diabatic heat storage over the Pacific Ocean from 20 degrees S to 60 degrees N through the synthesis of World Ocean Circulation Experiment (WOCE) products over 7 years from 1993-1999. We utilize WOCE reanalysis products from the following sources: diabatic heat storage (DHS) from the Scripps Institution of Oceanography (SIO); near-surface geostrophic and Ekman currents from the Earth and Space Research (ESR); and air-sea heat fluxes from Comprehensive Ocean-Atmosphere Data Set (COADS), National Centers for Environmental Prediction (NCEP), and European Center for Mid-Range Weather Forecasts (ECMWF). We interpolate these products onto a common grid, allowing the seasonal cycle of DHS to be modeled for comparison with that observed. Everywhere latent heat flux residuals dominate sensible heat flux residuals and shortwave heat flux residuals dominate longwave heat flux residuals, both comparable in magnitude to the residual horizontal heat advection. We find the root-mean-square (RMS) of the differences between observed and model residual DHS tendencies to be less than 15 W per square meters everywhere except in the Kuroshio extension. Comparable COADS and NCEP products perform better than ECMWF products in the extra-tropics, while the NCEP product performs best in the tropics. Radiative and turbulent air-sea heat flux residuals computed from ship-born measurements perform better than those computed from satellite cloud and wind measurements. Since the RMS differences derive largely from biases in measured wind speed and cloud fraction, least-squares minimization is used to correct the residual Ekman heat advection and air-sea heat flux. Minimization reduces RMS differences less than 5 W per square meters except in the Kuroshio extension, suggesting how winds, clouds, and exchange coefficients in the NCEP, ECMWF, and ESR products can be improved.

Photodynamics of oxybenzone sunscreen: Nonadiabatic dynamics simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Chun-Xiang; Guo, Wei-Wei; Xie, Bin-Bin

Herein we have used combined static electronic structure calculations and “on-the-fly” global-switching trajectory surface-hopping dynamics simulations to explore the photochemical mechanism of oxybenzone sunscreen. We have first employed the multi-configurational CASSCF method to optimize minima, conical intersections, and minimum-energy reaction paths related to excited-state intramolecular proton transfer (ESIPT) and excited-state decays in the {sup 1}ππ{sup ∗}, {sup 1}nπ{sup ∗}, and S{sub 0} states (energies are refined at the higher MS-CASPT2 level). According to the mapped potential energy profiles, we have identified two ultrafast excited-state deactivation pathways for the initially populated {sup 1}ππ{sup ∗} system. The first is the diabatic ESIPTmore » process along the {sup 1}ππ{sup ∗} potential energy profile. The generated {sup 1}ππ{sup ∗} keto species then decays to the S{sub 0} state via the keto {sup 1}ππ{sup ∗}/gs conical intersection. The second is internal conversion to the dark {sup 1}nπ{sup ∗} state near the {sup 1}ππ{sup ∗} /{sup 1}nπ{sup ∗} crossing point in the course of the diabatic {sup 1}ππ{sup ∗} ESIPT process. Our following dynamics simulations have shown that the ESIPT and {sup 1}ππ{sup ∗} → S{sub 0} internal conversion times are 104 and 286 fs, respectively. Finally, our present work demonstrates that in addition to the ESIPT process and the {sup 1}ππ{sup ∗} → S{sub 0} internal conversion in the keto region, the {sup 1}ππ{sup ∗} → {sup 1}nπ{sup ∗} internal conversion in the enol region plays as well an important role for the excited-state relaxation dynamics of oxybenzone.« less

Tropical Diabatic Heating and the Role of Convective Processes as Represented in Several Contemporary Climate Models

NASA Technical Reports Server (NTRS)

Robertson, Franklin R.; Roads, John; Oglesby, Robert; Marshall, Susan

2004-01-01

One of the most fundamental properties of the global heat balance is the net heat input into the tropical atmosphere that helps drive the planetary atmospheric circulation. Although broadly understood in terms of its gross structure and balance of source / sink terms, incorporation of the relevant processes in predictive models is still rather poor. The work reported here examines the tropical radiative and water cycle behavior as produced by four contemporary climate models. Among these are the NSIPP-2 (NASA Seasonal to Interannual Prediction Project) which uses the RAS convective parameterization; the FVCCM, a code using finite volume numerics and the CCM3.6 physics; FVCCM-MCRAS again having the finite volume numerics, but MCRAS convective parameterization and a different radiation treatment; and, finally, the NCEP GSM which uses the RAS. Using multi-decadal integrations with specified SSTs we examine the statistics of radiative / convective processes and associated energy transports, and then estimate model energy flux sensitivities to SST changes. In particular the behavior of the convective parameterizations is investigated. Additional model integrations are performed specifically to assess the importance representing convective inhibition in regulating convective cloud-top structure and moisture detrainment as well as controlling surface energy fluxes. To evaluate the results of these experiments, a number of satellite retrievals are used: TRMM retrievals of vertical reflectivity structure, rainfall rate, and inferred diabatic heating are analyzed to show both seasonal and interannual variations in vertical structure of latent heat release. Top-of-atmosphere radiative fluxes from ERBS and CERES are used to examine shortwave and longwave cloud forcing and to deduce required seasonal energy transports. Retrievals of cloud properties from ISCCP and water vapor variations from SSM/T-2 are also used to understand behavior of the humidity fields. These observations are supplemented with output form the DOE Reanalysis-2.

Maintenance of Austral Summertime Upper-Tropospheric Circulation over Tropical South America: The Bolivian High-Nordeste Low System.

NASA Astrophysics Data System (ADS)

Chen, Tsing-Chang; Weng, Shu-Ping; Schubert, Siegfried

1999-07-01

Using the NASA/GEOS reanalysis data for 1980-95, the austral-summer stationary eddies in the tropical-subtropical Southern Hemisphere are examined in two wave regimes: long and short wave (wave 1 and waves 2-6, respectively). The basic structure of the Bolivian high-Nordeste low (BH-NL) system is formed by a short-wave train across South America but modulated by the long-wave regime. The short-wave train exhibits a monsoonlike vertical phase reversal in the midtroposphere and a quarter-wave phase shift relative to the divergent circulation. As inferred from (a) the spatial relationship between the streamfunction and velocity potential and (b) the structure of the divergent circulation, the short-wave train forming the BH-NL system is maintained by South American local heating and remote African heating, while the long-wave regime is maintained by western tropical Pacific heating.The maintenance of the stationary waves in the two wave regimes is further illustrated by a simple diagnostic scheme that includes the velocity-potential maintenance equation (which links velocity potential and diabatic heating) and the streamfunction budget (which is the inverse Laplacian transform of the vorticity equation). Some simple relationships between streamfunction and velocity potential for both wave regimes are established to substantiate the links between diabatic heating and streamfunction; of particular interest is a Sverdrup balance in the short-wave regime. This simplified vorticity equation explains the vertical structure of the short-wave train associated with the BH-NL system and its spatial relationship with the divergent circulation.Based upon the diagnostic analysis of its maintenance a simple forced barotropic model is adopted to simulate the BH-NL system with idealized forcings, which imitates the real 200-mb divergence centers over South America, Africa, and the tropical Pacific. Numerical simulations demonstrate that the formation of the BH-NL system is affected not only by the African remote forcing, but also by the tropical Pacific forcing.

Non-adiabatic quantum reactive scattering in hyperspherical coordinates

DOE PAGES

Kendrick, Brian K.

2018-01-28

A new electronically non-adiabatic quantum reactive scattering methodology is presented based on a time-independent coupled channel formalism and the adiabatically adjusting principal axis hyperspherical coordinates of Pack and Parker [J. Chem. Phys. 87, 3888 (1987)]. The methodology computes the full state-to-state scattering matrix for A + B 2(v, j) ↔ AB(v', j') + B and A + AB(v, j) → A + AB(v', j') reactions that involve two coupled electronic states which exhibit a conical intersection. The methodology accurately treats all six degrees of freedom relative to the center-of-mass which includes non-zero total angular momentum J and identical particle exchangemore » symmetry. The new methodology is applied to the ultracold hydrogen exchange reaction for which large geometric phase effects have been recently reported [B. K. Kendrick et al., Phys. Rev. Lett. 115, 153201 (2015)]. Rate coefficients for the H/D + HD(v = 4, j = 0) → H/D + HD(v', j') reactions are reported for collision energies between 1 μK and 100 K (total energy ≈1.9 eV). A new diabatic potential energy matrix is developed based on the Boothroyd, Keogh, Martin, and Peterson (BKMP2) and double many body expansion plus single-polynomial (DSP) adiabatic potential energy surfaces for the ground and first excited electronic states of H 3, respectively. The rate coefficients computed using the new non-adiabatic methodology and diabatic potential matrix reproduce the recently reported rates that include the geometric phase and are computed using a single adiabatic ground electronic state potential energy surface (BKMP2). The dramatic enhancement and suppression of the ultracold rates due to the geometric phase are confirmed as well as its effects on several shape resonances near 1 K. In conclusion, the results reported here represent the first fully non-adiabatic quantum reactive scattering calculation for an ultracold reaction and validate the importance of the geometric phase on the Wigner threshold behavior.« less

The seasonal cycle of diabatic heat storage in the Pacific Ocean

USGS Publications Warehouse

White, Warren B.; Cayan, D.R.; Niiler, P.P.; Moisan, J.; Lagerloef, G.; Bonjean, F.; Legler, D.

2005-01-01

This study quantifies uncertainties in closing the seasonal cycle of diabatic heat storage (DHS) over the Pacific Ocean from 20??S to 60??N through the synthesis of World Ocean Circulation Experiment (WOCE) reanalysis products from 1993 to 1999. These products are DHS from Scripps Institution of Oceanography (SIO); near-surface geostrophic and Ekman currents from Earth and Space Research (ESR); and air-sea heat fluxes from Comprehensive Ocean-Atmosphere Data Set (COADS), National Centers for Environmental Prediction (NCEP), and European Center for Mid-Range Weather Forecasts (ECMWF). With these products, we compute residual heat budget components by differencing long-term monthly means from the long-term annual mean. This allows the seasonal cycle of the DHS tendency to be modeled. Everywhere latent heat flux residuals dominate sensible heat flux residuals, shortwave heat flux residuals dominate longwave heat flux residuals, and residual Ekman heat advection dominates residual geostrophic heat advection, with residual dissipation significant only in the Kuroshio-Oyashio current extension. The root-mean-square (RMS) of the differences between observed and model residual DHS tendencies (averaged over 10??latitude-by-20??longitude boxes) is <20 W m-2 in the interior ocean and <100 W m-2 in the Kuroshio-Oyashio current extension. This reveals that the residual DHS tendency is driven everywhere by some mix of residual latent heat flux, shortwave heat flux, and Ekman heat advection. Suppressing bias errors in residual air-sea turbulent heat fluxes and Ekman heat advection through minimization of the RMS differences reduces the latter to <10 W m-2 over the interior ocean and <25 W m -2 in the Kuroshio-Oyashio current extension. This reveals air-sea temperature and specific humidity differences from in situ surface marine weather observations to be a principal source of bias error, overestimated over most of ocean but underestimated near the Intertropical Convergence Zone. ?? 2005 Elsevier Ltd. All rights reserved.

Modeling the Frozen-In Anticyclone in the 2005 Arctic Summer Stratosphere

NASA Technical Reports Server (NTRS)

Allen, D. R.; Douglass, A. R.; Manney, G. L.; Strahan, S. E.; Krosschell, J. C.; Trueblood, J.

2010-01-01

Immediately following the breakup of the 2005 Arctic spring stratospheric vortex, a tropical air mass, characterized by low potential vorticity (PV) and high nitrous oxide (N2O), was advected poleward and became trapped in the easterly summer polar vortex. This feature, known as a "Frozen-In Anticyclone (FrIAC)", was observed in Earth Observing System (EOS) Aura Microwave Limb Sounder (MLS) data to span the potential temperature range from approximately 580 to 1100 K (approximately 25 to 40 km altitude) and to persist from late March to late August 2005. This study compares MLS N2O observations with simulations from the Global Modeling Initiative (GMI) chemistry and transport model, the GEOS-5/MERRA Replay model, and the VanLeer Icosahedral Triangular Advection isentropic transport model to elucidate the processes involved in the lifecycle of the FrIAC which is here divided into three distinct phases. During the "spin-up phase" (March to early April), strong poleward flow resulted in a tight isolated anticyclonic vortex at approximately 70-90 deg N, marked with elevated N2O. GMI, Replay, and VITA all reliably simulted the spin-up of the FrIAC, although the GMI and Replay peak N2O values were too low. The FrIAC became trapped in the developing summer easterly flow and circulated around the polar region during the "anticyclonic phase" (early April to the end of May). During this phase, the FrIAC crossed directly over the pole between the 7th and 14th of April. The VITA and Replay simulations transported the N2O anomaly intact during this crossing, in agreement with MLS, but unrealistic dispersion of the anomaly occurred in the GMI simulation due to excessive numerical mixing of the polar cap. The vortex associated with the FrIAC was apparently resistant to the weak vertical hear during the anticyclonic phase, and it thereby protected the embedded N20 anomaly from stretching. The vortex decayed in late May due to diabatic processes, leaving the N2O anomaly exposed to horizontal and vertical wind shears during the "shearing phase" (June to August). The observed lifetime of the FrIAC during this phase is consistent with time-scales calculated from the ambient horizontal and vertical wind shear. Replay maintained the horizontal structure of the N2O anomaly similar to NILS well into August. The VITA simulation also captured the horizontal structure of the FrIAC during this phase, but VITA eventually developed fine-scale N2O structure not observed in MLS data.

Towards a global model of spin-orbit coupling in the halocarbenes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nyambo, Silver; Karshenas, Cyrus; Reid, Scott A., E-mail: scott.reid@marquette.edu, E-mail: dawesr@mst.edu

We report a global analysis of spin-orbit coupling in the mono-halocarbenes, CH(D)X, where X = Cl, Br, and I. These are model systems for examining carbene singlet-triplet energy gaps and spin-orbit coupling. Over the past decade, rich data sets collected using single vibronic level emission spectroscopy and stimulated emission pumping spectroscopy have yielded much information on the ground vibrational level structure and clearly demonstrated the presence of perturbations involving the low-lying triplet state. To model these interactions globally, we compare two approaches. First, we employ a diabatic treatment of the spin-orbit coupling, where the coupling matrix elements are written inmore » terms of a purely electronic spin-orbit matrix element which is independent of nuclear coordinates, and an integral representing the overlap of the singlet and triplet vibrational wavefunctions. In this way, the structures, harmonic frequencies, and normal mode displacements from ab initio calculations were used to calculate the vibrational overlaps of the singlet and triplet state levels, including the full effects of Duschinsky mixing. These calculations have allowed many new assignments to be made, particularly for CHI, and provided spin-orbit coupling parameters and values for the singlet-triplet gaps. In a second approach, we have computed and fit full geometry dependent spin-orbit coupling surfaces and used them to compute matrix elements without the product form approximation. Those matrix elements were used in similar fits varying the anharmonic constants and singlet-triplet gap to reproduce the experimental levels. The derived spin-orbit parameters for carbenes CHX (X = Cl, Br, and I) show an excellent linear correlation with the atomic spin-orbit constant of the corresponding halogen, indicating that the spin-orbit coupling in the carbenes is consistently around 14% of the atomic value.« less

Photodissociation dynamics in the first absorption band of pyrrole. I. Molecular Hamiltonian and the Herzberg-Teller absorption spectrum for the A12(π σ* ) ←X˜ 1 A1(π π ) transition

NASA Astrophysics Data System (ADS)

Picconi, David; Grebenshchikov, Sergy Yu.

2018-03-01

This paper opens a series in which the photochemistry of the two lowest πσ* states of pyrrole and their interaction with each other and with the ground electronic state X ˜ are studied using ab initio quantum mechanics. New 24-dimensional potential energy surfaces for the photodissociation of the N-H bond and the formation of the pyrrolyl radical are calculated using the multiconfigurational perturbation theory (CASPT2) for the electronic states X ˜ (π π ) , 11A2(πσ*), and 11B1(πσ*) and locally diabatized. In this paper, the ab initio calculations are described and the photodissociation in the state 11A2(πσ*) is analyzed. The excitation 11 A2←X ˜ is mediated by the coordinate dependent transition dipole moment functions constructed using the Herzberg-Teller expansion. Nuclear dynamics, including 6, 11, and 15 active degrees of freedom, are studied using the multi-configurational time-dependent Hartree method. The focus is on the frequency resolved absorption spectrum as well as on the dissociation time scales and the resonance lifetimes. Calculations are compared with available experimental data. An approximate convolution method is developed and validated, with which absorption spectra can be calculated and assigned in terms of vibrational quantum numbers. The method represents the total absorption spectrum as a convolution of the diffuse spectrum of the detaching H-atom and the Franck-Condon spectrum of the heteroaromatic ring. Convolution calculation requires a minimal quantum chemical input and is a promising tool for studying the πσ* photodissociation in model biochromophores.

A diagnostic model to estimate winds and small-scale drag from Mars Observer PMIRR data

NASA Technical Reports Server (NTRS)

Barnes, J. R.

1993-01-01

Theoretical and modeling studies indicate that small-scale drag due to breaking gravity waves is likely to be of considerable importance for the circulation in the middle atmospheric region (approximately 40-100 km altitude) on Mars. Recent earth-based spectroscopic observations have provided evidence for the existence of circulation features, in particular, a warm winter polar region, associated with gravity wave drag. Since the Mars Observer PMIRR experiment will obtain temperature profiles extending from the surface up to about 80 km altitude, it will be extensively sampling middle atmospheric regions in which gravity wave drag may play a dominant role. Estimating the drag then becomes crucial to the estimation of the atmospheric winds from the PMIRR-observed temperatures. An interative diagnostic model based upon one previously developed and tested with earth satellite temperature data will be applied to the PMIRR measurements to produce estimates of the small-scale zonal drag and three-dimensional wind fields in the Mars middle atmosphere. This model is based on the primitive equations, and can allow for time dependence (the time tendencies used may be based upon those computed in a Fast Fourier Mapping procedure). The small-scale zonal drag is estimated as the residual in the zonal momentum equation; the horizontal winds having first been estimated from the meridional momentum equation and the continuity equation. The scheme estimates the vertical motions from the thermodynamic equation, and thus needs estimates of the diabatic heating based upon the observed temperatures. The latter will be generated using a radiative model. It is hoped that the diagnostic scheme will be able to produce good estimates of the zonal gravity wave drag in the Mars middle atmosphere, estimates that can then be used in other diagnostic or assimilation efforts, as well as more theoretical studies.

The East Atlantic - West Russia Teleconnection in the North Atlantic: Climate Impact and Relation to Rossby Wave Propagation

NASA Technical Reports Server (NTRS)

Lim, Young-Kwon

2014-01-01

Large-scale winter teleconnection of the East Atlantic - West Russia (EA-WR) over the Atlantic and surrounding regions is examined in order to quantify its impacts on temperature and precipitation and identify the physical mechanisms responsible for its existence. A rotated empirical orthogonal function (REOF) analysis of the upper-tropospheric monthly height field captures successfully the EA-WR pattern and its interannual variation, with the North Atlantic Oscillation as the first mode. EA-WRs climate impact extends from eastern North America to Eurasia. The positive (negative) EA-WR produces positive (negative) temperature anomalies over the eastern US, western Europe and Russia east of Caspian Sea, with negative (positive) anomalies over eastern Canada, eastern Europe including Ural Mountains and the Middle East. These anomalies are largely explained by lower-tropospheric temperature advections. Positive (negative) precipitation anomalies are found over the mid-latitude Atlantic and central Russia around 60E, where lower-level cyclonic (anticyclonic) circulation anomaly is dominant. The eastern Canada and the western Europe are characterized by negative (positive) precipitation anomalies.The EA-WR is found to be closely associated with Rossby wave propagation. Wave activity fluxes show that it is strongly tied to large-scale stationary waves. Furthermore, a stationary wave model (SWM) forced with vorticity transients in the mid-latitude Atlantic (approximately 40N) or diabatic heat source over the subtropical Atlantic near the Caribbean Sea produces well-organized EA-WR-like wave patterns, respectively. Sensitivity tests with the SWM indicate improvement in the simulation of the EA-WR when the mean state is modified to have a positive NAO component that enhances upper-level westerlies between 40-60N.

The impact of oceanic heat transport on the atmospheric circulation

NASA Astrophysics Data System (ADS)

Lucarini, Valerio; Lunkeit, Frank

2017-04-01

A general circulation model of intermediate complexity with an idealized Earth-like aquaplanet setup is used to study the impact of changes in the oceanic heat transport on the global atmospheric circulation. Focus is on the atmospheric mean meridional circulation and global thermodynamic properties. The atmosphere counterbalances to a large extent the imposed changes in the oceanic heat transport, but, nonetheless, significant modifications to the atmospheric general circulation are found. Increasing the strength of the oceanic heat transport up to 2.5 PW leads to an increase in the global mean near-surface temperature and to a decrease in its equator-to-pole gradient. For stronger transports, the gradient is reduced further, but the global mean remains approximately constant. This is linked to a cooling and a reversal of the temperature gradient in the tropics. Additionally, a stronger oceanic heat transport leads to a decline in the intensity and a poleward shift of the maxima of both the Hadley and Ferrel cells. Changes in zonal mean diabatic heating and friction impact the properties of the Hadley cell, while the behavior of the Ferrel cell is mostly controlled by friction. The efficiency of the climate machine, the intensity of the Lorenz energy cycle and the material entropy production of the system decline with increased oceanic heat transport. This suggests that the climate system becomes less efficient and turns into a state of reduced entropy production as the enhanced oceanic transport performs a stronger large-scale mixing between geophysical fluids with different temperatures, thus reducing the available energy in the climate system and bringing it closer to a state of thermal equilibrium.

Pairing-induced speedup of nuclear spontaneous fission

NASA Astrophysics Data System (ADS)

Sadhukhan, Jhilam; Dobaczewski, J.; Nazarewicz, W.; Sheikh, J. A.; Baran, A.

2014-12-01

Background: Collective inertia is strongly influenced at the level crossing at which the quantum system changes its microscopic configuration diabatically. Pairing correlations tend to make the large-amplitude nuclear collective motion more adiabatic by reducing the effect of these configuration changes. Competition between pairing and level crossing is thus expected to have a profound impact on spontaneous fission lifetimes. Purpose: To elucidate the role of nucleonic pairing on spontaneous fission, we study the dynamic fission trajectories of 264Fm and 240Pu using the state-of-the-art self-consistent framework. Methods: We employ the superfluid nuclear density functional theory with the Skyrme energy density functional SkM* and a density-dependent pairing interaction. Along with shape variables, proton and neutron pairing correlations are taken as collective coordinates. The collective inertia tensor is calculated within the nonperturbative cranking approximation. The fission paths are obtained by using the least action principle in a four-dimensional collective space of shape and pairing coordinates. Results: Pairing correlations are enhanced along the minimum-action fission path. For the symmetric fission of 264Fm, where the effect of triaxiality on the fission barrier is large, the geometry of the fission pathway in the space of the shape degrees of freedom is weakly impacted by pairing. This is not the case for 240Pu, where pairing fluctuations restore the axial symmetry of the dynamic fission trajectory. Conclusions: The minimum-action fission path is strongly impacted by nucleonic pairing. In some cases, the dynamical coupling between shape and pairing degrees of freedom can lead to a dramatic departure from the static picture. Consequently, in the dynamical description of nuclear fission, particle-particle correlations should be considered on the same footing as those associated with shape degrees of freedom.

a Diagnostic Study of Two Summer Depressions Over the Changjiang-Huaihe Valley

NASA Astrophysics Data System (ADS)

Dingchen, Hou

1987-09-01

Available from UMI in association with The British Library. Two summer depressions over the Changjiang-Huaihe Valley are investigated using data obtained from a synoptic observation network over East Asia and objectively analysed by applying a new scheme, which is mainly based on spline function interpolation. Detailed spatial structures and temporal evolution are documented in terms of pressure, temperature, moisture and wind fields. Vertical velocity fields are estimated using two independent methods, namely, the kinematic method and the quasi-geostrophic omega equation with consideration of stable and convective condensational heating. Quasi -Lagrangian budgets are computed for vorticity, kinetic energy, available potential energy, moisture and heat. The dynamic structures of the two depressions are analysed in terms of potential vorticity, moisture-related stabilities and geostrophic frontogenesis. Although their vertical structures and budget relations have some features typical of tropical disturbances, both depressions are closely related to a feeble Mei-yu front in the lower troposphere during their mature stage. Two different structures associated with the lower level frontal zone and a mid-upper layer warm belt are identified and related to the large scale circulation over East Asia. The adiabatic forcing under the quasi-geostrophic approximation is able to determine the general regions of ascent and descent associated with these depressions. On the other hand, the diabatic heating is the primary factor to account for the large magnitude of ascent, especially during the pre-storm and mature stages. Conditional symmetric instability and frontogenesis in the presence of small conditional symmetric stability are possible mechanisms in favour of the maintenance and development of the degressions. Based on these results, a conceptual model of the summer depressions over the Changjiang-Huaihe Valley is proposed.

The atmospheric heat engine response to climate change

NASA Astrophysics Data System (ADS)

Pauluis, O. M.

2014-12-01

Moist convection is characterized by complex interactions between dynamics and thermodynamics. As air parcels within the atmosphere, they experience multiple thermodynamic transformations, such as compression and expansion, diabatic heating and cooling, condensation and mixing. These transformations correspond to those of a heat engine that produces kinetic energy while transporting energy from a warm source to a colder sink. This atmospheric heat engine is however directly affected by moist processes. First, falling precipitation acts as a break on the circulation by dissipating a significant amount of kinetic energy. Second, evaporation of unsaturated water and diffusion of water vapor are irrevesible processes that also reduce the amount of work that can be produced. An important challenge is to quantify the impacts that these two effects have on the generation of kinetic energy. Here, I will introduce a new technique - the Mean Air Flow As Lagragian Dynamics Approximation (MAFALDA) - that can be used to systematically analyze the thermodynamic behavior of complex atmospheric flows. This approach relies on sorting the upward mass transport in terms of the equivalent potential temperature of the air parcels to obtain an isentropic streamfunction. This streamfunction is then used to determine the thermodynamic evolution of air parcels as they move through the atmosphere. This approach is applied to analyze how convective systems would behave in a warmer climate. It is shown that an increase in atmospheric temperature lead to a significant increase of the amount of kinetic energy that is produced per unit of mass of air transported. At the same time, the total generation of kinetic energy is only slightly affected. Taken together, these findings imply that, in a warming atmosphere, the number of intense convective events will be reduced, while their intensity should increase. I will also discuss the new possibility of systematically studying the thermodynamic transformation in atmospheric models.

Pairing-induced speedup of nuclear spontaneous fission

DOE PAGES

Sadhukhan, Jhilam; Dobaczewski, J.; Nazarewicz, W.; ...

2014-12-22

Collective inertia is strongly influenced at the level crossing at which the quantum system changes its microscopic configuration diabatically. Pairing correlations tend to make the large-amplitude nuclear collective motion more adiabatic by reducing the effect of these configuration changes. Competition between pairing and level crossing is thus expected to have a profound impact on spontaneous fission lifetimes. To elucidate the role of nucleonic pairing on spontaneous fission, we study the dynamic fission trajectories of 264Fm and 240Pu using the state-of-the-art self-consistent framework. We employ the superfluid nuclear density functional theory with the Skyrme energy density functional SkM* and a density-dependentmore » pairing interaction. Along with shape variables, proton and neutron pairing correlations are taken as collective coordinates. The collective inertia tensor is calculated within the nonperturbative cranking approximation. The fission paths are obtained by using the least action principle in a four-dimensional collective space of shape and pairing coordinates. Pairing correlations are enhanced along the minimum-action fission path. For the symmetric fission of 264Fm, where the effect of triaxiality on the fission barrier is large, the geometry of the fission pathway in the space of the shape degrees of freedom is weakly impacted by pairing. This is not the case for 240Pu, where pairing fluctuations restore the axial symmetry of the dynamic fission trajectory. The minimum-action fission path is strongly impacted by nucleonic pairing. In some cases, the dynamical coupling between shape and pairing degrees of freedom can lead to a dramatic departure from the static picture. As a result, in the dynamical description of nuclear fission, particle-particle correlations should be considered on the same footing as those associated with shape degrees of freedom.« less

Origin of low-frequency (intraseasonal) oscillations in the tropical atmosphere. II - Structure and propagation of mobile wave-CISK modes and their modification by lower boundary forcings

NASA Technical Reports Server (NTRS)

Sui, Chung-Hsiung; Lau, Ka-Ming

1989-01-01

An improved treatment of diabatic heating due to moist convection is introduced into the dynamical model of Lau and Peng (1987) to study the origin of intraseasonal oscillations in the tropics. It is found that the periods of slow-moving wave-CISK disturbances in the tropical troposphere with fixed sea surface temperature vary from 20 to 50 days. The results suggest that heating in the lower troposphere may be important in slowing down the wave-CISK modes. Also, it is shown that the intraseasonal oscillation can propagate around the globe even when the associated deep convection is only confined over warm sea surface temperatures.

Modelling charge transfer reactions with the frozen density embedding formalism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pavanello, Michele; Neugebauer, Johannes

2011-12-21

The frozen density embedding (FDE) subsystem formulation of density-functional theory is a useful tool for studying charge transfer reactions. In this work charge-localized, diabatic states are generated directly with FDE and used to calculate electronic couplings of hole transfer reactions in two {pi}-stacked nucleobase dimers of B-DNA: 5{sup '}-GG-3{sup '} and 5{sup '}-GT-3{sup '}. The calculations rely on two assumptions: the two-state model, and a small differential overlap between donor and acceptor subsystem densities. The resulting electronic couplings agree well with benchmark values for those exchange-correlation functionals that contain a high percentage of exact exchange. Instead, when semilocal GGA functionalsmore » are used the electronic couplings are grossly overestimated.« less

Thermodynamic constraint on the depth of the global tropospheric circulation.

PubMed

Thompson, David W J; Bony, Sandrine; Li, Ying

2017-08-01

The troposphere is the region of the atmosphere characterized by low static stability, vigorous diabatic mixing, and widespread condensational heating in clouds. Previous research has argued that in the tropics, the upper bound on tropospheric mixing and clouds is constrained by the rapid decrease with height of the saturation water vapor pressure and hence radiative cooling by water vapor in clear-sky regions. Here the authors contend that the same basic physics play a key role in constraining the vertical structure of tropospheric mixing, tropopause temperature, and cloud-top temperature throughout the globe. It is argued that radiative cooling by water vapor plays an important role in governing the depth and amplitude of large-scale dynamics at extratropical latitudes.

Modeling donor/acceptor interactions: Combined roles of theory and computation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Newton, M.D.

2000-03-05

An extended superexchange model for electron transfer (ET) matrix elements (H{sub DA}) has been formulated as a superposition of McConnell-type pathways and implemented by combined use of configuration interaction wave functions (obtained using the INDO/s model of Zerner and co-workers) and the generalized Muliken-Hush formulation of charge-localized diabatic states. Applications are made for et (and hold transfer) in several donor/bridge/acceptor radical anion (and cation) systems, (DBA){sup {+-}}, allowing detailed comparison with experimental H{sub DA} estimates. For the case of oligo phenylene ethynylene (OPE) bridges, the role of {pi} and {sigma} electronic manifolds for different distributions of phenylene torsion angles ismore » analyzed in detail.« less

Understanding dynamics of Martian winter polar vortex with “improved” moist-convective shallow water model

NASA Astrophysics Data System (ADS)

Rostami, M.; Zeitlin, V.

2017-12-01

We show how the properties of the Mars polar vortex can be understood in the framework of a simple shallow-water type model obtained by vertical averaging of the adiabatic “primitive” equations, and “improved” by inclusion of thermal relaxation and convective fluxes due to the phase transitions of CO 2, the major constituent of the Martian atmosphere. We perform stability analysis of the vortex, show that corresponding mean zonal flow is unstable, and simulate numerically non-linear saturation of the instability. We show in this way that, while non-linear adiabatic saturation of the instability tends to reorganize the vortex, the diabatic effects prevent this, and thus provide an explanation of the vortex form and longevity.

Compact beam splitters in coupled waveguides using shortcuts to adiabaticity

NASA Astrophysics Data System (ADS)

Chen, Xi; Wen, Rui-Dan; Shi, Jie-Long; Tseng, Shuo-Yen

2018-04-01

There are various works on adiabatic (three) waveguide coupler devices but most are focused on the quantum optical analogies and the physics itself. We successfully apply shortcuts to adiabaticity techniques to the coupled waveguide system with a suitable length for integrated optics devices. Especially, the counter-diabatic driving protocol followed by unitary transformation overcomes the previously unrealistic implemention, and is used to design feasible and robust 1 × 2 and 1 × 3 beam splitters for symmetric and asymmetric three waveguide couplers. Numerical simulations with the beam propagation method demonstrate that these shortcut designs for beam splitters are shorter than the adiabatic ones, and also have a better tolerance than parallel waveguides resonant beam splitters with respect to spacing errors and wavelength variation.

Ultrafast control of strong light-matter coupling

NASA Astrophysics Data System (ADS)

Lange, Christoph; Cancellieri, Emiliano; Panna, Dmitry; Whittaker, David M.; Steger, Mark; Snoke, David W.; Pfeiffer, Loren N.; West, Kenneth W.; Hayat, Alex

2018-01-01

We dynamically modulate strong light-matter coupling in a GaAs/AlGaAs microcavity using intense ultrashort laser pulses tuned below the interband exciton energy, which induce a transient Stark shift of the cavity polaritons. For 225-fs pulses, shorter than the cavity Rabi cycle period of 1000 fs, this shift decouples excitons and cavity photons for the duration of the pulse, interrupting the periodic energy exchange between photonic and electronic states. For 1500-fs pulses, longer than the Rabi cycle period, however, the Stark shift does not affect the strong coupling. The two regimes are marked by distinctly different line shapes in ultrafast reflectivity measurements—regardless of the Stark field intensity. The crossover marks the transition from adiabatic to diabatic switching of strong light-matter coupling.

The response of stationary planetary waves to tropospheric forcing

NASA Technical Reports Server (NTRS)

Alpert, J. C.; Geller, M. A.; Avery, S. K.

1983-01-01

The lower boundary forcing of airflow over topography, and the internal forcing that results from the geographical distribution of diabatic heating, are studied in light of a steady state, linear, quasi-geostrophic model of stationary waves on a sphere. The lower boundary vertical motions forced by airflow over topography depend on whether the horizontal deflection of airflow around topographic features is taken into account, the level of the wind profile at which flow over topography is assumed to take place, and the topographic data set that was used in the forcing formulation. The lower boundary forcing is taken to be given by the observed stationary planetary wave in lower boundary geopotential height, and the internal forcing is computed using the planetary wave propagation equation on the observed wave structure.

EOS Microwave Limb Sounder Observations of the Antarctic Polar Vortex Breakup in 2004

NASA Technical Reports Server (NTRS)

Manney, G. L.; Santee, M. L.; Livesey, N. J.; Froidevaux, L.; Read, W. G.; Pumphrey, H. C.; Waters, J. W.; Pawson, S.

2005-01-01

Observations from the Microwave Limb Sounder (MLS) on NASA's new Aura satellite give an unprecedentedly detailed picture of the spring Antarctic polar vortex breakup throughout the stratosphere. HCl is a particularly valuable tracer in the lower stratosphere after chlorine deactivation. MLS HCl, N2O, H2O broke up in the upper stratosphere by early October, in the midstratosphere by early November, and in the lower stratosphere by late December. The subvortex broke up just a few days later than the lower stratospheric vortex. Vortex remnants persisted in the midstratosphere through December, but only through early January 2005 in the lower stratosphere. MLS N2O observations show diabatic descent continuing throughout November, with evidence of weak ascent after late October in the lower stratospheric vortex core.

Simulations of surface winds at the Viking Lander sites using a one-level model

NASA Technical Reports Server (NTRS)

Bridger, Alison F. C.; Haberle, Robert M.

1992-01-01

The one-level model developed by Mass and Dempsey for use in predicting surface flows in regions of complex terrain was adapted to simulate surface flows at the Viking lander sites on Mars. In the one-level model, prediction equations for surface winds and temperatures are formulated and solved. Surface temperatures change with time in response to diabatic heating, horizontal advection, adiabatic heating and cooling effects, and horizontal diffusion. Surface winds can change in response to horizontal advection, pressure gradient forces, Coriolis forces, surface drag, and horizontal diffusion. Surface pressures are determined by integration of the hydrostatic equation from the surface to some reference level. The model has successfully simulated surface flows under a variety of conditions in complex-terrain regions on Earth.

Mesoscale Dynamical Regimes in the Midlatitudes

NASA Astrophysics Data System (ADS)

Craig, G. C.; Selz, T.

2018-01-01

The atmospheric mesoscales are characterized by a complex variety of meteorological phenomena that defy simple classification. Here a full space-time spectral analysis is carried out, based on a 7 day convection-permitting simulation of springtime midlatitude weather on a large domain. The kinetic energy is largest at synoptic scales, and on the mesoscale it is largely confined to an "advective band" where space and time scales are related by a constant of proportionality which corresponds to a velocity scale of about 10 m s-1. Computing the relative magnitude of different terms in the governing equations allows the identification of five dynamical regimes. These are tentatively identified as quasi-geostrophic flow, propagating gravity waves, stationary gravity waves related to orography, acoustic modes, and a weak temperature gradient regime, where vertical motions are forced by diabatic heating.

Estimates of the seasonal mean vertical velocity fields of the extratropical Northern Hemisphere

NASA Technical Reports Server (NTRS)

White, G. H.

1983-01-01

Indirect methods are employed to estimate the wintertime and summertime mean vertical velocity fields of the extratropical Northern Hemisphere and intercomparisons are made, together with comparisons with mean seasonal patterns of cloudiness and precipitation. Twice-daily NMC operational analyses produced general circulation statistics for 11 winters and 12 summers, permitting calculation of the seasonal NMC averages for 6 hr forecasts, solution of the omega equation, integration of continuity equation downward from 100 mb, and solution of the thermodynamic energy equation in the absence of diabatic heating. The methods all yielded similar vertical velocity patterns; however, the magnitude of the vertical velocities could not be calculated with great accuracy. Orography was concluded to have less of an effect in summer than in winter, when winds are stronger.

Ultrafast photodissociation dynamics of 1,4-diiodobenzene

NASA Astrophysics Data System (ADS)

Stankus, Brian; Zotev, Nikola; Rogers, David M.; Gao, Yan; Odate, Asami; Kirrander, Adam; Weber, Peter M.

2018-05-01

The photodissociation dynamics of 1,4-diiodobenzene is investigated using ultrafast time-resolved photoelectron spectroscopy. Following excitation by laser pulses at 271 nm, the excited-state dynamics is probed by resonance-enhanced multiphoton ionization with 405 nm probe pulses. A progression of Rydberg states, which come into resonance sequentially, provide a fingerprint of the dissociation dynamics of the molecule. The initial excitation decays with a lifetime of 33 ± 4 fs, in good agreement with a previous study. The spectrum is interpreted by reference to ab initio calculations at the CASPT2(18,14) level, including spin-orbit coupling. We propose that both the 5B1 and 6B1 states are excited initially, and based on the calculations, we identify diabatic spin-orbit coupled states corresponding to the main dissociation pathways.

CLIVAR Asian-Australian Monsoon Panel Report to Scientific Steering Group-18

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sperber, Ken R.; Hendon, Harry H.

2011-05-04

These are a set of slides on CLIVAR Asian-Australian Monsoon Panel Report to Scientific Steering Group-18. These are the major topics covered within: major activities over the past year, AAMP Monsoon Diagnostics/Metrics Task Team, Boreal Summer Asian Monsoon, Workshop on Modelling Monsoon Intraseasonal Variability, Workshop on Interdecadal Variability and Predictability of the Asian-Australian Monsoon, Evidence of Interdecadal Variability of the Asian-Australian Monsoon, Development of MJO metrics/process-oriented diagnostics/model evaluation/prediction with MJOTF and GCSS, YOTC MJOTF, GEWEX GCSS, AAMP MJO Diabatic Heating Experiment, Hindcast Experiment for Intraseasonal Prediction, Support and Coordination for CINDY2011/DYNAMO, Outreach to CORDEX, Interaction with FOCRAII, WWRP/WCRP Multi-Week Predictionmore » Project, Major Future Plans/Activities, Revised AAMP Terms of Reference, Issues and Challenges.« less

Dynamics of a Landau-Zener non-dissipative system with fluctuating energy levels

NASA Astrophysics Data System (ADS)

Fai, L. C.; Diffo, J. T.; Ateuafack, M. E.; Tchoffo, M.; Fouokeng, G. C.

2014-12-01

This paper considers a Landau-Zener (two-level) system influenced by a three-dimensional Gaussian and non-Gaussian coloured noise and finds a general form of the time dependent diabatic quantum bit (qubit) flip transition probabilities in the fast, intermediate and slow noise limits. The qubit flip probability is observed to mimic (for low-frequencies noise) that of the standard LZ problem. The qubit flip probability is also observed to be the measure of quantum coherence of states. The transition probability is observed to be tailored by non-Gaussian low-frequency noise and otherwise by Gaussian low-frequency coloured noise. Intermediate and fast noise limits are observed to alter the memory of the system in time and found to improve and control quantum information processing.

Presence and absence of electronic mixing in shorter-chain and longer-chain carotenoids: Assignment of the symmetries of 1Bu- and 3Ag- states located just below the 1Bu+ state

NASA Astrophysics Data System (ADS)

Sutresno, Adita; Kakitani, Yoshinori; Zuo, Ping; Li, Chunyong; Koyama, Yasushi; Nagae, Hiroyoshi

2007-10-01

In spheroidene (having the number of conjugated double bonds n = 10), stimulated emission was observed from the mixed vibronic levels of 1Bu+(0)+1Bu-(2) and 1Bu+(1)+1Bu-(3), whereas in lycopene, anhydrorhodovibrin and spirilloxanthin ( n = 11-13), stimulated emission, from the pure vibronic levels of 1Bu+(0) and 1Bu+(1). Thus, the 1Bu+ state can mix with the 1Bu- state but not with the 3Ag- state, both being located just below the 1Bu+ state. The presence and absence of the mixing of the neighboring diabatic states support the symmetries of the next low-lying 1Bu- and 3Ag- states.

The Role of the Stratosphere in Explosive Deepening of Extratropical Cyclones

NASA Astrophysics Data System (ADS)

Knippertz, Peter; Wilbraham, Robert; Trzeciak, Tomek; Owen, Jenny; Odell, Luke; Fink, Andreas H.; Pinto, Joaquim G.

2014-05-01

Using a combination of an automatic cyclone tracking method and a special version of the classical pressure tendency equation (PTE), changes in surface core pressure of extra-tropical cyclones can be related to contributions from horizontal temperature advection, vertical motion and diabatic processes, i.e. mainly latent heat release in clouds. Here, the PTE is evaluated in 3°x3° boxes located over the cyclone positions at 6-hourly basis, thus following the movement of a given storm at each time step. PTE calculations are performed from the surface to 100 hPa. Previous work has shown that this approach can be used to quantify the contribution of diabatic processes to cyclone deepening in an automated way, and can easily be applied to large gridded datasets, in this case ERA-Interim reanalyses. In order to close the mass budget in the PTE, geopotential height tendencies at the upper integration boundary (usually 100 hPa) need to be taken into account. Older studies have assumed this term to be negligible, and this has been confirmed with modern re-analysis data for many explosively deepening storms. However, some historical storms show a remarkable contribution from this term, indicating a substantial warming of the levels above 100hPa. An outstanding example is the Braer Storm of January 1993, which reached a record minimum core pressure of 914 hPa near Iceland. A stepwise increase of the upper integration boundary reveals that substantial geopotential height tendencies reach above 1 hPa. This unusual behaviour appears to be related to the propagation of a deep planetary wave trough from North America towards the North Atlantic basin. A similar but somewhat less dramatic behaviour was found for cyclone Wiebke. Another interesting example is storm Emma, which managed to sustain substantial deepening rates despite adverse positive geopotential height tendencies at 100 hPa. Future work will include a more robust statistical analysis of this problem and a better understanding of the nature and physical mechanism of the stratospheric influence on explosive cyclogenesis.

Nonadiabatic effects on the charge transfer rate constant: A numerical study of a simple model system

NASA Astrophysics Data System (ADS)

Shin, Seokmin; Metiu, Horia

1995-06-01

We use a minimal model to study the effects of the upper electronic states on the rate of a charge transfer reaction. The model consists of three ions and an electron, all strung on a line. The two ions at the ends of the structure are held fixed, but the middle ion and the electron are allowed to move in one dimension, along the line joining them. The system has two bound states, one in which the electron ties the movable ion to the fixed ion at the left, and the other in which the binding takes place to the fixed ion at the right. The transition between these bound states is a charge transfer reaction. We use the flux-flux correlation function theory to perform two calculations of the rate constant for this reaction. In one we obtain numerically the exact rate constant. In the other we calculate the exact rate constant for the case when the reaction proceeds exclusively on the ground adiabatic state. The difference between these calculations gives the magnitude of the nonadiabatic effects. We find that the nonadiabatic effects are fairly large even when the gap between the ground and the excited adiabatic state substantially exceeds the thermal energy. The rate in the nonadiabatic theory is always smaller than that of the adiabatic one. Both rate constants satisfy the Arrhenius formula. Their activation energies are very close but the nonadiabatic one is always higher. The nonadiabatic preexponential is smaller, due to the fact that the upper electronic state causes an early recrossing of the reactive flux. The description of this reaction in terms of two diabatic states, one for reactants and one for products, is not always adequate. In the limit when nonadiabaticity is small, we need to use a third diabatic state, in which the electron binds to the moving ion as the latter passes through the transition state; this is an atom transfer process. The reaction changes from an atom transfer to an electron transfer, as nonadiabaticity is increased.

Dynamics of Atmospheric Boundary Layers: Large-Eddy Simulations and Reduced Analytical Models

NASA Astrophysics Data System (ADS)

Momen, Mostafa

Real-world atmospheric and oceanic boundary layers (ABL) involve many inherent complexities, the understanding and modeling of which manifestly exceeds our current capabilities. Previous studies largely focused on the "textbook ABL", which is (quasi) steady and barotropic. However, it is evident that the "real-world ABL", even over flat terrain, rarely meets such simplifying assumptions. The present thesis aims to illustrate and model four complicating features of ABLs that have been overlooked thus far despite their ubiquity: 1) unsteady pressure gradients in neutral ABLs (Chapters 2 and 3), 2) interacting effects of unsteady pressure gradients and static stability in diabatic ABLs (Chapter 4), 3) time-variable buoyancy fluxes (Chapter 5) , and 4) impacts of baroclinicity in neutral and diabatic ABLs (Chapter 6). State-of-the-art large-eddy simulations will be used as a tool to explain the underlying physics and to validate analytical models we develop for these features. Chapter 2 focuses on the turbulence equilibrium: when the forcing time scale is comparable to the turbulence time scale, the turbulence is shown to be out of equilibrium, and the velocity profiles depart from the log-law; However, for longer, and surprisingly for shorter forcing times, quasi-equilibrium is maintained. In Chapter 3, a reduced analytical model, based on the Navier-Stokes equations, will be introduced and shown to be analogous to a damped oscillator where inertial, Coriolis, and friction forces mirror the mass, spring, and damper, respectively. When a steady buoyancy (stable or unstable) is superposed on the unsteady pressure gradient, the same model structure can be maintained, but the damping term, corresponding to friction forces and vertical coupling, needs to account for stability. However, for the reverse case with variable buoyancy flux and stability, the model needs to be extended to allow time-variable damper coefficient. These extensions of the analytical model are presented respectively in Chapters 4 and 5. Chapter 6 investigates the interacting effects of baroclinicity (direction and strength) and stability on ABLs. Cold advection and positive shear increased the friction velocity, the low-level jet elevation and strength while warm advection and negative shear acted opposite. Finally, Chapter 7 provides a synthesis and a future outlook.

GMS-based"Future Time" Rainfall Data Assimilation for Mesoscale Weather Prediction over Korean Peninsula and Future Prospects with GPM Satellite Measurements

NASA Technical Reports Server (NTRS)

Smith, Eric A.; Ou, Mi-Lim

2004-01-01

This study examines the use of satellite-derived nowcasted (short-term forecasted) rainfall over 3-hour time periods to gain an equivalent time increment in initializing a nonhydrostatic mesoscale model used for predicting convective rainfall events over the Korean peninsula. Infrared (IR) window measurements from the Japanese Geostationary Meteorological Satellite (GMS) are used to specify latent heating for a spinup period of the model - but in future time -- thus initializing in advance of actual time in the framework of a prediction scenario. The main scientific objective of the study is to investigate the strengths and weaknesses of this approach insofar as data assimilation, in which the nowcasted assimilation data are derived independently of the prognostic model itself. Although there have been various recent improvements in formulating the dynamics, thermodynamics, and microphysics of mesoscale models, as well as computer advances which allow the use of high resolution cloud-resolving grids and explicit latent heating over regional domains, spinup remains at the forefront of unresolved mesoscale modeling problems. In general, non-realistic spinup limits the skill in predicting the spatial-temporal distribution of convection and precipitation, primarily in the early hours of a. forecast, stemming from standard prognostic variables not representing the initial diabatic heating field produced by the ambient convection and cloud fields. The long-term goal of this research is to improve short-range (12-hour) quantitative precipitation forecasting (QPF) over the Korean peninsula through the use of innovative data assimilation methods based on geosynchronous satellite measurements. As a step in ths direction, a non-standard data assimilation experiment in conjunction with GMS-retrieved nowcasted rainfall information introduced to the mesoscale model is conducted. The 3-hourly precipitation forecast information is assimilated through nudging the associated diabatic heating during the early stages of a forecast period. This procedure is expected to enhance details in the moisture field during model integration, and thus improve spinup performance, assuming the errors in the future time latent heating data ate less than intrinsic model background errors.

The North Pacific as a Regulator of Summertime Climate Over North America and the Asian Monsoon

NASA Technical Reports Server (NTRS)

Lau, William K. M.; Wang, H.

2004-01-01

The interannual variability of summertime rainfall over the U.S. may be linked to climate anomalies over Pacific and East Asia through teleconnection patterns that may be components of recurring global climate modes in boreal summer (Lau and Weng 2002). In this study, maintenance of the boreal summer teleconnection patterns is investigated. The particular focus is on the potential effects of North Pacific air-sea interaction on climate anomalies over the U.S. Observational data, reanalysis and outputs of a series of NASA NSIPP AGCM and AGCM coupled to NASA GSFC MLO model experiments are used. Statistical analysis of observations and NSIPP AMIP type simulations indicates that, the interannual variability of observed warm season precipitation over the U.S. is related to SST variation in both tropical and North Pacific, whereas the NSIPP AMIP simulated summertime US. precipitation variation mainly reflects impact of ENS0 in tropical Pacific. This implies the potential importance of air-sea interaction in North Pacific in contributing to the interannual variability of observed summer climate over the U.S. The anomalous atmospheric circulation associated with the dominant summertime teleconnection modes in both observations and NSIPP AMIP simulations are further diagnosed, using stationary wave modeling approach. In observations, for the two dominant modes, both anomalous diabatic heating and anomalous transients significantly contribute to the anomalous circulation. The distributions of the anomalous diabatic heating and transient forcing are quadrature configured over North Pacific and North America, so that both forcings act constructively to maintain the teleconnection patterns. The contrast between observations and NSIPP AMIP simulations from stationary wave modeling diagnosis confirms the previous conclusion based on statistical analysis. To better appreciate the role of extra-tropical air-sea interaction in maintaining the summertime teleconnection pattern, various dynamical and physical fields and their inter- linkage in the series of NSIPP AGCM and AGCM coupled to MLO model experiments are examined in-depth. Based on comparison between different model experiments, we will discuss the physical and dynamical mechanisms through which the air-sea interaction in extratropics, and transient mean flow interactions over the North Pacific, affects interannual variation of U.S. climate during boreal summer.

Scale Interactions in the Tropics from a Simple Multi-Cloud Model

NASA Astrophysics Data System (ADS)

Niu, X.; Biello, J. A.

2017-12-01

Our lack of a complete understanding of the interaction between the moisture convection and equatorial waves remains an impediment in the numerical simulation of large-scale organization, such as the Madden-Julian Oscillation (MJO). The aim of this project is to understand interactions across spatial scales in the tropics from a simplified framework for scale interactions while a using a simplified framework to describe the basic features of moist convection. Using multiple asymptotic scales, Biello and Majda[1] derived a multi-scale model of moist tropical dynamics (IMMD[1]), which separates three regimes: the planetary scale climatology, the synoptic scale waves, and the planetary scale anomalies regime. The scales and strength of the observed MJO would categorize it in the regime of planetary scale anomalies - which themselves are forced from non-linear upscale fluxes from the synoptic scales waves. In order to close this model and determine whether it provides a self-consistent theory of the MJO. A model for diabatic heating due to moist convection must be implemented along with the IMMD. The multi-cloud parameterization is a model proposed by Khouider and Majda[2] to describe the three basic cloud types (congestus, deep and stratiform) that are most responsible for tropical diabatic heating. We implement a simplified version of the multi-cloud model that is based on results derived from large eddy simulations of convection [3]. We present this simplified multi-cloud model and show results of numerical experiments beginning with a variety of convective forcing states. Preliminary results on upscale fluxes, from synoptic scales to planetary scale anomalies, will be presented. [1] Biello J A, Majda A J. Intraseasonal multi-scale moist dynamics of the tropical atmosphere[J]. Communications in Mathematical Sciences, 2010, 8(2): 519-540. [2] Khouider B, Majda A J. A simple multicloud parameterization for convectively coupled tropical waves. Part I: Linear analysis[J]. Journal of the atmospheric sciences, 2006, 63(4): 1308-1323. [3] Dorrestijn J, Crommelin D T, Biello J A, et al. A data-driven multi-cloud model for stochastic parametrization of deep convection[J]. Philosophical Transactions of the Royal Society of London A: Mathematical, Physical and Engineering Sciences, 2013, 371(1991): 20120374.

Estimation of Mesoscale Atmospheric Latent Heating Profiles from TRMM Rain Statistics Utilizing a Simple One-Dimensional Model

NASA Technical Reports Server (NTRS)

Iacovazzi, Robert A., Jr.; Prabhakara, C.

2002-01-01

In this study, a model is developed to estimate mesoscale-resolution atmospheric latent heating (ALH) profiles. It utilizes rain statistics deduced from Tropical Rainfall Measuring Mission (TRMM) data, and cloud vertical velocity profiles and regional surface thermodynamic climatologies derived from other available data sources. From several rain events observed over tropical ocean and land, ALH profiles retrieved by this model in convective rain regions reveal strong warming throughout most of the troposphere, while in stratiform rain regions they usually show slight cooling below the freezing level and significant warming above. The mesoscale-average, or total, ALH profiles reveal a dominant stratiform character, because stratiform rain areas are usually much larger than convective rain areas. Sensitivity tests of the model show that total ALH at a given tropospheric level varies by less than +/- 10 % when convective and stratiform rain rates and mesoscale fractional rain areas are perturbed individually by +/- 15 %. This is also found when the non-uniform convective vertical velocity profiles are replaced by one that is uniform. Larger variability of the total ALH profiles arises when climatological ocean- and land-surface temperatures (water vapor mixing ratios) are independently perturbed by +/- 1.0 K (+/- 5%) and +/- 5.0 K (+/- 15%), respectively. At a given tropospheric level, such perturbations can cause a +/- 25% variation of total ALH over ocean, and a factor-of-two sensitivity over land. This sensitivity is reduced substantially if perturbations of surface thermodynamic variables do not change surface relative humidity, or are not extended throughout the entire model evaporation layer. The ALH profiles retrieved in this study agree qualitatively with tropical total diabatic heating profiles deduced in earlier studies. Also, from January and July 1999 ALH-profile climatologies generated separately with TRMM Microwave Imager and Precipitation Radar rain statistics, it is shown that ALH profiles can be retrieved utilizing diverse satellite-derived rain products that offer convective and stratiform discrimination. Therefore, the ALH retrieval model developed in this study can be used to make regional estimates of total diabatic heating profiles in the future Global Precipitation Measurement mission, and to assimilate these profiles into numerical weather forecast and climate models.

Estimation of Mesoscale Atmospheric Latent Heating Profiles from TRMM Rain Statistics Utilizing a Simple One-Dimensional Model

NASA Technical Reports Server (NTRS)

Iacovazzi, Robert A., Jr.; Prabhakara, C.; Lau, William K. M. (Technical Monitor)

2001-01-01

In this study, a model is developed to estimate mesoscale-resolution atmospheric latent heating (ALH) profiles. It utilizes rain statistics deduced from Tropical Rainfall Measuring Mission (TRMM) data, and cloud vertical velocity profiles and regional surface thermodynamic climatologies derived from other available data sources. From several rain events observed over tropical ocean and land, ALH profiles retrieved by this model in convective rain regions reveal strong warming throughout most of the troposphere, while in stratiform rain regions they usually show slight cooling below the freezing level and significant warming above. The mesoscale-average, or total, ALH profiles reveal a dominant stratiform character, because stratiform rain areas are usually much larger than convective rain areas. Sensitivity tests of the model show that total ALH at a given tropospheric level varies by less than +/- 10 % when convective and stratiform rain rates and mesoscale fractional rain areas are perturbed individually by 1 15 %. This is also found when the non-uniform convective vertical velocity profiles are replaced by one that is uniform. Larger variability of the total ALH profiles arises when climatological ocean- and land-surface temperatures (water vapor mixing ratios) are independently perturbed by +/- 1.0 K (+/- 5 %) and +/- 5.0 K (+/- 15 %), respectively. At a given tropospheric level, such perturbations can cause a +/- 25 % variation of total ALH over ocean, and a factor-of-two sensitivity over land. This sensitivity is reduced substantially if perturbations of surface thermodynamic variables do not change surface relative humidity, or are not extended throughout the entire model evaporation layer. The ALH profiles retrieved in this study agree qualitatively with tropical total diabatic heating profiles deduced in earlier studies. Also, from January and July 1999 ALH-profile climatologies generated separately with TRMM Microwave Imager and Precipitation Radar rain statistics, it is shown that ALH profiles can be retrieved utilizing diverse satellite-derived rain products that offer convective and stratiform discrimination. Therefore, the ALH retrieval model developed in this study can be used to make regional estimates of total diabatic heating profiles in the future Global Precipitation Measurement mission, and to assimilate these profiles into numerical weather forecast and climate models.

Superadiabatic Controlled Evolutions and Universal Quantum Computation.

PubMed

Santos, Alan C; Sarandy, Marcelo S

2015-10-29

Adiabatic state engineering is a powerful technique in quantum information and quantum control. However, its performance is limited by the adiabatic theorem of quantum mechanics. In this scenario, shortcuts to adiabaticity, such as provided by the superadiabatic theory, constitute a valuable tool to speed up the adiabatic quantum behavior. Here, we propose a superadiabatic route to implement universal quantum computation. Our method is based on the realization of piecewise controlled superadiabatic evolutions. Remarkably, they can be obtained by simple time-independent counter-diabatic Hamiltonians. In particular, we discuss the implementation of fast rotation gates and arbitrary n-qubit controlled gates, which can be used to design different sets of universal quantum gates. Concerning the energy cost of the superadiabatic implementation, we show that it is dictated by the quantum speed limit, providing an upper bound for the corresponding adiabatic counterparts.

Superadiabatic Controlled Evolutions and Universal Quantum Computation

PubMed Central

Santos, Alan C.; Sarandy, Marcelo S.

2015-01-01

Adiabatic state engineering is a powerful technique in quantum information and quantum control. However, its performance is limited by the adiabatic theorem of quantum mechanics. In this scenario, shortcuts to adiabaticity, such as provided by the superadiabatic theory, constitute a valuable tool to speed up the adiabatic quantum behavior. Here, we propose a superadiabatic route to implement universal quantum computation. Our method is based on the realization of piecewise controlled superadiabatic evolutions. Remarkably, they can be obtained by simple time-independent counter-diabatic Hamiltonians. In particular, we discuss the implementation of fast rotation gates and arbitrary n-qubit controlled gates, which can be used to design different sets of universal quantum gates. Concerning the energy cost of the superadiabatic implementation, we show that it is dictated by the quantum speed limit, providing an upper bound for the corresponding adiabatic counterparts. PMID:26511064

Interstate vibronic coupling constants between electronic excited states for complex molecules

NASA Astrophysics Data System (ADS)

Fumanal, Maria; Plasser, Felix; Mai, Sebastian; Daniel, Chantal; Gindensperger, Etienne

2018-03-01

In the construction of diabatic vibronic Hamiltonians for quantum dynamics in the excited-state manifold of molecules, the coupling constants are often extracted solely from information on the excited-state energies. Here, a new protocol is applied to get access to the interstate vibronic coupling constants at the time-dependent density functional theory level through the overlap integrals between excited-state adiabatic auxiliary wavefunctions. We discuss the advantages of such method and its potential for future applications to address complex systems, in particular, those where multiple electronic states are energetically closely lying and interact. We apply the protocol to the study of prototype rhenium carbonyl complexes [Re(CO)3(N,N)(L)]n+ for which non-adiabatic quantum dynamics within the linear vibronic coupling model and including spin-orbit coupling have been reported recently.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Chongqi; Harbich, Wolfgang; Sementa, Luca

Ligand-protected Au clusters are non-bleaching fluorescence markers in bio- and medical applications. We show that their fluorescence is an intrinsic property of the Au cluster itself. We find a very intense and sharp fluorescence peak located at λ =739.2 nm (1.68 eV) for Au20 clusters in a Ne matrix held at 6 K. The fluorescence reflects the HOMO-LUMO diabatic bandgap of the cluster. The cluster shows a very rich absorption fine structure reminiscent of well defined molecule-like quantum levels. These levels are resolved since Au20 has only one stable isomer (tetrahedral), therefore our sample is mono-disperse in cluster size andmore » conformation. Density-functional theory (DFT) and time-dependent DFT calculations clarify the nature of optical absorptionand predict both main absorption peaks and intrinsic fluorescence in good agreement with experiment.« less

Ab initio quantum chemical calculation of electron transfer matrix elements for large molecules

NASA Astrophysics Data System (ADS)

Zhang, Linda Yu; Friesner, Richard A.; Murphy, Robert B.

1997-07-01

Using a diabatic state formalism and pseudospectral numerical methods, we have developed an efficient ab initio quantum chemical approach to the calculation of electron transfer matrix elements for large molecules. The theory is developed at the Hartree-Fock level and validated by comparison with results in the literature for small systems. As an example of the power of the method, we calculate the electronic coupling between two bacteriochlorophyll molecules in various intermolecular geometries. Only a single self-consistent field (SCF) calculation on each of the monomers is needed to generate coupling matrix elements for all of the molecular pairs. The largest calculations performed, utilizing 1778 basis functions, required ˜14 h on an IBM 390 workstation. This is considerably less cpu time than would be necessitated with a supermolecule adiabatic state calculation and a conventional electronic structure code.

Global transport calculations with an equivalent barotropic system

NASA Technical Reports Server (NTRS)

Salby, Murry L.; O'Sullivan, Donal; Garcia, Rolando R.; Tribbia, Joseph

1990-01-01

Transport properties of the two-dimensional equations governing equivalent barotropic motion are investigated on the sphere. This system has ingredients such as forcing, equivalent depth, and thermal dissipation explicitly represented, and takes into account compression effects associated with vertical motion along isentropic surfaces. Horizontal transport properties of this system are investigated under adiabatic and diabatic conditions for different forms of dissipation, and over a range of resolutions. It is shown that forcing represetative of time-mean and amplified conditions at 10 mb leads to the behavior typical of observations at this level. The displacement of the polar night vortex and its distortion into a comma shape are evident, as is irreversible mixing under sufficiently strong forcing amplitude. It is shown that thermal dissipation influences the behavior significantly by inhibiting the amplification of unstable eddies and thereby the horizontal stirring of air.

Short-term climatic fluctuations forced by thermal anomalies

NASA Technical Reports Server (NTRS)

Hanna, A. F.

1982-01-01

A two level, global, spectral model using pressure as a vertical coordinate was developed. The system of equations describing the model is nonlinear and quasi-geostrophic (linear balance). Static stability is variable in the model. A moisture budget is calculated in the lower layer only. Convective adjustment is used to avoid supercritical temperature lapse rates. The mechanical forcing of topography is introduced as a vertical velocity at the lower boundary. Solar forcing is specified assuming a daily mean zenith angle. The differential diabatic heating between land and sea is paramterized. On land and sea ice surfaces, a steady state thermal energy equation is solved to calculate the surface temperature. On the oceans, the sea surface temperature is specified as the climatological average for January. The model is used to simulate the January, February and March circulations.

Momentum and Energy Assessments with NASA and Other Model and Data Assimilation Systems

NASA Technical Reports Server (NTRS)

Salstein, David; Nelson, Peter; Hu, Wen-Jie

2001-01-01

Support from the NASA Global Modeling and Analysis Program has been used for the following research objectives: 1) the study of aspects of dynamics of torques and angular momentum based on the Goddard GEOS and other analyses; 2) the study of how models participating in the second Atmospheric Model Intercomparison Project (AMIP-2) have success in simulating certain large-scale quantities; 3) the study of the energetics and momentum cycle from certain runs from the Goddard Laboratory for Atmospheres and other models as well; 4) the assessment of changes in diabatic heating and related energetics in the community climate model (CCM3); 5) the analysis of modes of climate of the atmosphere, especially the Arctic and North Atlantic Oscillations. Further information on these endeavors will be provided in published works and the Final Report of the project.

Energies and excited-state dynamics of 1Bu+, 1Bu- and 3Ag- states of carotenoids bound to LH2 antenna complexes from purple photosynthetic bacteria

NASA Astrophysics Data System (ADS)

Christiana, Rebecca; Miki, Takeshi; Kakitani, Yoshinori; Aoyagi, Shiho; Koyama, Yasushi; Limantara, Leenawaty

2009-10-01

Time-resolved pump-probe stimulated-emission and transient-absorption spectra were recorded after excitation with ˜30 fs pulses to the 1Bu+(0) and optically-forbidden diabatic levels of carotenoids, neurosporene, spheroidene and lycopene having n = 9-11 double bonds, bound to LH2 antenna complexes from Rhodobacter sphaeroides G1C, 2.4.1 and Rhodospirillum molischianum. The low-energy shift of stimulated emission from the covalent 1Bu-(0) and 3Ag-(0) levels slightly larger than that from the ionic 1Bu+(0) state suggests the polarization, whereas more efficient triplet generation suggests the twisting of the conjugated chain in Cars bound to the LH2 complexes, when compared to Cars free in solution.

Quantitative Assessment of the Integrated Response in Global Heat and Moisture Budgets to Changing Solar Irradiance

NASA Technical Reports Server (NTRS)

White, Warren B.; Cayan, Daniel R.; Dettinger, Michael; Sharber, James (Technical Monitor)

2001-01-01

Earlier, we found time sequences of basin- and global-average upper ocean temperature (that is, diabatic heat storage above the main pycnocline) for 40 years from 1955-1994 and of sea surface temperature for 95 years from 1900-1994 associated with changes in the Sun's radiative forcing on decadal and interdecadal timescales, lagging by 10 deg.- 30 deg. of phase and confined to the upper 60-120 m. Yet, the observed changes in upper ocean temperature (approx. 0.1 K) were approximately twice those expected from the Stefan-Boltzmann black-body radiation law for the Earth's surface, with phase lags (0 deg. to 30 deg. of phase) much shorter than the 90 deg. phase shift expected as well. Moreover, White et al. (1997, 1998) found the Earth's global decadal mode in covarying SST and SLP anomalies phase locked to the decadal signal in the Sun's irradiance. Yet, Allan (2000) found this decadal signal also characterized by patterns similar to those observed on biennial and interannual time scales; that is, the Troposphere Biennial Oscillation (TBO) and the El Nino and the Southern Oscillation (ENSO). This suggested that small changes in the Sun's total irradiance could excite this global decadal mode in the Earth's ocean-atmosphere-terrestrial system similar to those excited internally on biennial and interannual period scales. This is a significant finding, proving that energy budget models (that is, models based on globally-averaged radiation balances) yield unrealistic responses. Thus, the true response must include positive and negative feedbacks in the Earth's ocean-atmosphere-terrestrial system as its internal mode (that is, the natural mode of the system) respond in damped resonance to quasi-periodic decadal changes in the Sun's irradiance. Moreover, these responses are not much different from those occurring internally on biennial and interannual period scales.

Carbon Dioxide Clouds at High Altitude in the Tropics and in an Early Dense Martian Atmosphere

NASA Technical Reports Server (NTRS)

Colaprete, Anthony; Toon, Owen B.

2001-01-01

We use a time dependent, microphysical cloud model to study the formation of carbon dioxide clouds in the Martian atmosphere. Laboratory studies by Glandor et al. show that high critical supersaturations are required for cloud particle nucleation and that surface kinetic growth is not limited. These conditions, which are similar to those for cirrus clouds on Earth, lead to the formation of carbon dioxide ice particles with radii greater than 500 micrometers and concentrations of less than 0.1 cm(exp -3) for typical atmospheric conditions. Within the current Martian atmosphere, CO2 cloud formation is possible at the poles during winter and at high altitudes in the tropics during periods of increased atmospheric dust loading. In both cases, temperature perturbations of several degrees below the CO2 saturation temperature are required to nucleate new cloud particles suggesting that dynamical processes are the most common initiators of carbon dioxide clouds rather than diabatic cooling. The microphysical cloud model, coupled to a two-stream radiative transfer model, is used to reexamine the impact of CO2 clouds on the surface temperature within a dense CO2 atmosphere. The formation of carbon dioxide clouds leads to a warmer surface than what would be expected for clear sky conditions. The amount of warming is sensitive to the presence of dust and water vapor in the atmosphere, both of which act to dampen cloud effects. The radiative warming associated with cloud formation, as well as latent heating, work to dissipate the clouds when present. Thus, clouds never last for periods much longer than several days, limiting their overall effectiveness for warming the surface. The time average cloud optical depth is approximately unity leading to a 5-10 K warming, depending on the surface pressure. However, the surface temperature does not rise about the freezing point of liquid water even for pressures as high as 5 bars, at a solar luminosity of 75% the current value.

Vertical cross-spectral phases in atmospheric flow

NASA Astrophysics Data System (ADS)

Chougule, A.; Mann, J.; Kelly, M.

2014-11-01

The cross-spectral phases between velocity components at two heights are analyzed from observations at the Høvsøre test site under diabatic conditions. These phases represent the degree to which turbulence sensed at one height leads (or lags) in time the turbulence sensed at the other height. The phase angle of the cross-wind component is observed to be significantly greater than the phase for the along-wind component, which in turn is greater than the phase for the vertical component. The cross-wind and along-wind phases increase with stream-wise wavenumber and vertical separation distance, but there is no significant change in the phase angle of vertical velocity. The phase angles for all atmospheric stabilities show similar order in phasing. The phase angles from the Høvsøre observations under neutral condition are compared with a rapid distortion theory model which show similar order in phase shift.

Antarctic Polar Descent and Planetary Wave Activity Observed in ISAMS CO from April to July 1992

NASA Technical Reports Server (NTRS)

Allen, D. R.; Stanford, J. L.; Nakamura, N.; Lopez-Valverde, M. A.; Lopez-Puertas, M.; Taylor, F. W.; Remedios, J. J.

2000-01-01

Antarctic polar descent and planetary wave activity in the upper stratosphere and lower mesosphere are observed in ISAMS CO data from April to July 1992. CO-derived mean April-to-May upper stratosphere descent rates of 15 K/day (0.25 km/day) at 60 S and 20 K/day (0.33 km/day) at 80 S are compared with descent rates from diabatic trajectory analyses. At 60 S there is excellent agreement, while at 80 S the trajectory-derived descent is significantly larger in early April. Zonal wavenumber 1 enhancement of CO is observed on 9 and 28 May, coincident with enhanced wave 1 in UKMO geopotential height. The 9 May event extends from 40 to 70 km and shows westward phase tilt with height, while the 28 May event extends from 40 to 50 km and shows virtually no phase tilt with height.

A case study of microphysical structures and hydrometeor phase in convection using radar Doppler spectra at Darwin, Australia

NASA Astrophysics Data System (ADS)

Riihimaki, L. D.; Comstock, J. M.; Luke, E.; Thorsen, T. J.; Fu, Q.

2017-07-01

To understand the microphysical processes that impact diabatic heating and cloud lifetimes in convection, we need to characterize the spatial distribution of supercooled liquid water. To address this observational challenge, ground-based vertically pointing active sensors at the Darwin Atmospheric Radiation Measurement site are used to classify cloud phase within a deep convective cloud. The cloud cannot be fully observed by a lidar due to signal attenuation. Therefore, we developed an objective method for identifying hydrometeor classes, including mixed-phase conditions, using k-means clustering on parameters that describe the shape of the Doppler spectra from vertically pointing Ka-band cloud radar. This approach shows that multiple, overlapping mixed-phase layers exist within the cloud, rather than a single region of supercooled liquid. Diffusional growth calculations show that the conditions for the Wegener-Bergeron-Findeisen process exist within one of these mixed-phase microstructures.

Theoretical Studies of Dissociative Recombination of Electrons with SH+ Ions

NASA Astrophysics Data System (ADS)

Kashinski, D. O.; di Nallo, O. E.; Hickman, A. P.; Mezei, J. Zs.; Colboc, F.; Schneider, I. F.; Chakrabarti, K.; Talbi, D.

2017-04-01

We are investigating the dissociative recombination (DR) of electrons with the molecular ion SH+, i.e. e- +SH+ -> S + H . SH+ is found in the interstellar medium (ISM), and little is known concerning its chemistry. Understanding the role of DR of electrons with SH+ will lead to more accurate astrophysical models. Large active-space multi-reference configuration interaction (MRCI) electronic structure calculations were performed using the GAMESS code to obtain ground and excited 2 Π state potential energy curves (PECs) for several values of SH separation. Core-excited Rydberg states have proven to be of huge importance. The block diagonalization method was used to disentangle interacting states and form a diabatic representation of the PECs. Currently we are performing dynamics calculations using Multichannel Quantum Defect Theory (MQDT) to obtain DR rates. The status of the work will be presented at the conference. Work supported by the French CNRS, the NSF, the XSEDE, and USMA.

A comparative study of different methods for calculating electronic transition rates

NASA Astrophysics Data System (ADS)

Kananenka, Alexei A.; Sun, Xiang; Schubert, Alexander; Dunietz, Barry D.; Geva, Eitan

2018-03-01

We present a comprehensive comparison of the following mixed quantum-classical methods for calculating electronic transition rates: (1) nonequilibrium Fermi's golden rule, (2) mixed quantum-classical Liouville method, (3) mean-field (Ehrenfest) mixed quantum-classical method, and (4) fewest switches surface-hopping method (in diabatic and adiabatic representations). The comparison is performed on the Garg-Onuchic-Ambegaokar benchmark charge-transfer model, over a broad range of temperatures and electronic coupling strengths, with different nonequilibrium initial states, in the normal and inverted regimes. Under weak to moderate electronic coupling, the nonequilibrium Fermi's golden rule rates are found to be in good agreement with the rates obtained via the mixed quantum-classical Liouville method that coincides with the fully quantum-mechanically exact results for the model system under study. Our results suggest that the nonequilibrium Fermi's golden rule can serve as an inexpensive yet accurate alternative to Ehrenfest and the fewest switches surface-hopping methods.

ExoMol line lists XXVIII: The rovibronic spectrum of AlH

NASA Astrophysics Data System (ADS)

Yurchenko, Sergei N.; Williams, Henry; Leyland, Paul C.; Lodi, Lorenzo; Tennyson, Jonathan

2018-06-01

A new line list for AlH is produced. The WYLLoT line list spans two electronic states X 1Σ+ and A 1Π. A diabatic model is used to model the shallow potential energy curve of the A 1Π state, which has a strong pre-dissociative character with only two bound vibrational states. Both potential energy curves are empirical and were obtained by fitting to experimentally derived energies of the X 1Σ+ and A 1Π electronic states using the diatomic nuclear motion codes DPOTFIT and DUO. High temperature line lists plus partition functions and lifetimes for three isotopologues 27AlH, 27AlD and 26AlH were generated using ab initio dipole moments. The line lists cover both the X-X and A-X systems and are made available in electronic form at the CDS and ExoMol databases.

A diabatic circulation two-dimensional model with photochemistry - Simulations of ozone and long-lived tracers with surface sources

NASA Technical Reports Server (NTRS)

Stordal, F.; Isaksen, I. S. A.; Horntveth, K.

1985-01-01

Numerous studies have been concerned with the possibility of a reduction of the stratospheric ozone layer. Such a reduction could lead to an enhanced penetration of ultraviolet (UV) radiation to the ground, and, as a result, to damage in the case of several biological processes. It is pointed out that the distributions of many trace gases, such as ozone, are governed in part by transport processes. The present investigation presents a two-dimensional photochemistry-transport model using the residual circulation. The global distribution of both ozone and components with ground sources computed in this model is in good agreement with the observations even though slow diffusion is adopted. The agreement is particularly good in the Northern Hemisphere. The results provide additional support for the idea that tracer transport in the stratosphere is mainly of advective nature.

Nonperturbative quantum control via the nonresonant dynamic Stark effect

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sussman, Benjamin J.; Stolow, Albert; Department of Physics, Queen's University, Kingston, Ontario, K7L 3N6

2005-05-15

The nonresonant dynamic Stark effect (NRDSE) is investigated as a general tool for quantum control in the intermediate field strength regime (nonperturbative but nonionizing). We illustrate this scheme for the case of nonadiabatic molecular photodissociation at an avoided crossing. Using the NRDSE exclusively, both the electronic branching ratio and predissociation lifetime may be controlled. Infrared control pulses are used to modify the field-free dynamical evolution during traversal of the avoided crossing, thus controlling the nonadiabatic branching ratio. Predissociation lifetimes may be either increased or decreased using properly timed short infrared pulses to modify phase differences between the diabatic wave packets.more » In contrast with the limiting cases of perturbative control (interference between transitions) and strong field control with ionizing laser fields, control via the NRDSE may be thought of as reversibly modifying the effective Hamiltonian during system propagation.« less

A Numerical Study of Tropical Sea-Air Interactions Using a Cloud Resolving Model Coupled with an Ocean Mixed-Layer Model

NASA Technical Reports Server (NTRS)

Shie, Chung-Lin; Tao, Wei-Kuo; Johnson, Dan; Simpson, Joanne; Li, Xiaofan; Sui, Chung-Hsiung; Einaudi, Franco (Technical Monitor)

2001-01-01

Coupling a cloud resolving model (CRM) with an ocean mixed layer (OML) model can provide a powerful tool for better understanding impacts of atmospheric precipitation on sea surface temperature (SST) and salinity. The objective of this study is twofold. First, by using the three dimensional (3-D) CRM-simulated (the Goddard Cumulus Ensemble model, GCE) diabatic source terms, radiation (longwave and shortwave), surface fluxes (sensible and latent heat, and wind stress), and precipitation as input for the OML model, the respective impact of individual component on upper ocean heat and salt budgets are investigated. Secondly, a two-way air-sea interaction between tropical atmospheric climates (involving atmospheric radiative-convective processes) and upper ocean boundary layer is also examined using a coupled two dimensional (2-D) GCE and OML model. Results presented here, however, only involve the first aspect. Complete results will be presented at the conference.

Analytical optimal pulse shapes obtained with the aid of genetic algorithms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guerrero, Rubén D., E-mail: rdguerrerom@unal.edu.co; Arango, Carlos A.; Reyes, Andrés

2015-09-28

We propose a methodology to design optimal pulses for achieving quantum optimal control on molecular systems. Our approach constrains pulse shapes to linear combinations of a fixed number of experimentally relevant pulse functions. Quantum optimal control is obtained by maximizing a multi-target fitness function using genetic algorithms. As a first application of the methodology, we generated an optimal pulse that successfully maximized the yield on a selected dissociation channel of a diatomic molecule. Our pulse is obtained as a linear combination of linearly chirped pulse functions. Data recorded along the evolution of the genetic algorithm contained important information regarding themore » interplay between radiative and diabatic processes. We performed a principal component analysis on these data to retrieve the most relevant processes along the optimal path. Our proposed methodology could be useful for performing quantum optimal control on more complex systems by employing a wider variety of pulse shape functions.« less

Does Southern Ocean Surface Forcing Shape the Global Ocean Overturning Circulation?

NASA Astrophysics Data System (ADS)

Sun, Shantong; Eisenman, Ian; Stewart, Andrew L.

2018-03-01

Paleoclimate proxy data suggest that the Atlantic Meridional Overturning Circulation (AMOC) was shallower at the Last Glacial Maximum (LGM) than its preindustrial (PI) depth. Previous studies have suggested that this shoaling necessarily accompanies Antarctic sea ice expansion at the LGM. Here the influence of Southern Ocean surface forcing on the AMOC depth is investigated using ocean-only simulations from a state-of-the-art climate model with surface forcing specified from the output of previous coupled PI and LGM simulations. In contrast to previous expectations, we find that applying LGM surface forcing in the Southern Ocean and PI surface forcing elsewhere causes the AMOC to shoal only about half as much as when LGM surface forcing is applied globally. We show that this occurs because diapycnal mixing renders the Southern Ocean overturning circulation more diabatic than previously assumed, which diminishes the influence of Southern Ocean surface buoyancy forcing on the depth of the AMOC.

Factors governing water condensation in the Martian atmosphere

NASA Technical Reports Server (NTRS)

Colburn, David S.; Pollack, J. B.; Haberle, Robert M.

1988-01-01

Modeling results are presented suggesting a diurnal condensation cycle at high altitudes at some seasons and latitudes. In a previous paper, the use of atmospheric optical depth measurements at the Viking lander site to show diurnal variability of water condensation at different seasons of the Mars year was described. Factors influencing the amount of condensation include latitude, season, atmospheric dust content and water vapor content at the observation site. A one-dimensional radiative-convective model is used herein based on the diabatic heating routines under development for the Mars General Circulation Model. The model predicts atmospheric temperature profiles at any latitude, season, time of day and dust load. From these profiles and an estimate of the water vapor, one can estimate the maximum occurring at an early morning hour (AM) and the minimum in the late afternoon (PM). Measured variations in the atmospheric optical density between AM and PM measurements were interpreted as differences in AM and PM condensation.

Theoretical Studies of Dissociative Recombination of Electrons with SH+ Ions

NASA Astrophysics Data System (ADS)

Kashinski, D. O.; di Nallo, O. E.; Hickman, A. P.; Mezei, J. Zs.; Colboc, F.; Schneider, I. F.; Chakrabarti, K.; Talbi, D.

2016-05-01

We are investigating the dissociative recombination (DR) of electrons with the molecular ion SH+, i.e. e- +SH+ --> S + H . SH+ is found in the interstellar medium (ISM), and little is known concerning its chemistry. Understanding the role of DR of electrons with SH+ will lead to more accurate astrophysical models. Large active-space multi-reference configuration interaction (MRCI) electronic structure calculations were performed using the GAMESS code to obtain ground and excited 2 Π state potential energy curves (PECs) for several values of SH separation. Core-excited Rydberg states have proven to be of huge importance. The block diagonalization method was used to disentangle interacting states and form a diabatic representation of the PECs. Currently we are performing dynamics calculations using Multichannel Quantum Defect Theory (MQDT) to obtain DR rates. The status of the work will be presented at the conference. work supported by the French CNRS, the NSF, the XSEDE, and USMA.

Communication: CDFT-CI couplings can be unreliable when there is fractional charge transfer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mavros, Michael G.; Van Voorhis, Troy, E-mail: tvan@mit.edu

2015-12-21

Constrained density functional theory with configuration interaction (CDFT-CI) is a useful, low-cost tool for the computational prediction of electronic couplings between pseudo-diabatic constrained electronic states. Such couplings are of paramount importance in electron transfer theory and transition state theory, among other areas of chemistry. Unfortunately, CDFT-CI occasionally fails significantly, predicting a coupling that does not decay exponentially with distance and/or overestimating the expected coupling by an order of magnitude or more. In this communication, we show that the eigenvalues of the difference density matrix between the two constrained states can be used as an a priori metric to determine whenmore » CDFT-CI are likely to be reliable: when the eigenvalues are near 0 or ±1, transfer of a whole electron is occurring, and CDFT-CI can be trusted. We demonstrate the utility of this metric with several illustrative examples.« less

Sea surface temperature anomalies, planetary waves, and air-sea feedback in the middle latitudes

NASA Technical Reports Server (NTRS)

Frankignoul, C.

1985-01-01

Current analytical models for large-scale air-sea interactions in the middle latitudes are reviewed in terms of known sea-surface temperature (SST) anomalies. The scales and strength of different atmospheric forcing mechanisms are discussed, along with the damping and feedback processes controlling the evolution of the SST. Difficulties with effective SST modeling are described in terms of the techniques and results of case studies, numerical simulations of mixed-layer variability and statistical modeling. The relationship between SST and diabatic heating anomalies is considered and a linear model is developed for the response of the stationary atmosphere to the air-sea feedback. The results obtained with linear wave models are compared with the linear model results. Finally, sample data are presented from experiments with general circulation models into which specific SST anomaly data for the middle latitudes were introduced.

Tropical Forcing of the Summer East Atlantic Pattern

NASA Astrophysics Data System (ADS)

Wulff, C. Ole; Greatbatch, Richard J.; Domeisen, Daniela I. V.; Gollan, Gereon; Hansen, Felicitas

2017-11-01

The Summer East Atlantic (SEA) mode is the second dominant mode of summer low-frequency variability in the Euro-Atlantic region. Using reanalysis data, we show that SEA-related circulation anomalies significantly influence temperatures and precipitation over Europe. We present evidence that part of the interannual SEA variability is forced by diabatic heating anomalies of opposing signs in the tropical Pacific and Caribbean that induce an extratropical Rossby wave train. This precipitation dipole is related to SST anomalies characteristic of the developing El Niño-Southern Oscillation phases. Seasonal hindcast experiments forced with observed sea surface temperatures (SSTs) exhibit skill at capturing the interannual SEA variability corroborating the proposed mechanism and highlighting the possibility for improved prediction of boreal summer variability. Our results indicate that tropical forcing of the SEA likely played a role in the dynamics of the 2015 European heat wave.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sinitsyn, Nikolai A.

In this paper, I identify a nontrivial four-state Landau-Zener model for which transition probabilities between any pair of diabatic states can be determined analytically and exactly. The model describes an experimentally accessible system of two interacting qubits, such as a localized state in a Dirac material with both valley and spin degrees of freedom or a singly charged quantum dot (QD) molecule with spin orbit coupling. Application of the linearly time-dependent magnetic field induces a sequence of quantum level crossings with possibility of interference of different trajectories in a semiclassical picture. I argue that this system satisfies the criteria ofmore » integrability in the multistate Landau-Zener theory, which allows one to derive explicit exact analytical expressions for the transition probability matrix. Finally, I also argue that this model is likely a special case of a larger class of solvable systems, and present a six-state generalization as an example.« less

Impacts of raindrop evaporative cooling on tropical cyclone secondary eyewall formation

NASA Astrophysics Data System (ADS)

Ge, Xuyang; Guan, Liang; Yan, Ziyu

2018-06-01

The impacts of raindrop evaporative cooling on secondary eyewall formation (SEF) of simulated tropical cyclones are investigated using idealized numerical experiments. The results suggest that the raindrop evaporative cooling effect is beneficial to the development of secondary eyewall through the planetary boundary layer (PBL) cold pool process. The evaporative cooling-driven downdrafts bring about the surface cold pool beneath a precipitation cloud. This cold pool dynamics act as a lifting mechanism to trigger the outer convection. The radially outward propagation of spiral rainbands broadens the TC size, by which modifies the surface heat fluxes and thus outer convection. Furthermore, the unbalanced PBL process contributes to the SEF. The radially outward surface outflows forces convection at outer region and thus favors a larger TC size. A larger TC implies an enhanced inertial stability at the outer region, which favors a higher conversion efficiency of diabatic heating to kinetic energy.

Tropical forecasting - Predictability perspective

NASA Technical Reports Server (NTRS)

Shukla, J.

1989-01-01

Results are presented of classical predictability studies and forecast experiments with observed initial conditions to show the nature of initial error growth and final error equilibration for the tropics and midlatitudes, separately. It is found that the theoretical upper limit of tropical circulation predictability is far less than for midlatitudes. The error growth for a complete general circulation model is compared to a dry version of the same model in which there is no prognostic equation for moisture, and diabatic heat sources are prescribed. It is found that the growth rate of synoptic-scale errors for the dry model is significantly smaller than for the moist model, suggesting that the interactions between dynamics and moist processes are among the important causes of atmospheric flow predictability degradation. Results are then presented of numerical experiments showing that correct specification of the slowly varying boundary condition of SST produces significant improvement in the prediction of time-averaged circulation and rainfall over the tropics.

Synergistic interactions between an upper-level jet streak and diabatic processes that influence the development of a low-level jet and a secondary coastal cyclone

NASA Technical Reports Server (NTRS)

Uccellini, Louis W.; Petersen, Ralph A.; Kocin, Paul J.; Brill, Keith F.; Tuccillo, James J.

1987-01-01

A series of numerical simulations of the February 1979 Presidents Day cyclone is presented. The development of the low-level jet (LLJ) associated with the cyclone is described, and the mesoscale numerical model, initial analyses, and experimental design used in the study are discussed. Four numerical simulations are discussed and compared, including an adiabatic simulation that isolates the development of upper-level divergence along the axis of a subtropical jet streak and three other simulations that reveal the contributions of sensible and latent heat release in modifying lower-tropospheric wind fields and reducing the sea-level pressure. The formation of the LLJ is described through an evaluation of trajectories derived from the various model simulations. The effect of the LLJ on secondary cyclogenesis along the East Coast is described.

How Does Tropical Cyclone Size Affect the Onset Timing of Secondary Eyewall Formation?

NASA Astrophysics Data System (ADS)

Guan, Liang; Ge, Xuyang

2018-02-01

By using idealized numerical simulations, the impact of tropical cyclone size on secondary eyewall formation (SEF) is examined. Both unbalanced boundary layer and balanced processes are examined to reveal the underlying mechanism. The results show that a tropical cyclone (TC) with a larger initial size favors a quicker SEF and a larger outer eyewall. For a TC with a larger initial size, it will lead to a stronger surface entropy flux, and thus more active outer convection. Meanwhile, a greater inertial stability helps the conversion from diabatic heating to kinetic energy. Furthermore, the progressively broadening of the tangential wind field will induce significant boundary layer imbalances. This unbalanced boundary layer process results in a supergradient wind zone that acts as an important mechanism for triggering and maintaining deep convection. In short, different behaviors of balanced and unbalanced processes associated with the initial wind profile lead to different development rates of the secondary eyewall.

Global two dimensional chemistry model and simulation of atmospheric chemical composition

NASA Astrophysics Data System (ADS)

Zhang, Renjian; Wang, Mingxing; Zeng, Qingcun

2000-03-01

A global two-dimensional zonally averaged chemistry model is developed to study the chemi-cal composition of atmosphere. The region of the model is from 90°S to 90°N and from the ground to the altitude of 20 km with a resolution of 5° x 1 km. The wind field is residual circulation calcu-lated from diabatic rate. 34 species and 104 chemical and photochemical reactions are considered in the model. The sources of CH4, CO and NOx, which are divided into seasonal sources and non-seasonal sources, are parameterized as a function of latitude and time. The chemical composi-tion of atmosphere was simulated with emission level of CH4, CO and NOx in 1990. The results are compared with observations and other model results, showing that the model is successful to simu-late the atmospheric chemical composition and distribution of CH4.

Negligible shift of 3Ag- potential in longer-chain carotenoids as revealed by a single persistent peak of 3Ag-→1Ag- stimulated emission followed by 3Ag-←1Ag- transient-absorption

NASA Astrophysics Data System (ADS)

Li, Chunyong; Miki, Takeshi; Kakitani, Yoshinori; Koyama, Yasushi; Nagae, Hiroyoshi

2007-12-01

Upon excitation of lycopene, anhydrorhodovibrin or spirilloxanthin to the 1Bu+(0) state, stimulated emission followed by transient-absorption was observed as a single peak with the 3Ag-(0) energy that had been determined by measurement of resonance-Raman excitation profiles. This observation was explained in terms of negligible shift of the 3Ag- potential, in reference to the 1Ag- potential, where only the 3Ag-(υ)→1Ag-(υ) emission and the 3Ag-(υ)←1Ag-(υ) absorption become allowed during the vibrational relaxation of υ = 2 → 1 → 0, starting from the 3Ag-(2) level generated by diabatic internal conversion from the 1Bu+(0) level, in anhydrorhodovibrin, for example.

Communication: CDFT-CI couplings can be unreliable when there is fractional charge transfer

NASA Astrophysics Data System (ADS)

Mavros, Michael G.; Van Voorhis, Troy

2015-12-01

Constrained density functional theory with configuration interaction (CDFT-CI) is a useful, low-cost tool for the computational prediction of electronic couplings between pseudo-diabatic constrained electronic states. Such couplings are of paramount importance in electron transfer theory and transition state theory, among other areas of chemistry. Unfortunately, CDFT-CI occasionally fails significantly, predicting a coupling that does not decay exponentially with distance and/or overestimating the expected coupling by an order of magnitude or more. In this communication, we show that the eigenvalues of the difference density matrix between the two constrained states can be used as an a priori metric to determine when CDFT-CI are likely to be reliable: when the eigenvalues are near 0 or ±1, transfer of a whole electron is occurring, and CDFT-CI can be trusted. We demonstrate the utility of this metric with several illustrative examples.

Angular Distributions of Differential Electron Capture Cross Sections in Collisions Between Low-Velocity Highly-Charged Ions and Neutral Targets.

NASA Astrophysics Data System (ADS)

Waggoner, William Tracy

1990-01-01

Experimental capture cross sections d sigma / dtheta versus theta , are presented for various ions incident on neutral targets. First, distributions are presented for Ar ^{rm 8+} ions incident on H_{rm 2}, D _{rm 2}, and Ar targets. Energy gain studies indicate that capture occurs to primarily a 5d,f final state of Ar^{rm 7+} with some contributions from transfer ionization (T.I.) channels. Angular distribution spectra for all three targets are similar, with spectra having a main peak located at forward angles which is attributed to single capture events, and a secondary structure occurring at large angles which is attributed to T.I. contributions. A series of Ar^{rm 8+} on Ar spectra were collected using a retarding grid system as a low resolution energy spectrometer to resolve single capture events from T.I. events. The resulting single capture and T.I. angular distributions are presented. Results are discussed in terms of a classical deflection function employing a simple two state curve crossing model. Angular distributions for electron capture from He by C, N, O, F, and Ne ions with charge states from 5 ^+-8^+ are presented for projectile energies between 1.2 and 2.0 kV. Distributions for the same charge state but different ion species are simlar, but not identical with distributions for the 5 ^+ and 7^+ ions being strongly forward peaked, the 6^+ distributions are much less forward peaked with the O^{6+} distributions showing structure, the Ne^{8+} ion distribution appears to be an intermediate case between forward peaking and large angle scattering. These results are discussed in terms of classical deflection functions which utilize two state Coulomb diabatic curve crossing models. Finally, angular distributions are presented for electron capture from He by Ar^{rm 6+} ions at energies between 1287 eV and 296 eV. At large projectile energies the distribution is broad. As the energy decreases below 523 eV, distributions shift to forward angles with a second peak appearing outside the Coulomb angle, theta_{c} = Q/2E, which continues to grow in magnitude as the projectile energy decreases further. Results are compared with a model calculation employing a two state diabatic Coulomb curve crossing model and the classical deflection function.

Interannual-to-decadal air-sea interactions in the tropical Atlantic region

NASA Astrophysics Data System (ADS)

Ruiz-Barradas, Alfredo

2001-09-01

The present research identifies modes of atmosphere-ocean interaction in the tropical Atlantic region and the mechanisms by which air-sea interactions influence the regional climate. Novelties of the present work are (1)the use of relevant ocean and atmosphere variables important to identity coupled variability in the system. (2)The use of new data sets, including realistic diabatic heating. (3)The study of interactions between ocean and atmosphere relevant at interannual-to-decadal time scales. Two tropical modes of variability are identified during the period 1958-1993, the Atlantic Niño mode and the Interhemispheric mode. Those modes have defined structures in both ocean and atmosphere. Anomalous sea surface temperatures and winds are associated to anomalous placement of the Intertropical Convergence Zone (ITCZ). They develop maximum amplitude during boreal summer and spring, respectively. The anomalous positioning of the ITCZ produces anomalous precipitation in some places like Nordeste, Brazil and the Caribbean region. Through the use of a diagnostic primitive equation model, it is found that the most important terms controlling local anomalous surface winds over the ocean are boundary layer temperature gradients and diabatic heating anomalies at low levels (below 780 mb). The latter is of particular importance in the deep tropics in producing the anomalous meridional response to the surface circulation. Simulated latent heat anomalies indicate that a thermodynamic feedback establishes positive feedbacks at both sides of the equator and west of 20°W in the deep tropics and a negative feedback in front of the north west coast of Africa for the Interhemispheric mode. This thermodynamic feedback only establishes negative feedbacks for the Atlantic Niño mode. Transients establish some connection between the tropical Atlantic and other basins. Interhemispheric gradients of surface temperature in the tropical Atlantic influence winds in the midlatitude North Atlantic but winds and heating of the midlatitude North Atlantic have little impact on the deep tropics. The remote influence of El Niño-Southern Oscillation in the tropical Atlantic, similar to the Interhemispheric mode, is the result of two mechanisms triggered by anomalous warming in the central and eastern tropical Pacific: enhancement of the Atlantic Walker circulation, and coupled intrusion of negative 200 mb geopotential height anomalies and negative sea level pressure anomalies that induce southwesterly surface wind anomalies in the northern tropical Atlantic.

Issues in Establishing Causes of the 1988 Drought over North America.

NASA Astrophysics Data System (ADS)

Trenberth, Kevin E.; Branstator, Grant W.

1992-02-01

Progress toward understanding the causes of and physical mechanisms involved in the 1988 North American drought is reported. An earlier study demonstrated that major sea surface temperature (SST) anomalies in the tropical Pacific Ocean, in association with the 1988 La Niña, may have disrupted atmospheric heating patterns by changing the location and intensity of the intertropical convergence zone and that such heating anomalies could have initiated the circulation anomalies across North America responsible for the drought. A key issue of when the drought circulation anomalies developed and their relation to changes in tropical Pacific SSTs is examined. Although unusually dry soil moisture and heat waves persisted into August, the anomalous atmospheric conditions that brought on the drought occurred in April, May, and June of 1988. The evolution of the Pacific SSTs and tropical convection, as revealed by outgoing longwave radiation, is shown to be consistent with the development of the conditions favorable for initiating the drought circulation pattern in April through June of 1988. On the equator at 110°W, SST anomalies exceeded 2.75°C in only April, May, and June and were largest (4.1°C) in May 1988. The issues of how the 1988 La Niña differed from those in the past and the importance of the whole SST field in determining the anomalous diabatic heating are also discussed. Diagnostic calculations of atmospheric diabatic heating confirm that atmospheric heating anomalies existed in the tropical Pacific in association with the major SST anomalies during this time. The link between the anomalous heating and the tropical SSTs supports the view that influences external to the atmosphere were important and that the drought was not generated solely by mechanisms internal to the atmosphere. The distribution of diagnosed heating anomalies over North America, together with a planetary wave model response to idealized forcing, is described to clarify the possible role of soil moisture anomalies in perpetuating the drought. It is argued that feedback-caused soil moisture anomalies may have been secondary sources for the drought circulation but could not have been the primary instigator. For the most part, other diagnosed heating anomalies during the drought are found to have little influence on the North American region. Criteria to help judge the ability of general circulation models to simulate the drought are discussed.

Extratropical response to Fast and Slow episodes of Madden-Julian Oscillation in observation and using intervention experiments with CFSv2

NASA Astrophysics Data System (ADS)

Yadav, P.; Straus, D. M.

2017-12-01

The Madden-Julian Oscillation (MJO) is a potential source of predictability in the extratropics in extended range weather forecasting. The nature of MJO is sporadic and therefore, the mid-latitude response may depend on the nature of the MJO event, in particular the phase speed. We discuss the results of our observational and modeling study of mid-latitude circulation response to Fast and Slow MJO episodes using wintertime ERA-Interim reanalysis data and the CFSv2 coupled model of NOAA. The observational study shows that the mid-latitude response to different propagating speeds is not the same. The propagation speed is defined by the time the OLR takes to propagate from phase 3 to phase 6. The mid-latitude response is assessed in terms of composite maps and frequency of occurrence of robust circulation regimes. Fast episode composite anomalies of 500hPa height show a developing Rossby wave in the mid-Pacific with downstream propagation through MJO phases 2- 4. Development of NAO+ teleconnection pattern is stronger in Slow that in Fast MJO episodes, and occurs with a greater time lag after MJO heating is in the Indian Ocean (phase 3). Previous results find an increase in occurrence of NAO- regime following phase 6. We have found that much of this behavior is due to the slow episodes. Based on these observational results, intervention experiments using CFSv2 are designed to better understand the impact of heating/cooling and to estimate mid-latitude response to Fast and Slow MJO episodes. The added heating experiments consist of 31 year reforecasts for December 1 initial conditions from CFS reanalysis (1980-2011) in which the identical MJO evolution of three-dimensional diabatic heating has been added, thus producing fast and slow MJO episodes with well-defined phase speeds. We will discuss the results of these experiments with a focus on understanding the role of phase speed and interference in setting up the response, and to understand the mechanisms that distinguish fast and slow types of response We will also discuss the diagnostics using Predictable Component Analysis to distinguish the signal forced by common diabatic heating signal from noise, and weather regime response to fast and slow MJO using cluster analysis.

GPM SLH: Convective Latent Heating Estimated with GPM Dual-frequency Precipitation Radar Data

NASA Astrophysics Data System (ADS)

Takayabu, Y. N.; Hamada, A.; Yokoyama, C.; Ikuta, Y.; Shige, S.; Yamaji, M.; Kubota, T.

2017-12-01

Three dimensional diabatic heating distribution plays essential roles to determine large-scale circulation, as well as to generate mesoscale circulation associated with tropical convection (e.g. Hartmann et al., 1984; Houze et al. 1982). For mid-latitude systems also, diabatic heating contributes to generate PVs resulting in, for example, explosive intensifications of mid-lattitude storms (Boettcher and Wernli, 2011). Previously, with TRMM PR data, we developed a Spectral Latent Heating algorithm (SLH; Shige et al. 2004, etc.) for 36N-36S region. It was based on the spectral LH tables produced from a simulation utilizing the Goddard Cloud Ensemble Model forced with the TOGA-COARE data. With GPM DPR, the observation region is extended to 65N-65S. Here, we introduce a new version of SLH algorithm which is applicable also to the mid-latitude precipitation. A new global GPM SLH ver.5 product is released as one of NASA/JAXA GPM standard products on July 11, 2017. For GPM SLH mid-latitude algorithm, we employ the Japan Meteorological Agency (JMA)'s high resolution (horizontally 2km) Local Forecast Model (LFM) to construct the LUTs. With collaborations of JMA's forecast group, forecast data for 8 extratropical cyclone cases are collected and utilized. For mid-latitude precipitation, we have to deal with large temperature gradients and complex relationship between the freezing level and cloud base levels. LUTs are constructed for LH, Q1-QR, and Q2 (Yanai et al. 1973), for six different precipitation types: Convective and shallow stratiform LUTs are made against precipitation top heights. For deep stratiform and other precipitation, LUTs are made against maximum precipitation to handle the unknown cloud-bases. Finally, three-dimensional convective latent heating is retrieved, utilizing the LUTs and precipitation profile data from GPM 2AKu. We can confirm that retrieved LH looks very similar to simulated LH, for a consistency check. We also confirm a good continuities of mean LH distributions between tropics and mid-latitudes in horizontal as well as in vertical. Further analysis results will also be presented. Acknowledgments: This research was supported by JAXA PMM RA8 and the Environment Research and Technology Development Fund (2-1503) of Environmental Restoration and Conservation Agency.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuang, Zhiming; Gentine, Pierre

Over the duration of this project, we have made the following advances. 1) We have developed a novel approach to obtain a Lagrangian view of convection from high-resolution numerical model through Lagrangian tracking. This approach nicely complements the more traditionally used Eulerian statistics. We have applied this approach to a range of problem. 2) We have looked into improving and extending our parameterizations based on stochastically entraining parcels, developed previously for shallow convection. 3) This grant also supported our effort on a paper where we compared cumulus parameterizations and cloud resolving models in terms of their linear response functions. Thismore » work will help the community to better evaluate and develop cumulus parameterization. 4) We have applied Lagrangian tracking to shallow convection, deep convection with and without convective organization to better characterize their dynamics and the transition between them. 5) We have devised a novel way of using Lagrangian to identify cold pools, an area identified as of great interest by the ASR community. Our algorithm has a number of advantages and in particular can handle merging cold pools more gracefully than existing techniques. 6) We demonstrated that we can, for the first time, correctly reproduce both the diurnal and seasonal cycle of the hydrologic cycle in the Amazon using a strategy that explicitly represents convection but parameterizes large-scale circulation. In addition we showed that the main cause of the wet season is the presence of an early morning fog, which insulate the surface from top of the atmosphere shortwave radiation. In essence this fog makes the day shorter because radiation cannot penetrate to the surface in the early morning. This is why all fluxes are reduced in the wet season compared to the dry season. 7) We have investigated the life cycle of cold pools and the role of surface diabatic heating. We show that surface heating can kill cold pols and reduce the number of large cold pools and the organization of convection. The effect is quite dramatic over land where the entire distribution of cold pools is modified, and the cold pools are much warmer and more humid with surface diabatic heating below the cold pools. The PI and the co-PI continue to work together on parameterization of cold pools.« less

Solar cycle modulation of Southern Annular Mode -Energy-momentum analysis-

NASA Astrophysics Data System (ADS)

Kuroda, Y.

2016-12-01

Climate is affected by various factors, including oceanic changes and volcanic eruptions. 11-year solar cycle change is one of such important factors. Observational analysis shows that the Southern Annular Mode (SAM) in late-winter/spring show structural modulation associated with 11-year solar cycle. In fact, SAM-related signal tends to extend from surface to upper stratosphere and persistent longer period in the High Solar (HS) years, whereas it is restricted in the troposphere and not persist in the Low Solar (LS) years. In the present study, we used 35-year record of ERA-Interim reanalysis data and performed wave-energy and momentum analysis on the solar-cycle modulation of the SAM to examine key factors to create such solar-SAM relationship. It is found that enhanced wave-mean flow interaction tends to take place in the middle stratosphere in association with enhanced energy input from diabatic heating on September only in HS years. The result suggests atmospheric and solar conditions on September are keys to create solar-SAM relationship.

Unified semiclassical theory for the two-state system: an analytical solution for general nonadiabatic tunneling.

PubMed

Zhu, Chaoyuan; Lin, Sheng Hsien

2006-07-28

Unified semiclasical solution for general nonadiabatic tunneling between two adiabatic potential energy surfaces is established by employing unified semiclassical solution for pure nonadiabatic transition [C. Zhu, J. Chem. Phys. 105, 4159 (1996)] with the certain symmetry transformation. This symmetry comes from a detailed analysis of the reduced scattering matrix for Landau-Zener type of crossing as a special case of nonadiabatic transition and nonadiabatic tunneling. Traditional classification of crossing and noncrossing types of nonadiabatic transition can be quantitatively defined by the rotation angle of adiabatic-to-diabatic transformation, and this rotational angle enters the analytical solution for general nonadiabatic tunneling. The certain two-state exponential potential models are employed for numerical tests, and the calculations from the present general nonadiabatic tunneling formula are demonstrated in very good agreement with the results from exact quantum mechanical calculations. The present general nonadiabatic tunneling formula can be incorporated with various mixed quantum-classical methods for modeling electronically nonadiabatic processes in photochemistry.

Theory of high-order harmonic generation for gapless graphene

NASA Astrophysics Data System (ADS)

Zurrón, Óscar; Picón, Antonio; Plaja, Luis

2018-05-01

We study the high-harmonic spectrum emitted by a single-layer graphene, irradiated by an ultrashort intense infrared laser pulse. We show the emergence of the typical non-perturbative spectral features, harmonic plateau and cut-off, for mid-infrared driving fields, at fluences below the damage threshold. In contrast to previous works, using THz drivings, we demonstrate that the harmonic cut-off frequency saturates with the intensity. Our results are derived from the numerical integration of the time-dependent Schrödinger equation using a nearest neighbor tight-binding description of graphene. We also develop a saddle-point analysis that reveals a mechanism for harmonic emission in graphene different from that reported in atoms, molecules and finite gap solids. In graphene, the first step is initiated by the non-diabatic crossing of the valence band electron trajectories through the Dirac points, instead of tunneling ionization/excitation. We include a complete identification of the trajectories contributing to any particular high harmonic and reproduce the harmonic cut-off scaling with the driving intensity.

MS-CASPT2 study of hole transfer in guanine-indole complexes using the generalized Mulliken-Hush method: effective two-state treatment.

PubMed

Butchosa, C; Simon, S; Blancafort, L; Voityuk, A

2012-07-12

Because hole transfer from nucleobases to amino acid residues in DNA-protein complexes can prevent oxidative damage of DNA in living cells, computational modeling of the process is of high interest. We performed MS-CASPT2 calculations of several model structures of π-stacked guanine and indole and derived electron-transfer (ET) parameters for these systems using the generalized Mulliken-Hush (GMH) method. We show that the two-state model commonly applied to treat thermal ET between adjacent donor and acceptor is of limited use for the considered systems because of the small gap between the ground and first excited states in the indole radical cation. The ET parameters obtained within the two-state GMH scheme can deviate significantly from the corresponding matrix elements of the two-state effective Hamiltonian based on the GMH treatment of three adiabatic states. The computed values of diabatic energies and electronic couplings provide benchmarks to assess the performance of less sophisticated computational methods.

The relationship of extratropical outgoing longwave radiation to monthly geopotential teleconnection patterns

NASA Technical Reports Server (NTRS)

Charlock, Thomas P.; Bess, T. Dale; Smith, G. Louis; Rose, Fred G.

1990-01-01

The relationship between low frequency variations in extratropical fields of outgoing longwave radiation (OLR) and geopotential teleconnection patterns as determined by rotated principal components analysis of the NMC 500-mb heights is investigated in the Northern Hemisphere. The monthly broadband OLR is obtained from the Nimbus-6 and Nimbus-7 Wide-Field-Of-View radiometer record. Each of the main 500-mb teleconnection patterns has a characteristic signal in the OLR field for the month in which the 500-mb pattern occurs. The OLR signals mark cloud and diabatic heating events that are associated with the teleconnection patterns. A demonstration is given of correlation between extratropical monthly OLR and geopotential height. Coupled with the expected tropospheric response to radiation on monthly time scale. This demonstration stresses the importance of the radiation simulation in model studies of the low frequency variability of atmospheric circulation. The extratropical OLR does not appear to be a useful predictor for the 500-mb teleconnection patterns on a monthly time scale.

Moisture Budget of the MJO over the Maritime Continent

NASA Astrophysics Data System (ADS)

Kim, J. E.; Zhang, C.; Kiladis, G. N.; Bechtold, P.

2017-12-01

The Maritime Continent (MC) often acts as a barrier for the eastward propagation of the MJO originating from the Indian Ocean (IO). Convective anomalies associated with the MJO tend to weaken over the MC, and MJO convection sometimes fails to pass through the MC. MJO events observed during the DYNAMO field campaign during late 2011 to early 2012 are not an exception in this regard. Modulation of convection for DYNAMO MJOs over the MC is investigated using moisture budget analysis of a reforecast product by the ECMWF Integrated Forecasting System (IFS). Vertical profiles of diabatic drying and heating by physical processes from convection, microphysics, and radiation schemes in IFS under the weak temperature gradient (WTG) environment enable us to estimate vertically resolved processes that control local moistening and drying associated with the MJO. We will compare three-dimensional moisture budgets over the IO and MC to understand which processes contribute to the changes in the MJO propagation and intensity over the MC.

A case study of microphysical structures and hydrometeor phase in convection using radar Doppler spectra at Darwin, Australia

DOE PAGES

Riihimaki, Laura D.; Comstock, J. M.; Luke, E.; ...

2017-07-12

To understand the microphysical processes that impact diabatic heating and cloud lifetimes in convection, we need to characterize the spatial distribution of supercooled liquid water. To address this observational challenge, ground-based vertically pointing active sensors at the Darwin Atmospheric Radiation Measurement site are used to classify cloud phase within a deep convective cloud. The cloud cannot be fully observed by a lidar due to signal attenuation. Therefore, we developed an objective method for identifying hydrometeor classes, including mixed-phase conditions, using k-means clustering on parameters that describe the shape of the Doppler spectra from vertically pointing Ka-band cloud radar. Furthermore, thismore » approach shows that multiple, overlapping mixed-phase layers exist within the cloud, rather than a single region of supercooled liquid. Diffusional growth calculations show that the conditions for the Wegener-Bergeron-Findeisen process exist within one of these mixed-phase microstructures.« less

Dune mobility and aridity at the desert margin of northern China at a time of peak monsoon strength

USGS Publications Warehouse

Mason, J.A.; Lu, H.; Zhou, Y.; Miao, X.; Swinehart, J.B.; Liu, Z.; Goble, R.J.; Yi, S.

2009-01-01

Wind-blown sands were mobile at many sites along the desert margin in northern China during the early Holocene (11.5-8 ka ago), based on extensive new numerical dating. This mobility implies low effective moisture at the desert margin, in contrast to growing evidence for greater than modern monsoon precipitation at the same time in central and southern China. Dry conditions in the early Holocene at the desert margin can be explained through a dynamic link between enhanced diabatic heating in the core region of the strengthened monsoon and increased subsidence in drylands to the north, combined with high evapotranspiration rates due to high summer temperatures. After 8 ka ago, as the monsoon weakened and lower temperatures reduced evapotranspiration, eolian sands were stabilized by vegetation. Aridity and dune mobility at the desert margin and a strengthened monsoon can both be explained as responses to high summer insolation in the early Holocene. ?? 2009 Geological Society of America.

Photo-dynamics of roseoflavin and riboflavin in aqueous and organic solvents

NASA Astrophysics Data System (ADS)

Zirak, P.; Penzkofer, A.; Mathes, T.; Hegemann, P.

2009-03-01

Roseoflavin (8-dimethylamino-8-demethyl- D-riboflavin) and riboflavin in aqueous and organic solvents are studied by optical absorption spectroscopy, fluorescence spectroscopy, and fluorescence decay kinetics. Solvent polarity dependent absorption shifts are observed. The fluorescence quantum yields are solvent dependent. For roseoflavin the fluorescence decay shows a bi-exponential dependence (ps to sub-ps time constant, and 100 ps to a few ns time constant). The roseoflavin photo-dynamics is explained in terms of fast intra-molecular charge transfer (diabatic electron transfer) from the dimethylamino electron donor group to the pteridin carbonyl electron acceptor followed by intra-molecular charge recombination. The fast fluorescence component is due to direct locally-excited-state emission, and the slow fluorescence component is due to delayed locally-excited-state emission and charge transfer state emission. The fluorescence decay of riboflavin is mono-exponential. The S 1-state potential energy surface is determined by vibronic relaxation and solvation dynamics due to excited-state dipole moment changes (adiabatic optical electron transfer).

A case study of microphysical structures and hydrometeor phase in convection using radar Doppler spectra at Darwin, Australia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Riihimaki, Laura D.; Comstock, J. M.; Luke, E.

To understand the microphysical processes that impact diabatic heating and cloud lifetimes in convection, we need to characterize the spatial distribution of supercooled liquid water. To address this observational challenge, ground-based vertically pointing active sensors at the Darwin Atmospheric Radiation Measurement site are used to classify cloud phase within a deep convective cloud. The cloud cannot be fully observed by a lidar due to signal attenuation. Therefore, we developed an objective method for identifying hydrometeor classes, including mixed-phase conditions, using k-means clustering on parameters that describe the shape of the Doppler spectra from vertically pointing Ka-band cloud radar. Furthermore, thismore » approach shows that multiple, overlapping mixed-phase layers exist within the cloud, rather than a single region of supercooled liquid. Diffusional growth calculations show that the conditions for the Wegener-Bergeron-Findeisen process exist within one of these mixed-phase microstructures.« less

Theoretical Studies of Dissociative Recombination of Electrons with SH+ Ions

NASA Astrophysics Data System (ADS)

Kashinski, D. O.; di Nallo, O. E.; Hickman, A. P.; Mezei, J. Zs.; Schneider, I. F.; Talbi, D.

2015-05-01

We are investigating the dissociative recombination (DR) of electrons with the molecular ion SH+. (The process is e- +SH+ --> S + H .) SH+ is found in the interstellar medium (ISM), and little is known concerning its interstellar chemistry. The abundance of SH+ in the ISM suggests that destruction processes, like DR, are inefficient. Understanding the role of DR as a destruction pathway for SH+ will lead to more accurate astrophysical models. Large active-space multi-reference configuration interaction (MRCI) electronic structure calculations were performed to obtain excited-state potential energy curves (PECs) for several values of SH separation. Excited Rydberg states have proven to be of importance. The block diagonalization method was used to disentangle interacting states, forming a diabatic representation of the PECs. Currently we are performing Multichannel Quantum Defect Theory (MQDT) dynamics calculations to obtain DR rates. The status of the work will be presented at the conference. Work supported by the French CNRS, the NSF, the XSEDE, and USMA.

Asian pollution climatically modulates mid-latitude cyclones following hierarchical modelling and observational analysis

NASA Astrophysics Data System (ADS)

Wang, Yuan; Zhang, Renyi; Saravanan, R.

2014-01-01

Increasing levels of anthropogenic aerosols in Asia have raised considerable concern regarding its potential impact on the global atmosphere, but the magnitude of the associated climate forcing remains to be quantified. Here, using a novel hierarchical modelling approach and observational analysis, we demonstrate modulated mid-latitude cyclones by Asian pollution over the past three decades. Regional and seasonal simulations using a cloud-resolving model show that Asian pollution invigorates winter cyclones over the northwest Pacific, increasing precipitation by 7% and net cloud radiative forcing by 1.0 W m-2 at the top of the atmosphere and by 1.7 W m-2 at the Earth’s surface. A global climate model incorporating the diabatic heating anomalies from Asian pollution produces a 9% enhanced transient eddy meridional heat flux and reconciles a decadal variation of mid-latitude cyclones derived from the Reanalysis data. Our results unambiguously reveal a large impact of the Asian pollutant outflows on the global general circulation and climate.

Ozone perturbations by enhanced levels of CFCs, N2O, and CH4 A two-dimensional diabatic circulation study including uncertainty estimates

NASA Technical Reports Server (NTRS)

Isaksen, I. S. A.; Stordal, F.

1986-01-01

Observations made over the last few years suggest that the tropospheric concentrations of N2O, CH4, and O3 are increasing. Increases in the concentration of chlorofluorocarbons (CFCs) have been observed for some time. The present study is concerned with combined scenarios of future releases of N2O, CH4, and CFCs, which can affect the height profiles of ozone, while changes in latitudinal gradients of ozone may also be expected. Ozone perturbation calculations performed in the two-dimensional transport-chemistry model described by Stordal et al. (1985) are also presented, and the effects of increased levels of CFCs, N2O, and CH4 are examined. It is found that CH4 may be the most important ozone-perturbing trace species in connection with future tropospheric climatic impacts. A substantial increase in the tropospheric abundancy of CH4 could lead to large future ozone enhancements throughout the troposphere and lower stratosphere at middle and low latitudes.

Solvable four-state Landau-Zener model of two interacting qubits with path interference

DOE PAGES

Sinitsyn, Nikolai A.

2015-11-30

In this paper, I identify a nontrivial four-state Landau-Zener model for which transition probabilities between any pair of diabatic states can be determined analytically and exactly. The model describes an experimentally accessible system of two interacting qubits, such as a localized state in a Dirac material with both valley and spin degrees of freedom or a singly charged quantum dot (QD) molecule with spin orbit coupling. Application of the linearly time-dependent magnetic field induces a sequence of quantum level crossings with possibility of interference of different trajectories in a semiclassical picture. I argue that this system satisfies the criteria ofmore » integrability in the multistate Landau-Zener theory, which allows one to derive explicit exact analytical expressions for the transition probability matrix. Finally, I also argue that this model is likely a special case of a larger class of solvable systems, and present a six-state generalization as an example.« less

A quasi-biennial oscillation signal in general circulation model simulations.

PubMed

Cariolle, D; Amodei, M; Déqué, M; Mahfouf, J F; Simon, P; Teyssédre, H

1993-09-03

The quasi-biennial oscillation (QBO) is a free atmospheric mode that affects the equatorial lower stratosphere. With a quasi-regular frequency, the mean equatorial zonal wind alternates from easterly to westerly regimes. This oscillation is zonally symmetric about the equator, has its largest amplitude in the latitudinal band from 20 degrees S to 20 degrees N, and has a mean period of about 27 months. The QBO appears to originate in the momentum deposition produced by the damping in the stratosphere of equatorial waves excited by diabatic thermal processes in the troposphere. The results of three 10-year simulations obtained with three general circulation models are reported, all of which show the development in the stratosphere of a QBO signal with a period and a spatial propagating structure that are in good agreement with observations without any ad hoc parameterization of equatorial wave forcing. Although the amplitude of the oscillation in the simulations is still less than the observed value, the result is promising for the development of global climate models.

Momentum and Energy Assessments with NASA and Other Model and Data Assimilation Systems

NASA Technical Reports Server (NTRS)

Salstein, David; Nelson, Peter; Hu, Wen-Jie; Sud, Yogesh (Technical Monitor)

2001-01-01

Aspects of the angular momentum cycle, energetics, and related diagnostics from a number of models, including some from the Goddard Laboratory for Atmospheres, and from the Atmospheric Model Intercomparison Project (AMIP) are examined. Torques that dynamically excite changes in angular momentum, including strong torques at mountains were studied. The measure of how atmospheric mass from a strong weather signal can notably change the angular momentum is studied. For AMIP, there is a spread in the angular momentum amongst models, while the GLA model does reasonably well compared to the other models in the diagnostics examined, namely angular momentum and water vapor. Trends and interannual variability in water vapor over a lengthy period was examined. The role of the diabatic heating components, especially latent heating, in the energy cycle and the terms converting available potential energy to kinetic energy, among other parts of the energy cycle, are studied. Modes of climate of the atmosphere, especially the Arctic and North Atlantic Oscillations, are analyzed as well.

An Assessment of the Ozone Loss During the 1999-2000 SOLVE Arctic Campaign

NASA Technical Reports Server (NTRS)

Schoeberl, Mark R.; Newman, Paul A.; Lait, Leslie R.; McGee, Thomas J.; Burris, John F.; Browell, Edward V.; Grant, William B.; Richard, Eric; VonderGathen, Peter; Bevilacqua, Richard;

Avoided crossings, conical intersections, and low-lying excited states with a single reference method: the restricted active space spin-flip configuration interaction approach.

PubMed

Casanova, David

2012-08-28

The restricted active space spin-flip CI (RASCI-SF) performance is tested in the electronic structure computation of the ground and the lowest electronically excited states in the presence of near-degeneracies. The feasibility of the method is demonstrated by analyzing the avoided crossing between the ionic and neutral singlet states of LiF along the molecular dissociation. The two potential energy surfaces (PESs) are explored by means of the energies of computed adiabatic and approximated diabatic states, dipole moments, and natural orbital electronic occupancies of both states. The RASCI-SF methodology is also used to study the ground and first excited singlet surface crossing involved in the double bond isomerization of ethylene, as a model case. The two-dimensional PESs of the ground (S(0)) and excited (S(1)) states are calculated for the complete configuration space of torsion and pyramidalization molecular distortions. The parameters that define the state energetics in the vicinity of the S(0)/S(1) conical intersection region are compared to complete active space self-consistent field (CASSCF) results. These examples show that it is possible to describe strongly correlated electronic states using a single reference methodology without the need to expand the wavefunction to high levels of collective excitations. Finally, RASCI is also examined in the electronic structure characterization of the ground and 2(1)A(g)(-), 1(1)B(u)(+), 1(1)B(u)(-), and 1(3)B(u)(-) states of all-trans polyenes with two to seven double bonds and beyond. Transition energies are compared to configuration interaction singles, time-dependent density functional theory (TDDFT), CASSCF, and its second-order perturbation correction calculations, and to experimental data. The capability of RASCI-SF to describe the nature and properties of each electronic state is discussed in detail. This example is also used to expose the properties of different truncations of the RASCI wavefunction and to show the possibility to use an excitation operator with any number of α-to-β electronic promotions.

Ab initio quantum direct dynamics simulations of ultrafast photochemistry with Multiconfigurational Ehrenfest approach

NASA Astrophysics Data System (ADS)

Makhov, Dmitry V.; Symonds, Christopher; Fernandez-Alberti, Sebastian; Shalashilin, Dmitrii V.

2017-08-01

The Multiconfigurational Ehrenfest (MCE) method is a quantum dynamics technique which allows treatment of a large number of quantum nuclear degrees of freedom. This paper presents a review of MCE and its recent applications, providing a summary of the formalisms, including its ab initio direct dynamics versions and also giving a summary of recent results. Firstly, we describe the Multiconfigurational Ehrenfest version 2 (MCEv2) method and its applicability to direct dynamics and report new calculations which show that the approach converges to the exact result in model systems with tens of degrees of freedom. Secondly, we review previous ;on the fly; ab initio Multiple Cloning (AIMC-MCE) MCE dynamics results obtained for systems of a similar size, in which the calculations treat every electron and every nucleus of a polyatomic molecule on a fully quantum basis. We also review the Time Dependent Diabatic Basis (TDDB) version of the technique and give an example of its application. We summarise the details of the sampling techniques and interpolations used for calculation of the matrix elements, which make our approach efficient. Future directions of work are outlined.

A quantum dynamics study of the benzopyran ring opening guided by laser pulses

NASA Astrophysics Data System (ADS)

Saab, Mohamad; Doriol, Loïc Joubert; Lasorne, Benjamin; Guérin, Stéphane; Gatti, Fabien

2014-10-01

The ring-opening photoisomerization of benzopyran, which occurs via a photochemical route involving a conical intersection, has been studied with quantum dynamics calculations using the multi-configuration time-dependent Hartree method (MCTDH). We introduce a mechanistic strategy to control the conversion of benzopyran to merocyanine with laser pulses. We use a six-dimensional model developed in a previous work for the potential energy surfaces (PES) based on an extension of the vibronic-coupling Hamiltonian model (diabatization method by ansatz), which depends on the most active degrees of freedom. The main objective of these quantum dynamics simulations is to provide a set of strategies that could help experimentalists to control the photoreactivity vs. photostability ratio (selectivity). In this work we present: (i) a pump-dump technique used to control the photostability, (ii) a two-step strategy to enhance the reactivity of the system: first, a pure vibrational excitation in the electronic ground state that prepares the system and, second, an ultraviolet excitation that brings the system to the first adiabatic electronic state; (iii) finally the effect of a non-resonant pulse (Stark effect) on the dynamics.

The poleward shift of storm tracks under global warming: A Lagrangian perspective

NASA Astrophysics Data System (ADS)

Tamarin, T.; Kaspi, Y.

2017-10-01

Comprehensive models of climate change projections have shown that the latitudinal band of extratropical storms will likely shift poleward under global warming. Here we study this poleward shift from a Lagrangian storm perspective, through simulations with an idealized general circulation model. By employing a feature tracking technique to identify the storms, we demonstrate that the poleward motion of individual cyclones increases with increasing global mean temperature. A potential vorticity tendency analysis of the cyclone composites highlights two leading mechanisms responsible for enhanced poleward motion: nonlinear horizontal advection and diabatic heating associated with latent heat release. Our results imply that for a 4 K rise in the global mean surface temperature, the mean poleward displacement of cyclones increases by about 0.85° of latitude, and this occurs in addition to a poleward shift of about 0.6° in their mean genesis latitude. Changes in cyclone tracks may have a significant impact on midlatitude climate, especially in localized storm tracks such as the Atlantic and Pacific storm tracks, which may exhibit a more poleward deflected shape.

An accurate and linear-scaling method for calculating charge-transfer excitation energies and diabatic couplings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pavanello, Michele; Van Voorhis, Troy; Visscher, Lucas

2013-02-07

Quantum-mechanical methods that are both computationally fast and accurate are not yet available for electronic excitations having charge transfer character. In this work, we present a significant step forward towards this goal for those charge transfer excitations that take place between non-covalently bound molecules. In particular, we present a method that scales linearly with the number of non-covalently bound molecules in the system and is based on a two-pronged approach: The molecular electronic structure of broken-symmetry charge-localized states is obtained with the frozen density embedding formulation of subsystem density-functional theory; subsequently, in a post-SCF calculation, the full-electron Hamiltonian and overlapmore » matrix elements among the charge-localized states are evaluated with an algorithm which takes full advantage of the subsystem DFT density partitioning technique. The method is benchmarked against coupled-cluster calculations and achieves chemical accuracy for the systems considered for intermolecular separations ranging from hydrogen-bond distances to tens of Angstroms. Numerical examples are provided for molecular clusters comprised of up to 56 non-covalently bound molecules.« less

An accurate and linear-scaling method for calculating charge-transfer excitation energies and diabatic couplings.

PubMed

Pavanello, Michele; Van Voorhis, Troy; Visscher, Lucas; Neugebauer, Johannes

2013-02-07

Quantum-mechanical methods that are both computationally fast and accurate are not yet available for electronic excitations having charge transfer character. In this work, we present a significant step forward towards this goal for those charge transfer excitations that take place between non-covalently bound molecules. In particular, we present a method that scales linearly with the number of non-covalently bound molecules in the system and is based on a two-pronged approach: The molecular electronic structure of broken-symmetry charge-localized states is obtained with the frozen density embedding formulation of subsystem density-functional theory; subsequently, in a post-SCF calculation, the full-electron Hamiltonian and overlap matrix elements among the charge-localized states are evaluated with an algorithm which takes full advantage of the subsystem DFT density partitioning technique. The method is benchmarked against coupled-cluster calculations and achieves chemical accuracy for the systems considered for intermolecular separations ranging from hydrogen-bond distances to tens of Ångstroms. Numerical examples are provided for molecular clusters comprised of up to 56 non-covalently bound molecules.

Dependence of Tropical Cyclone Intensification on the Latitude under Vertical Shear

NASA Astrophysics Data System (ADS)

Bi, Mingyu; Ge, Xuyang; Li, Tim

2018-02-01

The sensitivity of tropical cyclone (TC) intensification to the ambient rotation effect under vertical shear is investigated. The results show that the vortices develop more rapidly with intermediate planetary vorticity, which suggests an optimal latitude for the TC development in the presence of vertical shear. This is different from the previous studies in which no mean flow is considered. It is found that the ambient rotation has two main effects. On the one hand, the boundary layer imbalance is largely controlled by the Coriolis parameter. For TCs at lower latitudes, due to the weaker inertial instability, the boundary inflow is promptly established, which results in a stronger moisture convergence and thus greater diabatic heating in the inner core region. On the other hand, the Coriolis parameter modulates the vertical realignment of the vortex with a higher Coriolis parameter, favoring a quicker vertical realignment and thus a greater potential for TC development. The combination of these two effects results in an optimal latitude for TC intensification in the presence of a vertical shear investigated.

Atmosphere and climate studies of Mars using the Mars Observer pressure modulator infrared radiometer

NASA Technical Reports Server (NTRS)

Mccleese, D. J.; Haskins, R. D.; Schofield, J. T.; Zurek, R. W.; Leovy, C. B.; Paige, D. A.; Taylor, F. W.

1992-01-01

Studies of the climate and atmosphere of Mars are limited at present by a lack of meteorological data having systematic global coverage with good horizontal and vertical resolution. The Mars Observer spacecraft in a low, nearly circular, polar orbit will provide an excellent platform for acquiring the data needed to advance significantly our understanding of the Martian atmosphere and its remarkable variability. The Mars Observer pressure modulator infrared radiometer (PMIRR) is a nine-channel limb and nadir scanning atmospheric sounder which will observe the atmosphere of Mars globally from 0 to 80 km for a full Martian year. PMIRR employs narrow-band radiometric channels and two pressure modulation cells to measure atmospheric and surface emission in the thermal infrared. PMIRR infrared and visible measurements will be combined to determine the radiative balance of the polar regions, where a sizeable fraction of the global atmospheric mass annually condenses onto and sublimes from the surface. Derived meteorological fields, including diabatic heating and cooling and the vertical variation of horizontal winds, are computed from the globally mapped fields retrieved from PMIRR data.

Observational-numerical Study of Maritime Extratropical Cyclones Using FGGE Data

NASA Technical Reports Server (NTRS)

Wash, C. H.; Elsberry, R. L.

1984-01-01

The accomplishments, current research, and future plans of a study investigating the development, maturation, and decay of maritime extratropical cyclones are reported. Three cases of explosive cyclogenesis during the first GARP global experiment (FGGE) DOP-1 were studied diagnostically using storm-following budgets derived from the ECMWF and GLAS level III-b analyses. Mass, vorticity and angular momentum budgets for the moving storm environment were computed for each case. Key results from these studies include: (1) demonstration that the FGGE analyses can be used to explore oceanic circulations; (2) isolation of the role of upper level jet streaks in the initiation of the explosive period in all three cases; and (3) illustration of the lower tropospheric destabilization during each rapid deepening period, which is primarily due to sensible heating of the cold air by the warmer ocean surface. The physics package of the Navy global forecast model was successfully utilized in a semi-prognostic mode to estimate diabatic components of oceanic cyclone systems. Fields of sensible and latent heat fluxes, radiational heating and inferred cloud structures were also computed.

Distant Influence of Kuroshio Eddies on North Pacific Weather Patterns?

PubMed

Ma, Xiaohui; Chang, Ping; Saravanan, R; Montuoro, Raffaele; Hsieh, Jen-Shan; Wu, Dexing; Lin, Xiaopei; Wu, Lixin; Jing, Zhao

2015-12-04

High-resolution satellite measurements of surface winds and sea-surface temperature (SST) reveal strong coupling between meso-scale ocean eddies and near-surface atmospheric flow over eddy-rich oceanic regions, such as the Kuroshio and Gulf Stream, highlighting the importance of meso-scale oceanic features in forcing the atmospheric planetary boundary layer (PBL). Here, we present high-resolution regional climate modeling results, supported by observational analyses, demonstrating that meso-scale SST variability, largely confined in the Kuroshio-Oyashio confluence region (KOCR), can further exert a significant distant influence on winter rainfall variability along the U.S. Northern Pacific coast. The presence of meso-scale SST anomalies enhances the diabatic conversion of latent heat energy to transient eddy energy, intensifying winter cyclogenesis via moist baroclinic instability, which in turn leads to an equivalent barotropic downstream anticyclone anomaly with reduced rainfall. The finding points to the potential of improving forecasts of extratropical winter cyclones and storm systems and projections of their response to future climate change, which are known to have major social and economic impacts, by improving the representation of ocean eddy-atmosphere interaction in forecast and climate models.

Dependence of tropical cyclone development on coriolis parameter: A theoretical model

NASA Astrophysics Data System (ADS)

Deng, Liyuan; Li, Tim; Bi, Mingyu; Liu, Jia; Peng, Melinda

2018-03-01

A simple theoretical model was formulated to investigate how tropical cyclone (TC) intensification depends on the Coriolis parameter. The theoretical framework includes a two-layer free atmosphere and an Ekman boundary layer at the bottom. The linkage between the free atmosphere and the boundary layer is through the Ekman pumping vertical velocity in proportion to the vorticity at the top of the boundary layer. The closure of this linear system assumes a simple relationship between the free atmosphere diabatic heating and the boundary layer moisture convergence. Under a set of realistic atmospheric parameter values, the model suggests that the most preferred latitude for TC development is around 5° without considering other factors. The theoretical result is confirmed by high-resolution WRF model simulations in a zero-mean flow and a constant SST environment on an f -plane with different Coriolis parameters. Given an initially balanced weak vortex, the TC-like vortex intensifies most rapidly at the reference latitude of 5°. Thus, the WRF model simulations confirm the f-dependent characteristics of TC intensification rate as suggested by the theoretical model.

Scattering matrix approach to the dissociative recombination of HCO{sup +} and N{sub 2}H{sup +}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fonseca dos Santos, S.; Douguet, N.; Orel, A. E.

We present a theoretical study of the indirect dissociative recombination of linear polyatomic ions at low collisional energies. The approach is based on the computation of the scattering matrix just above the ionization threshold and enables the explicit determination of all diabatic electronic couplings responsible for dissociative recombination. In addition, we use the multi-channel quantum-defect theory to demonstrate the precision of the scattering matrix by reproducing accurately ab initio Rydberg state energies of the neutral molecule. We consider the molecular ions N{sub 2}H{sup +} and HCO{sup +} as benchmark systems of astrophysical interest and improve former theoretical studies, which hadmore » repeatedly produced smaller cross sections than experimentally measured. Specifically, we demonstrate the crucial role of the previously overlooked stretching modes for linear polyatomic ions with large permanent dipole moment. The theoretical cross sections for both ions agree well with experimental data over a wide energy range. Finally, we consider the potential role of the HOC{sup +} isomer in the experimental cross sections of HCO{sup +} at energies below 10 meV.« less

Multilevel perspective on high-order harmonic generation in solids

NASA Astrophysics Data System (ADS)

Wu, Mengxi; Browne, Dana A.; Schafer, Kenneth J.; Gaarde, Mette B.

2016-12-01

We investigate high-order harmonic generation in a solid, modeled as a multilevel system dressed by a strong infrared laser field. We show that the cutoff energies and the relative strengths of the multiple plateaus that emerge in the harmonic spectrum can be understood both qualitatively and quantitatively by considering a combination of adiabatic and diabatic processes driven by the strong field. Such a model was recently used to interpret the multiple plateaus exhibited in harmonic spectra generated by solid argon and krypton [G. Ndabashimiye et al., Nature 534, 520 (2016), 10.1038/nature17660]. We also show that when the multilevel system originates from the Bloch state at the Γ point of the band structure, the laser-dressed states are equivalent to the Houston states [J. B. Krieger and G. J. Iafrate, Phys. Rev. B 33, 5494 (1986), 10.1103/PhysRevB.33.5494] and will therefore map out the band structure away from the Γ point as the laser field increases. This leads to a semiclassical three-step picture in momentum space that describes the high-order harmonic generation process in a solid.

Technical Report Series on Global Modeling and Data Assimilation. Volume 7: Proceedings of the Workshop on the GEOS-1 Five-year Assimilation

NASA Technical Reports Server (NTRS)

Suarez, Max J. (Editor); Schubert, Siegfried; Rood, Richard

1995-01-01

The primary objective of the three-day workshop on results from the Data Assimilation Office (DAO) five-year assimilation was to provide timely feedback from the data users concerning the strengths and weaknesses of version 1 of the Goddard Earth Observing System (GEOS-1) assimilated products. A second objective was to assess user satisfaction with the current methods of data access and retrieval. There were a total of 49 presentations, with about half (23) of the presentations from scientists from outside of Goddard. The first two days were devoted to applications of data: studies of the energy diagnostics, precipitation and diabatic heating, hydrological modeling and moisture transport, cloud forcing and validation, various aspects of intraseasonal, seasonal, and interannual variability, ocean wind stress applications, and validation of surface fluxes. The last day included talks from the National Meteorological Center (NMC), the National Center for Atmospheric Research (NCAR), the Center for Ocean-Land-Atmosphere Studies (COLA), the United States Navy, and the European Center for Medium Range Weather Forecasts (ECMWF).

Impact of variations of gravitational acceleration on the general circulation of the planetary atmosphere

NASA Astrophysics Data System (ADS)

Kilic, Cevahir; Raible, Christoph C.; Stocker, Thomas F.; Kirk, Edilbert

2017-01-01

Fundamental to the redistribution of energy in a planetary atmosphere is the general circulation and its meridional structure. We use a general circulation model of the atmosphere in an aquaplanet configuration with prescribed sea surface temperature and investigate the influence of the gravitational acceleration g on the structure of the circulation. For g =g0 = 9.81 ms-2 , three meridional cells exist in each hemisphere. Up to about g /g0 = 1.4 all cells increase in strength. Further increasing this ratio results in a weakening of the thermally indirect cell, such that a two- and finally a one-cell structure of the meridional circulation develops in each hemisphere. This transition is explained by the primary driver of the thermally direct Hadley cell: the diabatic heating at the equator which is proportional to g. The analysis of the energetics of the atmospheric circulation based on the Lorenz energy cycle supports this finding. For Earth-like gravitational accelerations transient eddies are primarily responsible for the meridional heat flux. For large gravitational accelerations, the direct zonal mean conversion of energy dominates the meridional heat flux.

Stationary Waves of the Ice Age Climate.

NASA Astrophysics Data System (ADS)

Cook, Kerry H.; Held, Isaac M.

1988-08-01

A linearized, steady state, primitive equation model is used to simulate the climatological zonal asymmetries (stationary eddies) in the wind and temperature fields of the 18 000 YBP climate during winter. We compare these results with the eddies simulated in the ice age experiments of Broccoli and Manabe, who used CLIMAP boundary conditions and reduced atmospheric CO2 in an atmospheric general circulation model (GCM) coupled with a static mixed layer ocean model. The agreement between the models is good, indicating that the linear model can be used to evaluate the relative influences of orography, diabatic heating, and transient eddy heat and momentum transports in generating stationary waves. We find that orographic forcing dominates in the ice age climate. The mechanical influence of the continental ice sheets on the atmosphere is responsible for most of the changes between the present day and ice age stationary eddies. This concept of the ice age climate is complicated by the sensitivity of the stationary eddies to the large increase in the magnitude of the zonal mean meridional temperature gradient simulated in the ice age GCM.

Experimental and Coupled-channels Investigation of the Radiative Properties of the N2 c4 (sup 1)Sigma+(sub u) - X (sup 1)Sigma+(sub g) Band System

NASA Technical Reports Server (NTRS)

Liu, Xianming; Shemansky, Donald E.; Malone, Charles P.; Johnson, Paul V.; Ajello, Joseph M.; Kanik, Isik; Heays, Alan N.; Lewis, Brenton R.; Gibson, Stephen T.; Stark, Glenn

2008-01-01

The emission properties of the N2 c(sup prime)(sub 4) (sup 1)Sigma+(sub u) - Chi (sup 1)Sigma+(sub g) band system have been investigated in a joint experimental and coupled-channels theoretical study. Relative intensities of the c(sup prime)(sub 4) (sup 1)Sigma+(sub u)(0) - Chi (sup 1)Sigma+(sub g)(v(sub i)) transitions, measured via electron-impact-induced emission spectroscopy, are combined with a coupled-channel Schroedinger equation (CSE) model of the N2 molecule, enabling determination of the diabatic electronic transition moment for the c(sup prime)(sub 4) (sup 1)Sigma+(sub u) - Chi (sup 1)Sigma+(sub g) system as a function of internuclear distance. The CSE probabilities are further verified by comparison with a high-resolution experimental spectrum. Spontaneous transition probabilities of the c(sup prime)(sub 4) (sup 1)Sigma+(sub u) - Chi (sup 1)Sigma+(sub g) modeling atmospheric emission, can now be calculated reliably.

An investigation of the Sutcliffe development theory

NASA Technical Reports Server (NTRS)

Dushan, J. D.

1973-01-01

Two case studies were used to test the Sutcliffe-Peterssen development theory for both cyclonic and anticyclonic development over the eastern United States. Each term was examined to determine when and where it made a significant contribution to the development process. Results indicate the advection of vorticity at the level of non-divergence exerts the dominant influence for initial cyclone development, and that the thermal terms (advection of thickness, stability, and diabatic influence) become important after development has begun. Anticyclonic development, however, depends primarily on the stability term throughout the life cycle of the anticyclone. Simple procedures for forecasting the development and movement of cyclones and anticyclones are listed. These rules indicate that routine National Meteorological Center analyses may be used to locate areas where the positive advection of 500-mb vorticity, indicative of cyclonic development, coincides with regions of severe weather activity. The development of anticyclones also is predicted easily. Regions of increasing stability, indicating anticyclonic development, may be located by use of National Meteorological Center radar summaries and analyses for 1000-500-mb thickness. A test of these techniques found them to be satisfactory for the case examined.

Molecular description of steady supersonic free jets

NASA Astrophysics Data System (ADS)

Montero, S.

2017-09-01

A detailed analysis of the non-local thermal equilibrium (n-LTE) problem in the paraxial zone of silence of supersonic free jets is reported. The study is based on a hybrid approach that combines Navier-Stokes equations with a kinetic equation derived from the generalized Boltzmann (Waldmann-Snider) equation. The resulting system is solved for those flow quantities not easily amenable to experimental measure (translational temperature, flow velocity, and entropy) in terms of the quantities that can be measured accurately (distance, number density, population of rotational states, and their gradients). The reported solutions are essentially exact and are formulated in terms of macroscopic quantities, as well as in terms of elementary collision processes. Emphasis is made on the influence of dissipative effects onto the flow (viscous and diabatic) and of the breakdown of thermal equilibrium onto the evolution of entropy and translational temperature. The influence of inelastic collisions onto these effects is analysed in depth. The reported equations are aimed at optimizing the experimental knowledge of the n-LTE problem and its quantitative interpretation in terms of state-to-state rates for inelastic collisions.

The Thermal Structure, Dust Loading, and Meridional Transport in the Martian Atmosphere during Late Southern Summer.

NASA Astrophysics Data System (ADS)

Santee, Michelle

The thermal structure, dust loading, and meridional transport in the Martian atmosphere are investigated using thermal emission spectra recorded by the Mariner 9 infrared interferometer spectrometer (IRIS). The analysis is restricted to a subset of the IRIS data consisting of approximately 2400 spectra spanning L_{S} = 343^circ-348^ circ, corresponding to late southern summer on Mars. Simultaneous retrieval of the vertical distribution of both atmospheric temperature and dust optical depth is accomplished through an iterative procedure which is performed on each spectrum. Although atmospheric temperatures decrease from equator to pole at lower altitudes, both dayside and nightside temperatures above about 0.1 mbar (~40 km) are warmer over the winter (north) polar region than over the equator or the summer (south) polar region. Zonal-mean zonal winds are derived from the atmospheric temperatures assuming gradient wind balance and zero surface zonal wind. Both hemispheres have intense mid-latitude westerly jets (with velocities of 80-90 m/s near 50 km); in the southern tropics the winds are strongly easterly (with velocities of 100 m/s near 50 km). A comprehensive radiative transfer model (Crisp, 1990) is used to compute solar heating and thermal cooling rates from the retrieved IRIS temperature and dust distributions. There are large net heating rates (up to 8 K/day) in the equatorial region and large net cooling rates (up to 20 K/day) in the polar regions. These net heating rates are used in a diagnostic stream function model which solves for the meridional and vertical components of the diabatic circulation simultaneously. The results show a vigorous two-cell circulation, with rising motion over the equatorial region ( ~1.5 cm/s), poleward flow in both hemispheres (~2 m/s), sinking motion over both polar regions (1-2 cm/s), and return flow in the lowest atmospheric levels. The meridional transport time scale is ~13 days. Water vapor desorbed from the low-latitude regolith during late northern winter/early northern spring may be transported upward by the ascending branch of this circulation, where it may be advected back to the polar regions by the high-altitude meridional winds. This process could provide a high-altitude source of water vapor for the formation and maintenance of the north polar hood.

Tropical Atlantic-Korea teleconnection pattern during boreal summer season

NASA Astrophysics Data System (ADS)

Ham, Yoo-Geun; Chikamoto, Yoshimitsu; Kug, Jong-Seong; Kimoto, Masahide; Mochizuki, Takashi

2017-10-01

The remote impact of tropical Atlantic sea surface temperature (SST) variability on Korean summer precipitation is examined based on observational data analysis along with the idealized and hindcast model experiments. Observations show a significant correlation (i.e. 0.64) between Korean precipitation anomalies (averaged over 120-130°E, 35-40°N) and the tropical Atlantic SST index (averaged over 60°W-20°E, 30°S-30°N) during the June-July-August (JJA) season for the 1979-2010 period. Our observational analysis and partial-data assimilation experiments using the coupled general circulation model demonstrate that tropical Atlantic SST warming induces the equatorial low-level easterly over the western Pacific through a reorganization of the global Walker Circulation, causing a decreased precipitation over the off-equatorial western Pacific. As a Gill-type response to this diabatic forcing, an anomalous low-level anticyclonic circulation appears over the Philippine Sea, which transports wet air from the tropics to East Asia through low-level southerly, resulting an enhanced precipitation in the Korean peninsula. Multi-model hindcast experiments also show that predictive skills of Korean summer precipitation are improved by utilizing predictions of tropical Atlantic SST anomalies as a predictor for Korean precipitation anomalies.

Signatures of a conical intersection in photofragment distributions and absorption spectra: Photodissociation in the Hartley band of ozone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Picconi, David; Grebenshchikov, Sergy Yu., E-mail: Sergy.Grebenshchikov@ch.tum.de

Photodissociation of ozone in the near UV is studied quantum mechanically in two excited electronic states coupled at a conical intersection located outside the Franck-Condon zone. The calculations, performed using recent ab initio PESs, provide an accurate description of the photodissociation dynamics across the Hartley/Huggins absorption bands. The observed photofragment distributions are reproduced in the two electronic dissociation channels. The room temperature absorption spectrum, constructed as a Boltzmann average of many absorption spectra of rotationally excited parent ozone, agrees with experiment in terms of widths and intensities of diffuse structures. The exit channel conical intersection contributes to the coherent broadeningmore » of the absorption spectrum and directly affects the product vibrational and translational distributions. The photon energy dependences of these distributions are strikingly different for fragments created along the adiabatic and the diabatic paths through the intersection. They can be used to reverse engineer the most probable geometry of the non-adiabatic transition. The angular distributions, quantified in terms of the anisotropy parameter β, are substantially different in the two channels due to a strong anticorrelation between β and the rotational angular momentum of the fragment O{sub 2}.« less

Combinatorial invariants and covariants as tools for conical intersections.

PubMed

Ryb, Itai; Baer, Roi

2004-12-01

The combinatorial invariant and covariant are introduced as practical tools for analysis of conical intersections in molecules. The combinatorial invariant is a quantity depending on adiabatic electronic states taken at discrete nuclear configuration points. It is invariant to the phase choice (gauge) of these states. In the limit that the points trace a loop in nuclear configuration space, the value of the invariant approaches the corresponding Berry phase factor. The Berry phase indicates the presence of an odd or even number of conical intersections on surfaces bounded by these loops. Based on the combinatorial invariant, we develop a computationally simple and efficient method for locating conical intersections. The method is robust due to its use of gauge invariant nature. It does not rely on the landscape of intersecting potential energy surfaces nor does it require the computation of nonadiabatic couplings. We generalize the concept to open paths and combinatorial covariants for higher dimensions obtaining a technique for the construction of the gauge-covariant adiabatic-diabatic transformation matrix. This too does not make use of nonadiabatic couplings. The importance of using gauge-covariant expressions is underlined throughout. These techniques can be readily implemented by standard quantum chemistry codes. (c) 2004 American Institute of Physics.

Global warming and South Indian monsoon rainfall-lessons from the Mid-Miocene.

PubMed

Reuter, Markus; Kern, Andrea K; Harzhauser, Mathias; Kroh, Andreas; Piller, Werner E

2013-04-01

Precipitation over India is driven by the Indian monsoon. Although changes in this atmospheric circulation are caused by the differential seasonal diabatic heating of Asia and the Indo-Pacific Ocean, it is so far unknown how global warming influences the monsoon rainfalls regionally. Herein, we present a Miocene pollen flora as the first direct proxy for monsoon over southern India during the Middle Miocene Climate Optimum. To identify climatic key parameters, such as mean annual temperature, warmest month temperature, coldest month temperature, mean annual precipitation, mean precipitation during the driest month, mean precipitation during the wettest month and mean precipitation during the warmest month the Coexistence Approach is applied. Irrespective of a ~ 3-4 °C higher global temperature during the Middle Miocene Climate Optimum, the results indicate a modern-like monsoonal precipitation pattern contrasting marine proxies which point to a strong decline of Indian monsoon in the Himalaya at this time. Therefore, the strength of monsoon rainfall in tropical India appears neither to be related to global warming nor to be linked with the atmospheric conditions over the Tibetan Plateau. For the future it implies that increased global warming does not necessarily entail changes in the South Indian monsoon rainfall.

Retrieved Latent Heating from TRMM

NASA Technical Reports Server (NTRS)

Tao, Wei-Kuo; Smith, Eric A.; Houze Jr, Robert

2008-01-01

The global hydrological cycle is central to the Earth's climate system, with rainfall and the physics of precipitation formation acting as the key links in the cycle. Two-thirds of global rainfall occurs in the tropics with the associated latent heating (LH) accounting for three-fourths of the total heat energy available to the Earth's atmosphere. In addition, fresh water provided by tropical rainfall and its variability exerts a large impact upon the structure and motions of the upper ocean layer. In the last decade, it has been established that standard products of LH from satellite measurements, particularly TRMM measurements, would be a valuable resource for scientific research and applications. Such products would enable new insights and investigations concerning the complexities of convection system life cycles, the diabatic heating controls and feedbacks related to meso-synoptic circulations and their forecasting, the relationship of tropical patterns of LH to the global circulation and climate, and strategies for improving cloud parameterizations in environmental prediction models. The status of retrieved TRMM LH products, TRMM LH inter-comparison and validation project, current TRMM LH applications and critic issues/action items (based on previous five TRMM LH workshops) is presented in this article.

Effect of proton transfer on the electronic coupling in DNA

NASA Astrophysics Data System (ADS)

Rak, Janusz; Makowska, Joanna; Voityuk, Alexander A.

2006-06-01

The effects of single and double proton transfer within Watson-Crick base pairs on donor-acceptor electronic couplings, Vda, in DNA are studied on the bases of quantum chemical calculations. Four dimers [AT,AT], [GC,GC], [GC,AT] and [GC,TA)] are considered. Three techniques - the generalized Mulliken-Hush scheme, the fragment charge method and the diabatic states method - are employed to estimate Vda for hole transfer between base pairs. We show that both single- and double proton transfer (PT) reactions may substantially affect the electronic coupling in DNA. The electronic coupling in [AT,AT] is predicted to be most sensitive to PT. Single PT within the first base pair in the dimer leads to increase in the hole transfer efficiency by a factor of 4, while proton transfer within the second pair should substantially, by 2.7 times, decrease the rate of charge transfer. Thus, directional asymmetry of the PT effects on the electronic coupling is predicted. The changes in the Vda matrix elements correlate with the topological properties of orbitals of donor and acceptor and can be qualitatively rationalized in terms of resonance structures of donor and acceptor. Atomic pair contributions to the Vda matrix elements are also analyzed.

Distant Influence of Kuroshio Eddies on North Pacific Weather Patterns?

PubMed Central

Ma, Xiaohui; Chang, Ping; Saravanan, R.; Montuoro, Raffaele; Hsieh, Jen-Shan; Wu, Dexing; Lin, Xiaopei; Wu, Lixin; Jing, Zhao

2015-01-01

High-resolution satellite measurements of surface winds and sea-surface temperature (SST) reveal strong coupling between meso-scale ocean eddies and near-surface atmospheric flow over eddy-rich oceanic regions, such as the Kuroshio and Gulf Stream, highlighting the importance of meso-scale oceanic features in forcing the atmospheric planetary boundary layer (PBL). Here, we present high-resolution regional climate modeling results, supported by observational analyses, demonstrating that meso-scale SST variability, largely confined in the Kuroshio-Oyashio confluence region (KOCR), can further exert a significant distant influence on winter rainfall variability along the U.S. Northern Pacific coast. The presence of meso-scale SST anomalies enhances the diabatic conversion of latent heat energy to transient eddy energy, intensifying winter cyclogenesis via moist baroclinic instability, which in turn leads to an equivalent barotropic downstream anticyclone anomaly with reduced rainfall. The finding points to the potential of improving forecasts of extratropical winter cyclones and storm systems and projections of their response to future climate change, which are known to have major social and economic impacts, by improving the representation of ocean eddy–atmosphere interaction in forecast and climate models. PMID:26635077

Underlying theory of a model for the Renner-Teller effect in tetra-atomic molecules: X(2)Πu electronic state of C2H2(+).

PubMed

Perić, M; Jerosimić, S; Mitić, M; Milovanović, M; Ranković, R

2015-05-07

In the present study, we prove the plausibility of a simple model for the Renner-Teller effect in tetra-atomic molecules with linear equilibrium geometry by ab initio calculations of the electronic energy surfaces and non-adiabatic matrix elements for the X(2)Πu state of C2H2 (+). This phenomenon is considered as a combination of the usual Renner-Teller effect, appearing in triatomic species, and a kind of the Jahn-Teller effect, similar to the original one arising in highly symmetric molecules. Only four parameters (plus the spin-orbit constant, if the spin effects are taken into account), which can be extracted from ab initio calculations carried out at five appropriate (planar) molecular geometries, are sufficient for building up the Hamiltonian matrix whose diagonalization results in the complete low-energy (bending) vibronic spectrum. The main result of the present study is the proof that the diabatization scheme, hidden beneath the apparent simplicity of the model, can safely be carried out, at small-amplitude bending vibrations, without cumbersome computation of non-adiabatic matrix elements at large number of molecular geometries.

El Nino's Family Tree (Invited)

NASA Astrophysics Data System (ADS)

Philander, S. G.

2013-12-01

Fluctuations in tropical Pacific rainfall and sea surface temperature (SST) patterns involve different processes on different timescales, but nonetheless have certain features (traits) in common so that all can be viewed as members of the same family. Best-known are the children El Niño and La Niña who, in their performance of the Southern Oscillation, move warm surface waters adiabatically back and forth across the Pacific. They and their nephews and nieces in the Atlantic and Indian Ocean all depend on favorable background conditions, especially a suitable depth for the thermocline whose tilt they oscillate to produce SST changes. The parents El Padre and La Madre are in control of that depth and invoke diabatic processes to change it gradually over the course of decades, at times making it so deep that El Niño becomes permanent. This is the spontaneous, natural branch of the family. Another branch responds to external forcing (externally imposed variations in sunlight) and has as members the cycles of the seasons, of obliquity, and of the precession of the equinoxes. These cousins, aunts and uncles of El Niño are protagonists in the drama of the recurrent Ice Ages.

Stability of Electrons in the Virtual Cathode Region of an IEC

NASA Astrophysics Data System (ADS)

Kim, Hyng-Jin; Miley, George; Momota, Hiromu

2003-04-01

In the Inertial Electrostatic Confinement (IEC) device, electrons are confined inside a virtual anode that in turn confines ions. Prior stability studies [1, 2] have considered systems in which one species is electrostatically confined by the other, and either or both species are out of local thermal equilibrium. In the present research, electron stability in the virtual cathode region of an ion injected IEC is being studied. The ion density in an IEC is non-uniform due to the radial electrostatic potential, and increases toward the center region. The potential near the virtual cathode is assumed to have a parabolic shape and is determined assuming that the net space charge density is constant in that region. The corresponding ion distribution function is assumed to have the form f = C [sigma] (H W) /L^0.5 and the electron response is taken to be diabatic. Then using a variational principle after linearizing the hydrodynamic equations, stability properties of the electron layer are determined. Results will be presented as a function of injected ion/electron current ratios. 1. L. Chacon and D. C. Barnes, Phys. Plasma 7, 4774 (2000). 2. D. C. Barnes, L. Chacon, and J. M. Finn, Phys. Plasmas 9, 4448 (2002).

Surface hopping with a manifold of electronic states. II. Application to the many-body Anderson-Holstein model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dou, Wenjie; Subotnik, Joseph E.; Nitzan, Abraham

We investigate a simple surface hopping (SH) approach for modeling a single impurity level coupled to a single phonon and an electronic (metal) bath (i.e., the Anderson-Holstein model). The phonon degree of freedom is treated classically with motion along–and hops between–diabatic potential energy surfaces. The hopping rate is determined by the dynamics of the electronic bath (which are treated implicitly). For the case of one electronic bath, in the limit of small coupling to the bath, SH recovers phonon relaxation to thermal equilibrium and yields the correct impurity electron population (as compared with numerical renormalization group). For the case ofmore » out of equilibrium dynamics, SH current-voltage (I-V) curve is compared with the quantum master equation (QME) over a range of parameters, spanning the quantum region to the classical region. In the limit of large temperature, SH and QME agree. Furthermore, we can show that, in the limit of low temperature, the QME agrees with real-time path integral calculations. As such, the simple procedure described here should be useful in many other contexts.« less

On the role of surface friction in tropical cyclone intensification

NASA Astrophysics Data System (ADS)

Wang, Yuqing

2017-04-01

Recent studies have debated on whether surface friction is positive or negative to tropical cyclone intensification in the view on angular momentum budget. That means whether the frictionally induced inward angular momentum transport can overcome the loss of angular momentum to the surface due to surface friction itself. Although this issue is still under debate, this study investigates another implicit dynamical effect, which modifies the radial location and strength of eyewall convection. We found that moderate surface friction is necessary for rapid intensity of tropical cyclones. This is demonstrated first by a simple coupled dynamical system that couples a multi-level boundary layer model and a shallow water equation model above with mass source parameterized by mass flux from the boundary layer model below, and then by a full physics model. The results show that surface friction leads to the inward penetration of inflow under the eyewall, shift the boundary layer mass convergence slightly inside the radius of maximum wind, and enhance the upward mass flux, and thus diabatic heating in the eyewall and intensification rate of a TC. This intensification process is different from the direct angular momentum budget previously used to explain the role of surface friction in tropical cyclone intensification.

Gas-liquid Phase Distribution and Void Fraction Measurements Using the MRI

NASA Technical Reports Server (NTRS)

Daidzic, N. E.; Schmidt, E.; Hasan, M. M.; Altobelli, S.

2004-01-01

We used a permanent-magnet MRI system to estimate the integral and spatially- and/or temporally-resolved void-fraction distributions and flow patterns in gas-liquid two-phase flows. Air was introduced at the bottom of the stagnant liquid column using an accurate and programmable syringe pump. Air flow rates were varied between 1 and 200 ml/min. The cylindrical non-conducting test tube in which two-phase flow was measured was placed in a 2.67 kGauss MRI with MRT spectrometer/imager. Roughly linear relationship has been obtained for the integral void-fraction, obtained by volume-averaging of the spatially-resolved signals, and the air flow rate in upward direction. The time-averaged spatially-resolved void fraction has also been obtained for the quasi-steady flow of air in a stagnant liquid column. No great accuracy is claimed as this was an exploratory proof-of-concept type of experiment. Preliminary results show that MRI a non-invasive and non-intrusive experimental technique can indeed provide a wealth of different qualitative and quantitative data and is especially well suited for averaged transport processes in adiabatic and diabatic multi-phase and/or multi-component flows.

The pure rotational spectrum of ZnS (X 1Σ +)

NASA Astrophysics Data System (ADS)

Zack, L. N.; Ziurys, L. M.

2009-10-01

The pure rotational spectrum of ZnS (X 1Σ +) has been measured using direct-absorption millimeter/sub-millimeter techniques in the frequency range 372-471 GHz. This study is the first spectroscopic investigation of this molecule. Spectra originating in four zinc isotopologues ( 64ZnS, 66ZnS, 68ZnS, and 67ZnS) were recorded in natural abundance in the ground vibrational state, and data from the v = 1 state were also measured for the two most abundant zinc species. Spectroscopic constants have been subsequently determined, and equilibrium parameters have been estimated. The equilibrium bond length was calculated to be re ˜ 2.0464 Å, which agrees well with theoretical predictions. In contrast, the dissociation energy of DE ˜ 3.12 eV calculated for ZnS, assuming a Morse potential, was significantly higher than past experimental and theoretical estimates, suggesting diabatic interaction with other potentials that lower the effective dissociation energy. Although ZnS is isovalent with ZnO, there appear to be subtle differences in bonding between the two species, as suggested by their respective force constants and bond length trends in the 3d series.

Effects of Greenhouse Gas Increase and Stratospheric Ozone Depletion on Stratospheric Mean Age of Air in 1960-2010

NASA Technical Reports Server (NTRS)

Li, Feng; Newman, Paul; Pawson, Steven; Perlwitz, Judith

2018-01-01

The relative impacts of greenhouse gas (GHG) increase and stratospheric ozone depletion on stratospheric mean age of air in the 1960-2010 period are quantified using the Goddard Earth Observing System Chemistry-�Climate Model. The experiment compares controlled simulations using a coupled atmosphere-�ocean version of the Goddard Earth Observing System Chemistry-�Climate Model, in which either GHGs or ozone depleting substances, or both factors evolve over time. The model results show that GHGs and ozone-depleting substances have about equal contributions to the simulated mean age decrease, but GHG increases account for about two thirds of the enhanced strength of the lower stratospheric residual circulation. It is also found that both the acceleration of the diabatic circulation and the decrease of the mean age difference between downwelling and upwelling regions are mainly caused by GHG forcing. The results show that ozone depletion causes an increase in the mean age of air in the Antarctic summer lower stratosphere through two processes: (1) a seasonal delay in the Antarctic polar vortex breakup that inhibits young midlatitude air from mixing with the older air inside the vortex, and (2) enhanced Antarctic downwelling that brings older air from middle and upper stratosphere into the lower stratosphere.

Recent climate extremes associated with the West Pacific Warming Mode

USGS Publications Warehouse

Funk, Chris; Hoell, Andrew

2017-01-01

Here we analyze empirical orthogonal functions (EOFs) of observations and a 30 member ensemble of Community Earth System Model version 1 (CESM1) simulations, and suggest that precipitation declines in the Greater Horn of Africa (GHA) and the northern Middle East/Southwestern Asia (NME/SWE: Iran, Iraq, Kuwait, Syria, Saudi Arabia north of 25°N, Israel, Jordan, and Lebanon) may be interpreted as an interaction between La Niña-like decadal variability and the West Pacific Warming Mode (WPWM). While they exhibit different SST patterns, warming of the Pacific cold tongue (ENSO) and warming of the western Pacific (WPWM) produce similar warm pool diabatic forcing, Walker circulation anomalies, and terrestrial teleconnections. CESM1 SST EOFs indicate that both La Niña-like WPWM warming and El Niño-like east Pacific warming will be produced by climate change. The temporal frequency of these changes, however, are distinct. WPWM varies decadally, while ENSO is dominated by interannual variability. Future WPWM and ENSO warming may manifest as a tendency toward warm West Pacific SST, punctuated by extreme warm East Pacific events. WPWM EOFs from Global Precipitation Climatology Project (GPCP) precipitation also identify dramatic WPWM-related declines in the Greater Horn of Africa and NME/SWE.

Simulation of solution phase electron transfer in a compact donor-acceptor dyad.

PubMed

Kowalczyk, Tim; Wang, Lee-Ping; Van Voorhis, Troy

2011-10-27

Charge separation (CS) and charge recombination (CR) rates in photosynthetic architectures are difficult to control, yet their ratio can make or break photon-to-current conversion efficiencies. A rational design approach to the enhancement of CS over CR requires a mechanistic understanding of the underlying electron-transfer (ET) process, including the role of the environment. Toward this goal, we introduce a QM/MM protocol for ET simulations and use it to characterize CR in the formanilide-anthraquinone dyad (FAAQ). Our simulations predict fast recombination of the charge-transfer excited state, in agreement with recent experiments. The computed electronic couplings show an electronic state dependence and are weaker in solution than in the gas phase. We explore the role of cis-trans isomerization on the CR kinetics, and we find strong correlation between the vertical energy gaps of the full simulations and a collective solvent polarization coordinate. Our approach relies on constrained density functional theory to obtain accurate diabatic electronic states on the fly for molecular dynamics simulations, while orientational and electronic polarization of the solvent is captured by a polarizable force field based on a Drude oscillator model. The method offers a unified approach to the characterization of driving forces, reorganization energies, electronic couplings, and nonlinear solvent effects in light-harvesting systems.

Tunneling Splittings in Vibronic Structure of CH_3F^+ ( X^2E): Studied by High Resolution Photoelectron Spectra and AB Initio Theoretical Method

NASA Astrophysics Data System (ADS)

Mo, Yuxiang; Gao, Shuming; Dai, Zuyang; Li, Hua

2013-06-01

We report a combined experimental and theoretical study on the vibronic structure of CH_3F^+. The results show that the tunneling splittings of vibrational energy levels occur in CH_3F^+ due to the Jahn-Teller effect. Experimentally, we have measured a high resolution ZEKE spectrum of CH_3F up to 3500 cm^-^1 above the ground state. Theoretically, we performed an ab initio calculation based on the diabatic model. The adiabatic potential energy surfaces (APES) of CH_3F^+ have been calculated at the MRCI/CAS/avq(t)z level and expressed by Taylor expansions with normal coordinates as variables. The energy gradients for the lower and upper APES, the derivative couplings between them and also the energies of the APES have been used to determine the coefficients in the Taylor expansion. The spin-vibronic energy levels have been calculated by accounting all six vibrational modes and their couplings. The experimental ZEKE spectra were assigned based on the theoretical calculations. W. Domcke, D. R. Yarkony, and H. Köpple (Eds.), Conical Intersections: Eletronic Structure, Dynamics and Spectroscopy (World Scientific, Singapore, 2004). M. S. Schuurman, D. E. Weinberg, and D. R. Yarkony, J. Chem. Phys. 127, 104309 (2007).

Influence of isentropic transport on seasonal ozone variations in the lower stratosphere and subtropical upper troposphere

NASA Technical Reports Server (NTRS)

Jing, P.; Cunnold, D. M.; Yang, E.-S.; Wang, H.-J.

2005-01-01

The isentropic cross-tropopause ozone transport has been estimated in both hemispheres in 1999 based on the potential vorticity mapping of Stratospheric Aerosol and Gas Experiment 11 ozone measurements and contour advection calculations using the NASA Goddard Space Flight Center Global and Modeling Assimilation Office analysis. The estimated net isentropic stratosphere-to-troposphere ozone flux is approx.118 +/- 61 x 10(exp9)kg/yr globally within the layer between 330 and 370 K in 1999; 60% of it is found in the Northern Hemisphere, and 40% is found in the Southern Hemisphere. The monthly average ozone fluxes are strongest in summer and weakest in winter in both hemispheres. The seasonal variations of ozone in the lower stratosphere (LS) and upper troposphere (UT) have been analyzed using ozonesonde observations from ozonesonde stations in the extratropics and subtropics, respectively. It is shown that observed ozone levels increase in the UT over subtropical ozonesonde stations and decrease in the LS over extratropical stations in late spring/early summer and that the ozone increases in the summertime subtropical UT are unlikely to be explained by photochemical ozone production and diabatic transport alone. We conclude that isentropic transport is a significant contributor to ozone levels in the subtropical upper troposphere, especially in summer.

Stratospheric Analysis and Forecasting in the Northern Winter of 1999/2000: The NASA DAO's GEOS-3 System

NASA Technical Reports Server (NTRS)

Pawson, Steven; Lamich, David; Ledvina, Andrea; Lucchesi, Robert; Owens, Tommy; Newman, Paul A.; Atlas, Robert (Technical Monitor)

2002-01-01

An evaluation is presented of the performance in the northern winter 1999/2000 of the GEOS-3 troposphere-stratosphere data assimilation system (DAS). The impacts of the two main input data types are assessed: upper-air soundings (sondes) provide wind and temperature information and satellite-based (Tiros Operational Vertical Sounders: TOVS) give estimates of the thermal structure. It is shown that in the low stratosphere (300-70hPa) the analyses are generally slightly warmer than the sonde data, but colder than the TOVS data; this relationship reverses between 70 and 10 hPa. There are geographical biases, related to the spatial and temporal coverage of the observation types and to the statistical weights assigned to them in the DAS. Forecasts show a tendency to reduce zonal asymmetries in the atmospheric flow and to suppress stratospheric temperature minima. In the DAS, the analysis increments compensate for this, but it leads to important biases in the multi-day forecasts. The analysis increments are as large as the diabatic forcing in the lower polar stratosphere, indicating a substantial model bias. The results provide important insights into the roles of different data types and the circulation model in producing accurate analyses for studies of polar chemistry and physical processes.

Emission shaping in fluorescent proteins: role of electrostatics and π-stacking.

PubMed

Park, Jae Woo; Rhee, Young Min

2016-02-07

For many decades, simulating the excited state properties of complex systems has been an intriguing but daunting task due to its high computational cost. Here, we apply molecular dynamics based techniques with interpolated potential energy surfaces toward calculating fluorescence spectra of the green fluorescent protein (GFP) and its variants in a statistically meaningful manner. With the GFP, we show that the diverse electrostatic tuning can shape the emission features in many different ways. By computationally modulating the electrostatic interactions between the chromophore phenoxy oxygen and its nearby residues, we demonstrate that we indeed can shift the emission to the blue or to the red side in a predictable manner. We rationalize the shifting effects of individual residues in the GFP based on the responses of both the adiabatic and the diabatic electronic states of the chromophore. We next exhibit that the yellow emitting variant, the Thr203Tyr mutant, generates changes in the electrostatic interactions and an additional π-stacking interaction. These combined effects indeed induce a red shift to emit the fluorescence into the yellow region. With the series of demonstrations, we suggest that our approach can provide sound rationales and useful insights in understanding different responses of various fluorescent complexes, which may be helpful in designing new light emitting proteins and other related systems in future studies.

Local atmospheric response to warm mesoscale ocean eddies in the Kuroshio-Oyashio Confluence region.

PubMed

Sugimoto, Shusaku; Aono, Kenji; Fukui, Shin

2017-09-19

In the extratropical regions, surface winds enhance upward heat release from the ocean to atmosphere, resulting in cold surface ocean: surface ocean temperature is negatively correlated with upward heat flux. However, in the western boundary currents and eddy-rich regions, the warmer surface waters compared to surrounding waters enhance upward heat release-a positive correlation between upward heat release and surface ocean temperature, implying that the ocean drives the atmosphere. The atmospheric response to warm mesoscale ocean eddies with a horizontal extent of a few hundred kilometers remains unclear because of a lack of observations. By conducting regional atmospheric model experiments, we show that, in the Kuroshio-Oyashio Confluence region, wintertime warm eddies heat the marine atmospheric boundary layer (MABL), and accelerate westerly winds in the near-surface atmosphere via the vertical mixing effect, leading to wind convergence around the eastern edge of eddies. The warm-eddy-induced convergence forms local ascending motion where convective precipitation is enhanced, providing diabatic heating to the atmosphere above MABL. Our results indicate that warm eddies affect not only near-surface atmosphere but also free atmosphere, and possibly synoptic atmospheric variability. A detailed understanding of warm eddy-atmosphere interaction is necessary to improve in weather and climate projections.

Analysis of geometric phase effects in the quantum-classical Liouville formalism.

PubMed

Ryabinkin, Ilya G; Hsieh, Chang-Yu; Kapral, Raymond; Izmaylov, Artur F

2014-02-28

We analyze two approaches to the quantum-classical Liouville (QCL) formalism that differ in the order of two operations: Wigner transformation and projection onto adiabatic electronic states. The analysis is carried out on a two-dimensional linear vibronic model where geometric phase (GP) effects arising from a conical intersection profoundly affect nuclear dynamics. We find that the Wigner-then-Adiabatic (WA) QCL approach captures GP effects, whereas the Adiabatic-then-Wigner (AW) QCL approach does not. Moreover, the Wigner transform in AW-QCL leads to an ill-defined Fourier transform of double-valued functions. The double-valued character of these functions stems from the nontrivial GP of adiabatic electronic states in the presence of a conical intersection. In contrast, WA-QCL avoids this issue by starting with the Wigner transform of single-valued quantities of the full problem. As a consequence, GP effects in WA-QCL can be associated with a dynamical term in the corresponding equation of motion. Since the WA-QCL approach uses solely the adiabatic potentials and non-adiabatic derivative couplings as an input, our results indicate that WA-QCL can capture GP effects in two-state crossing problems using first-principles electronic structure calculations without prior diabatization or introduction of explicit phase factors.

Seasonal Ozone Variations in the Isentropic Layer between 330 and 380 K as Observed by SAGE 2: Implications of Extratropical Cross-Tropopause Transport

NASA Technical Reports Server (NTRS)

Wang, Pi-Huan; Cunnold, Derek M.; Zawodny, Joseph M.; Pierce, R. Bradley; Olson, Jennifer R.; Kent, Geoffrey S.; Skeens, Kristi, M.

1998-01-01

To provide observational evidence on the extratropical cross-tropopause transport between the stratosphere and the troposphere via quasi-isentropic processes in the middleworld (the part of the atmosphere in which the isentropic surfaces intersect the tropopause), this report presents an analysis of the seasonal variations of the ozone latitudinal distribution in the isentropic layer between 330 K and 380 K based on the measurements from the Stratospheric Aerosol and Gas Experiment (SAGE) II. The results from SAGE II data analysis are consistent with (1) the buildup of ozone-rich air in the extratropical middleworld through the large-scale descending mass circulation during winter, (2) the spread of ozone-rich air in the isentropic layer from midlatitudes to subtropics via quasi-isentropic transport during spring, (3) significant photochemical ozone removal and the absence of an ozone-rich supply of air to the layer during summer, and (4) air mass exchange between the subtropics and the extratropics during the summer monsoon period. Thus the SAGE II observed ozone seasonal variations in the middleworld are consistent with the existing model calculated annual cycle of the diabatic circulation as well as the conceptual role of the eddy quasi-adiabatic transport in the stratosphere-troposphere exchange reported in the literature.

The tropopause inversion layer in baroclinic life cycles over the North Atlantic: a pre-WISE case study and climatology

NASA Astrophysics Data System (ADS)

Kaluza, Thorsten; Hoor, Peter; Kunkel, Daniel

2017-04-01

Studies of baroclinic life cycles recently revelead that the tropopause inversion layer (TIL) in the extratropics is significantly strengthened by diabatic processes related to moist tropospheric dynamics as well as by breaking of the baroclinic wave itself. However, these findings summarize the results from idealized model simulations and the contribution from processes related to baroclinic life cycles relative to other processes enhancing the lower stratospheric static stability (stratospheric dynamics, seasonal variation of radiative feedbacks) to the observed TIL at midlatitudes has yet to be assessed. Further the role of the TIL for stratosphere-troposphere exchange (STE) is currently still under debate. In preparation of the up-coming field campaign WISE (Wave driven isentropic exchange) we explore the state and variability of the TIL over the North Atlantic between August and October in analysis model data. We use high resolution operational analysis from the European Center for Medium Range Weather Forecast to study the mesoscale structure of the TIL. The main focus is on case studies of the TIL in real baroclinic life cycles, in particular on small scale enhancements within the baroclinic disturbances and the relation to STE. Moreover, a summary is presented about the quasi climatological state of the tropopause location and sharpness over the North Atlantic over recent years.

Optimizing Adiabaticity in a Trapped-Ion Quantum Simulator

NASA Astrophysics Data System (ADS)

Richerme, Phil; Senko, Crystal; Korenblit, Simcha; Smith, Jacob; Lee, Aaron; Monroe, Christopher

2013-05-01

Trapped-ion quantum simulators are a leading platform for the study of interacting spin systems, such as fully-connected Ising models with transverse and axial fields. Phonon-mediated spin-dependent optical dipole forces act globally on a linear chain of trapped Yb-171+ ions to generate the spin-spin couplings, with the form and range of such couplings controlled by laser frequencies and trap voltages. The spins are initially prepared along an effective transverse magnetic field, which is large compared to the Ising couplings and slowly ramped down during the quantum simulation. The system remains in the ground state throughout the evolution if the ramp is adiabatic, and the spin ordering is directly measured by state-dependent fluorescence imaging of the ions onto a camera. Two techniques can improve the identification of the ground state at the end of simulations that are unavoidably diabatic. First, we show an optimized ramp protocol that gives a maximal probability of measuring the true ground state given a finite ramp time. Second, we show that no spin ordering is more prevalent than the ground state(s), even for non-adiabatic ramps. This work is supported by grants from the U.S. Army Research Office with funding from the DARPA OLE program, IARPA, and the MURI program; and the NSF Physics Frontier Center at JQI.

Prospects for Improved Forecasts of Weather and Short-Term Climate Variability on Subseasonal (2-Week to 2-Month) Times Scales

NASA Technical Reports Server (NTRS)

Schubert, Siegfried; Dole, Randall; vandenDool, Huug; Suarez, Max; Waliser, Duane

2002-01-01

This workshop, held in April 2002, brought together various Earth Sciences experts to focus on the subseasonal prediction problem. While substantial advances have occurred over the last few decades in both weather and seasonal prediction, progress in improving predictions on these intermediate time scales (time scales ranging from about two weeks to two months) has been slow. The goals of the workshop were to get an assessment of the "state of the art" in predictive skill on these time scales, to determine the potential sources of "untapped" predictive skill, and to make recommendations for a course of action that will accelerate progress in this area. One of the key conclusions of the workshop was that there is compelling evidence for predictability at forecast lead times substantially longer than two weeks. Tropical diabatic heating and soil wetness were singled out as particularly important processes affecting predictability on these time scales. Predictability was also linked to various low-frequency atmospheric "phenomena" such as the annular modes in high latitudes (including their connections to the stratosphere), the Pacific/North American (PNA) pattern, and the Madden Julian Oscillation (MJO). The latter, in particular, was highlighted as a key source of untapped predictability in the tropics and subtropics, including the Asian and Australian monsoon regions.

Kinetics of First-Row Transition Metal Cations (V+, Fe+, Co+) with OCS at Thermal Energies.

PubMed

Sweeny, Brendan C; Ard, Shaun G; Shuman, Nicholas S; Viggiano, Albert A

2018-05-03

The temperature-dependent kinetics for reactions of V + , Fe + , and Co + with OCS are measured using a selected ion flow tube apparatus heated to 300-600 K. All three reactions proceed solely by C-S activation at thermal energies, resulting in metal sulfide cation formation. Previously calculated reaction pathways were employed to inform statistical modeling of these reactions for comparison to the data. As surmised previously, all three reactions at thermal energies require spin crossing, with the Fe + reaction crossing once circumventing a prohibitive transition state, before crossing again to form ground state products. The Fe + and Co + reaction efficiencies increase with energy. For the Co + reaction, and to a lesser extent the Fe + reaction, the apparent activation energies are less than the reaction endothermicities, possibly indicating increasing diabatic behavior of the spin crossings with energy. The V + reaction was well modeled assuming an entirely adiabatic spin crossing, such that the resultant avoided crossing behaves similarly to a tight transition state. The subsequent reaction of VS + with OCS producing VS 2 + is also investigated; the rate-limiting transition state energy derived from statistical modeling is poorly reproduced by quantum calculations using a variety of methods, highlighting the large (1-2 eV) uncertainty in calculated energetics of transition-metal containing species.

Fragment approach to constrained density functional theory calculations using Daubechies wavelets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ratcliff, Laura E.; Genovese, Luigi; Mohr, Stephan

2015-06-21

In a recent paper, we presented a linear scaling Kohn-Sham density functional theory (DFT) code based on Daubechies wavelets, where a minimal set of localized support functions are optimized in situ and therefore adapted to the chemical properties of the molecular system. Thanks to the systematically controllable accuracy of the underlying basis set, this approach is able to provide an optimal contracted basis for a given system: accuracies for ground state energies and atomic forces are of the same quality as an uncontracted, cubic scaling approach. This basis set offers, by construction, a natural subset where the density matrix ofmore » the system can be projected. In this paper, we demonstrate the flexibility of this minimal basis formalism in providing a basis set that can be reused as-is, i.e., without reoptimization, for charge-constrained DFT calculations within a fragment approach. Support functions, represented in the underlying wavelet grid, of the template fragments are roto-translated with high numerical precision to the required positions and used as projectors for the charge weight function. We demonstrate the interest of this approach to express highly precise and efficient calculations for preparing diabatic states and for the computational setup of systems in complex environments.« less

Mixing in the Extratropical Stratosphere: Model-measurements Comparisons using MLM Diagnostics

NASA Technical Reports Server (NTRS)

Ma, Jun; Waugh, Darryn W.; Douglass, Anne R.; Kawa, Stephan R.; Bhartia, P. K. (Technical Monitor)

2001-01-01

We evaluate transport processes in the extratropical lower stratosphere for both models and measurements with the help of equivalent length diagnostic from the modified Lagrangian-mean (MLM) analysis. This diagnostic is used to compare measurements of long-lived tracers made by the Cryogenic Limb Array Etalon Spectrometer (CLAES) on the Upper Atmosphere Research Satellite (UARS) with simulated tracers. Simulations are produced in Chemical and Transport Models (CTMs), in which meteorological fields are taken from the Goddard Earth Observing System Data Assimilation System (GEOS DAS), the Middle Atmosphere Community Climate Model (MACCM2), and the Geophysical Fluid Dynamics Laboratory (GFDL) "SKYHI" model, respectively. Time series of isentropic equivalent length show that these models are able to capture major mixing and transport properties observed by CLAES, such as the formation and destruction of polar barriers, the presence of surf zones in both hemispheres. Differences between each model simulation and the observation are examined in light of model performance. Among these differences, only the simulation driven by GEOS DAS shows one case of the "top-down" destruction of the Antarctic polar vortex, as observed in the CLAES data. Additional experiments of isentropic advection of artificial tracer by GEOS DAS winds suggest that diabatic movement might have considerable contribution to the equivalent length field in the 3D CTM diagnostics.

Analysis of geometric phase effects in the quantum-classical Liouville formalism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryabinkin, Ilya G.; Izmaylov, Artur F.; Chemical Physics Theory Group, Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6

2014-02-28

We analyze two approaches to the quantum-classical Liouville (QCL) formalism that differ in the order of two operations: Wigner transformation and projection onto adiabatic electronic states. The analysis is carried out on a two-dimensional linear vibronic model where geometric phase (GP) effects arising from a conical intersection profoundly affect nuclear dynamics. We find that the Wigner-then-Adiabatic (WA) QCL approach captures GP effects, whereas the Adiabatic-then-Wigner (AW) QCL approach does not. Moreover, the Wigner transform in AW-QCL leads to an ill-defined Fourier transform of double-valued functions. The double-valued character of these functions stems from the nontrivial GP of adiabatic electronic statesmore » in the presence of a conical intersection. In contrast, WA-QCL avoids this issue by starting with the Wigner transform of single-valued quantities of the full problem. As a consequence, GP effects in WA-QCL can be associated with a dynamical term in the corresponding equation of motion. Since the WA-QCL approach uses solely the adiabatic potentials and non-adiabatic derivative couplings as an input, our results indicate that WA-QCL can capture GP effects in two-state crossing problems using first-principles electronic structure calculations without prior diabatization or introduction of explicit phase factors.« less

The kinetic and available potential energy budget of a winter extratropical cyclone system

NASA Technical Reports Server (NTRS)

Smith, P. J.; Dare, P. M.

1986-01-01

The energy budget of an extratropical cyclone system which traversed North America and intensified through the period January 9-11, 1975 is presented. The objectives of the study are: (1) to document the complete energy budget of a significant winter cyclone event, and (2) to comment on the significance of latent heat release (LHR) in the cyclone's evolution. Results reveal an overall increase in both kinetic (K) and available potential energy (A). K increases are accounted for by boundary flux convergence of K, while A increases are due to generation by LHR and K to A conversion. In addition, the general A increase is accompanied by a 24 h oscillation that is explained largely by the flux quantity in the A budget equation and is correlated with a similar fluctuation in the K to A conversion. LHR does not appear to be critical in the development of this cyclone system. Rather, LHR acts to increase the intensity of the event. It is hypothesized that the direct influence that LHR had on the deepening cyclone's reduced mass was augmented by an indirect influence, in which pre-existing dry dynamical forcing was enhanced by diabatic heating, thus leading to accelerated cyclone development at a later time.

Process-Oriented Diagnostics of Tropical Cyclones in Global Climate Models

NASA Astrophysics Data System (ADS)

Moon, Y.; Kim, D.; Camargo, S. J.; Wing, A. A.; Sobel, A. H.; Bosilovich, M. G.; Murakami, H.; Reed, K. A.; Vecchi, G. A.; Wehner, M. F.; Zarzycki, C. M.; Zhao, M.

2017-12-01

Simulating tropical cyclone (TC) activity with global climate models (GCMs) remains a challenging problem. While some GCMs are able to simulate TC activity that is in good agreement with the observations, many other models exhibit strong biases. Decreasing horizontal grid spacing of the GCM simulations tends to improve the characteristics of simulated TCs, but this enhancement alone does not necessarily lead to greater skill in simulating TC activity. This study uses process-based diagnostics to identify model characteristics that could explain why some GCM simulations are able to produce more realistic TC activity than others. The diagnostics examine how convection, moisture, clouds and related processes are coupled at individual grid points, which yields useful information into how convective parameterizations interact with resolved model dynamics. These diagnostics share similarities with those originally developed to examine the Madden-Julian Oscillations in climate models. This study will examine TCs in eight different GCM simulations performed at NOAA/GFDL, NCAR and NASA that have different horizontal resolutions and ocean coupling. Preliminary results suggest that stronger TCs are closely associated with greater rainfall - thus greater diabatic heating - in the inner-core regions of the storms, which is consistent with previous theoretical studies. Other storm characteristics that can be used to infer why GCM simulations with comparable horizontal grid spacings produce different TC activity will be examined.

Improved prediction of severe thunderstorms over the Indian Monsoon region using high-resolution soil moisture and temperature initialization

PubMed Central

Osuri, K. K.; Nadimpalli, R.; Mohanty, U. C.; Chen, F.; Rajeevan, M.; Niyogi, D.

2017-01-01

The hypothesis that realistic land conditions such as soil moisture/soil temperature (SM/ST) can significantly improve the modeling of mesoscale deep convection is tested over the Indian monsoon region (IMR). A high resolution (3 km foot print) SM/ST dataset prepared from a land data assimilation system, as part of a national monsoon mission project, showed close agreement with observations. Experiments are conducted with (LDAS) and without (CNTL) initialization of SM/ST dataset. Results highlight the significance of realistic land surface conditions on numerical prediction of initiation, movement and timing of severe thunderstorms as compared to that currently being initialized by climatological fields in CNTL run. Realistic land conditions improved mass flux, convective updrafts and diabatic heating in the boundary layer that contributed to low level positive potential vorticity. The LDAS run reproduced reflectivity echoes and associated rainfall bands more efficiently. Improper representation of surface conditions in CNTL run limit the evolution boundary layer processes and thereby failed to simulate convection at right time and place. These findings thus provide strong support to the role land conditions play in impacting the deep convection over the IMR. These findings also have direct implications for improving heavy rain forecasting over the IMR, by developing realistic land conditions. PMID:28128293

On the description of conical intersections—A continuous representation of the local topography of seams of conical intersection of three or more electronic states: A generalization of the two state result

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Xiaolei, E-mail: virtualzx@gmail.com; Yarkony, David R., E-mail: yarkony@jhu.edu

2014-11-07

For conical intersections of two states (I,J = I + 1) the vectors defining the branching or g-h plane, the energy difference gradient vector g{sup I,J}, and the interstate coupling vector h{sup I,J}, can be made orthogonal by a one parameter rotation of the degenerate electronic eigenstates. The representation obtained from this rotation is used to construct the parameters that describe the vicinity of the conical intersection seam, the conical parameters, s{sup I,J}{sub x} (R), s{sup I,J}{sub y} (R), g{sup I,J}(R), and h{sup I,J}(R). As a result of the orthogonalization these parameters can be made continuous functions of R, themore » internuclear coordinates. In this work we generalize this notion to construct continuous parametrizations of conical intersection seams of three or more states. The generalization derives from a recently introduced procedure for using non-degenerate electronic states to construct coupled diabatic states that represent adiabatic states coupled by conical intersections. The procedure is illustrated using the seam of conical intersections of three states in parazolyl as an example.« less

Multiple Scale Analysis of the Dynamic State Index (DSI)

NASA Astrophysics Data System (ADS)

Müller, A.; Névir, P.

2016-12-01

The Dynamic State Index (DSI) is a novel parameter that indicates local deviations of the atmospheric flow field from a stationary, inviscid and adiabatic solution of the primitive equations of fluid mechanics. This is in contrast to classical methods, which often diagnose deviations from temporal or spatial mean states. We show some applications of the DSI to atmospheric flow phenomena on different scales. The DSI is derived from the Energy-Vorticity-Theory (EVT) which is based on two global conserved quantities, the total energy and Ertel's potential enstrophy. Locally, these global quantities lead to the Bernoulli function and the PV building together with the potential temperature the DSI.If the Bernoulli function and the PV are balanced, the DSI vanishes and the basic state is obtained. Deviations from the basic state provide an indication of diabatic and non-stationary weather events. Therefore, the DSI offers a tool to diagnose and even prognose different atmospheric events on different scales.On synoptic scale, the DSI can help to diagnose storms and hurricanes, where also the dipole structure of the DSI plays an important role. In the scope of the collaborative research center "Scaling Cascades in Complex Systems" we show high correlations between the DSI and precipitation on convective scale. Moreover, we compare the results with reduced models and different spatial resolutions.

Convection and Easterly Wave Structure Observed in the Eastern Pacific Warm-Pool during EPIC-2001

NASA Technical Reports Server (NTRS)

Peterson, Walter A.; Cifelli, R.; Boccippio, D.; Rutledge, S. A.; Fairall, C. W.; Arnold, James E. (Technical Monitor)

2002-01-01

During September-October 2001, the East Pacific Investigation of Climate Processes in the Coupled Ocean-Atmosphere System (EPIC-2001) ITCZ field campaign focused on studies of deep convection in the warm-pool region of the East Pacific. In addition to the TAO mooring array, observational platforms deployed during the field phase included the NOAA ship RN Ronald H. Brown, the NSF ship RN Horizon, and the NOAA P-3 and NCAR C-130 aircraft. This study combines C-band Doppler radar, rawinsonde, and surface heat flux data collected aboard the RN Brown to describe ITCZ convective structure and rainfall statistics in the eastern Pacific as a function of 3-5 day easterly wave phase. Three distinct easterly wave passages occurred during EPIC-2001. Wind and thermodynamic data reveal that the wave trough axes exhibited positively correlated U and V winds and a slight westward phase tilt with height. A relatively strong (weak) northeasterly deep tropospheric shear followed the trough (ridge) axis. Temperature and humidity perturbations exhibited mid-to upper level cooling (warming) and drying (moistening) in the northerly (trough and southerly) phase. At low levels warming (cooling) occurred in the northerly (southerly) phase with little change in the relative humidity, though mixed layer mixing ratios were larger during the northerly phase. When composited, radar, sounding, lightning and surface heat flux observations suggest the following systematic behavior as a function of wave phase: approximately zero to one quarter wavelength ahead of (behind) the wave trough in northerly (southerly) flow, larger (smaller) CAPE, lower (higher) CIN, weaker (stronger) tropospheric shear, higher (lower) conditional mean rain rates, higher (lower) lightning flash densities, and more (less) robust convective vertical structure occurred. Latent and sensible heat fluxes reached a minimum in the northerly phase and then increased through the trough, reaching a peak during the ridge phase (leading the peak in CAPE). From a radar echo coverage perspective, larger areas of light rain and slightly larger (10%) area averaged rain rates occurred in the vicinity of, and just behind, the trough axes in southerly flow. Importantly, the transition in convective structure observed across the trough axis when considered with the relatively small change in area mean rain rates suggests the presence of a transition in the vertical structure of diabatic heating across the easterly waves examined. The inferred transition in heating structure is supported by radar diagnosed divergence profiles that exhibit convective (stratiform) characteristics ahead of (behind) the trough.

Tropical cyclogenesis in a tropical wave critical layer: easterly waves

NASA Astrophysics Data System (ADS)

Dunkerton, T. J.; Montgomery, M. T.; Wang, Z.

2009-08-01

The development of tropical depressions within tropical waves over the Atlantic and eastern Pacific is usually preceded by a "surface low along the wave" as if to suggest a hybrid wave-vortex structure in which flow streamlines not only undulate with the waves, but form a closed circulation in the lower troposphere surrounding the low. This structure, equatorward of the easterly jet axis, is identified herein as the familiar critical layer of waves in shear flow, a flow configuration which arguably provides the simplest conceptual framework for tropical cyclogenesis resulting from tropical waves, their interaction with the mean flow, and with diabatic processes associated with deep moist convection. The recirculating Kelvin cat's eye within the critical layer represents a sweet spot for tropical cyclogenesis in which a proto-vortex may form and grow within its parent wave. A common location for storm development is given by the intersection of the wave's critical latitude and trough axis at the center of the cat's eye, with analyzed vorticity centroid nearby. The wave and vortex live together for a time, and initially propagate at approximately the same speed. In most cases this coupled propagation continues for a few days after a tropical depression is identified. For easterly waves, as the name suggests, the propagation is westward. It is shown that in order to visualize optimally the associated Lagrangian motions, one should view the flow streamlines, or stream function, in a frame of reference translating horizontally with the phase propagation of the parent wave. In this co-moving frame, streamlines are approximately equivalent to particle trajectories. The closed circulation is quasi-stationary, and a dividing streamline separates air within the cat's eye from air outside. The critical layer equatorward of the easterly jet axis is important to tropical cyclogenesis because its cat's eye provides (i) a region of cyclonic vorticity and weak deformation by the resolved flow, (ii) containment of moisture entrained by the developing gyre and/or lofted by deep convection therein, (iii) confinement of mesoscale vortex aggregation, (iv) a predominantly convective type of heating profile, and (v) maintenance or enhancement of the parent wave until the vortex becomes a self-sustaining entity and emerges from the wave as a tropical depression. The entire sequence is likened to the development of a marsupial infant in its mother's pouch. These ideas are formulated in three new hypotheses describing the flow kinematics and dynamics, moist thermodynamics and wave/vortex interactions comprising the "marsupial paradigm". A survey of 55 named tropical storms in 1998-2001 reveals that actual critical layers sometimes resemble the ideal east-west train of cat's eyes, but are usually less regular, with one or more recirculation regions in the co-moving frame. It is shown that the kinematics of isolated proto-vortices carried by the wave also can be visualized in a frame of reference translating at or near the phase speed of the parent wave. The proper translation speeds for wave and vortex may vary with height owing to vertical shear and wave-vortex interaction. Some implications for entrainment/containment of vorticity and moisture in the cat's eye are discussed from this perspective, based on the observational survey.

Vibronic eigenstates and the geometric phase effect in the 2E″ state of NO3.

PubMed

Eisfeld, Wolfgang; Viel, Alexandra

2017-01-21

The 2 E″ state of NO 3 , a prototype for the Jahn-Teller effect, has been an enigma and a challenge for a long time for both experiment and theory. We present a detailed theoretical study of the vibronic quantum dynamics in this electronic state, uncovering the effects of tunnelling, geometric phase, and symmetry. To this end, 45 vibronic levels of NO 3 in the 2 E″ state are determined accurately and analyzed thoroughly. The computation is based on a high quality diabatic potential representation of the two-sheeted surface of the 2 E″ state developed by us [W. Eisfeld et al., J. Chem. Phys. 140, 224109 (2014)] and on the multi-configuration time dependent Hartree approach. The vibrational eigenstates of the NO 3 - anion are determined and analyzed as well to gain a deeper understanding of the symmetry properties of such D 3h symmetric systems. To this end, 61 eigenstates of the NO 3 - anion ground state are computed using the single sheeted potential surface of the 1 A 1 state published in the same reference quoted above. The assignments of both the vibrational and vibronic levels are discussed. A simple model is proposed to rationalize the computed NO 3 spectrum strongly influenced by the Jahn-Teller couplings, the associated geometric phase effect, and the tunnelling. Comparison with the available spectroscopic data is also presented.

Relaxation mechanisms of UV-photoexcited DNA and RNA nucleobases

PubMed Central

Barbatti, Mario; Aquino, Adélia J. A.; Szymczak, Jaroslaw J.; Nachtigallová, Dana; Hobza, Pavel; Lischka, Hans

2010-01-01

A comprehensive effort in photodynamical ab initio simulations of the ultrafast deactivation pathways for all five nucleobases adenine, guanine, cytosine, thymine, and uracil is reported. These simulations are based on a complete nonadiabatic surface-hopping approach using extended multiconfigurational wave functions. Even though all five nucleobases share the basic internal conversion mechanisms, the calculations show a distinct grouping into purine and pyrimidine bases as concerns the complexity of the photodynamics. The purine bases adenine and guanine represent the most simple photodeactivation mechanism with the dynamics leading along a diabatic ππ* path directly and without barrier to the conical intersection seam with the ground state. In the case of the pyrimidine bases, the dynamics starts off in much flatter regions of the ππ* energy surface due to coupling of several states. This fact prohibits a clear formation of a single reaction path. Thus, the photodynamics of the pyrimidine bases is much richer and includes also nπ* states with varying importance, depending on the actual nucleobase considered. Trapping in local minima may occur and, therefore, the deactivation time to the ground state is also much longer in these cases. Implications of these findings are discussed (i) for identifying structural possibilities where singlet/triplet transitions can occur because of sufficient retention time during the singlet dynamics and (ii) concerning the flexibility of finding other deactivation pathways in substituted pyrimidines serving as candidates for alternative nucleobases. PMID:21115845

Latent Heating from TRMM Satellite Measurements

NASA Technical Reports Server (NTRS)

Tao, W.-K.; Smith, E.; Olson, W.

2005-01-01

Rainfall production is a fundamental process within the Earth;s hydrological cycle because it represents both a principal forcing term in surface water budgets, and its energetics corollary, latent heating, is the principal source of atmospheric diabatic heating. Latent heat release itself is a consequence of phase changes between the vapor, liquid, and frozen states of water. The properties of the vertical distribution of latent heat release modulate large-scale meridional and zonal circulations with the Tropics - as well as modify the energetic efficiencies of mid-latitude weather systems. This paper highlights the retrieval of observatory, which was launched in November 1997 as a joint American-Japanese space endeavor. Since then, TRMM measurements have been providing an accurate four-dimensional amount of rainfall over the global Tropics and sub-tropics - information which can be used to estimate the spacetime structure of latent heating across the Earth's low latitudes. A set of algorithm methodologies has and continues to be developed to estimate latent heating based on rain rate profile retrievals obtained from TRMM measurements. These algorithms are briefly described followed by a discussion of the foremost latent heating products that can be generate from them. The investigation then provides an overview of how TRMM-derived latent heating information is currently being used in conjunction with global weather and climate models, concluding with remarks intended to stimulate further research on latent heating retrieval from satellites.

Effect of quantum nuclear motion on hydrogen bonding

NASA Astrophysics Data System (ADS)

McKenzie, Ross H.; Bekker, Christiaan; Athokpam, Bijyalaxmi; Ramesh, Sai G.

2014-05-01

This work considers how the properties of hydrogen bonded complexes, X-H⋯Y, are modified by the quantum motion of the shared proton. Using a simple two-diabatic state model Hamiltonian, the analysis of the symmetric case, where the donor (X) and acceptor (Y) have the same proton affinity, is carried out. For quantitative comparisons, a parametrization specific to the O-H⋯O complexes is used. The vibrational energy levels of the one-dimensional ground state adiabatic potential of the model are used to make quantitative comparisons with a vast body of condensed phase data, spanning a donor-acceptor separation (R) range of about 2.4 - 3.0 Å, i.e., from strong to weak hydrogen bonds. The position of the proton (which determines the X-H bond length) and its longitudinal vibrational frequency, along with the isotope effects in both are described quantitatively. An analysis of the secondary geometric isotope effect, using a simple extension of the two-state model, yields an improved agreement of the predicted variation with R of frequency isotope effects. The role of bending modes is also considered: their quantum effects compete with those of the stretching mode for weak to moderate H-bond strengths. In spite of the economy in the parametrization of the model used, it offers key insights into the defining features of H-bonds, and semi-quantitatively captures several trends.

The Seasonal cycle of the Tropical Lower Stratospheric Water Vapor in Chemistry-Climate Models in Comparison with Observations

NASA Astrophysics Data System (ADS)

Wang, X.; Dessler, A. E.

2017-12-01

The seasonal cycle is one of the key features of the tropical lower stratospheric water vapor, so it is important that the climate models reproduce it. In this analysis, we evaluate how well the Goddard Earth Observing System Chemistry Climate Model (GEOSCCM) and the Whole Atmosphere Community Climate Model (WACCM) reproduce the seasonal cycle of tropical lower stratospheric water vapor. We do this by comparing the models to observations from the Microwave Limb Sounder (MLS) and the European Centre for Medium-Range Weather Forecasts (ECMWF) ERA-Interim (ERAi). We also evaluate if the chemistry-climate models (CCMs) reproduce the key transport and dehydration processes that regulate the seasonal cycle using a forward, domain filling, diabatic trajectory model. Finally, we explore the changes of the seasonal cycle during the 21st century in the two CCMs. Our results show general agreement in the seasonal cycles from the MLS, the ERAi, and the CCMs. Despite this agreement, there are some clear disagreements between the models and the observations on the details of transport and dehydration in the TTL. Finally, both the CCMs predict a moister seasonal cycle by the end of the 21st century. But they disagree on the changes of the seasonal amplitude, which is predicted to increase in the GEOSCCM and decrease in the WACCM.

A climatological study of the duration of Northern Hemisphere Cut-off low systems

NASA Astrophysics Data System (ADS)

Nieto, R.; Gimeno, L.; de La Torre, L.; Tesouro, M.; Añel, J. A.; Ribera, P.

2003-04-01

Cut-off low-pressure systems-COLS- are usually closed circulations at middle and upper troposphere developed from a deep trough in the westerlies. The importance of their study is due to both the convective severe events that can occur if they are over warm ocean and because they are important mechanisms of Stratosphere-troposphere exchange- STE-. A COL system would last about a couple of days before being destroyed by diabatic heating if there were not injection of new air into the COL with high potential vorticity. In the practice their duration range from 1 day to 17 days. There are previous climatological studies about the duration of COLs, but limited to five years. In this work we extended the study to a period of 41-year period (1958 to 1998). The identification of COLs were done using an approach based in imposing the three main physical characteristics of the conceptual model of COL (a. closed circulation and minimum of geopotential, minimum of equivalent thickness, and two baroclinic zones, one in front of the low and the other behind the low). Data from NCAR-NCEP reanalysis were used. Results confirmed previous studies that most of COL systems have a short time of life. The majority of COLs lasted 2-3 days and very few lasted more than 10 days.

Objectively classifying Southern Hemisphere extratropical cyclones

NASA Astrophysics Data System (ADS)

Catto, Jennifer

2016-04-01

There has been a long tradition in attempting to separate extratropical cyclones into different classes depending on their cloud signatures, airflows, synoptic precursors, or upper-level flow features. Depending on these features, the cyclones may have different impacts, for example in their precipitation intensity. It is important, therefore, to understand how the distribution of different cyclone classes may change in the future. Many of the previous classifications have been performed manually. In order to be able to evaluate climate models and understand how extratropical cyclones might change in the future, we need to be able to use an automated method to classify cyclones. Extratropical cyclones have been identified in the Southern Hemisphere from the ERA-Interim reanalysis dataset with a commonly used identification and tracking algorithm that employs 850 hPa relative vorticity. A clustering method applied to large-scale fields from ERA-Interim at the time of cyclone genesis (when the cyclone is first detected), has been used to objectively classify identified cyclones. The results are compared to the manual classification of Sinclair and Revell (2000) and the four objectively identified classes shown in this presentation are found to match well. The relative importance of diabatic heating in the clusters is investigated, as well as the differing precipitation characteristics. The success of the objective classification shows its utility in climate model evaluation and climate change studies.

A potential relation between stratosphere-troposphere exchange and the tropopause inversion layer in idealized baroclinic life cycle experiments

NASA Astrophysics Data System (ADS)

Kunkel, Daniel; Kaluza, Thorsten; Wirth, Volkmar; Hoor, Peter

2017-04-01

The tropopause inversion layer (TIL) as a well known feature of the lower stratosphere in the extratropics has often been suspected of impeding the exchange between stratospheric and tropospheric air masses (STE). However, it is still an open question whether a physical relation between STE and the TIL exists. We use a non-hydrostatic limited area model to simulate idealized baroclinic life cycles along with different diagnostics for STE such as Eulerian passive tracers and Lagrangian trajectories. Recent findings suggest a strenghtening of the TIL during such life cycles due to diabatic tropospheric processes as well as wave breaking. Moreover, STE also occurs frequently during such baroclinic life cycles, e.g., in the vicinity of tropopause folds, cut-off lows, or stratospheric streamers. Contradicting to current knowledge the analysis of static stability above the thermal tropopause and the identification of regions of STE show that a temporal and spatial co-location of a strong TIL and regions of transport from the troposphere into the stratosphere is possible. Evidence is further presented that such a co-location is related to tropospheric updrafts and small scale waves in the lower stratosphere. These findings are also supported by an analysis of baroclinic life cycles in high resolution operational analysis data from the European Center for Medium-Range Weather Forecasts (ECMWF).

The tropopause inversion layer at midlatitudes: Formation processes and relation to stratosphere-troposphere exchange

NASA Astrophysics Data System (ADS)

Kunkel, D.; Hoor, P. M.; Wirth, V.

2016-12-01

Recent studies revealed the existence of a quasi-permanent layer of enhanced static stability above the thermal tropopause. This so-called tropopause inversion layer (TIL) is evident in adiabatic baroclinic life cycles suggesting that dry dynamics contribute to its formation. However, compared to observations the TIL in these life cycles is too weak, indicating that other contributions from diabatic processes are relevant. Such processes could be related to moisture or radiation, or other non-linear, subgrid-scale processes such as gravity wave breaking. Moreover, whether there is a causal relation between the occurrence of the TIL and stratosphere-troposphere exchange (STE) is still under debate. In this study various types of baroclinic life cycles are simulated using a non-hydrostatic model in an idealized mid-latitude channel configuration. A simulation using only the dynamical core of the model serves as base simulation, which is modified subsequently by adding different processes. First, these processes such as vertical turbulence, cloud microphysics, radiation as well as surface fluxes for heat and momentum are added individually. In a second set of simulations combinations of these processes are studied to assess the relative importance of the individual processes in the formation of the TIL. Finally, the static stability is analyzed in regions of STE. These regions are identified with the help of passive tracer as well as a Lagrangian trajectory analysis.

Sensible and latent heat forced divergent circulations in the West African Monsoon System

NASA Astrophysics Data System (ADS)

Hagos, S.; Zhang, C.

2008-12-01

Field properties of divergent circulation are utilized to identify the roles of various diabatic processes in forcing moisture transport in the dynamics of the West African Monsoon and its seasonal cycle. In this analysis, the divergence field is treated as a set of point sources and is partitioned into two sub-sets corresponding to latent heat release and surface sensible heat flux at each respective point. The divergent circulation associated with each set is then calculated from the Poisson's equation using Gauss-Seidel iteration. Moisture transport by each set of divergent circulation is subsequently estimated. The results show different roles of the divergent circulations forced by surface sensible and latent heating in the monsoon dynamics. Surface sensible heating drives a shallow meridional circulation, which transports moisture deep into the continent at the polar side of the monsoon rain band and thereby promotes the seasonal northward migration of monsoon precipitation during the monsoon onset season. In contrast, the circulation directly associated with latent heating is deep and the corresponding moisture convergence is within the region of precipitation. Latent heating also induces dry air advection from the north. Neither effect promotes the seasonal northward migration of precipitation. The relative contributions of the processes associated with latent and sensible heating to the net moisture convergence, and hence the seasonal evolution of monsoon precipitation, depend on the background moisture.

Jet and storm track variability and change: adiabatic QG zonal averages and beyond... (Invited)

NASA Astrophysics Data System (ADS)

Robinson, W. A.

2013-12-01

The zonally averaged structures of extratropical jets and stormtracks, their slow variations, and their responses to climate change are all tightly constrained on the one hand by thermal wind balance and the necessary application of eddy torques to produce zonally averaged meridional motion, and, on the other hand, by the necessity that eddies propagate upshear to extract energy from the mean flow. Combining these constraints with the well developed theory of linear Rossby-wave propagation on zonally symmetric basic states has led to a large and growing number of plausible mechanisms to explain observed and modeled jet/storm track variability and responses to climate change and idealized forcing. Hidden within zonal averages is the reality that most baroclinic eddy activity is destroyed at the same latitude at which is generated: from one end to another of the fixed stormtracks in the Northern Hemisphere and baroclinic wave packets in the Southern Hemisphere. Ignored within adiabatic QG theory is the reality that baroclinic eddies gain significant energy from latent heating that involves sub-syntopic scale structures and dynamics. Here we use results from high-resolution regional and global simulations of the Northern Hemisphere storm tracks to explore the importance of non-zonal and diabatic dynamics in influencing jet change and variability and their influences on the much-studied zonal means.

Aerosol-Monsoon Interaction, maintenance and variability of the Asian Tropopause Aerosol Layer (ATAL)

NASA Astrophysics Data System (ADS)

Yuan, C.; Lau, W. K. M.; Li, Z.

2016-12-01

In recent years, the discovery of the Asian Tropopause Aerosol Layer (ATAL) from NASA satellite observations has sparked much interests in research on its composition, origin and relationships to the transport processes of atmospheric constituents in the upper troposphere and lower stratosphere (UTLS) and the variability of the Asian Monsoon Anticyclone (AMA). In this paper, based on analysis of MERRA2 reanalysis data, we present results showing that: 1) water vapor, aerosols and chemical gases (BC, OC, dust and CO) originated for the earth surface contribute significantly to the composition of the ATAL during the Asian summer monsoon, 2) one of the major pathways is via the strong large-scale vertical motion, and convective ascent over the Northern Himalayan Foothills during the peak phase of the Indian monsoon, 3) once transported into the UTLS , atmospheric constituents are capped by the Tropopuase inversion Layer (TIL) and advected around within and in the vicinity of the AMA forming the ATAL, 4) the ATAL is modulated by UTLS transport processes which undergo intrinsic monsoon intraseasonal oscillations with 20-30 day quasi-periodicity, coupled to lower tropospheric monsoon dynamics and diabatic heating processes, 5) the pre-monsoon accumulation of absorbing aerosols (BC, OC and dust) over the Indo-Gangetic Plain is more than likely to play an important role in enhancing the UTLS transport of atmospheric constituents from the earth surface to the ATAL.

Parameterization of Mixed Layer and Deep-Ocean Mesoscales Including Nonlinearity

NASA Technical Reports Server (NTRS)

Canuto, V. M.; Cheng, Y.; Dubovikov, M. S.; Howard, A. M.; Leboissetier, A.

2018-01-01

In 2011, Chelton et al. carried out a comprehensive census of mesoscales using altimetry data and reached the following conclusions: "essentially all of the observed mesoscale features are nonlinear" and "mesoscales do not move with the mean velocity but with their own drift velocity," which is "the most germane of all the nonlinear metrics."� Accounting for these results in a mesoscale parameterization presents conceptual and practical challenges since linear analysis is no longer usable and one needs a model of nonlinearity. A mesoscale parameterization is presented that has the following features: 1) it is based on the solutions of the nonlinear mesoscale dynamical equations, 2) it describes arbitrary tracers, 3) it includes adiabatic (A) and diabatic (D) regimes, 4) the eddy-induced velocity is the sum of a Gent and McWilliams (GM) term plus a new term representing the difference between drift and mean velocities, 5) the new term lowers the transfer of mean potential energy to mesoscales, 6) the isopycnal slopes are not as flat as in the GM case, 7) deep-ocean stratification is enhanced compared to previous parameterizations where being more weakly stratified allowed a large heat uptake that is not observed, 8) the strength of the Deacon cell is reduced. The numerical results are from a stand-alone ocean code with Coordinated Ocean-Ice Reference Experiment I (CORE-I) normal-year forcing.

Protonium Formation in Collisions of Antiprotons with Hydrogen Molecules

NASA Astrophysics Data System (ADS)

Cohen, James S.

1997-04-01

The first full-dynamics calculation of barp capture by the H2 molecule has been performed using the quasiclassical Kirschbaum-Wilets method with modifications for accurate treatment of the molecular structure. It had been speculated in calculations of heavy-negative-particle (μ^-) capture by the H atom(J. S. Cohen, R. L. Martin, and W. R. Wadt, Phys. Rev. A 27), 1821 (1983). that the capture cross section for the H2 molecule might be smaller than that for the atom at very low energies (based on the absence of adiabatic ionization for the molecule) but larger at higher energies (based on the molecule having two electrons and a higher ionization potential). This speculation seemed to be borne out by a diabatic-states calculation,(G. Ya. Korenman and V. P. Popov, AIP Conference Proceedings 181, p. 145 (1989).) which showed the two cross sections crossing at a center-of-mass energy of ~8 eV. However, both the qualitative argument and that calculation neglected the molecular vibrational and rotational dynamics. The present calculations show that the molecular degrees of freedom of the target are important and that the molecular capture cross section is always larger and extends to a higher collision energy ( ~80 eV vs. ~25 eV) than the atomic cross section. The distribution of n and l quantum numbers of the captured barp will also be presented.

Use of satellite data and modeling to assess the influence of stratospheric processes on the troposphere

NASA Astrophysics Data System (ADS)

Nathan, Terrence

1991-09-01

Over the past forty years, numerous linear stability studies have been performed in order to explain the origin and structure of observed waves in the atmosphere. Of these studies, only a small fraction have considered the stability of time-dependent, zonally varying flow or the influence of radiative-photochemical feedbacks on the stability of zonally uniform flow. The stability of such flows is described, and these flows may yield important information concerning the origin, structure, and transient time scales of free waves in the atmosphere. During the period 1990 to 1991, a beta-plane model that couples radiative transfer, ozone advection, and ozone photochemistry with the quasigeostrophic dynamical circulation was developed in order to study the diabatic effects of Newtonian cooling and ozone-dynamics interaction on the linear stability of free planetary waves in the atmosphere. The stability of a basic state consisting of a westward-moving wave and a zonal mean jet was examined using a linearized, nondivergent barotropic model on sphere. The sensitivity of the stability of the flow to the strength and structure of the zonal jet was emphasized. The current research is focused on the following problems: (1) examination of the finite amplitude interactions among radiation, ozone, and dynamics; and (2) examination of the role of seasonal forcing in short-term climate variability. The plans for next year are presented.

Effects of land cover change on the tropical circulation in a GCM

NASA Astrophysics Data System (ADS)

Jonko, Alexandra Karolina; Hense, Andreas; Feddema, Johannes Jan

2010-09-01

Multivariate statistics are used to investigate sensitivity of the tropical atmospheric circulation to scenario-based global land cover change (LCC), with the largest changes occurring in the tropics. Three simulations performed with the fully coupled Parallel Climate Model (PCM) are compared: (1) a present day control run; (2) a simulation with present day land cover and Intergovernmental Panel on Climate Change (IPCC) Special Report on Emission Scenarios (SRES) A2 greenhouse gas (GHG) projections; and (3) a simulation with SRES A2 land cover and GHG projections. Dimensionality of PCM data is reduced by projection onto a priori specified eigenvectors, consisting of Rossby and Kelvin waves produced by a linearized, reduced gravity model of the tropical circulation. A Hotelling T 2 test is performed on projection amplitudes. Effects of LCC evaluated by this method are limited to diabatic heating. A statistically significant and recurrent signal is detected for 33% of all tests performed for various combinations of parameters. Taking into account uncertainties and limitations of the present methodology, this signal can be interpreted as a Rossby wave response to prescribed LCC. The Rossby waves are shallow, large-scale motions, trapped at the equator and most pronounced in boreal summer. Differences in mass and flow fields indicate a shift of the tropical Walker circulation patterns with an anomalous subsidence over tropical South America.

Multi-scale forcing and the formation of subtropical desert and monsoon

NASA Astrophysics Data System (ADS)

Wu, G. X.; Liu, Y.; Zhu, X.; Li, W.; Ren, R.; Duan, A.; Liang, X.

2009-09-01

This study investigates three types of atmospheric forcing across the summertime subtropics that are shown to contribute in various ways to the occurrence of dry and wet climates in the subtropics. To explain the formation of desert over the western parts of continents and monsoon over the eastern parts, we propose a new mechanism of positive feedback between diabatic heating and vorticity generation that occurs via meridional advection of planetary vorticity and temperature. Monsoon and desert are demonstrated to coexist as twin features of multi-scale forcing, as follows. First, continent-scale heating over land and cooling over ocean induce the ascent of air over the eastern parts of continents and western parts of oceans, and descent over eastern parts of oceans and western parts of continents. Second, local-scale sea-breeze forcing along coastal regions enhances air descent over eastern parts of oceans and ascent over eastern parts of continents. This leads to the formation of the well-defined summertime subtropical LOSECOD quadruplet-heating pattern across each continent and adjacent oceans, with long-wave radiative cooling (LO) over eastern parts of oceans, sensible heating (SE) over western parts of continents, condensation heating (CO) over eastern parts of continents, and double dominant heating (D: LO+CO) over western parts of oceans. Such a quadruplet heating pattern corresponds to a dry climate over the western parts of continents and a wet climate over eastern parts. Third, regional-scale orographic-uplift-heating generates poleward ascending flow to the east of orography and equatorward descending flow to the west. The Tibetan Plateau (TP) is located over the eastern Eurasian continent. The TP-forced circulation pattern is in phase with that produced by continental-scale forcing, and the strongest monsoon and largest deserts are formed over the Afro-Eurasian Continent. In contrast, the Rockies and the Andes are located over the western parts of their respective continents, and orography-induced ascent is separated from ascent due to continental-scale forcing. Accordingly, the deserts and monsoon climate over these continents are not as strongly developed as those over the Eurasian Continent. A new mechanism of positive feedback between diabatic heating and vorticity generation, which occurs via meridional transfer of heat and planetary vorticity, is proposed as a means of explaining the formation of subtropical desert and monsoon. Strong low-level longwave radiative cooling over eastern parts of oceans and strong surface sensible heating on western parts of continents generate negative vorticity that is balanced by positive planetary vorticity advection from high latitudes. The equatorward flow generated over eastern parts of oceans produces cold sea-surface temperature and stable stratification, leading in turn to the formation of low stratus clouds and the maintenance of strong in situ longwave radiative cooling. The equatorward flow over western parts of continents carries cold, dry air, thereby enhancing local sensible heating as well as moisture release from the underlying soil. These factors result in a dry desert climate. Over the eastern parts of continents, condensation heating generates positive vorticity in the lower troposphere, which is balanced by negative planetary vorticity advection of the meridional flow from low latitudes. The flow brings warm and moist air, thereby enhancing local convective instability and condensation heating associated with rainfall. These factors produce a wet monsoonal climate. Overall, our results demonstrate that subtropical desert and monsoon coexist as a consequence of multi-scale forcing along the subtropics.

A study on spectral energy for the end of the twentieth century the basis of the NCEP reanalysis-II

NASA Astrophysics Data System (ADS)

Aranha, A. F.; Veiga, J. A.; Yoshida, M. C.

2013-05-01

The energy cycle proposed by Lorenz (1955) is composed of the behavior of the average energy from the atmosphere and characteristics of atmospheric energy deviations from this average, respectively called basic state and perturbed state. However, it is possible to discretize the energy contained in the atmosphere disturbed state, decomposing the fields of the various disturbances or harmonics wave type, so as to measure and analyze the energy of these disorders according to their number or wavelength, this methodology described second Saltzman (1957). Therefore, in view of the spectral analysis as a methodological basis, this work aims to study the energy contained by the atmosphere in disturbed state. Considering the terms of power generation potential available for nth waves due to diabatic heating, represented by (G(n)), potential energy of nth wave (P(n)) and kinetic energy of nth wave (K(n)) and the conversion of energy between the energy nth kinetic and potential energy of waves nth waves given by (C(n)). The variables used in the calculation of the terms above are, temperature (T) orthogonal components of the wind (u, v, w) and geopotential height (G) from a data set from the National Center for Environmental Prediction (NCEP) considering daily shared values on a regular grid with a spatial resolution of 2.5° × 2.5°, distributed in 12 pressure levels (1000, 925, 850, 700, 600, 500, 400, 300, 250, 200, 150, 100 hPa ) for the 1970 to 1999 period. The results show that for kinetic energy of disturbance to nth wave, the amount of energy is somewhat dammed during for the first 10 wave numbers in this range are the planetary waves and waves. Observing this way, we can conclude that these waves are responsible for much of the kinetic energy in disturbed state. A characteristic and a difference in the distribution of energy between kinetic energy and potential energy disturbed total available to disturbance, is the derivative of the energy wavenumber presented by P(n) as a derivative smoother, showing that the cascade potential energy no great leaps in energy between wavenumbers 10 onwards. The term conversion in potential energy of the disturbed state P(n) into kinetic energy of disorders K(n) reorensented by C(n) reveals important features in the energy spectrum. According to the results, the seasonal climatology of C(n), we note that the potential energy of the disturbed state feeds both the planetary waves and intermediate waves as synoptic scale. However, the production of kinetic energy of the waves from the energy potential of the perturbed state is greater for wavelengths larger or smaller number of waves. Note also that this term varies widely throughout the seasons. Importantly, negative values of C(n) are likely to occur, which would represent the conversion of kinetic energy into potential energy of the waves of the basic state. The values of the term climatological power generation potential available to nth waves due to diabatic heating, represented by G(n). The results show that the wavelength ranges 1 to 15 are primarily given for converting potential energy into kinetic energy.

A COMPARATIVE STUDY ON SPECTRAL ENERGETICS BETWEEN THE NCEP reanalysisII in current climate AND MODEL ECHAM5 in future scenarios

NASA Astrophysics Data System (ADS)

Aranha, A. F.; Veiga, J. P.

2013-12-01

Saltzman (1957) starting Lorenz Cycle (1955) derived a set of equations that show the energy contained in the basic state and the disturbed atmosphere, decomposing in various fields disturbance wave type, so as to quantify and analyze the energy of these disorders according to their number or wavelength. Based on the methodology Saltzman, this paper aims a comparative study between the energy of the disturbed state between the NCEP reanalysis-II for the current weather conditions and model ECHAM5 scenarios for future conditions of increased concentration of greenhouse gases (RCP26, RCP45 and RCP85), considering the terms of the generation of available potential energy to nth wave due to diabatic heating, represented by (Gn), the potential energy of nth wave (Pn) and kinetic energy of nth wave (Kn), as well as the conversion of energy between kinetic energy and potential energy nth wave of nth wave, given by (Cn). Two data sets were used in the calculation of the aforementioned terms. For the data set of NCEP and ECHAM5 were used variables, temperature (T), orthogonal wind components (u, v, w) and geopotential height (L), considering daily shared values on a regular grid with spatial resolutions of 2,5 x 2.5 and 1.875 x 1.875 graus, distributed on 12 and 15 levels of pressure (1000.0, 925.0, 850.0, 700.0, 600.0, 500.0, 400.0, 300.0, 250.0, 200.0, 150.0, 100.0 hPa), (1000.0, 850.0, 700.0, 500.0, 250.0, 150.0, 100.0, 70.0, 50.0, 30.0, 10.0, 3.0, 1.0, 0.3, 0.1 hPa) for the period of 1979-1999 and 2090-2100, respectively. The results show that most of the kinetic energy of disturbance to nth waves is concentrated in the first 15 wave numbers, both for the weather-NCEP II as to ECHAM5, having more significant increase in the profile and having a RCP85 energy cascade. This increase in kinetic energy was expected due to the increased energy in the system. For Pn, increasing the potential energy is also expected in view of the increased diabatic heating, but the energy jump is large spectrum in the range of 1 a 5, growth or accumulation of energy is visible in the figure wave, almost double the energy accumulated by the wave number 2, a derivative obeying the strong energy in the wave spectrum. We can conclude that the energy contained in a nonlinear way on the biggest waves are not shared aplenty. According to the results, the term conversion in Kn Pn, represented by Cn, reveals important characteristics in the energy spectrum. This we note that Pn feeds both the planetary waves and intermediate waves as synoptic scale. However, the production of Kn from Pn is added to the first wave specifically. It is also observed that Cn does not show large variations along the spectral profile. It is noteworthy that the energy conversions of RCP's are much smaller than the energy conversions NCEP-II, indicating that when there are increased concentrations of greenhouse gases is increasing Gen. therefore increased Pn and fall in Cn. Negative values of Cn are likely to occur, which would represent the conversion of kinetic energy into potential energy of the waves of the basic state.

The Renner-Teller effect in HCCCl(+)(X̃(2)Π) studied by zero-kinetic energy photoelectron spectroscopy and ab initio calculations.

PubMed

Sun, Wei; Dai, Zuyang; Wang, Jia; Mo, Yuxiang

2015-05-21

The spin-vibronic energy levels of the chloroacetylene cation up to 4000 cm(-1) above the ground state have been measured using the one-photon zero-kinetic energy photoelectron spectroscopic method. The spin-vibronic energy levels have also been calculated using a diabatic model, in which the potential energy surfaces are expressed by expansions of internal coordinates, and the Hamiltonian matrix equation is solved using a variational method with harmonic basis functions. The calculated spin-vibronic energy levels are in good agreement with the experimental data. The Renner-Teller (RT) parameters describing the vibronic coupling for the H-C≡C bending mode (ε4), Cl-C≡C bending mode (ε5), the cross-mode vibronic coupling (ε45) of the two bending vibrations, and their vibrational frequencies (ω4 and ω5) have also been determined using an effective Hamiltonian matrix treatment. In comparison with the spin-orbit interaction, the RT effect in the H-C≡C bending (ε4) mode is strong, while the RT effect in the Cl-C≡C bending mode is weak. There is a strong cross-mode vibronic coupling of the two bending vibrations, which may be due to a vibronic resonance between the two bending vibrations. The spin-orbit energy splitting of the ground state has been determined for the first time and is found to be 209 ± 2 cm(-1).

The East Asian Jet Stream and Asian-Pacific-American Climate

NASA Technical Reports Server (NTRS)

Yang, Song; Lau, K.-M.; Kim, K.-M.

2000-01-01

The upper-tropospheric westerly jet stream over subtropical East Asia and western Pacific, often referred to as East Asian Jet (EAJ), is an important atmospheric circulation system in the Asian-Pacific-American (APA) region during winter. It is characterized by variabilities on a wide range of time scales and exerts a strong impact on the weather and climate of the region. On the synoptic scale, the jet stream is closely linked to many phenomena such as cyclogenesis, frontogenesis, blocking, storm track activity, and the development of other atmospheric disturbances. On the seasonal time scale, the variation of the EAJ determines many characteristics of the seasonal transition of the atmospheric circulation especially over East Asia. The variabilities of the EAJ on these time scales have been relatively well documented. It has also been understood since decades ago that the interannual. variability of the EAJ is associated with many climate signals in the APA region. These signals include the persistent anomalies of the East Asian winter monsoon and the changes in diabatic heating and in the Hadley circulation. However, many questions remain for the year-to-year variabilities of the EAJ and their relation to the APA climate. For example, what is the relationship between the EAJ and El Nino/Southern Oscillation (ENSO)? Will the EAJ and ENSO play different roles in modulating the APA climate? How is the jet stream linked to the non-ENSO-related sea surface temperature (SST) anomalies and to the Pacific/North American (PNA) teleconnection pattern?

Numerical simulation of a mistral wind event occuring

NASA Astrophysics Data System (ADS)

Guenard, V.; Caccia, J. L.; Tedeschi, G.

2003-04-01

The experimental network of the ESCOMPTE field experiment (june-july 2001) is turned into account to investigate the Mistral wind affecting the Marseille area (South of France). Mistral wind is a northerly flow blowing across the Rhône valley and toward the Mediterranean sea resulting from the dynamical low pressure generated in the wake of the Alps ridge. It brings cold, dry air masses and clear sky conditions over the south-eastern part of France. Up to now, few scientific studies have been carried out on the Mistral wind especially the evolution of its 3-D structure so that its mesoscale numerical simulation is still relevant. Non-hydrostatic RAMS model is performed to better investigate this mesoscale phenomena. Simulations at a 12 km horizontal resolution are compared to boundary layer wind profilers and ground measurements. Preliminary results suit quite well with the Mistral statistical studies carried out by the operational service of Météo-France and observed wind profiles are correctly reproduced by the numerical model RAMS which appears to be an efficient tool for its understanding of Mistral. Owing to the absence of diabatic effect in Mistral events which complicates numerical simulations, the present work is the first step for the validation of RAMS model in that area. Further works will consist on the study of the interaction of Mistral wind with land-sea breeze. Also, RAMS simulations will be combined with aerosol production and ocean circulation models to supply chemists and oceanographers with some answers for their studies.

Numerical Hindcast Experiments for Study Tropical Convections and MJO Events during Year of Tropical Convection

NASA Astrophysics Data System (ADS)

Chern, J.; Tao, W.; Shen, B.

2011-12-01

The Madden-Julian oscillation (MJO) is the dominant component of intraseasonal variability in the tropic. It interacts and influences a wide range of weather and climate phenomena across different temporal and spatial scales. Despite the important role the MJO plays in the weather and climate system, past multi-model MJO intercomparison studies have shown that current global general circulation models (GCMs) still have considerable shortcomings in representing and forecasting this phenomenon. To improve representation of MJO and tropical convective cloud systems in global model, an Multiscale Modeling Framework (MMF) in which a cloud-resolving model takes the place of the sing-column cumulus parameterization used in convectional GCMs has been successfully developed at NAAS Goddard (Tao et al. 2009). To evaluate and improve the ability of this modeling system in representation and prediction of the MJO, several numerical hindcast experiments of a few selected MJO events during YOTC have been carried out. The ability of the model to simulate the MJO events is examined using diagnostic and skill metrics developed by the CLIVAR MJO Working Group Project as well as comparisons with a high-resolution global mesoscale model simulations, satellite observations, and analysis dataset. Several key variables associated with the MJO are investigated, including precipitation, outgoing longwave radiation, large-scale circulation, surface latent heat flux, low-level moisture convergence, vertical structure of moisture and hydrometers, and vertical diabatic heating profiles to gain insight of cloud processes associated with the MJO events.

Risk factors for the development of metabolic syndrome in obese children and adolescents.

PubMed

Folić, Nevena; Folić, Marko; Marković, Slavica; Andjelković, Marija; Janković, Slobodan

2015-01-01

High prevalence of metabolic syndrome (MetS) in children and adolescents is a great concern of the modern society. bjective: Our aim was to determine the influence of previously investigated, but also and potentially novel risk factors for the development of metabolic syndrome in children and adolescents. Observational case-control clinical study was conducted involving children and adolescents with obesity/metabolic syndrome, treated on inpatient basis from January 2008 to January 2012 at the Pediatric Clinic of the Clinical Centre Kragujevac, Kragujevac, Serbia. The group of"cases"(n=28) included patients aged 10-16 years with the diagnosis of metabolic syndrome according to the International Diabetes Federation (IDF) criteria, while the control group included twice as many obese patients (n=56) matched to the compared group. Presence of maternal gestational diabates (ORadjusted: 39.426; 95% Cl: 1.822-853.271; p=0.019), and/or lack of breastfeeding in the first six months of life (ORadjusted: 0.079; 95% CI: 0.009-0.716; p=0.024) were significant predictors for developing MetS. Also, microalbuminuria is associated with MetS in obese children and adolescants (ORadjusted: 1.686; 95% Cl: 1.188-2.393; p=0.003) CONCLUSION: Presence of maternal gestational diabetes and/or lack of infant breastfeeding are considered as relevant factors that may contribute to the increased risk of developing MetS syndrome, while microalbuminuria is frequently associated with MetS in obese children and adolescents.

Neutron imaging of diabatic two-phase flows relevant to air conditioning

DOE Office of Scientific and Technical Information (OSTI.GOV)

Geoghegan, Patrick J; Sharma, Vishaldeep

The design of the evaporator of an air conditioning system relies heavily on heat transfer coefficients and pressure drop correlations that predominantly involve an estimate of the changing void fraction and the underlying two-phase flow regime. These correlations dictate whether the resulting heat exchanger is oversized or not and the amount of refrigerant charge necessary to operate. The latter is particularly important when dealing with flammable or high GWP refrigerants. Traditional techniques to measure the void fraction and visualize the flow are either invasive to the flow or occur downstream of the evaporator, where some of the flow distribution willmore » have changed. Neutron imaging has the potential to visualize two-phase flow in-situ where an aluminium heat exchanger structure becomes essentially transparent to the penetrating neutrons. The subatomic particles are attenuated by the passing refrigerant flow. The resulting image may be directly related to the void fraction and the overall picture provides a clear insight into the flow regime present. This work presents neutron images of the refrigerant Isopentane as it passes through the flow channels of an aluminium evaporator at flowrates relevant to air conditioning. The flow in a 4mm square macro channel is compared to that in a 250 m by 750 m rectangular microchannel in terms of void fraction and regime. All neutron imaging experiments were conducted at the High Flux Isotope Reactor, an Oak Ridge National Laboratory facility« less

Assessment of dust aerosol effect on cloud properties over Northwest China using CERES SSF data

NASA Astrophysics Data System (ADS)

Huang, J.; Wang, X.; Wang, T.; Su, J.; Minnis, P.; Lin, B.; Hu, Y.; Yi, Y.

Dust aerosols not only have direct effects on the climate through reflection and absorption of the short and long wave radiation but also modify cloud properties such as the number concentration and size of cloud droplets indirect effect and contribute to diabatic heating in the atmosphere that often enhances cloud evaporation and reduces the cloud water path In this study indirect and semi-direct effects of dust aerosols are analyzed over eastern Asia using two years June 2002 to June 2004 of CERES Clouds and the Earth s Radiant Energy Budget Scanner and MODIS MODerate Resolution Imaging Spectroradiometer Aqua Edition 1B SSF Single Scanner Footprint data sets The statistical analysis shows evidence for both indirect and semi-direct effect of Asia dust aerosols The dust appears to reduce the ice cloud effective particle diameter and increase high cloud amount On average ice cloud effective particle diameters of cirrus clouds under dust polluted conditions dusty cloud are 11 smaller than those derived from ice clouds in dust-free atmospheric environments The water paths of dusty clouds are also considerably smaller than those of dust-free clouds Dust aerosols could warm clouds thereby increasing the evaporation of cloud droplets resulting in reduced cloud water path semi-direct effect The semi-direct effect may be dominated the interaction between dust aerosols and clouds over arid and semi-arid areas and partly contribute to reduced precipitation

Maintenance of Summer Monsoon Circulations: A Planetary-Scale Perspective.

NASA Astrophysics Data System (ADS)

Chen, Tsing-Chang

2003-06-01

The monsoon circulation, which is generally considered to be driven by the landmass-ocean thermal contrast, like a gigantic land-sea breeze circulation, exhibits a phase reversal in its vertical structure; a monsoon high aloft over a continental thermal low is juxtaposed with a midoceanic trough underlaid by an oceanic anticyclone. This classic monsoon circulation model is well matched by the monsoon circulation depicted with the observational data prior to the First Global Atmospheric Research Program (GARP) Global Experiment (FGGE). However, synthesizing findings of the global circulation portrayed with the post-FGGE data, it was found that some basic features of major monsoon circulations in Asia, North America, South America, and Australia differ from those of the classic monsoon circulation model. Therefore, a revision of the classic monsoon theory is suggested. With four different wave regimes selected to fit the horizontal dimensions of these monsoon circulations, basic features common to all four major monsoons are illustrated in terms of diagnostic analyses of the velocity potential maintenance equation (which relates diabatic heating and velocity potential) and the streamfunction budget (which links velocity potential and streamfunction) in these wave regimes. It is shown that a monsoon circulation is actually driven by the east-west differential heating and maintained dynamically by a balance between a vorticity source and advection. This dynamic balance is reflected by a spatial quadrature relationship between the monsoon divergent circulation and the monsoon high (low) at upper (lower) levels.

Microphysical and Kinematic Characteristics of Regions of Flash Initiation in a Supercell Storm and a Multicell Storm Observed During the DC3 Field Program

NASA Astrophysics Data System (ADS)

DiGangi, E.; MacGorman, D. R.; Ziegler, C.; Betten, D.; Biggerstaff, M. I.

2017-12-01

Lightning initiation in thunderstorms requires that the local electric field magnitude exceed breakdown values somewhere, and this tends to occur between regions of positive and negative charge, where the largest electric field magnitudes tend to occur. Past studies have demonstrated that, near updrafts, storms with very strong updrafts tend to elevate regions of charge and of flash initiations higher, as well as to have more flashes initiated by small pockets of charge, than in storms with much weaker updrafts. In all thunderstorms, the source of these charge regions is generally thought to be microscopic charge separation via the relative growth rate noninductive mechanism, followed by macroscopic charge separation via sedimentation, although other charge generation mechanisms can contribute to charge in some regions. Charge generation and lightning initiation are therefore inherently dependent on the microphysical and kinematic characteristics of a given storm. This study compares the results of a hydrometeor classification algorithm applied to C-band mobile radar data with mixing ratios calculated by a diabatic Lagrangian analysis retrieval from the dual-Doppler wind fields for two storms, the 29-30 May 2012 supercell storm and the 21 June 2012 multicell storm, observed during the Deep Convective Clouds and Chemistry experiment. Using these data, we then compare the inferred microphysical and kinematic characteristics of regions in which the Oklahoma Lightning Mapping Array indicated that flashes were initiated in these two very different storms.

Environments of Long-Lived Mesoscale Convective Systems Over the Central United States in Convection Permitting Climate Simulations

NASA Astrophysics Data System (ADS)

Yang, Qing; Houze, Robert A.; Leung, L. Ruby; Feng, Zhe

2017-12-01

Continental-scale convection-permitting simulations of the warm seasons of 2011 and 2012 using the Weather Research and Forecasting model reproduce realistic structure and frequency distribution of lifetime and event mean precipitation of mesoscale convective systems (MCSs) over the central United States. Analysis is performed to determine the environmental conditions conducive to generating long-lived MCSs. The simulations show that MCSs systematically form over the central Great Plains ahead of a trough in the westerlies in combination with an enhanced low-level moist jet from the Gulf of Mexico. These environmental properties at the time of storm initiation are most prominent for the MCSs that persist for the longest times. MCSs reaching lifetimes of 9 h or more occur closer to the approaching trough than shorter-lived MCSs. These long-lived MCSs exhibit the strongest feedback to the environment through diabatic heating in the trailing regions of the MCSs. The feedback strengthens the synoptic-scale trough associated with the MCS by producing an anomaly circulation characterized by a divergent perturbation at high levels over the MCS and a midlevel cyclonic circulation perturbation near the trough line in association with the trailing portion of the MCS. The quasi-balanced mesoscale vortex may help to maintain the MCS over a long period of time by feeding dry, cool air into the environment at the rear of the MCS region that enhances evaporative cooling and helps maintain the MCS.

Quantifying isentropic stratosphere-troposphere exchange of ozone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Huang; Chen, Gang; Tang, Qi

There is increased evidence that stratosphere-troposphere exchange (STE) of ozone has a significant impact on tropospheric chemistry and radiation. Traditional diagnostics of STE consider the ozone budget in the lowermost stratosphere (LMS) as a whole. However, this can only render the hemispherically integrated ozone flux and therefore does not distinguish the exchange of ozone into low latitudes from that into high latitudes. The exchange of ozone at different latitudes may have different tropospheric impacts. This present study extends the traditional approach from the entire LMS to individual isentropic layers in the LMS and therefore gives the meridional distribution of STEmore » by the latitudes where each isentropic surface intersects the tropopause. The specified dynamics version of the Whole Atmosphere Community Climate Model is used to estimate the STE ozone flux on each isentropic surface. It is found that net troposphere-to-stratosphere ozone transport occurs in low latitudes along the 350–380 K isentropic surfaces and that net stratosphere-to-troposphere ozone transport takes place in the extratropics along the 280–350 K isentropes. Particularly, the seasonal cycle of extratropical STE ozone flux in the Northern Hemisphere displays a maximum in late spring and early summer, following the seasonal migration of the upper tropospheric jet and associated isentropic mixing. Moreover, differential diabatic heating and isentropic mixing tend to induce STE ozone fluxes in opposite directions, but the net effect results in a spatiotemporal pattern similar to the STE ozone flux associated with isentropic mixing.« less

Quantifying isentropic stratosphere-troposphere exchange of ozone

DOE PAGES

Yang, Huang; Chen, Gang; Tang, Qi; ...

2016-03-25

There is increased evidence that stratosphere-troposphere exchange (STE) of ozone has a significant impact on tropospheric chemistry and radiation. Traditional diagnostics of STE consider the ozone budget in the lowermost stratosphere (LMS) as a whole. However, this can only render the hemispherically integrated ozone flux and therefore does not distinguish the exchange of ozone into low latitudes from that into high latitudes. The exchange of ozone at different latitudes may have different tropospheric impacts. This present study extends the traditional approach from the entire LMS to individual isentropic layers in the LMS and therefore gives the meridional distribution of STEmore » by the latitudes where each isentropic surface intersects the tropopause. The specified dynamics version of the Whole Atmosphere Community Climate Model is used to estimate the STE ozone flux on each isentropic surface. It is found that net troposphere-to-stratosphere ozone transport occurs in low latitudes along the 350–380 K isentropic surfaces and that net stratosphere-to-troposphere ozone transport takes place in the extratropics along the 280–350 K isentropes. Particularly, the seasonal cycle of extratropical STE ozone flux in the Northern Hemisphere displays a maximum in late spring and early summer, following the seasonal migration of the upper tropospheric jet and associated isentropic mixing. Moreover, differential diabatic heating and isentropic mixing tend to induce STE ozone fluxes in opposite directions, but the net effect results in a spatiotemporal pattern similar to the STE ozone flux associated with isentropic mixing.« less

A pseudoenergy wave-activity relation for ageostrophic and non-hydrostatic moist atmosphere

NASA Astrophysics Data System (ADS)

Ran, Ling-Kun; Ping, Fan

2015-05-01

By employing the energy-Casimir method, a three-dimensional virtual pseudoenergy wave-activity relation for a moist atmosphere is derived from a complete system of nonhydrostatic equations in Cartesian coordinates. Since this system of equations includes the effects of water substance, mass forcing, diabatic heating, and dissipations, the derived wave-activity relation generalizes the previous result for a dry atmosphere. The Casimir function used in the derivation is a monotonous function of virtual potential vorticity and virtual potential temperature. A virtual energy equation is employed (in place of the previous zonal momentum equation) in the derivation, and the basic state is stationary but can be three-dimensional or, at least, not necessarily zonally symmetric. The derived wave-activity relation is further used for the diagnosis of the evolution and propagation of meso-scale weather systems leading to heavy rainfall. Our diagnosis of two real cases of heavy precipitation shows that positive anomalies of the virtual pseudoenergy wave-activity density correspond well with the strong precipitation and are capable of indicating the movement of the precipitation region. This is largely due to the cyclonic vorticity perturbation and the vertically increasing virtual potential temperature over the precipitation region. Project supported by the National Basic Research Program of China (Grant No. 2013CB430105), the Key Program of the Chinese Academy of Sciences (Grant No. KZZD-EW-05), the National Natural Science Foundation of China (Grant No. 41175060), and the Project of CAMS, China (Grant No. 2011LASW-B15).

Large-Scale Meteorological Patterns Associated with Extreme Precipitation in the US Northeast

NASA Astrophysics Data System (ADS)

Agel, L. A.; Barlow, M. A.

2016-12-01

Patterns of daily large-scale circulation associated with Northeast US extreme precipitation are identified using both k-means clustering (KMC) and Self-Organizing Maps (SOM) applied to tropopause height. Tropopause height provides a compact representation of large-scale circulation patterns, as it is linked to mid-level circulation, low-level thermal contrasts and low-level diabatic heating. Extreme precipitation is defined as the top 1% of daily wet-day observations at 35 Northeast stations, 1979-2008. KMC is applied on extreme precipitation days only, while the SOM algorithm is applied to all days in order to place the extreme results into a larger context. Six tropopause patterns are identified on extreme days: a summertime tropopause ridge, a summertime shallow trough/ridge, a summertime shallow eastern US trough, a deeper wintertime eastern US trough, and two versions of a deep cold-weather trough located across the east-central US. Thirty SOM patterns for all days are identified. Results for all days show that 6 SOM patterns account for almost half of the extreme days, although extreme precipitation occurs in all SOM patterns. The same SOM patterns associated with extreme precipitation also routinely produce non-extreme precipitation; however, on extreme precipitation days the troughs, on average, are deeper and the downstream ridges more pronounced. Analysis of other fields associated with the large-scale patterns show various degrees of anomalously strong upward motion during, and moisture transport preceding, extreme precipitation events.

Photodissociation of water. II. Wave packet calculations for the photofragmentation of H2O and D2O in the B˜ band

NASA Astrophysics Data System (ADS)

van Harrevelt, Rob; van Hemert, Marc C.

2000-04-01

A complete three-dimensional quantum mechanical description of the photodissociation of water in the B˜ band, starting from its rotational ground state, is presented. In order to include B˜-X˜ vibronic coupling and the B˜-Ã Renner-Teller coupling, diabatic electronic states have been constructed from adiabatic electronic states and matrix elements of the electronic angular momentum operators, following the procedure developed by A. J. Dobbyn and P. J. Knowles [Mol. Phys. 91, 1107 (1997)], using the ab initio results discussed in the preceding paper. The dynamics is studied using wave packet methods, and the evolution of the time-dependent wave function is discussed in detail. Results for the H2O and D2O absorption spectra, OH(A)/OH(X) and OD(A)/OD(X) branching ratios, and rovibrational distributions of the OH and OD fragments are presented and compared with available experimental data. The present theoretical results agree at least qualitatively with the experiments. The calculations show that the absorption spectrum and the product state distributions are strongly influenced by long-lived resonances on the adiabatic B˜ state. It is also shown that molecular rotation plays an important role in the photofragmentation process, due to both the Renner-Teller B˜-X˜ mixing, and the strong effect of out-of-plane molecular rotations (K>0) on the dynamics at near linear HOH and HHO geometries.

Multireference configuration interaction study of the mixed Valence-Rydberg character of the C2H4 1(π,π*) V state

NASA Astrophysics Data System (ADS)

Krebs, Stefan; Buenker, Robert J.

1997-05-01

The spatial extension of the C2H41(π,π*) V state is investigated by means of low selection threshold multireference configuration interaction (CI) calculations employing two atomic orbital (AO) basis sets with different numbers of polarization and Rydberg functions. The results are shown to be nearly independent of the choice of one-electron basis (ground N, triplet T, and singlet V self-consistent field molecular orbitals (SCF MOs)) in forming the many-electron basis for the configuration interaction indicating that the AO basis limit has been closely approached in each case. The calculations indicate that the value for the <ΨV|Σxi2|ΨV>≡V matrix element falls in the 18±1 a02 range, 50% larger than the corresponding values computed for N and T, respectively, for the corresponding N and T states. This result is interpreted to be a consequence of the mixing of diabatic 1(π,π*) valence and 1(π,dπ) Rydberg states in the Franck-Condon region of the V-N transition. The corresponding excitation energy is computed to lie in the 7.90-7.95 eV range, indicating that there is a distinct nonverticality in the measured absorption spectrum which is caused in part by nonadiabatic interactions between the V and 1(π,3py) Rydberg states as a result of torsional motion of the C2H4 molecule.

The East Asian Atmospheric Water Cycle and Monsoon Circulation in the Met Office Unified Model

NASA Astrophysics Data System (ADS)

Rodríguez, José M.; Milton, Sean F.; Marzin, Charline

2017-10-01

In this study the low-level monsoon circulation and observed sources of moisture responsible for the maintenance and seasonal evolution of the East Asian monsoon are examined, studying the detailed water budget components. These observational estimates are contrasted with the Met Office Unified Model (MetUM) climate simulation performance in capturing the circulation and water cycle at a variety of model horizontal resolutions and in fully coupled ocean-atmosphere simulations. We study the role of large-scale circulation in determining the hydrological cycle by analyzing key systematic errors in the model simulations. MetUM climate simulations exhibit robust circulation errors, including a weakening of the summer west Pacific Subtropical High, which leads to an underestimation of the southwesterly monsoon flow over the region. Precipitation and implied diabatic heating biases in the South Asian monsoon and Maritime Continent region are shown, via nudging sensitivity experiments, to have an impact on the East Asian monsoon circulation. By inference, the improvement of these tropical biases with increased model horizontal resolution is hypothesized to be a factor in improvements seen over East Asia with increased resolution. Results from the annual cycle of the hydrological budget components in five domains show a good agreement between MetUM simulations and ERA-Interim reanalysis in northern and Tibetan domains. In simulations, the contribution from moisture convergence is larger than in reanalysis, and they display less precipitation recycling over land. The errors are closely linked to monsoon circulation biases.

Role of Longwave Cloud-Radiation Feedback in the Simulation of the Madden-Julian Oscillation

NASA Technical Reports Server (NTRS)

Kim, Daehyun; Ahn, Min-Seop; Kang, In-Sik; Del Genio, Anthony D.

2015-01-01

The role of the cloud-radiation interaction in the simulation of the Madden-Julian oscillation (MJO) is investigated. A special focus is on the enhancement of column-integrated diabatic heating due to the greenhouse effects of clouds and moisture in the region of anomalous convection. The degree of this enhancement, the greenhouse enhancement factor (GEF), is measured at different precipitation anomaly regimes as the negative ratio of anomalous outgoing longwave radiation to anomalous precipitation. Observations show that the GEF varies significantly with precipitation anomaly and with the MJO cycle. The greenhouse enhancement is greater in weak precipitation anomaly regimes and its effectiveness decreases monotonically with increasing precipitation anomaly. The GEF also amplifies locally when convection is strengthened in association with the MJO, especially in the weak precipitation anomaly regime (less than 5 mm day(exp -1)). A robust statistical relationship is found among CMIP5 climate model simulations between the GEF and the MJO simulation fidelity. Models that simulate a stronger MJO also simulate a greater GEF, especially in the weak precipitation anomaly regime (less than 5 mm day(exp -1)). Models with a greater GEF in the strong precipitation anomaly regime (greater than 30 mm day(-1)) represent a slightly slower MJO propagation speed. Many models that lack the MJO underestimate the GEF in general and in particular in the weak precipitation anomaly regime. The results herein highlight that the cloud-radiation interaction is a crucial process for climate models to correctly represent the MJO.

Response of rainy season duration over Asian monsoon region to astronomical forcing under glacial and interglacial conditions

NASA Astrophysics Data System (ADS)

Shi, Z.

2017-12-01

The responses of Asian summer monsoon and associated precipitation to astronomical forcing have beenintensively explored during the past decades, but debate still exists regarding whether or not the Asianmonsoon is controlled by northern or southern summer insolation. Various modeling studies have been conducted that support the potential roles played by the insolation in bothhemispheres. Among these previous studies, however, the main emphasis has been on the Asianmonsoon intensity, with the response of monsoon duration having received little consideration. In thepresent study, the response of the rainy season duration over different monsoon areas to astronomical forcingand its contribution to total annual precipitation are evaluated using an atmospheric general circulationmodel. The results show that the durations of the rainy seasons, especially their withdrawal, in northernEast Asia and the India-Bay of Bengal region, are sensitive to precession change under interglacial-likeconditions. Compared to those during stronger boreal summer insolation, the Asian monsoon associatedrainy seasons at weaker insolation last longer, although the peak intensity is smaller. Thislonger duration of rainfall, which results from the change in land-ocean thermal contrast associated withatmospheric diabatic heating, can counterbalance the weakened intensity in certain places and induce anopposite response of total annual precipitation. However, the duration effect of Asian monsoon is limitedunder glacial-like conditions. Nevertheless, monsoon duration is a factor that can dominate the astronomical-scalevariability of Asian monsoon, alongside the intensity, and it should therefore receive greaterattention when attempting to explain astronomical-scale monsoon change.

Seasonal prediction of US summertime ozone using statistical analysis of large scale climate patterns.

PubMed

Shen, Lu; Mickley, Loretta J

2017-03-07

We develop a statistical model to predict June-July-August (JJA) daily maximum 8-h average (MDA8) ozone concentrations in the eastern United States based on large-scale climate patterns during the previous spring. We find that anomalously high JJA ozone in the East is correlated with these springtime patterns: warm tropical Atlantic and cold northeast Pacific sea surface temperatures (SSTs), as well as positive sea level pressure (SLP) anomalies over Hawaii and negative SLP anomalies over the Atlantic and North America. We then develop a linear regression model to predict JJA MDA8 ozone from 1980 to 2013, using the identified SST and SLP patterns from the previous spring. The model explains ∼45% of the variability in JJA MDA8 ozone concentrations and ∼30% variability in the number of JJA ozone episodes (>70 ppbv) when averaged over the eastern United States. This seasonal predictability results from large-scale ocean-atmosphere interactions. Warm tropical Atlantic SSTs can trigger diabatic heating in the atmosphere and influence the extratropical climate through stationary wave propagation, leading to greater subsidence, less precipitation, and higher temperatures in the East, which increases surface ozone concentrations there. Cooler SSTs in the northeast Pacific are also associated with more summertime heatwaves and high ozone in the East. On average, models participating in the Atmospheric Model Intercomparison Project fail to capture the influence of this ocean-atmosphere interaction on temperatures in the eastern United States, implying that such models would have difficulty simulating the interannual variability of surface ozone in this region.

Nonadiabatic couplings in the collisional removal of O(2)(b (1)Sigma(g) (+),v) by O(2).

PubMed

Dayou, F; Hernández, M I; Campos-Martínez, J; Hernández-Lamoneda, R

2010-01-28

The effect of nonadiabatic couplings on the collisional removal of O(2)(b (1)Sigma(g) (+),v) by O(2)(X (3)Sigma(g) (-), v=0) is investigated. Two-dimensional adiabatic and quasidiabatic potential energy surfaces for the excited dimer states and the corresponding nonadiabatic radial couplings have been computed by means of ab initio calculations. Alternately, a two-state theoretical model, based on the Landau-Zener and Rosen-Zener-Demkov assumptions, has been employed to derive analytical forms for the nonadiabatic couplings and an adiabatic-to-diabatic transformation only depending on a reduced set of adiabatic energy terms. Compared to the ab initio results, the predictions of the model are found to be highly accurate. Quantum dynamics calculations for the removal of the first ten vibrational states of O(2)(b (1)Sigma(g) (+),v) indicate a clear dominant contribution of the vibration-electronic relaxation mechanism relative to the vibration-translation energy transfer. Although the present reduced-dimensionality model precludes any quantitative comparison with experiments, it is found that the removal probabilities for v=1-3 are qualitatively consistent with the experimental observations, once the vibrational structure of the fragments is corrected with spectroscopical terms. Besides, the model served to show how the computation of the adiabatic PESs just at the crossing seam was sufficient to describe the nonadiabatic dynamics related to a given geometrical arrangement. This implies considerable savings in the calculations which will eventually allow for larger accuracy in the ab initio calculations as well as higher dimensional treatments.

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. I. Theory for a dimer

NASA Astrophysics Data System (ADS)

Tiwari, Vivek; Peters, William K.; Jonas, David M.

2017-10-01

Non-adiabatic vibrational-electronic resonance in the excited electronic states of natural photosynthetic antennas drastically alters the adiabatic framework, in which electronic energy transfer has been conventionally studied, and suggests the possibility of exploiting non-adiabatic dynamics for directed energy transfer. Here, a generalized dimer model incorporates asymmetries between pigments, coupling to the environment, and the doubly excited state relevant for nonlinear spectroscopy. For this generalized dimer model, the vibrational tuning vector that drives energy transfer is derived and connected to decoherence between singly excited states. A correlation vector is connected to decoherence between the ground state and the doubly excited state. Optical decoherence between the ground and singly excited states involves linear combinations of the correlation and tuning vectors. Excitonic coupling modifies the tuning vector. The correlation and tuning vectors are not always orthogonal, and both can be asymmetric under pigment exchange, which affects energy transfer. For equal pigment vibrational frequencies, the nonadiabatic tuning vector becomes an anti-correlated delocalized linear combination of intramolecular vibrations of the two pigments, and the nonadiabatic energy transfer dynamics become separable. With exchange symmetry, the correlation and tuning vectors become delocalized intramolecular vibrations that are symmetric and antisymmetric under pigment exchange. Diabatic criteria for vibrational-excitonic resonance demonstrate that anti-correlated vibrations increase the range and speed of vibronically resonant energy transfer (the Golden Rule rate is a factor of 2 faster). A partial trace analysis shows that vibronic decoherence for a vibrational-excitonic resonance between two excitons is slower than their purely excitonic decoherence.

Vertical structure and physical processes of the Madden-Julian Oscillation: Biases and uncertainties at short range

NASA Astrophysics Data System (ADS)

Xavier, Prince K.; Petch, Jon C.; Klingaman, Nicholas P.; Woolnough, Steve J.; Jiang, Xianan; Waliser, Duane E.; Caian, Mihaela; Cole, Jason; Hagos, Samson M.; Hannay, Cecile; Kim, Daehyun; Miyakawa, Tomoki; Pritchard, Michael S.; Roehrig, Romain; Shindo, Eiki; Vitart, Frederic; Wang, Hailan

2015-05-01

An analysis of diabatic heating and moistening processes from 12 to 36 h lead time forecasts from 12 Global Circulation Models are presented as part of the "Vertical structure and physical processes of the Madden-Julian Oscillation (MJO)" project. A lead time of 12-36 h is chosen to constrain the large-scale dynamics and thermodynamics to be close to observations while avoiding being too close to the initial spin-up of the models as they adjust to being driven from the Years of Tropical Convection (YOTC) analysis. A comparison of the vertical velocity and rainfall with the observations and YOTC analysis suggests that the phases of convection associated with the MJO are constrained in most models at this lead time although the rainfall in the suppressed phase is typically overestimated. Although the large-scale dynamics is reasonably constrained, moistening and heating profiles have large intermodel spread. In particular, there are large spreads in convective heating and moistening at midlevels during the transition to active convection. Radiative heating and cloud parameters have the largest relative spread across models at upper levels during the active phase. A detailed analysis of time step behavior shows that some models show strong intermittency in rainfall and differences in the precipitation and dynamics relationship between models. The wealth of model outputs archived during this project is a very valuable resource for model developers beyond the study of the MJO. In addition, the findings of this study can inform the design of process model experiments, and inform the priorities for field experiments and future observing systems.

The response of European and Asian climate to global and regional aerosol emissions

NASA Astrophysics Data System (ADS)

Wilcox, Laura; Dunstone, Nick; Highwood, Eleanor; Bollasina, Massimo; Dong, Buwen; Sutton, Rowan

2017-04-01

Asia has the world's highest anthropogenic aerosol loading and has experienced a dramatic increase in emissions since the 1950s, which has continued in the 21st century, in stark contrast with European (and North American) emissions which started to decrease in the 1970s. We use a set of transient coupled model experiments (HadGEM2-GC2) to explore the regional climate effects of anthropogenic aerosol changes since the 1980s, with a focus on the European and Asian responses. Comparing simulations with globally varying aerosol emissions to an equivalent set with Asian emissions fixed at their 1971-1980 mean over Asia, we identify the contribution of Asian emissions to the total impact. Identifying thermodynamic and dynamic responses to global and regional aerosol changes, we diagnose atmospheric teleconnections and their interactions with local processes, and the mechanisms by which aerosol affects both European and Asian climate. It is found that Asian aerosols led to substantial changes in Asian climate, weakening the summer monsoon, which is a key driver of the observed precipitation changes there in recent decades. Asian emissions are also able to induce planetary-scale teleconnection patterns in both winter and summer. The impact of the regional diabatic heating anomaly propagates remotely by exciting northern hemisphere wave-trains which, enhanced by regional feedbacks, cause changes in near-surface climate over Europe. To examine the robustness of the mechanisms we identify in HadGEM2, we analyse similar sets of experiments from NorESM1-M and GFDL-CM3: models with very different climatologies and representations of aerosol processes.

Cloud Cover Increase with Increasing Aerosol Absorptivity: A Counterexample to the Conventional Semidirect Aerosol Effect

NASA Technical Reports Server (NTRS)

Perlwitz, Jan; Miller, Ron L.

2010-01-01

We reexamine the aerosol semidirect effect using a general circulation model and four cases of the single-scattering albedo of dust aerosols. Contrary to the expected decrease in low cloud cover due to heating by tropospheric aerosols, we find a significant increase with increasing absorptivity of soil dust particles in regions with high dust load, except during Northern Hemisphere winter. The strongest sensitivity of cloud cover to dust absorption is found over land during Northern Hemisphere summer. Here even medium and high cloud cover increase where the dust load is highest. The cloud cover change is directly linked to the change in relative humidity in the troposphere as a result of contrasting changes in specific humidity and temperature. More absorption by aerosols leads to larger diabatic heating and increased warming of the column, decreasing relative humidity. However, a corresponding increase in the specific humidity exceeds the temperature effect on relative humidity. The net effect is more low cloud cover with increasing aerosol absorption. The higher specific humidity where cloud cover strongly increases is attributed to an enhanced convergence of moisture driven by dust radiative heating. Although in some areas our model exhibits a reduction of low cloud cover due to aerosol heating consistent with the conventional description of the semidirect effect, we conclude that the link between aerosols and clouds is more varied, depending also on changes in the atmospheric circulation and the specific humidity induced by the aerosols. Other absorbing aerosols such as black carbon are expected to have a similar effect.

Characteristics of Mesoscale Organization in WRF Simulations of Convection during TWP-ICE

NASA Technical Reports Server (NTRS)

Del Genio, Anthony D.; Wu, Jingbo; Chen, Yonghua

2013-01-01

Compared to satellite-derived heating profiles, the Goddard Institute for Space Studies general circulation model (GCM) convective heating is too deep and its stratiform upper-level heating is too weak. This deficiency highlights the need for GCMs to parameterize the mesoscale organization of convection. Cloud-resolving model simulations of convection near Darwin, Australia, in weak wind shear environments of different humidities are used to characterize mesoscale organization processes and to provide parameterization guidance. Downdraft cold pools appear to stimulate further deep convection both through their effect on eddy size and vertical velocity. Anomalously humid air surrounds updrafts, reducing the efficacy of entrainment. Recovery of cold pool properties to ambient conditions over 5-6 h proceeds differently over land and ocean. Over ocean increased surface fluxes restore the cold pool to prestorm conditions. Over land surface fluxes are suppressed in the cold pool region; temperature decreases and humidity increases, and both then remain nearly constant, while the undisturbed environment cools diurnally. The upper-troposphere stratiform rain region area lags convection by 5-6 h under humid active monsoon conditions but by only 1-2 h during drier break periods, suggesting that mesoscale organization is more readily sustained in a humid environment. Stratiform region hydrometeor mixing ratio lags convection by 0-2 h, suggesting that it is strongly influenced by detrainment from convective updrafts. Small stratiform region temperature anomalies suggest that a mesoscale updraft parameterization initialized with properties of buoyant detrained air and evolving to a balance between diabatic heating and adiabatic cooling might be a plausible approach for GCMs.

On the strong and selective isotope effect in the UV excitation of N2 with implications toward the nebula and Martian atmosphere.

PubMed

Muskatel, B H; Remacle, F; Thiemens, Mark H; Levine, R D

2011-04-12

Isotopic effects associated with molecular absorption are discussed with reference to natural phenomena including early solar system processes, Titan and terrestrial atmospheric chemistry, and Martian atmospheric evolution. Quantification of the physicochemical aspects of the excitation and dissociation processes may lead to enhanced understanding of these environments. Here we examine a physical basis for an additional isotope effect during photolysis of molecular nitrogen due to the coupling of valence and Rydberg excited states. The origin of this isotope effect is shown to be the coupling of diabatic electronic states of different bonding nature that occurs after the excitation of these states. This coupling is characteristic of energy regimes where two or more excited states are nearly crossing or osculating. A signature of the resultant isotope effect is a window of rapid variation in the otherwise smooth distribution of oscillator strengths vs. frequency. The reference for the discussion is the numerical solution of the time dependent Schrödinger equation for both the electronic and nuclear modes with the light field included as part of the Hamiltonian. Pumping is to all extreme UV dipole-allowed, valence and Rydberg, excited states of N(2). The computed absorption spectra are convoluted with the solar spectrum to demonstrate the importance of including this isotope effect in planetary, interstellar molecular cloud, and nebular photochemical models. It is suggested that accidental resonance with strong discrete lines in the solar spectrum such as the CIII line at 97.703 nm can also have a marked effect.

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. I. Theory for a dimer.

PubMed

Tiwari, Vivek; Peters, William K; Jonas, David M

2017-10-21

Non-adiabatic vibrational-electronic resonance in the excited electronic states of natural photosynthetic antennas drastically alters the adiabatic framework, in which electronic energy transfer has been conventionally studied, and suggests the possibility of exploiting non-adiabatic dynamics for directed energy transfer. Here, a generalized dimer model incorporates asymmetries between pigments, coupling to the environment, and the doubly excited state relevant for nonlinear spectroscopy. For this generalized dimer model, the vibrational tuning vector that drives energy transfer is derived and connected to decoherence between singly excited states. A correlation vector is connected to decoherence between the ground state and the doubly excited state. Optical decoherence between the ground and singly excited states involves linear combinations of the correlation and tuning vectors. Excitonic coupling modifies the tuning vector. The correlation and tuning vectors are not always orthogonal, and both can be asymmetric under pigment exchange, which affects energy transfer. For equal pigment vibrational frequencies, the nonadiabatic tuning vector becomes an anti-correlated delocalized linear combination of intramolecular vibrations of the two pigments, and the nonadiabatic energy transfer dynamics become separable. With exchange symmetry, the correlation and tuning vectors become delocalized intramolecular vibrations that are symmetric and antisymmetric under pigment exchange. Diabatic criteria for vibrational-excitonic resonance demonstrate that anti-correlated vibrations increase the range and speed of vibronically resonant energy transfer (the Golden Rule rate is a factor of 2 faster). A partial trace analysis shows that vibronic decoherence for a vibrational-excitonic resonance between two excitons is slower than their purely excitonic decoherence.

Tropical Indian Ocean warming contributions to China winter climate trends since 1960

NASA Astrophysics Data System (ADS)

Wu, Qigang; Yao, Yonghong; Liu, Shizuo; Cao, DanDan; Cheng, Luyao; Hu, Haibo; Sun, Leng; Yao, Ying; Yang, Zhiqi; Gao, Xuxu; Schroeder, Steven R.

2018-01-01

This study investigates observed and modeled contributions of global sea surface temperature (SST) to China winter climate trends in 1960-2014, including increased precipitation, warming through about 1997, and cooling since then. Observations and Atmospheric Model Intercomparison Project (AMIP) simulations with prescribed historical SST and sea ice show that tropical Indian Ocean (TIO) warming and increasing rainfall causes diabatic heating that generates a tropospheric wave train with anticyclonic 500-hPa height anomaly centers in the TIO or equatorial western Pacific (TIWP) and northeastern Eurasia (EA) and a cyclonic anomaly over China, referred to as the TIWP-EA wave train. The cyclonic anomaly causes Indochina moisture convergence and southwesterly moist flow that enhances South China precipitation, while the northern anticyclone enhances cold surges, sometimes causing severe ice storms. AMIP simulations show a 1960-1997 China cooling trend by simulating increasing instead of decreasing Arctic 500-hPa heights that move the northern anticyclone into Siberia, but enlarge the cyclonic anomaly so it still simulates realistic China precipitation trend patterns. A separate idealized TIO SST warming simulation simulates the TIWP-EA feature more realistically with correct precipitation patterns and supports the TIWP-EA teleconnection as the primary mechanism for long-term increasing precipitation in South China since 1960. Coupled Model Intercomparison Project (CMIP) experiments simulate a reduced TIO SST warming trend and weak precipitation trends, so the TIWP-EA feature is absent and strong drying is simulated in South China for 1960-1997. These simulations highlight the need for accurately modeled SST to correctly attribute regional climate trends.

Why is the simulated climatology of tropical cyclones so sensitive to the choice of cumulus parameterization scheme in the WRF model?

NASA Astrophysics Data System (ADS)

Zhang, Chunxi; Wang, Yuqing

2018-01-01

The sensitivity of simulated tropical cyclones (TCs) to the choice of cumulus parameterization (CP) scheme in the advanced Weather Research and Forecasting Model (WRF-ARW) version 3.5 is analyzed based on ten seasonal simulations with 20-km horizontal grid spacing over the western North Pacific. Results show that the simulated frequency and intensity of TCs are very sensitive to the choice of the CP scheme. The sensitivity can be explained well by the difference in the low-level circulation in a height and sorted moisture space. By transporting moist static energy from dry to moist region, the low-level circulation is important to convective self-aggregation which is believed to be related to genesis of TC-like vortices (TCLVs) and TCs in idealized settings. The radiative and evaporative cooling associated with low-level clouds and shallow convection in dry regions is found to play a crucial role in driving the moisture-sorted low-level circulation. With shallow convection turned off in a CP scheme, relatively strong precipitation occurs frequently in dry regions. In this case, the diabatic cooling can still drive the low-level circulation but its strength is reduced and thus TCLV/TC genesis is suppressed. The inclusion of the cumulus momentum transport (CMT) in a CP scheme can considerably suppress genesis of TCLVs/TCs, while changes in the moisture-sorted low-level circulation and horizontal distribution of precipitation are trivial, indicating that the CMT modulates the TCLVs/TCs activities in the model by mechanisms other than the horizontal transport of moist static energy.

Intramolecular electron-transfer rates in mixed-valence triarylamines: measurement by variable-temperature ESR spectroscopy and comparison with optical data.

PubMed

Lancaster, Kelly; Odom, Susan A; Jones, Simon C; Thayumanavan, S; Marder, Seth R; Brédas, Jean-Luc; Coropceanu, Veaceslav; Barlow, Stephen

2009-02-11

The electron spin resonance spectra of the radical cations of 4,4'-bis[di(4-methoxyphenyl)amino]tolane, E-4,4'-bis[di(4-methoxyphenyl)amino]stilbene, and E,E-1,4-bis{4-[di(4-methoxyphenyl)amino]styryl}benzene in dichloromethane exhibit five lines over a wide temperature range due to equivalent coupling to two 14N nuclei, indicating either delocalization between both nitrogen atoms or rapid intramolecular electron transfer on the electron spin resonance time scale. In contrast, those of the radical cations of 1,4-bis{4-[di(4-methoxyphenyl)amino]phenylethynyl}benzene and E,E-1,4-bis{4-[di(4-n-butoxyphenyl)amino]styryl}-2,5-dicyanobenzene exhibit line shapes that vary strongly with temperature, displaying five lines at room temperature and only three lines at ca. 190 K, indicative of slow electron transfer on the electron spin resonance time scale at low temperatures. The rates of intramolecular electron transfer in the latter compounds were obtained by simulation of the electron spin resonance spectra and display an Arrhenius temperature dependence. The activation barriers obtained from Arrhenius plots are significantly less than anticipated from Hush analyses of the intervalence bands when the diabatic electron-transfer distance, R, is equated to the N[symbol: see text]N distance. Comparison of optical and electron spin resonance data suggests that R is in fact only ca. 40% of the N[symbol: see text]N distance, while the Arrhenius prefactor indicates that the electron transfer falls in the adiabatic regime.

Two-phase pressure drop in a helical coil flow boiling system

NASA Astrophysics Data System (ADS)

Hardik, B. K.; Prabhu, S. V.

2018-05-01

The objective of the present work is to study the two-phase pressure drop in helical coils. Literature on the two-phase pressure drop in a helical coil suggests the complexity in flow boiling inside a helical coil due to secondary flow. Most of correlations reported in the literature on the two-phase pressure drop in a helical coil are limited to a specific operating range. No general correlation is available for a helical coil which is applicable for all fluids. In the present study, an experimental databank collected containing a total of 832 data points includes the data from the present study and from the literature. The data includes diabatic pressure drop of two fluids namely water and R123. Data covers a range of parameters namely a mass flux of 120-2058 kg/m2 s, a heat flux of 18-2831 kW/m2, an exit quality of 0.03-1, a density ratio of 32-1404 and a coil to tube diameter ratio of 14-58. The databank is compared with eighteen empirical correlations which include well referred correlations of straight tubes and the available correlations of helical coils. The straight tube correlations are not working well for the present data set. The helical coil correlations work reasonably well for the present databank. A correlation is suggested to predict the two-phase pressure drop in helical coils. The present study suggests that the influence of a helical coil is completely included in the single phase pressure drop correlation for helical coils.

How do blockings relate to heavy precipitation events in Europe?

NASA Astrophysics Data System (ADS)

Lenggenhager, Sina; Romppainen, Olivia; Brönnimann, Stefan; Croci-Maspoli, Mischa

2017-04-01

Atmospheric blockings are quasi-stationary high pressure systems that persist for several days. Due to their longevity, blockings can be key features for extreme weather events. While several studies have shown their relevant role for temperatures extremes, the link between blockings and extreme precipitation and floods is still poorly understood. A case study of a Swiss lake flood event in the year 2000 reveals how different processes connected to blockings can favour the development of a flood. First upstream blocks helped to form strongly elongated troughs that are known to be associated with heavy precipitation events south of the Alps. Second recurrent precipitation events upstream of a block led to a moistening of the catchment and an increase of the lake level. Third the progression of the upstream weather systems was slowed and thereby the precipitation period over a catchment prolonged. Additionally, cloud diabatic processes in the flood region contributed to the establishment and maintenance of blocking anticyclones. Based on this case study we extend our analysis to all of Europe. Focusing on flood relevant precipitation events, i.e. extreme precipitation events that last for several days and affect larger areas, we show that different regions in Europe have very distinct seasonal precipitation patterns. Hence there is a strong seasonality in the occurrence of extreme events, depending on the geographical region. We further suggest that for different precipitation regimes, the preferred location of blockings varies strongly. Heavy precipitation events in southern France, for example, are often observed during Scandinavian blockings, while heavy precipitation events in south-eastern Europe coincide more often with eastern North-Atlantic blockings.

A Composite View of Ozone Evolution in the 1995-1996 Northern Winter Polar Vortex Developed from Airborne Lidar and Satellite Observations

NASA Technical Reports Server (NTRS)

Douglass, A. R.; Schoeberl, M. R.; Kawa, S. R.; Browell, E. V.

2000-01-01

The processes which contribute to the ozone evolution in the high latitude northern lower stratosphere are evaluated using a three dimensional model simulation and ozone observations. The model uses winds and temperatures from the Goddard Earth Observing System Data Assimilation System. The simulation results are compared with ozone observations from three platforms: the differential absorption lidar (DIAL) which was flown on the NASA DC-8 as part of the Vortex Ozone Transport Experiment; the Microwave Limb Sounder (MLS); the Polar Ozone and Aerosol Measurement (POAM II) solar occultation instrument. Time series for the different data sets are consistent with each other, and diverge from model time series during December and January. The model ozone in December and January is shown to be much less sensitive to the model photochemistry than to the model vertical transport, which depends on the model vertical motion as well as the model vertical gradient. We evaluate the dependence of model ozone evolution on the model ozone gradient by comparing simulations with different initial conditions for ozone. The modeled ozone throughout December and January most closely resembles observed ozone when the vertical profiles between 12 and 20 km within the polar vortex closely match December DIAL observations. We make a quantitative estimate of the uncertainty in the vertical advection using diabatic trajectory calculations. The net transport uncertainty is significant, and should be accounted for when comparing observations with model ozone. The observed and modeled ozone time series during December and January are consistent when these transport uncertainties are taken into account.

Five ab initio potential energy and dipole moment surfaces for hydrated NaCl and NaF. I. Two-body interactions.

PubMed

Wang, Yimin; Bowman, Joel M; Kamarchik, Eugene

2016-03-21

We report full-dimensional, ab initio-based potentials and dipole moment surfaces for NaCl, NaF, Na(+)H2O, F(-)H2O, and Cl(-)H2O. The NaCl and NaF potentials are diabatic ones that dissociate to ions. These are obtained using spline fits to CCSD(T)/aug-cc-pV5Z energies. In addition, non-linear least square fits using the Born-Mayer-Huggins potential are presented, providing accurate parameters based strictly on the current ab initio energies. The long-range behavior of the NaCl and NaF potentials is shown to go, as expected, accurately to the point-charge Coulomb interaction. The three ion-H2O potentials are permutationally invariant fits to roughly 20,000 coupled cluster CCSD(T) energies (awCVTZ basis for Na(+) and aVTZ basis for Cl(-) and F(-)), over a large range of distances and H2O intramolecular configurations. These potentials are switched accurately in the long range to the analytical ion-dipole interactions, to improve computational efficiency. Dipole moment surfaces are fits to MP2 data; for the ion-ion cases, these are well described in the intermediate- and long-range by the simple point-charge expression. The performance of these new fits is examined by direct comparison to additional ab initio energies and dipole moments along various cuts. Equilibrium structures, harmonic frequencies, and electronic dissociation energies are also reported and compared to direct ab initio results. These indicate the high fidelity of the new PESs.

Residual Circulation and Temperature Changes during the Evolution of Stratospheric Sudden Warmings Revealed in MERRA

NASA Astrophysics Data System (ADS)

Song, Byeong-Gwon; Chun, Hye-Yeong; Kim, Young-Ha

2015-04-01

A composite analysis for 21 stratospheric sudden warming (SSW) cases in 1979-2012 northern winter is performed using the MERRA reanalysis in order to investigate the changes in residual circulation and temperature during the SSW evolution. The SSW cases are classified as Type-1 and Type-2, based on the relative amplitude of planetary waves with zonal wavenumbers 1 and 2. The residual circulation induced by each forcing term in the transformed Eulerian mean (TEM) equation and the temperature advection associated with the circulation are calculated for both types of SSW. It is found that strong poleward and downward motion exists in the polar stratosphere just before the central date of SSW, which is induced primarily by the Eliassen-Palm flux divergence forcing (EPD). Gravity-wave drag (GWD) induces strong poleward and downward motion in the lower mesosphere. The temperature advection is significantly increased in the stratosphere before the central date of the SSW, as a result of the strong downward motion due to the EPD. However, the temperature change in the lower mesosphere is small despite the strong downward motion, because the vertical gradient of the potential temperature is relatively small at these altitudes. The temperature change in the stratosphere before the SSW is more rapid for Type-2 than Type-1. After the central date of SSW, the polar stratospheric temperature is recovered primarily by diabatic heating rather than by the residual circulation associated with wave forcing. Difference in the speed of temperature recovery between the two types of SSW is not significant.

Examples of data assimilation in mesoscale models

NASA Technical Reports Server (NTRS)

Carr, Fred; Zack, John; Schmidt, Jerry; Snook, John; Benjamin, Stan; Stauffer, David

1993-01-01

The keynote address was the problem of physical initialization of mesoscale models. The classic purpose of physical or diabatic initialization is to reduce or eliminate the spin-up error caused by the lack, at the initial time, of the fully developed vertical circulations required to support regions of large rainfall rates. However, even if a model has no spin-up problem, imposition of observed moisture and heating rate information during assimilation can improve quantitative precipitation forecasts, especially early in the forecast. The two key issues in physical initialization are the choice of assimilating technique and sources of hydrologic/hydrometeor data. Another example of data assimilation in mesoscale models was presented in a series of meso-beta scale model experiments with and 11 km version of the MASS model designed to investigate the sensitivity of convective initiation forced by thermally direct circulations resulting from differential surface heating to four dimensional assimilation of surface and radar data. The results of these simulations underscore the need to accurately initialize and simulate grid and sub-grid scale clouds in meso- beta scale models. The status of the application of the CSU-RAMS mesoscale model by the NOAA Forecast Systems Lab for producing real-time forecasts with 10-60 km mesh resolutions over (4000 km)(exp 2) domains for use by the aviation community was reported. Either MAPS or LAPS model data are used to initialize the RAMS model on a 12-h cycle. The use of MAPS (Mesoscale Analysis and Prediction System) model was discussed. Also discussed was the mesobeta-scale data assimilation using a triply-nested nonhydrostatic version of the MM5 model.

Influences of different PBL schemes on secondary eyewall formation and eyewall replacement cycle in simulated Typhoon Sinlaku (2008)

NASA Astrophysics Data System (ADS)

Zhang, Yutao; Jiang, Yuxin; Tan, Benkui

2013-06-01

The effects of different planetary boundary layer (PBL) processes on the secondary eyewall formation (SEF) and eyewall replacement cycle (ERC) in Typhoon Sinlaku (2008) are investigated by using the Weather Research and Forecasting (WRF) model with six different PBL schemes. The SEF and ERC have been successfully simulated with all the six PBL schemes and the mechanism for the SEF and ERC proposed in our previous study has been reconfirmed. It is demonstrated that both the intensification of the storm and the inward-moving outer spiral rainband contribute to the SEF. After the SEF, the associated diabatic heating enhances the secondary eyewall further, and the transfer of moist air from outer region to the primary eyewall is cut off by the secondary eyewall. In such a way, the primary eyewall dies and an ERC completes. It is found that some simulated features of the SEF and ERC, such as the time and location of the SEF and duration of the ERC, do vary from one simulation to another. In order to describe the features of the SEF and ERC quantitatively, a concentric eyewall index (CEI) is defined and a threshold of the CEI is suggested to determine the onset of the secondary eyewall. The differences in the simulated SEF and ERC are discussed and some possible causes are suggested. In addition, based on the CEI threshold and the conservation law of angular momentum, a formula to predict the location of SEF is also proposed and applied to all the six simulations. The success and failure of the formula are then discussed.

A Composite View of Ozone Evolution in the 1995-96 Northern Winter Polar Vortex Developed from Airborne Lidar and Satellite Observations

NASA Technical Reports Server (NTRS)

Douglass, Anne R.; Schoeberl, M. R.; Kawa, S. R.

2000-01-01

The processes which contribute to the ozone evolution in the high latitude lower stratosphere are evaluated using a three dimensional model simulation and ozone observations. The model uses winds and temperatures from the Goddard Earth Observing System Data Assimilation System. The simulation results are compared with ozone observations from three platforms: the differential absorption lidar (DIAL) which was flown on the NASA DC-8 as part of the Vortex Ozone Transport Experiment; the Microwave Limb Sounder (MLS) on the Upper Atmosphere Research Satellite; and the Polar Ozone and Aerosol Measurement (POAM II) solar occulation instrument, on board the French Satellite Pour I'Observations de la Terre. Comparisons of the different data sets with the model simulation are shown to provide complementary information and a consistent view of the ozone evolution. The model ozone in December and January is shown to be sensitive to the ozone vertical gradient and the model vertical transport, and only weakly sensitive to the model photochemistry. The most consistent comparison between observed and modeled ozone evolution is found for a simulation where the vertical profiles between 12 and 20 km within the polar vortex closely match December DIAL observations. Diabatic trajectory calculations are used to estimate the uncertainty due to vertical advection quantitatively. The transport uncertainty is significant, and should be accounted for when comparing observations with model ozone. The model ozone evolution during December and January is broadly consistent with the observations when these transport uncertainties are taken into account.

Mechanisms for the extratropical QBO in circulation and ozone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kinnersley, J.S.; Tung, K.K.

1999-06-15

A two-and-a-half-dimensional interactive stratospheric model, whose equatorial zonal wind was relaxed toward the observed Singapore zonal wind, was able to reproduce much of the observed quasi-biennial oscillation (QBO) variability in the column ozone, in its vertical distribution in the low and middle latitudes, and also in the high southern polar latitudes. To reveal the mechanisms responsible for producing the modeled QBO signal over the globe, several control runs were also performed. The authors find that the ozone variability in the lower stratosphere--and hence also in the column--is determined mainly by two dynamical mechanisms. In the low to midlatitudes it ismore » created by a direct QBO circulation. Unlike the classic picture of a nonseasonal two-cell QBO circulation symmetric about the equator, a more correct picture is a direct QBO circulation that is strongly seasonal, driven by the seasonality in diabatic heating, which is very weak in the summer hemisphere and strong in the winter hemisphere at low and midlatitudes. Transport by the climatological circulation and diffusion is found to be ineffective. At high latitudes, there is again a circulation anomaly, but here it is induced by the modulation of the planetary wave potential vorticity flux by the QBO. This so-called Holton-Tan mechanism is responsible for most of the QBO ozone signal poleward of 60[degree]. During spring in the modeled northern polar region, chaotic behavior is another important source of interannual variability, in addition to the interannual variability of planetary wave sources in the troposphere previously studied by the authors.« less