Efficient near-field wireless energy transfer using adiabatic system variations

DOEpatents

Hamam, Rafif E; Karalis, Aristeidis; Joannopoulos, John D; Soljacic, Marin

2014-09-16

Disclosed is a method for transferring energy wirelessly including transferring energy wirelessly from a first resonator structure to an intermediate resonator structure, wherein the coupling rate between the first resonator structure and the intermediate resonator structure is .kappa..sub.1B, transferring energy wirelessly from the intermediate resonator structure to a second resonator structure, wherein the coupling rate between the intermediate resonator structure and the second resonator structure is .kappa..sub.B2, and during the wireless energy transfers, adjusting at least one of the coupling rates .kappa..sub.1B and .kappa..sub.B2 to reduce energy accumulation in the intermediate resonator structure and improve wireless energy transfer from the first resonator structure to the second resonator structure through the intermediate resonator structure.

Single field double inflation and primordial black holes

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

Kannike, K.; Marzola, L.; Raidal, M.

Within the framework of scalar-tensor theories, we study the conditions that allow single field inflation dynamics on small cosmological scales to significantly differ from that of the large scales probed by the observations of cosmic microwave background. The resulting single field double inflation scenario is characterised by two consequent inflation eras, usually separated by a period where the slow-roll approximation fails. At large field values the dynamics of the inflaton is dominated by the interplay between its non-minimal coupling to gravity and the radiative corrections to the inflaton self-coupling. For small field values the potential is, instead, dominated by amore » polynomial that results in a hilltop inflation. Without relying on the slow-roll approximation, which is invalidated by the appearance of the intermediate stage, we propose a concrete model that matches the current measurements of inflationary observables and employs the freedom granted by the framework on small cosmological scales to give rise to a sizeable population of primordial black holes generated by large curvature fluctuations. We find that these features generally require a potential with a local minimum. We show that the associated primordial black hole mass function is only approximately lognormal.« less

Efficient near-field wireless energy transfer using adiabatic system variations

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

Hamam, Rafif E.; Karalis, Aristeidis; Joannopoulos, John D.

Disclosed is a method for transferring energy wirelessly including transferring energy wirelessly from a first resonator structure to an intermediate resonator structure, wherein the coupling rate between the first resonator structure and the intermediate resonator structure is .kappa..sub.1B, transferring energy wirelessly from the intermediate resonator structure to a second resonator structure, wherein the coupling rate between the intermediate resonator structure and the second resonator structure is .kappa..sub.B2, and during the wireless energy transfers, adjusting at least one of the coupling rates .kappa..sub.1B and .kappa..sub.B2 to reduce energy accumulation in the intermediate resonator structure and improve wireless energy transfer from themore » first resonator structure to the second resonator structure through the intermediate resonator structure.« less

Retarded correlators in kinetic theory: branch cuts, poles and hydrodynamic onset transitions

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

Romatschke, Paul

In this paper, the collective modes of an effective kinetic theory description based on the Boltzmann equation in a relaxation-time approximation applicable to gauge theories at weak but finite coupling and low frequencies are studied. Real time retarded two-point correlators of the energy-momentum tensor and the R-charge current are calculated at finite temperature in flat space-times for large N gauge theories. It is found that the real-time correlators possess logarithmic branch cuts which in the limit of large coupling disappear and give rise to non-hydrodynamic poles that are reminiscent of quasi-normal modes in black holes. In addition to branch cuts,more » correlators can have simple hydrodynamic poles, generalizing the concept of hydrodynamic modes to intermediate wavelength. Surprisingly, the hydrodynamic poles cease to exist for some critical value of the wavelength and coupling reminiscent of the properties of onset transitions.« less

Retarded correlators in kinetic theory: branch cuts, poles and hydrodynamic onset transitions

DOE PAGES

Romatschke, Paul

2016-06-24

In this paper, the collective modes of an effective kinetic theory description based on the Boltzmann equation in a relaxation-time approximation applicable to gauge theories at weak but finite coupling and low frequencies are studied. Real time retarded two-point correlators of the energy-momentum tensor and the R-charge current are calculated at finite temperature in flat space-times for large N gauge theories. It is found that the real-time correlators possess logarithmic branch cuts which in the limit of large coupling disappear and give rise to non-hydrodynamic poles that are reminiscent of quasi-normal modes in black holes. In addition to branch cuts,more » correlators can have simple hydrodynamic poles, generalizing the concept of hydrodynamic modes to intermediate wavelength. Surprisingly, the hydrodynamic poles cease to exist for some critical value of the wavelength and coupling reminiscent of the properties of onset transitions.« less

Dynamics of Monsoon-Induced Biennial Variability in ENSO

NASA Technical Reports Server (NTRS)

Kim, Kyu-Myong; Lau, K.-M.; Einaudi, Franco (Technical Monitor)

2000-01-01

The mechanism of the quasi-biennial tendency in El Nino Southern Oscillation (ENSO)-monsoon coupled system is investigated using an intermediate coupled model. The monsoon wind forcing is prescribed as a function of Sea Surface Temperature (SST) anomalies based on the relationship between zonal wind anomalies over the western Pacific to sea level change in the equatorial eastern Pacific. The key mechanism of quasi-biennial tendency in El Nino evolution is found to be in the strong coupling of ENSO to monsoon wind forcing over the western Pacific. Strong boreal summer monsoon wind forcing, which lags the maximum SST anomaly in the equatorial eastern Pacific approximately 6 months, tends to generate Kelvin waves of the opposite sign to anomalies in the eastern Pacific and initiates the turnabout in the eastern Pacific. Boreal winter monsoon forcing, which has zero lag with maximum SST in the equatorial eastern Pacific, tends to damp the ENSO oscillations.

Interaction of charge carriers with lattice and molecular phonons in crystalline pentacene

NASA Astrophysics Data System (ADS)

Girlando, Alberto; Grisanti, Luca; Masino, Matteo; Brillante, Aldo; Della Valle, Raffaele G.; Venuti, Elisabetta

2011-08-01

The computational protocol we have developed for the calculation of local (Holstein) and non-local (Peierls) carrier-phonon coupling in molecular organic semiconductors is applied to both the low temperature and high temperature bulk crystalline phases of pentacene. The electronic structure is calculated by the semimpirical INDO/S (Intermediate Neglect of Differential Overlap with Spectroscopic parametrization) method. In the phonon description, the rigid molecule approximation is removed, allowing mixing of low-frequency intra-molecular modes with inter-molecular (lattice) phonons. A clear distinction remains between the low-frequency phonons, which essentially modulate the transfer integral from a molecule to another (Peierls coupling), and the high-frequency intra-molecular phonons, which modulate the on-site energy (Holstein coupling). The results of calculation agree well with the values extracted from experiment. The comparison with similar calculations made for rubrene allows us to discuss the implications for the current models of mobility.

Enhancement of gaps in thin graphitic films for heterostructure formation

NASA Astrophysics Data System (ADS)

Hague, J. P.

2014-04-01

There are a large number of atomically thin graphitic films with a structure similar to that of graphene. These films have a spread of band gaps relating to their ionicity and, also, to the substrate on which they are grown. Such films could have a range of applications in digital electronics, where graphene is difficult to use. I use the dynamical cluster approximation to show how electron-phonon coupling between film and substrate can enhance these gaps in a way that depends on the range and strength of the coupling. It is found that one of the driving factors in this effect is a charge density wave instability for electrons on a honeycomb lattice that can open a gap in monolayer graphene. The enhancement at intermediate coupling is sufficiently large that spatially varying substrates and superstrates could be used to create heterostructures in thin graphitic films with position-dependent electron-phonon coupling and gaps, leading to advanced electronic components.

New viable region of an inert Higgs doublet dark matter model with scotogenic extension

NASA Astrophysics Data System (ADS)

Borah, Debasish; Gupta, Aritra

2017-12-01

We explore the intermediate dark matter mass regime of the inert Higgs doublet model, approximately between 400 and 550 GeV, which is allowed by latest constraints from direct and indirect detection experiments, but the thermal relic abundance remains suppressed. We extend the model by three copies of right-handed neutrinos, odd under the built-in Z2 symmetry of the model. This discrete Z2 symmetry of the model allows these right-handed neutrinos to couple to the usual lepton doublets through the inert Higgs doublet allowing the possibility of radiative neutrino mass in the scotogenic fashion. Apart from generating nonzero neutrino mass, such an extension can also revive the intermediate dark matter mass regime. The late decay of the lightest right-handed neutrino to dark matter makes it possible for the usual thermally underabundant dark matter in this intermediate mass regime to satisfy the correct relic abundance limit. The revival of this wide intermediate mass range can have relevance not only for direct and indirect search experiments but also for neutrino experiments as the long lifetime of the lightest right-handed neutrino also results in almost vanishing lightest neutrino mass.

Sensitive method to monitor trace quantities of benzanthrone in workers of dyestuff industries

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

Joshi, A.; Khanna, S.K.; Singh, G.B.

1986-03-01

Dyestuff workers coming in contact with benzanthrone (an intermediate used for the synthesis of a variety of dyes) develop skin lesions, gastritis, liver malfunctions, and sexual disturbances. A highly sensitive fluorometric method to monitor trace quantities of benzanthrone in urine, serum, and biological tissues for experimental studies, has been developed. Coupled with simple extraction and resolution, optimum fluorescence is obtained in an equal mixture of chloroform:methanol, detecting as low as 2 ng benzanthrone. This method is approximately 250 times more sensitive than currently available colorimetric assay.

Density matrix renormalization group study of a three-orbital Hubbard model with spin-orbit coupling in one dimension

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

Kaushal, Nitin; Herbrych, Jacek W.; Nocera, Alberto

Using the density matrix renormalization group technique we study the effect of spin-orbit coupling on a three-orbital Hubbard model in the (t 2g) 4 sector and in one dimension. Fixing the Hund coupling to a robust value compatible with some multiorbital materials, we present the phase diagram varying the Hubbard U and spin-orbit coupling λ, at zero temperature. Our results are shown to be qualitatively similar to those recently reported using the dynamical mean-field theory in higher dimensions, providing a robust basis to approximate many-body techniques. Among many results, we observe an interesting transition from an orbital-selective Mott phase tomore » an excitonic insulator with increasing λ at intermediate U. In the strong U coupling limit, we find a nonmagnetic insulator with an effective angular momentum <(J eff) 2>≠0 near the excitonic phase, smoothly connected to the <(J eff) 2>=0 regime. In conclusion, we also provide a list of quasi-one-dimensional materials where the physics discussed in this paper could be realized.« less

Density matrix renormalization group study of a three-orbital Hubbard model with spin-orbit coupling in one dimension

NASA Astrophysics Data System (ADS)

Kaushal, Nitin; Herbrych, Jacek; Nocera, Alberto; Alvarez, Gonzalo; Moreo, Adriana; Reboredo, F. A.; Dagotto, Elbio

2017-10-01

Using the density matrix renormalization group technique we study the effect of spin-orbit coupling on a three-orbital Hubbard model in the (t2g) 4 sector and in one dimension. Fixing the Hund coupling to a robust value compatible with some multiorbital materials, we present the phase diagram varying the Hubbard U and spin-orbit coupling λ , at zero temperature. Our results are shown to be qualitatively similar to those recently reported using the dynamical mean-field theory in higher dimensions, providing a robust basis to approximate many-body techniques. Among many results, we observe an interesting transition from an orbital-selective Mott phase to an excitonic insulator with increasing λ at intermediate U . In the strong U coupling limit, we find a nonmagnetic insulator with an effective angular momentum 〈(Jeff)2〉≠0 near the excitonic phase, smoothly connected to the 〈(Jeff)2〉=0 regime. We also provide a list of quasi-one-dimensional materials where the physics discussed in this paper could be realized.

Density matrix renormalization group study of a three-orbital Hubbard model with spin-orbit coupling in one dimension

DOE PAGES

Kaushal, Nitin; Herbrych, Jacek W.; Nocera, Alberto; ...

2017-10-09

Using the density matrix renormalization group technique we study the effect of spin-orbit coupling on a three-orbital Hubbard model in the (t 2g) 4 sector and in one dimension. Fixing the Hund coupling to a robust value compatible with some multiorbital materials, we present the phase diagram varying the Hubbard U and spin-orbit coupling λ, at zero temperature. Our results are shown to be qualitatively similar to those recently reported using the dynamical mean-field theory in higher dimensions, providing a robust basis to approximate many-body techniques. Among many results, we observe an interesting transition from an orbital-selective Mott phase tomore » an excitonic insulator with increasing λ at intermediate U. In the strong U coupling limit, we find a nonmagnetic insulator with an effective angular momentum <(J eff) 2>≠0 near the excitonic phase, smoothly connected to the <(J eff) 2>=0 regime. In conclusion, we also provide a list of quasi-one-dimensional materials where the physics discussed in this paper could be realized.« less

Relativistic coupled-cluster-theory analysis of energies, hyperfine-structure constants, and dipole polarizabilities of Cd+

NASA Astrophysics Data System (ADS)

Li, Cheng-Bin; Yu, Yan-Mei; Sahoo, B. K.

2018-02-01

Roles of electron correlation effects in the determination of attachment energies, magnetic-dipole hyperfine-structure constants, and electric-dipole (E 1 ) matrix elements of the low-lying states in the singly charged cadmium ion (Cd+) have been analyzed. We employ the singles and doubles approximated relativistic coupled-cluster (RCC) method to calculate these properties. Intermediate results from the Dirac-Hartree-Fock approximation,the second-order many-body perturbation theory, and considering only the linear terms of the RCC method are given to demonstrate propagation of electron correlation effects in this ion. Contributions from important RCC terms are also given to highlight the importance of various correlation effects in the evaluation of these properties. At the end, we also determine E 1 polarizabilities (αE 1) of the ground and 5 p 2P1 /2 ;3 /2 states of Cd+ in the ab initio approach. We estimate them again by replacing some of the E 1 matrix elements and energies from the measurements to reduce their uncertainties so that they can be used in the high-precision experiments of this ion.

Synchronization in interdependent networks

NASA Astrophysics Data System (ADS)

Um, Jaegon; Minnhagen, Petter; Kim, Beom Jun

2011-06-01

We explore the synchronization behavior in interdependent systems, where the one-dimensional (1D) network (the intranetwork coupling strength JI) is ferromagnetically intercoupled (the strength J) to the Watts-Strogatz (WS) small-world network (the intranetwork coupling strength JII). In the absence of the internetwork coupling (J =0), the former network is well known not to exhibit the synchronized phase at any finite coupling strength, whereas the latter displays the mean-field transition. Through an analytic approach based on the mean-field approximation, it is found that for the weakly coupled 1D network (JI≪1) the increase of J suppresses synchrony, because the nonsynchronized 1D network becomes a heavier burden for the synchronization process of the WS network. As the coupling in the 1D network becomes stronger, it is revealed by the renormalization group (RG) argument that the synchronization is enhanced as JI is increased, implying that the more enhanced partial synchronization in the 1D network makes the burden lighter. Extensive numerical simulations confirm these expected behaviors, while exhibiting a reentrant behavior in the intermediate range of JI. The nonmonotonic change of the critical value of JII is also compared with the result from the numerical RG calculation.

Carbinolamine Formation and Dehydration in a DNA Repair Enzyme Active Site

PubMed Central

Dodson, M. L.; Walker, Ross C.; Lloyd, R. Stephen

2012-01-01

In order to suggest detailed mechanistic hypotheses for the formation and dehydration of a key carbinolamine intermediate in the T4 pyrimidine dimer glycosylase (T4PDG) reaction, we have investigated these reactions using steered molecular dynamics with a coupled quantum mechanics–molecular mechanics potential (QM/MM). We carried out simulations of DNA abasic site carbinolamine formation with and without a water molecule restrained to remain within the active site quantum region. We recovered potentials of mean force (PMF) from thirty replicate reaction trajectories using Jarzynski averaging. We demonstrated feasible pathways involving water, as well as those independent of water participation. The water–independent enzyme–catalyzed reaction had a bias–corrected Jarzynski–average barrier height of approximately for the carbinolamine formation reaction and ) for the reverse reaction at this level of representation. When the proton transfer was facilitated with an intrinsic quantum water, the barrier height was approximately in the forward (formation) reaction and for the reverse. In addition, two modes of unsteered (free dynamics) carbinolamine dehydration were observed: in one, the quantum water participated as an intermediate proton transfer species, and in the other, the active site protonated glutamate hydrogen was directly transferred to the carbinolamine oxygen. Water–independent unforced proton transfer from the protonated active site glutamate carboxyl to the unprotonated N–terminal amine was also observed. In summary, complex proton transfer events, some involving water intermediates, were studied in QM/MM simulations of T4PDG bound to a DNA abasic site. Imine carbinolamine formation was characterized using steered QM/MM molecular dynamics. Dehydration of the carbinolamine intermediate to form the final imine product was observed in free, unsteered, QM/MM dynamics simulations, as was unforced acid-base transfer between the active site carboxylate and the N–terminal amine. PMID:22384015

Method and apparatus for varying accelerator beam output energy

DOEpatents

Young, Lloyd M.

1998-01-01

A coupled cavity accelerator (CCA) accelerates a charged particle beam with rf energy from a rf source. An input accelerating cavity receives the charged particle beam and an output accelerating cavity outputs the charged particle beam at an increased energy. Intermediate accelerating cavities connect the input and the output accelerating cavities to accelerate the charged particle beam. A plurality of tunable coupling cavities are arranged so that each one of the tunable coupling cavities respectively connect an adjacent pair of the input, output, and intermediate accelerating cavities to transfer the rf energy along the accelerating cavities. An output tunable coupling cavity can be detuned to variably change the phase of the rf energy reflected from the output coupling cavity so that regions of the accelerator can be selectively turned off when one of the intermediate tunable coupling cavities is also detuned.

The structural coupling between ATPase activation and recovery stroke in the myosin II motor.

PubMed

Koppole, Sampath; Smith, Jeremy C; Fischer, Stefan

2007-07-01

Before the myosin motor head can perform the next power stroke, it undergoes a large conformational transition in which the converter domain, bearing the lever arm, rotates approximately 65 degrees . Simultaneous with this "recovery stroke," myosin activates its ATPase function by closing the Switch-2 loop over the bound ATP. This coupling between the motions of the converter domain and of the 40 A-distant Switch-2 loop is essential to avoid unproductive ATP hydrolysis. The coupling mechanism is determined here by finding a series of optimized intermediates between crystallographic end structures of the recovery stroke (Dictyostelium discoideum), yielding movies of the transition at atomic detail. The successive formation of two hydrogen bonds by the Switch-2 loop is correlated with the successive see-saw motions of the relay and SH1 helices that hold the converter domain. SH1 helix and Switch-2 loop communicate via a highly conserved loop that wedges against the SH1-helix upon Switch-2 closing.

Dilatonic imprints on exact gravitational wave signatures

NASA Astrophysics Data System (ADS)

McCarthy, Fiona; KubizÅák, David; Mann, Robert B.

2018-05-01

By employing the moduli space approximation, we analytically calculate the gravitational wave signatures emitted upon the merger of two extremally charged dilatonic black holes. We probe several values of the dilatonic coupling constant a , and find significant departures from the Einstein-Maxwell (a =0 ) counterpart studied in [Phys. Rev. D 96, 061501 (2017), 10.1103/PhysRevD.96.061501]. For (low-energy) string theory black holes (a =1 ) there are no coalescence orbits and only a memory effect is observed, whereas for an intermediate value of the coupling (a =1 /√{3 } ) the late-time merger signature becomes exponentially suppressed, compared to the polynomial decay in the a =0 case without a dilaton. Such an imprint shows a clear difference between the case with and without a scalar field (as, for example, predicted by string theory) in black hole mergers.

Electron transfer, ionization, and excitation in atomic collisions. Progress report, June 15, 1992--June 14, 1995

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

Winter, T.G.; Alston, S.G.

The research program of Winter and Alston addresses the fundamental processes of electron transfer, ionization, and excitation in ion-atom, ion-ion, and ion-molecule collisions. Attention is focussed on one- and two-electron systems and, more recently, quasi-one-electron systems whose electron-target-core interaction can be accurately modeled by one-electron potentials. The basic computational approaches can then be taken with few, if any, approximations, and the underlying collisional mechanisms can be more clearly revealed. Winter has focussed on intermediate collision energies (e.g., proton energies for p-He{sup +} collisions on the order of 100 kilo-electron volts), in which many electron states are strongly coupled during themore » collision and a coupled-state approach, such as a coupled-Sturmian-pseudostate approach, is appropriate. Alston has concentrated on higher collision energies (million electron-volt energies), or asymmetric collision systems, for which the coupling of the projectile is weaker with, however, many more target states being coupled together so that high-order perturbation theory is essential. Several calculations by Winter and Alston are described, as set forth in the original proposal.« less

Solvation suppression of ion recombination in gas discharge afterglow

NASA Astrophysics Data System (ADS)

Amirov, R. Kh.; Lankin, A. V.; Norman, G. E.

2018-03-01

An effect which suppresses recombination in ion plasmas is considered both theoretically and experimentally. Experimental results are presented for the ion recombination rate in fluorine plasma, which are obtained from data for the gas discharge afterglow. To interpret them, a suppression factor is considered: ion solvation in weakly ionized plasma. It is shown that the recombination process has a two-stage character with the formation of intermediate metastable ion pairs. The pairs consist of negative and positive ion-molecular clusters. A theoretical explanation is given for the slowing down of the ion recombination with the increase of the Coulomb coupling compared to the ion recombination rate calculated in the ideal plasma approximation. The approximate similarity of the recombination rate of the ion temperature and concentration and reasons for the slight deviation from the similarity are elucidated.

Tunable in-line fiber optic comb filter using a side-polished single-mode fiber coupler with LiNbO 3 overlay and intermediate coupling layer

NASA Astrophysics Data System (ADS)

Sohn, Kyung-Rak; Song, Jae-Won

2002-03-01

Using a side-polished single-mode fiber covered with a polished LiNbO 3 overlay and an intermediate coupling layer, tunable fiber-optic comb filters are demonstrated. The device behaviors based on the modal properties of the fiber and the planar LiNbO 3 waveguide are analyzed by two dimensional beam propagation methods (2-D BPM) and discussed the role of an intermediate coupling layer in terms of coupling efficiency. We also show that the thermo-optic effects of this layer can be utilized to tune the comb filter. When the polished x-cut LiNbO 3 with 200 μm thickness is used as a multimode overlay waveguide, the comb output spectra with free spectral range of 4 nm are measured in 1550 nm wavelength range. The tuning rate as a function of the refractive index of an intermediate coupling layer, Δλ/ Δnb, is about -0.129 nm/-0.001. The experimental results are in good agreement with the calculated results.

Surface-confined Ullmann coupling of thiophene substituted porphyrins

NASA Astrophysics Data System (ADS)

Beggan, J. P.; Boyle, N. M.; Pryce, M. T.; Cafolla, A. A.

2015-09-01

The covalent coupling of (5,10,15,20-tetrabromothien-2-ylporphyrinato)zinc(II) (TBrThP) molecules on the Ag(111) surface has been investigated under ultra-high-vacuum conditions, using scanning tunnelling microscopy and x-ray photoelectron spectroscopy. The findings provide atomic-level insight into surface-confined Ullmann coupling of thiophene substituted porphyrins, analyzing the progression of organometallic intermediate to final coupled state. Adsorption of the TBrThP molecules on the Ag(111) surface at room temperature is found to result in the reductive dehalogenation of the bromothienyl substituents and the subsequent formation of single strand and crosslinked coordination networks. The coordinated substrate atoms bridge the proximal thienyl groups of the organometallic intermediate, while the cleaved bromine atoms are bound on the adjacent Ag(111) surface. The intermediate complex displays a thermal lability at ˜423 K that results in the dissociation of the proximal thienyl groups with the concomitant loss of the surface bound bromine. At the thermally induced dissociation of the intermediate complex the resultant thienylporphyrin derivatives covalently couple, leading to the formation of a polymeric network of thiophene linked and meso-meso fused porphyrins.

Segmented SiGe-PbTe couples

NASA Technical Reports Server (NTRS)

Eggers, P. E.; Mueller, J. J.

1969-01-01

New design of segmented couples incorporates an intermediate junction contacted by pressure, and eliminates transition members that bond materials differing in thermal expansion. Development of a reproducible and reliable intermediate junction between PbTe and SiGe will be applicable to direct conversion of energy.

The electron-furfural scattering dynamics for 63 energetically open electronic states

NASA Astrophysics Data System (ADS)

da Costa, Romarly F.; do N. Varella, Márcio T.; Bettega, Márcio H. F.; Neves, Rafael F. C.; Lopes, Maria Cristina A.; Blanco, Francisco; García, Gustavo; Jones, Darryl B.; Brunger, Michael J.; Lima, Marco A. P.

2016-03-01

We report on integral-, momentum transfer- and differential cross sections for elastic and electronically inelastic electron collisions with furfural (C5H4O2). The calculations were performed with two different theoretical methodologies, the Schwinger multichannel method with pseudopotentials (SMCPP) and the independent atom method with screening corrected additivity rule (IAM-SCAR) that now incorporates a further interference (I) term. The SMCPP with N energetically open electronic states (Nopen) at either the static-exchange (Nopen ch-SE) or the static-exchange-plus-polarisation (Nopen ch-SEP) approximation was employed to calculate the scattering amplitudes at impact energies lying between 5 eV and 50 eV, using a channel coupling scheme that ranges from the 1ch-SEP up to the 63ch-SE level of approximation depending on the energy considered. For elastic scattering, we found very good overall agreement at higher energies among our SMCPP cross sections, our IAM-SCAR+I cross sections and the experimental data for furan (a molecule that differs from furfural only by the substitution of a hydrogen atom in furan with an aldehyde functional group). This is a good indication that our elastic cross sections are converged with respect to the multichannel coupling effect for most of the investigated intermediate energies. However, although the present application represents the most sophisticated calculation performed with the SMCPP method thus far, the inelastic cross sections, even for the low lying energy states, are still not completely converged for intermediate and higher energies. We discuss possible reasons leading to this discrepancy and point out what further steps need to be undertaken in order to improve the agreement between the calculated and measured cross sections.

The electron-furfural scattering dynamics for 63 energetically open electronic states

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

Costa, Romarly F. da; Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Santo André, São Paulo 09210-580; Varella, Márcio T. do N

We report on integral-, momentum transfer- and differential cross sections for elastic and electronically inelastic electron collisions with furfural (C{sub 5}H{sub 4}O{sub 2}). The calculations were performed with two different theoretical methodologies, the Schwinger multichannel method with pseudopotentials (SMCPP) and the independent atom method with screening corrected additivity rule (IAM-SCAR) that now incorporates a further interference (I) term. The SMCPP with N energetically open electronic states (N{sub open}) at either the static-exchange (N{sub open} ch-SE) or the static-exchange-plus-polarisation (N{sub open} ch-SEP) approximation was employed to calculate the scattering amplitudes at impact energies lying between 5 eV and 50 eV, using a channelmore » coupling scheme that ranges from the 1ch-SEP up to the 63ch-SE level of approximation depending on the energy considered. For elastic scattering, we found very good overall agreement at higher energies among our SMCPP cross sections, our IAM-SCAR+I cross sections and the experimental data for furan (a molecule that differs from furfural only by the substitution of a hydrogen atom in furan with an aldehyde functional group). This is a good indication that our elastic cross sections are converged with respect to the multichannel coupling effect for most of the investigated intermediate energies. However, although the present application represents the most sophisticated calculation performed with the SMCPP method thus far, the inelastic cross sections, even for the low lying energy states, are still not completely converged for intermediate and higher energies. We discuss possible reasons leading to this discrepancy and point out what further steps need to be undertaken in order to improve the agreement between the calculated and measured cross sections.« less

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

Song, Kok Wee; Koshelev, Alexei E.

Electronic nematicity plays an important role in iron-based superconductors. These materials have a layered structure and the theoretical description of their magnetic and nematic transitions has been well established in the two-dimensional approximation, i.e., when the layers can be treated independently. However, the interaction between iron layers mediated by electron tunneling may cause nontrivial three-dimensional behavior. Starting from the simplest model for orbital nematic in a single layer, we investigate the influence of interlayer tunneling on the bulk nematic order and a possible preemptive state where this order is only formed near the surface. In addition, we found that themore » interlayer tunneling suppresses the bulk nematicity, which makes favorable the formation of a surface nematic order above the bulk transition temperature. The purely electronic tunneling Hamiltonian, however, favors a nematic order parameter that alternates from layer to layer. The uniform bulk state typically observed experimentally may be stabilized by the coupling with the elastic lattice deformation. Depending on the strength of this coupling, we found three regimes: (i) surface nematic and alternating bulk order, (ii) surface nematic and uniform bulk order, and (iii) uniform bulk order without the intermediate surface phase. Lastly, the intermediate surface-nematic state may resolve the current controversy about the existence of a weak nematic transition in the compound BaFe 2As 2-xP x .« less

Atomic structure considerations for the low-temperature opacity of Sn

DOE PAGES

Colgan, J.; Kilcrease, D. P.; Abdallah, J.; ...

2017-03-31

Here, we have begun a preliminary investigation into the opacity of Sn at low temperatures (< 50 eV). The emissivity and opacity of Sn is a crucial factor in determining the utility of Sn in EUV lithography, with numerous industrial implications. To this end, we have been exploring the accuracy of some approximations used in opacity models for the relevant ion stages of Sn (neutral through ~ 18 times ionized). We also find that the use of intermediate-coupling, as compared to full configuration-interaction, is not adequate to obtain accurate line positions of the important bound-bound transitions in Sn. One requiresmore » full configuration-interaction to properly describe the strong mixing between the various n=4 sub-shells that give rise to the Δn= 0 transitions that dominate the opacity spectrum at low temperatures. Furthermore, since calculations that include full configuration-interaction for large numbers of configurations quickly become computationally prohibitive, we have explored hybrid calculations, in which full configuration-interaction is retained for the most important transitions, while intermediate-coupling is employed for all other transitions. After extensive exploration of the atomic structure properties, local-thermodynamic-equilibrium (LTE) opacities are generated using the ATOMIC code at selected temperatures and densities and compared to experiment.« less

Atomic structure considerations for the low-temperature opacity of Sn

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

Colgan, J.; Kilcrease, D. P.; Abdallah, J.

Here, we have begun a preliminary investigation into the opacity of Sn at low temperatures (< 50 eV). The emissivity and opacity of Sn is a crucial factor in determining the utility of Sn in EUV lithography, with numerous industrial implications. To this end, we have been exploring the accuracy of some approximations used in opacity models for the relevant ion stages of Sn (neutral through ~ 18 times ionized). We also find that the use of intermediate-coupling, as compared to full configuration-interaction, is not adequate to obtain accurate line positions of the important bound-bound transitions in Sn. One requiresmore » full configuration-interaction to properly describe the strong mixing between the various n=4 sub-shells that give rise to the Δn= 0 transitions that dominate the opacity spectrum at low temperatures. Furthermore, since calculations that include full configuration-interaction for large numbers of configurations quickly become computationally prohibitive, we have explored hybrid calculations, in which full configuration-interaction is retained for the most important transitions, while intermediate-coupling is employed for all other transitions. After extensive exploration of the atomic structure properties, local-thermodynamic-equilibrium (LTE) opacities are generated using the ATOMIC code at selected temperatures and densities and compared to experiment.« less

Surface nematic order in iron pnictides

NASA Astrophysics Data System (ADS)

Song, Kok Wee; Koshelev, Alexei E.

2016-09-01

Electronic nematicity plays an important role in iron-based superconductors. These materials have a layered structure and the theoretical description of their magnetic and nematic transitions has been well established in the two-dimensional approximation, i.e., when the layers can be treated independently. However, the interaction between iron layers mediated by electron tunneling may cause nontrivial three-dimensional behavior. Starting from the simplest model for orbital nematic in a single layer, we investigate the influence of interlayer tunneling on the bulk nematic order and a possible preemptive state where this order is only formed near the surface. We found that the interlayer tunneling suppresses the bulk nematicity, which makes favorable the formation of a surface nematic order above the bulk transition temperature. The purely electronic tunneling Hamiltonian, however, favors a nematic order parameter that alternates from layer to layer. The uniform bulk state typically observed experimentally may be stabilized by the coupling with the elastic lattice deformation. Depending on the strength of this coupling, we found three regimes: (i) surface nematic and alternating bulk order, (ii) surface nematic and uniform bulk order, and (iii) uniform bulk order without the intermediate surface phase. The intermediate surface-nematic state may resolve the current controversy about the existence of a weak nematic transition in the compound BaFe2As2 -xPx .

Dynamics and manipulation of entanglement in coupled harmonic systems with many degrees of freedom

NASA Astrophysics Data System (ADS)

Plenio, M. B.; Hartley, J.; Eisert, J.

2004-03-01

We study the entanglement dynamics of a system consisting of a large number of coupled harmonic oscillators in various configurations and for different types of nearest-neighbour interactions. For a one-dimensional chain, we provide compact analytical solutions and approximations to the dynamical evolution of the entanglement between spatially separated oscillators. Key properties such as the speed of entanglement propagation, the maximum amount of transferred entanglement and the efficiency for the entanglement transfer are computed. For harmonic oscillators coupled by springs, corresponding to a phonon model, we observe a non-monotonic transfer efficiency in the initially prepared amount of entanglement, i.e. an intermediate amount of initial entanglement is transferred with the highest efficiency. In contrast, within the framework of the rotating-wave approximation (as appropriate, e.g. in quantum optical settings) one finds a monotonic behaviour. We also study geometrical configurations that are analogous to quantum optical devices (such as beamsplitters and interferometers) and observe characteristic differences when initially thermal or squeezed states are entering these devices. We show that these devices may be switched on and off by changing the properties of an individual oscillator. They may therefore be used as building blocks of large fixed and pre-fabricated but programmable structures in which quantum information is manipulated through propagation. We discuss briefly possible experimental realizations of systems of interacting harmonic oscillators in which these effects may be confirmed experimentally.

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

Makhov, Dmitry V.; Shalashilin, Dmitrii V.; Glover, William J.

We present a new algorithm for ab initio quantum nonadiabatic molecular dynamics that combines the best features of ab initio Multiple Spawning (AIMS) and Multiconfigurational Ehrenfest (MCE) methods. In this new method, ab initio multiple cloning (AIMC), the individual trajectory basis functions (TBFs) follow Ehrenfest equations of motion (as in MCE). However, the basis set is expanded (as in AIMS) when these TBFs become sufficiently mixed, preventing prolonged evolution on an averaged potential energy surface. We refer to the expansion of the basis set as “cloning,” in analogy to the “spawning” procedure in AIMS. This synthesis of AIMS and MCEmore » allows us to leverage the benefits of mean-field evolution during periods of strong nonadiabatic coupling while simultaneously avoiding mean-field artifacts in Ehrenfest dynamics. We explore the use of time-displaced basis sets, “trains,” as a means of expanding the basis set for little cost. We also introduce a new bra-ket averaged Taylor expansion (BAT) to approximate the necessary potential energy and nonadiabatic coupling matrix elements. The BAT approximation avoids the necessity of computing electronic structure information at intermediate points between TBFs, as is usually done in saddle-point approximations used in AIMS. The efficiency of AIMC is demonstrated on the nonradiative decay of the first excited state of ethylene. The AIMC method has been implemented within the AIMS-MOLPRO package, which was extended to include Ehrenfest basis functions.« less

Intermediate boundary conditions for LOD, ADI and approximate factorization methods

NASA Technical Reports Server (NTRS)

Leveque, R. J.

1985-01-01

A general approach to determining the correct intermediate boundary conditions for dimensional splitting methods is presented. The intermediate solution U is viewed as a second order accurate approximation to a modified equation. Deriving the modified equation and using the relationship between this equation and the original equation allows us to determine the correct boundary conditions for U*. This technique is illustrated by applying it to locally one dimensional (LOD) and alternating direction implicit (ADI) methods for the heat equation in two and three space dimensions. The approximate factorization method is considered in slightly more generality.

DNA intermediates and telomere addition during genome reorganization in Euplotes crassus.

PubMed

Roth, M; Prescott, D M

1985-06-01

Three gene-sized molecules cloned intact from macronuclear DNA served as hybridization probes to study excision of these molecules from chromosomes and their processing during macronuclear development in the hypotrich Euplotes crassus. These molecules occur in integrated forms within polytene chromosomal DNA during macronuclear developmental. After transection of the polytene chromosomes, the three molecules occur in intermediate forms. One of the three molecules first appeared in a large intermediate that was subsequently replaced by a second intermediate, approximately 140 bp larger than the final molecule. The other two macronuclear molecules were detected only in intermediates approximately 140 bp larger than the mature form. These penultimate intermediates are larger by virtue of oversized telomeres, which are pared to yield the mature gene-sized molecules.

Characterization of the product radical structure in the Co(II)-product radical pair state of coenzyme B12-dependent ethanolamine deaminase by using three-pulse 2H ESEEM spectroscopy.

PubMed

Warncke, Kurt

2005-03-08

Molecular structural features of the product radical in the Co(II)-product radical pair catalytic intermediate state in coenzyme B(12)- (adenosylcobalamin-) dependent ethanolamine deaminase from Salmonella typhimurium have been characterized by using X-band three-pulse electron spin-echo envelope modulation (ESEEM) spectroscopy in the disordered solid state. The Co(II)-product radical pair state was prepared by cryotrapping holoenzyme during steady-state turnover on excess 1,1,2,2-(2)H(4)-aminoethanol or natural abundance, (1)H(4)-aminoethanol. Simulation of the (2)H/(1)H quotient ESEEM (obtained at two microwave frequencies, 8.9 and 10.9 GHz) from the interaction of the unpaired electron localized at C2 of the product radical with nearby (2)H nuclei requires four types of coupled (2)H, which are assigned as follows: (a) a single strongly coupled (effective dipole distance, r(eff) = 2.3 A) (2)H in the C5' methyl group of 5'-deoxyadenosine, (b) two weakly coupled (r(eff) = 4.2 A) (2)H in the C5' methyl group, (c) one (2)H coupling from a beta-(2)H bonded to C1 of the product radical (isotropic hyperfine coupling, A(iso) = 4.7 MHz), and (d) a second type of C1 beta-(2)H coupling (A(iso) = 7.7 MHz). The two beta-(2)H couplings are proposed to arise from two C1-C2 rotamer states of the product radical that are present in approximately equal proportion. A model is presented, in which C5' is positioned at a distance of 3.3 A from C2, which is comparable with the C1-C5' distance in the Co(II)-substrate radical pair intermediate. Therefore, the C5'methyl group remains in close (van der Waals) contact with the substrate and product radical species during the radical rearrangement step of the catalytic cycle, and the C5' center is the sole mediator of radical pair recombination in ethanolamine deaminase.

Identification of the substrate radical intermediate derived from ethanolamine during catalysis by ethanolamine ammonia-lyase.

PubMed

Bender, Güneş; Poyner, Russell R; Reed, George H

2008-10-28

Rapid-mix freeze-quench (RMFQ) methods and electron paramagnetic resonance (EPR) spectroscopy have been used to characterize the steady-state radical in the deamination of ethanolamine catalyzed by adenosylcobalamin (AdoCbl)-dependent ethanolamine ammonia-lyase (EAL). EPR spectra of the radical intermediates formed with the substrates, [1-13C]ethanolamine, [2-13C]ethanolamine, and unlabeled ethanolamine were acquired using RMFQ trapping methods from 10 ms to completion of the reaction. Resolved 13C hyperfine splitting in EPR spectra of samples prepared with [1-13C]ethanolamine and the absence of such splitting in spectra of samples prepared with [2-13C]ethanolamine show that the unpaired electron is localized on C1 (the carbinol carbon) of the substrate. The 13C splitting from C1 persists from 10 ms throughout the time course of substrate turnover, and there was no evidence of a detectable amount of a product like radical having unpaired spin on C2. These results correct an earlier assignment for this radical intermediate [Warncke, K., et al. (1999) J. Am. Chem. Soc. 121, 10522-10528]. The EPR signals of the substrate radical intermediate are altered by electron spin coupling to the other paramagnetic species, cob(II)alamin, in the active site. The dipole-dipole and exchange interactions as well as the 1-13C hyperfine splitting tensor were analyzed via spectral simulations. The sign of the isotropic exchange interaction indicates a weak ferromagnetic coupling of the two unpaired electrons. A Co2+-radical distance of 8.7 A was obtained from the magnitude of the dipole-dipole interaction. The orientation of the principal axes of the 13C hyperfine splitting tensor shows that the long axis of the spin-bearing p orbital on C1 of the substrate radical makes an angle of approximately 98 degrees with the unique axis of the d(z2) orbital of Co2+.

Argentate(i) and (iii) complexes as intermediates in silver-mediated cross-coupling reactions.

PubMed

Weske, Sebastian; Hardin, Richard A; Auth, Thomas; O'Hair, Richard A J; Koszinowski, Konrad; Ogle, Craig A

2018-04-30

Despite the potential of silver to mediate synthetically valuable cross-coupling reactions, the operating mechanisms have remained unknown. Here, we use a combination of rapid-injection NMR spectroscopy, electrospray-ionization mass spectrometry, and quantum chemical calculations to demonstrate that these transformations involve argentate(i) and (iii) complexes as key intermediates.

Mechanistic Significance of the Si–O–Pd Bond in the Palladium-Catalyzed Cross-Coupling Reactions of Arylsilanolates

PubMed Central

2016-01-01

Through the combination of reaction kinetics (both stoichiometric and catalytic), solution- and solid-state characterization of arylpalladium(II) arylsilanolates, and computational analysis, the intermediacy of covalent adducts containing Si–O–Pd linkages in the cross-coupling reactions of arylsilanolates has been unambiguously established. Two mechanistically distinct pathways have been demonstrated: (1) transmetalation via a neutral 8-Si-4 intermediate that dominates in the absence of free silanolate (i.e., stoichiometric reactions of arylpalladium(II) arylsilanolate complexes), and (2) transmetalation via an anionic 10-Si-5 intermediate that dominates in the cross-coupling under catalytic conditions (i.e., in the presence of free silanolate). Arylpalladium(II) arylsilanolate complexes bearing various phosphine ligands have been isolated, fully characterized, and evaluated for their kinetic competence under thermal (stoichiometric) and anionic (catalytic) conditions. Comparison of the rates for thermal and anionic activation suggested, but did not prove, that intermediates containing the Si–O–Pd linkage were involved in the cross-coupling process. The isolation of a coordinatively unsaturated, T-shaped arylpalladium(II) arylsilanolate complex ligated with t-Bu3P allowed the unambiguous demonstration of the operation of both pathways involving 8-Si-4 and 10-Si-5 intermediates. Three kinetic regimes were identified: (1) with 0.5–1.0 equiv of added silanolate (with respect to arylpalladium bromide), thermal transmetalation via a neutral 8-Si-4 intermediate; (2) with 1.0–5.0 equiv of added silanolate, activated transmetalation via an anionic 10-Si-5 intermediate; and (3) with >5.0 equiv of added silanolate, concentration-independent (saturation) activated transmetalation via an anionic 10-Si-5 intermediate. Transition states for the intramolecular transmetalation of neutral (8-Si-4) and anionic (10-Si-5) intermediates have been located computationally, and the anionic pathway is favored by 1.8 kcal/mol. The energies of all intermediates and transition states are highly dependent on the configuration around the palladium atom. PMID:25945516

Magnetic braking of stellar cores in red giants and supergiants

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

Maeder, André; Meynet, Georges, E-mail: andre.maeder@unige, E-mail: georges.meynet@unige.ch

2014-10-01

Magnetic configurations, stable on the long term, appear to exist in various evolutionary phases, from main-sequence stars to white dwarfs and neutron stars. The large-scale ordered nature of these fields, often approximately dipolar, and their scaling according to the flux conservation scenario favor a fossil field model. We make some first estimates of the magnetic coupling between the stellar cores and the outer layers in red giants and supergiants. Analytical expressions of the truncation radius of the field coupling are established for a convective envelope and for a rotating radiative zone with horizontal turbulence. The timescales of the internal exchangesmore » of angular momentum are considered. Numerical estimates are made on the basis of recent model grids. The direct magnetic coupling of the core to the extended convective envelope of red giants and supergiants appears unlikely. However, we find that the intermediate radiative zone is fully coupled to the core during the He-burning and later phases. This coupling is able to produce a strong spin down of the core of red giants and supergiants, also leading to relatively slowly rotating stellar remnants such as white dwarfs and pulsars. Some angular momentum is also transferred to the outer convective envelope of red giants and supergiants during the He-burning phase and later.« less

Two-level system in spin baths: Non-adiabatic dynamics and heat transport

NASA Astrophysics Data System (ADS)

Segal, Dvira

2014-04-01

We study the non-adiabatic dynamics of a two-state subsystem in a bath of independent spins using the non-interacting blip approximation, and derive an exact analytic expression for the relevant memory kernel. We show that in the thermodynamic limit, when the subsystem-bath coupling is diluted (uniformly) over many (infinite) degrees of freedom, our expression reduces to known results, corresponding to the harmonic bath with an effective, temperature-dependent, spectral density function. We then proceed and study the heat current characteristics in the out-of-equilibrium spin-spin-bath model, with a two-state subsystem bridging two thermal spin-baths of different temperatures. We compare the behavior of this model to the case of a spin connecting boson baths, and demonstrate pronounced qualitative differences between the two models. Specifically, we focus on the development of the thermal diode effect, and show that the spin-spin-bath model cannot support it at weak (subsystem-bath) coupling, while in the intermediate-strong coupling regime its rectifying performance outplays the spin-boson model.

Incredible negative values of effective electromechanical coupling coefficient for surface acoustic waves in piezoelectrics.

PubMed

Mozhaev, V G; Weihnacht, M

2000-07-01

The extraordinary case of increase in velocity of surface acoustic waves (SAW) caused by electrical shorting of the surface of the superstrong piezoelectric crystal potassium niobate, KNbO3, is numerically found. The explanation of this effect is based on considering SAWs as coupled Rayleigh and Bleustein-Gulyaev modes. A general procedure of approximate decoupling of the modes is suggested for piezoelectric crystals of arbitrary anisotropy. The effect under study takes place when the phase velocity of uncoupled sagittally polarized Rayleigh waves is intermediate between the phase velocities of uncoupled shear-horizontal Bleustein Gulyaev waves at the free and metallized surfaces. In this case, the metallization of the surface by an infinitely thin layer may cause a crossover of the velocity curves of the uncoupled waves. The presence of the mode coupling results in splitting of the curves with transition from one uncoupled branch to the other. This transition is responsible for the increase in SAW velocity, which appears to be greater than its common decrease produced by electrical shorting of the substrate surface.

Flash photolysis of rhodopsin in the cat retina

PubMed Central

1981-01-01

The bleaching of rhodopsin by short-duration flashes of a xenon discharge lamp was studied in vivo in the cat retina with the aid of a rapid, spectral-scan fundus reflectometer. Difference spectra recorded over a broad range of intensities showed that the bleaching efficacy of high-intensity flashes was less than that of longer duration, steady lights delivering the same amount of energy. Both the empirical results and those derived from a theoretical analysis of flash photolysis indicate that, under the conditions of these experiments, the upper limit of the flash bleaching of rhodopsin in cat is approximately 90%. Although the fact that a full bleach could not be attained is attributable to photoreversal, i.e., the photic regeneration of rhodopsin from its light-sensitive intermediates, the 90% limit is considerably higher than the 50% (or lower) value obtained under other experimental circumstances. Thus, it appears that the duration (approximately 1 ms) and spectral composition of the flash, coupled with the kinetic parameters of the thermal and photic reactions in the cat retina, reduce the light-induced regeneration of rhodopsin to approximately 10%. PMID:7252476

Surface nematic order in iron pnictides

DOE PAGES

Song, Kok Wee; Koshelev, Alexei E.

2016-09-09

Electronic nematicity plays an important role in iron-based superconductors. These materials have a layered structure and the theoretical description of their magnetic and nematic transitions has been well established in the two-dimensional approximation, i.e., when the layers can be treated independently. However, the interaction between iron layers mediated by electron tunneling may cause nontrivial three-dimensional behavior. Starting from the simplest model for orbital nematic in a single layer, we investigate the influence of interlayer tunneling on the bulk nematic order and a possible preemptive state where this order is only formed near the surface. In addition, we found that themore » interlayer tunneling suppresses the bulk nematicity, which makes favorable the formation of a surface nematic order above the bulk transition temperature. The purely electronic tunneling Hamiltonian, however, favors a nematic order parameter that alternates from layer to layer. The uniform bulk state typically observed experimentally may be stabilized by the coupling with the elastic lattice deformation. Depending on the strength of this coupling, we found three regimes: (i) surface nematic and alternating bulk order, (ii) surface nematic and uniform bulk order, and (iii) uniform bulk order without the intermediate surface phase. Lastly, the intermediate surface-nematic state may resolve the current controversy about the existence of a weak nematic transition in the compound BaFe 2As 2-xP x .« less

Flow chemistry as a discovery tool to access sp2-sp3 cross-coupling reactions via diazo compounds.

PubMed

Tran, Duc N; Battilocchio, Claudio; Lou, Shing-Bong; Hawkins, Joel M; Ley, Steven V

2015-02-01

The work takes advantage of an important feature of flow chemistry, whereby the generation of a transient species (or reactive intermediate) can be followed by a transfer step into another chemical environment, before the intermediate is reacted with a coupling partner. This concept is successfully applied to achieve a room temperature sp 2 -sp 3 cross coupling of boronic acids with diazo compounds, these latter species being generated from hydrazones under flow conditions using MnO 2 as the oxidant.

Electrostatic attraction of coupled Wigner crystals: finite temperature effects.

PubMed

Lau, A W; Pincus, P; Levine, D; Fertig, H A

2001-05-01

In this paper we present a unified physical picture for the electrostatic attraction between two coupled planar Wigner crystals at finite temperature. This model may facilitate our conceptual understanding of counterion-mediated attractions between (highly) similarly charged planes. By adopting an elastic theory, we show that the total attractive force between them can be (approximately) decomposed into a short-ranged and a long-ranged component. They are evaluated below the melting temperature of the Wigner crystals. In particular, we analyze the temperature dependence of the short-ranged attraction, arising from ground-state configuration, and we argue that thermal fluctuations may drastically reduce its strength. Also, the long-range force agrees exactly with that based on the charge-fluctuation approach. Furthermore, we take quantum contributions to the long-ranged (fluctuation-induced) attraction into account and show how the fractional power law, which scales as d(-7/2) for large interplanar distance d at zero temperature, crosses over to the classical regime d(-3) via an intermediate regime of d(-2).

Ice-shelf collapse from subsurface warming as a trigger for Heinrich events

PubMed Central

Marcott, Shaun A.; Clark, Peter U.; Padman, Laurie; Klinkhammer, Gary P.; Springer, Scott R.; Liu, Zhengyu; Otto-Bliesner, Bette L.; Carlson, Anders E.; Ungerer, Andy; Padman, June; He, Feng; Cheng, Jun; Schmittner, Andreas

2011-01-01

Episodic iceberg-discharge events from the Hudson Strait Ice Stream (HSIS) of the Laurentide Ice Sheet, referred to as Heinrich events, are commonly attributed to internal ice-sheet instabilities, but their systematic occurrence at the culmination of a large reduction in the Atlantic meridional overturning circulation (AMOC) indicates a climate control. We report Mg/Ca data on benthic foraminifera from an intermediate-depth site in the northwest Atlantic and results from a climate-model simulation that reveal basin-wide subsurface warming at the same time as large reductions in the AMOC, with temperature increasing by approximately 2 °C over a 1–2 kyr interval prior to a Heinrich event. In simulations with an ocean model coupled to a thermodynamically active ice shelf, the increase in subsurface temperature increases basal melt rate under an ice shelf fronting the HSIS by a factor of approximately 6. By analogy with recent observations in Antarctica, the resulting ice-shelf loss and attendant HSIS acceleration would produce a Heinrich event. PMID:21808034

Two-dimensional electronic spectra from the hierarchical equations of motion method: Application to model dimers

NASA Astrophysics Data System (ADS)

Chen, Liping; Zheng, Renhui; Shi, Qiang; Yan, YiJing

2010-01-01

We extend our previous study of absorption line shapes of molecular aggregates using the Liouville space hierarchical equations of motion (HEOM) method [L. P. Chen, R. H. Zheng, Q. Shi, and Y. J. Yan, J. Chem. Phys. 131, 094502 (2009)] to calculate third order optical response functions and two-dimensional electronic spectra of model dimers. As in our previous work, we have focused on the applicability of several approximate methods related to the HEOM method. We show that while the second order perturbative quantum master equations are generally inaccurate in describing the peak shapes and solvation dynamics, they can give reasonable peak amplitude evolution even in the intermediate coupling regime. The stochastic Liouville equation results in good peak shapes, but does not properly describe the excited state dynamics due to the lack of detailed balance. A modified version of the high temperature approximation to the HEOM gives the best agreement with the exact result.

Influence of xc functional on thermal-elastic properties of Ceria: A DFT-based Debye-Grüneisen model approach

NASA Astrophysics Data System (ADS)

Lee, Ji-Hwan; Tak, Youngjoo; Lee, Taehun; Soon, Aloysius

Ceria (CeO2-x) is widely studied as a choice electrolyte material for intermediate-temperature (~ 800 K) solid oxide fuel cells. At this temperature, maintaining its chemical stability and thermal-mechanical integrity of this oxide are of utmost importance. To understand their thermal-elastic properties, we firstly test the influence of various approximations to the density-functional theory (DFT) xc functionals on specific thermal-elastic properties of both CeO2 and Ce2O3. Namely, we consider the local-density approximation (LDA), the generalized gradient approximation (GGA-PBE) with and without additional Hubbard U as applied to the 4 f electron of Ce, as well as the recently popularized hybrid functional due to Heyd-Scuseria-Ernzehof (HSE06). Next, we then couple this to a volume-dependent Debye-Grüneisen model to determine the thermodynamic quantities of ceria at arbitrary temperatures. We find an explicit description of the strong correlation (e.g. via the DFT + U and hybrid functional approach) is necessary to have a good agreement with experimental values, in contrast to the mean-field treatment in standard xc approximations (such as LDA or GGA-PBE). We acknowledge support from Samsung Research Funding Center of Samsung Electronics (SRFC-MA1501-03).

Evidence for changes in the nucleotide conformation in the active site of H(+)-ATPase as determined by pulsed EPR spectroscopy.

PubMed

Schneider, B; Sigalat, C; Amano, T; Zimmermann, J L

2000-12-19

The conformation of di- and triphosphate nucleosides in the active site of ATPsynthase (H(+)-ATPase) from thermophilic Bacillus PS3 (TF1) and their interaction with Mg(2+)/Mn(2+) cations have been investigated using EPR, ESEEM, and HYSCORE spectroscopies. For a ternary complex formed by a stoichiometric mixture of TF1, Mn(2+), and ADP, the ESEEM and HYSCORE data reveal a (31)P hyperfine interaction with Mn(2+) (|A((31)P)| approximately 5.20 MHz), significantly larger than that measured for the complex formed by Mn(2+) and ADP in solution (|A((31)P)| approximately 4.50 MHz). The Q-band EPR spectrum of the Mn.TF1.ADP complex indicates that the Mn(2+) binds in a slightly distorted environment with |D| approximately 180 x 10(-4) cm(-1) and |E| approximately 50 x 10(-4) cm(-1). The increased hyperfine coupling with (31)P in the presence of TF1 reflects the specific interaction between the central Mn(2+) and the ADP beta-phosphate, illustrating the role of the enzyme active site in positioning the phosphate chain of the substrate for efficient catalysis. Results with the ternary Mn.TF1.ATP and Mn.TF1.AMP-PNP complexes are interpreted in a similar way with two hyperfine couplings being resolved for each complex (|A((31)P(beta))| approximately 4.60 MHz and |A((31)P(gamma))| approximately 5.90 MHz with ATP, and |A((31)P(beta))| approximately 4.20 MHz and |A((31)P(gamma))| approximately 5.40 MHz with AMP-PNP). In these complexes, the increased hyperfine coupling with (31)P(gamma) compared with (31)P(beta) reflects the smaller Mn.P distance with the gamma-phosphate compared with the beta-phosphate as found in the crystal structure of the analogous enzyme from mitochondria [3.53 vs 3.70 A (Abrahams, J. P., Leslie, A. G. W., Lutter, R., and Walker, J. E. (1994) Nature 370, 621-628)] and the different binding modes of the two phosphate groups. The ESEEM and HYSCORE data of a complex formed with Mn(2+), ATP, and the isolated beta subunit show that the (31)P hyperfine coupling is close to that measured in the absence of the protein, indicating a poorly structured nucleotide site in the isolated beta subunit in the presence of ATP. The inhibition data obtained for TF1 incubated in the presence of Mg(2+), ADP, Al(NO(3))(3), and NaF indicate the formation of the inhibited complex with the transition state analogue namely Mg.TF1.ADP.AlF(x) with the equilibrium dissociation constant K(D) = 350 microM and rate constant k = 0.02 min(-1). The ESEEM and HYSCORE data obtained for an inhibited TF1 sample, Mn.TF1.ADP.AlF(x), confirm the formation of the transition state analogue with distinct spectroscopic footprints that can be assigned to Mn.(19)F and Mn.(27)Al hyperfine interactions. The (31)P(beta) hyperfine coupling that is measured in the inhibited complex with the transition state analogue (|A((31)P(beta))| approximately 5.10 MHz) is intermediate between those measured in the presence of ADP and ATP and suggests an increase in the bond between Mn and the P(beta) from ADP upon formation of the transition state.

The Supersymmetric Fat Higgs

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

Harnik, Roni

2004-10-27

Supersymmetric models have traditionally been assumed to be perturbative up to high scales due to the requirement of calculable unification. In this note I review the recently proposed `Fat Higgs' model which relaxes the requirement of perturbativity. In this framework, an NMSSM-like trilinear coupling becomes strong at some intermediate scale. The NMSSM Higgses are meson composites of an asymptotically-free gauge theory. This allows us to raise the mass of the Higgs, thus alleviating the MSSM of its fine tuning problem. Despite the strong coupling at an intermediate scale, the UV completion allows us to maintain gauge coupling unification.

An alternative pathway for marine nitrous oxide production at oxic-anoxic interfaces from coupled biotic-abiotic reactions

NASA Astrophysics Data System (ADS)

Glass, J. B.; Stanton, C. L.; Ochoa, H.; Haslun, J. A.; Gandhi, H.; Taillefert, M.; Dichristina, T. J.; Stewart, F. J.; Klotz, M. G.; Ostrom, N. E.

2016-02-01

Marine emissions of nitrous oxide (N2O), a potent greenhouse gas, comprise approximately a third of global sources. Recent evidence suggests that the dominant source of N2O in seawater is the activity of ammonia-oxidizing Thaumarchaeota that lack characterized N2O-generating enzymes. Nitrous oxide may arise from a novel enzyme and/or abiotic reactions between nitrification intermediates, hydroxylamine (NH2OH) and nitric oxide (NO), and redox-active metals in seawater. Isotopic site preference, or difference in δ15N between the two nitrogen atoms in N2O, has been used as tracer for microbial N2O production pathways (-10 to 0‰ for nitrifier-denitrification and denitrification vs. 30-37‰ for nitrification via NH2OH oxidation). Seawater N2O site preference falls in between these two characterized end members, suggesting simultaneous production via a combination of both microbial pathways or via a novel mechanism with intermediate site preference. Here we show significant N2O production in abiotic experiments after addition of iron to seawater containing NH2OH and NO. The N2O produced from chemical reduction of NO by Fe(II) had a site preference of 16‰ whereas N2O produced from abiotic NH2OH oxidation had a site preference of 31‰. We propose that coupled biotic-abiotic N2O production pathways could contribute significant sources of N2O at marine oxic-anoxic interfaces.

An improved coupled-states approximation including the nearest neighbor Coriolis couplings for diatom-diatom inelastic collision

NASA Astrophysics Data System (ADS)

Yang, Dongzheng; Hu, Xixi; Zhang, Dong H.; Xie, Daiqian

2018-02-01

Solving the time-independent close coupling equations of a diatom-diatom inelastic collision system by using the rigorous close-coupling approach is numerically difficult because of its expensive matrix manipulation. The coupled-states approximation decouples the centrifugal matrix by neglecting the important Coriolis couplings completely. In this work, a new approximation method based on the coupled-states approximation is presented and applied to time-independent quantum dynamic calculations. This approach only considers the most important Coriolis coupling with the nearest neighbors and ignores weaker Coriolis couplings with farther K channels. As a result, it reduces the computational costs without a significant loss of accuracy. Numerical tests for para-H2+ortho-H2 and para-H2+HD inelastic collision were carried out and the results showed that the improved method dramatically reduces the errors due to the neglect of the Coriolis couplings in the coupled-states approximation. This strategy should be useful in quantum dynamics of other systems.

QUINONE METHIDES IN LIGNIFICATION

USDA-ARS?s Scientific Manuscript database

Quinone methides play an important role in lignification. They are produced directly, as intermediates, when lignin monomers, be they hydroxycinnamyl alcohols, hydroxycinnamaldehydes, or hydroxycinnamates, couple or cross-couple at their 8-positions. A variety of post-coupling quinone methide rearom...

Occurrence and Characteristics of a Rapid Exchange of Phosphate Oxygens Catalyzed by Sarcoplasmic Reticulum Vesicles

DOE R&D Accomplishments Database

Kanazawa, T.; Boyer, P. D.

1972-01-01

Sarcoplasmic reticulum vesicles isolated from skeletal muscle actively take up Ca{sup ++} from the medium in the presence of Mg{sup ++} and ATP. This transport is coupled to ATP hydrolysis catalyzed by membrane-bound Ca{sup++}, Mg{sup ++}-ATPase which is activated by concurrent presence of Ca{sup ++} and Mg{sup ++}. Considerable informations have accumulated that give insight into the ATPase and its coupling to the calcium transport. The hydrolysis of ATP by this enzyme occurs through a phosphorylated intermediate. Formation and decomposition of the intermediate show vectorial requirements for Ca{sup ++} and Mg{sup ++}, suggesting an intimate involvement of the intermediate in the transport process. ATP synthesis from P{sub i} and ADP coupled to outflow of Ca{sup ++} from sarcoplasmic reticulum vesicles has recently been demonstrated. This indicates the reversibility of the entire process of calcium transport in sarcoplasmic reticulum vesicles.

Homoclinic snaking in the discrete Swift-Hohenberg equation

NASA Astrophysics Data System (ADS)

Kusdiantara, R.; Susanto, H.

2017-12-01

We consider the discrete Swift-Hohenberg equation with cubic and quintic nonlinearity, obtained from discretizing the spatial derivatives of the Swift-Hohenberg equation using central finite differences. We investigate the discretization effect on the bifurcation behavior, where we identify three regions of the coupling parameter, i.e., strong, weak, and intermediate coupling. Within the regions, the discrete Swift-Hohenberg equation behaves either similarly or differently from the continuum limit. In the intermediate coupling region, multiple Maxwell points can occur for the periodic solutions and may cause irregular snaking and isolas. Numerical continuation is used to obtain and analyze localized and periodic solutions for each case. Theoretical analysis for the snaking and stability of the corresponding solutions is provided in the weak coupling region.

Negative tunnel magnetoresistance and differential conductance in transport through double quantum dots

NASA Astrophysics Data System (ADS)

Trocha, Piotr; Weymann, Ireneusz; Barnaś, Józef

2009-10-01

Spin-dependent transport through two coupled single-level quantum dots weakly connected to ferromagnetic leads with collinear magnetizations is considered theoretically. Transport characteristics, including the current, linear and nonlinear conductances, and tunnel magnetoresistance are calculated using the real-time diagrammatic technique in the parallel, serial, and intermediate geometries. The effects due to virtual tunneling processes between the two dots via the leads, associated with off-diagonal coupling matrix elements, are also considered. Negative differential conductance and negative tunnel magnetoresistance have been found in the case of serial and intermediate geometries, while no such behavior has been observed for double quantum dots coupled in parallel. It is also shown that transport characteristics strongly depend on the magnitude of the off-diagonal coupling matrix elements.

Alkynyl Moiety for Triggering 1,2‐Metallate Shifts: Enantiospecific sp2–sp3 Coupling of Boronic Esters with p‐Arylacetylenes

PubMed Central

Ganesh, Venkataraman; Odachowski, Marcin

2017-01-01

Abstract The enantiospecific coupling of secondary and tertiary boronic esters to aromatics has been investigated. Using p‐lithiated phenylacetylenes and a range of boronic esters coupling has been achieved by the addition of N‐bromosuccinimide (NBS). The alkyne functionality of the intermediate boronate complex reacts with NBS triggering the 1,2‐migration of the group on boron to carbon giving a dearomatized bromoallene intermediate. At this point elimination and rearomatization occurs with neopentyl boronic esters, giving the coupled products. However, using pinacol boronic esters, the boron moiety migrates to the adjacent carbon resulting in formation of ortho boron‐incorporated coupled products. The synthetic utility of the boron incorporated product has been demonstrated by orthogonal transformation of both the alkyne and boronic ester functionalities. PMID:28618129

A diagrammatic formulation of the kinetic theory of fluctuations in equilibrium classical fluids. VI. Binary collision approximations for the memory function for self-correlation functions

NASA Astrophysics Data System (ADS)

Noah-Vanhoucke, Joyce E.; Andersen, Hans C.

2007-08-01

We use computer simulation results for a dense Lennard-Jones fluid for a range of temperatures to test the accuracy of various binary collision approximations for the memory function for density fluctuations in liquids. The approximations tested include the moderate density approximation of the generalized Boltzmann-Enskog memory function (MGBE) of Mazenko and Yip [Statistical Mechanics. Part B. Time-Dependent Processes, edited by B. J. Berne (Plenum, New York, 1977)], the binary collision approximation (BCA) and the short time approximation (STA) of Ranganathan and Andersen [J. Chem. Phys. 121, 1243 (2004); J. Phys. Chem. 109, 21437 (2005)] and various other approximations we derived by using diagrammatic methods. The tests are of two types. The first is a comparison of the correlation functions predicted by each approximate memory function with the simulation results, especially for the self-longitudinal current correlation (SLCC) function. The second is a direct comparison of each approximate memory function with a memory function numerically extracted from the correlation function data. The MGBE memory function is accurate at short times but decays to zero too slowly and gives a poor description of the correlation function at intermediate times. The BCA is exact at zero time, but it predicts a correlation function that diverges at long times. The STA gives a reasonable description of the SLCC but does not predict the correct temperature dependence of the negative dip in the function that is associated with caging at low temperatures. None of the other binary collision approximations is a systematic improvement on the STA. The extracted memory functions have a rapidly decaying short time part, much like the STA, and a much smaller, more slowly decaying part of the type predicted by a mode coupling theory. Theories that use mode coupling commonly include a binary collision term in the memory function but do not discuss in detail the nature of that term. It is clear from the present work that the short time part of the memory function has a behavior associated with brief binary repulsive collisions, such as those described by the STA. Collisions that include attractive as well as repulsive interactions, such as those of the MGBE, have a much longer duration, and theories that include them have memory functions that decay to zero much too slowly to provide a good first approximation of the correlation function. This leads us to speculate that the memory function for density fluctuations can be usefully regarded as a sum of at least three parts: a contribution from repulsive binary collisions (the STA or something similar to it), another short time part that is related to all the other interactions (but whose nature is not understood), and a longer time slowly decaying part that describes caging (of the type predicted by the mode coupling theory).

Shallow seismic source parameter determination using intermediate-period surface wave amplitude spectra

NASA Astrophysics Data System (ADS)

Fox, Benjamin D.; Selby, Neil D.; Heyburn, Ross; Woodhouse, John H.

2012-09-01

Estimating reliable depths for shallow seismic sources is important in both seismo-tectonic studies and in seismic discrimination studies. Surface wave excitation is sensitive to source depth, especially at intermediate and short-periods, owing to the approximate exponential decay of surface wave displacements with depth. A new method is presented here to retrieve earthquake source parameters from regional and teleseismic intermediate period (100-15 s) fundamental-mode surface wave recordings. This method makes use of advances in mapping global dispersion to allow higher frequency surface wave recordings at regional and teleseismic distances to be used with more confidence than in previous studies and hence improve the resolution of depth estimates. Synthetic amplitude spectra are generated using surface wave theory combined with a great circle path approximation, and a grid of double-couple sources are compared with the data. Source parameters producing the best-fitting amplitude spectra are identified by minimizing the least-squares misfit in logarithmic amplitude space. The F-test is used to search the solution space for statistically acceptable parameters and the ranges of these variables are used to place constraints on the best-fitting source. Estimates of focal mechanism, depth and scalar seismic moment are determined for 20 small to moderate sized (4.3 ≤Mw≤ 6.4) earthquakes. These earthquakes are situated across a wide range of geographic and tectonic locations and describe a range of faulting styles over the depth range 4-29 km. For the larger earthquakes, comparisons with other studies are favourable, however existing source determination procedures, such as the CMT technique, cannot be performed for the smaller events. By reducing the magnitude threshold at which robust source parameters can be determined, the accuracy, especially at shallow depths, of seismo-tectonic studies, seismic hazard assessments, and seismic discrimination investigations can be improved by the application of this methodology.

Intermediate Bandgap Solar Cells From Nanostructured Silicon

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

Black, Marcie

2014-10-30

This project aimed to demonstrate increased electronic coupling in silicon nanostructures relative to bulk silicon for the purpose of making high efficiency intermediate bandgap solar cells using silicon. To this end, we formed nanowires with controlled crystallographic orientation, small diameter, <111> sidewall faceting, and passivated surfaces to modify the electronic band structure in silicon by breaking down the symmetry of the crystal lattice. We grew and tested these silicon nanowires with <110>-growth axes, which is an orientation that should produce the coupling enhancement.

Gas turbine engine adapted for use in combination with an apparatus for separating a portion of oxygen from compressed air

DOEpatents

Bland, Robert J [Oviedo, FL; Horazak, Dennis A [Orlando, FL

2012-03-06

A gas turbine engine is provided comprising an outer shell, a compressor assembly, at least one combustor assembly, a turbine assembly and duct structure. The outer shell includes a compressor section, a combustor section, an intermediate section and a turbine section. The intermediate section includes at least one first opening and at least one second opening. The compressor assembly is located in the compressor section to define with the compressor section a compressor apparatus to compress air. The at least one combustor assembly is coupled to the combustor section to define with the combustor section a combustor apparatus. The turbine assembly is located in the turbine section to define with the turbine section a turbine apparatus. The duct structure is coupled to the intermediate section to receive at least a portion of the compressed air from the compressor apparatus through the at least one first opening in the intermediate section, pass the compressed air to an apparatus for separating a portion of oxygen from the compressed air to produced vitiated compressed air and return the vitiated compressed air to the intermediate section via the at least one second opening in the intermediate section.

Cyclohexane isomerization. Unimolecular dynamics of the twist-boat intermediate.

PubMed

Kakhiani, Khatuna; Lourderaj, Upakarasamy; Hu, Wenfang; Birney, David; Hase, William L

2009-04-23

Direct dynamics simulations were performed at the HF/6-31G level of theory to investigate the intramolecular and unimolecuar dynamics of the twist-boat (TB) intermediate on the cyclohexane potential energy surface (PES). Additional calculations were performed at the MP2/aug-cc-pVDZ level of theory to further characterize the PES's stationary points. The trajectories were initiated at the C(1) and C(2) half-chair transition states (TSs) connecting a chair conformer with a TB intermediate, via an intrinsic reaction coordinate (IRC). Energy was added in accord with a microcanonical ensemble at the average energy for experiments at 263 K. Important nontransition state theory (TST), non-IRC, and non-RRKM dynamics were observed in the simulations. Trajectories initially directed toward the chair conformer had a high probability of recrossing the TS, with approximately 30% forming a TB intermediate instead of accessing the potential energy well for the conformer. The TB intermediate initially formed was not necessarily the one connected to the TS via the IRC. Of the trajectories initiated at the C(2) half-chair TS and initially directed toward the chair conformer, 35% formed a TB intermediate instead of the chair conformer. Also, of the trajectories forming a TB intermediate, only 16% formed the TB intermediate connected with the C(2) TS via the IRC. Up to eight consecutive TB --> TB isomerizations were followed, and non-RRKM behavior was observed in their dynamics. A TB can isomerize to two different TBs, one by a clockwise rotation of C-C-C-C dihedral angles and the other by a counterclockwise rotation. In contrast to RRKM theory, which predicts equivalent probabilities for these rotations, the trajectory dynamics show they are not equivalent and depend on whether the C(1) or C(2) half-chair TS is initially excited. Non-RRKM dynamics is also observed in the isomerization of the TB intermediates to the chair conformers. RRKM theory assumes equivalent probabilities for isomerizing to the two chair conformers. In contrast, for the first and following TB intermediate formed, there is a preference to isomerize to the chair conformer connected to the TS at which the trajectories were initiated. For the first TB intermediate formed, approximately 30% of the isomerization is to a chair conformer, but this fraction decreases for the later formed TB intermediates and becomes approximately 10% for the eighth consecutive TB intermediate formed.

Study to assess the effects of magnetohydrodynamic electromagnetic pulse on electric power systems, phase 1, volume 3

NASA Astrophysics Data System (ADS)

Legro, J. R.; Abi-Samra, N. C.; Tesche, F. M.

1985-05-01

In addition to the initial transients designated as fast transient high-altitude EMP (HEMP) and intermediate time EMP, electromagnetic signals are also perceived at times from seconds to hundreds of seconds after a high-altitude nuclear burst. This signal was defined by the term magnetohydrodynamic-electromagnetic pulse (MHD-EMP). The MHD-EMP phenomena was detected in actual weapon tests and predicted from theoretical models. A preliminary research effort to investigate the nature and coupling of the MHD-EMP environments to electric power systems documented the construction of approximate system response network models, and the development of a unified methodology to assess equipment and systematic vulnerability are defined. The MHD-EMP environment is compared to a qualitatively similar natural event, the electromagnetic environment produced by geomagnetic storms.

Models for Convectively Coupled Tropical Waves

NASA Astrophysics Data System (ADS)

Majda, A. J.

2001-05-01

\\small{The tropical Western Pacific is a key area with large input on short-term climate. There are many recent observations of convective complexes feeding into equatorially trapped planetary waves [5], [6] which need a theoretical explanation and also are poorly treated in contemporary General Circulation Models (GCM's). This area presents wonderful new research opportunities for applied mathematicians interested in nonlinear waves interacting over many spatio-temporal scales. This talk describes some ongoing recent activities of the speaker related to these important issues. A simplified intermediate model for analyzing and parametrizing convectively coupled tropical waves is introduced in [2]. This model has two baroclinic modes of vertical structure, a direct heating mode and a stratiform mode. The key essential parameter in these models is the area fraction occupied by deep convection, σ c. The unstable convectively coupled waves that emerge from perturbation of a radiative convective equilibrium are discussed in detail through linearized stability analysis. Without any mean flow, for an overall cooling rate of 1 K/day as the area fraction parameter increases from σ c=0.001 to σ c=0.0014 the waves pass from a regime with stable moist convective damping (MCD) to a regime of ``stratiform'' instability with convectively coupled waves propagating at speeds of roughly 15~m~s-1,instabilities for a band wavelengths in the super-cluster regime, O(1000) to O(2000) km, and a vertical structure in the upper troposphere lags behind that in the lower troposphere - thus, these convectively coupled waves in the model reproduce several key features of convectively coupled waves in the troposphere processed from recent observational data by Wheeler and Kiladis ([5], [6]). As the parameter σ c is increased further to values such as σ c=0.01, the band of unstable waves increase and spreads toward mesoscale wavelengths of O(100) km while the same wave structure and quantitative features mentioned above are retained wave structure and quantitative features mentioned above are retained for O(1000) km. A detailed analysis of the temporal development of instability of these convectively coupled waves is presented here. In the first stage of instability, a high CAPE region generates deep convection and front-to-rear ascending flow with enhanced vertical shear in a stratiform wake region. Thus, these intermediate models may be useful prototypes for studying the parametrization of upscale convective momentum transport due to organized convection [4], [3]. In the second stage of instability, detailed analysis of the CAPE budget establishes that the effects of the second baroclinic mode in the stratiform wake produce new CAPE, which regenerates the first half of the wake cycle. Finally, since these convectively coupled stratiform waves do not require a barotropic mean flow, a barotropic mean flow which alters the surface fluxes, is added to study the effect of their stability. These effects of a barotropic mean flow are secondary; an easterly mean flow enhances instability of the eastward propagating convectively coupled waves and diminishes the instability of the westward propagating waves through a WISHE mechanism. Finally, new models for treating the equatorial wave guide [1], [8] which are intermediate between full meriodonal resolution and the equatorial long wave approximation will be discussed. If time permits, the use of these models in efficient numerical schemes which allow for cloud resolving modeling [7], but also include large scale interaction in the equatorial wave guide will be outlined [8].}

Glutamatergic drive along the septo-temporal axis of hippocampus boosts prelimbic oscillations in the neonatal mouse

PubMed Central

Ahlbeck, Joachim; Song, Lingzhen; Chini, Mattia; Bitzenhofer, Sebastian H

2018-01-01

The long-range coupling within prefrontal-hippocampal networks that account for cognitive performance emerges early in life. The discontinuous hippocampal theta bursts have been proposed to drive the generation of neonatal prefrontal oscillations, yet the cellular substrate of these early interactions is still unresolved. Here, we selectively target optogenetic manipulation of glutamatergic projection neurons in the CA1 area of either dorsal or intermediate/ventral hippocampus at neonatal age to elucidate their contribution to the emergence of prefrontal oscillatory entrainment. We show that despite stronger theta and ripples power in dorsal hippocampus, the prefrontal cortex is mainly coupled with intermediate/ventral hippocampus by phase-locking of neuronal firing via dense direct axonal projections. Theta band-confined activation by light of pyramidal neurons in intermediate/ventral but not dorsal CA1 that were transfected by in utero electroporation with high-efficiency channelrhodopsin boosts prefrontal oscillations. Our data causally elucidate the cellular origin of the long-range coupling in the developing brain. PMID:29631696

Precision measurement of the electromagnetic dipole strengths in Be11

NASA Astrophysics Data System (ADS)

Kwan, E.; Wu, C. Y.; Summers, N. C.; Hackman, G.; Drake, T. E.; Andreoiu, C.; Ashley, R.; Ball, G. C.; Bender, P. C.; Boston, A. J.; Boston, H. C.; Chester, A.; Close, A.; Cline, D.; Cross, D. S.; Dunlop, R.; Finlay, A.; Garnsworthy, A. B.; Hayes, A. B.; Laffoley, A. T.; Nano, T.; Navrátil, P.; Pearson, C. J.; Pore, J.; Quaglioni, S.; Svensson, C. E.; Starosta, K.; Thompson, I. J.; Voss, P.; Williams, S. J.; Wang, Z. M.

2014-05-01

The electromagnetic dipole strength in Be11 between the bound states has been measured using low-energy projectile Coulomb excitation at bombarding energies of 1.73 and 2.09 MeV/nucleon on a Pt196 target. An electric dipole transition probability B(E1;1/2-→1/2+)=0.102(2) e2fm was determined using the semi-classical code Gosia, and a value of 0.098(4) e2fm was determined using the Extended Continuum Discretized Coupled Channels method with the quantum mechanical code FRESCO. These extracted B(E1) values are consistent with the average value determined by a model-dependent analysis of intermediate energy Coulomb excitation measurements and are approximately 14% lower than that determined by a lifetime measurement. The much-improved precisions of 2% and 4% in the measured B(E1) values between the bound states deduced using Gosia and the Extended Continuum Discretized Coupled Channels method, respectively, compared to the previous accuracy of ˜10% will help in our understanding of and better improve the realistic inter-nucleon interactions.

Emergent causality and the N-photon scattering matrix in waveguide QED

NASA Astrophysics Data System (ADS)

Sánchez-Burillo, E.; Cadarso, A.; Martín-Moreno, L.; García-Ripoll, J. J.; Zueco, D.

2018-01-01

In this work we discuss the emergence of approximate causality in a general setup from waveguide QED—i.e. a one-dimensional propagating field interacting with a scatterer. We prove that this emergent causality translates into a structure for the N-photon scattering matrix. Our work builds on the derivation of a Lieb-Robinson-type bound for continuous models and for all coupling strengths, as well as on several intermediate results, of which we highlight: (i) the asymptotic independence of space-like separated wave packets, (ii) the proper definition of input and output scattering states, and (iii) the characterization of the ground state and correlations in the model. We illustrate our formal results by analyzing the two-photon scattering from a quantum impurity in the ultrastrong coupling regime, verifying the cluster decomposition and ground-state nature. Besides, we generalize the cluster decomposition if inelastic or Raman scattering occurs, finding the structure of the S-matrix in momentum space for linear dispersion relations. In this case, we compute the decay of the fluorescence (photon-photon correlations) caused by this S-matrix.

Flow chemistry as a discovery tool to access sp2–sp3 cross-coupling reactions via diazo compounds† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc03072a Click here for additional data file.

PubMed Central

Tran, Duc N.; Battilocchio, Claudio; Lou, Shing-Bong; Hawkins, Joel M.

2015-01-01

The work takes advantage of an important feature of flow chemistry, whereby the generation of a transient species (or reactive intermediate) can be followed by a transfer step into another chemical environment, before the intermediate is reacted with a coupling partner. This concept is successfully applied to achieve a room temperature sp2–sp3 cross coupling of boronic acids with diazo compounds, these latter species being generated from hydrazones under flow conditions using MnO2 as the oxidant. PMID:29560199

Hybridization-mediated anisotropic coupling in plutonium compounds

NASA Astrophysics Data System (ADS)

Banerjea, Amitava; Cooper, Bernard R.; Thayamballi, Pradeep

1984-09-01

The magnetic behavior of a class of cerium and light actinide compounds containing moderately delocalized f electrons has been explained on the basis of an anisotropic two-ion interaction that arises from the hybridization of band electrons and the f electrons. This theory, first developed by Siemann and Cooper for cerium compounds using the treatment of Coqblin and Schrieffer for the hybridization, was later generalized by Thayamballi and Cooper to fn systems in the L-S and j-j coupling limits. We here extend the theory to the case of intermediate intraionic coupling and further include the possibility of long-period antiferromagnetic structures. In particular, we have considered the Pu3+(f5) ion in PuSb. The theory reproduces the experimentally observed magnetic behavior of PuSb quite closely, predicting a phase transition from a low-temperature ferromagnetic phase to a long-period antiferromagnetic phase at about 75 K, for a fitting to a Néel temperature of 85 K, with ordered moments close to the experimental values. However, while the modulation in the long-period antiferromagnetic phase has been experimentally observed to be longitudinal, the theory predicts a transverse modulation with moments aligned along the cube edge. We also present the T=0 magnetic excitation spectrum in the ferromagnetic phase calculated on the basis of this theory using the random-phase approximation.

Spin–orbit coupling, minimal model and potential Cooper-pairing from repulsion in BiS2-superconductors

NASA Astrophysics Data System (ADS)

Cobo-Lopez, Sergio; Saeed Bahramy, Mohammad; Arita, Ryotaro; Akbari, Alireza; Eremin, Ilya

2018-04-01

We develop the realistic minimal electronic model for recently discovered BiS2 superconductors including the spin–orbit (SO) coupling based on the first-principles band structure calculations. Due to strong SO coupling, characteristic for the Bi-based systems, the tight-binding low-energy model necessarily includes p x , p y , and p z orbitals. We analyze a potential Cooper-pairing instability from purely repulsive interaction for the moderate electronic correlations using the so-called leading angular harmonics approximation. For small and intermediate doping concentrations we find the dominant instabilities to be {d}{x2-{y}2}-wave, and s ±-wave symmetries, respectively. At the same time, in the absence of the sizable spin fluctuations the intra and interband Coulomb repulsions are of the same strength, which yield the strongly anisotropic behavior of the superconducting gaps on the Fermi surface. This agrees with recent angle resolved photoemission spectroscopy findings. In addition, we find that the Fermi surface topology for BiS2 layered systems at large electron doping can resemble the doped iron-based pnictide superconductors with electron and hole Fermi surfaces maintaining sufficient nesting between them. This could provide further boost to increase T c in these systems.

Probing the Non-Native H Helix Translocation in Apomyoglobin Folding Intermediates

PubMed Central

2015-01-01

Apomyoglobin folds via sequential helical intermediates that are formed by rapid collapse of the A, B, G, and H helix regions. An equilibrium molten globule with a similar structure is formed near pH 4. Previous studies suggested that the folding intermediates are kinetically trapped states in which folding is impeded by non-native packing of the G and H helices. Fluorescence spectra of mutant proteins in which cysteine residues were introduced at several positions in the G and H helices show differential quenching of W14 fluorescence, providing direct evidence of translocation of the H helix relative to helices A and G in both the kinetic and equilibrium intermediates. Förster resonance energy transfer measurements show that a 5-({2-[(acetyl)amino]ethyl}amino)naphthalene-1-sulfonic acid acceptor coupled to K140C (helix H) is closer to Trp14 (helix A) in the equilibrium molten globule than in the native state, by a distance that is consistent with sliding of the H helix in an N-terminal direction by approximately one helical turn. Formation of an S108C–L135C disulfide prevents H helix translocation in the equilibrium molten globule by locking the G and H helices into their native register. By enforcing nativelike packing of the A, G, and H helices, the disulfide resolves local energetic frustration and facilitates transient docking of the E helix region onto the hydrophobic core but has only a small effect on the refolding rate. The apomyoglobin folding landscape is highly rugged, with several energetic bottlenecks that frustrate folding; relief of any one of the major identified bottlenecks is insufficient to speed progression to the transition state. PMID:24857522

Very early reaction intermediates detected by microsecond time scale kinetics of cytochrome cd1-catalyzed reduction of nitrite.

PubMed

Sam, Katharine A; Strampraad, Marc J F; de Vries, Simon; Ferguson, Stuart J

2008-10-10

Paracoccus pantotrophus cytochrome cd(1) is a nitrite reductase found in the periplasm of many denitrifying bacteria. It catalyzes the reduction of nitrite to nitric oxide during the denitrification part of the biological nitrogen cycle. Previous studies of early millisecond intermediates in the nitrite reduction reaction have shown, by comparison with pH 7.0, that at the optimum pH, approximately pH 6, the earliest intermediates were lost in the dead time of the instrument. Access to early time points (approximately 100 micros) through use of an ultra-rapid mixing device has identified a spectroscopically novel intermediate, assigned as the Michaelis complex, formed from reaction of fully reduced enzyme with nitrite. Spectroscopic observation of the subsequent transformation of this species has provided data that demand reappraisal of the general belief that the two subunits of the enzyme function independently.

Atomic Data and Spectral Line Intensities for Ne III

NASA Technical Reports Server (NTRS)

Bhatia, A. K.; Thomas, R. J.; Landi, E.; Fisher, Richard R. (Technical Monitor)

2002-01-01

A number of satellites and rockets have been launched to observe radiation from the Sun and other astrophysical objects. Line radiation is emitted when the electron impact excited levels decay to the lower levels by photon emission. From this radiation, the physical parameters such as electron temperature and density of the astrophysical plasma, elemental abundance, and opacity can be inferred. Ne III lines have been observed in H II regions, Ne-rich filaments in supernovae, and planetary nebulae. The allowed line at 489.50 Angstroms due to the transition 2s(sup 2) 2p(sup 5) (sup 3) P2 (goes to) 2s(sup 2)2p(sup 4)(sup 3)P2 has been identified in the solar spectrum by Vernazza and Reeves using Skylab observations. Other Ne III lines in the solar EUV spectrum have been reported by Thomas and Neupert based on observations from the Solar EUV Rocket Telescope and Spectrograph (SERTS) instrument. Atomic data for Ne III have been calculated by using a set of programs developed at, University College, London. The Superstructure and Distorted Wave (DW) programs have been updated over the years. In the Superstructure program, configuration interaction can be taken into account and radial functions are calculated in a modified Thomas-Fermi-Amaldi potential. This is a statistical potential and depends on parameters lambda 1 which are determined by optimizing the weighted sum of term energies. They are found to be lambda(sub 0)=1.2467, lambda(sub 1)=1.1617, and lambda(sub 2)=1.0663. The relativistic corrections are included by using the Breit-Pauli Hamiltonian as a perturbation to the nonrelativistic Hamiltonian. The same potential is used to calculate reactance matrices in the DW approximation in LS coupling. Collision strengths in intermediate coupling are obtained by using term coupling coefficients obtained from the Superstructure program. In this calculation, the configurations used are 2s(sup 2)2p(sup 4), 2s2p(sup 5), 2s(sup 2)2p(sup 3)3s, 2s(sup 2)p(sup 3)3d giving rise to 57 fine-structure levels in intermediate coupling.

K-shell photoabsorption and photoionization of trace elements. II. Isoelectronic sequences with electron number 12 ≤N ≤ 18

NASA Astrophysics Data System (ADS)

Mendoza, C.; Bautista, M. A.; Palmeri, P.; Quinet, P.; Witthoeft, M. C.; Kallman, T. R.

2017-08-01

Context. We are concerned with improving the diagnostic potential of the K lines and edges of elements with low cosmic abundances, namely F, Na, P, Cl, K, Sc, Ti, V, Cr, Mn, Co, Cu, and Zn, that are observed in the X-ray spectra of supernova remnants, galaxy clusters, and accreting black holes and neutron stars. Aims: Since accurate photoabsorption and photoionization cross sections are needed in their spectral models, they have been computed for isoelectronic sequences with electron number 12 ≤ N ≤ 18 using a multi-channel method. Methods: Target representations are obtained with the atomic structure code autostructure, and ground-state cross sections are computed with the Breit-Pauli R-matrix method (bprm) in intermediate coupling, including damping (radiative and Auger) effects. Results: Following the findings in our earlier work on sequences with 2 ≤ N ≤ 11, the contributions from channels associated with the 2s-hole [2s] μ target configurations and those containing 3d orbitals are studied in the Mg (N = 12) and Ar (N = 18) isoelectronic sequences. Cross sections for the latter ions are also calculated in the isolated-resonance approximation as implemented in autostructure and compared with bprm to test their accuracy. Conclusions: It is confirmed that the collisional channels associated with the [2s] μ target configurations must be taken into account owing to significant increases in the monotonic background cross section between the L and K edges. Target configurations with 3d orbitals give rise to fairly conspicuous unresolved transition arrays in the L-edge region, but to a much lesser extent in the K-edge that is our main concern; therefore, they have been neglected throughout owing to their computationally intractable channel inventory, thus allowing the computation of cross sections for all the ions with 12 ≤ N ≤ 18 in intermediate coupling with bprm. We find that the isolated-resonance approximations performs satisfactorily and will be our best choice to tackle the systems with ground configuration 3p63dm (3 ≤ m ≤ 8) in isoelectronic sequences with N> 20.

A luminous X-ray outburst from an intermediate-mass black hole in an off-centre star cluster

NASA Astrophysics Data System (ADS)

Lin, Dacheng; Strader, Jay; Carrasco, Eleazar R.; Page, Dany; Romanowsky, Aaron J.; Homan, Jeroen; Irwin, Jimmy A.; Remillard, Ronald A.; Godet, Olivier; Webb, Natalie A.; Baumgardt, Holger; Wijnands, Rudy; Barret, Didier; Duc, Pierre-Alain; Brodie, Jean P.; Gwyn, Stephen D. J.

2018-06-01

A unique signature for the presence of massive black holes in very dense stellar regions is occasional giant-amplitude outbursts of multi-wavelength radiation from tidal disruption and subsequent accretion of stars that make a close approach to the black holes1. Previous strong tidal disruption event (TDE) candidates were all associated with the centres of largely isolated galaxies2-6. Here, we report the discovery of a luminous X-ray outburst from a massive star cluster at a projected distance of 12.5 kpc from the centre of a large lenticular galaxy. The luminosity peaked at 1043 erg s-1 and decayed systematically over 10 years, approximately following a trend that supports the identification of the event as a TDE. The X-ray spectra were all very soft, with emission confined to be ≲3.0 keV, and could be described with a standard thermal disk. The disk cooled significantly as the luminosity decreased—a key thermal-state signature often observed in accreting stellar-mass black holes. This thermal-state signature, coupled with very high luminosities, ultrasoft X-ray spectra and the characteristic power-law evolution of the light curve, provides strong evidence that the source contains an intermediate-mass black hole with a mass tens of thousand times that of the solar mass. This event demonstrates that one of the most effective means of detecting intermediate-mass black holes is through X-ray flares from TDEs in star clusters.

The ATLAS diboson resonance in non-supersymmetric SO(10)

DOE PAGES

Evans, Jason L.; Nagata, Natsumi; Olive, Keith A.; ...

2016-02-18

SO(10) grand uni cation accommodates intermediate gauge symmetries with which gauge coupling uni cation can be realized without supersymmetry. In this paper, we discuss the possibility that a new massive gauge boson associated with an intermediate gauge symmetry explains the excess observed in the diboson resonance search recently reported by the ATLAS experiment. The model we find has two intermediate symmetries, SU(4) C Ⓧ SU(2) L Ⓧ SU(2) R and SU(3) C Ⓧ SU(2) L Ⓧ SU(2)R Ⓧ U(1) B-L, where the latter gauge group is broken at the TeV scale. This model achieves gauge coupling uni cation with amore » uni cation scale su fficiently high to avoid proton decay. In addition, this model provides a good dark matter candidates, whose stability is guaranteed by a Z 2 symmetry present after the spontaneous breaking of the intermediate gauge symmetries. In addition, we discuss prospects for testing these models in the forthcoming LHC experiments and dark matter detection experiments.« less

Coupling of oceanic carbon and nitrogen facilitates spatially resolved quantitative reconstruction of nitrate inventories.

PubMed

Glock, Nicolaas; Erdem, Zeynep; Wallmann, Klaus; Somes, Christopher J; Liebetrau, Volker; Schönfeld, Joachim; Gorb, Stanislav; Eisenhauer, Anton

2018-03-23

Anthropogenic impacts are perturbing the global nitrogen cycle via warming effects and pollutant sources such as chemical fertilizers and burning of fossil fuels. Understanding controls on past nitrogen inventories might improve predictions for future global biogeochemical cycling. Here we show the quantitative reconstruction of deglacial bottom water nitrate concentrations from intermediate depths of the Peruvian upwelling region, using foraminiferal pore density. Deglacial nitrate concentrations correlate strongly with downcore δ 13 C, consistent with modern water column observations in the intermediate Pacific, facilitating the use of δ 13 C records as a paleo-nitrate-proxy at intermediate depths and suggesting that the carbon and nitrogen cycles were closely coupled throughout the last deglaciation in the Peruvian upwelling region. Combining the pore density and intermediate Pacific δ 13 C records shows an elevated nitrate inventory of >10% during the Last Glacial Maximum relative to the Holocene, consistent with a δ 13 C-based and δ 15 N-based 3D ocean biogeochemical model and previous box modeling studies.

Identification of oxidative coupling products of xylenols arising from laboratory-scale phytoremediation.

PubMed

Poerschmann, J; Schultze-Nobre, L; Ebert, R U; Górecki, T

2015-01-01

Oxidative coupling reactions take place during the passage of xylenols through a laboratory-scale helophyte-based constructed wetland system. Typical coupling product groups including tetramethyl-[1,1'-biphenyl] diols and tetramethyl diphenylether monools as stable organic intermediates could be identified by a combination of pre-chromatographic derivatization and GC/MS analysis. Structural assignment of individual analytes was performed by an increment system developed by Zenkevich to pre-calculate retention sequences. The most abundant analyte turned out to be 3,3',5,5'-tetramethyl-[1,1'-biphenyl]-4,4'-diol, which can be formed by a combination of radicals based on 2,6-xylenol or by an attack of a 2,6-xylenol-based radical on 2,6-xylenol. Organic intermediates originating from oxidative coupling could also be identified in anaerobic constructed wetland systems. This finding suggested the presence of (at least partly) oxic conditions in the rhizosphere. Copyright © 2014 Elsevier Ltd. All rights reserved.

Microsystem enabled photovoltaic modules and systems

DOEpatents

Nielson, Gregory N; Sweatt, William C; Okandan, Murat

2015-05-12

A microsystem enabled photovoltaic (MEPV) module including: an absorber layer; a fixed optic layer coupled to the absorber layer; a translatable optic layer; a translation stage coupled between the fixed and translatable optic layers; and a motion processor electrically coupled to the translation stage to controls motion of the translatable optic layer relative to the fixed optic layer. The absorber layer includes an array of photovoltaic (PV) elements. The fixed optic layer includes an array of quasi-collimating (QC) micro-optical elements designed and arranged to couple incident radiation from an intermediate image formed by the translatable optic layer into one of the PV elements such that it is quasi-collimated. The translatable optic layer includes an array of focusing micro-optical elements corresponding to the QC micro-optical element array. Each focusing micro-optical element is designed to produce a quasi-telecentric intermediate image from substantially collimated radiation incident within a predetermined field of view.

Temperature-Dependent Function of the Glutamine Phosphoribosylpyrophosphate Amidotransferase Ammonia Channel and Coupling with Glycinamide Ribonucleotide Synthetase in a Hyperthermophile†

PubMed Central

Bera, Aloke Kumar; Chen, Sihong; Smith, Janet L.; Zalkin, Howard

2000-01-01

Genes encoding glutamine phosphoribosylpyrophosphate amidotransferase (GPAT) and glycinamide ribonucleotide synthetase (GARS) from Aquifex aeolicus were expressed in Escherichia coli, and the enzymes were purified to near homogeneity. Both enzymes were maximally active at a temperature of at least 90°C, with half-lives of 65 min for GPAT and 60 h for GARS at 80°C. GPAT activity is known to depend upon channeling of NH3 from a site in an N-terminal glutaminase domain to a distal phosphoribosylpyrophosphate site in a C-terminal domain where synthesis of phosphoribosylamine (PRA) takes place. The efficiency of channeling of NH3 for synthesis of PRA was found to increase from 34% at 37°C to a maximum of 84% at 80°C. The mechanism for transfer of PRA to GARS is not established, but diffusion between enzymes as a free intermediate appears unlikely based on a calculated PRA half-life of approximately 0.6 s at 90°C. Evidence was obtained for coupling between GPAT and GARS for PRA transfer. The coupling was temperature dependent, exhibiting a transition between 37 and 50°C, and remained relatively constant up to 90°C. The calculated PRA chemical half-life, however, decreased by a factor of 20 over this temperature range. These results provide evidence that coupling involves direct PRA transfer through GPAT-GARS interaction rather than free diffusion. PMID:10850988

Temperature-dependent function of the glutamine phosphoribosylpyrophosphate amidotransferase ammonia channel and coupling with glycinamide ribonucleotide synthetase in a hyperthermophile.

PubMed

Bera, A K; Chen, S; Smith, J L; Zalkin, H

2000-07-01

Genes encoding glutamine phosphoribosylpyrophosphate amidotransferase (GPAT) and glycinamide ribonucleotide synthetase (GARS) from Aquifex aeolicus were expressed in Escherichia coli, and the enzymes were purified to near homogeneity. Both enzymes were maximally active at a temperature of at least 90 degrees C, with half-lives of 65 min for GPAT and 60 h for GARS at 80 degrees C. GPAT activity is known to depend upon channeling of NH(3) from a site in an N-terminal glutaminase domain to a distal phosphoribosylpyrophosphate site in a C-terminal domain where synthesis of phosphoribosylamine (PRA) takes place. The efficiency of channeling of NH(3) for synthesis of PRA was found to increase from 34% at 37 degrees C to a maximum of 84% at 80 degrees C. The mechanism for transfer of PRA to GARS is not established, but diffusion between enzymes as a free intermediate appears unlikely based on a calculated PRA half-life of approximately 0.6 s at 90 degrees C. Evidence was obtained for coupling between GPAT and GARS for PRA transfer. The coupling was temperature dependent, exhibiting a transition between 37 and 50 degrees C, and remained relatively constant up to 90 degrees C. The calculated PRA chemical half-life, however, decreased by a factor of 20 over this temperature range. These results provide evidence that coupling involves direct PRA transfer through GPAT-GARS interaction rather than free diffusion.

Inflation from Minkowski space

DOE PAGES

Pirtskhalava, David; Santoni, Luca; Trincherini, Enrico; ...

2014-12-23

Here, we propose a class of scalar models that, once coupled to gravity, lead to cosmologies that smoothly and stably connect an inflationary quasi-de Sitter universe to a low, or even zero-curvature, maximally symmetric spacetime in the asymptotic past, strongly violating the null energy condition (H • >>H2) at intermediate times. The models are deformations of the conformal galileon lagrangian and are therefore based on symmetries, both exact and approximate, that ensure the quantum robustness of the whole picture. The resulting cosmological backgrounds can be viewed as regularized extensions of the galilean genesis scenario, or, equivalently, as ‘early-time-complete’ realizations ofmore » inflation. The late-time inflationary dynamics possesses phenomenologically interesting properties: it can produce a large tensor-to-scalar ratio within the regime of validity of the effective field theory and can lead to sizeable equilateral nongaussianities.« less

Lifetime enhancement for multiphoton absorption in intermediate band solar cells

NASA Astrophysics Data System (ADS)

Bezerra, Anibal T.; Studart, Nelson

2017-08-01

A semiconductor structure consisting of two coupled quantum wells embedded into the intrinsic region of a p-i-n junction is proposed as an intermediate band solar cell with a photon ratchet state, which would lead to increasing the cell efficiency. The conduction subband of the right-hand side quantum well works as the intermediated band, whereas the excited conduction subband of the left-hand side quantum well operates as the ratchet state. The photoelectrons in the intermediate band are scattered through the thin wells barrier and accumulated into the ratchet subband. A rate equation model for describing the charge transport properties is presented. The efficiency of the current generation is analyzed by studying the occupation of the wells subbands, taking into account the charge dynamic behavior provided by the electrical contacts connected to the cell. The current generation efficiency depends essentially from the relations between the generation, recombination rates and the scattering rate to the ratchet state. The inclusion of the ratchet states led to both an increase and a decrease in the cell current depending on the transition rates. This suggests that the coupling between the intermediate band and the ratchet state is a key point in developing an efficient solar cell.

Dual Expander Cycle Rocket Engine with an Intermediate, Closed-cycle Heat Exchanger

NASA Technical Reports Server (NTRS)

Greene, William D. (Inventor)

2008-01-01

A dual expander cycle (DEC) rocket engine with an intermediate closed-cycle heat exchanger is provided. A conventional DEC rocket engine has a closed-cycle heat exchanger thermally coupled thereto. The heat exchanger utilizes heat extracted from the engine's fuel circuit to drive the engine's oxidizer turbomachinery.

Four-Photon Stark Induced Ladder Climbing Prepares Large Ensemble of H2in Selected High Lying Vibrational Levels

NASA Astrophysics Data System (ADS)

Mukherjee, Nandini; Perreault, William; Zare, Richard

2017-04-01

To selectively prepare highly vibrationally excited quantum states of molecules like H2, we present a novel multi-photon ladder-climbing technique where the successive rungs of the ladder are connected by Stark-induced adiabatic Raman passage (SARP). Previously, we have demonstrated that SARP achieves complete population transfer from the v = 0 to the v = 1 and v = 4 levels of H2. We show here that SARP can be generalized into a continuously coupled, multiphoton adiabatic passage which uses one or more intermediate states having strong Raman coupling to access highly vibrationally excited states weakly coupled to the ground state. As an example, we consider the case of four-photon coherent excitation to high vibrational levels of H2 via an intermediate level coupled to both the initial and target levels by two-photon SARP. Using a sequence of commercially available single mode, nanosecond lasers, a pump pulse partially overlapping with two Stokes pulses, we show that the complete population of v = 0 can be selectively transferred to the most weakly coupled v = 6 and v = 9 vibrational levels of H2, without leaving any population stranded in the intermediate level. The present method provides a practical way of generating an entangled pair of fragments without resorting to an ultracold system. This work has been supported by US Army Research Office under ARO Grant No. W911NF-16-1-1061.

Concentration transport calculations by an original C++ program with interediate fidelity physics through user-defined buildings with an emphasis on release scenarios in radiological facilities

NASA Astrophysics Data System (ADS)

Sayre, George Anthony

The purpose of this dissertation was to develop the C ++ program Emergency Dose to calculate transport of radionuclides through indoor spaces using intermediate fidelity physics that provides improved spatial heterogeneity over well-mixed models such as MELCORRTM and much lower computation times than CFD codes such as FLUENTRTM . Modified potential flow theory, which is an original formulation of potential flow theory with additions of turbulent jet and natural convection approximations, calculates spatially heterogeneous velocity fields that well-mixed models cannot predict. Other original contributions of MPFT are: (1) generation of high fidelity boundary conditions relative to well-mixed-CFD coupling methods (conflation), (2) broadening of potential flow applications to arbitrary indoor spaces previously restricted to specific applications such as exhaust hood studies, and (3) great reduction of computation time relative to CFD codes without total loss of heterogeneity. Additionally, the Lagrangian transport module, which is discussed in Sections 1.3 and 2.4, showcases an ensemble-based formulation thought to be original to interior studies. Velocity and concentration transport benchmarks against analogous formulations in COMSOLRTM produced favorable results with discrepancies resulting from the tetrahedral meshing used in COMSOLRTM outperforming the Cartesian method used by Emergency Dose. A performance comparison of the concentration transport modules against MELCORRTM showed that Emergency Dose held advantages over the well-mixed model especially in scenarios with many interior partitions and varied source positions. A performance comparison of velocity module against FLUENTRTM showed that viscous drag provided the largest error between Emergency Dose and CFD velocity calculations, but that Emergency Dose's turbulent jets well approximated the corresponding CFD jets. Overall, Emergency Dose was found to provide a viable intermediate solution method for concentration transport with relatively low computation times.

Three-dimensional infinite order sudden quantum theory for indirect photodissociation processes. Application to the photofragment yield spectrum of NOCl in the region of the T1(13A″) ←S0(11A') transition. Fragment rotational distributions and thermal averages

NASA Astrophysics Data System (ADS)

Grinberg, Horacio; Freed, Karl F.; Williams, Carl J.

1997-08-01

The analytical infinite order sudden (IOS) quantum theory of triatomic photodissociation, developed in paper I, is applied to study the indirect photodissociation of NOCl through a real or virtual intermediate state. The theory uses the IOS approximation for the dynamics in the final dissociative channels and an Airy function approximation for the continuum functions. The transition is taken as polarized in the plane of the molecule; symmetric top wave functions are used for both the initial and intermediate bound states; and simple semiempirical model potentials are employed for each state. The theory provides analytical expressions for the photofragment yield spectrum for producing particular final fragment ro-vibrational states as a function of the photon excitation energy. Computations are made of the photofragment excitation spectrum of NOCl in the region of the T1(13A″)←S0(11A') transition for producing the NO fragment in the vibrational states nNO=0, 1, and 2. The computed spectra for the unexcited nNO==0 and excited nNO=2 states are in reasonable agreement with experiment. However, some discrepancies are observed for the singly excited nNO=1 vibrational state, indicating deficiencies in the semiempirical potential energy surface. Computations for two different orientations of the in-plane transition dipole moment produce very similar excitation spectra. Calculations of fragment rotational distributions are performed for high values of the total angular momentum J, a feature that would be very difficult to perform with close-coupled methods. Computations are also made of the thermally averaged rotational energy distributions to simulate the conditions in actual supersonic jet experiments.

Structural relaxation in supercooled orthoterphenyl.

PubMed

Chong, S-H; Sciortino, F

2004-05-01

We report molecular-dynamics simulation results performed for a model of molecular liquid orthoterphenyl in supercooled states, which we then compare with both experimental data and mode-coupling-theory (MCT) predictions, aiming at a better understanding of structural relaxation in orthoterphenyl. We pay special attention to the wave number dependence of the collective dynamics. It is shown that the simulation results for the model share many features with experimental data for real system, and that MCT captures the simulation results at the semiquantitative level except for intermediate wave numbers connected to the overall size of the molecule. Theoretical results at the intermediate wave number region are found to be improved by taking into account the spatial correlation of the molecule's geometrical center. This supports the idea that unusual dynamical properties at the intermediate wave numbers, reported previously in simulation studies for the model and discernible in coherent neutron-scattering experimental data, are basically due to the coupling of the rotational motion to the geometrical-center dynamics. However, there still remain qualitative as well as quantitative discrepancies between theoretical prediction and corresponding simulation results at the intermediate wave numbers, which call for further theoretical investigation.

Coupling apparatus for a metal vapor laser

DOEpatents

Ball, D.G.; Miller, J.L.

1993-02-23

Coupling apparatus for a large bore metal vapor laser is disclosed. The coupling apparatus provides for coupling high voltage pulses (approximately 40 KV) to a metal vapor laser with a high repetition rate (approximately 5 KHz). The coupling apparatus utilizes existing thyratron circuits and provides suitable power input to a large bore metal vapor laser while maintaining satisfactory operating lifetimes for the existing thyratron circuits.

Coupling apparatus for a metal vapor laser

DOEpatents

Ball, Don G.; Miller, John L.

1993-01-01

Coupling apparatus for a large bore metal vapor laser is disclosed. The coupling apparatus provides for coupling high voltage pulses (approximately 40 KV) to a metal vapor laser with a high repetition rate (approximately 5 KHz). The coupling apparatus utilizes existing thyratron circuits and provides suitable power input to a large bore metal vapor laser while maintaining satisfactory operating lifetimes for the existing thyratron circuits.

RNA sequencing to determine the contribution of kinase receptor transactivation to G protein coupled receptor signalling in vascular smooth muscle cells.

PubMed

Kamato, Danielle; Bhaskarala, Venkata Vijayanand; Mantri, Nitin; Oh, Tae Gyu; Ling, Dora; Janke, Reearna; Zheng, Wenhua; Little, Peter J; Osman, Narin

2017-01-01

G protein coupled receptor (GPCR) signalling covers three major mechanisms. GPCR agonist engagement allows for the G proteins to bind to the receptor leading to a classical downstream signalling cascade. The second mechanism is via the utilization of the β-arrestin signalling molecule and thirdly via transactivation dependent signalling. GPCRs can transactivate protein tyrosine kinase receptors (PTKR) to activate respective downstream signalling intermediates. In the past decade GPCR transactivation dependent signalling was expanded to show transactivation of serine/threonine kinase receptors (S/TKR). Kinase receptor transactivation enormously broadens the GPCR signalling paradigm. This work utilizes next generation RNA-sequencing to study the contribution of transactivation dependent signalling to total protease activated receptor (PAR)-1 signalling. Transactivation, assessed as gene expression, accounted for 50 percent of the total genes regulated by thrombin acting through PAR-1 in human coronary artery smooth muscle cells. GPCR transactivation of PTKRs is approximately equally important as the transactivation of the S/TKR with 209 and 177 genes regulated respectively, via either signalling pathway. This work shows that genome wide studies can provide powerful insights into GPCR mediated signalling pathways.

Synthesis of Formate Esters and Formamides Using an Au/TiO2-Catalyzed Aerobic Oxidative Coupling of Paraformaldehyde

PubMed Central

Metaxas, Ioannis; Vasilikogiannaki, Eleni

2017-01-01

A simple method for the synthesis of formate esters and formamides is presented based on the Au/TiO2-catalyzed aerobic oxidative coupling between alcohols or amines and formaldehyde. The suitable form of formaldehyde is paraformaldehyde, as cyclic trimeric 1,3,5-trioxane is inactive. The reaction proceeds via the formation of an intermediate hemiacetal or hemiaminal, respectively, followed by the Au nanoparticle-catalyzed aerobic oxidation of the intermediate. Typically, the oxidative coupling between formaldehyde (2 equiv) and amines occurs quantitatively at room temperature within 4 h, and there is no need to add a base as in analogous coupling reactions. The oxidative coupling between formaldehyde (typically 3 equiv) and alcohols is unprecedented and occurs more slowly, yet in good to excellent yields and selectivity. Minor side-products (2–12%) from the acetalization of formaldehyde by the alcohol are also formed. The catalyst is recyclable and can be reused after a simple filtration in five consecutive runs with a small loss of activity. PMID:29231853

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

Chilese, Francis C.; Torczynski, John R.; Garcia, Rudy

An apparatus for use with extreme ultraviolet (EUV) light comprising A) a duct having a first end opening, a second end opening and an intermediate opening intermediate the first end opening the second end opening, B) an optical component disposed to receive EUV light from the second end opening or to send light through the second end opening, and C) a source of low pressure gas at a first pressure to flow through the duct, the gas having a high transmission of EUV light, fluidly coupled to the intermediate opening. In addition to or rather than gas flow the apparatusmore » may have A) a low pressure gas with a heat control unit thermally coupled to at least one of the duct and the optical component and/or B) a voltage device to generate voltage between a first portion and a second portion of the duet with a grounded insulative portion therebetween.« less

Low-lying intruder and tensor-driven structures in 82As revealed by β decay at a new movable-tape-based experimental setup

NASA Astrophysics Data System (ADS)

Etilé, A.; Verney, D.; Arsenyev, N. N.; Bettane, J.; Borzov, I. N.; Cheikh Mhamed, M.; Cuong, P. V.; Delafosse, C.; Didierjean, F.; Gaulard, C.; Van Giai, Nguyen; Goasduff, A.; Ibrahim, F.; Kolos, K.; Lau, C.; Niikura, M.; Roccia, S.; Severyukhin, A. P.; Testov, D.; Tusseau-Nenez, S.; Voronov, V. V.

2015-06-01

The β decay of 82Ge Ge was re-investigated using the newly commissioned tape station BEDO at the electron-driven ISOL (isotope separation on line) facility ALTO operated by the Institut de Physique Nucléaire, Orsay. The original motivation of this work was focused on the sudden occurrence in the light N =49 odd-odd isotonic chain of a large number of J ≤1 states (positive or negative parity) in 80Ga by providing a reliable intermediate example, viz., 82As. The extension of the 82As level scheme towards higher energies from the present work has revealed three potential 1+ states above the already known one at 1092 keV. In addition our data allow ruling out the hypothesis that the 843 keV level could be a 1+ state. A detailed analysis of the level scheme using both an empirical core-particle coupling model and a fully microscopic treatment within a Skyrme-QRPA (quasiparticle random-phase approximation) approach using the finite-rank separable approximation was performed. From this analysis two conclusions can be drawn: (i) the presence of a large number of low-lying low-spin negative parity states is due to intruder states stemming from above the N =50 shell closure, and (ii) the sudden increase, from 82As to 80Ga, of the number of low-lying 1+ states and the corresponding Gamow-Teller fragmentation are naturally reproduced by the inclusion of tensor correlations and couplings to 2p-2h excitations.

Characterization of MgB2 Superconducting Hot Electron Bolometers

NASA Technical Reports Server (NTRS)

Cunnane, D.; Kawamura, J. H.; Wolak, M. A.; Acharya, N.; Tan, T.; Xi, X. X.; Karasik, B. S.

2014-01-01

Hot-Electron Bolometer (HEB) mixers have proven to be the best tool for high-resolution spectroscopy at the Terahertz frequencies. However, the current state of the art NbN mixers suffer from a small intermediate frequency (IF) bandwidth as well as a low operating temperature. MgB2 is a promising material for HEB mixer technology in view of its high critical temperature and fast thermal relaxation allowing for a large IF bandwidth. In this work, we have fabricated and characterized thin-film (approximately 15 nanometers) MgB2-based spiral antenna-coupled HEB mixers on SiC substrate. We achieved the IF bandwidth greater than 8 gigahertz at 25 degrees Kelvin and the device noise temperature less than 4000 degrees Kelvin at 9 degrees Kelvin using a 600 gigahertz source. Using temperature dependencies of the radiation power dissipated in the device we have identified the optical loss in the integrated microantenna responsible as a cause of the limited sensitivity of the current mixer devices. From the analysis of the current-voltage (IV) characteristics, we have derived the effective thermal conductance of the mixer device and estimated the required local oscillator power in an optimized device to be approximately 1 microwatts.

State and Parameter Estimation for a Coupled Ocean--Atmosphere Model

NASA Astrophysics Data System (ADS)

Ghil, M.; Kondrashov, D.; Sun, C.

2006-12-01

The El-Nino/Southern-Oscillation (ENSO) dominates interannual climate variability and plays, therefore, a key role in seasonal-to-interannual prediction. Much is known by now about the main physical mechanisms that give rise to and modulate ENSO, but the values of several parameters that enter these mechanisms are an important unknown. We apply Extended Kalman Filtering (EKF) for both model state and parameter estimation in an intermediate, nonlinear, coupled ocean--atmosphere model of ENSO. The coupled model consists of an upper-ocean, reduced-gravity model of the Tropical Pacific and a steady-state atmospheric response to the sea surface temperature (SST). The model errors are assumed to be mainly in the atmospheric wind stress, and assimilated data are equatorial Pacific SSTs. Model behavior is very sensitive to two key parameters: (i) μ, the ocean-atmosphere coupling coefficient between SST and wind stress anomalies; and (ii) δs, the surface-layer coefficient. Previous work has shown that δs determines the period of the model's self-sustained oscillation, while μ measures the degree of nonlinearity. Depending on the values of these parameters, the spatio-temporal pattern of model solutions is either that of a delayed oscillator or of a westward propagating mode. Estimation of these parameters is tested first on synthetic data and allows us to recover the delayed-oscillator mode starting from model parameter values that correspond to the westward-propagating case. Assimilation of SST data from the NCEP-NCAR Reanalysis-2 shows that the parameters can vary on fairly short time scales and switch between values that approximate the two distinct modes of ENSO behavior. Rapid adjustments of these parameters occur, in particular, during strong ENSO events. Ways to apply EKF parameter estimation efficiently to state-of-the-art coupled ocean--atmosphere GCMs will be discussed.

Rotational excitation of symmetric top molecules by collisions with atoms: Close coupling, coupled states, and effective potential calculations for NH3-He

NASA Technical Reports Server (NTRS)

Green, S.

1976-01-01

The formalism for describing rotational excitation in collisions between symmetric top rigid rotors and spherical atoms is presented both within the accurate quantum close coupling framework and also the coupled states approximation of McGuire and Kouri and the effective potential approximation of Rabitz. Calculations are reported for thermal energy NH3-He collisions, treating NH3 as a rigid rotor and employing a uniform electron gas (Gordon-Kim) approximation for the intermolecular potential. Coupled states are found to be in nearly quantitative agreement with close coupling results while the effective potential method is found to be at least qualitatively correct. Modifications necessary to treat the inversion motion in NH3 are discussed.

Experimental identification of nonlinear coupling between (intermediate, small)-scale microturbulence and an MHD mode in the core of a superconducting tokamak

NASA Astrophysics Data System (ADS)

Sun, P. J.; Li, Y. D.; Ren, Y.; Zhang, X. D.; Wu, G. J.; Xu, L. Q.; Chen, R.; Li, Q.; Zhao, H. L.; Zhang, J. Z.; Shi, T. H.; Wang, Y. M.; Lyu, B.; Hu, L. Q.; Li, J.; The EAST Team

2018-01-01

In this paper, we present clear experimental evidence of core region nonlinear coupling between (intermediate, small)-scale microturbulence and an magnetohydrodynamics (MHD) mode during the current ramp-down phase in a set of L-mode plasma discharges in the experimental advanced superconducting tokamak (EAST, Wan et al (2006 Plasma Sci. Technol. 8 253)). Density fluctuations of broadband microturbulence (k\\perpρi˜2{-}5.2 ) and the MHD mode (toroidal mode number m = -1 , poloidal mode number n = 1 ) are measured simultaneously, using a four-channel tangential CO2 laser collective scattering diagnostic in core plasmas. The nonlinear coupling between the broadband microturbulence and the MHD mode is directly demonstrated by showing a statistically significant bicoherence and modulation of turbulent density fluctuation amplitude by the MHD mode.

Dioxygen Binding, Activation, and Reduction to H2O by Cu Enzymes.

PubMed

Solomon, Edward I

2016-07-05

Oxygen intermediates in copper enzymes exhibit unique spectroscopic features that reflect novel geometric and electronic structures that are key to reactivity. This perspective will describe: (1) the bonding origin of the unique spectroscopic features of the coupled binuclear copper enzymes and how this overcomes the spin forbiddenness of O2 binding and activates monooxygenase activity, (2) how the difference in exchange coupling in the non-coupled binuclear Cu enzymes controls the reaction mechanism, and (3) how the trinuclear Cu cluster present in the multicopper oxidases leads to a major structure/function difference in enabling the irreversible reductive cleavage of the O-O bond with little overpotential and generating a fully oxidized intermediate, different from the resting enzyme studied by crystallography, that is key in enabling fast PCET in the reductive half of the catalytic cycle.

Computer program for determining rotational line intensity factors for diatomic molecules

NASA Technical Reports Server (NTRS)

Whiting, E. E.

1973-01-01

A FORTRAN IV computer program, that provides a new research tool for determining reliable rotational line intensity factors (also known as Honl-London factors), for most electric and magnetic dipole allowed diatomic transitions, is described in detail. This users manual includes instructions for preparing the input data, a program listing, detailed flow charts, and three sample cases. The program is applicable to spin-allowed dipole transitions with either or both states intermediate between Hund's case (a) and Hund's case (b) coupling and to spin-forbidden dipole transitions with either or both states intermediate between Hund's case (c) and Hund's case (b) coupling.

Nitrogen fixation sustained productivity in the wake of the Palaeoproterozoic Great Oxygenation Event.

PubMed

Luo, Genming; Junium, Christopher K; Izon, Gareth; Ono, Shuhei; Beukes, Nicolas J; Algeo, Thomas J; Cui, Ying; Xie, Shucheng; Summons, Roger E

2018-03-07

The marine nitrogen cycle is dominated by redox-controlled biogeochemical processes and, therefore, is likely to have been revolutionised in response to Earth-surface oxygenation. The details, timing, and trajectory of nitrogen cycle evolution, however, remain elusive. Here we couple nitrogen and carbon isotope records from multiple drillcores through the Rooihoogte-Timeball Hill Formations from across the Carletonville area of the Kaapvaal Craton where the Great Oxygenation Event (GOE) and its aftermath are recorded. Our data reveal that aerobic nitrogen cycling, featuring metabolisms involving nitrogen oxyanions, was well established prior to the GOE and that ammonium may have dominated the dissolved nitrogen inventory. Pronounced signals of diazotrophy imply a stepwise evolution, with a temporary intermediate stage where both ammonium and nitrate may have been scarce. We suggest that the emergence of the modern nitrogen cycle, with metabolic processes that approximate their contemporary balance, was retarded by low environmental oxygen availability.

Development of a New 47-Group Library for the CASL Neutronics Simulators

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

Kim, Kang Seog; Williams, Mark L; Wiarda, Dorothea

The CASL core simulator MPACT is under development for the neutronics and thermal-hydraulics coupled simulation for the pressurized light water reactors. The key characteristics of the MPACT code include a subgroup method for resonance self-shielding, and a whole core solver with a 1D/2D synthesis method. The ORNL AMPX/SCALE code packages have been significantly improved to support various intermediate resonance self-shielding approximations such as the subgroup and embedded self-shielding methods. New 47-group AMPX and MPACT libraries based on ENDF/B-VII.0 have been generated for the CASL core simulator MPACT of which group structure comes from the HELIOS library. The new 47-group MPACTmore » library includes all nuclear data required for static and transient core simulations. This study discusses a detailed procedure to generate the 47-group AMPX and MPACT libraries and benchmark results for the VERA progression problems.« less

Molecular dynamics simulation of the polymer electrolyte poly(ethylene oxide)/LiClO(4). II. Dynamical properties.

PubMed

Siqueira, Leonardo J A; Ribeiro, Mauro C C

2006-12-07

The dynamical properties of the polymer electrolyte poly(ethylene oxide) (PEO)LiClO(4) have been investigated by molecular dynamics simulations. The effect of changing salt concentration and temperature was evaluated on several time correlation functions. Ionic displacements projected on different directions reveal anisotropy in short-time (rattling) and long-time (diffusive) dynamics of Li(+) cations. It is shown that ionic mobility is coupled to the segmental motion of the polymeric chain. Structural relaxation is probed by the intermediate scattering function F(k,t) at several wave vectors. Good agreement was found between calculated and experimental F(k,t) for pure PEO. A remarkable slowing down of polymer relaxation is observed upon addition of the salt. The ionic conductivity estimated by the Nernst-Einstein equation is approximately ten times higher than the actual conductivity calculated by the time correlation function of charge current.

G protein-coupled estrogen receptor 1/G protein-coupled receptor 30 localizes in the plasma membrane and traffics intracellularly on cytokeratin intermediate filaments.

PubMed

Sandén, Caroline; Broselid, Stefan; Cornmark, Louise; Andersson, Krister; Daszkiewicz-Nilsson, Joanna; Mårtensson, Ulrika E A; Olde, Björn; Leeb-Lundberg, L M Fredrik

2011-03-01

G protein-coupled receptor 30 [G protein-coupled estrogen receptor 1 (GPER1)], has been introduced as a membrane estrogen receptor and a candidate cancer biomarker and therapeutic target. However, several questions surround the subcellular localization and signaling of this receptor. In native cells, including mouse myoblast C(2)C(12) cells, Madin-Darby canine kidney epithelial cells, and human ductal breast epithelial tumor T47-D cells, G-1, a GPER1 agonist, and 17β-estradiol stimulated GPER1-dependent cAMP production, a defined plasma membrane (PM) event, and recruitment of β-arrestin2 to the PM. Staining of fixed and live cells showed that GPER1 was localized both in the PM and on intracellular structures. One such intracellular structure was identified as cytokeratin (CK) intermediate filaments, including those composed of CK7 and CK8, but apparently not endoplasmic reticulum, Golgi, or microtubules. Reciprocal coimmunoprecipitation of GPER1 and CKs confirmed an association of these proteins. Live staining also showed that the PM receptors constitutively internalize apparently to reach CK filaments. Receptor localization was supported using FLAG- and hemagglutinin-tagged GPER1. We conclude that GPER1-mediated stimulation of cAMP production and β-arrestin2 recruitment occur in the PM. Furthermore, the PM receptors constitutively internalize and localize intracellularly on CK. This is the first observation that a G protein-coupled receptor is capable of associating with intermediate filaments, which may be important for GPER1 regulation in epithelial cells and the relationship of this receptor to cancer.

Coupled assimilation for an intermediated coupled ENSO prediction model

NASA Astrophysics Data System (ADS)

Zheng, Fei; Zhu, Jiang

2010-10-01

The value of coupled assimilation is discussed using an intermediate coupled model in which the wind stress is the only atmospheric state which is slavery to model sea surface temperature (SST). In the coupled assimilation analysis, based on the coupled wind-ocean state covariance calculated from the coupled state ensemble, the ocean state is adjusted by assimilating wind data using the ensemble Kalman filter. As revealed by a series of assimilation experiments using simulated observations, the coupled assimilation of wind observations yields better results than the assimilation of SST observations. Specifically, the coupled assimilation of wind observations can help to improve the accuracy of the surface and subsurface currents because the correlation between the wind and ocean currents is stronger than that between SST and ocean currents in the equatorial Pacific. Thus, the coupled assimilation of wind data can decrease the initial condition errors in the surface/subsurface currents that can significantly contribute to SST forecast errors. The value of the coupled assimilation of wind observations is further demonstrated by comparing the prediction skills of three 12-year (1997-2008) hindcast experiments initialized by the ocean-only assimilation scheme that assimilates SST observations, the coupled assimilation scheme that assimilates wind observations, and a nudging scheme that nudges the observed wind stress data, respectively. The prediction skills of two assimilation schemes are significantly better than those of the nudging scheme. The prediction skills of assimilating wind observations are better than assimilating SST observations. Assimilating wind observations for the 2007/2008 La Niña event triggers better predictions, while assimilating SST observations fails to provide an early warning for that event.

Stabilization of Two Radicals with One Metal: A Stepwise Coupling Model for Copper-Catalyzed Radical–Radical Cross-Coupling

PubMed Central

Qi, Xiaotian; Zhu, Lei; Bai, Ruopeng; Lan, Yu

2017-01-01

Transition metal-catalyzed radical–radical cross-coupling reactions provide innovative methods for C–C and C–heteroatom bond construction. A theoretical study was performed to reveal the mechanism and selectivity of the copper-catalyzed C–N radical–radical cross-coupling reaction. The concerted coupling pathway, in which a C–N bond is formed through the direct nucleophilic addition of a carbon radical to the nitrogen atom of the Cu(II)–N species, is demonstrated to be kinetically unfavorable. The stepwise coupling pathway, which involves the combination of a carbon radical with a Cu(II)–N species before C–N bond formation, is shown to be probable. Both the Mulliken atomic spin density distribution and frontier molecular orbital analysis on the Cu(II)–N intermediate show that the Cu site is more reactive than that of N; thus, the carbon radical preferentially react with the metal center. The chemoselectivity of the cross-coupling is also explained by the differences in electron compatibility of the carbon radical, the nitrogen radical and the Cu(II)–N intermediate. The higher activation free energy for N–N radical–radical homo-coupling is attributed to the mismatch of Cu(II)–N species with the nitrogen radical because the electrophilicity for both is strong. PMID:28272407

Use of Data to Improve Seasonal-to-Interannual Forecasts Simulated by Intermediate Coupled Models

NASA Technical Reports Server (NTRS)

Perigaud, C.; Cassou, C.; Dewitte, B.; Fu, L-L.; Neelin, J.

1999-01-01

This paper provides a detailed illustration that it can be much more beneficial for ENSO forecasting to use data to improve the model parameterizations rather than to modify the initial conditions to gain in consistency with the simulated coupled system.

Theoretical Advances in Sequential Data Assimilation for the Atmosphere and Oceans

NASA Astrophysics Data System (ADS)

Ghil, M.

2007-05-01

We concentrate here on two aspects of advanced Kalman--filter-related methods: (i) the stability of the forecast- assimilation cycle, and (ii) parameter estimation for the coupled ocean-atmosphere system. The nonlinear stability of a prediction-assimilation system guarantees the uniqueness of the sequentially estimated solutions in the presence of partial and inaccurate observations, distributed in space and time; this stability is shown to be a necessary condition for the convergence of the state estimates to the true evolution of the turbulent flow. The stability properties of the governing nonlinear equations and of several data assimilation systems are studied by computing the spectrum of the associated Lyapunov exponents. These ideas are applied to a simple and an intermediate model of atmospheric variability and we show that the degree of stabilization depends on the type and distribution of the observations, as well as on the data assimilation method. These results represent joint work with A. Carrassi, A. Trevisan and F. Uboldi. Much is known by now about the main physical mechanisms that give rise to and modulate the El-Nino/Southern- Oscillation (ENSO), but the values of several parameters that enter these mechanisms are an important unknown. We apply Extended Kalman Filtering (EKF) for both model state and parameter estimation in an intermediate, nonlinear, coupled ocean-atmosphere model of ENSO. Model behavior is very sensitive to two key parameters: (a) "mu", the ocean-atmosphere coupling coefficient between the sea-surface temperature (SST) and wind stress anomalies; and (b) "delta-s", the surface-layer coefficient. Previous work has shown that "delta- s" determines the period of the model's self-sustained oscillation, while "mu' measures the degree of nonlinearity. Depending on the values of these parameters, the spatio-temporal pattern of model solutions is either that of a delayed oscillator or of a westward propagating mode. Assimilation of SST data from the NCEP- NCAR Reanalysis-2 shows that the parameters can vary on fairly short time scales and switch between values that approximate the two distinct modes of ENSO behavior. Rapid adjustments of these parameters occur, in particular, during strong ENSO events. Ways to apply EKF parameter estimation efficiently to state-of-the-art coupled ocean-atmosphere GCMs will be discussed. These results arise from joint work with D. Kondrashov and C.-j. Sun.

Stereospecific Cross-Coupling of Secondary Alkyl β-Trifluoroboratoamides

PubMed Central

Sandrock, Deidre L.; Jean-Gérard, Ludivine; Chen, Cheng-yi; Dreher, Spencer D.; Molander, Gary A.

2010-01-01

The stereospecific cross-coupling of enantioenriched non-benzylic secondary alkyl boron compounds has been achieved. The high selectivity toward product formation over an undesired β-H elimination pathway is achieved via an intramolecular coordination of an ancillary carbonyl to the metal center in the diorganopalladium intermediate. PMID:21077687

A chimeric path to neuronal synchronization

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

Essaki Arumugam, Easwara Moorthy; Spano, Mark L.

2015-01-15

Synchronization of neuronal activity is associated with neurological disorders such as epilepsy. This process of neuronal synchronization is not fully understood. To further our understanding, we have experimentally studied the progression of this synchronization from normal neuronal firing to full synchronization. We implemented nine FitzHugh-Nagumo neurons (a simplified Hodgkin-Huxley model) via discrete electronics. For different coupling parameters (synaptic strengths), the neurons in the ring were either unsynchronized or completely synchronized when locally coupled in a ring. When a single long-range connection (nonlocal coupling) was introduced, an intermediate state known as a chimera appeared. The results indicate that (1) epilepsy ismore » likely not only a dynamical disease but also a topological disease, strongly tied to the connectivity of the underlying network of neurons, and (2) the synchronization process in epilepsy may not be an “all or none” phenomenon, but can pass through an intermediate stage (chimera)« less

Viscoelastic relaxations of high alcohols and alkanes: Effects of heterogeneous structure and translation-orientation coupling

NASA Astrophysics Data System (ADS)

Yamaguchi, Tsuyoshi

2017-03-01

The frequency-dependent shear viscosity of high alcohols and linear alkanes, including 1-butanol, 1-octanol, 1-dodecanol, n-hexane, n-decane, and n-tetradecane, was calculated using molecular dynamics simulation. The relaxation of all the liquids was bimodal. The correlation functions of the collective orientation were also evaluated. The analysis of these functions showed that the slower relaxation mode of alkanes is assigned to the translation-orientation coupling, while that of high alcohols is not. The X-ray structure factors of all the alcohols showed prepeaks, as have been reported in the literature, and the intermediate scattering functions were calculated at the prepeak. Comparing the intermediate scattering function with the frequency-dependent shear viscosity based on the mode-coupling theory, it was demonstrated that the slower viscoelastic relaxation of the alcohols is assigned to the relaxation of the heterogeneous structure described by the prepeak.

A chimeric path to neuronal synchronization

NASA Astrophysics Data System (ADS)

Essaki Arumugam, Easwara Moorthy; Spano, Mark L.

2015-01-01

Synchronization of neuronal activity is associated with neurological disorders such as epilepsy. This process of neuronal synchronization is not fully understood. To further our understanding, we have experimentally studied the progression of this synchronization from normal neuronal firing to full synchronization. We implemented nine FitzHugh-Nagumo neurons (a simplified Hodgkin-Huxley model) via discrete electronics. For different coupling parameters (synaptic strengths), the neurons in the ring were either unsynchronized or completely synchronized when locally coupled in a ring. When a single long-range connection (nonlocal coupling) was introduced, an intermediate state known as a chimera appeared. The results indicate that (1) epilepsy is likely not only a dynamical disease but also a topological disease, strongly tied to the connectivity of the underlying network of neurons, and (2) the synchronization process in epilepsy may not be an "all or none" phenomenon, but can pass through an intermediate stage (chimera).

3D light harnessing based on coupling engineering between 1D-2D Photonic Crystal membranes and metallic nano-antenna.

PubMed

Belarouci, Ali; Benyattou, Taha; Letartre, Xavier; Viktorovitch, Pierre

2010-09-13

A new approach is proposed for the optimum addressing of a metallic nano-antenna (NA) with a free space optical beam. This approach relies on the use of an intermediate resonator structure that provides the appropriate modal conversion of the incoming beam. More precisely, the intermediate resonator consists in a Photonic Crystal (PC) membrane resonant structure that takes benefit of surface addressable slow Bloch modes. First, a phenomenological approach including a deep physical understanding of the NA-PC coupling and its optimization is presented. In a second step, the main features of this analysis are confirmed by numerical simulations (FDTD).

Combustor assembly in a gas turbine engine

DOEpatents

Wiebe, David J; Fox, Timothy A

2013-02-19

A combustor assembly in a gas turbine engine. The combustor assembly includes a combustor device coupled to a main engine casing, a first fuel injection system, a transition duct, and an intermediate duct. The combustor device includes a flow sleeve for receiving pressurized air and a liner disposed radially inwardly from the flow sleeve. The first fuel injection system provides fuel that is ignited with the pressurized air creating first working gases. The intermediate duct is disposed between the liner and the transition duct and defines a path for the first working gases to flow from the liner to the transition duct. An intermediate duct inlet portion is associated with a liner outlet and allows movement between the intermediate duct and the liner. An intermediate duct outlet portion is associated with a transition duct inlet section and allows movement between the intermediate duct and the transition duct.

Increasing Constructive Behavior of Intermediate Grade Students through the Use of The Response Cost Strategy

ERIC Educational Resources Information Center

Bauer, Heather; Burno, Carolyn; Millstone, Teresa

2009-01-01

The purpose of this research project was to increase constructive behavior of intermediate grade students through the use of the response cost strategy. Approximately 70 students participated in this study. Three teacher researchers conducted the research in an elementary school and two middle schools in different counties near a major mid-western…

Interfacial thermal transport with strong system-bath coupling: A phonon delocalization effect

NASA Astrophysics Data System (ADS)

He, Dahai; Thingna, Juzar; Cao, Jianshu

2018-05-01

We study the effect of system-bath coupling strength on quantum thermal transport through the interface of two weakly coupled anharmonic molecular chains by using a quantum self-consistent phonon approach. The approach inherently assumes that the two segments (anharmonic molecular chains) are approximately in local thermal equilibrium with respect to the baths that they are connected to and transforms the strongly anharmonic system into an effective harmonic one with a temperature-dependent transmission. Despite the approximations, the approach is ideal for our setup, wherein the weak interfacial coupling guarantees an approximate local thermal equilibrium of each segment and short chain length (less than the phonon mean-free path) ensues from the effective harmonic approximation. Remarkably, the heat current shows a resonant to bi-resonant transition due to the variations in the interfacial coupling and temperature, which is attributed to the delocalization of phonon modes. Delocalization occurs only in the strong system-bath coupling regime and we utilize it to model a thermal rectifier whose ratio can be nonmonotonically tuned not only with the intrinsic system parameters but also with the external temperature.

NMR Structural Profiling of Transcriptional Intermediates Reveals Riboswitch Regulation by Metastable RNA Conformations.

PubMed

Helmling, Christina; Wacker, Anna; Wolfinger, Michael T; Hofacker, Ivo L; Hengesbach, Martin; Fürtig, Boris; Schwalbe, Harald

2017-02-22

Gene repression induced by the formation of transcriptional terminators represents a prime example for the coupling of RNA synthesis, folding, and regulation. In this context, mapping the changes in available conformational space of transcription intermediates during RNA synthesis is important to understand riboswitch function. A majority of riboswitches, an important class of small metabolite-sensing regulatory RNAs, act as transcriptional regulators, but the dependence of ligand binding and the subsequent allosteric conformational switch on mRNA transcript length has not yet been investigated. We show a strict fine-tuning of binding and sequence-dependent alterations of conformational space by structural analysis of all relevant transcription intermediates at single-nucleotide resolution for the I-A type 2'dG-sensing riboswitch from Mesoplasma florum by NMR spectroscopy. Our results provide a general framework to dissect the coupling of synthesis and folding essential for riboswitch function, revealing the importance of metastable states for RNA-based gene regulation.

Enantioselective synthesis of chiral isotopomers of 1-alkanols by a ZACA-Cu-catalyzed cross-coupling protocol.

PubMed

Xu, Shiqing; Oda, Akimichi; Negishi, Ei-ichi

2014-12-01

Chiral compounds arising from the replacement of hydrogen atoms by deuterium are very important in organic chemistry and biochemistry. Some of these chiral compounds have a non-measurable specific rotation, owing to very small differences between the isotopomeric groups, and exhibit cryptochirality. This particular class of compounds is difficult to synthesize and characterize. Herein, we present a catalytic and highly enantioselective conversion of terminal alkenes to various β and more remote chiral isotopomers of 1-alkanols, with ≥99 % enantiomeric excess (ee), by the Zr-catalyzed asymmetric carboalumination of alkenes (ZACA) and Cu-catalyzed cross-coupling reactions. ZACA-in situ iodinolysis of allyl alcohol and ZACA-in situ oxidation of TBS-protected ω-alkene-1-ols protocols were applied to the synthesis of both (R)- and (S)-difunctional intermediates with 80-90 % ee. These intermediates were readily purified to provide enantiomerically pure (≥99 % ee) compounds by lipase-catalyzed acetylation. These functionally rich intermediates serve as very useful synthons for the construction of various chiral isotopomers of 1-alkanols in excellent enantiomeric purity (≥99 % ee) by introducing deuterium-labeled groups by Cu-catalyzed cross-coupling reactions without epimerization. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of a coupled level set and immersed boundary method for predicting dam break flows

NASA Astrophysics Data System (ADS)

Yu, C. H.; Sheu, Tony W. H.

2017-12-01

Dam-break flow over an immersed stationary object is investigated using a coupled level set (LS)/immersed boundary (IB) method developed in Cartesian grids. This approach adopts an improved interface preserving level set method which includes three solution steps and the differential-based interpolation immersed boundary method to treat fluid-fluid and solid-fluid interfaces, respectively. In the first step of this level set method, the level set function ϕ is advected by a pure advection equation. The intermediate step is performed to obtain a new level set value through a new smoothed Heaviside function. In the final solution step, a mass correction term is added to the re-initialization equation to ensure the new level set is a distance function and to conserve the mass bounded by the interface. For accurately calculating the level set value, the four-point upwinding combined compact difference (UCCD) scheme with three-point boundary combined compact difference scheme is applied to approximate the first-order derivative term shown in the level set equation. For the immersed boundary method, application of the artificial momentum forcing term at points in cells consisting of both fluid and solid allows an imposition of velocity condition to account for the presence of solid object. The incompressible Navier-Stokes solutions are calculated using the projection method. Numerical results show that the coupled LS/IB method can not only predict interface accurately but also preserve the mass conservation excellently for the dam-break flow.

Numerical simulation of electromagnetic fields and impedance of CERN LINAC4 H(-) source taking into account the effect of the plasma.

PubMed

Grudiev, A; Lettry, J; Mattei, S; Paoluzzi, M; Scrivens, R

2014-02-01

Numerical simulation of the CERN LINAC4 H(-) source 2 MHz RF system has been performed taking into account a realistic geometry from 3D Computer Aided Design model using commercial FEM high frequency simulation code. The effect of the plasma has been added to the model by the approximation of a homogenous electrically conducting medium. Electric and magnetic fields, RF power losses, and impedance of the circuit have been calculated for different values of the plasma conductivity. Three different regimes have been found depending on the plasma conductivity: (1) Zero or low plasma conductivity results in RF electric field induced by the RF antenna being mainly capacitive and has axial direction; (2) Intermediate conductivity results in the expulsion of capacitive electric field from plasma and the RF power coupling, which is increasing linearly with the plasma conductivity, is mainly dominated by the inductive azimuthal electric field; (3) High conductivity results in the shielding of both the electric and magnetic fields from plasma due to the skin effect, which reduces RF power coupling to plasma. From these simulations and measurements of the RF power coupling on the CERN source, a value of the plasma conductivity has been derived. It agrees well with an analytical estimate calculated from the measured plasma parameters. In addition, the simulated and measured impedances with and without plasma show very good agreement as well demonstrating validity of the plasma model used in the RF simulations.

Cu-catalyzed cross-coupling reactions of epoxides with organoboron compounds.

PubMed

Lu, Xiao-Yu; Yang, Chu-Ting; Liu, Jing-Hui; Zhang, Zheng-Qi; Lu, Xi; Lou, Xin; Xiao, Bin; Fu, Yao

2015-02-11

A copper-catalyzed cross-coupling reaction of epoxides with arylboronates is described. This reaction is not limited to aromatic epoxides, because aliphatic epoxides are also suitable substrates. In addition, N-sulfonyl aziridines can be successfully converted into the products. This reaction provides convenient access to β-phenethyl alcohols, which are valuable synthetic intermediates.

Theoretical model for the discrete flexoelectric effect and a description for the sequence of intermediate smectic phases with increasing periodicity.

PubMed

Emelyanenko, A V; Osipov, M A

2003-11-01

A general phenomenological description and a simple molecular model is proposed for the "discrete" flexoelectric effect in tilted smectic liquid crystal phases. This effect defines a polarization in a smectic layer induced by a difference of director orientations in the two smectic layers adjacent to it. It is shown that the "discrete" flexoelectric effect is determined by electrostatic dipole-quadrupole interaction between positionally correlated molecules located in adjacent smectic layers, while the corresponding dipole-dipole interaction is responsible for a coupling between polarization vectors in neighboring layers. It is shown that a simple phenomenological model of a ferrielectric smectic liquid crystal, which has recently been proposed in the literature, can be used to describe the whole sequence of intermediate chiral smectic C* phases with increasing periods, and to determine the nonplanar structure of each phase without additional assumptions. In this sequence the phases with three- and four-layer periodicities have the same structure, as observed in the experiment. The theory predicts also the structure of intermediate phases with longer periods that have not been studied experimentally so far. The structures of intermediate phases with periodicities of up to nine layers are presented together with the phase diagrams, and a relationship between molecular chirality and the three-dimensional structure of intermediate phases is discussed. It is considered also how the coupling between the spontaneous polarization determined by molecular chirality and the induced polarization determined by the discrete flexoelectric effect stabilizes the nonplanar structure of intermediate phases.

Remodeling of intermediate metabolism in the diatom Phaeodactylum tricornutum under nitrogen stress

PubMed Central

Levitan, Orly; Dinamarca, Jorge; Zelzion, Ehud; Lun, Desmond S.; Guerra, L. Tiago; Kim, Min Kyung; Kim, Joomi; Van Mooy, Benjamin A. S.; Bhattacharya, Debashish; Falkowski, Paul G.

2015-01-01

Diatoms are unicellular algae that accumulate significant amounts of triacylglycerols as storage lipids when their growth is limited by nutrients. Using biochemical, physiological, bioinformatics, and reverse genetic approaches, we analyzed how the flux of carbon into lipids is influenced by nitrogen stress in a model diatom, Phaeodactylum tricornutum. Our results reveal that the accumulation of lipids is a consequence of remodeling of intermediate metabolism, especially reactions in the tricarboxylic acid and the urea cycles. Specifically, approximately one-half of the cellular proteins are cannibalized; whereas the nitrogen is scavenged by the urea and glutamine synthetase/glutamine 2-oxoglutarate aminotransferase pathways and redirected to the de novo synthesis of nitrogen assimilation machinery, simultaneously, the photobiological flux of carbon and reductants is used to synthesize lipids. To further examine how nitrogen stress triggers the remodeling process, we knocked down the gene encoding for nitrate reductase, a key enzyme required for the assimilation of nitrate. The strain exhibits 40–50% of the mRNA copy numbers, protein content, and enzymatic activity of the wild type, concomitant with a 43% increase in cellular lipid content. We suggest a negative feedback sensor that couples photosynthetic carbon fixation to lipid biosynthesis and is regulated by the nitrogen assimilation pathway. This metabolic feedback enables diatoms to rapidly respond to fluctuations in environmental nitrogen availability. PMID:25548193

Merging mechanical and electromechanical bandgaps in locally resonant metamaterials and metastructures

NASA Astrophysics Data System (ADS)

Sugino, C.; Ruzzene, M.; Erturk, A.

2018-07-01

Locally resonant metamaterials are characterized by bandgaps at wavelengths much larger than the lattice size. Such locally resonant bandgaps can be formed using mechanical or electromechanical resonators. However, the nature of bandgap formation in mechanical and electromechanical (particularly piezoelectric) metamaterials is fundamentally different since the former is associated with a dynamic modal mass, while the latter is due to a dynamic modal stiffness. Next-generation metamaterials and resulting metastructures (i.e. finite configurations with specified boundary conditions) hosting mechanical resonators as well as piezoelectric interfaces connected to resonating circuits can enable the formation of two bandgaps, right above and below the design frequency of the mechanical and electrical resonators, respectively, yielding a wider bandgap and enhanced design flexibility as compared to using a purely mechanical, or a purely electromechanical configuration. In this work, we establish a fully coupled framework for hybrid mechanical-electromechanical metamaterials and finite metastructures. Combined bandgap size is approximated in closed form as a function of the added mass ratio of the resonators and the system-level electromechanical coupling for the infinite resonators approximation. Case studies are presented for a hybrid metamaterial cantilever under bending vibration to understand the interaction of these two locally resonant metamaterial domains in bandgap formation. Specifically, it is shown that the mechanical and electromechanical bandgaps do not fully merge for a finite number of resonators in an undamped setting. However, the presence of even light damping in the resonators suppresses the intermediate resonances emerging within the combined bandgap, enabling seamless merging of the two bandgaps in real-world structures that have damping. The overall concept of combining mechanical and electromechanical bandgaps in the same single metastructure can be leveraged in more complex topologies of piezoelectric metamaterial-based solids and structures.

Formation of a quinoneimine intermediate of 4-fluoro-N-methylaniline by FMO1: carbon oxidation plus defluorination.

PubMed

Driscoll, James P; Aliagas, Ignacio; Harris, Jennifer J; Halladay, Jason S; Khatib-Shahidi, Sheerin; Deese, Alan; Segraves, Nathaniel; Khojasteh-Bakht, S Cyrus

2010-05-17

Here, we report on the mechanism by which flavin-containing monooxygenase 1 (FMO1) mediates the formation of a reactive intermediate of 4-fluoro-N-methylaniline. FMO1 catalyzed a carbon oxidation reaction coupled with defluorination that led to the formation of 4-N-methylaminophenol, which was a reaction first reported by Boersma et al. (Boersma et al. (1993) Drug Metab. Dispos. 21 , 218 - 230). We propose that a labile 1-fluoro-4-(methylimino)cyclohexa-2,5-dienol intermediate was formed leading to an electrophilic quinoneimine intermediate. The identification of N-acetylcysteine adducts by LC-MS/MS and NMR further supports the formation of a quinoneimine intermediate. Incubations containing stable labeled oxygen (H(2)(18)O or (18)O(2)) and ab initio calculations were performed to support the proposed reaction mechanism.

The Mechanism of Viral Replication. Structure of Replication Complexes of Encephalomyocarditis Virus

PubMed Central

Thach, Sigrid S.; Dobbertin, Darrell; Lawrence, Charles; Golini, Fred; Thach, Robert E.

1974-01-01

The structure of the purified replicative intermediate of encephalomyocarditis virus was determined by electron microscopy. Approximately 80% of the replicative intermediate complexes were characterized by a filament of double-stranded RNA of widely variable length, which had a “bush” of single-stranded RNA at one end. In many examples one or more additional single-stranded bushes were appended internally to the double-stranded RNA filament. These results support the view that before deproteinization, replicative intermediate contains little if any double-stranded RNA. Images PMID:4366773

Anisotropy of critical correlations in moderately delocalized cerium and actinide systems

NASA Astrophysics Data System (ADS)

Kioussis, Nicholas; Cooper, Bernard R.

1986-09-01

The equilibrium and excitation magnetic behavior of a class of cerium and light actinide compounds have been explained previously, in a theory first developed by Siemann and Cooper, in terms of a band-f-electron anisotropic hybridization-mediated two-ion interaction of the Coqblin-Schrieffer type. Using the same theory, we present here a calculation, within the random-phase approximation, of the longitudinal component of the static wave-vector-dependent susceptibility in the paramagnetic phase. The calculations have been performed in the presence of a cubic crystal field (CF) and yield results for the ratio of inverse critical correlation lengths, κ/κ⊥, parallel and perpendicular to the moment direction, that compare well with those of diffuse critical neutron scattering experiments. In Ce3+ (f1) compounds, we find that as the CF interaction (Γ7 ground state) predominates over the two-ion interaction, the relative strength of the coupling within the ferromagnetic \\{001\\} planes (with moments perpendicular to the planes) and that between the \\{001\\} planes is gradually reversed, resulting in a ratio κ/κ⊥ smaller than unity, as is experimentally observed. We also present results for the effect of differing intraionic (L-S, intermediate, and j-j) coupling on κ/κ⊥ for the case of Pu3+(f5) and U3+(f3) compounds.

Interaction function of oscillating coupled neurons

PubMed Central

Dodla, Ramana; Wilson, Charles J.

2013-01-01

Large scale simulations of electrically coupled neuronal oscillators often employ the phase coupled oscillator paradigm to understand and predict network behavior. We study the nature of the interaction between such coupled oscillators using weakly coupled oscillator theory. By employing piecewise linear approximations for phase response curves and voltage time courses, and parameterizing their shapes, we compute the interaction function for all such possible shapes and express it in terms of discrete Fourier modes. We find that reasonably good approximation is achieved with four Fourier modes that comprise of both sine and cosine terms. PMID:24229210

Chimera states for coupled oscillators.

PubMed

Abrams, Daniel M; Strogatz, Steven H

2004-10-22

Arrays of identical oscillators can display a remarkable spatiotemporal pattern in which phase-locked oscillators coexist with drifting ones. Discovered two years ago, such "chimera states" are believed to be impossible for locally or globally coupled systems; they are peculiar to the intermediate case of nonlocal coupling. Here we present an exact solution for this state, for a ring of phase oscillators coupled by a cosine kernel. We show that the stable chimera state bifurcates from a spatially modulated drift state, and dies in a saddle-node bifurcation with an unstable chimera state.

Copper(I)-catalyzed substitution reactions of propargylic amines: importance of C(sp)-C(sp3) bond cleavage in generation of iminium intermediates.

PubMed

Sugiishi, Tsuyuka; Kimura, Akifumi; Nakamura, Hiroyuki

2010-04-21

Substitution reactions of propargylic amines proceed in the presence of copper(I) catalysts. Mechanistic studies showed that C(sp)-C(sp(3)) bond cleavage assisted by nitrogen lone-pair electrons is essential for the reaction, and the resulting iminium intermediates undergo amine exchange, aldehyde exchange, and alkyne addition reactions. Because iminium intermediates are key to aldehyde-alkyne-amine (A(3)) coupling reactions, this transformation is effective not only for reconstruction of propargylic amines but also for chiral induction of racemic compounds in the presence of chiral catalysts.

Oxygen evolution from BF3/MnO4-.

PubMed

Yiu, Shek-Man; Man, Wai-Lun; Wang, Xin; Lam, William W Y; Ng, Siu-Mui; Kwong, Hoi-Ki; Lau, Kai-Chung; Lau, Tai-Chu

2011-04-14

MnO(4)(-) is activated by BF(3) to undergo intramolecular coupling of two oxo ligands to generate O(2). DFT calculations suggest that there should be a spin intercrossing between the singlet and triplet potential energy surfaces on going from the active intermediate [MnO(2)(OBF(3))(2)](-) to the O···O coupling transition state.

[Enhanced prenatal HIV couple oriented counselling session and couple communication about HIV (ANRS 12127 Prenahtest Trial)].

PubMed

Plazy, M; Orne-Gliemann, J; Balestre, E; Miric, M; Darak, S; Butsashvili, M; Tchendjou, P; Dabis, F; Desgrées du Loû, A

2013-08-01

The Prenahtest study investigated the efficacy of a couple-oriented HIV counselling session (COC) in encouraging couple HIV counselling and testing, and improving intra-couple communication about sexual and reproductive health. We report here on the effect of COC on intra-couple communication about HIV. Within this 4-country trial (India, Georgia, Dominican Republic and Cameroon), 484 to 491 pregnant women per site were recruited and individually randomized to receive either the COC intervention, enhanced counselling with role playing, or standard post-test HIV counselling. Women were interviewed at recruitment, before HIV testing (T0), and 2 to 8 weeks after post-test HIV counselling (T1). Four dichotomous variables documented intra-couple communication about HIV at T1: 1) discussion about HIV, 2) discussion about condom use, 3) suggesting HIV testing and 4) suggesting couple HIV counselling to the partner. An intra-couple HIV communication index was created: low degree of communication ("yes" response to zero or one of the four variables), intermediate degree of communication ("yes" to two or three variables) or high degree of communication ("yes" to the four variables). To estimate the impact of COC on the intra-couple HIV communication index, multivariable logistic regressions were conducted. One thousand six hundred and seven women were included in the analysis of whom 54 (3.4%) were HIV-infected (49 in Cameroon). In the four countries, the counselling group was associated with intra-couple HIV communication (P≤0.03): women allocated to the COC group were significantly more likely to report high or intermediate degrees of intra-couple communication about HIV (versus low degree of communication) than women allocated to standard counselling. COC improved short-term communication about HIV within couples in different sociocultural contexts, a positive finding for a couple approach to HIV prevention. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

Optical coupling elements for coherent optical multiport receivers

NASA Astrophysics Data System (ADS)

Langenhorst, Ralf

1992-05-01

Three by three (3 by 3) and four by four (4 by 4) port coupling elements and receivers for heterodyne multiport systems are realized. Commercial (3 by 3) fiber coupling elements were used to achieve a usual (3 by 3) port receiver and a (3 by 3) port receiver in pushpull switching, whose concept was theoretically and experimentally analyzed. It is established that intensity oscillations of laser sources are suppressed by pushpull switching. The influence of thermal noise of opto-electronic input levels is shown to be weaker than in usual (3 by 3) port and (4 by 4) port receivers. Thermal noise effect in pushpull switching is similar to this one in heterodyne receivers. An integrated optical coupling element in LiNbO3 was made with bridge circuit from four waveguide coupling elements and two phase converters, which are electro-optically tunable so that a continuous regulation of intermediate frequency phase can be compensated by temperature variations of the element. To obtain fiber-to-fiber losses lower than a dB, a compact crystal optical coupling element was developed with reference to polarization properties of optical waves. This element supplied the eight necessary intermediate frequency output signals. A direct experimental comparison of bandwidth efficiency of multiport and heterodyne receivers shows a factor two in optical area and a factor three in electrical frequency area.

A Tidal Disruption Event in a Nearby Galaxy Hosting an Intermediate Mass Black Hole

NASA Technical Reports Server (NTRS)

Donato, D; Cenko, S. B.; Covino, S.; Troja, E.; Pursimo, T.; Cheung, C. C.; Fox, O.; Kutyrev, A.; Campana, S.; Fugazza, D.;

Real-time contrast ultrasound muscle perfusion imaging with intermediate-power imaging coupled with acoustically durable microbubbles.

PubMed

Seol, Sang-Hoon; Davidson, Brian P; Belcik, J Todd; Mott, Brian H; Goodman, Reid M; Ammi, Azzdine; Lindner, Jonathan R

2015-06-01

There is growing interest in limb contrast-enhanced ultrasound (CEU) perfusion imaging for the evaluation of peripheral artery disease. Because of low resting microvascular blood flow in skeletal muscle, signal enhancement during limb CEU is prohibitively low for real-time imaging. The aim of this study was to test the hypothesis that this obstacle can be overcome by intermediate- rather than low-power CEU when performed with an acoustically resilient microbubble agent. Viscoelastic properties of Definity and Sonazoid were assessed by measuring bulk modulus during incremental increases in ambient pressure to 200 mm Hg. Comparison of in vivo microbubble destruction and signal enhancement at a mechanical index (MI) of 0.1 to 0.4 was performed by sequential reduction in pulsing interval from 10 to 0.05 sec during limb CEU at 7 MHz in mice and 1.8 MHz in dogs. Destruction was also assessed by broadband signal generation during passive cavitation detection. Real-time CEU perfusion imaging with destruction-replenishment was then performed at 1.8 MHz in dogs using an MI of 0.1, 0.2, or 0.3. Sonazoid had a higher bulk modulus than Definity (66 ± 12 vs 29 ± 2 kPa, P = .02) and exhibited less inertial cavitation (destruction) at MIs ≥ 0.2. On in vivo CEU, maximal signal intensity increased incrementally with MI for both agents and was equivalent between agents except at an MI of 0.1 (60% and 85% lower for Sonazoid at 7 and 1.8 MHz, respectively, P < .05). However, on progressive shortening of the pulsing interval, Definity was nearly completely destroyed at MIs ≥ 0.2 at 1.8 and 7 MHz, whereas Sonazoid was destroyed only at 1.8 MHz at MIs ≥ 0.3. As a result, real-time CEU perfusion imaging demonstrated approximately fourfold greater enhancement for Sonazoid at an MI of 0.3 to 0.4. Robust signal enhancement during real-time CEU perfusion imaging of the limb is possible when using intermediate-power imaging coupled with a durable microbubble contrast agent. Copyright © 2015 American Society of Echocardiography. All rights reserved.

Minimum Energy of Multicomponent Distillation Systems Using Minimum Additional Heat and Mass Integration Sections

DOE PAGES

Jiang, Zheyu; Ramapriya, Gautham Madenoor; Tawarmalani, Mohit; ...

2018-04-20

Heat and mass integration to consolidate distillation columns in a multicomponent distillation configuration can lead to a number of new energy efficient and cost effective configurations. In this paper, we identify a powerful and simple-to-use fact about heat and mass integration. The newly developed heat and mass integrated configurations, which we call as HMP configurations, involve first introducing thermal couplings to all intermediate transfer streams, followed by consolidating columns associated with a lighter pure product reboiler and a heavier pure product condenser. A systematic method of enumerating all HMP configurations is introduced. We compare the energy savings of HMP configurationsmore » with the well-known fully thermally coupled (FTC) configurations. We demonstrate that HMP configurations can have very similar and sometimes even the same minimum total vapor duty requirement as the FTC configuration, while using far less number of column sections, intermediate transfer streams, and thermal couplings than the FTC configurations.« less

Tracking Site-specific C-C Coupling of Formaldehyde Molecules on Rutile TiO2(110)

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

Zhu, Ke; Xia, Yaobiao; Tang, Miru

2015-06-25

Direct imaging of site-specific reactions of individual mole-cules as a function of temperature is a long-sought goal in molecular science. Here, we report the direct visualization of molecular coupling of formaldehyde on reduced rutile TiO2(110) surfaces as we track the same set of molecules when the temperature is increased from 75 to 170 K using scanning tunneling microscope (STM). Our recent study showed that formaldehyde preferably adsorbs on bridging-bonded oxygen (Ob) vacancy (VO) defect site. Herein, images from the same area as the temperature is increased show that VO-bound formaldehyde couples with Ti-bound formaldehyde forming a diolate intermediate. Exposure ofmore » formaldehyde at room temperature leads to diolate as the majority species on the surface and no VO-bound formaldehyde is observed. The diolate species are the key reaction intermediates in the formation of ethylene reported in previous ensemble-averaged studies.« less

Electronic transport properties of intermediately coupled superconductors: PdTe2 and Cu0.04PdTe2

NASA Astrophysics Data System (ADS)

Hooda, M. K.; Yadav, C. S.

2018-01-01

We have investigated the electrical resistivity (1.8-480 K), Seebeck coefficient (2.5-300 K) and thermal conductivity (2.5-300 K) of PdTe2 and 4% Cu intercalated PdTe2 compounds. The electrical resistivity for the compounds shows a Bloch-Gruneisen-type linear temperature (T) dependence for 100 \\text{K}, and Fermi liquid behavior (ρ (T) \\propto T2) for T<50 \\text{K} . Seebeck coefficient data exhibit a strong competition between Normal (N) and Umklapp (U) scattering processes at low T. The low-T, thermal conductivity (κ) of the compounds is strongly dominated by the electronic contribution, and exhibits a rare linear T-dependence below 10 K. However, high-T, κ (T) shows the usual 1/T -dependence, dominated by the U-scattering process. The electron-phonon coupling parameters, estimated from the low-T, specific-heat data and first-principle electronic structure calculations suggest that PdTe2 and Cu0.04PdTe2 are intermediately coupled superconductors.

Minimum Energy of Multicomponent Distillation Systems Using Minimum Additional Heat and Mass Integration Sections

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

Jiang, Zheyu; Ramapriya, Gautham Madenoor; Tawarmalani, Mohit

Heat and mass integration to consolidate distillation columns in a multicomponent distillation configuration can lead to a number of new energy efficient and cost effective configurations. In this paper, we identify a powerful and simple-to-use fact about heat and mass integration. The newly developed heat and mass integrated configurations, which we call as HMP configurations, involve first introducing thermal couplings to all intermediate transfer streams, followed by consolidating columns associated with a lighter pure product reboiler and a heavier pure product condenser. A systematic method of enumerating all HMP configurations is introduced. We compare the energy savings of HMP configurationsmore » with the well-known fully thermally coupled (FTC) configurations. We demonstrate that HMP configurations can have very similar and sometimes even the same minimum total vapor duty requirement as the FTC configuration, while using far less number of column sections, intermediate transfer streams, and thermal couplings than the FTC configurations.« less

Voltage-Dependent Gating: Novel Insights from KCNQ1 Channels

PubMed Central

Cui, Jianmin

2016-01-01

Gating of voltage-dependent cation channels involves three general molecular processes: voltage sensor activation, sensor-pore coupling, and pore opening. KCNQ1 is a voltage-gated potassium (Kv) channel whose distinctive properties have provided novel insights on fundamental principles of voltage-dependent gating. 1) Similar to other Kv channels, KCNQ1 voltage sensor activation undergoes two resolvable steps; but, unique to KCNQ1, the pore opens at both the intermediate and activated state of voltage sensor activation. The voltage sensor-pore coupling differs in the intermediate-open and the activated-open states, resulting in changes of open pore properties during voltage sensor activation. 2) The voltage sensor-pore coupling and pore opening require the membrane lipid PIP2 and intracellular ATP, respectively, as cofactors, thus voltage-dependent gating is dependent on multiple stimuli, including the binding of intracellular signaling molecules. These mechanisms underlie the extraordinary KCNE1 subunit modification of the KCNQ1 channel and have significant physiological implications. PMID:26745405

Use of a biosynthetic intermediate to explore the chemical diversity of pseudo-natural fungal polyketides.

PubMed

Asai, Teigo; Tsukada, Kento; Ise, Satomi; Shirata, Naoki; Hashimoto, Makoto; Fujii, Isao; Gomi, Katsuya; Nakagawara, Kosuke; Kodama, Eiichi N; Oshima, Yoshiteru

2015-09-01

The structural complexity and diversity of natural products make them attractive sources for potential drug discovery, with their characteristics being derived from the multi-step combination of enzymatic and non-enzymatic conversions of intermediates in each biosynthetic pathway. Intermediates that exhibit multipotent behaviour have great potential for use as starting points in diversity-oriented synthesis. Inspired by the biosynthetic pathways that form complex metabolites from simple intermediates, we developed a semi-synthetic process that combines heterologous biosynthesis and artificial diversification. The heterologous biosynthesis of fungal polyketide intermediates led to the isolation of novel oligomers and provided evidence for ortho-quinonemethide equivalency in their isochromene form. The intrinsic reactivity of the isochromene polyketide enabled us to access various new chemical entities by modifying and remodelling the polyketide core and through coupling with indole molecules. We thus succeeded in generating exceptionally diverse pseudo-natural polyketides through this process and demonstrated an advanced method of using biosynthetic intermediates.

Use of a biosynthetic intermediate to explore the chemical diversity of pseudo-natural fungal polyketides

NASA Astrophysics Data System (ADS)

Asai, Teigo; Tsukada, Kento; Ise, Satomi; Shirata, Naoki; Hashimoto, Makoto; Fujii, Isao; Gomi, Katsuya; Nakagawara, Kosuke; Kodama, Eiichi N.; Oshima, Yoshiteru

2015-09-01

The structural complexity and diversity of natural products make them attractive sources for potential drug discovery, with their characteristics being derived from the multi-step combination of enzymatic and non-enzymatic conversions of intermediates in each biosynthetic pathway. Intermediates that exhibit multipotent behaviour have great potential for use as starting points in diversity-oriented synthesis. Inspired by the biosynthetic pathways that form complex metabolites from simple intermediates, we developed a semi-synthetic process that combines heterologous biosynthesis and artificial diversification. The heterologous biosynthesis of fungal polyketide intermediates led to the isolation of novel oligomers and provided evidence for ortho-quinonemethide equivalency in their isochromene form. The intrinsic reactivity of the isochromene polyketide enabled us to access various new chemical entities by modifying and remodelling the polyketide core and through coupling with indole molecules. We thus succeeded in generating exceptionally diverse pseudo-natural polyketides through this process and demonstrated an advanced method of using biosynthetic intermediates.

Hydroxyacetone production from C 3 Criegee intermediates

DOE PAGES

Taatjes, Craig A.; Liu, Fang; Rotavera, Brandon; ...

2016-12-21

Hydroxyacetone (CH 3C(O)CH 2OH) is observed as a stable end product from reactions of the (CH 3) 2COO Criegee intermediate, acetone oxide, in a flow tube coupled with multiplexed photoionization mass spectrometer detection. In the experiment, the isomers at m/z = 74 are distinguished by their different photoionization spectra and reaction times. Hydroxyacetone is observed as a persistent signal at longer reaction times at a higher photoionization threshold of ca. 9.7 eV than Criegee intermediate and definitively identified by comparison with the known photoionization spectrum. Complementary electronic structure calculations reveal multiple possible reaction pathways for hydroxyacetone formation, including unimolecular isomerizationmore » via hydrogen atom transfer and –OH group migration as well as self-reaction of Criegee intermediates. Varying the concentration of Criegee intermediates suggests contributions from both unimolecular and self-reaction pathways to hydroxyacetone. As a result, the hydroxyacetone end product can provide an effective, stable marker for the production of transient Criegee intermediates in future studies of alkene ozonolysis.« less

On the accuracy of the 'decoupled l-dominant' approximation for atom-molecule scattering

NASA Technical Reports Server (NTRS)

Green, S.

1976-01-01

Cross sections for rotational excitation and spectral pressure broadening of HD, HCl, CO, and HCN due to collisions with low energy He atoms have been computed within the 'decoupled l-dominant' (DLD) approximation and are compared with accurate close coupling results and also with two similar approximations, the effective potential of Rabitz and the coupled states of McGuire and Kouri. DLD predictions of state-to-state cross sections are rather good, being only slightly less accurate than coupled states results. DLD is far superior to either the coupled states or effective potential methods for pressure broadening calculations, although it may not be uniformly of the quantitative accuracy desirable for obtaining intermolecular potentials from experimental data.

HST3D; a computer code for simulation of heat and solute transport in three-dimensional ground-water flow systems

USGS Publications Warehouse

Kipp, K.L.

1987-01-01

The Heat- and Soil-Transport Program (HST3D) simulates groundwater flow and associated heat and solute transport in three dimensions. The three governing equations are coupled through the interstitial pore velocity, the dependence of the fluid density on pressure, temperature, the solute-mass fraction , and the dependence of the fluid viscosity on temperature and solute-mass fraction. The solute transport equation is for only a single, solute species with possible linear equilibrium sorption and linear decay. Finite difference techniques are used to discretize the governing equations using a point-distributed grid. The flow-, heat- and solute-transport equations are solved , in turn, after a particle Gauss-reduction scheme is used to modify them. The modified equations are more tightly coupled and have better stability for the numerical solutions. The basic source-sink term represents wells. A complex well flow model may be used to simulate specified flow rate and pressure conditions at the land surface or within the aquifer, with or without pressure and flow rate constraints. Boundary condition types offered include specified value, specified flux, leakage, heat conduction, and approximate free surface, and two types of aquifer influence functions. All boundary conditions can be functions of time. Two techniques are available for solution of the finite difference matrix equations. One technique is a direct-elimination solver, using equations reordered by alternating diagonal planes. The other technique is an iterative solver, using two-line successive over-relaxation. A restart option is available for storing intermediate results and restarting the simulation at an intermediate time with modified boundary conditions. This feature also can be used as protection against computer system failure. Data input and output may be in metric (SI) units or inch-pound units. Output may include tables of dependent variables and parameters, zoned-contour maps, and plots of the dependent variables versus time. (Lantz-PTT)

Aggregate-scale heterogeneity in iron (hydr)oxide reductive transformations

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

Tufano, K.J.; Benner, S.G.; Mayer, K.U.

There is growing awareness of the complexity of potential reaction pathways and the associated solid-phase transformations during the reduction of Fe (hydr)oxides, especially ferrihydrite. An important observation in static and advective-dominated systems is that microbially produced Fe(II) accelerates Ostwald ripening of ferrihydrite, thus promoting the formation of thermodynamically more stable ferric phases (lepidocrocite and goethite) and, at higher Fe(II) surface loadings, the precipitation of magnetite; high Fe(II) levels can also lead to green rust formation, and with high carbonate levels siderite may also be formed. This study expands this emerging conceptual model to a diffusion-dominated system that mimics an idealizedmore » micropore of a ferrihydrite-coated soil aggregate undergoing reduction. Using a novel diffusion cell, coupled with micro-x-ray fluorescence and absorption spectroscopies, we determined that diffusion-controlled gradients in Fe{sup 2+}{sub (aq)} result in a complex array of spatially distributed secondary mineral phases. At the diffusive pore entrance, where Fe{sup 2+} concentrations are highest, green rust and magnetite are the dominant secondary Fe (hydr)oxides (30 mol% Fe each). At intermediate distances from the inlet, green rust is not observed and the proportion of magnetite decreases from approximately 30 to <10%. Across this same transect, the proportion of goethite increases from undetectable up to >50%. At greater distances from the advective-diffusive boundary, goethite is the dominant phase, comprising between 40 and 95% of the Fe. In the presence of magnetite, lepidocrocite forms as a transient-intermediate phase during ferrihydrite-to-goethite conversion; in the absence of magnetite, conversion to goethite is more limited. These experimental observations, coupled with results of reactive transport modeling, confirm the conceptual model and illustrate the potential importance of diffusion-generated concentration gradients in dissolved Fe{sup 2+} on the fate of ferrihydrite during reduction in structured soils.« less

The costs and service implications of substituting intermediate care for acute hospital care.

PubMed

Mayhew, Leslie; Lawrence, David

2006-05-01

Intermediate care is part of a package of initiatives introduced by the UK Government mainly to relieve pressure on acute hospital beds and reduce delayed discharge (bed blocking). Intermediate care involves caring for patients in a range of settings, such as in the home or community or in nursing and residential homes. This paper considers the scope of intermediate care and its role in relation to acute hospital services. In particular, it develops a framework that can be used to inform decisions about the most cost-effective care pathways for given clinical situations, and also for wider planning purposes. It does this by providing a model for evaluating the costs of intermediate care services provided by different agencies and techniques for calibrating the model locally. It finds that consistent application of the techniques over a period of time, coupled with sound planning and accounting, should result in savings to the health economy.

Study on the spin-states of cobalt-based double-layer perovskite Sr2Y0.5Ca0.5Co2O7

NASA Astrophysics Data System (ADS)

He, H.; Zhang, W. Y.

2008-02-01

The spin-states of cobalt based perovskite compounds depend sensitively on the valence state and local crystal environment of Co ions and the rich physical properties arise from strong coupling among charge, spin, and orbital degrees of freedom. While extensive studies have been carried out in the past, most of them concentrated on the isotropic compound LaCoO3. In this paper, using the unrestricted Hartree-Fock approximation and the real-space recursion method, we have investigated the competition of various magnetically ordered spin-states of anisotropic double-layered perovskite Sr2Y0.5Ca0.5Co2O7. The energy comparison among these states shows that the nearest-neighbor high-spin-intermediate-spin ferromagnetically ordered state is the relevant magnetic ground state of the compound. The magnetic structure and sizes of magnetic moments are consistent with the recent experimental observation.

Magnetic specific heat and structural phase transitions in (CH3)4NMnCl3 (TMMC) and TMMC:Cu2+ studied by crystal optics

NASA Astrophysics Data System (ADS)

Levola, T.; Kleemann, W.

1985-10-01

High-resolution refractive index (RI) and linear birefringence (LB) measurements are performed on the one-dimensional antiferromagnet tetramethyl ammonium manganese trichloride (TMMC) in order to reveal the temperature dependence of the magnetic short-range order. In agreement with values obtained by other methods an exchange constant J/kB=-7.3 K is reliably extracted. Anomalies of the in-plane LB and of the ordinary RI at the hexagonal-to-monoclinic structural phase transition (Tc=126 K) are successfully described with the use of linear elasto-optic response theory and the Landau approximation, which accounts for symmetry-adapted coupling between the components of the order parameter and of the spontaneous strain. Cu2+ ions, substituting Mn2+ ions of TMMC at a rate exceeding x=1.5%, are shown to stabilize an intermediate, possibly incommensurate phase. Its stability range is marked by very drastic decreases &=145 K and &=55 K for x=4.5%, respectively.

Utilizing a CdTe quantum dots-enzyme hybrid system for the determination of both phenolic compounds and hydrogen peroxide.

PubMed

Yuan, Jipei; Guo, Weiwei; Wang, Erkang

2008-02-15

In this paper, we attempt to construct a simple and sensitive detection method for both phenolic compounds and hydrogen peroxide, with the successful combination of the unique property of quantum dots and the specificity of enzymatic reactions. In the presence of H2O2 and horseradish peroxidase, phenolic compounds can quench quantum dots' photoluminescence efficiently, and the extent of quenching is severalfold to more than 100-fold increase. Quinone intermediates produced from the enzymatic catalyzed oxidation of phenolic compounds were believed to play the main role in the photoluminescence quenching. Using a quantum dots-enzyme system, the detection limits for phenolic compounds and hydrogen peroxide were detected to be approximately 10(-7) mol L(-1). The coupling of efficient quenching of quantum dot photoluminescence by quinone and the effective enzymatic reactions make this a simple and sensitive method for phenolic compound detection and great potential in the development of H2O2 biosensors for various analytes.

Two-magnon excitations in resonant inelastic x-ray scattering studied within spin density wave formalism

NASA Astrophysics Data System (ADS)

Nomura, Takuji

2017-10-01

We study two-magnon excitations in resonant inelastic x-ray scattering (RIXS) at the transition-metal K edge. Instead of working with effective Heisenberg spin models, we work with a Hubbard-type model (d -p model) for a typical insulating cuprate La2CuO4 . For the antiferromagnetic ground state within the spin density wave (SDW) mean-field formalism, we calculate the dynamical correlation function within the random-phase approximation (RPA), and then obtain two-magnon excitation spectra by calculating the convolution of it. Coupling between the K -shell hole and the magnons in the intermediate state is calculated by means of diagrammatic perturbation expansion in the Coulomb interaction. The calculated momentum dependence of RIXS spectra agrees well with that of experiments. A notable difference from previous calculations based on the Heisenberg spin models is that RIXS spectra have a large two-magnon weight near the zone center, which may be confirmed by further careful high-resolution experiments.

Advanced PIC-MCC simulation for the investigation of step-ionization effect in intermediate-pressure capacitively coupled plasmas

NASA Astrophysics Data System (ADS)

Kim, Jin Seok; Hur, Min Young; Kim, Chang Ho; Kim, Ho Jun; Lee, Hae June

2018-03-01

A two-dimensional parallelized particle-in-cell simulation has been developed to simulate a capacitively coupled plasma reactor. The parallelization using graphics processing units is applied to resolve the heavy computational load. It is found that the step-ionization plays an important role in the intermediate gas pressure of a few Torr. Without the step-ionization, the average electron density decreases while the effective electron temperature increases with the increase of gas pressure at a fixed power. With the step-ionization, however, the average electron density increases while the effective electron temperature decreases with the increase of gas pressure. The cases with the step-ionization agree well with the tendency of experimental measurement. The electron energy distribution functions show that the population of electrons having intermediate energy from 4.2 to 12 eV is relaxed by the step-ionization. Also, it was observed that the power consumption by the electrons is increasing with the increase of gas pressure by the step-ionization process, while the power consumption by the ions decreases with the increase of gas pressure.

Effects of a Health Behavior Change Model-Based HIV/STI Prevention Intervention on Condom Use among Heterosexual Couples: A Randomized Trial

ERIC Educational Resources Information Center

Harvey, S. Marie; Kraft, Joan Marie; West, Stephen G.; Taylor, Aaron B.; Pappas-DeLuca, Katina A.; Beckman, Linda J.

2009-01-01

This study examines an intervention for heterosexual couples to prevent human immunodeficiency virus/sexually transmitted infections. It also evaluates the effect of the intervention, which is based on current models of health behavior change, on intermediate outcomes (individual and relationship factors) and consistency of condom use. Eligible…

Non-Kondo many-body physics in a Majorana-based Kondo type system

NASA Astrophysics Data System (ADS)

van Beek, Ian J.; Braunecker, Bernd

2016-09-01

We carry out a theoretical analysis of a prototypical Majorana system, which demonstrates the existence of a Majorana-mediated many-body state and an associated intermediate low-energy fixed point. Starting from two Majorana bound states, hosted by a Coulomb-blockaded topological superconductor and each coupled to a separate lead, we derive an effective low-energy Hamiltonian, which displays a Kondo-like character. However, in contrast to the Kondo model which tends to a strong- or weak-coupling limit under renormalization, we show that this effective Hamiltonian scales to an intermediate fixed point, whose existence is contingent upon teleportation via the Majorana modes. We conclude by determining experimental signatures of this fixed point, as well as the exotic many-body state associated with it.

Symmetric rotating-wave approximation for the generalized single-mode spin-boson system

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

Albert, Victor V.; Scholes, Gregory D.; Brumer, Paul

2011-10-15

The single-mode spin-boson model exhibits behavior not included in the rotating-wave approximation (RWA) in the ultra and deep-strong coupling regimes, where counter-rotating contributions become important. We introduce a symmetric rotating-wave approximation that treats rotating and counter-rotating terms equally, preserves the invariances of the Hamiltonian with respect to its parameters, and reproduces several qualitative features of the spin-boson spectrum not present in the original rotating-wave approximation both off-resonance and at deep-strong coupling. The symmetric rotating-wave approximation allows for the treatment of certain ultra- and deep-strong coupling regimes with similar accuracy and mathematical simplicity as does the RWA in the weak-coupling regime.more » Additionally, we symmetrize the generalized form of the rotating-wave approximation to obtain the same qualitative correspondence with the addition of improved quantitative agreement with the exact numerical results. The method is readily extended to higher accuracy if needed. Finally, we introduce the two-photon parity operator for the two-photon Rabi Hamiltonian and obtain its generalized symmetric rotating-wave approximation. The existence of this operator reveals a parity symmetry similar to that in the Rabi Hamiltonian as well as another symmetry that is unique to the two-photon case, providing insight into the mathematical structure of the two-photon spectrum, significantly simplifying the numerics, and revealing some interesting dynamical properties.« less

An approximate Riemann solver for hypervelocity flows

NASA Technical Reports Server (NTRS)

Jacobs, Peter A.

1991-01-01

We describe an approximate Riemann solver for the computation of hypervelocity flows in which there are strong shocks and viscous interactions. The scheme has three stages, the first of which computes the intermediate states assuming isentropic waves. A second stage, based on the strong shock relations, may then be invoked if the pressure jump across either wave is large. The third stage interpolates the interface state from the two initial states and the intermediate states. The solver is used as part of a finite-volume code and is demonstrated on two test cases. The first is a high Mach number flow over a sphere while the second is a flow over a slender cone with an adiabatic boundary layer. In both cases the solver performs well.

A Jacobi collocation approximation for nonlinear coupled viscous Burgers' equation

NASA Astrophysics Data System (ADS)

Doha, Eid H.; Bhrawy, Ali H.; Abdelkawy, Mohamed A.; Hafez, Ramy M.

2014-02-01

This article presents a numerical approximation of the initial-boundary nonlinear coupled viscous Burgers' equation based on spectral methods. A Jacobi-Gauss-Lobatto collocation (J-GL-C) scheme in combination with the implicit Runge-Kutta-Nyström (IRKN) scheme are employed to obtain highly accurate approximations to the mentioned problem. This J-GL-C method, based on Jacobi polynomials and Gauss-Lobatto quadrature integration, reduces solving the nonlinear coupled viscous Burgers' equation to a system of nonlinear ordinary differential equation which is far easier to solve. The given examples show, by selecting relatively few J-GL-C points, the accuracy of the approximations and the utility of the approach over other analytical or numerical methods. The illustrative examples demonstrate the accuracy, efficiency, and versatility of the proposed algorithm.

Ground-state phases of the spin-1 J1-J2 Heisenberg antiferromagnet on the honeycomb lattice

NASA Astrophysics Data System (ADS)

Li, P. H. Y.; Bishop, R. F.

2016-06-01

We study the zero-temperature quantum phase diagram of a spin-1 Heisenberg antiferromagnet on the honeycomb lattice with both nearest-neighbor exchange coupling J1>0 and frustrating next-nearest-neighbor coupling J2≡κ J1>0 , using the coupled cluster method implemented to high orders of approximation, and based on model states with different forms of classical magnetic order. For each we calculate directly in the bulk thermodynamic limit both ground-state low-energy parameters (including the energy per spin, magnetic order parameter, spin stiffness coefficient, and zero-field uniform transverse magnetic susceptibility) and their generalized susceptibilities to various forms of valence-bond crystalline (VBC) order, as well as the energy gap to the lowest-lying spin-triplet excitation. In the range 0 <κ <1 we find evidence for four distinct phases. Two of these are quasiclassical phases with antiferromagnetic long-range order, one with two-sublattice Néel order for κ <κc1=0.250(5 ) , and another with four-sublattice Néel-II order for κ >κc 2=0.340 (5 ) . Two different paramagnetic phases are found to exist in the intermediate region. Over the range κc1<κ<κci=0.305 (5 ) we find a gapless phase with no discernible magnetic order, which is a strong candidate for being a quantum spin liquid, while over the range κci<κ <κc 2 we find a gapped phase, which is most likely a lattice nematic with staggered dimer VBC order that breaks the lattice rotational symmetry.

Alternative definition of excitation amplitudes in multi-reference state-specific coupled cluster

NASA Astrophysics Data System (ADS)

Garniron, Yann; Giner, Emmanuel; Malrieu, Jean-Paul; Scemama, Anthony

2017-04-01

A central difficulty of state-specific Multi-Reference Coupled Cluster (MR-CC) in the multi-exponential Jeziorski-Monkhorst formalism concerns the definition of the amplitudes of the single and double excitation operators appearing in the exponential wave operators. If the reference space is a complete active space (CAS), the number of these amplitudes is larger than the number of singly and doubly excited determinants on which one may project the eigenequation, and one must impose additional conditions. The present work first defines a state-specific reference-independent operator T˜ ^ m which acting on the CAS component of the wave function |Ψ0m⟩ maximizes the overlap between (1 +T˜ ^ m ) |Ψ0m⟩ and the eigenvector of the CAS-SD (Singles and Doubles) Configuration Interaction (CI) matrix |ΨCAS-SDm⟩ . This operator may be used to generate approximate coefficients of the triples and quadruples, and a dressing of the CAS-SD CI matrix, according to the intermediate Hamiltonian formalism. The process may be iterated to convergence. As a refinement towards a strict coupled cluster formalism, one may exploit reference-independent amplitudes provided by (1 +T˜ ^ m ) |Ψ0m⟩ to define a reference-dependent operator T^ m by fitting the eigenvector of the (dressed) CAS-SD CI matrix. The two variants, which are internally uncontracted, give rather similar results. The new MR-CC version has been tested on the ground state potential energy curves of 6 molecules (up to triple-bond breaking) and two excited states. The non-parallelism error with respect to the full-CI curves is of the order of 1 mEh.

Efficient and accurate local approximations to coupled-electron pair approaches: An attempt to revive the pair natural orbital method

NASA Astrophysics Data System (ADS)

Neese, Frank; Wennmohs, Frank; Hansen, Andreas

2009-03-01

Coupled-electron pair approximations (CEPAs) and coupled-pair functionals (CPFs) have been popular in the 1970s and 1980s and have yielded excellent results for small molecules. Recently, interest in CEPA and CPF methods has been renewed. It has been shown that these methods lead to competitive thermochemical, kinetic, and structural predictions. They greatly surpass second order Møller-Plesset and popular density functional theory based approaches in accuracy and are intermediate in quality between CCSD and CCSD(T) in extended benchmark studies. In this work an efficient production level implementation of the closed shell CEPA and CPF methods is reported that can be applied to medium sized molecules in the range of 50-100 atoms and up to about 2000 basis functions. The internal space is spanned by localized internal orbitals. The external space is greatly compressed through the method of pair natural orbitals (PNOs) that was also introduced by the pioneers of the CEPA approaches. Our implementation also makes extended use of density fitting (or resolution of the identity) techniques in order to speed up the laborious integral transformations. The method is called local pair natural orbital CEPA (LPNO-CEPA) (LPNO-CPF). The implementation is centered around the concepts of electron pairs and matrix operations. Altogether three cutoff parameters are introduced that control the size of the significant pair list, the average number of PNOs per electron pair, and the number of contributing basis functions per PNO. With the conservatively chosen default values of these thresholds, the method recovers about 99.8% of the canonical correlation energy. This translates to absolute deviations from the canonical result of only a few kcal mol-1. Extended numerical test calculations demonstrate that LPNO-CEPA (LPNO-CPF) has essentially the same accuracy as parent CEPA (CPF) methods for thermochemistry, kinetics, weak interactions, and potential energy surfaces but is up to 500 times faster. The method performs best in conjunction with large and flexible basis sets. These results open the way for large-scale chemical applications.

Efficient and accurate local approximations to coupled-electron pair approaches: An attempt to revive the pair natural orbital method.

PubMed

Neese, Frank; Wennmohs, Frank; Hansen, Andreas

2009-03-21

Coupled-electron pair approximations (CEPAs) and coupled-pair functionals (CPFs) have been popular in the 1970s and 1980s and have yielded excellent results for small molecules. Recently, interest in CEPA and CPF methods has been renewed. It has been shown that these methods lead to competitive thermochemical, kinetic, and structural predictions. They greatly surpass second order Moller-Plesset and popular density functional theory based approaches in accuracy and are intermediate in quality between CCSD and CCSD(T) in extended benchmark studies. In this work an efficient production level implementation of the closed shell CEPA and CPF methods is reported that can be applied to medium sized molecules in the range of 50-100 atoms and up to about 2000 basis functions. The internal space is spanned by localized internal orbitals. The external space is greatly compressed through the method of pair natural orbitals (PNOs) that was also introduced by the pioneers of the CEPA approaches. Our implementation also makes extended use of density fitting (or resolution of the identity) techniques in order to speed up the laborious integral transformations. The method is called local pair natural orbital CEPA (LPNO-CEPA) (LPNO-CPF). The implementation is centered around the concepts of electron pairs and matrix operations. Altogether three cutoff parameters are introduced that control the size of the significant pair list, the average number of PNOs per electron pair, and the number of contributing basis functions per PNO. With the conservatively chosen default values of these thresholds, the method recovers about 99.8% of the canonical correlation energy. This translates to absolute deviations from the canonical result of only a few kcal mol(-1). Extended numerical test calculations demonstrate that LPNO-CEPA (LPNO-CPF) has essentially the same accuracy as parent CEPA (CPF) methods for thermochemistry, kinetics, weak interactions, and potential energy surfaces but is up to 500 times faster. The method performs best in conjunction with large and flexible basis sets. These results open the way for large-scale chemical applications.

A nonperturbative light-front coupled-cluster method

NASA Astrophysics Data System (ADS)

Hiller, J. R.

2012-10-01

The nonperturbative Hamiltonian eigenvalue problem for bound states of a quantum field theory is formulated in terms of Dirac's light-front coordinates and then approximated by the exponential-operator technique of the many-body coupled-cluster method. This approximation eliminates any need for the usual approximation of Fock-space truncation. Instead, the exponentiated operator is truncated, and the terms retained are determined by a set of nonlinear integral equations. These equations are solved simultaneously with an effective eigenvalue problem in the valence sector, where the number of constituents is small. Matrix elements can be calculated, with extensions of techniques from standard coupled-cluster theory, to obtain form factors and other observables.

Physical Applications of a Simple Approximation of Bessel Functions of Integer Order

ERIC Educational Resources Information Center

Barsan, V.; Cojocaru, S.

2007-01-01

Applications of a simple approximation of Bessel functions of integer order, in terms of trigonometric functions, are discussed for several examples from electromagnetism and optics. The method may be applied in the intermediate regime, bridging the "small values regime" and the "asymptotic" one, and covering, in this way, an area of great…

Approximate analytic expression for the Skyrmions crystal

NASA Astrophysics Data System (ADS)

Grandi, Nicolás; Sturla, Mauricio

2018-01-01

We find approximate solutions for the two-dimensional nonlinear Σ-model with Dzyalioshinkii-Moriya term, representing magnetic Skyrmions. They are built in an analytic form, by pasting different approximate solutions found in different regions of space. We verify that our construction reproduces the phenomenology known from numerical solutions and Monte Carlo simulations, giving rise to a Skyrmion lattice at an intermediate range of magnetic field, flanked by spiral and spin-polarized phases for low and high magnetic fields, respectively.

Management of light absorption in extraordinary optical transmission based ultra-thin-film tandem solar cells

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

Mashooq, Kishwar; Talukder, Muhammad Anisuzzaman, E-mail: anis@eee.buet.ac.bd

2016-05-21

Although ultra-thin-film solar cells can be attractive in reducing the cost, they suffer from low absorption as the thickness of the active layer is usually much smaller than the wavelength of incident light. Different nano-photonic techniques, including plasmonic structures, are being explored to increase the light absorption in ultra-thin-film solar cells. More than one layer of active materials with different energy bandgaps can be used in tandem to increase the light absorption as well. However, due to different amount of light absorption in different active layers, photo-generated currents in different active layers will not be the same. The current mismatchmore » between the tandem layers makes them ineffective in increasing the efficiency. In this work, we investigate the light absorption properties of tandem solar cells with two ultra-thin active layers working as two subcells and a metal layer with periodically perforated holes in-between the two subcells. While the metal layer helps to overcome the current mismatch, the periodic holes increase the absorption of incident light by helping extraordinary optical transmission of the incident light from the top to the bottom subcell, and by coupling the incident light to plasmonic and photonic modes within ultra-thin active layers. We extensively study the effects of the geometry of holes in the intermediate metal layer on the light absorption properties of tandem solar cells with ultra-thin active layers. We also study how different metals in the intermediate layer affect the light absorption; how the geometry of holes in the intermediate layer affects the absorption when the active layer materials are changed; and how the intermediate metal layer affects the collection of photo-generated electron-hole pairs at the terminals. We find that in a solar cell with 6,6-phenyl C61-butyric acid methyl ester top subcell and copper indium gallium selenide bottom subcell, if the periodic holes in the metal layer are square or polygon, total absorption remains approximately the same. However, the total absorption suffers significantly if the holes are triangle. The transmission spectra of incident light into the bottom subcell, and hence the absorption, change significantly for square and circle holes if the active materials change to cadmium selenide (CdSe) and cadmium telluride (CdTe) in the top and bottom subcells, respectively. Although the intermediate metal layer may induce electron-hole pair recombination due to surface defects, the short-circuit current density of an ultra-thin plasmonic solar cell with an intermediate metal layer with two-dimensional hole array is >9% of that of a structure without the intermediate metal layer.« less

Diffusion Filters for Variational Data Assimilation of Sea Surface Temperature in an Intermediate Climate Model

DTIC Science & Technology

2015-01-01

over data-dense regions. After that, a perfect twin data assimilation experiment framework is designed to study the effect of the GDF on the state...is designed to study the effect of the GDF on the state estimation based on an intermediate coupled model. In this framework, the assimilation model...observation. Considering = , (4) is equal to () = 1 2 + 1 2 ( − ) −1 ( − ) . (5) The effect of in (5) can

Combining geographic information system, multicriteria evaluation techniques and fuzzy logic in siting MSW landfills

NASA Astrophysics Data System (ADS)

Gemitzi, Alexandra; Tsihrintzis, Vassilios A.; Voudrias, Evangelos; Petalas, Christos; Stravodimos, George

2007-01-01

This study presents a methodology for siting municipal solid waste landfills, coupling geographic information systems (GIS), fuzzy logic, and multicriteria evaluation techniques. Both exclusionary and non-exclusionary criteria are used. Factors, i.e., non-exclusionary criteria, are divided in two distinct groups which do not have the same level of trade off. The first group comprises factors related to the physical environment, which cannot be expressed in terms of monetary cost and, therefore, they do not easily trade off. The second group includes those factors related to human activities, i.e., socioeconomic factors, which can be expressed as financial cost, thus showing a high level of trade off. GIS are used for geographic data acquisition and processing. The analytical hierarchy process (AHP) is the multicriteria evaluation technique used, enhanced with fuzzy factor standardization. Besides assigning weights to factors through the AHP, control over the level of risk and trade off in the siting process is achieved through a second set of weights, i.e., order weights, applied to factors in each factor group, on a pixel-by-pixel basis, thus taking into account the local site characteristics. The method has been applied to Evros prefecture (NE Greece), an area of approximately 4,000 km2. The siting methodology results in two intermediate suitability maps, one related to environmental and the other to socioeconomic criteria. Combination of the two intermediate maps results in the final composite suitability map for landfill siting.

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

Fernandes, P. A.; Lynch, K. A.

Here, we define the observational parameter regime necessary for observing low-altitude ionospheric origins of high-latitude ion upflow/outflow. We present measurement challenges and identify a new analysis technique which mitigates these impediments. To probe the initiation of auroral ion upflow, it is necessary to examine the thermal ion population at 200-350 km, where typical thermal energies are tenths of eV. Interpretation of the thermal ion distribution function measurement requires removal of payload sheath and ram effects. We use a 3-D Maxwellian model to quantify how observed ionospheric parameters such as density, temperature, and flows affect in situ measurements of the thermalmore » ion distribution function. We define the viable acceptance window of a typical top-hat electrostatic analyzer in this regime and show that the instrument's energy resolution prohibits it from directly observing the shape of the particle spectra. To extract detailed information about measured particle population, we define two intermediate parameters from the measured distribution function, then use a Maxwellian model to replicate possible measured parameters for comparison to the data. Liouville's theorem and the thin-sheath approximation allow us to couple the measured and modeled intermediate parameters such that measurements inside the sheath provide information about plasma outside the sheath. We apply this technique to sounding rocket data to show that careful windowing of the data and Maxwellian models allows for extraction of the best choice of geophysical parameters. More widespread use of this analysis technique will help our community expand its observational database of the seed regions of ionospheric outflows.« less

Interpretation of ES, CS, and IOS approximations within a translational-internal coupling scheme. II. Application to atom--diatom kinetic cross sections

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

Coombe, D.A.; Snider, R.F.

1980-02-15

ES, CS, and IOS approximations to atom--diatom kinetic cross sections are derived. In doing so, reduced S-matrices in a translational-internal coupling scheme are stressed. This entails the insertion of recently obtained approximate reduced S-matrices in the translational-internal coupling scheme into previously derived general expressions for the kinetic cross sections. Of special interest is the structure (rotational j quantum number dependence) of the kinetic cross sections associated with the Senftleben Beenakker effects and of pure internal state relaxation phenomena. The viscomagnetic effect is used as an illustrative example. It is found in particular that there is a great similarity of structuremore » between the energy sudden (and IOS) approximation and the previously derived distorted wave Born results.« less

Vibrationally-resolved Charge Transfer of O^3+ Ions with Molecular Hydrogen

NASA Astrophysics Data System (ADS)

Wang, J. G.; Stancil, P. C.; Turner, A. R.; Cooper, D. L.

2003-05-01

Charge transfer processes due to collisions of ground state O^3+ ions with H2 are investigated using the quantum-mechanical molecular-orbital close-coupling (MOCC) method. The MOCC calculations utilize ab initio adiabatic potentials and nonadiabatic radial coupling matrix elements obtained with the spin-coupled valence-bond approach. Vibrationally-resolved cross sections for energies between 0.1 eV/u and 2 keV/u using the infinite order sudden approximation (IOSA), vibrational sudden approximation (VSA), and electronic approximation (EA), but including Frank-Condon factors (the centroid approximation) will be presented. Comparison with existing experimental data for total cross sections shows best agreement with IOSA and discrepancies for VSA and EA. Triplet-singlet cross section ratios obtained with IOSA are found generally to be in harmony with experiment. JGW and PCS acknowledge support from NASA grant 11453.

Recent advances in approximation concepts for optimum structural design

NASA Technical Reports Server (NTRS)

Barthelemy, Jean-Francois M.; Haftka, Raphael T.

1991-01-01

The basic approximation concepts used in structural optimization are reviewed. Some of the most recent developments in that area since the introduction of the concept in the mid-seventies are discussed. The paper distinguishes between local, medium-range, and global approximations; it covers functions approximations and problem approximations. It shows that, although the lack of comparative data established on reference test cases prevents an accurate assessment, there have been significant improvements. The largest number of developments have been in the areas of local function approximations and use of intermediate variable and response quantities. It also appears that some new methodologies are emerging which could greatly benefit from the introduction of new computer architecture.

A walk through the approximations of ab initio multiple spawning

NASA Astrophysics Data System (ADS)

Mignolet, Benoit; Curchod, Basile F. E.

2018-04-01

Full multiple spawning offers an in principle exact framework for excited-state dynamics, where nuclear wavefunctions in different electronic states are represented by a set of coupled trajectory basis functions that follow classical trajectories. The couplings between trajectory basis functions can be approximated to treat molecular systems, leading to the ab initio multiple spawning method which has been successfully employed to study the photochemistry and photophysics of several molecules. However, a detailed investigation of its approximations and their consequences is currently missing in the literature. In this work, we simulate the explicit photoexcitation and subsequent excited-state dynamics of a simple system, LiH, and we analyze (i) the effect of the ab initio multiple spawning approximations on different observables and (ii) the convergence of the ab initio multiple spawning results towards numerically exact quantum dynamics upon a progressive relaxation of these approximations. We show that, despite the crude character of the approximations underlying ab initio multiple spawning for this low-dimensional system, the qualitative excited-state dynamics is adequately captured, and affordable corrections can further be applied to ameliorate the coupling between trajectory basis functions.

A walk through the approximations of ab initio multiple spawning.

PubMed

Mignolet, Benoit; Curchod, Basile F E

2018-04-07

Full multiple spawning offers an in principle exact framework for excited-state dynamics, where nuclear wavefunctions in different electronic states are represented by a set of coupled trajectory basis functions that follow classical trajectories. The couplings between trajectory basis functions can be approximated to treat molecular systems, leading to the ab initio multiple spawning method which has been successfully employed to study the photochemistry and photophysics of several molecules. However, a detailed investigation of its approximations and their consequences is currently missing in the literature. In this work, we simulate the explicit photoexcitation and subsequent excited-state dynamics of a simple system, LiH, and we analyze (i) the effect of the ab initio multiple spawning approximations on different observables and (ii) the convergence of the ab initio multiple spawning results towards numerically exact quantum dynamics upon a progressive relaxation of these approximations. We show that, despite the crude character of the approximations underlying ab initio multiple spawning for this low-dimensional system, the qualitative excited-state dynamics is adequately captured, and affordable corrections can further be applied to ameliorate the coupling between trajectory basis functions.

Recent Developments in C-H Activation for Materials Science in the Center for Selective C-H Activation.

PubMed

Zhang, Junxiang; Kang, Lauren J; Parker, Timothy C; Blakey, Simon B; Luscombe, Christine K; Marder, Seth R

2018-04-16

Abstract : Organic electronics is a rapidly growing field driven in large part by the synthesis of ∏-conjugated molecules and polymers. Traditional aryl cross-coupling reactions such as the Stille and Suzuki have been used extensively in the synthesis of ∏-conjugated molecules and polymers, but the synthesis of intermediates necessary for traditional cross-couplings can include multiple steps with toxic and hazardous reagents. Direct arylation through C-H bond activation has the potential to reduce the number of steps and hazards while being more atom-economical. Within the Center for Selective C-H Functionalization (CCHF), we have been developing C-H activation methodology for the synthesis of ∏-conjugated materials of interest, including direct arylation of difficult-to-functionalize electron acceptor intermediates and living polymerization of ∏-conjugated polymers through C-H activation.

Picosecond time-resolved absorption and fluorescence dynamics in the artificial bacteriorhodopsin pigment BR6.11.

PubMed

Brack, T L; Delaney, J K; Atkinson, G H; Albeck, A; Sheves, M; Ottolenghi, M

1993-08-01

The picosecond molecular dynamics in an artificial bacteriorhodopsin (BR) pigment containing a structurally modified all-trans retinal chromphore with a six-membered ring bridging the C11=C12-C13 positions (BR6.11) are measured by picosecond transient absorption and picosecond time-resolved fluorescence spectroscopy. Time-dependent intensity and spectral changes in absorption in the 570-650-nm region are monitored for delays as long as 5 ns after the 7-ps, 573-nm excitation of BR6.11. Two intermediates, J6.11 and K6.11/1, both with enhanced absorption to the red (> 600 nm) of the BR6.11 spectrum are observed within approximately 50 ps. The J6.11 intermediate decays with a time constant of 12 +/- 3 ps to form K6.11/1. The K6.11/1 intermediate decays with an approximately 100-ps time constant to form a third intermediate, K6.11/2, which is observed through diminished 650-nm absorption (relative to that of K6.11/1). No other transient absorption changes are found during the remainder of the initial 5-ns period of the BR6.11 photoreaction. Fluorescence in the 650-900-nm region is observed from BR6.11, K6.11/1, and K6.11/2, but no emission assignable to J6.11 is found. The BR6.11 fluroescence spectrum has a approximately 725-nm maximum which is blue-shifted by approximately 15 nm relative to that of native BR-570 and is 4.2 +/- 1.5 times larger in intensity (same sample optical density). No differences in the profile of the fluorescence spectra of BR6.11 and the intermediates K6.11/1 and K6.11/2 are observed. Following ground-state depletion of the BR6.11 population, the time-resolved fluroescence intensity monitored at 725 nm increases with two time constants, 12 +/- 3 and approximately 100 ps, both of which correlate well with changes in the picosecond transient absorption data. The resonance Raman spectrum of ground-state BR6.11, measured with low-energy, 560-nm excitation, is significantly different from the spectrum of native BR-570, thus confirming that the picosecond transient absorption and picosecond time resolved fluorescence data are assignable to BR6.11 and its photoreaction alone and not to BR-570 reformed during there constitution process (<5% of the BR6.11 sample could be attributed to native BR-570).The J6.11 and K6.11 absorption and fluorescence data presented here are generally analogous to those measured for native J-625 and K-590, respectively, and therefore, the primary events in the BR6.11 photoreaction can be correlated with those in the native BR photocycle. The BR6.11 photoreaction, however, exhibits important differences including slower formation rates for J and K intermediates as well as the presence of a second K intermediate. These results demonstrate that the restricted motion in the C11=C12-C13 region of retinal found in BR6.11 does not greatly change the overall photoreaction mechanism,but does alter the rates at which processes occur.

Kinetic and spectroscopic characterization of tungsten-substituted DMSO reductase from Rhodobacter sphaeroides.

PubMed

Pacheco, Josué; Niks, Dimitri; Hille, Russ

2018-03-01

We have examined the kinetic and spectroscopic properties of a tungsten-substituted form of DMSO reductase from Rhodobacter sphaeroides, an enzyme that normally possesses molybdenum. Partial reduction with sodium dithionite yields a well-resolved W(V) EPR signal of the so-called "high-g split" type that exhibits markedly greater g-anisotropy than the corresponding Mo(V) signal of the native form of the enzyme, with the g values shifted to higher magnetic field by as much as Δg ave  = 0.056. Deuteration of the enzyme confirms that the coupled proton is solvent-exchangeable, allowing us to accurately simulate the tungsten hyperfine coupling. Global curve-fitting analysis of UV/vis absorption spectra observed in the course of the reaction of the tungsten-substituted enzyme with sodium dithionite affords a well-defined absorption spectrum for the W(V) species. Surprisingly, the absorption spectrum for this species exhibits significantly larger molar extinction coefficients than either the reduced or the oxidized spectrum. This spectrum, in conjunction with those for fully oxidized W(VI) and fully reduced W(IV) enzyme, has been used to deconvolute the absorption spectra seen in the course of turnover, in the which enzyme is reacted with sodium dithionite and DMSO, demonstrating that the W(V) is an authentic catalytic intermediate that accumulates to approximately 50% of the total enzyme in the steady state.

Magnetic exchange couplings from noncollinear perturbation theory: dinuclear CuII complexes.

PubMed

Phillips, Jordan J; Peralta, Juan E

2014-08-07

To benchmark the performance of a new method based on noncollinear coupled-perturbed density functional theory [J. Chem. Phys. 138, 174115 (2013)], we calculate the magnetic exchange couplings in a series of triply bridged ferromagnetic dinuclear Cu(II) complexes that have been recently synthesized [Phys. Chem. Chem. Phys. 15, 1966 (2013)]. We find that for any basis-set the couplings from our noncollinear coupled-perturbed methodology are practically identical to those of spin-projected energy-differences when a hybrid density functional approximation is employed. This demonstrates that our methodology properly recovers a Heisenberg description for these systems, and is robust in its predictive power of magnetic couplings. Furthermore, this indicates that the failure of density functional theory to capture the subtle variation of the exchange couplings in these complexes is not simply an artifact of broken-symmetry methods, but rather a fundamental weakness of current approximate density functionals for the description of magnetic couplings.

Enhanced performance CCD output amplifier

DOEpatents

Dunham, Mark E.; Morley, David W.

1996-01-01

A low-noise FET amplifier is connected to amplify output charge from a che coupled device (CCD). The FET has its gate connected to the CCD in common source configuration for receiving the output charge signal from the CCD and output an intermediate signal at a drain of the FET. An intermediate amplifier is connected to the drain of the FET for receiving the intermediate signal and outputting a low-noise signal functionally related to the output charge signal from the CCD. The amplifier is preferably connected as a virtual ground to the FET drain. The inherent shunt capacitance of the FET is selected to be at least equal to the sum of the remaining capacitances.

Methyl Radicals in Oxidative Coupling of Methane Directly Confirmed by Synchrotron VUV Photoionization Mass Spectroscopy

PubMed Central

Luo, Liangfeng; Tang, Xiaofeng; Wang, Wendong; Wang, Yu; Sun, Shaobo; Qi, Fei; Huang, Weixin

2013-01-01

Gas-phase methyl radicals have been long proposed as the key intermediate in catalytic oxidative coupling of methane, but the direct experimental evidence still lacks. Here, employing synchrotron VUV photoionization mass spectroscopy, we have directly observed the formation of gas-phase methyl radicals during oxidative coupling of methane catalyzed by Li/MgO catalysts. The concentration of gas-phase methyl radicals correlates well with the yield of ethylene and ethane products. These results lead to an enhanced fundamental understanding of oxidative coupling of methane that will facilitate the exploration of new catalysts with improved performance. PMID:23567985

Synchronization of heteroclinic circuits through learning in coupled neural networks

NASA Astrophysics Data System (ADS)

Selskii, Anton; Makarov, Valeri A.

2016-01-01

The synchronization of oscillatory activity in neural networks is usually implemented by coupling the state variables describing neuronal dynamics. Here we study another, but complementary mechanism based on a learning process with memory. A driver network, acting as a teacher, exhibits winner-less competition (WLC) dynamics, while a driven network, a learner, tunes its internal couplings according to the oscillations observed in the teacher. We show that under appropriate training the learner can "copy" the coupling structure and thus synchronize oscillations with the teacher. The replication of the WLC dynamics occurs for intermediate memory lengths only, consequently, the learner network exhibits a phenomenon of learning resonance.

Dexter energy transfer pathways

PubMed Central

Skourtis, Spiros S.; Liu, Chaoren; Antoniou, Panayiotis; Virshup, Aaron M.; Beratan, David N.

2016-01-01

Energy transfer with an associated spin change of the donor and acceptor, Dexter energy transfer, is critically important in solar energy harvesting assemblies, damage protection schemes of photobiology, and organometallic opto-electronic materials. Dexter transfer between chemically linked donors and acceptors is bridge mediated, presenting an enticing analogy with bridge-mediated electron and hole transfer. However, Dexter coupling pathways must convey both an electron and a hole from donor to acceptor, and this adds considerable richness to the mediation process. We dissect the bridge-mediated Dexter coupling mechanisms and formulate a theory for triplet energy transfer coupling pathways. Virtual donor–acceptor charge-transfer exciton intermediates dominate at shorter distances or higher tunneling energy gaps, whereas virtual intermediates with an electron and a hole both on the bridge (virtual bridge excitons) dominate for longer distances or lower energy gaps. The effects of virtual bridge excitons were neglected in earlier treatments. The two-particle pathway framework developed here shows how Dexter energy-transfer rates depend on donor, bridge, and acceptor energetics, as well as on orbital symmetry and quantum interference among pathways. PMID:27382185

Dexter energy transfer pathways.

PubMed

Skourtis, Spiros S; Liu, Chaoren; Antoniou, Panayiotis; Virshup, Aaron M; Beratan, David N

2016-07-19

Energy transfer with an associated spin change of the donor and acceptor, Dexter energy transfer, is critically important in solar energy harvesting assemblies, damage protection schemes of photobiology, and organometallic opto-electronic materials. Dexter transfer between chemically linked donors and acceptors is bridge mediated, presenting an enticing analogy with bridge-mediated electron and hole transfer. However, Dexter coupling pathways must convey both an electron and a hole from donor to acceptor, and this adds considerable richness to the mediation process. We dissect the bridge-mediated Dexter coupling mechanisms and formulate a theory for triplet energy transfer coupling pathways. Virtual donor-acceptor charge-transfer exciton intermediates dominate at shorter distances or higher tunneling energy gaps, whereas virtual intermediates with an electron and a hole both on the bridge (virtual bridge excitons) dominate for longer distances or lower energy gaps. The effects of virtual bridge excitons were neglected in earlier treatments. The two-particle pathway framework developed here shows how Dexter energy-transfer rates depend on donor, bridge, and acceptor energetics, as well as on orbital symmetry and quantum interference among pathways.

Structure of a low-population binding intermediate in protein-RNA recognition

PubMed Central

Bardaro, Michael F.; Aprile, Francesco A.; Varani, Gabriele; Vendruscolo, Michele

2016-01-01

The interaction of the HIV-1 protein transactivator of transcription (Tat) and its cognate transactivation response element (TAR) RNA transactivates viral transcription and represents a paradigm for the widespread occurrence of conformational rearrangements in protein-RNA recognition. Although the structures of free and bound forms of TAR are well characterized, the conformations of the intermediates in the binding process are still unknown. By determining the free energy landscape of the complex using NMR residual dipolar couplings in replica-averaged metadynamics simulations, we observe two low-population intermediates. We then rationally design two mutants, one in the protein and another in the RNA, that weaken specific nonnative interactions that stabilize one of the intermediates. By using surface plasmon resonance, we show that these mutations lower the release rate of Tat, as predicted. These results identify the structure of an intermediate for RNA-protein binding and illustrate a general strategy to achieve this goal with high resolution. PMID:27286828

Vibrational and rotational transitions in low-energy electron-diatomic-molecule collisions. I - Close-coupling theory in the moving body-fixed frame. II - Hybrid theory and close-coupling theory: An /l subscript z-prime/-conserving close-coupling approximation

NASA Technical Reports Server (NTRS)

Choi, B. H.; Poe, R. T.

1977-01-01

A detailed vibrational-rotational (V-R) close-coupling formulation of electron-diatomic-molecule scattering is developed in which the target molecular axis is chosen to be the z-axis and the resulting coupled differential equation is solved in the moving body-fixed frame throughout the entire interaction region. The coupled differential equation and asymptotic boundary conditions in the body-fixed frame are given for each parity, and procedures are outlined for evaluating V-R transition cross sections on the basis of the body-fixed transition and reactance matrix elements. Conditions are discussed for obtaining identical results from the space-fixed and body-fixed formulations in the case where a finite truncated basis set is used. The hybrid theory of Chandra and Temkin (1976) is then reformulated, relevant expressions and formulas for the simultaneous V-R transitions of the hybrid theory are obtained in the same forms as those of the V-R close-coupling theory, and distorted-wave Born-approximation expressions for the cross sections of the hybrid theory are presented. A close-coupling approximation that conserves the internuclear axis component of the incident electronic angular momentum (l subscript z-prime) is derived from the V-R close-coupling formulation in the moving body-fixed frame.

Reversal bending fatigue testing

DOEpatents

Wang, Jy-An John; Wang, Hong; Tan, Ting

2014-10-21

Embodiments for apparatuses for testing reversal bending fatigue in an elongated beam are disclosed. Embodiments are configured to be coupled to first and second end portions of the beam and to apply a bending moment to the beam and create a pure bending condition in an intermediate portion of the beam. Embodiments are further configured to cyclically alternate the direction of the bending moment applied to the beam such that the intermediate portion of the beam cyclically bends in opposite directions in a pure bending condition.

πN scattering and γN → Nπ photoproduction within the unitary improved Born approximation

NASA Astrophysics Data System (ADS)

Mariano, A.

2007-07-01

Following the programme of describing consistently several processes where the isobar Δ(1232 MeV) nucleon resonance appears as an intermediate state, in this work we propose to unitarize our old improved Born approximation already used to describe successfully π+p elastic and radiative scattering, to treat pion photoproduction. First we add the effect of final state interactions and make a new determination of the mass, width and the coupling constant to the pion-nucleon state of the Δ resonance. Then extending the model for pion photoproduction and using the resonance parameters determined previously, we are able to define effective form factors (at k2γ = 0) for the γN → Δ vertex with values GM = 2.97 ± 0.08 and GE = 0.055 ± 0.010, by fitting the data for the M3/21+ and E3/21+ multipoles. These values are fully consistent with recent chiral effective field theory calculations, and using them we can predict satisfactorily the data for other multipoles and the photoproduction cross section. Finally, we intend a model-independent determination of the bare form factors making a dynamical dressing of the vertex, getting G0M = 1.69 ± 0.02, G0E = 0.028 ± 0.008 and R0EM = -1.67 ± 0.45%, which are compared with different quark models.

The Ketene-Surrogate Coupling: Catalytic Conversion of Aryl Iodides to Aryl Ketenes via Ynol Ethers**

PubMed Central

Zhang, Wenhan; Ready, Joseph M.

2014-01-01

tert-Butoxyacetylene is shown to undergo Sonogashira coupling with aryl iodides to yield aryl-substituted tert-butyl ynol ethers. These intermediates participate in a [1,5]-hydride shift, which results in the extrusion of isobutylene and the generation of aryl ketenes. The ketenes are trapped in situ with multiple nucleophiles or undergoelectrocyclic ring closure to yield hydroxynaphthalenes and quinolines. PMID:24975840

Formulation and application of optimal homotopty asymptotic method to coupled differential-difference equations.

PubMed

Ullah, Hakeem; Islam, Saeed; Khan, Ilyas; Shafie, Sharidan; Fiza, Mehreen

2015-01-01

In this paper we applied a new analytic approximate technique Optimal Homotopy Asymptotic Method (OHAM) for treatment of coupled differential-difference equations (DDEs). To see the efficiency and reliability of the method, we consider Relativistic Toda coupled nonlinear differential-difference equation. It provides us a convenient way to control the convergence of approximate solutions when it is compared with other methods of solution found in the literature. The obtained solutions show that OHAM is effective, simpler, easier and explicit.

Formulation and Application of Optimal Homotopty Asymptotic Method to Coupled Differential - Difference Equations

PubMed Central

Ullah, Hakeem; Islam, Saeed; Khan, Ilyas; Shafie, Sharidan; Fiza, Mehreen

2015-01-01

In this paper we applied a new analytic approximate technique Optimal Homotopy Asymptotic Method (OHAM) for treatment of coupled differential- difference equations (DDEs). To see the efficiency and reliability of the method, we consider Relativistic Toda coupled nonlinear differential-difference equation. It provides us a convenient way to control the convergence of approximate solutions when it is compared with other methods of solution found in the literature. The obtained solutions show that OHAM is effective, simpler, easier and explicit. PMID:25874457

Interpretation of ES, CS, and IOS approximations within a translational--internal coupling scheme. I. Atom--diatom collisions

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

Coombe, D.A.; Snider, R.F.

1979-12-01

Rotational invariance is applied to the description of atom--diatom collisions in a translational--internal coupling scheme, to obtain energy sudden (ES), centrifugal sudden (CS), and infinite order sudden (IOS) approximations to the reduced scattering S matrix S (j-barlambda-bar;L;jlambda). The method of presentation emphasizes that the translational--internal coupling scheme is actually the more natural description of collision processes in which one or more directions are assumed to be conserved.

T sub 1-echo sequence: Protecting the State of a Qubit in the Presence of Coherent Interaction

DTIC Science & Technology

2012-09-25

memory is at energy m, and they are coupled with a coupling strength v⊥. We write the coupling in the rotating - wave approximation , assuming q,m...important for the time evolution. In the validity range of the rotating - wave approximation , the above Hamiltonian preserves the total number of...excited state) in total is involved in the dynamics, the underlying Jaynes - Cummings Hamiltonian will lead to the same results as the ones presented here

Multi-shell spherical GaAs /AlxGa1-x As quantum dot shells-size distribution as a mechanism to generate intermediate band energy levels

NASA Astrophysics Data System (ADS)

Rodríguez-Magdaleno, K. A.; Pérez-Álvarez, R.; Martínez-Orozco, J. C.; Pernas-Salomón, R.

2017-04-01

In this work the generation of an intermediate band of energy levels from multi-shell spherical GaAs /AlxGa1-x As quantum dot shells-size distribution is reported. Within the effective mass approximation the electronic structure of a GaAs spherical quantum-dot surrounded by one, two and three shells is studied in detail using a numerically stable transfer matrix method. We found that a shells-size distribution characterized by continuously wider GaAs domains is a suitable mechanism to generate the intermediate band whose width is also dependent on the Aluminium concentration x. Our results suggest that this effective mechanism can be used for the design of wider intermediate band than reported in other quantum systems with possible solar cells enhanced performance.

Trapping and spectroscopic characterization of an FeIII-superoxo intermediate from a nonheme mononuclear iron-containing enzyme

PubMed Central

Mbughuni, Michael M.; Chakrabarti, Mrinmoy; Hayden, Joshua A.; Bominaar, Emile L.; Hendrich, Michael P.; Münck, Eckard; Lipscomb, John D.

2010-01-01

intermediates are well known in heme enzymes, but none have been characterized in the nonheme mononuclear FeII enzyme family. Many steps in the O2 activation and reaction cycle of FeII-containing homoprotocatechuate 2,3-dioxygenase are made detectable by using the alternative substrate 4-nitrocatechol (4NC) and mutation of the active site His200 to Asn (H200N). Here, the first intermediate (Int-1) observed after adding O2 to the H200N-4NC complex is trapped and characterized using EPR and Mössbauer (MB) spectroscopies. Int-1 is a high-spin (S1 = 5/2) FeIII antiferromagnetically (AF) coupled to an S2 = 1/2 radical (J ≈ 6 cm-1 in ). It exhibits parallel-mode EPR signals at g = 8.17 from the S = 2 multiplet, and g = 8.8 and 11.6 from the S = 3 multiplet. These signals are broadened significantly by hyperfine interactions (A17O ≈ 180 MHz). Thus, Int-1 is an AF-coupled species. The experimental observations are supported by density functional theory calculations that show nearly complete transfer of spin density to the bound O2. Int-1 decays to form a second intermediate (Int-2). MB spectra show that it is also an AF-coupled FeIII-radical complex. Int-2 exhibits an EPR signal at g = 8.05 arising from an S = 2 state. The signal is only slightly broadened by (< 3% spin delocalization), suggesting that Int-2 is a peroxo-FeIII-4NC semiquinone radical species. Our results demonstrate facile electron transfer between FeII, O2, and the organic ligand, thereby supporting the proposed wild-type enzyme mechanism. PMID:20837547

pH-Dependent Singlet O2 Oxidation Kinetics of Guanine and 9-Methylguanine: An Online Mass Spectrometry and Spectroscopy Study Combined with Theoretical Exploration.

PubMed

Lu, Wenchao; Sun, Yan; Zhou, Wenjing; Liu, Jianbo

2018-01-11

We report a kinetic and mechanistic study on the title reactions, in which 1 O 2 was generated by the reaction of H 2 O 2 with Cl 2 and bubbled into an aqueous solution of guanine and 9-methylguanine (9MG) at different pH values. Oxidation kinetics and product branching ratios were measured using online electrospray ionization mass spectrometry coupled with absorption and emission spectrophotometry, and product structures were determined by collision-induced dissociation (CID) tandem mass spectrometry. Experiments revealed strong pH dependence of the reactions. The oxidation of guanine is noticeable only in basic solution, while the oxidation of 9MG is weak in acidic solution, increases in neutral solution, and becomes intensive in basic solution. 5-Guanidinohydantoin (Gh) and spiroiminodihydantoin (Sp) were detected as the major oxidation products of guanine and 9MG, and Sp became dominant in basic solution. A reaction intermediate was captured in mass spectra, and assigned to gem-diol on the basis of CID measurements. This intermediate served as the precursor for the formation of Gh. After taking into account solution compositions at each pH, first-order oxidation rate constants were extracted for individual species: that is, 3.2-3.6 × 10 7 M -1 s -1 for deprotonated guanine, and 1.2 × 10 6 and 4.6-4.9 × 10 7 M -1 s -1 for neutral and deprotonated 9MG, respectively. Guided by approximately spin-projected density-functional-theory-calculated reaction potential energy surfaces, the kinetics for the initial 1 O 2 addition to guanine and 9MG was evaluated using transition state theory (TST). The comparison between TST modeling and experiment confirms that 1 O 2 addition is rate-limiting for oxidation, which forms endoperoxide and peroxide intermediates as determined in previous measurements of the same systems in the gas phase.

The second national audit of intermediate care.

PubMed

Young, John; Gladman, John R F; Forsyth, Duncan R; Holditch, Claire

2015-03-01

Intermediate care services have developed internationally to expedite discharge from hospital and to provide an alternative to an emergency hospital admission. Inconsistencies in the evidence base and under-developed governance structures led to concerns about the care quality, outcomes and provision of intermediate care in the NHS. The National Audit of Intermediate Care was therefore established by an interdisciplinary group. The second national audit reported in 2013 and included crisis response teams, home-based and bed-based services in approximately a half of the NHS. The main findings were evidence of weak local strategic planning, considerable under-provision, delays in accessing the services and lack of mental health involvement in care. There was a very high level of positive patient experience reported across all types of intermediate care, though reported involvement with care decisions was less satisfactory. © The Author 2014. Published by Oxford University Press on behalf of the British Geriatrics Society. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Direct production of OH radicals upon CH overtone activation of (CH{sub 3}){sub 2}COO Criegee intermediates

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

Liu, Fang; Beames, Joseph M.; Lester, Marsha I., E-mail: milester@sas.upenn.edu

2014-12-21

Ozonolysis of alkenes, a principle non-photolytic source of atmospheric OH radicals, proceeds through unimolecular decay of energized carbonyl oxide intermediates, known as Criegee intermediates. In this work, cold dimethyl-substituted Criegee intermediates are vibrationally activated in the CH stretch overtone region to drive the 1,4 hydrogen transfer reaction that leads to OH radical products. IR excitation of (CH{sub 3}){sub 2}COO reveals the vibrational states with sufficient oscillator strength, coupling to the reaction coordinate, and energy to surmount the effective barrier (≤ 16.0 kcal mol{sup −1}) to reaction. Insight on the dissociation dynamics is gleaned from homogeneous broadening of the spectral features,more » indicative of rapid intramolecular vibrational energy redistribution and/or reaction, as well as the quantum state distribution of the OH X{sup 2}Π (v = 0) products. The experimental results are compared with complementary electronic structure calculations, which provide the IR absorption spectrum and geometric changes along the intrinsic reaction coordinate. Additional theoretical analysis reveals the vibrational modes and couplings that permit (CH{sub 3}){sub 2}COO to access to the transition state region for reaction. The experimental and theoretical results are compared with an analogous recent study of the IR activation of syn-CH{sub 3}CHOO and its unimolecular decay to OH products [F. Liu, J. M. Beames, A. S. Petit, A. B. McCoy, and M. I. Lester, Science 345, 1596 (2014)].« less

Rhodium-Catalyzed Dehydrogenative Borylation of Cyclic Alkenes

PubMed Central

Kondoh, Azusa; Jamison, Timothy F.

2010-01-01

A rhodium-catalyzed dehydrogenative borylation of cyclic alkenes is described. This reaction provides direct access to cyclic 1-alkenylboronic acid pinacol esters, useful intermediates in organic synthesis. Suzuki-Miyaura cross-coupling applications are also presented. PMID:20107646

Low-loss and energy efficient modulation in silicon photonic waveguides by adiabatic elimination scheme

NASA Astrophysics Data System (ADS)

Mrejen, Michael; Suchowski, Haim; Bachelard, Nicolas; Wang, Yuan; Zhang, Xiang

2017-07-01

High-speed Silicon Photonics calls for solutions providing a small footprint, high density, and minimum crosstalk, as exemplified by the recent development of integrated optical modulators. Yet, the performances of such modulators are hindered by intrinsic material losses, which results in low energy efficiency. Using the concept of Adiabatic Elimination, here, we introduce a scheme allowing for the low-loss modulation in densely packed waveguides. Our system is composed of two waveguides, whose coupling is mediated by an intermediate third waveguide. The signal is carried by the two outer modes, while the active control of their coupling is achieved via the intermediate dark mode. The modulation is performed by the manipulation of the central-waveguide mode index, leaving the signal-carrying waveguides unaffected by the loss. We discuss how Adiabatic Elimination provides a solution for mitigating signal losses and designing relatively compact, broadband, and energy-efficient integrated optical modulators.

Energetics of a uranothorite (Th 1–xU xSiO 4) solid solution

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

Guo, Xiaofeng; Szenknect, Stephanie; Mesbah, Adel

High-temperature oxide melt solution calorimetric measurements were completed to determine the enthalpies of formation of the uranothorite, (USiO 4) x–(ThSiO 4) 1–x, solid solution. Phase-pure samples with x values of 0, 0.11, 0.21, 0.35, 0.71, and 0.84 were prepared, purified, and characterized by powder X-ray diffraction, electron probe microanalysis, thermogravimetric analysis and differential scanning calorimetry coupled with in situ mass spectrometry, and high-temperature oxide melt solution calorimetry. This work confirms the energetic metastability of coffinite, USiO 4, and U-rich intermediate silicate phases with respect to a mixture of binary oxides. Furthermore, variations in unit cell parameters and negative excess volumesmore » of mixing, coupled with strongly exothermic enthalpies of mixing in the solid solution, suggest short-range cation ordering that can stabilize intermediate compositions, especially near x = 0.5.« less

Energetics of a uranothorite (Th 1–xU xSiO 4) solid solution

DOE PAGES

Guo, Xiaofeng; Szenknect, Stephanie; Mesbah, Adel; ...

2016-10-11

High-temperature oxide melt solution calorimetric measurements were completed to determine the enthalpies of formation of the uranothorite, (USiO 4) x–(ThSiO 4) 1–x, solid solution. Phase-pure samples with x values of 0, 0.11, 0.21, 0.35, 0.71, and 0.84 were prepared, purified, and characterized by powder X-ray diffraction, electron probe microanalysis, thermogravimetric analysis and differential scanning calorimetry coupled with in situ mass spectrometry, and high-temperature oxide melt solution calorimetry. This work confirms the energetic metastability of coffinite, USiO 4, and U-rich intermediate silicate phases with respect to a mixture of binary oxides. Furthermore, variations in unit cell parameters and negative excess volumesmore » of mixing, coupled with strongly exothermic enthalpies of mixing in the solid solution, suggest short-range cation ordering that can stabilize intermediate compositions, especially near x = 0.5.« less

Studies of regional-scale climate variability and change. Hidden Markov models and coupled ocean-atmosphere modes

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

Ghil, M.; Kravtsov, S.; Robertson, A. W.

2008-10-14

This project was a continuation of previous work under DOE CCPP funding, in which we had developed a twin approach of probabilistic network (PN) models (sometimes called dynamic Bayesian networks) and intermediate-complexity coupled ocean-atmosphere models (ICMs) to identify the predictable modes of climate variability and to investigate their impacts on the regional scale. We had developed a family of PNs (similar to Hidden Markov Models) to simulate historical records of daily rainfall, and used them to downscale GCM seasonal predictions. Using an idealized atmospheric model, we had established a novel mechanism through which ocean-induced sea-surface temperature (SST) anomalies might influencemore » large-scale atmospheric circulation patterns on interannual and longer time scales; we had found similar patterns in a hybrid coupled ocean-atmosphere-sea-ice model. The goal of the this continuation project was to build on these ICM results and PN model development to address prediction of rainfall and temperature statistics at the local scale, associated with global climate variability and change, and to investigate the impact of the latter on coupled ocean-atmosphere modes. Our main results from the grant consist of extensive further development of the hidden Markov models for rainfall simulation and downscaling together with the development of associated software; new intermediate coupled models; a new methodology of inverse modeling for linking ICMs with observations and GCM results; and, observational studies of decadal and multi-decadal natural climate results, informed by ICM results.« less

Energetic Coupling between Ligand Binding and Dimerization in E. coli Phosphoglycerate Mutase

PubMed Central

Gardner, Nathan W.; Monroe, Lyman K.; Kihara, Daisuke; Park, Chiwook

2016-01-01

Energetic coupling of two molecular events in a protein molecule is ubiquitous in biochemical reactions mediated by proteins, such as catalysis and signal transduction. Here, we investigate energetic coupling between ligand binding and folding of a dimer using a model system that shows three-state equilibrium unfolding in an exceptional quality. The homodimeric E. coli cofactor-dependent phosphoglycerate mutase (dPGM) was found to be stabilized by ATP in a proteome-wide screen, although dPGM does not require or utilize ATP for enzymatic function. We investigated the effect of ATP on the thermodynamic stability of dPGM using equilibrium unfolding. In the absence of ATP, dPGM populates a partially unfolded, monomeric intermediate during equilibrium unfolding. However, addition of 1.0 mM ATP drastically reduces the population of the intermediate by selectively stabilizing the native dimer. Using a computational ligand docking method, we predicted ATP binds to the active site of the enzyme using the triphosphate group. By performing equilibrium unfolding and isothermal titration calorimetry with active-site variants of dPGM, we confirmed that active-site residues are involved in ATP binding. Our findings show that ATP promotes dimerization of the protein by binding to the active site, which is distal from the dimer interface. This cooperativity suggests an energetic coupling between the active-site and the dimer interface. We also propose a structural link to explain how ligand binding to the active site is energetically coupled with dimerization. PMID:26919584

Upper bound on the Abelian gauge coupling from asymptotic safety

NASA Astrophysics Data System (ADS)

Eichhorn, Astrid; Versteegen, Fleur

2018-01-01

We explore the impact of asymptotically safe quantum gravity on the Abelian gauge coupling in a model including a charged scalar, confirming indications that asymptotically safe quantum fluctuations of gravity could trigger a power-law running towards a free fixed point for the gauge coupling above the Planck scale. Simultaneously, quantum gravity fluctuations balance against matter fluctuations to generate an interacting fixed point, which acts as a boundary of the basin of attraction of the free fixed point. This enforces an upper bound on the infrared value of the Abelian gauge coupling. In the regime of gravity couplings which in our approximation also allows for a prediction of the top quark and Higgs mass close to the experimental value [1], we obtain an upper bound approximately 35% above the infrared value of the hypercharge coupling in the Standard Model.

Direct Determinations of the πNN Coupling Constants

NASA Astrophysics Data System (ADS)

Ericson, T. E. O.; Loiseau, B.

1998-11-01

A novel extrapolation method has been used to deduce directly the charged πN N coupling constant from backward np differential scattering cross sections. The extracted value, g2c = 14.52(0.26) is higher than the indirectly deduced values obtained in nucleon-nucleon energy-dependent partial-wave analyses. Our preliminary direct value from a reanalysis of the GMO sum-rule points to an intermediate value of g2c about 13.97(30).

VizieR Online Data Catalog: Atomic Data from the Iron Project LXVI. Fe18+ (Butler+,

NASA Astrophysics Data System (ADS)

Butler, K.; Badnell, N. R.

2008-07-01

Accurate electron collisional data are required for the analysis of the Fe XIX astrophysical spectrum, in particular in the Sun. Such an analysis can provide information on the physical characteristics of the coronal plasma. An extensive target is used in an R-matrix scattering calculation to provide the necessary data for Fe18+. The use of the R-matrix method includes the resonance contribution lacking in the distorted wave approach and the large target improves the accuracy of the close-coupling approximation. The R-Matrix package described by Berrington et al. (1995) as provided by the UK RmaX project has been used to calculate electron collisional data among 342 levels of Fe18+. We have used the intermediate-coupling frame-transformation (ICFT) method (Griffin et al., 1998) to transform data obtained in a 166 term LS-coupling calculation. Contributions from the mass and Darwin interactions have also been included in the Hamiltonian. Collision strengths for all transitions between the 342 levels of Fe18+ are presented. They are tabulated over a wide range of electron temperatures of astrophysical interest. The results are compared with the earlier Iron Project work of Butler & Zeippen (2001, Cat. ) and also with that of McLaughlin et al. (2001MNRAS.328..442M) and Landi & Gu (2006ApJ...640.1171L). The agreement is reasonable for the low-lying transitions. Larger differences are found for the more highly excited states. The file structure is described in detail in http://www.adas.ac.uk/man/appxa-04.pdf A sample program to extract a single upsilon is provided. (3 data files).

Intermediate Models of Planetary Circulations in the Atmosphere and Ocean.

NASA Astrophysics Data System (ADS)

McWilliams, James C.; Gent, Peter R.

1980-08-01

Large-scale extratropical motions (with dimensions comparable to, or somewhat smaller than, the planetary radius) in the atmosphere and ocean exhibit a more restricted range of phenomena than are admissible in the primitive equations for fluid motions, and there have been many previous proposals for simpler, more phenomenologically limited models of these motions. The oldest and most successful of these is the quasi-geostrophic model. An extensive discussion is made of models intermediate between the quasi-geostrophic and primitive ones, some of which have been previously proposed [e.g., the balance equations (BE), where tendencies in the equation for the divergent component of velocity are neglected, or the geostrophic momentum approximation (GM), where ageostrophic accelerations are neglected relative to geostrophic ones] and some of which are derived here. Virtues of these models are assessed in the dual measure of nearly geostrophic momentum balance (i.e., small Rossby number) and approximate frontal structure (i.e., larger along-axis velocities and length scales than their cross-axis counterparts), since one or both of these circumstances is usually characteristic of planetary motions. Consideration is also given to various coordinate transformations, since they can yield simpler expressions for the governing differential equations of the intermediate models. In particular, a new set of coordinates is proposed, isentropic geostrophic coordinates,(IGC), which has the advantage of making implicit the advections due to ageostrophic horizontal and vertical velocities under various approximations. A generalization of quasi-geostrophy is made. named hypo-geostrophy (HG), which is an asymptotic approximation of one higher order accuracy in Rossby number. The governing equations are simplest in IGC for both HG and GM; we name the latter in these coordinates isentropic semi-geostrophy (ISG), in analogy to Hoskins' (1975) semi-geostrophy (SG). HG, GM and BE are, in our opinion, the three most valuable intermediate models for future consideration. HG and BE are superior to GM asymptotically in small Rossby number, but HG in IGC and GM are superior to HG in other coordinates and BE in frontal asymptotics. GM has global (not asymptotic) integral invariants of energy and enstrophy, which HG lacks, and this may assure physically better solutions in weakly asymptotic situations. BE has one global (energy) and one asymptotic (enstrophy) invariant. BE has difficulties of solution existence and uniqueness. Further progress in the search for intermediate models requires obtaining an extensive set of solutions for these models for comparison with quasi-geostrophic and primitive equation solutions.

Coupled-cavity drift-tube linac

DOEpatents

Billen, James H.

1996-01-01

A coupled-cavity drift-tube linac (CCDTL) combines features of the Alvarez drift-tube linac (DTL) and the .pi.-mode coupled-cavity linac (CCL). In one embodiment, each accelerating cavity is a two-cell, 0-mode DTL. The center-to-center distance between accelerating gaps is .beta..lambda., where .lambda. is the free-space wavelength of the resonant mode. Adjacent accelerating cavities have oppositely directed electric fields, alternating in phase by 180 degrees. The chain of cavities operates in a .pi./2 structure mode so the coupling cavities are nominally unexcited. The CCDTL configuration provides an rf structure with high shunt impedance for intermediate velocity charged particles, i.e., particles with energies in the 20-200 MeV range.

Coupled-cavity drift-tube linac

DOEpatents

Billen, J.H.

1996-11-26

A coupled-cavity drift-tube linac (CCDTL) combines features of the Alvarez drift-tube linac (DTL) and the {pi}-mode coupled-cavity linac (CCL). In one embodiment, each accelerating cavity is a two-cell, 0-mode DTL. The center-to-center distance between accelerating gaps is {beta}{lambda}, where {lambda} is the free-space wavelength of the resonant mode. Adjacent accelerating cavities have oppositely directed electric fields, alternating in phase by 180 degrees. The chain of cavities operates in a {pi}/2 structure mode so the coupling cavities are nominally unexcited. The CCDTL configuration provides an rf structure with high shunt impedance for intermediate velocity charged particles, i.e., particles with energies in the 20-200 MeV range. 5 figs.

A variationally coupled FE-BE method for elasticity and fracture mechanics

NASA Technical Reports Server (NTRS)

Lu, Y. Y.; Belytschko, T.; Liu, W. K.

1991-01-01

A new method for coupling finite element and boundary element subdomains in elasticity and fracture mechanics problems is described. The essential feature of this new method is that a single variational statement is obtained for the entire domain, and in this process the terms associated with tractions on the interfaces between the subdomains are eliminated. This provides the additional advantage that the ambiguities associated with the matching of discontinuous tractions are circumvented. The method leads to a direct procedure for obtaining the discrete equations for the coupled problem without any intermediate steps. In order to evaluate this method and compare it with previous methods, a patch test for coupled procedures has been devised. Evaluation of this variationally coupled method and other methods, such as stiffness coupling and constraint traction matching coupling, shows that this method is substantially superior. Solutions for a series of fracture mechanics problems are also reported to illustrate the effectiveness of this method.

Non-equilibrium dynamics of artificial quantum matter

NASA Astrophysics Data System (ADS)

Babadi, Mehrtash

The rapid progress of the field of ultracold atoms during the past two decades has set new milestones in our control over matter. By cooling dilute atomic gases and molecules to nano-Kelvin temperatures, novel quantum mechanical states of matter can be realized and studied on a table-top experimental setup while bulk matter can be tailored to faithfully simulate abstract theoretical models. Two of such models which have witnessed significant experimental and theoretical attention are (1) the two-component Fermi gas with resonant s-wave interactions, and (2) the single-component Fermi gas with dipole-dipole interactions. This thesis is devoted to studying the non-equilibrium collective dynamics of these systems using the general framework of quantum kinetic theory. We present a concise review of the utilized mathematical methods in the first two chapters, including the Schwinger-Keldysh formalism of non-equilibrium quantum fields, two-particle irreducible (2PI) effective actions and the framework of quantum kinetic theory. We study the collective dynamics of the dipolar Fermi gas in a quasi-two-dimensional optical trap in chapter 3 and provide a detailed account of its dynamical crossover from the collisionless to the hydrodynamical regime. Chapter 4 is devoted to studying the dynamics of the attractive Fermi gas in the normal phase. Starting from the self-consistent T-matrix (pairing fluctuation) approximation, we systematically derive a set of quantum kinetic equations and show that they provide a globally valid description of the dynamics of the attractive Fermi gas, ranging from the weak-coupling Fermi liquid phase to the intermediate non-Fermi liquid pairing pseudogap regime and finally the strong-coupling Bose liquid phase. The shortcomings of the self-consistent T-matrix approximation in two spatial dimensions are discussed along with a proposal to overcome its unphysical behaviors. The developed kinetic formalism is finally utilized to reproduce and interpret the findings of a recent experiment done on the collective dynamics of trapped two-dimensional ultracold gases.

Experimental study of vorticity-strain rate interaction in turbulent partially-premixed jet flames using tomographic particle image velocimetry

DOE PAGES

Coriton, Bruno; Frank, Jonathan H.

2016-02-16

In turbulent flows, the interaction between vorticity, ω, and strain rate, s, is considered a primary mechanism for the transfer of energy from large to small scales through vortex stretching. The ω-s coupling in turbulent jet flames is investigated using tomographic particle image velocimetry (TPIV). TPIV provides a direct measurement of the three-dimensional velocity field from which ω and s are determined. The effects of combustion and mean shear on the ω-s interaction are investigated in turbulent partially premixed methane/air jet flames with high and low probabilities of localized extinction as well as in a non-reacting isothermal air jet withmore » Reynolds number of approximately 13,000. Results show that combustion causes structures of high vorticity and strain rate to agglomerate in highly correlated, elongated layers that span the height of the probe volume. In the non-reacting jet, these structures have a more varied morphology, greater fragmentation, and are not as well correlated. The enhanced spatiotemporal correlation of vorticity and strain rate in the stable flame results in stronger ω-s interaction characterized by increased enstrophy and strain-rate production rates via vortex stretching and straining, respectively. The probability of preferential local alignment between ω and the eigenvector of the intermediate principal strain rate, s 2, which is intrinsic to the ω-s coupling in turbulent flows, is larger in the flames and increases with the flame stability. The larger mean shear in the flame imposes a preferential orientation of ω and s 2 tangential to the shear layer. The extensive and compressive principal strain rates, s 1 and s 3, respectively, are preferentially oriented at approximately 45° with respect to the jet axis. As a result, the production rates of strain and vorticity tend to be dominated by instances in which ω is parallel to the s 1¯-s 2¯ plane and orthogonal to s 3¯.« less

On the effects of ENSO on ocean biogeochemistry in the Northern Humboldt Current System (NHCS): A modeling study

NASA Astrophysics Data System (ADS)

Mogollón, Rodrigo; Calil, Paulo H. R.

2017-08-01

The response of the ocean biogeochemistry to intense El Niño Southern Oscillation (ENSO) events in the Northern Humboldt Current System (NHCS) is assessed with an eddy-resolving coupled physical-biogeochemical model. El Niño (EN) 1997-1998 and La Niña (LN) 1999-2000 are well reproduced, inducing large spatial and temporal variability of biogeochemical properties at three coastal upwelling centers along the Peruvian coast (Chimbote 9.4°S, Callao 12.1°S, and Pisco 14°S). During EN, the upper limit of the Oxygen Minimum Zone (OMZ) experiences an offshore displacement of, approximately, 60 km and a deepening of, approximately, 150 m when compared to neutral-ENSO conditions, thus ventilating the upper 100 m of the water column. In contrast, during LN, the OMZ tongue outcrops over the continental shelf deoxygenating the water column at all locations. During LN, at the southernmost location, enhanced Eddy Kinetic Energy (EKE) induces a leaking of the coastal nutrient inventory by horizontally advecting nitrogen from the nearshore region into the oligotrophic ocean. This leads to a reduction of biological production in the coastal zone. During EN, nitrification is an order of magnitude larger than denitrification in supplying the nitrite coastal pool. During LN peak, nitrification is reduced by 80%, while denitrification becomes equally important, evidencing a coupling between these two oxygen-dependent processes. The nitrogen removal due to suboxic activity is mostly controlled by the Anaerobic Ammonium Oxidation (Anammox) in the southern domain during neutral-ENSO conditions. Our results show that during EN, denitrification contributes with 60% of the total nitrogen removal. In contrast, Anammox contributes with 70% during LN. The outgassing of nitrous oxide (N2O), an intermediate product of denitrification, is reduced and enhanced during EN and LN, respectively, and it is strongly modulated by the spatiotemporal variability of oxygen in the environment.

Coupled electron-ion Monte Carlo simulation of hydrogen molecular crystals

NASA Astrophysics Data System (ADS)

Rillo, Giovanni; Morales, Miguel A.; Ceperley, David M.; Pierleoni, Carlo

2018-03-01

We performed simulations for solid molecular hydrogen at high pressures (250 GPa ≤ P ≤ 500 GPa) along two isotherms at T = 200 K (phase III) and at T = 414 K (phase IV). At T = 200 K, we considered likely candidates for phase III, the C2c and Cmca12 structures, while at T = 414 K in phase IV, we studied the Pc48 structure. We employed both Coupled Electron-Ion Monte Carlo (CEIMC) and Path Integral Molecular Dynamics (PIMD). The latter is based on Density Functional Theory (DFT) with the van der Waals approximation (vdW-DF). The comparison between the two methods allows us to address the question of the accuracy of the exchange-correlation approximation of DFT for thermal and quantum protons without recurring to perturbation theories. In general, we find that atomic and molecular fluctuations in PIMD are larger than in CEIMC which suggests that the potential energy surface from vdW-DF is less structured than the one from quantum Monte Carlo. We find qualitatively different behaviors for systems prepared in the C2c structure for increasing pressure. Within PIMD, the C2c structure is dynamically partially stable for P ≤ 250 GPa only: it retains the symmetry of the molecular centers but not the molecular orientation; at intermediate pressures, it develops layered structures like Pbcn or Ibam and transforms to the metallic Cmca-4 structure at P ≥ 450 GPa. Instead, within CEIMC, the C2c structure is found to be dynamically stable at least up to 450 GPa; at increasing pressure, the molecular bond length increases and the nuclear correlation decreases. For the other two structures, the two methods are in qualitative agreement although quantitative differences remain. We discuss various structural properties and the electrical conductivity. We find that these structures become conducting around 350 GPa but the metallic Drude-like behavior is reached only at around 500 GPa, consistent with recent experimental claims.

Tachyon warm-intermediate inflationary universe model in high dissipative regime

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

Setare, M.R.; Kamali, V., E-mail: rezakord@ipm.ir, E-mail: vkamali1362@gmail.com

2012-08-01

We consider tachyonic warm-inflationary models in the context of intermediate inflation. We derive the characteristics of this model in slow-roll approximation and develop our model in two cases, 1- For a constant dissipative parameter Γ. 2- Γ as a function of tachyon field φ. We also describe scalar and tensor perturbations for this scenario. The parameters appearing in our model are constrained by recent observational data. We find that the level of non-Gaussianity for this model is comparable with non-tachyonic model.

Direct catalytic cross-coupling of organolithium compounds

NASA Astrophysics Data System (ADS)

Giannerini, Massimo; Fañanás-Mastral, Martín; Feringa, Ben L.

2013-08-01

Catalytic carbon-carbon bond formation based on cross-coupling reactions plays a central role in the production of natural products, pharmaceuticals, agrochemicals and organic materials. Coupling reactions of a variety of organometallic reagents and organic halides have changed the face of modern synthetic chemistry. However, the high reactivity and poor selectivity of common organolithium reagents have largely prohibited their use as a viable partner in direct catalytic cross-coupling. Here we report that in the presence of a Pd-phosphine catalyst, a wide range of alkyl-, aryl- and heteroaryl-lithium reagents undergo selective cross-coupling with aryl- and alkenyl-bromides. The process proceeds quickly under mild conditions (room temperature) and avoids the notorious lithium halogen exchange and homocoupling. The preparation of key alkyl-, aryl- and heterobiaryl intermediates reported here highlights the potential of these cross-coupling reactions for medicinal chemistry and material science.

Diels-Alder and Stille Coupling Approach for the Short Protecting-Group-Free Synthesis of Mycophenolic Acid, Its Phenylsulfenyl and Phenylselenyl Analogues, and Reactive Oxygen Species (ROS) Probing Capacity in Water.

PubMed

Halle, Mahesh B; Yudhistira, Tesla; Lee, Woo-Hyun; Mulay, Sandip V; Churchill, David G

2018-06-15

A short, protecting-group-free synthesis is achieved. The synthesis is step-efficient and general. A Diels-Alder and Stille cross-coupling approach includes key transformations, allowing for a competitive synthesis which involves a rare halophenol Stille cross-coupling study. The phenylselenyl and phenylsulfenyl analogues were prepared as novel compounds in good overall yield. The applicability of one of the intermediates as a potential probe for reactive oxygen species (ROS) in water is investigated.

Ginzburg-Landau theory, strong coupling corrections and exchange enhancements: Can spin fluctuations give high T c's?

NASA Astrophysics Data System (ADS)

Quader, Khandker F.; Salamon, M. B.

1988-06-01

Ginzburg-Landau theory is used to explore the thermodynamic and electrodynamic properties of YBa 2Cu 3O 7-δ, and to determine γ, m ∗/m and the exchange enhancement. This material is found to be in a moderately strong coupling regime, intermediate between dirty and clean limits; strong coupling corrections are estimated. It is shown that, irrespective of the choice of the carrier density, spin fluctuations are unable to give a sufficiently large T c. An upper bound is given for the T c due spin-fluctuation-mediated pairing.

Copper-Catalyzed Cyclopropanol Ring Opening Csp(3)-Csp(3) Cross-Couplings with (Fluoro)Alkyl Halides.

PubMed

Ye, Zhishi; Gettys, Kristen E; Shen, Xingyu; Dai, Mingji

2015-12-18

Novel and general copper-catalyzed cyclopropanol ring opening cross-coupling reactions with difluoroalkyl bromides, perfluoroalkyl iodides, monofluoroalkyl bromides, and 2-bromo-2-alkylesters to synthesize various β-(fluoro)alkylated ketones are reported. The reactions feature mild conditions and excellent functional group compatibility and can be scaled up to gram scale. Preliminary mechanistic studies suggest the involvement of radical intermediates. The difluoroalkyl-alkyl cross-coupling products can also be readily converted to more valuable and diverse gem-difluoro-containing compounds by taking advantage of the carbonyl group resulting from cyclopropanol ring opening.

The contribution of NOAA/CMDL ground-based measurements to understanding long-term stratospheric changes

NASA Astrophysics Data System (ADS)

Montzka, S. A.; Butler, J. H.; Dutton, G.; Thompson, T. M.; Hall, B.; Mondeel, D. J.; Elkins, J. W.

2005-05-01

The El-Nino/Southern-Oscillation (ENSO) dominates interannual climate variability and plays, therefore, a key role in seasonal-to-interannual prediction. Much is known by now about the main physical mechanisms that give rise to and modulate ENSO, but the values of several parameters that enter these mechanisms are an important unknown. We apply Extended Kalman Filtering (EKF) for both model state and parameter estimation in an intermediate, nonlinear, coupled ocean--atmosphere model of ENSO. The coupled model consists of an upper-ocean, reduced-gravity model of the Tropical Pacific and a steady-state atmospheric response to the sea surface temperature (SST). The model errors are assumed to be mainly in the atmospheric wind stress, and assimilated data are equatorial Pacific SSTs. Model behavior is very sensitive to two key parameters: (i) μ, the ocean-atmosphere coupling coefficient between SST and wind stress anomalies; and (ii) δs, the surface-layer coefficient. Previous work has shown that δs determines the period of the model's self-sustained oscillation, while μ measures the degree of nonlinearity. Depending on the values of these parameters, the spatio-temporal pattern of model solutions is either that of a delayed oscillator or of a westward propagating mode. Estimation of these parameters is tested first on synthetic data and allows us to recover the delayed-oscillator mode starting from model parameter values that correspond to the westward-propagating case. Assimilation of SST data from the NCEP-NCAR Reanalysis-2 shows that the parameters can vary on fairly short time scales and switch between values that approximate the two distinct modes of ENSO behavior. Rapid adjustments of these parameters occur, in particular, during strong ENSO events. Ways to apply EKF parameter estimation efficiently to state-of-the-art coupled ocean--atmosphere GCMs will be discussed.

Consistent nonlinear deterministic and stochastic evolution equations for deep to shallow water wave shoaling

NASA Astrophysics Data System (ADS)

Vrecica, Teodor; Toledo, Yaron

2015-04-01

One-dimensional deterministic and stochastic evolution equations are derived for the dispersive nonlinear waves while taking dissipation of energy into account. The deterministic nonlinear evolution equations are formulated using operational calculus by following the approach of Bredmose et al. (2005). Their formulation is extended to include the linear and nonlinear effects of wave dissipation due to friction and breaking. The resulting equation set describes the linear evolution of the velocity potential for each wave harmonic coupled by quadratic nonlinear terms. These terms describe the nonlinear interactions between triads of waves, which represent the leading-order nonlinear effects in the near-shore region. The equations are translated to the amplitudes of the surface elevation by using the approach of Agnon and Sheremet (1997) with the correction of Eldeberky and Madsen (1999). The only current possibility for calculating the surface gravity wave field over large domains is by using stochastic wave evolution models. Hence, the above deterministic model is formulated as a stochastic one using the method of Agnon and Sheremet (1997) with two types of stochastic closure relations (Benney and Saffman's, 1966, and Hollway's, 1980). These formulations cannot be applied to the common wave forecasting models without further manipulation, as they include a non-local wave shoaling coefficients (i.e., ones that require integration along the wave rays). Therefore, a localization method was applied (see Stiassnie and Drimer, 2006, and Toledo and Agnon, 2012). This process essentially extracts the local terms that constitute the mean nonlinear energy transfer while discarding the remaining oscillatory terms, which transfer energy back and forth. One of the main findings of this work is the understanding that the approximated non-local coefficients behave in two essentially different manners. In intermediate water depths these coefficients indeed consist of rapidly oscillating terms, but as the water depth becomes shallow they change to an exponential growth (or decay) behavior. Hence, the formerly used localization technique cannot be justified for the shallow water region. A new formulation is devised for the localization in shallow water, it approximates the nonlinear non-local shoaling coefficient in shallow water and matches it to the one fitting to the intermediate water region. This allows the model behavior to be consistent from deep water to intermediate depths and up to the shallow water regime. Various simulations of the model were performed for the cases of intermediate, and shallow water, overall the model was found to give good results in both shallow and intermediate water depths. The essential difference between the shallow and intermediate nonlinear shoaling physics is explained via the dominating class III Bragg resonances phenomenon. By inspecting the resonance conditions and the nature of the dispersion relation, it is shown that unlike in the intermediate water regime, in shallow water depths the formation of resonant interactions is possible without taking into account bottom components. References Agnon, Y. & Sheremet, A. 1997 Stochastic nonlinear shoaling of directional spectra. J. Fluid Mech. 345, 79-99. Benney, D. J. & Saffman, P. G. 1966 Nonlinear interactions of random waves. Proc. R. Soc. Lond. A 289, 301-321. Bredmose, H., Agnon, Y., Madsen, P.A. & Schaffer, H.A. 2005 Wave transformation models with exact second-order transfer. European J. of Mech. - B/Fluids 24 (6), 659-682. Eldeberky, Y. & Madsen, P. A. 1999 Deterministic and stochastic evolution equations for fully dispersive and weakly nonlinear waves. Coastal Engineering 38, 1-24. Kaihatu, J. M. & Kirby, J. T. 1995 Nonlinear transformation of waves in infinite water depth. Phys. Fluids 8, 175-188. Holloway, G. 1980 Oceanic internal waves are not weak waves. J. Phys. Oceanogr. 10, 906-914. Stiassnie, M. & Drimer, N. 2006 Prediction of long forcing waves for harbor agitation studies. J. of waterways, port, coastal and ocean engineering 132(3), 166-171. Toledo, Y. & Agnon, Y. 2012 Stochastic evolution equations with localized nonlinear shoaling coefficients. European J. of Mech. - B/Fluids 34, 13-18.

Short- and long-time diffusion and dynamic scaling in suspensions of charged colloidal particles

NASA Astrophysics Data System (ADS)

Banchio, Adolfo J.; Heinen, Marco; Holmqvist, Peter; Nägele, Gerhard

2018-04-01

We report on a comprehensive theory-simulation-experimental study of collective and self-diffusion in concentrated suspensions of charge-stabilized colloidal spheres. In theory and simulation, the spheres are assumed to interact directly by a hard-core plus screened Coulomb effective pair potential. The intermediate scattering function, fc(q, t), is calculated by elaborate accelerated Stokesian dynamics (ASD) simulations for Brownian systems where many-particle hydrodynamic interactions (HIs) are fully accounted for, using a novel extrapolation scheme to a macroscopically large system size valid for all correlation times. The study spans the correlation time range from the colloidal short-time to the long-time regime. Additionally, Brownian Dynamics (BD) simulation and mode-coupling theory (MCT) results of fc(q, t) are generated where HIs are neglected. Using these results, the influence of HIs on collective and self-diffusion and the accuracy of the MCT method are quantified. It is shown that HIs enhance collective and self-diffusion at intermediate and long times. At short times self-diffusion, and for wavenumbers outside the structure factor peak region also collective diffusion, are slowed down by HIs. MCT significantly overestimates the slowing influence of dynamic particle caging. The dynamic scattering functions obtained in the ASD simulations are in overall good agreement with our dynamic light scattering (DLS) results for a concentration series of charged silica spheres in an organic solvent mixture, in the experimental time window and wavenumber range. From the simulation data for the time derivative of the width function associated with fc(q, t), there is indication of long-time exponential decay of fc(q, t), for wavenumbers around the location of the static structure factor principal peak. The experimental scattering functions in the probed time range are consistent with a time-wavenumber factorization scaling behavior of fc(q, t) that was first reported by Segrè and Pusey [Phys. Rev. Lett. 77, 771 (1996)] for suspensions of hard spheres. Our BD simulation and MCT results predict a significant violation of exact factorization scaling which, however, is approximately restored according to the ASD results when HIs are accounted for, consistent with the experimental findings for fc(q, t). Our study of collective diffusion is amended by simulation and theoretical results for the self-intermediate scattering function, fs(q, t), and its non-Gaussian parameter α2(t) and for the particle mean squared displacement W(t) and its time derivative. Since self-diffusion properties are not assessed in standard DLS measurements, a method to deduce W(t) approximately from fc(q, t) is theoretically validated.

Asymptotic response of observables from divergent weak-coupling expansions: a fractional-calculus-assisted Padé technique.

PubMed

Dhatt, Sharmistha; Bhattacharyya, Kamal

2012-08-01

Appropriate constructions of Padé approximants are believed to provide reasonable estimates of the asymptotic (large-coupling) amplitude and exponent of an observable, given its weak-coupling expansion to some desired order. In many instances, however, sequences of such approximants are seen to converge very poorly. We outline here a strategy that exploits the idea of fractional calculus to considerably improve the convergence behavior. Pilot calculations on the ground-state perturbative energy series of quartic, sextic, and octic anharmonic oscillators reveal clearly the worth of our endeavor.

Prediction of G-protein-coupled receptor classes in low homology using Chou's pseudo amino acid composition with approximate entropy and hydrophobicity patterns.

PubMed

Gu, Q; Ding, Y S; Zhang, T L

2010-05-01

We use approximate entropy and hydrophobicity patterns to predict G-protein-coupled receptors. Adaboost classifier is adopted as the prediction engine. A low homology dataset is used to validate the proposed method. Compared with the results reported, the successful rate is encouraging. The source code is written by Matlab.

Lidar cross-sections of soot fractal aggregates: Assessment of equivalent-sphere models

NASA Astrophysics Data System (ADS)

Ceolato, Romain; Gaudfrin, Florian; Pujol, Olivier; Riviere, Nicolas; Berg, Matthew J.; Sorensen, Christopher M.

2018-06-01

This work assesses the ability of equivalent-sphere models to reproduce the optical properties of soot aggregates relevant for lidar remote sensing, i.e. the backscattering and extinction cross sections. Lidar cross-sections are computed with a spectral discrete dipole approximation model over the visible-to-infrared (400-5000 nm) spectrum and compared with equivalent-sphere approximations. It is shown that the equivalent-sphere approximation, applied to fractal aggregates, has a limited ability to calculate such cross-sections well. The approximation should thus be used with caution for the computation of broadband lidar cross-sections, especially backscattering, at small and intermediate wavelengths (e.g. UV to visible).

Body mass index and outcomes in patients receiving chemotherapy for intermediate-grade B-cell non-Hodgkin lymphoma.

PubMed

Jones, Jeffrey A; Fayad, Luis E; Elting, Linda S; Rodriguez, Maria A

2010-09-01

We conducted a retrospective cohort study examining the influence of obesity on treatment outcome and survival among 712 patients with intermediate-grade B-cell NHL receiving frontline therapy between 1988 and 2001. Baseline adiposity was approximated by body mass index categorized according to the World Health Organization schema. Logistic and Cox proportional hazards regression modeling was used to adjust for baseline patient demographic, disease, and treatment variables. Approximately 37% of cohort patients were overweight (BMI 25 to <30 kg/m(2)) and more than 23% were obese (BMI >or= 30 kg/m(2)). Risk factors were similar across groups and treatment intensity did not vary by BMI. Median follow-up was 45.7 and 62.8 months for PFS and OS, respectively. After adjustment for other significant prognostic factors, BMI in the overweight range was associated with significantly reduced hazard for both PFS (OR 0.72, p = 0.011) and OS (OR 0.74, p = 0.030). Increased BMI is associated with significantly improved survival among patients with treatment-naive, intermediate-grade B-cell NHL. Prospective confirmation of these results is warranted given the increasing prevalence of both NHL and obesity.

Estimation of the volatility distribution of organic aerosol combining thermodenuder and isothermal dilution measurements

NASA Astrophysics Data System (ADS)

Louvaris, Evangelos E.; Karnezi, Eleni; Kostenidou, Evangelia; Kaltsonoudis, Christos; Pandis, Spyros N.

2017-10-01

A method is developed following the work of Grieshop et al. (2009) for the determination of the organic aerosol (OA) volatility distribution combining thermodenuder (TD) and isothermal dilution measurements. The approach was tested in experiments that were conducted in a smog chamber using organic aerosol (OA) produced during meat charbroiling. A TD was operated at temperatures ranging from 25 to 250 °C with a 14 s centerline residence time coupled to a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a scanning mobility particle sizer (SMPS). In parallel, a dilution chamber filled with clean air was used to dilute isothermally the aerosol of the larger chamber by approximately a factor of 10. The OA mass fraction remaining was measured as a function of temperature in the TD and as a function of time in the isothermal dilution chamber. These two sets of measurements were used together to estimate the volatility distribution of the OA and its effective vaporization enthalpy and accommodation coefficient. In the isothermal dilution experiments approximately 20 % of the OA evaporated within 15 min. Almost all the OA evaporated in the TD at approximately 200 °C. The resulting volatility distributions suggested that around 60-75 % of the cooking OA (COA) at concentrations around 500 µg m-3 consisted of low-volatility organic compounds (LVOCs), 20-30 % of semivolatile organic compounds (SVOCs), and around 10 % of intermediate-volatility organic compounds (IVOCs). The estimated effective vaporization enthalpy of COA was 100 ± 20 kJ mol-1 and the effective accommodation coefficient was 0.06-0.07. Addition of the dilution measurements to the TD data results in a lower uncertainty of the estimated vaporization enthalpy as well as the SVOC content of the OA.

AmeriFlux US-Wi2 Intermediate red pine (IRP)

DOE Data Explorer

Chen, Jiquan [Michigan State University

2016-01-01

This is the AmeriFlux version of the carbon flux data for the site US-Wi2 Intermediate red pine (IRP). Site Description - The Wisconsin Intermediate Red Pine site is located in the Washburn Ranger District of the northeastern section of Chequamegon National Forest. A member of the northern coniferous-deciduous biome, surveys from the mid-19th century indicate the region consisted of a mixed stand of red, white, and jack pines. After extensive timber harvesting, wildfires, and farming activity, the region turned into a fragmented mosaic of stands of various ages and composition. The intermediate red pine site is one of ten sites that collectively represent the successional stages of development in the predominant stand types of a physically homogeneous landscape. Thinned every 7 years until they reach 100 to 150 years of age, the red pine plantations of all ages occupy approximately 25% of the region.

Effects of relativity of RTEX in collisions of U sup q+ with light targets

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

Chen, Mau Hsiung.

1990-11-07

We have calculated the resonant transfer and excitation cross sections in collisions of U{sup q+} (q = 82, 89, 90) ion with H{sub 2}, He and C in impulse approximation using the multi-configuration Dirac-Fock method. The calculations were carried out in intermediate coupling with configuration interaction. The quantum electrodynamic and finite nuclear size corrections were included in the calculations of transition energies. The Auger rates were calculated including the contributions from Coulomb as well as the transverse Breit interactions. For U{sup 89+} and U{sup 90+}, effects of relatively not only shift the peak positions but also change the peak structure.more » The total dielectronic recombination strength has been found to increase by 50% due to the effects of relativity. The present theoretical RTEX cross sections for U{sup 90+} in hydrogen agree well with experiment. For U{sup 82+}, Breit interaction had been found to have little effect on the RTEX cross sections involving L-shell excitation. However, the spin-orbit interaction can still make significant change in the peak structure. 24 refs., 4 figs.« less

Highly efficient and autocatalytic H2₂ dissociation for CO₂ reduction into formic acid with zinc.

PubMed

Jin, Fangming; Zeng, Xu; Liu, Jianke; Jin, Yujia; Wang, Lunying; Zhong, Heng; Yao, Guodong; Huo, Zhibao

2014-03-28

Artificial photosynthesis, specifically H2O dissociation for CO2 reduction with solar energy, is regarded as one of the most promising methods for sustainable energy and utilisation of environmental resources. However, a highly efficient conversion still remains extremely challenging. The hydrogenation of CO2 is regarded as the most commercially feasible method, but this method requires either exotic catalysts or high-purity hydrogen and hydrogen storage, which are regarded as an energy-intensive process. Here we report a highly efficient method of H2O dissociation for reducing CO2 into chemicals with Zn powder that produces formic acid with a high yield of approximately 80%, and this reaction is revealed for the first time as an autocatalytic process in which an active intermediate, ZnH(-) complex, serves as the active hydrogen. The proposed process can assist in developing a new concept for improving artificial photosynthetic efficiency by coupling geochemistry, specifically the metal-based reduction of H2O and CO2, with solar-driven thermochemistry for reducing metal oxide into metal.

Biotemplated synthesis of high specific surface area copper-doped hollow spherical titania and its photocatalytic research for degradating chlorotetracycline

NASA Astrophysics Data System (ADS)

Bu, Dan; Zhuang, Huisheng

2013-01-01

Copper-doped titania (Cu/TiO2) hollow microspheres were fabricated using the rape pollen as biotemplates via an improved sol-gel method and a followed calcinations process. In the fabricated process, a titanium(IV)-isopropoxide-based sol directly coated onto the surface of rape pollen. Subsequently, after calcinations, rape pollen was removed by high temperature and the hollow microsphere structure was retained. The average diameter of as-obtained hollow microspheres is 15-20 μm and the thickness of shell is approximately 0.6 μm. Knowing from XRD results, the main crystal phase of microspheres is anatase, coupled with rutile. The specific surface area varied between 141.80 m2/g and 172.51 m2/g. This hollow sphere photocatalysts with high specific surface area exhibited stronger absorption ability and higher photoactivity, stimulated by visible light. The degradation process of chlortetracycline (CTC) solution had been studied. The degradated results indicate that CTC could be effective degradated by fabricated hollow spherical materials. And the intermediate products formed in the photocatalytic process had been identified.

Design of a unidirectional composite momentum wheel rim

NASA Astrophysics Data System (ADS)

Shogrin, Bradley; Jones, William R., Jr.; Prahl, Joseph M.

1995-05-01

A preliminary study comparing twelve unidirectional-fiber composite systems to five metal materials conventionally used in momentum wheels is presented. Six different fibers are considered in the study: E-Glass, S-Glass, Boron, AS, T300, and Kevlar. Because of the possibility of high momentum requirements, and thus high stresses, only two matrix materials are considered: a high-modulus (HM) and a intermediate-modulus-high-strength (IMHS) matrix. Each of the six fibers are coupled with each of the two matrix materials. In an effort to optimize the composite system, each composite is considered while varying the fiber volume ratio from 0.0 to 0.7 in increments of 0.1. For fiber volume ratios above 0.2, all twelve unidirectional-fiber composite systems meet the study's requirements with higher factors of safety and less mass than the five conventional isotropic (metal) materials. For example, at a fiber volume ratio of 0.6, the Kevlar/IMHS composite system has a safety factor 4.5 times greater than that of a steel (maraging) system and an approximately 10 percent reduction in weight.

Ionization competition effects on population distribution and radiative opacity of mixture plasmas

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

Li, Yongjun; Gao, Cheng; Tian, Qinyun

2015-11-15

Ionization competition arising from the electronic shell structures of various atomic species in the mixture plasmas was investigated, taking SiO{sub 2} as an example. Using a detailed-level-accounting approximation, we studied the competition effects on the charge state population distribution and spectrally resolved and Planck and Rosseland mean radiative opacities of mixture plasmas. A set of coupled equations for ionization equilibria that include all components of the mixture plasmas are solved to determine the population distributions. For a given plasma density, competition effects are found at three distinct temperature ranges, corresponding to the ionization of M-, L-, and K-shell electrons ofmore » Si. Taking the effects into account, the spectrally resolved and Planck and Rosseland mean opacities are systematically investigated over a wide range of plasma densities and temperatures. For a given mass density, the Rosseland mean decreases monotonically with plasma temperature, whereas Planck mean does not. Although the overall trend is a decrease, the Planck mean increases over a finite intermediate temperature regime. A comparison with the available experimental and theoretical results is made.« less

Highly efficient and autocatalytic H2O dissociation for CO2 reduction into formic acid with zinc

PubMed Central

Jin, Fangming; Zeng, Xu; Liu, Jianke; Jin, Yujia; Wang, Lunying; Zhong, Heng; Yao, Guodong; Huo, Zhibao

2014-01-01

Artificial photosynthesis, specifically H2O dissociation for CO2 reduction with solar energy, is regarded as one of the most promising methods for sustainable energy and utilisation of environmental resources. However, a highly efficient conversion still remains extremely challenging. The hydrogenation of CO2 is regarded as the most commercially feasible method, but this method requires either exotic catalysts or high-purity hydrogen and hydrogen storage, which are regarded as an energy-intensive process. Here we report a highly efficient method of H2O dissociation for reducing CO2 into chemicals with Zn powder that produces formic acid with a high yield of approximately 80%, and this reaction is revealed for the first time as an autocatalytic process in which an active intermediate, ZnH− complex, serves as the active hydrogen. The proposed process can assist in developing a new concept for improving artificial photosynthetic efficiency by coupling geochemistry, specifically the metal-based reduction of H2O and CO2, with solar-driven thermochemistry for reducing metal oxide into metal. PMID:24675820

Statistical models of global Langmuir mixing

NASA Astrophysics Data System (ADS)

Li, Qing; Fox-Kemper, Baylor; Breivik, Øyvind; Webb, Adrean

2017-05-01

The effects of Langmuir mixing on the surface ocean mixing may be parameterized by applying an enhancement factor which depends on wave, wind, and ocean state to the turbulent velocity scale in the K-Profile Parameterization. Diagnosing the appropriate enhancement factor online in global climate simulations is readily achieved by coupling with a prognostic wave model, but with significant computational and code development expenses. In this paper, two alternatives that do not require a prognostic wave model, (i) a monthly mean enhancement factor climatology, and (ii) an approximation to the enhancement factor based on the empirical wave spectra, are explored and tested in a global climate model. Both appear to reproduce the Langmuir mixing effects as estimated using a prognostic wave model, with nearly identical and substantial improvements in the simulated mixed layer depth and intermediate water ventilation over control simulations, but significantly less computational cost. Simpler approaches, such as ignoring Langmuir mixing altogether or setting a globally constant Langmuir number, are found to be deficient. Thus, the consequences of Stokes depth and misaligned wind and waves are important.

Control of Synchronization Regimes in Networks of Mobile Interacting Agents

NASA Astrophysics Data System (ADS)

Perez-Diaz, Fernando; Zillmer, Ruediger; Groß, Roderich

2017-05-01

We investigate synchronization in a population of mobile pulse-coupled agents with a view towards implementations in swarm-robotics systems and mobile sensor networks. Previous theoretical approaches dealt with range and nearest-neighbor interactions. In the latter case, a synchronization-hindering regime for intermediate agent mobility is found. We investigate the robustness of this intermediate regime under practical scenarios. We show that synchronization in the intermediate regime can be predicted by means of a suitable metric of the phase response curve. Furthermore, we study more-realistic K -nearest-neighbor and cone-of-vision interactions, showing that it is possible to control the extent of the synchronization-hindering region by appropriately tuning the size of the neighborhood. To assess the effect of noise, we analyze the propagation of perturbations over the network and draw an analogy between the response in the hindering regime and stable chaos. Our findings reveal the conditions for the control of clock or activity synchronization of agents with intermediate mobility. In addition, the emergence of the intermediate regime is validated experimentally using a swarm of physical robots interacting with cone-of-vision interactions.

Spin-orbit splitted excited states using explicitly-correlated equation-of-motion coupled-cluster singles and doubles eigenvectors

NASA Astrophysics Data System (ADS)

Bokhan, Denis; Trubnikov, Dmitrii N.; Perera, Ajith; Bartlett, Rodney J.

2018-04-01

An explicitly-correlated method of calculation of excited states with spin-orbit couplings, has been formulated and implemented. Developed approach utilizes left and right eigenvectors of equation-of-motion coupled-cluster model, which is based on the linearly approximated explicitly correlated coupled-cluster singles and doubles [CCSD(F12)] method. The spin-orbit interactions are introduced by using the spin-orbit mean field (SOMF) approximation of the Breit-Pauli Hamiltonian. Numerical tests for several atoms and molecules show good agreement between explicitly-correlated results and the corresponding values, calculated in complete basis set limit (CBS); the highly-accurate excitation energies can be obtained already at triple- ζ level.

Electrostatic analyzer measurements of ionospheric thermal ion populations

DOE PAGES

Fernandes, P. A.; Lynch, K. A.

2016-07-09

Here, we define the observational parameter regime necessary for observing low-altitude ionospheric origins of high-latitude ion upflow/outflow. We present measurement challenges and identify a new analysis technique which mitigates these impediments. To probe the initiation of auroral ion upflow, it is necessary to examine the thermal ion population at 200-350 km, where typical thermal energies are tenths of eV. Interpretation of the thermal ion distribution function measurement requires removal of payload sheath and ram effects. We use a 3-D Maxwellian model to quantify how observed ionospheric parameters such as density, temperature, and flows affect in situ measurements of the thermalmore » ion distribution function. We define the viable acceptance window of a typical top-hat electrostatic analyzer in this regime and show that the instrument's energy resolution prohibits it from directly observing the shape of the particle spectra. To extract detailed information about measured particle population, we define two intermediate parameters from the measured distribution function, then use a Maxwellian model to replicate possible measured parameters for comparison to the data. Liouville's theorem and the thin-sheath approximation allow us to couple the measured and modeled intermediate parameters such that measurements inside the sheath provide information about plasma outside the sheath. We apply this technique to sounding rocket data to show that careful windowing of the data and Maxwellian models allows for extraction of the best choice of geophysical parameters. More widespread use of this analysis technique will help our community expand its observational database of the seed regions of ionospheric outflows.« less

Freshening of Antarctic Intermediate Water in the South Atlantic Ocean in 2005-2014

NASA Astrophysics Data System (ADS)

Yao, Wenjun; Shi, Jiuxin; Zhao, Xiaolong

2017-07-01

Basin-scale freshening of Antarctic Intermediate Water (AAIW) is reported to have occurred in the South Atlantic Ocean during the period from 2005 to 2014, as shown by the gridded monthly means of the Array for Real-time Geostrophic Oceanography (Argo) data. This phenomenon was also revealed by two repeated transects along a section at 30° S, performed during the World Ocean Circulation Experiment Hydrographic Program. Freshening of the AAIW was compensated for by a salinity increase of thermocline water, indicating a hydrological cycle intensification. This was supported by the precipitation-minus-evaporation change in the Southern Hemisphere from 2000 to 2014. Freshwater input from atmosphere to ocean surface increased in the subpolar high-precipitation region and vice versa in the subtropical high-evaporation region. Against the background of hydrological cycle changes, a decrease in the transport of Agulhas Leakage (AL), which was revealed by the simulated velocity field, was proposed to be a contributor to the associated freshening of AAIW. Further calculation showed that such a decrease could account for approximately 53 % of the observed freshening (mean salinity reduction of about 0.012 over the AAIW layer). The estimated variability of AL was inferred from a weakening of wind stress over the South Indian Ocean since the beginning of the 2000s, which would facilitate freshwater input from the source region. The mechanical analysis of wind data here was qualitative, but it is contended that this study would be helpful to validate and test predictably coupled sea-air model simulations.

Gauge coupling unification and nonequilibrium thermal dark matter.

PubMed

Mambrini, Yann; Olive, Keith A; Quevillon, Jérémie; Zaldívar, Bryan

2013-06-14

We study a new mechanism for the production of dark matter in the Universe which does not rely on thermal equilibrium. Dark matter is populated from the thermal bath subsequent to inflationary reheating via a massive mediator whose mass is above the reheating scale T(RH). To this end, we consider models with an extra U(1) gauge symmetry broken at some intermediate scale (M(int) ≃ 10(10)-10(12) GeV). We show that not only does the model allow for gauge coupling unification (at a higher scale associated with grand unification) but it can provide a dark matter candidate which is a standard model singlet but charged under the extra U(1). The intermediate scale gauge boson(s) which are predicted in several E6/SO(10) constructions can be a natural mediator between dark matter and the thermal bath. We show that the dark matter abundance, while never having achieved thermal equilibrium, is fixed shortly after the reheating epoch by the relation T(RH)(3)/M(int)(4). As a consequence, we show that the unification of gauge couplings which determines M(int) also fixes the reheating temperature, which can be as high as T(RH) ≃ 10(11) GeV.

Modulation of kinetic Alfvén waves in an intermediate low-beta magnetoplasma

NASA Astrophysics Data System (ADS)

Chatterjee, Debjani; Misra, A. P.

2018-05-01

We study the amplitude modulation of nonlinear kinetic Alfvén waves (KAWs) in an intermediate low-beta magnetoplasma. Starting from a set of fluid equations coupled to the Maxwell's equations, we derive a coupled set of nonlinear partial differential equations (PDEs) which govern the evolution of KAW envelopes in the plasma. The modulational instability (MI) of such KAW envelopes is then studied by a nonlinear Schrödinger equation derived from the coupled PDEs. It is shown that the KAWs can evolve into bright envelope solitons or can undergo damping depending on whether the characteristic ratio ( α ) of the Alfvén to ion-acoustic speeds remains above or below a critical value. The parameter α is also found to shift the MI domains around the k x k z plane, where k x ( k z ) is the KAW number perpendicular (parallel) to the external magnetic field. The growth rate of MI, as well as the frequency shift and the energy transfer rate, are obtained and analyzed. The results can be useful for understanding the existence and formation of bright and dark envelope solitons, or damping of KAW envelopes in space plasmas, e.g., interplanetary space, solar winds, etc.

Ti-Catalyzed Multicomponent Oxidative Carboamination of Alkynes with Alkenes and Diazenes

PubMed Central

Davis-Gilbert, Zachary W.; Yao, Letitia J.; Tonks, Ian A.

2017-01-01

The inter- or intramolecular oxidative carboamination of alkynes catalyzed by [py2TiCl2NPh]2 is reported. These multicomponent reactions couple alkenes, alkynes and diazenes to form either α,β-unsaturated imines or α-(iminomethyl)cyclopropanes via a TiII/TiIV redox cycle. Each of these products is formed from a common azatitanacyclohexene intermediate that undergoes either β-H elimination or α,γ-coupling, wherein the selectivity is under substrate control. PMID:27790910

Mobility-induced persistent chimera states

NASA Astrophysics Data System (ADS)

Petrungaro, Gabriela; Uriu, Koichiro; Morelli, Luis G.

2017-12-01

We study the dynamics of mobile, locally coupled identical oscillators in the presence of coupling delays. We find different kinds of chimera states in which coherent in-phase and antiphase domains coexist with incoherent domains. These chimera states are dynamic and can persist for long times for intermediate mobility values. We discuss the mechanisms leading to the formation of these chimera states in different mobility regimes. This finding could be relevant for natural and technological systems composed of mobile communicating agents.

Perturbation solutions of combustion instability problems

NASA Technical Reports Server (NTRS)

Googerdy, A.; Peddieson, J., Jr.; Ventrice, M.

1979-01-01

A method involving approximate modal analysis using the Galerkin method followed by an approximate solution of the resulting modal-amplitude equations by the two-variable perturbation method (method of multiple scales) is applied to two problems of pressure-sensitive nonlinear combustion instability in liquid-fuel rocket motors. One problem exhibits self-coupled instability while the other exhibits mode-coupled instability. In both cases it is possible to carry out the entire linear stability analysis and significant portions of the nonlinear stability analysis in closed form. In the problem of self-coupled instability the nonlinear stability boundary and approximate forms of the limit-cycle amplitudes and growth and decay rates are determined in closed form while the exact limit-cycle amplitudes and growth and decay rates are found numerically. In the problem of mode-coupled instability the limit-cycle amplitudes are found in closed form while the growth and decay rates are found numerically. The behavior of the solutions found by the perturbation method are in agreement with solutions obtained using complex numerical methods.

Elastic scattering and vibrational excitation for electron impact on para-benzoquinone

NASA Astrophysics Data System (ADS)

Jones, D. B.; Blanco, F.; García, G.; da Costa, R. F.; Kossoski, F.; Varella, M. T. do N.; Bettega, M. H. F.; Lima, M. A. P.; White, R. D.; Brunger, M. J.

2017-12-01

We report on theoretical elastic and experimental vibrational-excitation differential cross sections (DCSs) for electron scattering from para-benzoquinone (C6H4O2), in the intermediate energy range 15-50 eV. The calculations were conducted with two different theoretical methodologies, the Schwinger multichannel method with pseudopotentials (SMCPP) and the independent atom method with screening corrected additivity rule (IAM-SCAR) that also now incorporates a further interference (I) term. The SMCPP with N energetically open electronic states (Nopen) at the static-exchange-plus-polarisation (Nopench-SEP) level was used to calculate the scattering amplitudes using a channel coupling scheme that ranges from 1ch-SE up to the 89ch-SEP level of approximation. We found that in going from the 38ch-SEP to the 89ch-SEP, at all energies considered here, the elastic DCSs did not change significantly in terms of both their shapes and magnitudes. This is a good indication that our SMCPP 89ch-SEP elastic DCSs are converged with respect to the multichannel coupling effect for the investigated intermediate energies. While agreement between our IAM-SCAR+I and SMCPP 89ch-SEP computations improves as the incident electron energy increases from 15 eV, overall the level of accord is only marginal. This is particularly true at middle scattering angles, suggesting that our SCAR and interference corrections are failing somewhat for this molecule below 50 eV. We also report experimental DCS results, using a crossed-beam apparatus, for excitation of some of the unresolved ("hybrid") vibrational quanta (bands I-III) of para-benzoquinone. Those data were derived from electron energy loss spectra that were measured over a scattered electron angular range of 10°-90° and put on an absolute scale using our elastic SMCPP 89ch-SEP DCS results. The energy resolution of our measurements was ˜80 meV, which is why, at least in part, the observed vibrational features were only partially resolved. To the best of our knowledge, there are no other experimental or theoretical vibrational excitation results against which we might compare the present measurements.

Photovoltaic efficiency of intermediate band solar cells based on CdTe/CdMnTe coupled quantum dots

NASA Astrophysics Data System (ADS)

Prado, Silvio J.; Marques, Gilmar E.; Alcalde, Augusto M.

2017-11-01

In this work we show the calculation of optimized efficiencies of intermediate band solar cells (IBSCs) based on Mn-doped II-VI CdTe/CdMnTe coupled quantum dot (QD) structures. We focus our attention on the combined effects of geometrical and Mn-doping parameters on optical properties and solar cell efficiency. In the framework of {k \\cdot p} theory, we accomplish detailed calculations of electronic structure, transition energies, optical selection rules and their corresponding intra- and interband oscillator strengths. With these results and by following the intermediate band model, we have developed a strategy which allows us to find optimal photovoltaic efficiency values. We also show that the effects of band admixture which can lead to degradation of optical transitions and reduction of efficiency can be partly minimized by a careful selection of the structural parameters and Mn-concentration. Thus, the improvement of band engineering is mandatory for any practical implementation of QD systems as IBSC hardware. Finally, our calculations show that it is possible to reach significant efficiency, up to  ∼26%, by selecting a restricted space of parameters such as quantum dot size and shape and Mn-concentration effects, to improve the modulation of optical absorption in the structures.

Photovoltaic efficiency of intermediate band solar cells based on CdTe/CdMnTe coupled quantum dots.

PubMed

Prado, Silvio J; Marques, Gilmar E; Alcalde, Augusto M

2017-11-08

In this work we show the calculation of optimized efficiencies of intermediate band solar cells (IBSCs) based on Mn-doped II-VI CdTe/CdMnTe coupled quantum dot (QD) structures. We focus our attention on the combined effects of geometrical and Mn-doping parameters on optical properties and solar cell efficiency. In the framework of [Formula: see text] theory, we accomplish detailed calculations of electronic structure, transition energies, optical selection rules and their corresponding intra- and interband oscillator strengths. With these results and by following the intermediate band model, we have developed a strategy which allows us to find optimal photovoltaic efficiency values. We also show that the effects of band admixture which can lead to degradation of optical transitions and reduction of efficiency can be partly minimized by a careful selection of the structural parameters and Mn-concentration. Thus, the improvement of band engineering is mandatory for any practical implementation of QD systems as IBSC hardware. Finally, our calculations show that it is possible to reach significant efficiency, up to  ∼26%, by selecting a restricted space of parameters such as quantum dot size and shape and Mn-concentration effects, to improve the modulation of optical absorption in the structures.

Permanganate ion oxidations. IX. Manganese intermediates (complexes) in the oxidation of 2,4(1H,3H)-pyrimidinediones.

PubMed

Freeman, F; Karchefski, E M

1976-10-04

Uniquely stable manganese intermediates (complexes) are formed from the permanganate ion oxidation of the 5,6-carbon-carbon double bond in several 2,4(1H,3H)-pyrimidinediones [uracil, (compound 7), 5-methyluracil (thymine, compound 5), and 6-methyluracil (compound 8)]. These manganese complexes, which represent some of the most stable intermediate manganese species observed thus far in the oxidation of carbon-carbon double bonds, show absorption maxima in the 285-296 nm region (epsilon max approximately 4500). The relative reactivities of 6-methyluracil: uracil: thymine are 1: 23 : 194 and the bimolecular oxidation process is characterized by relatively small deltaH++ values and large negative deltaS++ values.

Stability of iterative procedures with errors for approximating common fixed points of a couple of q-contractive-like mappings in Banach spaces

NASA Astrophysics Data System (ADS)

Zeng, Lu-Chuan; Yao, Jen-Chih

2006-09-01

Recently, Agarwal, Cho, Li and Huang [R.P. Agarwal, Y.J. Cho, J. Li, N.J. Huang, Stability of iterative procedures with errors approximating common fixed points for a couple of quasi-contractive mappings in q-uniformly smooth Banach spaces, J. Math. Anal. Appl. 272 (2002) 435-447] introduced the new iterative procedures with errors for approximating the common fixed point of a couple of quasi-contractive mappings and showed the stability of these iterative procedures with errors in Banach spaces. In this paper, we introduce a new concept of a couple of q-contractive-like mappings (q>1) in a Banach space and apply these iterative procedures with errors for approximating the common fixed point of the couple of q-contractive-like mappings. The results established in this paper improve, extend and unify the corresponding ones of Agarwal, Cho, Li and Huang [R.P. Agarwal, Y.J. Cho, J. Li, N.J. Huang, Stability of iterative procedures with errors approximating common fixed points for a couple of quasi-contractive mappings in q-uniformly smooth Banach spaces, J. Math. Anal. Appl. 272 (2002) 435-447], Chidume [C.E. Chidume, Approximation of fixed points of quasi-contractive mappings in Lp spaces, Indian J. Pure Appl. Math. 22 (1991) 273-386], Chidume and Osilike [C.E. Chidume, M.O. Osilike, Fixed points iterations for quasi-contractive maps in uniformly smooth Banach spaces, Bull. Korean Math. Soc. 30 (1993) 201-212], Liu [Q.H. Liu, On Naimpally and Singh's open questions, J. Math. Anal. Appl. 124 (1987) 157-164; Q.H. Liu, A convergence theorem of the sequence of Ishikawa iterates for quasi-contractive mappings, J. Math. Anal. Appl. 146 (1990) 301-305], Osilike [M.O. Osilike, A stable iteration procedure for quasi-contractive maps, Indian J. Pure Appl. Math. 27 (1996) 25-34; M.O. Osilike, Stability of the Ishikawa iteration method for quasi-contractive maps, Indian J. Pure Appl. Math. 28 (1997) 1251-1265] and many others in the literature.

Single-Electron Transmetalation via Photoredox/Nickel Dual Catalysis: Unlocking a New Paradigm for sp(3)-sp(2) Cross-Coupling.

PubMed

Tellis, John C; Kelly, Christopher B; Primer, David N; Jouffroy, Matthieu; Patel, Niki R; Molander, Gary A

2016-07-19

The important role of transition metal-catalyzed cross-coupling in expanding the frontiers of accessible chemical territory is unquestionable. Despite empowering chemists with Herculean capabilities in complex molecule construction, contemporary protocols are not without their Achilles' heel: Csp(3)-Csp(2)/sp(3) coupling. The underlying challenge in sp(3) cross-couplings is 2-fold: (i) methods employing conventional, bench-stable precursors are universally reliant on extreme reaction conditions because of the high activation barrier of transmetalation; (ii) circumvention of this barrier invariably relies on use of more reactive precursors, thereby sacrificing functional group tolerance, operational simplicity, and broad applicability. Despite the ubiquity of this problem, the nature of the transmetalation step has remained unchanged from the seminal reports of Negishi, Suzuki, Kumada, and Stille, thus suggesting that the challenges in Csp(3)-Csp(2)/sp(3) coupling result from inherent mechanistic constraints in the traditional cross-coupling paradigm. Rather than submitting to the limitations of this conventional approach, we envisioned that a process rooted in single-electron reactivity could furnish the same key metalated intermediate posited in two-electron transmetalation, while demonstrating entirely complementary reactivity patterns. Inspired by literature reports on the susceptibility of organoboron reagents toward photochemical, single-electron oxidative fragmentation, realization of a conceptually novel open shell transmetalation framework was achieved in the facile coupling of benzylic trifluoroborates with aryl halides via cooperative visible-light activated photoredox and Ni cross-coupling catalysis. Following this seminal study, we disclosed a suite of protocols for the cross-coupling of secondary alkyl, α-alkoxy, α-amino, and α-trifluoromethylbenzyltrifluoroborates. Furthermore, the selective cross-coupling of Csp(3) organoboron moieties in the presence of Csp(2) organoboron motifs was also demonstrated, highlighting the nuances of this approach to transmetalation. Computational modeling of the reaction mechanism uncovered useful details about the intermediates and transition-state structures involved in the nickel catalytic cycle. Most notably, a unique dynamic kinetic resolution process, characterized by radical homolysis/recombination equilibrium of a Ni(III) intermediate, was discovered. This process was ultimately found to be responsible for stereoselectivity in an enantioselective variant of these cross-couplings. Prompted by the intrinsic limitations of organotrifluoroborates, we sought other radical feedstocks and quickly identified alkylbis(catecholato)silicates as viable radical precursors for Ni/photoredox dual catalysis. These hypervalent silicate species have several notable benefits, including more favorable redox potentials that allow extension to primary alkyl systems incorporating unprotected amines as well as compatibility with less expensive Ru-based photocatalysts. Additionally, these reagents exhibit an amenability to alkenyl halide cross-coupling while simultaneously expanding the aryl halide scope. In the process of exploring these reagents, we serendipitously discovered a method to effect thioetherification of aryl halides via a H atom transfer mechanism. This latter discovery emphasizes that this robust cross-coupling paradigm is "blind" to the origins of the radical, opening opportunities for a wealth of new discoveries. Taken together, our studies in the area of photoredox/nickel dual catalysis have validated single-electron transmetalation as a powerful platform for enabling conventionally challenging Csp(3)-Csp(2) cross-couplings. More broadly, these findings represent the power of rational design in catalysis and the strategic use of mechanistic knowledge and manipulation for the development of new synthetic methods.

Born distorted-wave approximation applied to the H+ + He collisions at intermediate and high energies

NASA Astrophysics Data System (ADS)

Rahmanian, M.; Fathi, R.; Shojaei, F.

2017-11-01

The single-charge transfer process in collision of protons with helium atoms in their ground states is investigated. The model utilizes the second-order three-body Born distorted-wave approximation (BDW-3B) with correct Coulomb boundary conditions to calculate the differential and total cross sections at intermediate and high energies. The role of the passive electrons and electron-electron correlations are studied by comparing our results and the BDW-4B calculations with the complete perturbation potential. The present results are also compared with other theories, and the Thomas scattering mechanism is investigated. The obtained results are also compared with the recent experimental measurements. For the prior differential cross sections, the comparisons show better agreement with the experiments at smaller scattering angles. The agreement between the total cross sections and the BDW-4B results as well as the experimental data is good at higher impact energies.

Development of a polysilicon process based on chemical vapor deposition, phase 1 and phase 2

NASA Technical Reports Server (NTRS)

Plahutnik, F.; Arvidson, A.; Sawyer, D.; Sharp, K.

1982-01-01

High-purity polycrystalline silicon was produced in an experimental, intermediate and advanced CVD reactor. Data from the intermediate and advanced reactors confirmed earlier results obtained in the experimental reactor. Solar cells were fabricated by Westinghouse Electric and Applied Solar Research Corporation which met or exceeded baseline cell efficiencies. Feedstocks containing trichlorosilane or silicon tetrachloride are not viable as etch promoters to reduce silicon deposition on bell jars. Neither are they capable of meeting program goals for the 1000 MT/yr plant. Post-run CH1 etch was found to be a reasonably effective method of reducing silicon deposition on bell jars. Using dichlorosilane as feedstock met the low-cost solar array deposition goal (2.0 gh-1-cm-1), however, conversion efficiency was approximately 10% lower than the targeted value of 40 mole percent (32 to 36% achieved), and power consumption was approximately 20 kWh/kg over target at the reactor.

Radiation/convection coupling in rocket motors and plumes

NASA Technical Reports Server (NTRS)

Farmer, R. C.; Saladino, A. J.

1993-01-01

The three commonly used propellant systems - H2/O2, RP-1/O2, and solid propellants - primarily radiate as molecular emitters, non-scattering small particles, and scattering larger particles, respectively. Present technology has accepted the uncoupling of the radiation analysis from that of the flowfield. This approximation becomes increasingly inaccurate as one considers plumes, interior rocket chambers, and nuclear rocket propulsion devices. This study will develop a hierarchy of methods which will address radiation/convection coupling in all of the aforementioned propulsion systems. The nature of the radiation/convection coupled problem is that the divergence of the radiative heat flux must be included in the energy equation and that the local, volume-averaged intensity of the radiation must be determined by a solution of the radiative transfer equation (RTE). The intensity is approximated by solving the RTE along several lines of sight (LOS) for each point in the flowfield. Such a procedure is extremely costly; therefore, further approximations are needed. Modified differential approximations are being developed for this purpose. It is not obvious which order of approximations are required for a given rocket motor analysis. Therefore, LOS calculations have been made for typical rocket motor operating conditions in order to select the type approximations required. The results of these radiation calculations, and the interpretation of these intensity predictions are presented herein.

Is Earth F**ked? Dynamical Futility of Global Environmental Management and Possibilities for Sustainability via Direct Action Activism

NASA Astrophysics Data System (ADS)

wErnEr, B.

2012-12-01

Environmental challenges are dynamically generated within the dominant global culture principally by the mismatch between short-time-scale market and political forces driving resource extraction/use and longer-time-scale accommodations of the Earth system to these changes. Increasing resource demand is leading to the development of two-way, nonlinear interactions between human societies and environmental systems that are becoming global in extent, either through globalized markets and other institutions or through coupling to global environmental systems such as climate. These trends are further intensified by dissipation-reducing technological advances in transactions, communication and transport, which suppress emergence of longer-time-scale economic and political levels of description and facilitate long-distance connections, and by predictive environmental modeling, which strengthens human connections to a short-time-scale virtual Earth, and weakens connections to the longer time scales of the actual Earth. Environmental management seeks to steer fast scale economic and political interests of a coupled human-environmental system towards longer-time-scale consideration of benefits and costs by operating within the confines of the dominant culture using a linear, engineering-type connection to the system. Perhaps as evidenced by widespread inability to meaningfully address such global environmental challenges as climate change and soil degradation, nonlinear connections reduce the ability of managers to operate outside coupled human-environmental systems, decreasing their effectiveness in steering towards sustainable interactions and resulting in managers slaved to short-to-intermediate-term interests. In sum, the dynamics of the global coupled human-environmental system within the dominant culture precludes management for stable, sustainable pathways and promotes instability. Environmental direct action, resistance taken from outside the dominant culture, as in protests, blockades and sabotage by indigenous peoples, workers, anarchists and other activist groups, increases dissipation within the coupled system over fast to intermediate scales and pushes for changes in the dominant culture that favor transition to a stable, sustainable attractor. These dynamical relationships are illustrated and explored using a numerical model that simulates the short-, intermediate- and long-time-scale dynamics of the coupled human-environmental system. At fast scales, economic and political interests exploit environmental resources through a maze of environmental management and resistance, guided by virtual Earth predictions. At intermediate scales, managers become slaved to economic and political interests, which adapt to and repress resistance, and resistance is guided by patterns of environmental destruction. At slow scales, resistance interacts with the cultural context, which co-evolves with the environment. The transition from unstable dynamics to sustainability is sensitively dependent on the level of participation in and repression of resistance. Because of their differing impact inside and outside the dominant culture, virtual Earth predictions can either promote or oppose sustainability. Supported by the National Science Foundation, Geomorphology and Land Use Dynamics Program.

Multi-component fermionic dark matter and IceCube PeV scale neutrinos in left-right model with gauge unification

NASA Astrophysics Data System (ADS)

Borah, Debasish; Dasgupta, Arnab; Dey, Ujjal Kumar; Patra, Sudhanwa; Tomar, Gaurav

2017-09-01

We consider a simple extension of the minimal left-right symmetric model (LRSM) in order to explain the PeV neutrino events seen at the IceCube experiment from a heavy decaying dark matter. The dark matter sector is composed of two fermions: one at PeV scale and the other at TeV scale such that the heavier one can decay into the lighter one and two neutrinos. The gauge annihilation cross sections of PeV dark matter are not large enough to generate its relic abundance within the observed limit. We include a pair of real scalar triplets Ω L,R which can bring the thermally overproduced PeV dark matter abundance into the observed range through late time decay and consequent entropy release thereby providing a consistent way to obtain the correct relic abundance without violating the unitarity bound on dark matter mass. Another scalar field, a bitriplet under left-right gauge group is added to assist the heavier dark matter decay. The presence of an approximate global U(1) X symmetry can naturally explain the origin of tiny couplings required for long-lived nature of these decaying particles. We also show, how such an extended LRSM can be incorporated within a non-supersymmetric SO(10) model where the gauge coupling unification at a very high scale naturally accommodate a PeV scale intermediate symmetry, required to explain the PeV events at IceCube.

From dissipative dynamics to studies of heat transfer at the nanoscale: analysis of the spin-boson model.

PubMed

Boudjada, Nazim; Segal, Dvira

2014-11-26

We study in a unified manner the dissipative dynamics and the transfer of heat in the two-bath spin-boson model. We use the Bloch-Redfield (BR) formalism, valid in the very weak system-bath coupling limit, the noninteracting-blip approximation (NIBA), applicable in the nonadiabatic limit, and iterative, numerically exact path integral tools. These methodologies were originally developed for the description of the dissipative dynamics of a quantum system, and here they are applied to explore the problem of quantum energy transport in a nonequilibrium setting. Specifically, we study the weak-to-intermediate system-bath coupling regime at high temperatures kBT/ħ > ε, with ε as the characteristic frequency of the two-state system. The BR formalism and NIBA can lead to close results for the dynamics of the reduced density matrix (RDM) in a certain range of parameters. However, relatively small deviations in the RDM dynamics propagate into significant qualitative discrepancies in the transport behavior. Similarly, beyond the strict nonadiabatic limit NIBA's prediction for the heat current is qualitatively incorrect: It fails to capture the turnover behavior of the current with tunneling energy and temperature. Thus, techniques that proved meaningful for describing the RDM dynamics, to some extent even beyond their rigorous range of validity, should be used with great caution in heat transfer calculations, because qualitative-serious failures develop once parameters are mildly stretched beyond the techniques' working assumptions.

Coupling electrokinetics with microbial biodegradation enhances the removal of cycloparaffinic hydrocarbons in soils.

PubMed

Yuan, Ye; Guo, Shuhai; Li, Fengmei; Wu, Bo; Yang, Xuelian; Li, Xuan

2016-12-15

An innovative approach that couples electrokinetics with microbial degradation to breakdown cycloparaffinic hydrocarbons in soils is described. Soils were spiked with cyclododecane, used as a model pollutant, at approximately 1000mgkg -1 . A mixture of petroleum-utilizing bacteria was added to achieve about 10 6 -10 7 CFUg -1 . Then, three treatments were applied for 25 days: (1) no electric field, control; (2) a constant voltage gradient of 1.3Vcm -1 in one direction; and (3) the same electric field, but with periodical switching of polarity. The degradation pathway of cyclododecane was not changed by the electric field, but the dynamic processes were remarkably enhanced, especially when the electric field was periodically switched. After 25 days, 79.9% and 87.0% of the cyclododecane was degraded in tests 2 and 3, respectively; both much higher than the 61.5% degraded in test 1. Analysis of the intermediate products strongly indicated that the competitive advantage of the electric field was the increase in ring-breaking of cyclododecane, resulting in greater concentrations of linear substances that were more susceptible to microbial attack, that is, β-oxidation. The conditions near the cathode were more favorable for the growth and metabolism of microorganisms, which also enhanced β-oxidation of the linear alkanoic acids. Therefore, when the electric field polarity was periodically switched, the functions of both the anode and cathode electrodes were applied across the whole soil cell, further increasing the degradation efficiency. Copyright © 2016 Elsevier B.V. All rights reserved.

5-Oxyoprolinase: Structure and mechanism of action

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

Li, L.

1988-01-01

5-Oxoprolinase catalyzes the endergonic cleavage of 5-oxo-L-proline to L-glutamate, coupled to the exergonic hydrolysis of ATP to ADP and P{sub i}. In the present studies, the enzyme present in a strain of Pseudomonas putida was found to be composed of two protein components. Component A catalyzes 5-oxo-L-proline-dependent cleavage of ATP without 5-oxyoproline decyclization. Component B is required to couple ATP hydrolysis to the ring-opening of 5-oxoproline. The two components have been purified to apparent homogeneity. When the 5-oxoprolinase reactions were carried out to 90% completion in H{sub 2} {sup 18}O, the residual 5-oxoproline contained {sup 18}O in the amide carbonylmore » group. Glutamate and P{sub i} isolated from the complete reactions conducted in H{sub 2}{sup 18}O were mono- and di-labeled with the isotope. No isotope was incorporated into 5-oxoproline if Component A was used alone. Studies with 5-oxoproline analogs showed that dilabeling of P{sub i} occurred only in coupled or partially coupled reactions. Using 5-({sup 18}O)oxo-L-(5-{sup 13}C)proline, the reactions were further analyzed by {sup 13}C-NMR. 5-Oxoprolinase from rat kidney was used as a comparison in all mechanistic studies, and similar results were obtained. These findings are consistent with the view that the reaction involves enzyme-bound, phosphorylated intermediates, and provided strong evidence for a phosphorylated tetrahedral intermediate, the formation of which is required for the coupling.« less

Simulated E-Bomb Effects on Electronically Equipped Targets

DTIC Science & Technology

2009-09-01

coupling model program (CEMPAT), pursuing a feasible geometry of attack, practical antennas, best coupling approximations of ground conductivity and...procedure to determine these possible effects is to estimate the electromagnetic coupling from first principles and simulations using a coupling model ...Applications .................................... 16 B. SYSTEM OF INTEREST MODEL AS A TARGET ............................. 16 1. Shielding Methods, as

Final Report on Hierarchical Coupled Modeling and Prediction of Regional Climate Change in the Atlantic Sector

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

Saravanan, Ramalingam

2011-10-30

During the course of this project, we have accomplished the following: a) Carried out studies of climate changes in the past using a hierarchy of intermediate coupled models (Chang et al., 2008; Wan et al 2009; Wen et al., 2010a,b) b) Completed the development of a Coupled Regional Climate Model (CRCM; Patricola et al., 2011a,b) c) Carried out studies testing hypotheses testing the origin of systematic errors in the CRCM (Patricola et al., 2011a,b) d) Carried out studies of the impact of air-sea interaction on hurricanes, in the context of barrier layer interactions (Balaguru et al)

Highly efficient coupler for dielectric slot waveguides and hybrid plasmonic waveguides

NASA Astrophysics Data System (ADS)

Yu, Jiyao; Ohtera, Yasuo; Yamada, Hirohito

2018-05-01

A compact, highly efficient optical coupler for dielectric slot waveguides and hybrid plasmonic waveguides based on transition layers (air slot grooves) was investigated. The power-coupling efficiency of 75% for the direct coupling case increased to 90% following the insertion of an intermediate section. By performing time-averaged Poynting vector analysis, we successfully separated the factors of transmission, reflection, and radiation at the coupler interface. We found that the insertion of optimal air grooves into the coupler structure contributed to the improvement of coupling performance. The proposed compact structure is characterized by a high transmission efficiency, low reflection, small length, and broad-band spectrum response.

Predicting synchrony in heterogeneous pulse coupled oscillators

NASA Astrophysics Data System (ADS)

Talathi, Sachin S.; Hwang, Dong-Uk; Miliotis, Abraham; Carney, Paul R.; Ditto, William L.

2009-08-01

Pulse coupled oscillators (PCOs) represent an ubiquitous model for a number of physical and biological systems. Phase response curves (PRCs) provide a general mathematical framework to analyze patterns of synchrony generated within these models. A general theoretical approach to account for the nonlinear contributions from higher-order PRCs in the generation of synchronous patterns by the PCOs is still lacking. Here, by considering a prototypical example of a PCO network, i.e., two synaptically coupled neurons, we present a general theory that extends beyond the weak-coupling approximation, to account for higher-order PRC corrections in the derivation of an approximate discrete map, the stable fixed point of which can predict the domain of 1:1 phase locked synchronous states generated by the PCO network.

Approximate solution of coupled cluster equations: application to the coupled cluster doubles method and non-covalent interacting systems.

PubMed

Smiga, Szymon; Fabiano, Eduardo

2017-11-15

We have developed a simplified coupled cluster (SCC) methodology, using the basic idea of scaled MP2 methods. The scheme has been applied to the coupled cluster double equations and implemented in three different non-iterative variants. This new method (especially the SCCD[3] variant, which utilizes a spin-resolved formalism) has been found to be very efficient and to yield an accurate approximation of the reference CCD results for both total and interaction energies of different atoms and molecules. Furthermore, we demonstrate that the equations determining the scaling coefficients for the SCCD[3] approach can generate non-empirical SCS-MP2 scaling coefficients which are in good agreement with previous theoretical investigations.

Prominent mitochondrial DNA recombination intermediates in human heart muscle.

PubMed

Kajander, O A; Karhunen, P J; Holt, I J; Jacobs, H T

2001-11-01

Recombination intermediates containing four-way (Holliday) junctions are generated during DNA repair and replication in many systems, including yeast mitochondrial DNA (mtDNA). In contrast, convincing evidence for recombination in mammalian mtDNA is lacking. We have used two-dimensional agarose-gel electrophoresis to analyse non-linear forms of mtDNA in human heart muscle. Replication intermediates from both the coupled and strand-asynchronous mtDNA replication pathways were detected. An additional class of non-linear molecules, with the electrophoretic properties of four-way junctions, was also prominent. These molecules were insensitive to topoisomerase I or RNase H, but were diminished by branch migration or RuvC treatment. Junctional molecules were detected in all regions of the mitochondrial genome, were found in myocardial DNA from young and old adults, but were present at lower levels in skeletal muscle and placenta. We suggest that they could represent intermediates of mtDNA repair, given their prevalence in the oxyradical-rich environment of heart muscle mitochondria.

Rh(III)-Catalyzed Decarboxylative Coupling of Acrylic Acids with Unsaturated Oxime Esters: Carboxylic Acids Serve as Traceless Activators

PubMed Central

2015-01-01

α,β-Unsaturated carboxylic acids undergo Rh(III)-catalyzed decarboxylative coupling with α,β-unsaturated O-pivaloyl oximes to provide substituted pyridines in good yield. The carboxylic acid, which is removed by decarboxylation, serves as a traceless activating group, giving 5-substituted pyridines with very high levels of regioselectivity. Mechanistic studies rule out a picolinic acid intermediate, and an isolable rhodium complex sheds further light on the reaction mechanism. PMID:24512241

N-Methylamino Pyrimidyl Amides (MAPA): Highly Reactive, Electronically-Activated Amides in Catalytic N-C(O) Cleavage.

PubMed

Meng, Guangrong; Lalancette, Roger; Szostak, Roman; Szostak, Michal

2017-09-01

Despite recent progress in catalytic cross-coupling technologies, the direct activation of N-alkyl-N-aryl amides has been a challenging transformation. Here, we report the first Suzuki cross-coupling of N-methylamino pyrimidyl amides (MAPA) enabled by the controlled n N → π Ar conjugation and the resulting remodeling of the partial double bond character of the amide bond. The new mode of amide activation is suitable for generating acyl-metal intermediates from unactivated primary and secondary amides.

The electromagnetic interchange mode in a partially ionized collisional plasma. [spread F region

NASA Technical Reports Server (NTRS)

Hudson, M. K.; Kennel, C. F.

1974-01-01

A collisional electromagnetic dispersion relation is derived from two-fluid theory for the interchange mode coupled to the Alfven, acoustic, drift and entropy modes in a partially ionized plasma. The fundamental electromagnetic nature of the interchange model is noted; coupling to the intermediate Alfven mode is strongly stabilizing for finite k sub z. Both ion viscous and ion-neutral stabilization are included, and it was found that collisions destroy the ion finite Larmor radius cutoff at short perpendicular wavelengths.

Thermalization after an interaction quench in the Hubbard model.

PubMed

Eckstein, Martin; Kollar, Marcus; Werner, Philipp

2009-07-31

We use nonequilibrium dynamical mean-field theory to study the time evolution of the fermionic Hubbard model after an interaction quench. Both in the weak-coupling and in the strong-coupling regime the system is trapped in quasistationary states on intermediate time scales. These two regimes are separated by a sharp crossover at U(c)dyn=0.8 in units of the bandwidth, where fast thermalization occurs. Our results indicate a dynamical phase transition which should be observable in experiments on trapped fermionic atoms.

Substrate Binding Drives Active-Site Closing of Human Blood Group B Galactosyltransferase as Revealed by Hot-Spot Labeling and NMR Spectroscopy Experiments.

PubMed

Weissbach, Sophie; Flügge, Friedemann; Peters, Thomas

2018-05-04

Crystallography has shown that human blood group A (GTA) and B (GTB) glycosyltransferases undergo transitions between "open", "semiclosed", and "closed" conformations upon substrate binding. However, the timescales of the corresponding conformational reorientations are unknown. Crystal structures show that the Trp and Met residues are located at "conformational hot spots" of the enzymes. Therefore, we utilized 15 N side-chain labeling of Trp residues and 13 C-methyl labeling of Met residues to study substrate-induced conformational transitions of GTB. Chemical-shift perturbations (CSPs) of Met and Trp residues in direct contact with substrate ligands reflect binding kinetics, whereas the CSPs of Met and Trp residues at remote sites reflect conformational changes of the enzyme upon substrate binding. Acceptor binding is fast on the chemical-shift timescale with rather small CSPs in the range of less than approximately 20 Hz. Donor binding matches the intermediate exchange regime to yield an estimate for exchange rate constants of approximately 200-300 Hz. Donor or acceptor binding to GTB saturated with acceptor or donor substrate, respectively, is slow (<10 Hz), as are coupled protein motions, reflecting mutual allosteric control of donor and acceptor binding. Remote CSPs suggest that substrate binding drives the enzyme into the closed state required for catalysis. These findings should contribute to better understanding of the mechanism of glycosyl transfer of GTA and GTB. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hazardous Waste Cleanup: Chemtura Corporation in Perth Amboy, New Jersey

EPA Pesticide Factsheets

The Chemtura Corporation (formerly Crompton Corp.) is located at 10 Convery Boulevard in Perth Amboy, New Jersey. The site encompasses approximately 25 acres, and is an active facility that manufactures chemicals and chemical intermediates for a variety

Coupled electron-nuclear dynamics: Charge migration and charge transfer initiated near a conical intersection

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

Mendive-Tapia, David; Vacher, Morgane; Bearpark, Michael J.

Coupled electron-nuclear dynamics, implemented using the Ehrenfest method, has been used to study charge migration with fixed nuclei, together with charge transfer when nuclei are allowed to move. Simulations were initiated at reference geometries of neutral benzene and 2-phenylethylamine (PEA), and at geometries close to potential energy surface crossings in the cations. Cationic eigenstates, and the so-called sudden approximation, involving removal of an electron from a correlated ground-state wavefunction for the neutral species, were used as initial conditions. Charge migration without coupled nuclear motion could be observed if the Ehrenfest simulation, using the sudden approximation, was started near a conicalmore » intersection where the states were both strongly coupled and quasi-degenerate. Further, the main features associated with charge migration were still recognizable when the nuclear motion was allowed to couple. In the benzene radical cation, starting from the reference neutral geometry with the sudden approximation, one could observe sub-femtosecond charge migration with a small amplitude, which results from weak interaction with higher electronic states. However, we were able to engineer large amplitude charge migration, with a period between 10 and 100 fs, corresponding to oscillation of the electronic structure between the quinoid and anti-quinoid cationic electronic configurations, by distorting the geometry along the derivative coupling vector from the D{sub 6h} Jahn-Teller crossing to lower symmetry where the states are not degenerate. When the nuclear motion becomes coupled, the period changes only slightly. In PEA, in an Ehrenfest trajectory starting from the D{sub 2} eigenstate and reference geometry, a partial charge transfer occurs after about 12 fs near the first crossing between D{sub 1}, D{sub 2} (N{sup +}-Phenyl, N-Phenyl{sup +}). If the Ehrenfest propagation is started near this point, using the sudden approximation without coupled nuclear motion, one observes an oscillation of the spin density – charge migration – between the N atom and the phenyl ring with a period of 4 fs. When the nuclear motion becomes coupled, this oscillation persists in a damped form, followed by an effective charge transfer after 30 fs.« less

Coupled electron-nuclear dynamics: Charge migration and charge transfer initiated near a conical intersection

NASA Astrophysics Data System (ADS)

Mendive-Tapia, David; Vacher, Morgane; Bearpark, Michael J.; Robb, Michael A.

2013-07-01

Coupled electron-nuclear dynamics, implemented using the Ehrenfest method, has been used to study charge migration with fixed nuclei, together with charge transfer when nuclei are allowed to move. Simulations were initiated at reference geometries of neutral benzene and 2-phenylethylamine (PEA), and at geometries close to potential energy surface crossings in the cations. Cationic eigenstates, and the so-called sudden approximation, involving removal of an electron from a correlated ground-state wavefunction for the neutral species, were used as initial conditions. Charge migration without coupled nuclear motion could be observed if the Ehrenfest simulation, using the sudden approximation, was started near a conical intersection where the states were both strongly coupled and quasi-degenerate. Further, the main features associated with charge migration were still recognizable when the nuclear motion was allowed to couple. In the benzene radical cation, starting from the reference neutral geometry with the sudden approximation, one could observe sub-femtosecond charge migration with a small amplitude, which results from weak interaction with higher electronic states. However, we were able to engineer large amplitude charge migration, with a period between 10 and 100 fs, corresponding to oscillation of the electronic structure between the quinoid and anti-quinoid cationic electronic configurations, by distorting the geometry along the derivative coupling vector from the D6h Jahn-Teller crossing to lower symmetry where the states are not degenerate. When the nuclear motion becomes coupled, the period changes only slightly. In PEA, in an Ehrenfest trajectory starting from the D2 eigenstate and reference geometry, a partial charge transfer occurs after about 12 fs near the first crossing between D1, D2 (N+-Phenyl, N-Phenyl+). If the Ehrenfest propagation is started near this point, using the sudden approximation without coupled nuclear motion, one observes an oscillation of the spin density - charge migration - between the N atom and the phenyl ring with a period of 4 fs. When the nuclear motion becomes coupled, this oscillation persists in a damped form, followed by an effective charge transfer after 30 fs.

Persistence and failure of mean-field approximations adapted to a class of systems of delay-coupled excitable units

NASA Astrophysics Data System (ADS)

Franović, Igor; Todorović, Kristina; Vasović, Nebojša; Burić, Nikola

2014-02-01

We consider the approximations behind the typical mean-field model derived for a class of systems made up of type II excitable units influenced by noise and coupling delays. The formulation of the two approximations, referred to as the Gaussian and the quasi-independence approximation, as well as the fashion in which their validity is verified, are adapted to reflect the essential properties of the underlying system. It is demonstrated that the failure of the mean-field model associated with the breakdown of the quasi-independence approximation can be predicted by the noise-induced bistability in the dynamics of the mean-field system. As for the Gaussian approximation, its violation is related to the increase of noise intensity, but the actual condition for failure can be cast in qualitative, rather than quantitative terms. We also discuss how the fulfillment of the mean-field approximations affects the statistics of the first return times for the local and global variables, further exploring the link between the fulfillment of the quasi-independence approximation and certain forms of synchronization between the individual units.

Cylindrical electron beam diode

DOEpatents

Bolduc, Paul E.

1976-01-01

A diode discharge device may include a tubular anode concentrically encircled by and spaced from a tubular cathode electrode with ends intermediate the ends of said anode electrode, and a metal conductive housing having a tubular wall disposed around the cathode electrode with end walls connected to the anode electrode. High energy electron current coupling is through an opening in the housing tubular wall to a portion of the cathode electrode intermediate its ends. Suitable utilization means may be within the anode electrode at positions to be irradiated by electrons emitted from the cathode electrode and transmitted through the anode walls.

Glauber exchange amplitudes. [electron scattering from H atoms

NASA Technical Reports Server (NTRS)

Madan, R. N.

1975-01-01

The extrapolation method of Ochkur, valid for intermediate energies (about 50 eV), is applied to the exchange form of the Glauber amplitudes. In the case of elastic scattering of electrons from hydrogen atoms at 54.4 Ev the 'post' and 'prior' forms of the exchange amplitude are equivalent, whereas for the case of inelastic scattering there is a minute discrepancy between the two forms of the amplitude. The results are compared with the close-coupling calculation. The investigation is expected to be useful for optically forbidden exchange-allowed transitions due to electron impact at intermediate energies.

Assaying Oxidative Coupling Activity of CYP450 Enzymes.

PubMed

Agarwal, Vinayak

2018-01-01

Cytochrome P450 (CYP450) enzymes are ubiquitous catalysts in natural product biosynthetic schemes where they catalyze numerous different transformations using radical intermediates. In this protocol, we describe procedures to assay the activity of a marine bacterial CYP450 enzyme Bmp7 which catalyzes the oxidative radical coupling of polyhalogenated aromatic substrates. The broad substrate tolerance of Bmp7, together with rearrangements of the aryl radical intermediates leads to a large number of products to be generated by the enzymatic action of Bmp7. The complexity of the product pool generated by Bmp7 thus presents an analytical challenge for structural elucidation. To address this challenge, we describe mass spectrometry-based procedures to provide structural insights into aryl crosslinked products generated by Bmp7, which can complement subsequent spectroscopic experiments. Using the procedures described here, for the first time, we show that Bmp7 can efficiently accept polychlorinated aryl substrates, in addition to the physiological polybrominated substrates for the biosynthesis of polyhalogenated marine natural products. © 2018 Elsevier Inc. All rights reserved.

Oxidase catalysis via aerobically generated hypervalent iodine intermediates

NASA Astrophysics Data System (ADS)

Maity, Asim; Hyun, Sung-Min; Powers, David C.

2018-02-01

The development of sustainable oxidation chemistry demands strategies to harness O2 as a terminal oxidant. Oxidase catalysis, in which O2 serves as a chemical oxidant without necessitating incorporation of oxygen into reaction products, would allow diverse substrate functionalization chemistry to be coupled to O2 reduction. Direct O2 utilization suffers from intrinsic challenges imposed by the triplet ground state of O2 and the disparate electron inventories of four-electron O2 reduction and two-electron substrate oxidation. Here, we generate hypervalent iodine reagents—a broadly useful class of selective two-electron oxidants—from O2. This is achieved by intercepting reactive intermediates of aldehyde autoxidation to aerobically generate hypervalent iodine reagents for a broad array of substrate oxidation reactions. The use of aryl iodides as mediators of aerobic oxidation underpins an oxidase catalysis platform that couples substrate oxidation directly to O2 reduction. We anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis.

Marital Status and Satisfaction Five Years Following a Randomized Clinical Trial Comparing Traditional versus Integrative Behavioral Couple Therapy

ERIC Educational Resources Information Center

Christensen, Andrew; Atkins, David C.; Baucom, Brian; Yi, Jean

2010-01-01

Objective: To follow distressed married couples for 5 years after their participation in a randomized clinical trial. Method: A total of 134 chronically and seriously distressed married couples were randomly assigned to approximately 8 months of either traditional behavioral couple therapy (TBCT; Jacobson & Margolin, 1979) or integrative…

Analytical solution and applications of three qubits in three coupled modes without rotating wave approximation

NASA Astrophysics Data System (ADS)

Zhang, Jian-Song; Zhang, Liu-Juan; Chen, Ai-Xi; Abdel-Aty, Mahmoud

2018-06-01

We study the dynamics of the three-qubit system interacting with multi-mode without rotating wave approximation (RWA). A physical realization of the system without direct qubits interactions with dephasing bath is proposed. It is shown that non-Markovian characters of the purity of the three qubits and the coupling strength of modes are stronger enough the RWA is no longer valid. The influences of the dephasing of qubits and interactions of modes on the dynamics of genuine multipartite entanglement and bipartite correlations of qubits are investigated. The multipartite and bipartite quantum correlations could be generated faster if we increase the coupling strength of modes and the RWA is not valid when the coupling strength is strong enough. The unitary transformations approach adopted here can be extended to other systems such as circuit or cavity quantum electrodynamic systems in the strong coupling regime.

Influence of Coupled Radiation and Ablation on the Aerothermodynamic Environment of Planetary Entry Vehicles

NASA Technical Reports Server (NTRS)

Johnston, Christopher O.; Gnoffo, Peter A.; Mazaheri, Alireza

2013-01-01

A review of recently published coupled radiation and ablation capabilities involving the simulation of hypersonic flowfields relevant to Earth, Mars, or Venus entry is presented. The three fundamental mechanisms of radiation coupling are identified as radiative cooling, precursor photochemistry, and ablation-radiation interaction. The impact of these mechanisms are shown to be significant for a 3 m radius sphere entering Earth at hypothetical Mars return conditions (approximately 15 km/s). To estimate the influence precursor absorption on the radiative flux for a wide range of conditions, a simplified approach is developed that requires only the non-precursor solution. Details of a developed coupled ablation approach, which is capable of treating both massively ablating flowfields in the sublimation regime and weakly ablating diffusion Climited oxidation cases, are presented. A review of the two primary uncoupled ablation approximations, identified as the blowing correction and film coefficient approximations, is made and their impact for Earth and Mars entries is shown to be significant for recession and convective heating predictions. Fully coupled ablation and radiation simulations are presented for the Mars return sphere throughout its entire trajectory. Applying to the Mars return sphere the Pioneer- Venus heritage carbon phenolic heatshield, which has properties available in the open literature, the differences between steady state ablation and coupling to a material response code are shown to be significant.

Ab initio electronic structure calculations for metallic intermediate band formation in photovoltaic materials

NASA Astrophysics Data System (ADS)

Wahnón, P.; Tablero, C.

2002-04-01

A metallic isolated band in the middle of the band gap of several III-V semiconductors has been predicted as photovoltaic materials with the possibility of providing substantially enhanced efficiencies. We have investigated the electronic band structures and lattice constants of GanAsmM and GanPmM with M=Sc, Ti, V, and Cr, to identify whether this isolated band is likely to exist by means of accurate calculations. For this task, we use the SIESTA program, an ab initio periodic density-functional method, fully self consistent in the local-density approximation. Norm-conserving, nonlocal pseudopotentials and confined linear combination of atomic orbitals have been used. We have carried out a case study of GanAsmTi and GanPmTi energy-band structure including analyses of the effect of the basis set, fine k-point mesh to ensure numerical convergence, structural parameters, and generalized gradient approximation for exchange and correlation corrections. We find the isolated intermediate band when one Ti atom replaces the position of one As (or P) atom in the crystal structure. For this kind of compound we show that the intermediate band relative position inside the band gap and width are sensitive to the dynamic relaxation of the crystal and the size of the basis set.

Hierarchical sinuous-antenna phased array for millimeter wavelengths

NASA Astrophysics Data System (ADS)

Cukierman, Ari; Lee, Adrian T.; Raum, Christopher; Suzuki, Aritoki; Westbrook, Benjamin

2018-03-01

We present the design, fabrication, and measured performance of a hierarchical sinuous-antenna phased array coupled to superconducting transition-edge-sensor (TES) bolometers for millimeter wavelengths. The architecture allows for dual-polarization wideband sensitivity with a beam width that is approximately frequency-independent. We report on measurements of a prototype device, which uses three levels of triangular phased arrays to synthesize beams that are approximately constant in width across three frequency bands covering a 3:1 bandwidth. The array element is a lens-coupled sinuous antenna. The device consists of an array of hemispherical lenses coupled to a lithographed wafer, which integrates TESs, planar sinuous antennas, and microwave circuitry including band-defining filters. The approximately frequency-independent beam widths improve coupling to telescope optics and keep the sensitivity of an experiment close to optimal across a broad frequency range. The design can be straightforwardly modified for use with non-TES lithographed cryogenic detectors such as kinetic inductance detectors. Additionally, we report on the design and measurements of a broadband 180° hybrid that can simplify the design of future multichroic focal planes including but not limited to hierarchical phased arrays.

Quantum close coupling calculation of transport and relaxation properties for Hg-H2 system

NASA Astrophysics Data System (ADS)

Nemati-Kande, Ebrahim; Maghari, Ali

2016-11-01

Quantum mechanical close coupling calculation of the state-to-state transport and relaxation cross sections have been done for Hg-H2 molecular system using a high-level ab initio potential energy surface. Rotationally averaged cross sections were also calculated to obtain the energy dependent Senftleben-Beenakker cross sections at the energy range of 0.005-25,000 cm-1. Boltzmann averaging of the energy dependent Senftleben-Beenakker cross sections showed the temperature dependency over a wide temperature range of 50-2500 K. Interaction viscosity and diffusion coefficients were also calculated using close coupling cross sections and full classical Mason-Monchick approximation. The results were compared with each other and with the available experimental data. It was found that Mason-Monchick approximation for viscosity is more reliable than diffusion coefficient. Furthermore, from the comparison of the experimental diffusion coefficients with the result of the close coupling and Mason-Monchick approximation, it was found that the Hg-H2 potential energy surface used in this work can reliably predict diffusion coefficient data.

Review of rigorous coupled-wave analysis and of homogeneous effective medium approximations for high spatial-frequency surface-relief gratings

NASA Technical Reports Server (NTRS)

Glytsis, Elias N.; Brundrett, David L.; Gaylord, Thomas K.

1993-01-01

A review of the rigorous coupled-wave analysis as applied to the diffraction of electro-magnetic waves by gratings is presented. The analysis is valid for any polarization, angle of incidence, and conical diffraction. Cascaded and/or multiplexed gratings as well as material anisotropy can be incorporated under the same formalism. Small period rectangular groove gratings can also be modeled using approximately equivalent uniaxial homogeneous layers (effective media). The ordinary and extraordinary refractive indices of these layers depend on the gratings filling factor, the refractive indices of the substrate and superstrate, and the ratio of the freespace wavelength to grating period. Comparisons of the homogeneous effective medium approximations with the rigorous coupled-wave analysis are presented. Antireflection designs (single-layer or multilayer) using the effective medium models are presented and compared. These ultra-short period antireflection gratings can also be used to produce soft x-rays. Comparisons of the rigorous coupled-wave analysis with experimental results on soft x-ray generation by gratings are also included.

Evidence for Intermediate Polars as the Origin of the Galactic Center Hard X-Ray Emission

NASA Technical Reports Server (NTRS)

Hailey, Charles J.; Mori, Kaya; Perez, Kerstin; Canipe, Alicia M.; Hong, Jaesub; Tomsick, John A.; Boggs, Steven E.; Christensen, Finn E.; Craig, William W.; Fornasini, Francesa;

New cross-coupling reaction of arylbromide with arylboric acid catalyzed by nano metals

NASA Astrophysics Data System (ADS)

An, Zhong W.; Chen, Xin B.

2002-06-01

Synthetic method of compounds 4,4'-bis-(trans-4- alkylcyclohexyl) biphenyl by cross-coupling reaction of arylboric acid and arylbromide in the presence of cetrimonium bromide over nano Ni or Cu catalyst is presented. The reaction is carried out under reflux temperature in THF/H2O for 15 h with yield 60% to approximately 65% for nano nickel and 25% to approximately 30% for nano copper.

Evidence for a Shared Mechanism in the Formation of Urea-Induced Kinetic and Equilibrium Intermediates of Horse Apomyoglobin from Ultrarapid Mixing Experiments.

PubMed

Mizukami, Takuya; Abe, Yukiko; Maki, Kosuke

2015-01-01

In this study, the equivalence of the kinetic mechanisms of the formation of urea-induced kinetic folding intermediates and non-native equilibrium states was investigated in apomyoglobin. Despite having similar structural properties, equilibrium and kinetic intermediates accumulate under different conditions and via different mechanisms, and it remains unknown whether their formation involves shared or distinct kinetic mechanisms. To investigate the potential mechanisms of formation, the refolding and unfolding kinetics of horse apomyoglobin were measured by continuous- and stopped-flow fluorescence over a time range from approximately 100 μs to 10 s, along with equilibrium unfolding transitions, as a function of urea concentration at pH 6.0 and 8°C. The formation of a kinetic intermediate was observed over a wider range of urea concentrations (0-2.2 M) than the formation of the native state (0-1.6 M). Additionally, the kinetic intermediate remained populated as the predominant equilibrium state under conditions where the native and unfolded states were unstable (at ~0.7-2 M urea). A continuous shift from the kinetic to the equilibrium intermediate was observed as urea concentrations increased from 0 M to ~2 M, which indicates that these states share a common kinetic folding mechanism. This finding supports the conclusion that these intermediates are equivalent. Our results in turn suggest that the regions of the protein that resist denaturant perturbations form during the earlier stages of folding, which further supports the structural equivalence of transient and equilibrium intermediates. An additional folding intermediate accumulated within ~140 μs of refolding and an unfolding intermediate accumulated in <1 ms of unfolding. Finally, by using quantitative modeling, we showed that a five-state sequential scheme appropriately describes the folding mechanism of horse apomyoglobin.

Reduction of matrix effects in inductively coupled plasma mass spectrometry by flow injection with an unshielded torch.

PubMed

Gross, Cory T; McIntyre, Sally M; Houk, R S

2009-06-15

Solution samples with matrix concentrations above approximately 0.1% generally present difficulties for analysis by inductively coupled plasma mass spectrometry (ICP-MS) because of cone clogging and matrix effects. Flow injection (FI) is coupled to ICP-MS to reduce deposition from samples such as 1% sodium salts (as NaCl) and seawater (approximately 3% dissolved salts). Surprisingly, matrix effects are also less severe during flow injection, at least for some matrix elements on the particular instrument used. Sodium chloride at 1% Na and undiluted seawater cause only 2 to 29% losses of signal for typical analyte elements. A heavy matrix element (Bi) at 0.1% also induces only approximately 14% loss of analyte signal. However, barium causes a much worse matrix effect, that is, approximately 90% signal loss at 5000 ppm Na. Also, matrix effects during FI are much more severe when a grounded metal shield is inserted between the load coil and the torch, which is the most common mode of operation for the particular ICP-MS device used.

Highly efficient perturbative + variational strategy based on orthogonal valence bond theory for the evaluation of magnetic coupling constants. Application to the trinuclear Cu(ii) site of multicopper oxidases.

PubMed

Tenti, Lorenzo; Maynau, Daniel; Angeli, Celestino; Calzado, Carmen J

2016-07-21

A new strategy based on orthogonal valence-bond analysis of the wave function combined with intermediate Hamiltonian theory has been applied to the evaluation of the magnetic coupling constants in two AF systems. This approach provides both a quantitative estimate of the J value and a detailed analysis of the main physical mechanisms controlling the coupling, using a combined perturbative + variational scheme. The procedure requires a selection of the dominant excitations to be treated variationally. Two methods have been employed: a brute-force selection, using a logic similar to that of the CIPSI approach, or entanglement measures, which identify the most interacting orbitals in the system. Once a reduced set of excitations (about 300 determinants) is established, the interaction matrix is dressed at the second-order of perturbation by the remaining excitations of the CI space. The diagonalization of the dressed matrix provides J values in good agreement with experimental ones, at a very low-cost. This approach demonstrates the key role of d → d* excitations in the quantitative description of the magnetic coupling, as well as the importance of using an extended active space, including the bridging ligand orbitals, for the binuclear model of the intermediates of multicopper oxidases. The method is a promising tool for dealing with complex systems containing several active centers, as an alternative to both pure variational and DFT approaches.

Highly enantioselective synthesis of γ-, δ-, and ε-chiral 1-alkanols via Zr-catalyzed asymmetric carboalumination of alkenes (ZACA)–Cu- or Pd-catalyzed cross-coupling

PubMed Central

Xu, Shiqing; Oda, Akimichi; Kamada, Hirofumi; Negishi, Ei-ichi

2014-01-01

Despite recent advances of asymmetric synthesis, the preparation of enantiomerically pure (≥99% ee) compounds remains a challenge in modern organic chemistry. We report here a strategy for a highly enantioselective (≥99% ee) and catalytic synthesis of various γ- and more-remotely chiral alcohols from terminal alkenes via Zr-catalyzed asymmetric carboalumination of alkenes (ZACA reaction)–Cu- or Pd-catalyzed cross-coupling. ZACA–in situ oxidation of tert-butyldimethylsilyl (TBS)-protected ω-alkene-1-ols produced both (R)- and (S)-α,ω-dioxyfunctional intermediates (3) in 80–88% ee, which were readily purified to the ≥99% ee level by lipase-catalyzed acetylation through exploitation of their high selectivity factors. These α,ω-dioxyfunctional intermediates serve as versatile synthons for the construction of various chiral compounds. Their subsequent Cu-catalyzed cross-coupling with various alkyl (primary, secondary, tertiary, cyclic) Grignard reagents and Pd-catalyzed cross-coupling with aryl and alkenyl halides proceeded smoothly with essentially complete retention of stereochemical configuration to produce a wide variety of γ-, δ-, and ε-chiral 1-alkanols of ≥99% ee. The MαNP ester analysis has been applied to the determination of the enantiomeric purities of δ- and ε-chiral primary alkanols, which sheds light on the relatively undeveloped area of determination of enantiomeric purity and/or absolute configuration of remotely chiral primary alcohols. PMID:24912191

Advanced Reactors-Intermediate Heat Exchanger (IHX) Coupling: Theoretical Modeling and Experimental Validation

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

Utgikar, Vivek; Sun, Xiaodong; Christensen, Richard

2016-12-29

The overall goal of the research project was to model the behavior of the advanced reactorintermediate heat exchange system and to develop advanced control techniques for off-normal conditions. The specific objectives defined for the project were: 1. To develop the steady-state thermal hydraulic design of the intermediate heat exchanger (IHX); 2. To develop mathematical models to describe the advanced nuclear reactor-IHX-chemical process/power generation coupling during normal and off-normal operations, and to simulate models using multiphysics software; 3. To develop control strategies using genetic algorithm or neural network techniques and couple these techniques with the multiphysics software; 4. To validate themore » models experimentally The project objectives were accomplished by defining and executing four different tasks corresponding to these specific objectives. The first task involved selection of IHX candidates and developing steady state designs for those. The second task involved modeling of the transient and offnormal operation of the reactor-IHX system. The subsequent task dealt with the development of control strategies and involved algorithm development and simulation. The last task involved experimental validation of the thermal hydraulic performances of the two prototype heat exchangers designed and fabricated for the project at steady state and transient conditions to simulate the coupling of the reactor- IHX-process plant system. The experimental work utilized the two test facilities at The Ohio State University (OSU) including one existing High-Temperature Helium Test Facility (HTHF) and the newly developed high-temperature molten salt facility.« less

Split Dirac Supersymmetry: An Ultraviolet Completion of Higgsino Dark Matter

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

Fox, Patrick J.; Kribs, Graham D.; Martin, Adam

2014-10-07

Motivated by the observation that the Higgs quartic coupling runs to zero at an intermediate scale, we propose a new framework for models of split supersymmetry, in which gauginos acquire intermediate scale Dirac masses ofmore » $$\\sim 10^{8-11}$$ GeV. Scalar masses arise from one-loop finite contributions as well as direct gravity-mediated contributions. Like split supersymmetry, one Higgs doublet is fine-tuned to be light. The scale at which the Dirac gauginos are introduced to make the Higgs quartic zero is the same as is necessary for gauge coupling unification. Thus, gauge coupling unification persists (nontrivially, due to adjoint multiplets), though with a somewhat higher unification scale $$\\gtrsim 10^{17}$$ GeV. The $$\\mu$$-term is naturally at the weak scale, and provides an opportunity for experimental verification. We present two manifestations of Split Dirac Supersymmetry. In the "Pure Dirac" model, the lightest Higgsino must decay through R-parity violating couplings, leading to an array of interesting signals in colliders. In the "Hypercharge Impure" model, the bino acquires a Majorana mass that is one-loop suppressed compared with the Dirac gluino and wino. This leads to weak scale Higgsino dark matter whose overall mass scale, as well as the mass splitting between the neutral components, is naturally generated from the same UV dynamics. We outline the challenges to discovering pseudo-Dirac Higgsino dark matter in collider and dark matter detection experiments.« less

Electron-phonon coupling in superconducting β-PdBi{sub 2}

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

Sharma, Ramesh; Dwivedi, Shalini; Sharma, Yamini, E-mail: sharma.yamini62@gmail.com

2015-06-24

We have studied the electronic, transport and vibrational properties of low temperature superconductor β-PdBi{sub 2}. The band manifold clearly demonstrates the 2D-layered structure with multiple gaps. The intersection of bands at E{sub F} in the Γ-P, Γ-N directions gives rise to complicated Fermi surface topology, which contains quite complicated multiple connected sheets, as well as hole and electron-like pockets. From the low temperature specific heat, we have estimated the electron-phonon coupling constant λ{sub el-ph} which has a very high value of 3.66. The vibrational properties clearly illustrates that the strong coupling makes the lattice unstable. The calculated properties confirm thatmore » β-PdBi{sub 2} is an intermediate coupling superconductor.« less

Body frame close coupling wave packet approach to gas phase atom-rigid rotor inelastic collisions

NASA Technical Reports Server (NTRS)

Sun, Y.; Judson, R. S.; Kouri, D. J.

1989-01-01

The close coupling wave packet (CCWP) method is formulated in a body-fixed representation for atom-rigid rotor inelastic scattering. For J greater than j-max (where J is the total angular momentum and j is the rotational quantum number), the computational cost of propagating the coupled channel wave packets in the body frame is shown to scale approximately as N exp 3/2, where N is the total number of channels. For large numbers of channels, this will be much more efficient than the space frame CCWP method previously developed which scales approximately as N-squared under the same conditions.

Collision for Li++He System. I. Potential Curves and Non-Adiabatic Coupling Matrix Elements

NASA Astrophysics Data System (ADS)

Yoshida, Junichi; O-Ohata, Kiyosi

1984-02-01

The potential curves and the non-adiabatic coupling matrix elements for the Li++He collision system were computed. The SCF molecular orbitals were constructed with the CGTO atomic bases centered on each nucleus and the center of mass of two nuclei. The SCF and CI calculations were done at various internuclear distances in the range of 0.1˜25.0 a.u. The potential energies and the wavefunctions were calculated with good approximation over whole internuclear distance. The non-adiabatic coupling matrix elements were calculated with the tentative method in which the ETF are approximately taken into account.

Stable finite element approximations of two-phase flow with soluble surfactant

NASA Astrophysics Data System (ADS)

Barrett, John W.; Garcke, Harald; Nürnberg, Robert

2015-09-01

A parametric finite element approximation of incompressible two-phase flow with soluble surfactants is presented. The Navier-Stokes equations are coupled to bulk and surfaces PDEs for the surfactant concentrations. At the interface adsorption, desorption and stress balances involving curvature effects and Marangoni forces have to be considered. A parametric finite element approximation for the advection of the interface, which maintains good mesh properties, is coupled to the evolving surface finite element method, which is used to discretize the surface PDE for the interface surfactant concentration. The resulting system is solved together with standard finite element approximations of the Navier-Stokes equations and of the bulk parabolic PDE for the surfactant concentration. Semidiscrete and fully discrete approximations are analyzed with respect to stability, conservation and existence/uniqueness issues. The approach is validated for simple test cases and for complex scenarios, including colliding drops in a shear flow, which are computed in two and three space dimensions.

Two-parametric {\\delta'} -interactions: approximation by Schrödinger operators with localized rank-two perturbations

NASA Astrophysics Data System (ADS)

Golovaty, Yuriy

2018-06-01

We construct a norm resolvent approximation to the family of point interactions , by Schrödinger operators with localized rank-two perturbations coupled with short range potentials. In particular, a new approximation to the -interactions is obtained.

Spin-correlated doublet pairs as intermediate states in charge separation processes

NASA Astrophysics Data System (ADS)

Kraffert, Felix; Behrends, Jan

2017-10-01

Spin-correlated charge-carrier pairs play a crucial role as intermediate states in charge separation both in natural photosynthesis as well as in solar cells. Using transient electron paramagnetic resonance (trEPR) spectroscopy in combination with spectral simulations, we study spin-correlated polaron pairs in polymer:fullerene blends as organic solar cells materials. The semi-analytical simulations presented here are based on the well-established theoretical description of spin-correlated radical pairs in biological systems, however, explicitly considering the disordered nature of polymer:fullerene blends. The large degree of disorder leads to the fact that many different relative orientations between both polarons forming the spin-correlated pairs have to be taken into account. This has important implications for the spectra, which differ significantly from those of spin-correlated radical pairs with a fixed relative orientation. We systematically study the influence of exchange and dipolar couplings on the trEPR spectra and compare the simulation results to measured X- and Q-band trEPR spectra. Our results demonstrate that assuming dipolar couplings alone does not allow us to reproduce the experimental spectra. Due to the rather delocalised nature of polarons in conjugated organic semiconductors, a significant isotropic exchange coupling needs to be included to achieve good agreement between experiments and simulations.

Nickel-catalyzed cross-coupling of photoredox-generated radicals: uncovering a general manifold for stereoconvergence in nickel-catalyzed cross-couplings.

PubMed

Gutierrez, Osvaldo; Tellis, John C; Primer, David N; Molander, Gary A; Kozlowski, Marisa C

2015-04-22

The cross-coupling of sp(3)-hybridized organoboron reagents via photoredox/nickel dual catalysis represents a new paradigm of reactivity for engaging alkylmetallic reagents in transition-metal-catalyzed processes. Reported here is an investigation into the mechanistic details of this important transformation using density functional theory. Calculations bring to light a new reaction pathway involving an alkylnickel(I) complex generated by addition of an alkyl radical to Ni(0) that is likely to operate simultaneously with the previously proposed mechanism. Analysis of the enantioselective variant of the transformation reveals an unexpected manifold for stereoinduction involving dynamic kinetic resolution (DKR) of a Ni(III) intermediate wherein the stereodetermining step is reductive elimination. Furthermore, calculations suggest that the DKR-based stereoinduction manifold may be responsible for stereoselectivity observed in numerous other stereoconvergent Ni-catalyzed cross-couplings and reductive couplings.

Controllability of impulse controlled systems of heat equations coupled by constant matrices

NASA Astrophysics Data System (ADS)

Qin, Shulin; Wang, Gengsheng

2017-11-01

This paper studies the approximate and null controllability for impulse controlled systems of heat equations coupled by a pair (A , B) of constant matrices. We present a necessary and sufficient condition for the approximate controllability, which is exactly Kalman's controllability rank condition of (A , B). We prove that when such a system is approximately controllable, the approximate controllability over an interval [ 0 , T ] can be realized by adding controls at arbitrary q (A , B) different control instants 0 <τ1 <τ2 < ⋯ <τ q (A , B) < T, provided that τ q (A , B) -τ1

Coupling compositional liquid gas Darcy and free gas flows at porous and free-flow domains interface

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

Masson, R., E-mail: roland.masson@unice.fr; Team COFFEE INRIA Sophia Antipolis Méditerranée; Trenty, L., E-mail: laurent.trenty@andra.fr

This paper proposes an efficient splitting algorithm to solve coupled liquid gas Darcy and free gas flows at the interface between a porous medium and a free-flow domain. This model is compared to the reduced model introduced in [6] using a 1D approximation of the gas free flow. For that purpose, the gas molar fraction diffusive flux at the interface in the free-flow domain is approximated by a two point flux approximation based on a low-frequency diagonal approximation of a Steklov–Poincaré type operator. The splitting algorithm and the reduced model are applied in particular to the modelling of the massmore » exchanges at the interface between the storage and the ventilation galleries in radioactive waste deposits.« less

Dynamics of two-dimensional monolayer water confined in hydrophobic and charged environments.

PubMed

Kumar, Pradeep; Han, Sungho

2012-09-21

We perform molecular dynamics simulations to study the effect of charged surfaces on the intermediate and long time dynamics of water in nanoconfinements. Here, we use the transferable interaction potential with five points (TIP5P) model of a water molecule confined in both hydrophobic and charged surfaces. For a single molecular layer of water between the surfaces, we find that the temperature dependence of the lateral diffusion constant of water up to very high temperatures remains Arrhenius with a high activation energy. In case of charged surfaces, however, the dynamics of water in the intermediate time regime is drastically modified presumably due to the transient coupling of dipoles of water molecules with electric field fluctuations induced by charges on the confining surfaces. Specifically, the lateral mean square displacements display a distinct super-diffusive behavior at intermediate time scale, defined as the time scale between ballistic and diffusive regimes. This change in the intermediate time-scale dynamics in the charged confinement leads to the enhancement of long-time dynamics as reflected in increasing diffusion constant. We introduce a simple model for a possible explanation of the super-diffusive behavior and find it to be in good agreement with our simulation results. Furthermore, we find that confinement and the surface polarity enhance the low frequency vibration in confinement compared to bulk water. By introducing a new effective length scale of coupling between translational and orientational motions, we find that the length scale increases with the increasing strength of the surface polarity. Further, we calculate the correlation between the diffusion constant and the excess entropy and find a disordering effect of polar surfaces on the structure of water. Finally, we find that the empirical relation between the diffusion constant and the excess entropy holds for a monolayer of water in nanoconfinement.

Intermediate couplings: NMR at the solids-liquids interface

NASA Astrophysics Data System (ADS)

Spence, Megan

2006-03-01

Anisotropic interactions like dipolar couplings and chemical shift anisotropy have long offered solid-state NMR spectroscopists valuable structural information. Recently, solution-state NMR structural studies have begun to exploit residual dipolar couplings of biological molecules in weakly anisotropic solutions. These residual couplings are about 0.1% of the coupling magnitudes observed in the solid state, allowing simple, high-resolution NMR spectra to be retained. In this work, we examine the membrane-associated opioid, leucine enkephalin (lenk), in which the ordering is ten times larger than that for residual dipolar coupling experiments, requiring a combination of solution-state and solid-state NMR techniques. We adapted conventional solid-state NMR techniques like adiabatic cross- polarization and REDOR for use with such a system, and measured small amide bond dipolar couplings in order to determine the orientation of the amide bonds (and therefore the peptide) with respect to the membrane surface. However, the couplings measured indicate large structural rearrangements on the surface and contradict the published structures obtained by NOESY constraints, a reminder that such methods are of limited use in the presence of large-scale dynamics.

On the incorporation of the geometric phase in general single potential energy surface dynamics: A removable approximation to ab initio data.

PubMed

Malbon, Christopher L; Zhu, Xiaolei; Guo, Hua; Yarkony, David R

2016-12-21

For two electronic states coupled by conical intersections, the line integral of the derivative coupling can be used to construct a complex-valued multiplicative phase factor that makes the real-valued adiabatic electronic wave function single-valued, provided that the curl of the derivative coupling is zero. Unfortunately for ab initio determined wave functions, the curl is never rigorously zero. However, when the wave functions are determined from a coupled two diabatic state Hamiltonian H d (fit to ab initio data), the resulting derivative couplings are by construction curl free, except at points of conical intersection. In this work we focus on a recently introduced diabatization scheme that produces the H d by fitting ab initio determined energies, energy gradients, and derivative couplings to the corresponding H d determined quantities in a least squares sense, producing a removable approximation to the ab initio determined derivative coupling. This approach and related numerical issues associated with the nonremovable ab initio derivative couplings are illustrated using a full 33-dimensional representation of phenol photodissociation. The use of this approach to provide a general framework for treating the molecular Aharonov Bohm effect is demonstrated.

On the stereochemical course of palladium-catalyzed cross-coupling of allylic silanolate salts with aromatic bromides.

PubMed

Denmark, Scott E; Werner, Nathan S

2010-03-17

The stereochemical course of palladium-catalyzed cross-coupling reactions of an enantioenriched, alpha-substituted, allylic silanolate salt with aromatic bromides has been investigated. The allylic silanolate salt was prepared in high geometrical (Z/E, 94:6) and high enantiomeric (94:6 er) purity by a copper-catalyzed S(N)2' reaction of a resolved allylic carbamate. Eight different aromatic bromides underwent cross-coupling with excellent constitutional site-selectivity and excellent stereospecificity. Stereochemical correlation established that the transmetalation event proceeds through a syn S(E)' mechanism which is interpreted in terms of an intramolecular delivery of the arylpalladium electrophile through a key intermediate that contains a discrete Si-O-Pd linkage.

Metastability in the Spin-1 Blume-Emery-Griffiths Model within Constant Coupling Approximation

NASA Astrophysics Data System (ADS)

Ekiz, C.

2017-02-01

In this paper, the equilibrium properties of spin-1 Blume-Emery-Griffiths model are studied by using constant-coupling approximation. The dipolar and quadrupolar order parameters, the stable, metastable and unstable states and free energy of the model are investigated. The states are defined in terms of local minima of the free energy of system. The numerical calculations are presented for several values of exchange interactions on the simple cubic lattice with q = 6.

Synchronization of three electrochemical oscillators: From local to global coupling

NASA Astrophysics Data System (ADS)

Liu, Yifan; Sebek, Michael; Mori, Fumito; Kiss, István Z.

2018-04-01

We investigate the formation of synchronization patterns in an oscillatory nickel electrodissolution system in a network obtained by superimposing local and global coupling with three electrodes. We explored the behavior through numerical simulations using kinetic ordinary differential equations, Kuramoto type phase models, and experiments, in which the local to global coupling could be tuned by cross resistances between the three nickel wires. At intermediate coupling strength with predominant global coupling, two of the three oscillators, whose natural frequencies are closer, can synchronize. By adding even a relatively small amount of local coupling (about 9%-25%), a spatially organized partially synchronized state can occur where one of the two synchronized elements is in the center. A formula was derived for predicting the critical coupling strength at which full synchronization will occur independent of the permutation of the natural frequencies of the oscillators over the network. The formula correctly predicts the variation of the critical coupling strength as a function of the global coupling fraction, e.g., with local coupling the critical coupling strength is about twice than that required with global coupling. The results show the importance of the topology of the network on the synchronization properties in a simple three-oscillator setup and could provide guidelines for decrypting coupling topology from identification of synchronization patterns.

An intermediate orbit calculated from three position vectors: accuracy of approximation of a perturbed motion. (Russian Title: Промежуточная орбита, вычисленная по трем векторам положения: точность аппроксимации возмущенного движения)

NASA Astrophysics Data System (ADS)

Shefer, V. A.

2015-12-01

We examine intermediate perturbed orbit proposed by the author previously, defined from the three position vectors of a small celestial body. It is shown theoretically, that at a small reference time interval covering the body positions the approximation accuracy of real motion by this orbit corresponds approximately to the fourth order of tangency. The smaller reference interval of time, the better this correspondence. Laws of variation of the methodical errors in constructing intermediate orbit subject to the length of reference time interval are deduced. According to these laws, the convergence rate of the method to the exact solution (upon reducing the reference interval of time) in the general case is higher by three orders of magnitude than in the case of conventional methods using Keplerian unperturbed orbit. The considered orbit is among the most accurate in set of orbits of their class determined by the order of tangency. The theoretical results are validated by numerical examples. The work was supported by the Ministry of Education and Science of the Russian Federation, project no. 2014/223(1567).

Higher harmonic flow coefficients of identified hadrons in Pb-Pb collisions at √{s_{NN}}=2.76 TeV

NASA Astrophysics Data System (ADS)

Adam, J.; Adamová, D.; Aggarwal, M. M.; Aglieri Rinella, G.; Agnello, M.; Agrawal, N.; Ahammed, Z.; Ahmad, S.; Ahn, S. U.; Aiola, S.; Akindinov, A.; Alam, S. N.; Albuquerque, D. S. D.; Aleksandrov, D.; Alessandro, B.; Alexandre, D.; Alfaro Molina, R.; Alici, A.; Alkin, A.; Alme, J.; Alt, T.; Altinpinar, S.; Altsybeev, I.; Alves Garcia Prado, C.; An, M.; Andrei, C.; Andrews, H. A.; Andronic, A.; Anguelov, V.; Antičić, T.; Antinori, F.; Antonioli, P.; Aphecetche, L.; Appelshäuser, H.; Arcelli, S.; Arnaldi, R.; Arnold, O. W.; Arsene, I. C.; Arslandok, M.; Audurier, B.; Augustinus, A.; Averbeck, R.; Azmi, M. D.; Badalà, A.; Baek, Y. W.; Bagnasco, S.; Bailhache, R.; Bala, R.; Balasubramanian, S.; Baldisseri, A.; Baral, R. C.; Barbano, A. M.; Barbera, R.; Barile, F.; Barnaföldi, G. G.; Barnby, L. S.; Barret, V.; Bartalini, P.; Barth, K.; Bartke, J.; Bartsch, E.; Basile, M.; Bastid, N.; Basu, S.; Bathen, B.; Batigne, G.; Batista Camejo, A.; Batyunya, B.; Batzing, P. C.; Bearden, I. G.; Beck, H.; Bedda, C.; Behera, N. K.; Belikov, I.; Bellini, F.; Bello Martinez, H.; Bellwied, R.; Belmont, R.; Belmont-Moreno, E.; Beltran, L. G. E.; Belyaev, V.; Bencedi, G.; Beole, S.; Berceanu, I.; Bercuci, A.; Berdnikov, Y.; Berenyi, D.; Bertens, R. A.; Berzano, D.; Betev, L.; Bhasin, A.; Bhat, I. R.; Bhati, A. K.; Bhattacharjee, B.; Bhom, J.; Bianchi, L.; Bianchi, N.; Bianchin, C.; Bielčík, J.; Bielčíková, J.; Bilandzic, A.; Biro, G.; Biswas, R.; Biswas, S.; Bjelogrlic, S.; Blair, J. T.; Blau, D.; Blume, C.; Bock, F.; Bogdanov, A.; Bøggild, H.; Boldizsár, L.; Bombara, M.; Bonora, M.; Book, J.; Borel, H.; Borissov, A.; Borri, M.; Bossú, F.; Botta, E.; Bourjau, C.; Braun-Munzinger, P.; Bregant, M.; Breitner, T.; Broker, T. A.; Browning, T. A.; Broz, M.; Brucken, E. J.; Bruna, E.; Bruno, G. E.; Budnikov, D.; Buesching, H.; Bufalino, S.; Buncic, P.; Busch, O.; Buthelezi, Z.; Butt, J. B.; Buxton, J. T.; Cabala, J.; Caffarri, D.; Cai, X.; Caines, H.; Calero Diaz, L.; Caliva, A.; Calvo Villar, E.; Camerini, P.; Carena, F.; Carena, W.; Carnesecchi, F.; Castillo Castellanos, J.; Castro, A. J.; Casula, E. A. R.; Ceballos Sanchez, C.; Cepila, J.; Cerello, P.; Cerkala, J.; Chang, B.; Chapeland, S.; Chartier, M.; Charvet, J. L.; Chattopadhyay, S.; Chattopadhyay, S.; Chauvin, A.; Chelnokov, V.; Cherney, M.; Cheshkov, C.; Cheynis, B.; Chibante Barroso, V.; Chinellato, D. D.; Cho, S.; Chochula, P.; Choi, K.; Chojnacki, M.; Choudhury, S.; Christakoglou, P.; Christensen, C. H.; Christiansen, P.; Chujo, T.; Chung, S. U.; Cicalo, C.; Cifarelli, L.; Cindolo, F.; Cleymans, J.; Colamaria, F.; Colella, D.; Collu, A.; Colocci, M.; Conesa Balbastre, G.; Conesa del Valle, Z.; Connors, M. E.; Contreras, J. G.; Cormier, T. M.; Corrales Morales, Y.; Cortés Maldonado, I.; Cortese, P.; Cosentino, M. R.; Costa, F.; Crkovska, J.; Crochet, P.; Cruz Albino, R.; Cuautle, E.; Cunqueiro, L.; Dahms, T.; Dainese, A.; Danisch, M. C.; Danu, A.; Das, D.; Das, I.; Das, S.; Dash, A.; Dash, S.; De, S.; De Caro, A.; de Cataldo, G.; de Conti, C.; de Cuveland, J.; De Falco, A.; De Gruttola, D.; De Marco, N.; De Pasquale, S.; De Souza, R. D.; Deisting, A.; Deloff, A.; Dénes, E.; Deplano, C.; Dhankher, P.; Di Bari, D.; Di Mauro, A.; Di Nezza, P.; Di Ruzza, B.; Diaz Corchero, M. A.; Dietel, T.; Dillenseger, P.; Divià, R.; Djuvsland, Ø.; Dobrin, A.; Domenicis Gimenez, D.; Dönigus, B.; Dordic, O.; Drozhzhova, T.; Dubey, A. K.; Dubla, A.; Ducroux, L.; Dupieux, P.; Ehlers, R. J.; Elia, D.; Endress, E.; Engel, H.; Epple, E.; Erazmus, B.; Erdemir, I.; Erhardt, F.; Espagnon, B.; Estienne, M.; Esumi, S.; Eulisse, G.; Eum, J.; Evans, D.; Evdokimov, S.; Eyyubova, G.; Fabbietti, L.; Fabris, D.; Faivre, J.; Fantoni, A.; Fasel, M.; Feldkamp, L.; Feliciello, A.; Feofilov, G.; Ferencei, J.; Fernández Téllez, A.; Ferreiro, E. G.; Ferretti, A.; Festanti, A.; Feuillard, V. J. G.; Figiel, J.; Figueredo, M. A. S.; Filchagin, S.; Finogeev, D.; Fionda, F. M.; Fiore, E. M.; Floris, M.; Foertsch, S.; Foka, P.; Fokin, S.; Fragiacomo, E.; Francescon, A.; Francisco, A.; Frankenfeld, U.; Fronze, G. G.; Fuchs, U.; Furget, C.; Furs, A.; Fusco Girard, M.; Gaardhøje, J. J.; Gagliardi, M.; Gago, A. M.; Gajdosova, K.; Gallio, M.; Galvan, C. D.; Gangadharan, D. R.; Ganoti, P.; Gao, C.; Garabatos, C.; Garcia-Solis, E.; Garg, K.; Gargiulo, C.; Gasik, P.; Gauger, E. F.; Germain, M.; Gheata, M.; Ghosh, P.; Ghosh, S. K.; Gianotti, P.; Giubellino, P.; Giubilato, P.; Gladysz-Dziadus, E.; Glässel, P.; Goméz Coral, D. M.; Gomez Ramirez, A.; Gonzalez, A. S.; Gonzalez, V.; González-Zamora, P.; Gorbunov, S.; Görlich, L.; Gotovac, S.; Grabski, V.; Grachov, O. A.; Graczykowski, L. K.; Graham, K. L.; Grelli, A.; Grigoras, A.; Grigoras, C.; Grigoriev, V.; Grigoryan, A.; Grigoryan, S.; Grinyov, B.; Grion, N.; Gronefeld, J. M.; Grosse-Oetringhaus, J. F.; Grosso, R.; Gruber, L.; Guber, F.; Guernane, R.; Guerzoni, B.; Gulbrandsen, K.; Gunji, T.; Gupta, A.; Gupta, R.; Guzman, I. B.; Haake, R.; Hadjidakis, C.; Haiduc, M.; Hamagaki, H.; Hamar, G.; Hamon, J. C.; Harris, J. W.; Harton, A.; Hatzifotiadou, D.; Hayashi, S.; Heckel, S. T.; Hellbär, E.; Helstrup, H.; Herghelegiu, A.; Herrera Corral, G.; Herrmann, F.; Hess, B. A.; Hetland, K. F.; Hillemanns, H.; Hippolyte, B.; Horak, D.; Hosokawa, R.; Hristov, P.; Hughes, C.; Humanic, T. J.; Hussain, N.; Hussain, T.; Hutter, D.; Hwang, D. S.; Ilkaev, R.; Inaba, M.; Incani, E.; Ippolitov, M.; Irfan, M.; Isakov, V.; Ivanov, M.; Ivanov, V.; Izucheev, V.; Jacak, B.; Jacazio, N.; Jacobs, P. M.; Jadhav, M. B.; Jadlovska, S.; Jadlovsky, J.; Jahnke, C.; Jakubowska, M. J.; Janik, M. A.; Jayarathna, P. H. S. Y.; Jena, C.; Jena, S.; Jimenez Bustamante, R. T.; Jones, P. G.; Jusko, A.; Kalinak, P.; Kalweit, A.; Kang, J. H.; Kaplin, V.; Kar, S.; Karasu Uysal, A.; Karavichev, O.; Karavicheva, T.; Karayan, L.; Karpechev, E.; Kebschull, U.; Keidel, R.; Keijdener, D. L. D.; Keil, M.; Mohisin Khan, M.; Khan, P.; Khan, S. A.; Khanzadeev, A.; Kharlov, Y.; Khatun, A.; Kileng, B.; Kim, D. W.; Kim, D. J.; Kim, D.; Kim, H.; Kim, J. S.; Kim, J.; Kim, M.; Kim, S.; Kim, T.; Kirsch, S.; Kisel, I.; Kiselev, S.; Kisiel, A.; Kiss, G.; Klay, J. L.; Klein, C.; Klein, J.; Klein-Bösing, C.; Klewin, S.; Kluge, A.; Knichel, M. L.; Knospe, A. G.; Kobdaj, C.; Kofarago, M.; Kollegger, T.; Kolojvari, A.; Kondratiev, V.; Kondratyeva, N.; Kondratyuk, E.; Konevskikh, A.; Kopcik, M.; Kour, M.; Kouzinopoulos, C.; Kovalenko, O.; Kovalenko, V.; Kowalski, M.; Koyithatta Meethaleveedu, G.; Králik, I.; Kravčáková, A.; Krivda, M.; Krizek, F.; Kryshen, E.; Krzewicki, M.; Kubera, A. M.; Kučera, V.; Kuhn, C.; Kuijer, P. G.; Kumar, A.; Kumar, J.; Kumar, L.; Kumar, S.; Kurashvili, P.; Kurepin, A.; Kurepin, A. B.; Kuryakin, A.; Kweon, M. J.; Kwon, Y.; La Pointe, S. L.; La Rocca, P.; Ladron de Guevara, P.; Lagana Fernandes, C.; Lakomov, I.; Langoy, R.; Lapidus, K.; Lara, C.; Lardeux, A.; Lattuca, A.; Laudi, E.; Lea, R.; Leardini, L.; Lee, S.; Lehas, F.; Lehner, S.; Lemmon, R. C.; Lenti, V.; Leogrande, E.; León Monzón, I.; León Vargas, H.; Leoncino, M.; Lévai, P.; Li, S.; Li, X.; Lien, J.; Lietava, R.; Lindal, S.; Lindenstruth, V.; Lippmann, C.; Lisa, M. A.; Ljunggren, H. M.; Lodato, D. F.; Loenne, P. I.; Loginov, V.; Loizides, C.; Lopez, X.; López Torres, E.; Lowe, A.; Luettig, P.; Lunardon, M.; Luparello, G.; Lupi, M.; Lutz, T. H.; Maevskaya, A.; Mager, M.; Mahajan, S.; Mahmood, S. M.; Maire, A.; Majka, R. D.; Malaev, M.; Maldonado Cervantes, I.; Malinina, L.; Mal'Kevich, D.; Malzacher, P.; Mamonov, A.; Manko, V.; Manso, F.; Manzari, V.; Mao, Y.; Marchisone, M.; Mareš, J.; Margagliotti, G. V.; Margotti, A.; Margutti, J.; Marín, A.; Markert, C.; Marquard, M.; Martin, N. A.; Martinengo, P.; Martínez, M. I.; Martínez García, G.; Martinez Pedreira, M.; Mas, A.; Masciocchi, S.; Masera, M.; Masoni, A.; Mastroserio, A.; Matyja, A.; Mayer, C.; Mazer, J.; Mazzilli, M.; Mazzoni, M. A.; Meddi, F.; Melikyan, Y.; Menchaca-Rocha, A.; Meninno, E.; Mercado Pérez, J.; Meres, M.; Mhlanga, S.; Miake, Y.; Mieskolainen, M. M.; Mikhaylov, K.; Milano, L.; Milosevic, J.; Mischke, A.; Mishra, A. N.; Mishra, T.; Miskowiec, D.; Mitra, J.; Mitu, C. M.; Mohammadi, N.; Mohanty, B.; Molnar, L.; Montaño Zetina, L.; Montes, E.; Moreira De Godoy, D. A.; Moreno, L. A. P.; Moretto, S.; Morreale, A.; Morsch, A.; Muccifora, V.; Mudnic, E.; Mühlheim, D.; Muhuri, S.; Mukherjee, M.; Mulligan, J. D.; Munhoz, M. G.; Münning, K.; Munzer, R. H.; Murakami, H.; Murray, S.; Musa, L.; Musinsky, J.; Naik, B.; Nair, R.; Nandi, B. K.; Nania, R.; Nappi, E.; Naru, M. U.; Natal da Luz, H.; Nattrass, C.; Navarro, S. R.; Nayak, K.; Nayak, R.; Nayak, T. K.; Nazarenko, S.; Nedosekin, A.; Negrao De Oliveira, R. A.; Nellen, L.; Ng, F.; Nicassio, M.; Niculescu, M.; Niedziela, J.; Nielsen, B. S.; Nikolaev, S.; Nikulin, S.; Nikulin, V.; Noferini, F.; Nomokonov, P.; Nooren, G.; Noris, J. C. C.; Norman, J.; Nyanin, A.; Nystrand, J.; Oeschler, H.; Oh, S.; Oh, S. K.; Ohlson, A.; Okatan, A.; Okubo, T.; Oleniacz, J.; Oliveira Da Silva, A. C.; Oliver, M. H.; Onderwaater, J.; Oppedisano, C.; Orava, R.; Oravec, M.; Ortiz Velasquez, A.; Oskarsson, A.; Otwinowski, J.; Oyama, K.; Ozdemir, M.; Pachmayer, Y.; Pagano, D.; Pagano, P.; Paić, G.; Pal, S. K.; Palni, P.; Pan, J.; Pandey, A. K.; Papikyan, V.; Pappalardo, G. S.; Pareek, P.; Park, W. J.; Parmar, S.; Passfeld, A.; Paticchio, V.; Patra, R. N.; Paul, B.; Pei, H.; Peitzmann, T.; Peng, X.; Pereira Da Costa, H.; Peresunko, D.; Perez Lezama, E.; Peskov, V.; Pestov, Y.; Petráček, V.; Petrov, V.; Petrovici, M.; Petta, C.; Piano, S.; Pikna, M.; Pillot, P.; Pimentel, L. O. D. L.; Pinazza, O.; Pinsky, L.; Piyarathna, D. B.; Ploskon, M.; Planinic, M.; Pluta, J.; Pochybova, S.; Podesta-Lerma, P. L. M.; Poghosyan, M. G.; Polichtchouk, B.; Poljak, N.; Poonsawat, W.; Pop, A.; Poppenborg, H.; Porteboeuf-Houssais, S.; Porter, J.; Pospisil, J.; Prasad, S. K.; Preghenella, R.; Prino, F.; Pruneau, C. A.; Pshenichnov, I.; Puccio, M.; Puddu, G.; Pujahari, P.; Punin, V.; Putschke, J.; Qvigstad, H.; Rachevski, A.; Raha, S.; Rajput, S.; Rak, J.; Rakotozafindrabe, A.; Ramello, L.; Rami, F.; Raniwala, R.; Raniwala, S.; Räsänen, S. S.; Rascanu, B. T.; Rathee, D.; Ravasenga, I.; Read, K. F.; Redlich, K.; Reed, R. J.; Rehman, A.; Reichelt, P.; Reidt, F.; Ren, X.; Renfordt, R.; Reolon, A. R.; Reshetin, A.; Reygers, K.; Riabov, V.; Ricci, R. A.; Richert, T.; Richter, M.; Riedler, P.; Riegler, W.; Riggi, F.; Ristea, C.; Rodríguez Cahuantzi, M.; Rodriguez Manso, A.; Røed, K.; Rogochaya, E.; Rohr, D.; Röhrich, D.; Ronchetti, F.; Ronflette, L.; Rosnet, P.; Rossi, A.; Roukoutakis, F.; Roy, A.; Roy, C.; Roy, P.; Rubio Montero, A. J.; Rui, R.; Russo, R.; Ryabinkin, E.; Ryabov, Y.; Rybicki, A.; Saarinen, S.; Sadhu, S.; Sadovsky, S.; Šafařík, K.; Sahlmuller, B.; Sahoo, P.; Sahoo, R.; Sahoo, S.; Sahu, P. K.; Saini, J.; Sakai, S.; Saleh, M. A.; Salzwedel, J.; Sambyal, S.; Samsonov, V.; Šándor, L.; Sandoval, A.; Sano, M.; Sarkar, D.; Sarkar, N.; Sarma, P.; Scapparone, E.; Scarlassara, F.; Schiaua, C.; Schicker, R.; Schmidt, C.; Schmidt, H. R.; Schmidt, M.; Schuchmann, S.; Schukraft, J.; Schutz, Y.; Schwarz, K.; Schweda, K.; Scioli, G.; Scomparin, E.; Scott, R.; Šefčík, M.; Seger, J. E.; Sekiguchi, Y.; Sekihata, D.; Selyuzhenkov, I.; Senosi, K.; Senyukov, S.; Serradilla, E.; Sevcenco, A.; Shabanov, A.; Shabetai, A.; Shadura, O.; Shahoyan, R.; Shangaraev, A.; Sharma, A.; Sharma, M.; Sharma, M.; Sharma, N.; Sheikh, A. I.; Shigaki, K.; Shou, Q.; Shtejer, K.; Sibiriak, Y.; Siddhanta, S.; Sielewicz, K. M.; Siemiarczuk, T.; Silvermyr, D.; Silvestre, C.; Simatovic, G.; Simonetti, G.; Singaraju, R.; Singh, R.; Singhal, V.; Sinha, T.; Sitar, B.; Sitta, M.; Skaali, T. B.; Slupecki, M.; Smirnov, N.; Snellings, R. J. M.; Snellman, T. W.; Song, J.; Song, M.; Song, Z.; Soramel, F.; Sorensen, S.; Sozzi, F.; Spiriti, E.; Sputowska, I.; Spyropoulou-Stassinaki, M.; Stachel, J.; Stan, I.; Stankus, P.; Stenlund, E.; Steyn, G.; Stiller, J. H.; Stocco, D.; Strmen, P.; Suaide, A. A. P.; Sugitate, T.; Suire, C.; Suleymanov, M.; Suljic, M.; Sultanov, R.; Šumbera, M.; Sumowidagdo, S.; Swain, S.; Szabo, A.; Szarka, I.; Szczepankiewicz, A.; Szymanski, M.; Tabassam, U.; Takahashi, J.; Tambave, G. J.; Tanaka, N.; Tarhini, M.; Tariq, M.; Tarzila, M. G.; Tauro, A.; Tejeda Muñoz, G.; Telesca, A.; Terasaki, K.; Terrevoli, C.; Teyssier, B.; Thäder, J.; Thakur, D.; Thomas, D.; Tieulent, R.; Tikhonov, A.; Timmins, A. R.; Toia, A.; Trogolo, S.; Trombetta, G.; Trubnikov, V.; Trzaska, W. H.; Tsuji, T.; Tumkin, A.; Turrisi, R.; Tveter, T. S.; Ullaland, K.; Uras, A.; Usai, G. L.; Utrobicic, A.; Vala, M.; Valencia Palomo, L.; Van Der Maarel, J.; Van Hoorne, J. W.; van Leeuwen, M.; Vanat, T.; Vande Vyvre, P.; Varga, D.; Vargas, A.; Vargyas, M.; Varma, R.; Vasileiou, M.; Vasiliev, A.; Vauthier, A.; Vázquez Doce, O.; Vechernin, V.; Veen, A. M.; Velure, A.; Vercellin, E.; Vergara Limón, S.; Vernet, R.; Vickovic, L.; Viinikainen, J.; Vilakazi, Z.; Villalobos Baillie, O.; Villatoro Tello, A.; Vinogradov, A.; Vinogradov, L.; Virgili, T.; Vislavicius, V.; Viyogi, Y. P.; Vodopyanov, A.; Völkl, M. A.; Voloshin, K.; Voloshin, S. A.; Volpe, G.; von Haller, B.; Vorobyev, I.; Vranic, D.; Vrláková, J.; Vulpescu, B.; Wagner, B.; Wagner, J.; Wang, H.; Wang, M.; Watanabe, D.; Watanabe, Y.; Weber, M.; Weber, S. G.; Weiser, D. F.; Wessels, J. P.; Westerhoff, U.; Whitehead, A. M.; Wiechula, J.; Wikne, J.; Wilk, G.; Wilkinson, J.; Willems, G. A.; Williams, M. C. S.; Windelband, B.; Winn, M.; Yalcin, S.; Yang, P.; Yano, S.; Yin, Z.; Yokoyama, H.; Yoo, I.-K.; Yoon, J. H.; Yurchenko, V.; Zaborowska, A.; Zaccolo, V.; Zaman, A.; Zampolli, C.; Zanoli, H. J. C.; Zaporozhets, S.; Zardoshti, N.; Zarochentsev, A.; Závada, P.; Zaviyalov, N.; Zbroszczyk, H.; Zgura, I. S.; Zhalov, M.; Zhang, H.; Zhang, X.; Zhang, Y.; Zhang, C.; Zhang, Z.; Zhao, C.; Zhigareva, N.; Zhou, D.; Zhou, Y.; Zhou, Z.; Zhu, H.; Zhu, J.; Zichichi, A.; Zimmermann, A.; Zimmermann, M. B.; Zinovjev, G.; Zyzak, M.

2016-09-01

The elliptic, triangular, quadrangular and pentagonal anisotropic flow coefficients for π±, K± and p+overline{p} in Pb-Pb collisions at √{s_{NN}}=2.76 TeV were measured with the ALICE detector at the Large Hadron Collider. The results were obtained with the Scalar Product method, correlating the identified hadrons with reference particles from a different pseudorapidity region. Effects not related to the common event symmetry planes (non-flow) were estimated using correlations in pp collisions and were subtracted from the measurement. The obtained flow coefficients exhibit a clear mass ordering for transverse momentum ( p T) values below ≈ 3 GeV/ c. In the intermediate p T region (3 < p T < 6 GeV/ c), particles group at an approximate level according to the number of constituent quarks, suggesting that coalescence might be the relevant particle production mechanism in this region. The results for p T < 3 GeV/ c are described fairly well by a hydrodynamical model (iEBE-VISHNU) that uses initial conditions generated by A Multi-Phase Transport model (AMPT) and describes the expansion of the fireball using a value of 0.08 for the ratio of shear viscosity to entropy density ( η/s), coupled to a hadronic cascade model (UrQMD). Finally, expectations from AMPT alone fail to quantitatively describe the measurements for all harmonics throughout the measured transverse momentum region. However, the comparison to the AMPT model highlights the importance of the late hadronic rescattering stage to the development of the observed mass ordering at low values of p T and of coalescence as a particle production mechanism for the particle type grouping at intermediate values of p T for all harmonics. [Figure not available: see fulltext.

Higher harmonic flow coefficients of identified hadrons in Pb-Pb collisions at $$\\sqrt{s_{\\mathrm{NN}}}=2.76 $$ TeV

DOE PAGES

Adam, J.; Adamová, D.; Aggarwal, M. M.; ...

2016-09-28

The elliptic, triangular, quadrangular and pentagonal anisotropic flow coefficients for π ± , K ± and p +more » $$\\bar{p}$$ in Pb-Pb collisions at √s NN=2.76 TeV were measured with the ALICE detector at the Large Hadron Collider. The results were obtained with the Scalar Product method, correlating the identified hadrons with reference particles from a different pseudorapidity region. Effects not related to the common event symmetry planes (non-flow) were estimated using correlations in pp collisions and were subtracted from the measurement. The obtained flow coefficients exhibit a clear mass ordering for transverse momentum (p T ) values below ≈ 3 GeV/c. In the intermediate p T region (3 < p T < 6 GeV/c), particles group at an approximate level according to the number of constituent quarks, suggesting that coalescence might be the relevant particle production mechanism in this region. The results for p T < 3 GeV/c are described fairly well by a hydrodynamical model (iEBE-VISHNU) that uses initial conditions generated by A Multi-Phase Transport model (AMPT) and describes the expansion of the fireball using a value of 0.08 for the ratio of shear viscosity to entropy density (η/s), coupled to a hadronic cascade model (UrQMD). Finally, expectations from AMPT alone fail to quantitatively describe the measurements for all harmonics throughout the measured transverse momentum region. However, the comparison to the AMPT model highlights the importance of the late hadronic rescattering stage to the development of the observed mass ordering at low values of p T and of coalescence as a particle production mechanism for the particle type grouping at intermediate values of p T for all harmonics.« less

Catalytic processing of lactic acid over Pt/Nb(2)O(5).

PubMed

Serrano-Ruiz, Juan Carlos; Dumesic, James A

2009-01-01

Dilute aqueous solutions of lactic acid (30 %wt.) can be catalytically processed at 573 K and 57 bar over a low-metal-content Pt(0.1 %)/Nb(2)O(5) catalyst in a spontaneously separating organic phase rich in valuable products such as C(4)-C(7) ketones. An increase in the lactic acid concentration to 60 wt % allows conversion of approximately 50 % of the carbon feed in this organic layer, while maintaining good stability of the catalyst. Experiments at low conversion showed that lactic acid reacts first over Pt(0.1 %)/Nb(2)O(5) to produce acetaldehyde and propanoic acid (along with CO and CO(2) in the gas phase). These compounds (less oxygenated than lactic acid but still reactive) are the key intermediates in the overall process, and they react differently depending on the nature of the catalyst support. In particular, reaction kinetics studies with propanoic acid as feed showed that Pt(0.1 %)/Nb(2)O(5) favored the formation of pentanones by ketonization reactions, whereas a monofunctional Pt(0.1 %)/carbon catalyst produced ethane and CO(x) by decomposition reactions. In the same manner, acetaldehyde was preferentially hydrogenated to ethanol over Pt(0.1 %)/carbon, whereas the presence of niobia allowed this intermediate to react (by successive aldol condensations) to form C(4)-C(7) condensation products stored in the organic phase. Finally, reaction pathways are proposed to explain the catalytic processing of lactic acid over bifunctional Pt(0.1 %)/Nb(2)O(5). In this scheme, metal sites catalyze hydrogenation reactions and niobia promotes C--C coupling processes (ketonization and aldol condensation), in contrast to C--C cleavage reactions which take place preferentially over Pt(0.1 %)/carbon and lead to loss of carbon in the gas effluent as CO, CO(2), and methane.

Modeling rock weathering in small watersheds

NASA Astrophysics Data System (ADS)

Pacheco, Fernando A. L.; Van der Weijden, Cornelis H.

2014-05-01

Many mountainous watersheds are conceived as aquifer media where multiple groundwater flow systems have developed (Tóth, 1963), and as bimodal landscapes where differential weathering of bare and soil-mantled rock has occurred (Wahrhaftig, 1965). The results of a weathering algorithm (Pacheco and Van der Weijden, 2012a, 2014), which integrates topographic, hydrologic, rock structure and chemical data to calculate weathering rates at the watershed scale, validated the conceptual models in the River Sordo basin, a small watershed located in the Marão cordillera (North of Portugal). The coupling of weathering, groundwater flow and landscape evolution analyses, as accomplished in this study, is innovative and represents a remarkable achievement towards regionalization of rock weathering at the watershed scale. The River Sordo basin occupies an area of approximately 51.2 km2 and was shaped on granite and metassediment terrains between the altitudes 185-1300 m. The groundwater flow system is composed of recharge areas located at elevations >700 m, identified on the basis of δ18O data. Discharge cells comprehend terminations of local, intermediate and regional flow systems, identified on the basis of spring density patterns, infiltration depth estimates based on 87Sr/86Sr data, and spatial distributions of groundwater pH and natural mineralization. Intermediate and regional flow systems, defined where infiltration depths >125 m, develop solely along the contact zone between granites and metassediments, because fractures in this region are profound and their density is very large. Weathering is accelerated where rocks are covered by thick soils, being five times faster relative to sectors of the basin where rocks are covered by thin soils. Differential weathering of bare and soil-mantled rock is also revealed by the spatial distribution of calculated aquifer hydraulic diffusivities and groundwater travel times.

General relativistic corrections to the weak lensing convergence power spectrum

NASA Astrophysics Data System (ADS)

Giblin, John T.; Mertens, James B.; Starkman, Glenn D.; Zentner, Andrew R.

2017-11-01

We compute the weak lensing convergence power spectrum, Cℓκκ, in a dust-filled universe using fully nonlinear general relativistic simulations. The spectrum is then compared to more standard, approximate calculations by computing the Bardeen (Newtonian) potentials in linearized gravity and partially utilizing the Born approximation. We find corrections to the angular power spectrum amplitude of order ten percent at very large angular scales, ℓ˜2 - 3 , and percent-level corrections at intermediate angular scales of ℓ˜20 - 30 .

Synthesis of the carbocyclic core of the cornexistins by ring-closing metathesis.

PubMed

Clark, J Stephen; Marlin, Frederic; Nay, Bastien; Wilson, Claire

2003-01-09

An advanced intermediate in the synthesis of the phytotoxins cornexistin and hydroxycornexistin has been synthesized. Sequential palladium-mediated sp(2)-sp(3) fragment coupling and ring-closing diene metathesis have been used to construct the nine-membered carbocyclic core found in the natural products. [reaction--see text

Annulation of o-Quinodimethanes through N-Heterocyclic Carbene Catalysis for the Synthesis of 1-Isochromanones.

PubMed

Janssen-Müller, Daniel; Singha, Santanu; Olyschläger, Theresa; Daniliuc, Constantin G; Glorius, Frank

2016-09-02

The activation of 2-(bromomethyl)benzaldehydes using N-heterocyclic carbenes represents a novel approach to the generation of o-quinodimethane (o-QDM) intermediates. Coupling with ketones such as phenylglyoxylates, isatins, or trifluoromethyl ketones via [4 + 2] annulation gives access to functionalized 1-isochromanones.

Nickel-catalyzed coupling reaction of alkyl halides with aryl Grignard reagents in the presence of 1,3-butadiene: mechanistic studies of four-component coupling and competing cross-coupling reactions† †Electronic supplementary information (ESI) available: Detailed experimental and computational results, procedures, characterization data, copies of NMR charts, and crystallographic data. CCDC 1572238. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04675h

PubMed Central

Fukuoka, Asuka; Yokoyama, Wataru; Min, Xin; Hisaki, Ichiro; Kuniyasu, Hitoshi

2018-01-01

We describe the mechanism, substituent effects, and origins of the selectivity of the nickel-catalyzed four-component coupling reactions of alkyl fluorides, aryl Grignard reagents, and two molecules of 1,3-butadiene that affords a 1,6-octadiene carbon framework bearing alkyl and aryl groups at the 3- and 8-positions, respectively, and the competing cross-coupling reaction. Both the four-component coupling reaction and the cross-coupling reaction are triggered by the formation of anionic nickel complexes, which are generated by the oxidative dimerization of two molecules of 1,3-butadiene on Ni(0) and the subsequent complexation with the aryl Grignard reagents. The C–C bond formation of the alkyl fluorides with the γ-carbon of the anionic nickel complexes leads to the four-component coupling product, whereas the cross-coupling product is yielded via nucleophilic attack of the Ni center toward the alkyl fluorides. These steps are found to be the rate-determining and selectivity-determining steps of the whole catalytic cycle, in which the C–F bond of the alkyl fluorides is activated by the Mg cation rather than a Li or Zn cation. ortho-Substituents of the aryl Grignard reagents suppressed the cross-coupling reaction leading to the selective formation of the four-component products. Such steric effects of the ortho-substituents were clearly demonstrated by crystal structure characterizations of ate complexes and DFT calculations. The electronic effects of the para-substituent of the aryl Grignard reagents on both the selectivity and reaction rates are thoroughly discussed. The present mechanistic study offers new insight into anionic complexes, which are proposed as the key intermediates in catalytic transformations even though detailed mechanisms are not established in many cases, and demonstrates their synthetic utility as promising intermediates for C–C bond forming reactions, providing useful information for developing efficient and straightforward multicomponent reactions. PMID:29719693

Initial design for an experimental investigation of strongly coupled plasma behavior in the Atlas facility

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

Munson, C.P.; Benage, J.F. Jr.; Taylor, A.J.

Atlas is a high current ({approximately} 30 MA peak, with a current risetime {approximately} 4.5 {micro}sec), high energy (E{sub stored} = 24 MJ, E{sub load} = 3--6 MJ), pulsed power facility which is being constructed at Los Alamos National Laboratory with a scheduled completion date in the year 2000. When operational, this facility will provide a platform for experiments in high pressure shocks (> 20 Mbar), adiabatic compression ({rho}/{rho}{sub 0} > 5, P > 10 Mbar), high magnetic fields ({approximately} 2,000 T), high strain and strain rates ({var_epsilon} > 200%, d{var_epsilon}/dt {approximately} 10{sup 4} to 10{sup 6} s{sup {minus}1}), hydrodynamicmore » instabilities of materials in turbulent regimes, magnetized target fusion, equation of state, and strongly coupled plasmas. For the strongly coupled plasma experiments, an auxiliary capacitor bank will be used to generate a moderate density (< 0.1 solid), relatively cold ({approximately} 1 eV) plasma by ohmic heating of a conducting material of interest such as titanium. This stargate plasma will be compressed against a central column containing diagnostic instrumentation by a cylindrical conducting liner that is driven radially inward by current from the main Atlas capacitor bank. The plasma is predicted to reach densities of {approximately} 1.1 times solid, achieve ion and electron temperatures of {approximately} 10 eV, and pressures of {approximately} 4--5 Mbar. This is a density/temperature regime which is expected to experience strong coupling, but only partial degeneracy. X-ray radiography is planned for measurements of the material density at discrete times during the experiments; diamond Raman measurements are anticipated for determination of the pressure. In addition, a neutron resonance spectroscopic technique is being evaluated for possible determination of the temperature (through low percentage doping of the titanium with a suitable resonant material). Initial target plasma formation experiments are being planned on an existing pulsed power facility at LANL and will be completed before the start of operation of Atlas.« less

Application of Chan-Lam cross coupling for the synthesis of N-heterocyclic carbene precursors bearing strong electron donating or withdrawing groups

NASA Astrophysics Data System (ADS)

Huang, Liliang; He, Chengxiang; Sun, Zhihua

2015-07-01

Chan-Lam cross coupling allowed efficient synthesis of N,N’-disubstituted ortho-phenylene diamines bearing strong electron donating or withdrawing groups, such as nitro or methoxy groups, with moderate to high yields. These diamines can then be turned into N-heterocyclic carbene precursors after condensation with trimethyl orthoformate. The same strategy can also be utilized for the synthesis of N-monosubstituted aniline derivatives containing a functionalized ortho-aminomethyl group as intermediates for chiral 6-membered ring carbene precursors.

DMSO/Tf2O-mediated cross-coupling of tryptamine with substituted aniline to access C3a-N1'-linked pyrroloindoline alkaloids.

PubMed

Tayu, Masanori; Ishizaki, Takako; Higuchi, Kazuhiro; Kawasaki, Tomomi

2015-04-07

The cross-coupling of tryptamine with substituted aniline to access C3a-nitrogen-linked pyrroloindolines has been developed via the consecutive cyclization of tryptamine with DMSO/Tf2O and the substitution of 3a-pyrroloindolylthionium intermediate with aniline. The use of 2,3-dihydrotryptamine instead of aniline enabled easy access to 3a-(1-indolyl)pyrroloindoline and the concise synthesis of C3a-N1'-linked pyrroloindoline alkaloid (±)-psychotriasine was accomplished.

Molecular electronics with single molecules in solid-state devices.

PubMed

Moth-Poulsen, Kasper; Bjørnholm, Thomas

2009-09-01

The ultimate aim of molecular electronics is to understand and master single-molecule devices. Based on the latest results on electron transport in single molecules in solid-state devices, we focus here on new insights into the influence of metal electrodes on the energy spectrum of the molecule, and on how the electron transport properties of the molecule depend on the strength of the electronic coupling between it and the electrodes. A variety of phenomena are observed depending on whether this coupling is weak, intermediate or strong.

Intermediate inflation from a non-canonical scalar field

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

Rezazadeh, K.; Karami, K.; Karimi, P., E-mail: rezazadeh86@gmail.com, E-mail: KKarami@uok.ac.ir, E-mail: parvin.karimi67@yahoo.com

2015-09-01

We study the intermediate inflation in a non-canonical scalar field framework with a power-like Lagrangian. We show that in contrast with the standard canonical intermediate inflation, our non-canonical model is compatible with the observational results of Planck 2015. Also, we estimate the equilateral non-Gaussianity parameter which is in well agreement with the prediction of Planck 2015. Then, we obtain an approximation for the energy scale at the initial time of inflation and show that it can be of order of the Planck energy scale, i.e. M{sub P} ∼ 10{sup 18}GeV. We will see that after a short period of time, inflation entersmore » in the slow-roll regime that its energy scale is of order M{sub P}/100 ∼ 10{sup 16}GeV and the horizon exit takes place in this energy scale. We also examine an idea in our non-canonical model to overcome the central drawback of intermediate inflation which is the fact that inflation never ends. We solve this problem without disturbing significantly the nature of the intermediate inflation until the time of horizon exit.« less

Deconvoluting Protein (Un)folding Structural Ensembles Using X-Ray Scattering, Nuclear Magnetic Resonance Spectroscopy and Molecular Dynamics Simulation

PubMed Central

Nasedkin, Alexandr; Marcellini, Moreno; Religa, Tomasz L.; Freund, Stefan M.; Menzel, Andreas; Fersht, Alan R.; Jemth, Per; van der Spoel, David; Davidsson, Jan

2015-01-01

The folding and unfolding of protein domains is an apparently cooperative process, but transient intermediates have been detected in some cases. Such (un)folding intermediates are challenging to investigate structurally as they are typically not long-lived and their role in the (un)folding reaction has often been questioned. One of the most well studied (un)folding pathways is that of Drosophila melanogaster Engrailed homeodomain (EnHD): this 61-residue protein forms a three helix bundle in the native state and folds via a helical intermediate. Here we used molecular dynamics simulations to derive sample conformations of EnHD in the native, intermediate, and unfolded states and selected the relevant structural clusters by comparing to small/wide angle X-ray scattering data at four different temperatures. The results are corroborated using residual dipolar couplings determined by NMR spectroscopy. Our results agree well with the previously proposed (un)folding pathway. However, they also suggest that the fully unfolded state is present at a low fraction throughout the investigated temperature interval, and that the (un)folding intermediate is highly populated at the thermal midpoint in line with the view that this intermediate can be regarded to be the denatured state under physiological conditions. Further, the combination of ensemble structural techniques with MD allows for determination of structures and populations of multiple interconverting structures in solution. PMID:25946337

Deconvoluting Protein (Un)folding Structural Ensembles Using X-Ray Scattering, Nuclear Magnetic Resonance Spectroscopy and Molecular Dynamics Simulation.

PubMed

Nasedkin, Alexandr; Marcellini, Moreno; Religa, Tomasz L; Freund, Stefan M; Menzel, Andreas; Fersht, Alan R; Jemth, Per; van der Spoel, David; Davidsson, Jan

2015-01-01

The folding and unfolding of protein domains is an apparently cooperative process, but transient intermediates have been detected in some cases. Such (un)folding intermediates are challenging to investigate structurally as they are typically not long-lived and their role in the (un)folding reaction has often been questioned. One of the most well studied (un)folding pathways is that of Drosophila melanogaster Engrailed homeodomain (EnHD): this 61-residue protein forms a three helix bundle in the native state and folds via a helical intermediate. Here we used molecular dynamics simulations to derive sample conformations of EnHD in the native, intermediate, and unfolded states and selected the relevant structural clusters by comparing to small/wide angle X-ray scattering data at four different temperatures. The results are corroborated using residual dipolar couplings determined by NMR spectroscopy. Our results agree well with the previously proposed (un)folding pathway. However, they also suggest that the fully unfolded state is present at a low fraction throughout the investigated temperature interval, and that the (un)folding intermediate is highly populated at the thermal midpoint in line with the view that this intermediate can be regarded to be the denatured state under physiological conditions. Further, the combination of ensemble structural techniques with MD allows for determination of structures and populations of multiple interconverting structures in solution.

Characteristic-based and interface-sharpening algorithm for high-order simulations of immiscible compressible multi-material flows

NASA Astrophysics Data System (ADS)

He, Zhiwei; Tian, Baolin; Zhang, Yousheng; Gao, Fujie

2017-03-01

The present work focuses on the simulation of immiscible compressible multi-material flows with the Mie-Grüneisen-type equation of state governed by the non-conservative five-equation model [1]. Although low-order single fluid schemes have already been adopted to provide some feasible results, the application of high-order schemes (introducing relatively small numerical dissipation) to these flows may lead to results with severe numerical oscillations. Consequently, attempts to apply any interface-sharpening techniques to stop the progressively more severe smearing interfaces for a longer simulation time may result in an overshoot increase and in some cases convergence to a non-physical solution occurs. This study proposes a characteristic-based interface-sharpening algorithm for performing high-order simulations of such flows by deriving a pressure-equilibrium-consistent intermediate state (augmented with approximations of pressure derivatives) for local characteristic variable reconstruction and constructing a general framework for interface sharpening. First, by imposing a weak form of the jump condition for the non-conservative five-equation model, we analytically derive an intermediate state with pressure derivatives treated as additional parameters of the linearization procedure. Based on this intermediate state, any well-established high-order reconstruction technique can be employed to provide the state at each cell edge. Second, by designing another state with only different reconstructed values of the interface function at each cell edge, the advection term in the equation of the interface function is discretized twice using any common algorithm. The difference between the two discretizations is employed consistently for interface compression, yielding a general framework for interface sharpening. Coupled with the fifth-order improved accurate monotonicity-preserving scheme [2] for local characteristic variable reconstruction and the tangent of hyperbola for the interface capturing scheme [3] for designing other reconstructed values of the interface function, the present algorithm is examined using some typical tests, with the Mie-Grüneisen-type equation of state used for characterizing the materials of interest in both one- and two-dimensional spaces. The results of these tests verify the effectiveness of the present algorithm: essentially non-oscillatory and interface-sharpened results are obtained.

Short- and long-time diffusion and dynamic scaling in suspensions of charged colloidal particles.

PubMed

Banchio, Adolfo J; Heinen, Marco; Holmqvist, Peter; Nägele, Gerhard

2018-04-07

We report on a comprehensive theory-simulation-experimental study of collective and self-diffusion in concentrated suspensions of charge-stabilized colloidal spheres. In theory and simulation, the spheres are assumed to interact directly by a hard-core plus screened Coulomb effective pair potential. The intermediate scattering function, f c (q, t), is calculated by elaborate accelerated Stokesian dynamics (ASD) simulations for Brownian systems where many-particle hydrodynamic interactions (HIs) are fully accounted for, using a novel extrapolation scheme to a macroscopically large system size valid for all correlation times. The study spans the correlation time range from the colloidal short-time to the long-time regime. Additionally, Brownian Dynamics (BD) simulation and mode-coupling theory (MCT) results of f c (q, t) are generated where HIs are neglected. Using these results, the influence of HIs on collective and self-diffusion and the accuracy of the MCT method are quantified. It is shown that HIs enhance collective and self-diffusion at intermediate and long times. At short times self-diffusion, and for wavenumbers outside the structure factor peak region also collective diffusion, are slowed down by HIs. MCT significantly overestimates the slowing influence of dynamic particle caging. The dynamic scattering functions obtained in the ASD simulations are in overall good agreement with our dynamic light scattering (DLS) results for a concentration series of charged silica spheres in an organic solvent mixture, in the experimental time window and wavenumber range. From the simulation data for the time derivative of the width function associated with f c (q, t), there is indication of long-time exponential decay of f c (q, t), for wavenumbers around the location of the static structure factor principal peak. The experimental scattering functions in the probed time range are consistent with a time-wavenumber factorization scaling behavior of f c (q, t) that was first reported by Segrè and Pusey [Phys. Rev. Lett. 77, 771 (1996)] for suspensions of hard spheres. Our BD simulation and MCT results predict a significant violation of exact factorization scaling which, however, is approximately restored according to the ASD results when HIs are accounted for, consistent with the experimental findings for f c (q, t). Our study of collective diffusion is amended by simulation and theoretical results for the self-intermediate scattering function, f s (q, t), and its non-Gaussian parameter α 2 (t) and for the particle mean squared displacement W(t) and its time derivative. Since self-diffusion properties are not assessed in standard DLS measurements, a method to deduce W(t) approximately from f c (q, t) is theoretically validated.

TRANSFORMATION OF CARBON TETRACHLORIDE IN THE PRESENCE OF SULFIDE, BIOTITE, AND VERMICULITE

EPA Science Inventory

Carbon tetrachloride is transformed in aqueous solutions containing dissolved hydrogen sulfide more rapidly in the presence of the minerals biotite and vermiculite than in homogeneous systems. Approximately 8045% of the CC4 was transformed to COP via the measured intermediate, CS...

Fano-Agarwal couplings and non-rotating wave approximation in single-photon timed Dicke subradiance

NASA Astrophysics Data System (ADS)

Mirza, Imran M.; Begzjav, Tuguldur

2016-04-01

Recently a new class of single-photon timed Dicke (TD) subradiant states has been introduced with possible applications in single-photon-based quantum information storage and on demand ultrafast retrieval (Scully M. O., Phys. Rev. Lett., 115 (2015) 243602). However, the influence of any kind of virtual processes on the decay of these new kind of subradiant states has been left as an open question. In the present paper, we focus on this problem in detail. In particular, we investigate how pure Fano-Agarwal couplings and other virtual processes arising from non-rotating wave approximation impact the decay of otherwise sub- and superradiant states. In addition to the overall virtual couplings among all TD states, we also focus on the dominant role played by the couplings between specific TD states.

Electron-impact ionization of Ne (2 p ) and Ar (3 p ) at intermediate energies: Role of the postcollision interaction

NASA Astrophysics Data System (ADS)

Hu, Xiaoqing; Gao, Cong-Zhang; Chen, Zhanbin; Wang, Jianguo; Wu, Yong; Wang, Yang

2017-11-01

We present the absolute triple differential cross section (TDCS) for single ionization of Ne (2 p ) at an impact energy of 599.6 eV and Ar (3 p ) at 195 eV. The role of the postcollision interaction (PCI) is studied using a high-order distorted-wave Born approximation model with a continuum distorted-waves expansion. Both the second- and third-order effects are considered in the present calculations, and the third-order distorted wave Born approximation model is reported in the (e ,2 e ) reaction. The calculated results show satisfactory agreement with experimental data. The magnitude of the absolute TDCS is enhanced by a factor 2-3 when the strength factor γ of the PCI amplitude is summarized just from 0 to 2. This proves that the PCI plays an important role in the absolute TDCS of the (e ,2 e ) reaction in the intermediate-energy region.

Two- and three-photon ionization in the noble gases

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

McGuire, E.J.

1981-08-01

By using a characteristic Green's function for an exactly solvable Schroedinger equation with an approximation to the central potential of Hermann and Skillman, the cross section for nonresonant two- and three-photon ionization of Ne, Ar, Kr, and Xe were calculated in jl coupling. Expressions for cross sections in jl coupling are given. Comparison with the Ar two-photon cross section of Pindzola and Kelly, calculated using the many-body theory, the dipole-length approximation, and LS coupling shows a disagreement of as much as a factor of 2. The disagreement appears to arise from distortion introduced by shifting the Green's-function resonances to experimentalmore » values.« less

Communication: Vibrational and vibronic coherences in the two dimensional spectroscopy of coupled electron-nuclear motion.

PubMed

Albert, Julian; Falge, Mirjam; Gomez, Sandra; Sola, Ignacio R; Hildenbrand, Heiko; Engel, Volker

2015-07-28

We theoretically investigate the photon-echo spectroscopy of coupled electron-nuclear quantum dynamics. Two situations are treated. In the first case, the Born-Oppenheimer (adiabatic) approximation holds. It is then possible to interpret the two-dimensional (2D) spectra in terms of vibrational motion taking place in different electronic states. In particular, pure vibrational coherences which are related to oscillations in the time-dependent third-order polarization can be identified. This concept fails in the second case, where strong non-adiabatic coupling leads to the breakdown of the Born-Oppenheimer-approximation. Then, the 2D-spectra reveal a complicated vibronic structure and vibrational coherences cannot be disentangled from the electronic motion.

Lag and anticipating synchronization without time-delay coupling.

PubMed

Corron, Ned J; Blakely, Jonathan N; Pethel, Shawn D

2005-06-01

We describe a new method for achieving approximate lag and anticipating synchronization in unidirectionally coupled chaotic oscillators. The method uses a specific parameter mismatch between the drive and response that is a first-order approximation to true time-delay coupling. As a result, an adjustable lag or anticipation effect can be achieved without the need for a variable delay line, making the method simpler and more economical to implement in many physical systems. We present a stability analysis, demonstrate the method numerically, and report experimental observation of the effect in radio-frequency electronic oscillators. In the circuit experiments, both lag and anticipation are controlled by tuning a single capacitor in the response oscillator.

The Taxometrics of Marriage: Is Marital Discord Categorical?

PubMed Central

Beach, Steven R. H.; Amir, Nader; Fincham, Frank D.; Leonard, Kenneth E.

2014-01-01

This study used taxometric methods to investigate the latent structure of the construct of marital adjustment as indexed by the Marital Adjustment Test (MAT; H. J. Locke & K. M. Wallace, 1959). That is, the authors examined whether marital adjustment is best thought of as a “dimension” of adjustment only or whether there also are categorical differences between “discordant” and “nondiscordant” couples. Analyses of data provided by 447 couples married for approximately 2 years provided converging evidence for a latent category of marital discord, suggesting that marital discord can be viewed as a qualitatively distinct state experienced by approximately 20% of the couples in the current sample. Implications for marital assessment are outlined. PMID:15982105

Communication: Vibrational and vibronic coherences in the two dimensional spectroscopy of coupled electron-nuclear motion

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

Albert, Julian; Falge, Mirjam; Hildenbrand, Heiko

2015-07-28

We theoretically investigate the photon-echo spectroscopy of coupled electron-nuclear quantum dynamics. Two situations are treated. In the first case, the Born-Oppenheimer (adiabatic) approximation holds. It is then possible to interpret the two-dimensional (2D) spectra in terms of vibrational motion taking place in different electronic states. In particular, pure vibrational coherences which are related to oscillations in the time-dependent third-order polarization can be identified. This concept fails in the second case, where strong non-adiabatic coupling leads to the breakdown of the Born-Oppenheimer-approximation. Then, the 2D-spectra reveal a complicated vibronic structure and vibrational coherences cannot be disentangled from the electronic motion.

Nonlinear Loading-Rate-Dependent Force Response of Individual Vimentin Intermediate Filaments to Applied Strain

NASA Astrophysics Data System (ADS)

Block, Johanna; Witt, Hannes; Candelli, Andrea; Peterman, Erwin J. G.; Wuite, Gijs J. L.; Janshoff, Andreas; Köster, Sarah

2017-01-01

The mechanical properties of eukaryotic cells are to a great extent determined by the cytoskeleton, a composite network of different filamentous proteins. Among these, intermediate filaments (IFs) are exceptional in their molecular architecture and mechanical properties. Here we directly record stress-strain curves of individual vimentin IFs using optical traps and atomic force microscopy. We find a strong loading rate dependence of the mechanical response, supporting the hypothesis that IFs could serve to protect eukaryotic cells from fast, large deformations. Our experimental results show different unfolding regimes, which we can quantitatively reproduce by an elastically coupled system of multiple two-state elements.

Trapping para-Quinone Methide Intermediates with Ferrocene: Synthesis and Preliminary Biological Evaluation of New Phenol-Ferrocene Conjugates.

PubMed

González-Pelayo, Silvia; López, Enol; Borge, Javier; de-Los-Santos-Álvarez, Noemí; López, Luis A

2018-06-01

The reaction of para -hydroxybenzyl alcohols with ferrocene in the presence of a catalytic amount of InCl₃ provided ferrocenyl phenol derivatives, an interesting class of organometallic compounds with potential applications in medicinal chemistry. This transformation exhibited a reasonable substrate scope delivering the desired products in synthetically useful yields. Evidence of involvement of a para -quinone methide intermediate in this coupling process was also provided. Preliminary biological evaluation demonstrated that some of the ferrocene derivatives available by this methodology exhibit significant cytotoxicity against several cancer cell lines with IC 50 values within the range of 1.07⁻4.89 μM.

Electrochemical Detection of Transient Cobalt Hydride Intermediates of Electrocatalytic Hydrogen Production

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

Wiedner, Eric S.; Bullock, R. Morris

2016-07-06

We report the use of variable scan rate cyclic voltammetry to detect transient CoIIIH and CoIIH intermediates of electrocatalytic H2 production by CoII(dmgBF2)2(CH3CN)2 and [CoII(PtBu2NPh2)(CH3CN)3]2+. In both cases, reduction of the CoIIIH intermediate was observed to coincide with the CoII/I couple, and the resulting CoIIH intermediate is protonated by acid to afford H2. Our studies indicate that in electrocatalytic H2 production, protonation of CoIIH is rate-limiting for CoII(dmgBF2)2(CH3CN)2, and protonation of CoI is rate-limiting for [CoII(PtBu2NPh2)(CH3CN)3]2+. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy,more » Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.« less

Structure determination of a key intermediate of the enantioselective Pd complex catalyzed allylic substitution reaction

PubMed

Junker; Reif; Steinhagen; Junker; Felli; Reggelin; Griesinger

2000-09-01

The structure of a catalytic intermediate with important implications for the interpretation of the stereochemical outcome of the palladium complex catalyzed allylic substitution with phosphino-oxazoline (PHOX) ligands is determined by liquid state NMR. The complex displays a novel structure that is highly distorted compared with other palladium eta2-olefin complexes known so far. The structure has been determined from nuclear overhauser data (NOE), scalar coupling constants, and long range projection angle restraints derived from dipole dipole cross-correlated relaxation of multiple quantum coherence. The latter restraints have been implemented into a distance geometry protocol. The projection angle restraints yield a higher precision in the determination of the relative orientation of the two molecular moieties and are essential to provide an exact structural definition of the olefinic part of the catalytic intermediate with respect to the ligand.

Activation pathway of Src kinase reveals intermediate states as novel targets for drug design

PubMed Central

Shukla, Diwakar; Meng, Yilin; Roux, Benoît; Pande, Vijay S.

2014-01-01

Unregulated activation of Src kinases leads to aberrant signaling, uncontrolled growth, and differentiation of cancerous cells. Reaching a complete mechanistic understanding of large scale conformational transformations underlying the activation of kinases could greatly help in the development of therapeutic drugs for the treatment of these pathologies. In principle, the nature of conformational transition could be modeled in silico via atomistic molecular dynamics simulations, although this is very challenging due to the long activation timescales. Here, we employ a computational paradigm that couples transition pathway techniques and Markov state model-based massively distributed simulations for mapping the conformational landscape of c-src tyrosine kinase. The computations provide the thermodynamics and kinetics of kinase activation for the first time, and help identify key structural intermediates. Furthermore, the presence of a novel allosteric site in an intermediate state of c-src that could be potentially utilized for drug design is predicted. PMID:24584478

Broadband Microwave Study of Reaction Intermediates and Products Through the Pyrolysis of Oxygenated Biofuels

NASA Astrophysics Data System (ADS)

Abeysekera, Chamara; Hernandez-Castillo, Alicia O.; Fritz, Sean; Zwier, Timothy S.

2017-06-01

The rapidly growing list of potential plant-derived biofuels creates a challenge for the scientific community to provide a molecular-scale understanding of their combustion. Development of accurate combustion models rests on a foundation of experimental data on the kinetics and product branching ratios of their individual reaction steps. Therefore, new spectroscopic tools are necessary to selectively detect and characterize fuel components and reactive intermediates generated by pyrolysis and combustion. Substituted furans, including furanic ethers, are considered second-generation biofuel candidates. Following the work of the Ellison group, an 8-18 GHz microwave study was carried out on the unimolecular and bimolecular decomposition of the smallest furanic ether, 2-methoxy furan, and it`s pyrolysis intermediate, the 2-furanyloxy radical, formed in a high-temperature pyrolysis source coupled to a supersonic expansion. Details of the experimental setup and analysis of the spectrum of the radical will be discussed.

Coupling of solar photoelectro-Fenton with a BDD anode and solar heterogeneous photocatalysis for the mineralization of the herbicide atrazine.

PubMed

Garza-Campos, Benjamín R; Guzmán-Mar, Jorge Luis; Reyes, Laura Hinojosa; Brillas, Enric; Hernández-Ramírez, Aracely; Ruiz-Ruiz, Edgar J

2014-02-01

Here, the synergetic effect of coupling solar photoelectro-Fenton (SPEF) and solar heterogeneous photocatalysis (SPC) on the mineralization of 200mL of a 20mg L(-1) atrazine solution, prepared from the commercial herbicide Gesaprim, at pH 3.0 was studied. Uniform, homogeneous and adherent anatase-TiO2 films onto glass spheres of 5mm diameter were prepared by the sol-gel dip-coating method and used as catalyst for SPC. However, this procedure yielded a poor removal of the substrate because of the low oxidation ability of positive holes and OH formed at the catalyst surface to destroy it. Atrazine decay was improved using anodic oxidation (AO), electro-Fenton (EF), SPEF and coupled SPEF-SPC at 100mA. The electrolytic cell contained a boron-doped diamond (BDD) anode and H2O2 was generated at a BDD cathode fed with an air flow. The removal and mineralization of atrazine increased when more oxidizing agents were generated in the sequence AO

Coupled multipolar interactions in small-particle metallic clusters.

PubMed

Pustovit, Vitaly N; Sotelo, Juan A; Niklasson, Gunnar A

2002-03-01

We propose a new formalism for computing the optical properties of small clusters of particles. It is a generalization of the coupled dipole-dipole particle-interaction model and allows one in principle to take into account all multipolar interactions in the long-wavelength limit. The method is illustrated by computations of the optical properties of N = 6 particle clusters for different multipolar approximations. We examine the effect of separation between particles and compare the optical spectra with the discrete-dipole approximation and the generalized Mie theory.

Coupled-mode theory and Fano resonances in guided-mode resonant gratings: the conical diffraction mounting.

PubMed

Bykov, Dmitry A; Doskolovich, Leonid L; Soifer, Victor A

2017-01-23

We study resonances of guided-mode resonant gratings in conical mounting. By developing 2D time-dependent coupled-mode theory we obtain simple approximations of the transmission and reflection coefficients. Being functions of the incident light's frequency and in-plane wave vector components, the obtained approximations can be considered as multi-variable generalizations of the Fano line shape. We show that the approximations are in good agreement with the rigorously calculated transmission and reflection spectra. We use the developed theory to investigate angular tolerances of the considered structures and to obtain mode excitation conditions. In particular, we obtain the cross-polarization mode excitation conditions in the case of conical mounting.

Dielectronic recombination data for dynamic finite-density plasmas. XV. The silicon isoelectronic sequence

NASA Astrophysics Data System (ADS)

Kaur, Jagjit; Gorczyca, T. W.; Badnell, N. R.

2018-02-01

Context. We aim to present a comprehensive theoretical investigation of dielectronic recombination (DR) of the silicon-like isoelectronic sequence and provide DR and radiative recombination (RR) data that can be used within a generalized collisional-radiative modelling framework. Aims: Total and final-state level-resolved DR and RR rate coefficients for the ground and metastable initial levels of 16 ions between P+ and Zn16+ are determined. Methods: We carried out multi-configurational Breit-Pauli DR calculations for silicon-like ions in the independent processes, isolated resonance, distorted wave approximation. Both Δnc = 0 and Δnc = 1 core excitations are included using LS and intermediate coupling schemes. Results: Results are presented for a selected number of ions and compared to all other existing theoretical and experimental data. The total dielectronic and radiative recombination rate coefficients for the ground state are presented in tabulated form for easy implementation into spectral modelling codes. These data can also be accessed from the Atomic Data and Analysis Structure (ADAS) OPEN-ADAS database. This work is a part of an assembly of a dielectronic recombination database for the modelling of dynamic finite-density plasmas.

Dipole saturated absorption modeling in gas phase: Dealing with a Gaussian beam

NASA Astrophysics Data System (ADS)

Dupré, Patrick

2018-01-01

With the advent of new accurate and sensitive spectrometers, cf. combining optical cavities (for absorption enhancement), the requirement for reliable molecular transition modeling is becoming more pressing. Unfortunately, there is no trivial approach which can provide a definitive formalism allowing us to solve the coupled systems of equations associated with nonlinear absorption. Here, we propose a general approach to deal with any spectral shape of the electromagnetic field interacting with a molecular species under saturation conditions. The development is specifically applied to Gaussian-shaped beams. To make the analytical expressions tractable, approximations are proposed. Finally, two or three numerical integrations are required for describing the Lamb-dip profile. The implemented model allows us to describe the saturated absorption under low pressure conditions where the broadening by the transit-time may dominate the collision rates. The model is applied to two specific overtone transitions of the molecular acetylene. The simulated line shapes are discussed versus the collision and the transit-time rates. The specific collisional and collision-free regimes are illustrated, while the Rabi frequency controls the intermediate regime. We illustrate how to recover the input parameters by fitting the simulated profiles.

Causal mediation analysis with a latent mediator.

PubMed

Albert, Jeffrey M; Geng, Cuiyu; Nelson, Suchitra

2016-05-01

Health researchers are often interested in assessing the direct effect of a treatment or exposure on an outcome variable, as well as its indirect (or mediation) effect through an intermediate variable (or mediator). For an outcome following a nonlinear model, the mediation formula may be used to estimate causally interpretable mediation effects. This method, like others, assumes that the mediator is observed. However, as is common in structural equations modeling, we may wish to consider a latent (unobserved) mediator. We follow a potential outcomes framework and assume a generalized structural equations model (GSEM). We provide maximum-likelihood estimation of GSEM parameters using an approximate Monte Carlo EM algorithm, coupled with a mediation formula approach to estimate natural direct and indirect effects. The method relies on an untestable sequential ignorability assumption; we assess robustness to this assumption by adapting a recently proposed method for sensitivity analysis. Simulation studies show good properties of the proposed estimators in plausible scenarios. Our method is applied to a study of the effect of mother education on occurrence of adolescent dental caries, in which we examine possible mediation through latent oral health behavior. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Model of non-stationary, inhomogeneous turbulence

DOE PAGES

Bragg, Andrew D.; Kurien, Susan; Clark, Timothy T.

2016-07-08

Here, we compare results from a spectral model for non-stationary, inhomogeneous turbulence (Besnard et al. in Theor Comp Fluid Dyn 8:1–35, 1996) with direct numerical simulation (DNS) data of a shear-free mixing layer (SFML) (Tordella et al. in Phys Rev E 77:016309, 2008). The SFML is used as a test case in which the efficacy of the model closure for the physical-space transport of the fluid velocity field can be tested in a flow with inhomogeneity, without the additional complexity of mean-flow coupling. The model is able to capture certain features of the SFML quite well for intermediate to longmore » times, including the evolution of the mixing-layer width and turbulent kinetic energy. At short-times, and for more sensitive statistics such as the generation of the velocity field anisotropy, the model is less accurate. We propose two possible causes for the discrepancies. The first is the local approximation to the pressure-transport and the second is the a priori spherical averaging used to reduce the dimensionality of the solution space of the model, from wavevector to wavenumber space. DNS data are then used to gauge the relative importance of both possible deficiencies in the model.« less

Analytic derivative couplings and first-principles exciton/phonon coupling constants for an ab initio Frenkel-Davydov exciton model: Theory, implementation, and application to compute triplet exciton mobility parameters for crystalline tetracene.

PubMed

Morrison, Adrian F; Herbert, John M

2017-06-14

Recently, we introduced an ab initio version of the Frenkel-Davydov exciton model for computing excited-state properties of molecular crystals and aggregates. Within this model, supersystem excited states are approximated as linear combinations of excitations localized on molecular sites, and the electronic Hamiltonian is constructed and diagonalized in a direct-product basis of non-orthogonal configuration state functions computed for isolated fragments. Here, we derive and implement analytic derivative couplings for this model, including nuclear derivatives of the natural transition orbital and symmetric orthogonalization transformations that are part of the approximation. Nuclear derivatives of the exciton Hamiltonian's matrix elements, required in order to compute the nonadiabatic couplings, are equivalent to the "Holstein" and "Peierls" exciton/phonon couplings that are widely discussed in the context of model Hamiltonians for energy and charge transport in organic photovoltaics. As an example, we compute the couplings that modulate triplet exciton transport in crystalline tetracene, which is relevant in the context of carrier diffusion following singlet exciton fission.

Scaling of electromagnetic transducers for shunt damping and energy harvesting

NASA Astrophysics Data System (ADS)

Elliott, Stephen J.; Zilletti, Michele

2014-04-01

In order for an electromagnetic transducer to operate well as either a mechanical shunt damper or as a vibration energy harvester, it must have good electromechanical coupling. A simple two-port analysis is used to derive a non-dimensional measure of electromechanical coupling, which must be large compared with unity for efficient operation in both of these applications. The two-port parameters for an inertial electromagnetic transducer are derived, from which this non-dimensional coupling parameter can be evaluated. The largest value that this parameter takes is approximately equal to the square of the magnetic flux density times the length of wire in the field, divided by the mechanical damping times the electrical resistance. This parameter is found to be only of the order of one for voice coil devices that weigh approximately 1 kg, and so such devices are generally not efficient, within the definition used here, in either of these applications. The non-dimensional coupling parameter is found to scale in approximate proportion to the device's characteristic length, however, and so although miniaturised devices are less efficient, greater efficiency can be obtained with large devices, such as those used to control civil engineering structures.

The role of electronic dopant on full band in-plane RKKY coupling in armchair graphene nanoribbons-magnetic impurity system

NASA Astrophysics Data System (ADS)

Hoi, Bui Dinh; Yarmohammadi, Mohsen

2018-05-01

Motivated by the growing interest in solving the obstacles of spintronics applications, we study the Ruderman-Kittel-Kasuya-Yosida (RKKY) effective pairwise interaction between magnetic impurities interacting through the π -electrons embedded in both electronically doped-semiconducting and metallic armchair graphene nanoribbons. In terms of the Green's function formalism, treated in a tight-binding approximation with hopping beyond Dirac cone approximation, the RKKY coupling is an attraction or a repulsion depending on the magnetic impurities distances. Our results show that the RKKY coupling in semiconducting nanoribbons is much more affected by doping than metallic ones. Furthermore, we found that the RKKY coupling increases with ribbon width, while there exist some critical electronic concentrations in RKKY interaction oscillations. On the other hand, we find an unusual incoming wave-vector direction for electrons which describes more clearly the ferro- and antiferromagnetic spin configurations in such system. Also, the RKKY coupling at low and high-temperature regions has been addressed for both ferro- and antiferromagnetic spin arrangements.

Entanglement dynamics of two independent Jaynes-Cummings atoms without the rotating-wave approximation

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

Chen Qinghu; Department of Physics, Zhejiang University, Hangzhou 310027; Yang Yuan

2010-11-15

Entanglement evolution of two independent Jaynes-Cummings atoms without the rotating-wave approximation (RWA) is studied by a numerically exact approach. Previous results based on the RWA are essentially modified in the strong-coupling regime (g{>=}0.1), which has been reached in the recent experiments on the flux qubit coupled to the LC resonator. For the initial Bell state with anticorrelated spins, entanglement sudden death (ESD) is absent in the RWA but does appear in the present numerical calculation without the RWA. Aperiodic entanglement evolution in the strong-coupling regime is observed. The strong atom-cavity coupling facilitates the ESD. The sign of the detuning playsmore » an essential role in the entanglement evolution for strong coupling, which is irrelevant in the RWA. Analytical results based on an unitary transformation are also given, which could not modify the RWA picture essentially. It is suggested that the activation of the photons may be the origin of ESD in this system.« less

Phonon assisted carrier motion on the Wannier-Stark ladder

NASA Astrophysics Data System (ADS)

Cheung, Alfred; Berciu, Mona

2014-03-01

It is well known that at zero temperature and in the absence of electron-phonon coupling, the presence of an electric field leads to localization of carriers residing in a single band of finite bandwidth. In this talk, we will present an implementation of the self-consistent Born approximation (SCBA) to study the effect of weak electron-phonon coupling on the motion of a carrier in a biased system. At moderate and strong electron-phonon coupling, we supplement the SCBA, describing the string of phonons left behind by the carrier, with the momentum average approximation to describe the phonon cloud that accompanies the resulting polaron. We find that coupling to the lattice delocalizes the carrier, as expected, although long-lived resonances resulting from the Wannier-Stark states of the polaron may appear in certain regions of the parameter space. We end with a discussion of how our method can be improved to model disorder, other types of electron-phonon coupling, and electron-hole pair dissociation in a biased system.

Stochastic bifurcations in the nonlinear parallel Ising model.

PubMed

Bagnoli, Franco; Rechtman, Raúl

2016-11-01

We investigate the phase transitions of a nonlinear, parallel version of the Ising model, characterized by an antiferromagnetic linear coupling and ferromagnetic nonlinear one. This model arises in problems of opinion formation. The mean-field approximation shows chaotic oscillations, by changing the couplings or the connectivity. The spatial model shows bifurcations in the average magnetization, similar to that seen in the mean-field approximation, induced by the change of the topology, after rewiring short-range to long-range connection, as predicted by the small-world effect. These coherent periodic and chaotic oscillations of the magnetization reflect a certain degree of synchronization of the spins, induced by long-range couplings. Similar bifurcations may be induced in the randomly connected model by changing the couplings or the connectivity and also the dilution (degree of asynchronism) of the updating. We also examined the effects of inhomogeneity, mixing ferromagnetic and antiferromagnetic coupling, which induces an unexpected bifurcation diagram with a "bubbling" behavior, as also happens for dilution.

Practical approximation method for firing-rate models of coupled neural networks with correlated inputs

NASA Astrophysics Data System (ADS)

Barreiro, Andrea K.; Ly, Cheng

2017-08-01

Rapid experimental advances now enable simultaneous electrophysiological recording of neural activity at single-cell resolution across large regions of the nervous system. Models of this neural network activity will necessarily increase in size and complexity, thus increasing the computational cost of simulating them and the challenge of analyzing them. Here we present a method to approximate the activity and firing statistics of a general firing rate network model (of the Wilson-Cowan type) subject to noisy correlated background inputs. The method requires solving a system of transcendental equations and is fast compared to Monte Carlo simulations of coupled stochastic differential equations. We implement the method with several examples of coupled neural networks and show that the results are quantitatively accurate even with moderate coupling strengths and an appreciable amount of heterogeneity in many parameters. This work should be useful for investigating how various neural attributes qualitatively affect the spiking statistics of coupled neural networks.

Approximate analytical solutions of a pair of coupled anharmonic oscillators

NASA Astrophysics Data System (ADS)

Alam, Nasir; Mandal, Swapan; Öhberg, Patrik

2015-02-01

The Hamiltonian and the corresponding equations of motion involving the field operators of two quartic anharmonic oscillators indirectly coupled via a linear oscillator are constructed. The approximate analytical solutions of the coupled differential equations involving the non-commuting field operators are solved up to the second order in the anharmonic coupling. In the absence of nonlinearity these solutions are used to calculate the second order variances and hence the squeezing in pure and in mixed modes. The higher order quadrature squeezing and the amplitude squared squeezing of various field modes are also investigated where the squeezing in pure and in mixed modes are found to be suppressed. Moreover, the absence of a nonlinearity prohibits the higher order quadrature and higher ordered amplitude squeezing of the input coherent states. It is established that the mere coupling of two oscillators through a third one is unable to produce any squeezing effects of input coherent light, but the presence of a nonlinear interaction may provide squeezed states and other nonclassical phenomena.

Adhesive permeability affects coupling of resin cements that utilise self-etching primers to dentine.

PubMed

Carvalho, R M; Pegoraro, T A; Tay, F R; Pegoraro, L F; Silva, N R F A; Pashley, D H

2004-01-01

To examine the effects of an experimental bonding technique that reduces the permeability of the adhesive layer on the coupling of resin cements to dentine. Extracted human third molars had their mid to deep dentin surface exposed flat by transversally sectioning the crowns. Resin composite overlays were constructed and cemented to the surfaces using either Panavia F (Kuraray) or Bistite II DC (Tokuyama) resin cements mediated by their respective one-step or two-step self-etch adhesives. Experimental groups were prepared in the same way, except that the additional layer of a low-viscosity bonding resin (LVBR, Scotchbond Multi-Purpose Plus, 3M ESPE) was placed on the bonded dentine surface before luting the overlays with the respective resin cements. The bonded assemblies were stored for 24 h in water at 37 degrees C and subsequently prepared for microtensile bond strength testing. Beams of approximately 0.8 mm(2) were tested in tension at 0.5 mm/min in a universal tester. Fractured surfaces were examined under scanning electron microscopy (SEM). Additional specimens were prepared and examined with TEM using a silver nitrate-staining technique. Two-way ANOVA showed significant interactions between materials and bonding protocols (p<0.05). When bonded according to manufacturer's directions, Panavia F produced bond strengths that were significantly lower than Bistite II DC (p<0.05). The placement of an additional layer of a LVBR improved significantly the bond strengths of Panavia F (p<0.05), but not of Bistite II DC (p>0.05). SEM observation of the fractured surfaces in Panavia F showed rosette-like features that were exclusive for specimens bonded according to manufacturer's directions. Such features corresponded well with the ultrastructure of the interfaces that showed more nanoleakage associated with the more permeable adhesive interface. The application of the additional layer of the LVBR reduced the amount of silver impregnation for both adhesives suggesting that reduced permeability of the adhesives resulted in improved coupling of the resin cements to dentin. Placement of an intermediate layer of a LVBR between the bonded dentine surface and the resin cements resulted in improved coupling of Panavia F to dentine.

Analysis of Serine Codon Conservation Reveals Diverse Phenotypic Constraints on Hepatitis C Virus Glycoprotein Evolution

PubMed Central

Koutsoudakis, George; Urbanowicz, Richard A.; Mirza, Deeman; Ginkel, Corinne; Riebesehl, Nina; Calland, Noémie; Albecka, Anna; Price, Louisa; Hudson, Natalia; Descamps, Véronique; Backx, Matthijs; McClure, C. Patrick; Duverlie, Gilles; Pecheur, Eve-Isabelle; Dubuisson, Jean; Perez-del-Pulgar, Sofia; Forns, Xavier; Steinmann, Eike; Tarr, Alexander W.; Pietschmann, Thomas

2014-01-01

Serine is encoded by two divergent codon types, UCN and AGY, which are not interchangeable by a single nucleotide substitution. Switching between codon types therefore occurs via intermediates (threonine or cysteine) or via simultaneous tandem substitutions. Hepatitis C virus (HCV) chronically infects 2 to 3% of the global population. The highly variable glycoproteins E1 and E2 decorate the surface of the viral envelope, facilitate cellular entry, and are targets for host immunity. Comparative sequence analysis of globally sampled E1E2 genes, coupled with phylogenetic analysis, reveals the signatures of multiple archaic codon-switching events at seven highly conserved serine residues. Limited detection of intermediate phenotypes indicates that associated fitness costs restrict their fixation in divergent HCV lineages. Mutational pathways underlying codon switching were probed via reverse genetics, assessing glycoprotein functionality using multiple in vitro systems. These data demonstrate selection against intermediate phenotypes can act at the structural/functional level, with some intermediates displaying impaired virion assembly and/or decreased capacity for target cell entry. These effects act in residue/isolate-specific manner. Selection against intermediates is also provided by humoral targeting, with some intermediates exhibiting increased epitope exposure and enhanced neutralization sensitivity, despite maintaining a capacity for target cell entry. Thus, purifying selection against intermediates limits their frequencies in globally sampled strains, with divergent functional constraints at the protein level restricting the fixation of deleterious mutations. Overall our study provides an experimental framework for identification of barriers limiting viral substitutional evolution and indicates that serine codon-switching represents a genomic “fossil record” of historical purifying selection against E1E2 intermediate phenotypes. PMID:24173227

Consumer Education Learning Activities.

ERIC Educational Resources Information Center

Forkner, Jerry; Schatz, Gail

This handbook contains model lessons on consumer education for use with intermediate, junior high, and high school students. The handbook was developed as a result of a grant which the Social Science Education Consortium received to conduct three consumer education workshops for approximately 100 Colorado teachers and school administrators. Many…

Microwave irradiation decreases ATP, increases free [Mg2+], and alters in vivo intracellular reactions in rat brain

PubMed Central

Srivastava, Shireesh; Kashiwaya, Yoshihiro; Chen, Xuesong; Geiger, Jonathan D.; Pawlosky, Robert; Veech, Richard L.

2012-01-01

Rapid inactivation of metabolism is essential for accurately determining the concentrations of metabolic intermediates in the in vivo state. We compared a broad spectrum of energetic intermediate metabolites and neurotransmitters in brains obtained by microwave irradiation to those obtained by freeze blowing, the most rapid method of extracting and freezing rat brain. The concentrations of many intermediates, cytosolic free NAD(P)+/NAD(P)H ratios, as well as neurotransmitters were not affected by the microwave procedure. However, the brain concentrations of ATP were about 30% lower, whereas those of ADP, AMP, and GDP were higher in the microwave-irradiated compared with the freeze-blown brains. In addition, the hydrolysis of approximately 1 μmol/g of ATP, a major in vivo Mg2+-binding site, was related to approximately five-fold increase in free [Mg2+] (0.53 ± 0.07 mM in freeze blown vs. 2.91 mM ± 0.48 mM in microwaved brains), as determined from the ratio [citrate]/[isocitrate]. Consequently, many intracellular properties, such as the phosphorylation potential and the ΔG’ of ATP hydrolysis were significantly altered in microwaved tissue. The determinations of some glycolytic and TCA cycle metabolites, the phosphorylation potential, and the ΔG’ of ATP hydrolysis do not represent the in vivo state when using microwave-fixed brain tissue. PMID:23013291

Versatile van der Waals Density Functional Based on a Meta-Generalized Gradient Approximation

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

Peng, Haowei; Yang, Zeng-Hui; Perdew, John P.

A “best-of-both-worlds” van der Waals (vdW) density functional is constructed, seamlessly supplementing the strongly constrained and appropriately normed (SCAN) meta-generalized gradient approximation for short- and intermediate-range interactions with the long-range vdW interaction from r VV 10 , the revised Vydrov–van Voorhis nonlocal correlation functional. The resultant SCAN + r VV 10 is the only vdW density functional to date that yields excellent interlayer binding energies and spacings, as well as intralayer lattice constants in 28 layered materials. Its versatility for various kinds of bonding is further demonstrated by its good performance for 22 interactions between molecules; the cohesive energies andmore » lattice constants of 50 solids; the adsorption energy and distance of a benzene molecule on coinage-metal surfaces; the binding energy curves for graphene on Cu(111), Ni(111), and Co(0001) surfaces; and the rare-gas solids. We argue that a good semilocal approximation should (as SCAN does) capture the intermediate-range vdW through its exchange term. We have found an effective range of the vdW interaction between 8 and 16 Å for systems considered here, suggesting that this interaction is negligibly small at the larger distances where it reaches its asymptotic power-law decay.« less

Versatile van der Waals Density Functional Based on a Meta-Generalized Gradient Approximation

DOE PAGES

Peng, Haowei; Yang, Zeng-Hui; Perdew, John P.; ...

2016-10-12

A “best-of-both-worlds” van der Waals (vdW) density functional is constructed, seamlessly supplementing the strongly constrained and appropriately normed (SCAN) meta-generalized gradient approximation for short- and intermediate-range interactions with the long-range vdW interaction from r VV 10 , the revised Vydrov–van Voorhis nonlocal correlation functional. The resultant SCAN + r VV 10 is the only vdW density functional to date that yields excellent interlayer binding energies and spacings, as well as intralayer lattice constants in 28 layered materials. Its versatility for various kinds of bonding is further demonstrated by its good performance for 22 interactions between molecules; the cohesive energies andmore » lattice constants of 50 solids; the adsorption energy and distance of a benzene molecule on coinage-metal surfaces; the binding energy curves for graphene on Cu(111), Ni(111), and Co(0001) surfaces; and the rare-gas solids. We argue that a good semilocal approximation should (as SCAN does) capture the intermediate-range vdW through its exchange term. We have found an effective range of the vdW interaction between 8 and 16 Å for systems considered here, suggesting that this interaction is negligibly small at the larger distances where it reaches its asymptotic power-law decay.« less

FORUM: Bioinspired Heme, Heme/non-heme Diiron, Heme/copper and Inorganic NOx Chemistry: ·NO(g) Oxidation, Peroxynitrite-Metal Chemistry and ·NO(g) Reductive Coupling

PubMed Central

Schopfer, Mark P.; Wang, Jun; Karlin, Kenneth D.

2010-01-01

The focus of this Forum review highlights work from our own laboratories and those of others in the area of biochemical and biologically inspired inorganic chemistry dealing with nitric oxide (nitrogen monoxide, ·NO(g)) and its biological roles and reactions. The latter focus is on (i) oxidation of ·NO(g) to nitrate by nitric oxide dioxygenases (NOD’s), and (ii) reductive coupling of two molecules of ·NO(g) to give N2O(g). In the former case, NOD’s are described and the highlighting of possible peroxynitrite-heme intermediates and consequences of this are given by discussion of recent works with myoglobin and a synthetic heme model system for NOD action. Summaries of recent copper complex chemistries with ·NO(g) and O2(g) leading to peroxynitrite species are given. The coverage of biological reductive coupling of ·NO(g) deals with bacterial nitric oxide reductases (NOR’s) with heme/non-heme diiron active sites, and on heme/Cu oxidases such as cytochrome c oxidase which can mediate the same chemistry. Recent designed protein and synthetic model compound (heme/non-heme diiron or heme/copper) as functional mimics are discussed in some detail. We also highlight examples from the chemical literature, not necessarily involving biologically relevant metal ions, which describe the oxidation of ·NO(g) to nitrate (or nitrite) and possible peroxynitrite intermediates, or reductive coupling of ·NO(g) to give nitrous oxide. PMID:20666386

Approximate analytic solutions to coupled nonlinear Dirac equations

DOE PAGES

Khare, Avinash; Cooper, Fred; Saxena, Avadh

2017-01-30

Here, we consider the coupled nonlinear Dirac equations (NLDEs) in 1+11+1 dimensions with scalar–scalar self-interactions g 1 2/2(more » $$\\bar{ψ}$$ψ) 2 + g 2 2/2($$\\bar{Φ}$$Φ) 2 + g 2 3($$\\bar{ψ}$$ψ)($$\\bar{Φ}$$Φ) as well as vector–vector interactions g 1 2/2($$\\bar{ψ}$$γμψ)($$\\bar{ψ}$$γμψ) + g 2 2/2($$\\bar{Φ}$$γμΦ)($$\\bar{Φ}$$γμΦ) + g 2 3($$\\bar{ψ}$$γμψ)($$\\bar{Φ}$$γμΦ). Writing the two components of the assumed rest frame solution of the coupled NLDE equations in the form ψ=e –iω1tR 1cosθ,R 1sinθΦ=e –iω2tR 2cosη,R 2sinη, and assuming that θ(x),η(x) have the same functional form they had when g3 = 0, which is an approximation consistent with the conservation laws, we then find approximate analytic solutions for Ri(x) which are valid for small values of g 3 2/g 2 2 and g 3 2/g 1 2. In the nonrelativistic limit we show that both of these coupled models go over to the same coupled nonlinear Schrödinger equation for which we obtain two exact pulse solutions vanishing at x → ±∞.« less

Approximate analytic solutions to coupled nonlinear Dirac equations

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

Khare, Avinash; Cooper, Fred; Saxena, Avadh

Here, we consider the coupled nonlinear Dirac equations (NLDEs) in 1+11+1 dimensions with scalar–scalar self-interactions g 1 2/2(more » $$\\bar{ψ}$$ψ) 2 + g 2 2/2($$\\bar{Φ}$$Φ) 2 + g 2 3($$\\bar{ψ}$$ψ)($$\\bar{Φ}$$Φ) as well as vector–vector interactions g 1 2/2($$\\bar{ψ}$$γμψ)($$\\bar{ψ}$$γμψ) + g 2 2/2($$\\bar{Φ}$$γμΦ)($$\\bar{Φ}$$γμΦ) + g 2 3($$\\bar{ψ}$$γμψ)($$\\bar{Φ}$$γμΦ). Writing the two components of the assumed rest frame solution of the coupled NLDE equations in the form ψ=e –iω1tR 1cosθ,R 1sinθΦ=e –iω2tR 2cosη,R 2sinη, and assuming that θ(x),η(x) have the same functional form they had when g3 = 0, which is an approximation consistent with the conservation laws, we then find approximate analytic solutions for Ri(x) which are valid for small values of g 3 2/g 2 2 and g 3 2/g 1 2. In the nonrelativistic limit we show that both of these coupled models go over to the same coupled nonlinear Schrödinger equation for which we obtain two exact pulse solutions vanishing at x → ±∞.« less

Isoscalar and isovector giant resonances in a self-consistent phonon coupling approach

NASA Astrophysics Data System (ADS)

Lyutorovich, N.; Tselyaev, V.; Speth, J.; Krewald, S.; Grümmer, F.; Reinhard, P.-G.

2015-10-01

We present fully self-consistent calculations of isoscalar giant monopole and quadrupole as well as isovector giant dipole resonances in heavy and light nuclei. The description is based on Skyrme energy-density functionals determining the static Hartree-Fock ground state and the excitation spectra within random-phase approximation (RPA) and RPA extended by including the quasiparticle-phonon coupling at the level of the time-blocking approximation (TBA). All matrix elements were derived consistently from the given energy-density functional and calculated without any approximation. As a new feature in these calculations, the single-particle continuum was included thus avoiding the artificial discretization usually implied in RPA and TBA. The step to include phonon coupling in TBA leads to small, but systematic, down shifts of the centroid energies of the giant resonances. These shifts are similar in size for all Skyrme parametrizations investigated here. After all, we demonstrate that one can find Skyrme parametrizations which deliver a good simultaneous reproduction of all three giant resonances within TBA.

Variational extension of the mean spherical approximation to arbitrary dimensions

NASA Astrophysics Data System (ADS)

Velázquez, Esov S.; Blum, Lesser; Frisch, Harry L.

1997-10-01

We generalize a variational principle for the mean spherical approximation for a system of charged hard spheres in 3D to arbitrary dimensions. We first construct a free energy variational trial function from the Debye-Hückel excess charging internal energy at a finite concentration and an entropy obtained at the zero-concentration limit by thermodynamic integration. In three dimensions the minimization of this expression with respect to the screening parameter leads to the mean spherical approximation, usually obtained by solution of the Ornstein-Zernike equation. This procedure, which interpolates naturally between the zero concentration/coupling limit and the high-concentration/ coupling limit, is extended to arbitrary dimensions. We conjecture that this result is also equivalent to the MSA as originally defined, although a technical proof of this point is left for the future. The Onsager limit T ΔS MSA / ΔE MSA → 0 for infinite concentration/coupling is satisfied for all d ≠ 2, while for d=2 this limit is 1.

Phenomenology of Heavy Quarkonia and Quantum Chromodynamics

NASA Astrophysics Data System (ADS)

Schmitz, Stefan Josef Anton

Heavy quarkonia, the cc, b(')b, and soon to be discovered t(')t families of states, are studied in the framework of potential theory. The earlier proposed, flavor independent "Riverside"-potential is fit to masses of cc and b(')b states and their electronic widths are calculated. An unusual feature of the potential is the use of a parameter b which controls the small r or "asymptotic freedom" behavior and which can be related to the QCD scale parameter (LAMDA)(,MS). This param- eter b is virtually undetermined by the cc and b(')b spectra, merely excluding the range b < 4 or (LAMDA)(,MS) < 120MeV and slightly favoring (LAMDA)(,MS) (DBLTURN) 250MeV. It is shown how even minimal information on the t(')t states will restrict the (LAMDA)(,MS) value to a range of the order of 50MeV. A recent Lattice Gauge potential shows a remarkable closeness to the phenomenological approach. In view of the approximations involved, the difference between the two potentials is small. This difference is investigated in terms of the strong coupling constant (alpha) which can be extracted from both potentials. In the main r regime the Lattice Gauge (alpha) is markedly smaller than the phenomenological one. It is shown that the absence of intermediate, virtual quark loops in the Lattice Gauge calculation, i.e. the so-called quenched approximation, accounts for at least some and possibly most of that difference. Overall, the phenomenology of heavy quarkonia as studied in this work is in no conflict with QCD.

Analog quantum simulation of the Rabi model in the ultra-strong coupling regime.

PubMed

Braumüller, Jochen; Marthaler, Michael; Schneider, Andre; Stehli, Alexander; Rotzinger, Hannes; Weides, Martin; Ustinov, Alexey V

2017-10-03

The quantum Rabi model describes the fundamental mechanism of light-matter interaction. It consists of a two-level atom or qubit coupled to a quantized harmonic mode via a transversal interaction. In the weak coupling regime, it reduces to the well-known Jaynes-Cummings model by applying a rotating wave approximation. The rotating wave approximation breaks down in the ultra-strong coupling regime, where the effective coupling strength g is comparable to the energy ω of the bosonic mode, and remarkable features in the system dynamics are revealed. Here we demonstrate an analog quantum simulation of an effective quantum Rabi model in the ultra-strong coupling regime, achieving a relative coupling ratio of g/ω ~ 0.6. The quantum hardware of the simulator is a superconducting circuit embedded in a cQED setup. We observe fast and periodic quantum state collapses and revivals of the initial qubit state, being the most distinct signature of the synthesized model.An analog quantum simulation scheme has been explored with a quantum hardware based on a superconducting circuit. Here the authors investigate the time evolution of the quantum Rabi model at ultra-strong coupling conditions, which is synthesized by slowing down the system dynamics in an effective frame.

Atomic data from the IRON project. LXVI. Electron impact excitation of Fe18+

NASA Astrophysics Data System (ADS)

Butler, K.; Badnell, N. R.

2008-10-01

Context: Accurate electron collisional data are required for the analysis of the Fe xix astrophysical spectrum, in particular in the sun. Such an analysis can provide information on the physical characteristics of the coronal plasma. Aims: An extensive target is used in an R-matrix scattering calculation to provide the necessary data for Fe18+. The use of the R-matrix method includes the resonance contribution lacking in the distorted wave approach and the large target improves the accuracy of the close-coupling approximation. Methods: The R-Matrix package described by Berrington et al. (1995, Comput. Phys. Commun., 92, 290) as provided by the UK RmaX project has been used to calculate electron collisional data among 342 levels of Fe18+. We have used the intermediate-coupling frame-transformation (ICFT) method (Griffin et al. 1998, J. Phys. B: At. Mol. Opt. Phys., 31, 3713) to transform data obtained in a 166 term LS-coupling calculation. Contributions from the mass and Darwin interactions have also been included in the Hamiltonian. Results: Collision stengths for all transitions between the 342 levels of Fe18+ are presented. They are tabulated over a wide range of electron temperatures of astrophysical interest. The results are compared with the earlier Iron Project work of Butler & Zeippen (2001, A&A, 372, 1083) and also with that of McLaughlin et al. (2001, J. Phys. B: At. Mol. Opt. Phys., 34, 4521) and Landi & Gu (2006, ApJ, 640, 1171). The agreement is reasonable for the low-lying transitions. Larger differences are found for the more highly excited states. Full Table 4 is only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A/489/1369

A finite parallel zone model to interpret and extend Giddings' coupling theory for the eddy-dispersion in porous chromatographic media.

PubMed

Desmet, Gert

2013-11-01

The finite length parallel zone (FPZ)-model is proposed as an alternative model for the axial- or eddy-dispersion caused by the occurrence of local velocity biases or flow heterogeneities in porous media such as those used in liquid chromatography columns. The mathematical plate height expression evolving from the model shows that the A- and C-term band broadening effects that can originate from a given velocity bias should be coupled in an exponentially decaying way instead of harmonically as proposed in Giddings' coupling theory. In the low and high velocity limit both models converge, while a 12% difference can be observed in the (practically most relevant) intermediate range of reduced velocities. Explicit expressions for the A- and C-constants appearing in the exponential decay-based plate height expression have been derived for each of the different possible velocity bias levels (single through-pore and particle level, multi-particle level and trans-column level). These expressions allow to directly relate the band broadening originating from these different levels to the local fundamental transport parameters, hence offering the possibility to include a velocity-dependent and, if, needed retention factor-dependent transversal dispersion coefficient. Having developed the mathematics for the general case wherein a difference in retention equilibrium establishes between the two parallel zones, the effect of any possible local variations in packing density and/or retention capacity on the eddy-dispersion can be explicitly accounted for as well. It is furthermore also shown that, whereas the lumped transport parameter model used in the basic variant of the FPZ-model only provides a first approximation of the true decay constant, the model can be extended by introducing a constant correction factor to correctly account for the continuous transversal dispersion transport in the velocity bias zones. Copyright © 2013 Elsevier B.V. All rights reserved.

Hybridization and electron-phonon coupling in ferroelectric BaTiO3 probed by resonant inelastic x-ray scattering

NASA Astrophysics Data System (ADS)

Fatale, S.; Moser, S.; Miyawaki, J.; Harada, Y.; Grioni, M.

2016-11-01

We investigated the ferroelectric perovskite material BaTiO3 by resonant inelastic x-ray scattering (RIXS) at the Ti L3 edge. We observe with decreasing temperature a transfer of spectral weight from the elastic to the charge-transfer spectral features, indicative of increasing Ti 3 d -O 2 p hybridization. When the incident photon energy selects transitions to the Ti 3 d eg manifold, the quasielastic RIXS response exhibits a tail indicative of phonon excitations. A fit of the spectral line shape by a theoretical model allows us to estimate the electron-phonon coupling strength M ˜0.25 eV, which places BaTiO3 in the intermediate coupling regime.

Redox and Lewis acid relay catalysis: a titanocene/zinc catalytic platform in the development of multicomponent coupling reactions.

PubMed

Gianino, Joseph B; Campos, Catherine A; Lepore, Antonio J; Pinkerton, David M; Ashfeld, Brandon L

2014-12-19

A titanocene-catalyzed multicomponent coupling is described herein. Using catalytic titanocene, phosphine, and zinc dust, zinc acetylides can be generated from the corresponding iodoalkynes to affect sequential nucleophilic additions to aromatic aldehydes. The intermediate propargylic alkoxides are trapped in situ with acetic anhydride, which are susceptible to a second nucleophilic displacement upon treatment with a variety of electron-rich species, including acetylides, allyl silanes, electron-rich aromatics, silyl enol ethers, and silyl ketene acetals. Additionally, employing cyclopropane carboxaldehydes led to ring-opened products resulting from iodine incorporation. Taken together, these results form the basis for a new mode of three-component coupling reactions, which allows for rapid access to value added products in a single synthetic operation.

Cross-coupling effects in circuit-QED stimulated Raman adiabatic passage

NASA Astrophysics Data System (ADS)

Vepsäläinen, A.; Paraoanu, G. S.

2018-03-01

Stimulated Raman adiabatic passage is a quantum protocol that can be used for robust state preparation in a three-level system. It has been commonly employed in quantum optics, but recently this technique has drawn attention also in circuit quantum electrodynamics. The protocol relies on two slowly varying drive pulses that couple the initial and the target state via an intermediate state, which remains unpopulated. Here we study the detrimental effect of the parasitic couplings of the drives into transitions other than those required by the protocol. The effect is most prominent in systems with almost harmonic energy level structure, such as the transmon. We show that under these conditions in the presence of decoherence there exists an optimal STIRAP amplitude for population transfer.

Improved RF Isolation Amplifier

NASA Technical Reports Server (NTRS)

Stevens, G. L.; Macconnell, J.

1985-01-01

Circuit has high reverse isolation and wide bandwidth. Wideband isolation amplifier has low intermodulation distortion and high reverse isolation. Circuit does not require selected or matched components or directional coupling device. Circuit used in applications requiring high reverse isolation such as receiver intermediate-frequency (IF) strips and frequency distribution systems. Also applicable in RF and video signaling.

Novel Devices Using Multifunctional ZnO and Its Nanostructures

DTIC Science & Technology

2008-12-01

bias, the electron density increases to a very high level, and the SAW will propagate with the slower short- circuit velocity, vsc . For intermediate...will propagate at a velocity v, which is between voc and vsc . The value of v will be determined by the charge density, the effective coupling of the

School Improvement through Government Agencies: Loose or Tight Coupling?

ERIC Educational Resources Information Center

Bush, Tony

2017-01-01

In seeking to improve student outcomes, governments may choose to exercise direct control over schools, as in many centralised systems, or to provide frameworks for intermediate bodies to engage in improvement activities. One such body is the National College for School Leadership (NCSL), now the National College for Teaching and Leadership (NCTL)…

Heat capacity of high-purity lanthanum

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

Pan, P.H.; Finnemore, D.K.; Bevolo, A.J.

1980-04-01

A study of the specific heat of high-purity single-phase dhcp La shows that this material is an intrinsic type-II superconductor with a kappa of about 2.4. The temperature dependence of the free energy is characteristic of an intermediate coupling superconductor with 2..delta../k/sub B/T/sub c/ approx. = 3.7.

Devices, systems, and methods for harvesting energy and methods for forming such devices

DOEpatents

Kotter, Dale K.; Novack, Steven D.

2012-12-25

Energy harvesting devices include a substrate coupled with a photovoltaic material and a plurality of resonance elements associated with the substrate. The resonance elements are configured to collect energy in at least visible and infrared light spectra. Each resonance element is capacitively coupled with the photovoltaic material, and may be configured to resonate at a bandgap energy of the photovoltaic material. Systems include a photovoltaic material coupled with a feedpoint of a resonance element. Methods for harvesting energy include exposing a resonance element having a resonant electromagnetic radiation having a frequency between approximately 20 THz and approximately 1,000 THz, absorbing at least a portion of the electromagnetic radiation with the resonance element, and resonating the resonance element at a bandgap energy of an underlying photovoltaic material. Methods for forming an energy harvesting device include forming resonance elements on a substrate and capacitively coupling the resonance elements with a photovoltaic material.

Electron–vibration coupling induced renormalization in the photoemission spectrum of diamondoids

DOE PAGES

Gali, Adam; Demján, Tamás; Vörös, Márton; ...

2016-04-22

The development of theories and methods devoted to the accurate calculation of the electronic quasi-particle states and levels of molecules, clusters and solids is of prime importance to interpret the experimental data. These quantum systems are often modelled by using the Born–Oppenheimer approximation where the coupling between the electrons and vibrational modes is not fully taken into account, and the electrons are treated as pure quasi-particles. Here, we show that in small diamond cages, called diamondoids, the electron–vibration coupling leads to the breakdown of the electron quasi-particle picture. More importantly, we demonstrate that the strong electron–vibration coupling is essential tomore » properly describe the overall lineshape of the experimental photoemission spectrum. This cannot be obtained by methods within Born–Oppenheimer approximation. Furthermore, we deduce a link between the vibronic states found by our many-body perturbation theory approach and the well-known Jahn–Teller effect.« less

Electron–vibration coupling induced renormalization in the photoemission spectrum of diamondoids

PubMed Central

Gali, Adam; Demján, Tamás; Vörös, Márton; Thiering, Gergő; Cannuccia, Elena; Marini, Andrea

2016-01-01

The development of theories and methods devoted to the accurate calculation of the electronic quasi-particle states and levels of molecules, clusters and solids is of prime importance to interpret the experimental data. These quantum systems are often modelled by using the Born–Oppenheimer approximation where the coupling between the electrons and vibrational modes is not fully taken into account, and the electrons are treated as pure quasi-particles. Here, we show that in small diamond cages, called diamondoids, the electron–vibration coupling leads to the breakdown of the electron quasi-particle picture. More importantly, we demonstrate that the strong electron–vibration coupling is essential to properly describe the overall lineshape of the experimental photoemission spectrum. This cannot be obtained by methods within Born–Oppenheimer approximation. Moreover, we deduce a link between the vibronic states found by our many-body perturbation theory approach and the well-known Jahn–Teller effect. PMID:27103340

Reactivity of [K₃(phen)₈][Cu(NPh₂)₂]₃--a possible intermediate in the copper(I)-catalyzed N-arylation of N-phenylaniline.

PubMed

Tseng, Chia-Kai; Lee, Chi-Rung; Tseng, Mei-Chun; Han, Chien-Chung; Shyu, Shin-Guang

2014-05-21

Complex [K3(phen)8][Cu(NPh2)2]3 (1, phen = phenanthroline) was isolated from the catalytic C-N cross coupling reaction based on the CuI-phen-tBuOK catalytic system. Complex 1 can react with 4-iodotoluene to give 4-methyl-N,N-diphenylaniline (3a) in 50% yield (based on all available NPh2(-) ligands of complex 1). In addition, 1 can also work as an effective catalyst for the C-N coupling reactions under the same reaction conditions, indicating that 1 may be an effective intermediate of the catalytic system. In the presence of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), a radical scavenger, the stoichiometric reaction between complex 1 and 4-iodotoluene was significantly quenched to give a low yield of 12%. The results suggest that the radical path dominates in the reaction, with (phen)KNPh2 as the possible radical source. The structures of 1 and (phen)KNPh2 were both determined by single crystal X-ray diffraction studies.

Crossover behavior of the thermal conductance and Kramers’ transition rate theory

DOE PAGES

Velizhanin, Kirill A.; Sahu, Subin; Chien, Chih -Chun; ...

2015-12-04

Kramers’ theory frames chemical reaction rates in solution as reactants overcoming a barrier in the presence of friction and noise. For weak coupling to the solution, the reaction rate is limited by the rate at which the solution can restore equilibrium after a subset of reactants have surmounted the barrier to become products. For strong coupling, there are always sufficiently energetic reactants. However, the solution returns many of the intermediate states back to the reactants before the product fully forms. Here, we demonstrate that the thermal conductance displays an analogous physical response to the friction and noise that drive themore » heat current through a material or structure. A crossover behavior emerges where the thermal reservoirs dominate the conductance at the extremes and only in the intermediate region are the intrinsic properties of the lattice manifest. Finally, not only does this shed new light on Kramers’ classic turnover problem, this result is significant for the design of devices for thermal management and other applications, as well as the proper simulation of transport at the nanoscale.« less

Photocatalytic Conversion of Nitrobenzene to Aniline through Sequential Proton-Coupled One-Electron Transfers from a Cadmium Sulfide Quantum Dot

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

Jensen, Stephen C.; Bettis Homan, Stephanie; Weiss, Emily A.

2016-01-28

This paper describes the use of cadmium sulfide quantum dots (CdS QDs) as visible-light photocatalysts for the reduction of nitrobenzene to aniline through six sequential photoinduced, proton-coupled electron transfers. At pH 3.6–4.3, the internal quantum yield of photons-to-reducing electrons is 37.1% over 54 h of illumination, with no apparent decrease in catalyst activity. Monitoring of the QD exciton by transient absorption reveals that, for each step in the catalytic cycle, the sacrificial reductant, 3-mercaptopropionic acid, scavenges the excitonic hole in ~5 ps to form QD•–; electron transfer to nitrobenzene or the intermediates nitrosobenzene and phenylhydroxylamine then occurs on the nanosecondmore » time scale. The rate constants for the single-electron transfer reactions are correlated with the driving forces for the corresponding proton-coupled electron transfers. This result suggests, but does not prove, that electron transfer, not proton transfer, is rate-limiting for these reactions. Nuclear magnetic resonance analysis of the QD–molecule systems shows that the photoproduct aniline, left unprotonated, serves as a poison for the QD catalyst by adsorbing to its surface. Performing the reaction at an acidic pH not only encourages aniline to desorb but also increases the probability of protonated intermediates; the latter effect probably ensures that recruitment of protons is not rate-limiting.« less

Ab initio characterization of electron transfer coupling in photoinduced systems: generalized Mulliken-Hush with configuration-interaction singles.

PubMed

Chen, Hung-Cheng; Hsu, Chao-Ping

2005-12-29

To calculate electronic couplings for photoinduced electron transfer (ET) reactions, we propose and test the use of ab initio quantum chemistry calculation for excited states with the generalized Mulliken-Hush (GMH) method. Configuration-interaction singles (CIS) is proposed to model the locally excited (LE) and charge-transfer (CT) states. When the CT state couples with other high lying LE states, affecting coupling values, the image charge approximation (ICA), as a simple solvent model, can lower the energy of the CT state and decouple the undesired high-lying local excitations. We found that coupling strength is weakly dependent on many details of the solvent model, indicating the validity of the Condon approximation. Therefore, a trustworthy value can be obtained via this CIS-GMH scheme, with ICA used as a tool to improve and monitor the quality of the results. Systems we tested included a series of rigid, sigma-linked donor-bridge-acceptor compounds where "through-bond" coupling has been previously investigated, and a pair of molecules where "through-space" coupling was experimentally demonstrated. The calculated results agree well with experimentally inferred values in the coupling magnitudes (for both systems studied) and in the exponential distance dependence (for the through-bond series). Our results indicate that this new scheme can properly account for ET coupling arising from both through-bond and through-space mechanisms.

Capturing a flavivirus pre-fusion intermediate.

PubMed

Kaufmann, Bärbel; Chipman, Paul R; Holdaway, Heather A; Johnson, Syd; Fremont, Daved H; Kuhn, Richard J; Diamond, Michael S; Rossmann, Michael G

2009-11-01

During cell entry of flaviviruses, low endosomal pH triggers the rearrangement of the viral surface glycoproteins to a fusion-active state that allows the release of the infectious RNA into the cytoplasm. In this work, West Nile virus was complexed with Fab fragments of the neutralizing mAb E16 and was subsequently exposed to low pH, trapping the virions in a pre-fusion intermediate state. The structure of the complex was studied by cryo-electron microscopy and provides the first structural glimpse of a flavivirus fusion intermediate near physiological conditions. A radial expansion of the outer protein layer of the virion was observed compared to the structure at pH 8. The resulting approximately 60 A-wide shell of low density between lipid bilayer and outer protein layer is likely traversed by the stem region of the E glycoprotein. By using antibody fragments, we have captured a structural intermediate of a virus that likely occurs during cell entry. The trapping of structural transition states by antibody fragments will be applicable for other processes in the flavivirus life cycle and delineating other cellular events that involve conformational rearrangements.

Individualizing In-Service Teacher Preparation for ISCS Teachers.

ERIC Educational Resources Information Center

Snyder, William R.

Described is a program which attempts to prepare teachers in a fashion that approximates the instructional setting which is expected in science classrooms utilizing the Intermediate Science Curriculum Study (ISCS) programs. It is specifically designed to support the in-service preparation of ISCS teachers. It includes two basic categories of…

Evidence for a Shared Mechanism in the Formation of Urea-Induced Kinetic and Equilibrium Intermediates of Horse Apomyoglobin from Ultrarapid Mixing Experiments

PubMed Central

Mizukami, Takuya; Abe, Yukiko; Maki, Kosuke

2015-01-01

In this study, the equivalence of the kinetic mechanisms of the formation of urea-induced kinetic folding intermediates and non-native equilibrium states was investigated in apomyoglobin. Despite having similar structural properties, equilibrium and kinetic intermediates accumulate under different conditions and via different mechanisms, and it remains unknown whether their formation involves shared or distinct kinetic mechanisms. To investigate the potential mechanisms of formation, the refolding and unfolding kinetics of horse apomyoglobin were measured by continuous- and stopped-flow fluorescence over a time range from approximately 100 μs to 10 s, along with equilibrium unfolding transitions, as a function of urea concentration at pH 6.0 and 8°C. The formation of a kinetic intermediate was observed over a wider range of urea concentrations (0–2.2 M) than the formation of the native state (0–1.6 M). Additionally, the kinetic intermediate remained populated as the predominant equilibrium state under conditions where the native and unfolded states were unstable (at ~0.7–2 M urea). A continuous shift from the kinetic to the equilibrium intermediate was observed as urea concentrations increased from 0 M to ~2 M, which indicates that these states share a common kinetic folding mechanism. This finding supports the conclusion that these intermediates are equivalent. Our results in turn suggest that the regions of the protein that resist denaturant perturbations form during the earlier stages of folding, which further supports the structural equivalence of transient and equilibrium intermediates. An additional folding intermediate accumulated within ~140 μs of refolding and an unfolding intermediate accumulated in <1 ms of unfolding. Finally, by using quantitative modeling, we showed that a five-state sequential scheme appropriately describes the folding mechanism of horse apomyoglobin. PMID:26244984

Analytical ground state for the Jaynes-Cummings model with ultrastrong coupling

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

Zhang Yuanwei; Institute of Theoretical Physics, Shanxi University, Taiyuan 030006; Chen Gang

2011-06-15

We present a generalized variational method to analytically obtain the ground-state properties of the Jaynes-Cummings model with the ultrastrong coupling. An explicit expression for the ground-state energy, which agrees well with the numerical simulation in a wide range of the experimental parameters, is given. In particular, the introduced method can successfully solve this Jaynes-Cummings model with the positive detuning (the atomic resonant level is larger than the photon frequency), which cannot be treated in the adiabatical approximation and the generalized rotating-wave approximation. Finally, we also demonstrate analytically how to control the mean photon number by means of the current experimentalmore » parameters including the photon frequency, the coupling strength, and especially the atomic resonant level.« less

Real-space mapping of the strongly coupled plasmons of nanoparticle dimers.

PubMed

Kim, Deok-Soo; Heo, Jinhwa; Ahn, Sung-Hyun; Han, Sang Woo; Yun, Wan Soo; Kim, Zee Hwan

2009-10-01

We carried out the near-field optical imaging of isolated and dimerized gold nanocubes to directly investigate the strong coupling between two adjacent nanoparticles. The high-resolution (approximately 10 nm) local field maps (intensities and phases) of self-assembled nanocube dimers reveal antisymmetric plasmon modes that are starkly different from a simple superposition of two monomeric dipole plasmons, which is fully reproduced by the electrodynamics simulations. The result decisively proves that, for the closely spaced pair of nanoparticles (interparticle distance/particle size approximately 0.04), the strong Coulombic attraction between the charges at the interparticle gap dominates over the intraparticle charge oscillations, resulting in a hybridized dimer plasmon mode that is qualitatively different from those expected from a simple dipole-dipole coupling model.

Synthesis and structure-activity relationships of novel lincomycin derivatives. Part 4: synthesis of novel lincomycin analogs modified at the 6- and 7-positions and their potent antibacterial activities.

PubMed

Wakiyama, Yoshinari; Kumura, Ko; Umemura, Eijiro; Ueda, Kazutaka; Watanabe, Takashi; Yamada, Keiko; Okutomi, Takafumi; Ajito, Keiichi

2017-07-01

To modify lincomycin (LCM) at the C-6 and the C-7 positions, we firstly prepared various substituted proline intermediates (7, 11-15 and 17). These proline intermediates were coupled with methyl 1-thio-α-lincosamide and tetrakis-O-trimethylsilylation followed by selective deprotection of the TMS group at the 7-position gave a wide variety of key intermediates (23-27, 47 and 50). Then, we synthesized a variety of novel LCM analogs modified at the 7-position in application of the Mitsunobu reaction, an S N 2 reaction, and a Pd-catalyzed cross-coupling reaction. Compounds 34 and 35 (1'-NH derivatives) exhibited enhanced antibacterial activities against resistant pathogens with erm gene compared with the corresponding 1'-N-methyl derivatives (3 and 37). On the basis of reported SAR, we modified the 4'-position of LCM derivatives possessing a 5-(2-nitrophenyl)-1,3,4-thiadiazol-2-yl group at the C-7 position. Compound 56 showed significantly potent antibacterial activities against S. pneumoniae and S. pyogenes with erm gene, and its activities against S. pneumoniae with erm gene were improved compared with those of 34 and 57. Although we synthesized novel analogs by transformation of a C-7 substituent focusing on the 1'-demethyl framework to prepare very potent analogs 73 and 75, it was impossible to generate novel derivatives exhibiting stronger antibacterial activities against S. pneumoniae with erm gene compared with 56.

Real-time and high accuracy frequency measurements for intermediate frequency narrowband signals

NASA Astrophysics Data System (ADS)

Tian, Jing; Meng, Xiaofeng; Nie, Jing; Lin, Liwei

2018-01-01

Real-time and accurate measurements of intermediate frequency signals based on microprocessors are difficult due to the computational complexity and limited time constraints. In this paper, a fast and precise methodology based on the sigma-delta modulator is designed and implemented by first generating the twiddle factors using the designed recursive scheme. This scheme requires zero times of multiplications and only half amounts of addition operations by using the discrete Fourier transform (DFT) and the combination of the Rife algorithm and Fourier coefficient interpolation as compared with conventional methods such as DFT and Fast Fourier Transform. Experimentally, when the sampling frequency is 10 MHz, the real-time frequency measurements with intermediate frequency and narrowband signals have a measurement mean squared error of ±2.4 Hz. Furthermore, a single measurement of the whole system only requires approximately 0.3 s to achieve fast iteration, high precision, and less calculation time.

Nature of electrogenerated intermediates in nitro-substituted nor-β-lapachones: the structure of radical species during successive electron transfer in multiredox centers.

PubMed

Armendáriz-Vidales, Georgina; Hernández-Muñoz, Lindsay S; González, Felipe J; de Souza, Antonio A; de Abreu, Fabiane C; Jardim, Guilherme A M; da Silva, Eufrânio N; Goulart, Marilia O F; Frontana, Carlos

2014-06-06

Electrochemical, spectroelectrochemical, and theoretical studies of the reduction reactions in nor-β-lapachone derivatives including a nitro redox center showed that reduction of the compounds involves the formation of several radical intermediates, including a biradical dianion resultant from the separate reduction of the quinone and nitro groups in the molecules. Theoretical descriptions of the corresponding Fukui functions f(αα)⁺ and f(ββ)⁺(r) and LUMO densities considering finite differences and frozen core approximations for describing the changes in electron and spin densities of the system allowed us to confirm these results. A description of the potential relationship with the obtained results and biological activity selectivity indexes suggests that both the formation of stable biradical dianion species and the stability of the semiquinone intermediates during further reduction are determining factors in the description of their biological activity.

Surface waves on multilayer hyperbolic metamaterials: Operator approach to effective medium approximation

NASA Astrophysics Data System (ADS)

Popov, Vladislav; Lavrinenko, Andrei V.; Novitsky, Andrey

2018-03-01

In this paper, we elaborate on the operator effective medium approximation developed recently in Popov et al. [Phys. Rev. B 94, 085428 (2016), 10.1103/PhysRevB.94.085428] to get insight into the surface polariton excitation at the interface of a multilayer hyperbolic metamaterial (HMM). In particular, we find that HMMs with bilayer unit cells support the TE- and TM-polarized surface waves beyond the Maxwell Garnett approximation due to the spatial dispersion interpreted as effective magnetoelectric coupling. The latter is also responsible for the dependence of surface wave propagation on the order of layers in the unit cell. Elimination of the magnetoelectric coupling in three-layer unit cells complying with inversion symmetry restores the qualitative regularity of the Maxwell Garnett approximation, as well as strongly suppresses the influence of the order of layers in the unit cell.

Spontaneous light emission by atomic hydrogen: Fermi's golden rule without cheating

NASA Astrophysics Data System (ADS)

Debierre, V.; Durt, T.; Nicolet, A.; Zolla, F.

2015-10-01

Focusing on the 2 p- 1 s transition in atomic hydrogen, we investigate through first order perturbation theory the time evolution of the survival probability of an electron initially taken to be in the excited (2 p) state. We examine both the results yielded by the standard dipole approximation for the coupling between the atom and the electromagnetic field - for which we propose a cutoff-independent regularisation - and those yielded by the exact coupling function. In both cases, Fermi's golden rule is shown to be an excellent approximation for the system at hand: we found its maximal deviation from the exact behaviour of the system to be of order 10-8 /10-7. Our treatment also yields a rigorous prescription for the choice of the optimal cutoff frequency in the dipole approximation. With our cutoff, the predictions of the dipole approximation are almost indistinguishable at all times from the exact dynamics of the system.

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

Franović, Igor, E-mail: franovic@ipb.ac.rs; Todorović, Kristina; Burić, Nikola

We use the mean-field approach to analyze the collective dynamics in macroscopic networks of stochastic Fitzhugh-Nagumo units with delayed couplings. The conditions for validity of the two main approximations behind the model, called the Gaussian approximation and the Quasi-independence approximation, are examined. It is shown that the dynamics of the mean-field model may indicate in a self-consistent fashion the parameter domains where the Quasi-independence approximation fails. Apart from a network of globally coupled units, we also consider the paradigmatic setup of two interacting assemblies to demonstrate how our framework may be extended to hierarchical and modular networks. In both cases,more » the mean-field model can be used to qualitatively analyze the stability of the system, as well as the scenarios for the onset and the suppression of the collective mode. In quantitative terms, the mean-field model is capable of predicting the average oscillation frequency corresponding to the global variables of the exact system.« less

Radiative cooling in shock-heated hydrogen-helium plasmas. [for planetary entry probe heat shields

NASA Technical Reports Server (NTRS)

Poon, P. T. Y.; Stickford, G. H., Jr.

1978-01-01

Axial and off-axis radiative cooling of cylindrical shock-heated hydrogen-helium plasmas is investigated theoretically and experimentally. The coupled fluid dynamic-radiative transfer equations are solved by a combination of approximation techniques aimed at simplifying the computation of the flux divergence term, namely, the quasi-isothermal approximation and the exponential approximation developed for the solid angle integration. The accuracy of the approximation schemes has been assessed and found acceptable for applying the methods to the rapid computation of the radiatively coupled flow problem. Radiative cooling experiments were conducted in a 6-inch annular arc accelerator shock tube (ANAA) for an initial pressure of 1 torr and shock speeds from 35 to 45 Km/sec. The results indicate that the lateral cooling is small compared with the axial cooling, and that better agreement is achieved between the data and the theoretical results by inclusion of the lateral temperature gradient.

Laboratory simulation of infrared astrophysical features. Ph.D. Thesis; [emission spectra of comets

NASA Technical Reports Server (NTRS)

Rose, L. A.

1977-01-01

Intermediate resolution emission spectroscopy was used to study a group of 9 terrestrial silicates, 1 synthetic silicate, 6 meteorites and 2 lunar soils; comparisons were made with the intermediate resolution spectra of Comet Kohoutek in order to determine which materials best simulate the 10um astrophysical feature. Mixtures of silicates which would yield spectra matching the spectrum of the comet in the 10um region include: (1) A hydrous layer lattice silicate in combination with a high temperature condensate; (2) an amorphous magnesium silicate in combination with a high temperature condensate and (3) glassy olivine and glassy anorthite in approximately equal proportions.

Frictional Properties of Main Fault Gouge of Mont Terri, Switzerland

NASA Astrophysics Data System (ADS)

Aoki, K.; Seshimo, K.; Guglielmi, Y.; Nussbaum, C.; Shimamoto, T.; Ma, S.; Yao, L.; Kametaka, M.; Sakai, T.

2016-12-01

JAEA participated in the Fault Slip Experiment of Mont Terri Project which aims at understanding (i) the conditions for slip activation and stability of clay faults, and (ii) the evolution of the coupling between fault slip, pore pressure and fluids migration. The experiment uses SIMFIP probe to estimate (i) the hydraulic and elastic properties of fault zone elements, (ii) the state of stresses across the fault zone and (iii) the fault zone apparent strength properties (friction coefficient and cohesion). To elaborate on the Fault Slip Experiment, JAEA performed friction experiment of borehole cores of depths 47.2m and 37.3m using a rotary-shear low to high-velocity friction apparatus at Institute of Geology, China Earthquake Administration. Friction experiments were performed either dry with room humidity or with 30wt% of H2O, at a normal stress of 1.38 MPa and at low to intermediate slip rates ranging 0.21 microns/s to 2.1mm/s. Sample from a depth of 37.3 m is a fault rock with scaly fabric with calcite veins, whereas that from 47.2 m in depth is a pelitic rock that disaggregates easily with water. Main experimental results are summarized as follows. (1) Gouge samples from both depths exhibit slight velocity-strengthening at V below 0.021 mm/s and notable velocity strengthening at V above approximately 0.021 mm/s. Frictional regimes can be classified into low-velocity and intermediate-velocity regimes, characterized by slight and clear velocity-strengthening behaviors, respectively. (2) Wet gouge from a depth of 47.2 m has mss of 0.12 0.2 at low V and 0.11 0.24 at intermediate V, while dry gouge from the same depth has mss two to three times as high as that for the wet gouge from the same depth. (3) In contrast, both dry and wet gouges from a depth of 37.3 m has mss of around 0.4 to 0.74 at low V and from around 0.45 to 0.75 at intermediate V. There are almost no differences between the dry and wet gouges from this depth (4) The wet gouge from 47.2 m depths has clear slip zone at the gouge-moving piston interface, but clear slip zones are missing in wet gouge from 37.3 m depth. (5) It is hoped that the frictional strength from the present experiments would give some insight on the initiation conditions of fault slip during fluid injection. Results of four other depths will be discussed at the session.

Introducing electron capture into the unitary-convolution-approximation energy-loss theory at low velocities

NASA Astrophysics Data System (ADS)

Schiwietz, G.; Grande, P. L.

2011-11-01

Recent developments in the theoretical treatment of electronic energy losses of bare and screened ions in gases are presented. Specifically, the unitary-convolution-approximation (UCA) stopping-power model has proven its strengths for the determination of nonequilibrium effects for light as well as heavy projectiles at intermediate to high projectile velocities. The focus of this contribution will be on the UCA and its extension to specific projectile energies far below 100 keV/u, by considering electron-capture contributions at charge-equilibrium conditions.

Dinosaur Fossils Predict Body Temperatures

PubMed Central

Allen, Andrew P; Charnov, Eric L

2006-01-01

Perhaps the greatest mystery surrounding dinosaurs concerns whether they were endotherms, ectotherms, or some unique intermediate form. Here we present a model that yields estimates of dinosaur body temperature based on ontogenetic growth trajectories obtained from fossil bones. The model predicts that dinosaur body temperatures increased with body mass from approximately 25 °C at 12 kg to approximately 41 °C at 13,000 kg. The model also successfully predicts observed increases in body temperature with body mass for extant crocodiles. These results provide direct evidence that dinosaurs were reptiles that exhibited inertial homeothermy. PMID:16817695

Dinosaur fossils predict body temperatures.

PubMed

Gillooly, James F; Allen, Andrew P; Charnov, Eric L

2006-07-01

Perhaps the greatest mystery surrounding dinosaurs concerns whether they were endotherms, ectotherms, or some unique intermediate form. Here we present a model that yields estimates of dinosaur body temperature based on ontogenetic growth trajectories obtained from fossil bones. The model predicts that dinosaur body temperatures increased with body mass from approximately 25 degrees C at 12 kg to approximately 41 degrees C at 13,000 kg. The model also successfully predicts observed increases in body temperature with body mass for extant crocodiles. These results provide direct evidence that dinosaurs were reptiles that exhibited inertial homeothermy.

Measurements of a potential interference with laser-induced fluorescence measurements of ambient OH from the ozonolysis of biogenic alkenes

NASA Astrophysics Data System (ADS)

Rickly, Pamela; Stevens, Philip S.

2018-01-01

Reactions of the hydroxyl radical (OH) play a central role in the chemistry of the atmosphere, and measurements of its concentration can provide a rigorous test of our understanding of atmospheric oxidation. Several recent studies have shown large discrepancies between measured and modeled OH concentrations in forested areas impacted by emissions of biogenic volatile organic compounds (BVOCs), where modeled concentrations were significantly lower than measurements. A potential reason for some of these discrepancies involves interferences associated with the measurement of OH using the laser-induced fluorescence-fluorescence assay by gas expansion (LIF-FAGE) technique in these environments. In this study, a turbulent flow reactor operating at atmospheric pressure was coupled to a LIF-FAGE cell and the OH signal produced from the ozonolysis of α-pinene, β-pinene, ocimene, isoprene, and 2-methyl-3-buten-2-ol (MBO) was measured. To distinguish between OH produced from the ozonolysis reactions and any OH artifact produced inside the LIF-FAGE cell, an external chemical scrubbing technique was used, allowing for the direct measurement of any interference. An interference under high ozone (between 2 × 1013 and 10 × 1013 cm-3) and BVOC concentrations (between approximately 0.1 × 1012 and 40 × 1012 cm-3) was observed that was not laser generated and was independent of the ozonolysis reaction time. For the ozonolysis of α- and β-pinene, the observed interference accounted for approximately 40 % of the total OH signal, while for the ozonolysis of ocimene the observed interference accounted for approximately 70 % of the total OH signal. Addition of acetic acid to the reactor eliminated the interference, suggesting that the source of the interference in these experiments involved the decomposition of stabilized Criegee intermediates (SCIs) inside the FAGE detection cell. Extrapolation of these measurements to ambient concentrations suggests that these interferences should be below the detection limit of the instrument.

Multistabilities and symmetry-broken one-color and two-color states in closely coupled single-mode lasers.

PubMed

Clerkin, Eoin; O'Brien, Stephen; Amann, Andreas

2014-03-01

We theoretically investigate the dynamics of two mutually coupled, identical single-mode semi-conductor lasers. For small separation and large coupling between the lasers, symmetry-broken one-color states are shown to be stable. In this case the light outputs of the lasers have significantly different intensities while at the same time the lasers are locked to a single common frequency. For intermediate coupling we observe stable symmetry-broken two-color states, where both lasers lase simultaneously at two optical frequencies which are separated by up to 150 GHz. Using a five-dimensional model, we identify the bifurcation structure which is responsible for the appearance of symmetric and symmetry-broken one-color and two-color states. Several of these states give rise to multistabilities and therefore allow for the design of all-optical memory elements on the basis of two coupled single-mode lasers. The switching performance of selected designs of optical memory elements is studied numerically.

A metalloenzyme-like catalytic system for the chemoselective oxidative cross-coupling of primary amines to imines under ambient conditions.

PubMed

Largeron, Martine; Fleury, Maurice-Bernard

2015-02-23

The direct oxidative cross-coupling of primary amines is a challenging transformation as homocoupling is usually preferred. We report herein the chemoselective preparation of cross-coupled imines through the synergistic combination of low loadings of Cu(II) metal-catalyst and o-iminoquinone organocatalyst under ambient conditions. This homogeneous cooperative catalytic system has been inspired by the reaction of copper amine oxidases, a family of metalloenzymes with quinone organic cofactors that mediate the selective oxidation of primary amines to aldehydes. After optimization, the desired cross-coupled imines are obtained in high yields with broad substrate scope through a transamination process that leads to the homocoupled imine intermediate, followed by dynamic transimination. The ability to carry out the reactions at room temperature and with ambient air, rather than molecular oxygen as the oxidant, and equimolar amounts of each coupling partner is particularly attractive from an environmentally viewpoint. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multistabilities and symmetry-broken one-color and two-color states in closely coupled single-mode lasers

NASA Astrophysics Data System (ADS)

Clerkin, Eoin; O'Brien, Stephen; Amann, Andreas

2014-03-01

We theoretically investigate the dynamics of two mutually coupled, identical single-mode semi-conductor lasers. For small separation and large coupling between the lasers, symmetry-broken one-color states are shown to be stable. In this case the light outputs of the lasers have significantly different intensities while at the same time the lasers are locked to a single common frequency. For intermediate coupling we observe stable symmetry-broken two-color states, where both lasers lase simultaneously at two optical frequencies which are separated by up to 150 GHz. Using a five-dimensional model, we identify the bifurcation structure which is responsible for the appearance of symmetric and symmetry-broken one-color and two-color states. Several of these states give rise to multistabilities and therefore allow for the design of all-optical memory elements on the basis of two coupled single-mode lasers. The switching performance of selected designs of optical memory elements is studied numerically.

Alkyne–Aldehyde Reductive C–C Coupling through Ruthenium-Catalyzed Transfer Hydrogenation: Direct Regio- and Stereoselective Carbonyl Vinylation to Form Trisubstituted Allylic Alcohols in the Absence of Premetallated Reagents

PubMed Central

Leung, Joyce C.; Patman, Ryan L.; Sam, Brannon

2011-01-01

Nonsymmetric 1,2-disubstituted alkynes engage in reductive coupling to a variety of aldehydes under the conditions of ruthenium-catalyzed transfer hydrogenation by employing formic acid as the terminal reductant and delivering the products of carbonyl vinylation with good to excellent levels of regioselectivity and with complete control of olefin stereochemistry. As revealed in an assessment of the ruthenium counterion, iodide plays an essential role in directing the regioselectivity of C–C bond formation. Isotopic labeling studies corroborate reversible catalytic propargyl C–H oxidative addition in advance of the C–C coupling, and demonstrate that the C–C coupling products do not experience reversible dehydrogenation by way of enone intermediates. This transfer hydrogenation protocol enables carbonyl vinylation in the absence of stoichiometric metallic reagents. PMID:21953608

Fermion masses through four-fermion condensates

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

Ayyar, Venkitesh; Chandrasekharan, Shailesh

Fermion masses can be generated through four-fermion condensates when symmetries prevent fermion bilinear condensates from forming. This less explored mechanism of fermion mass generation is responsible for making four reduced staggered lattice fermions massive at strong couplings in a lattice model with a local four-fermion coupling. The model has a massless fermion phase at weak couplings and a massive fermion phase at strong couplings. In particular there is no spontaneous symmetry breaking of any lattice symmetries in both these phases. Recently it was discovered that in three space-time dimensions there is a direct second order phase transition between the twomore » phases. Here we study the same model in four space-time dimensions and find results consistent with the existence of a narrow intermediate phase with fermion bilinear condensates, that separates the two asymptotic phases by continuous phase transitions.« less

Beam echoes in the presence of coupling

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

Gross, Axel

2017-10-03

Transverse beam echoes could provide a new technique of measuring diusion characteristics orders of magnitude faster than the current methods; however, their interaction with many accelerator parameters is poorly understood. Using a program written in C, we explored the relationship between coupling and echo strength. We found that echoes could be generated in both dimensions, even with a dipole kick in only one dimension. We found that the echo eects are not destroyed even when there is strong coupling, falling o only at extremely high coupling values. We found that at intermediate values of skew quadrupole strength, the decoherence timemore » of the beam is greatly increased, causing a destruction of the echo eects. We found that this is caused by a narrowing of the tune width of the particles. Results from this study will help to provide recommendations to IOTA (Integrable Optics Test Accelerator) for their upcoming echo experiment.« less

Non-canonical distribution and non-equilibrium transport beyond weak system-bath coupling regime: A polaron transformation approach

NASA Astrophysics Data System (ADS)

Xu, Dazhi; Cao, Jianshu

2016-08-01

The concept of polaron, emerged from condense matter physics, describes the dynamical interaction of moving particle with its surrounding bosonic modes. This concept has been developed into a useful method to treat open quantum systems with a complete range of system-bath coupling strength. Especially, the polaron transformation approach shows its validity in the intermediate coupling regime, in which the Redfield equation or Fermi's golden rule will fail. In the polaron frame, the equilibrium distribution carried out by perturbative expansion presents a deviation from the canonical distribution, which is beyond the usual weak coupling assumption in thermodynamics. A polaron transformed Redfield equation (PTRE) not only reproduces the dissipative quantum dynamics but also provides an accurate and efficient way to calculate the non-equilibrium steady states. Applications of the PTRE approach to problems such as exciton diffusion, heat transport and light-harvesting energy transfer are presented.

Vector-like quarks and leptons, SU(5) ⊗ SU(5) grand unification, and proton decay

NASA Astrophysics Data System (ADS)

Lee, Chang-Hun; Mohapatra, Rabindra N.

2017-02-01

SU(5) ⊗ SU(5) provides a minimal grand unification scheme for fermions and gauge forces if there are vector-like quarks and leptons in nature. We explore the gauge coupling unification in a non-supersymmetric model of this type, and study its implications for proton decay. The properties of vector-like quarks and intermediate scales that emerge from coupling unification play a central role in suppressing proton decay. We find that in this model, the familiar decay mode p → e +π0 may have a partial lifetime within the reach of currently planned experiments.

Iron-catalyzed oxidative biaryl cross-couplings via mixed diaryl titanates: significant influence of the order of combining aryl Grignard reagents with titanate.

PubMed

Liu, Kun Ming; Wei, Juan; Duan, Xin Fang

2015-03-18

The mixed diaryl titanates were used for the first time to modify the reactivity of two aryl Grignard reagents. Two titanate intermediates, Ar[Ar'Ti(OR)3]MgX and Ar'[ArTi(OR)3]MgX, formed via alternating the sequence of combining Grignard reagents with ClTi(OR)3 showed a significant reactivity difference. Taking advantage of such different reactivity, two highly structurally similar aryl groups could be facilely assembled through iron-catalyzed oxidative cross-couplings using oxygen as the oxidant.

Electron Capture in Proton Collisions with CO.

NASA Astrophysics Data System (ADS)

Stancil, P. C.; Schultz, D. R.; Kimura, M.; Gu, J.-P.; Hirsch, G.; Buenker, R. J.; Li, Y.

1999-10-01

Electron capture by protons following collisions with carbon monoxide is studied with a variety of theoretical approaches including quantal and semiclassical molecular-orbital close-coupling (MOCC) and classical trajectory Monte Carlo (CTMC) techniques. The MOCC treatments utilize potential surfaces and couplings computed for a range of H^+-CO orientation angles and C-O separations. Results including integral, differential, electronic state-selective, and vibrational state-selective cross sections will be presented for low- to intermediate-energies. Comparison with experiment will be made where possible and the relevance of the reaction in astrophysics and atmospheric physics will be discussed.

Domino-Fluorination-Protodefluorination Enables Decarboxylative Cross-Coupling of α-Oxocarboxylic Acids with Styrene via Photoredox Catalysis.

PubMed

Zhang, Muliang; Xi, Junwei; Ruzi, Rehanguli; Li, Nan; Wu, Zhongkai; Li, Weipeng; Zhu, Chengjian

2017-09-15

Domino-fluorination-protodefluorination decarboxylative cross-coupling of α-keto acids with styrene has been developed via photoredox catalysis. The critical part of this strategy is the formation of the carbon-fluorine (C-F) bond by the capture of a carbon-centered radical intermediate, which will overcome side reactions during the styrene radical functionalization process. Experimental studies have provided evidence indicating a domino-fluorination-protodefluorination pathway with α-keto acid initiating the photoredox cycle. The present catalytic protocol also affords a novel approach for the construction of α,β-unsaturated ketones under mild conditions.

Surface-Activated Coupling Reactions Confined on a Surface.

PubMed

Dong, Lei; Liu, Pei Nian; Lin, Nian

2015-10-20

Chemical reactions may take place in a pure phase of gas or liquid or at the interface of two phases (gas-solid or liquid-solid). Recently, the emerging field of "surface-confined coupling reactions" has attracted intensive attention. In this process, reactants, intermediates, and products of a coupling reaction are adsorbed on a solid-vacuum or a solid-liquid interface. The solid surface restricts all reaction steps on the interface, in other words, the reaction takes place within a lower-dimensional, for example, two-dimensional, space. Surface atoms that are fixed in the surface and adatoms that move on the surface often activate the surface-confined coupling reactions. The synergy of surface morphology and activity allow some reactions that are inefficient or prohibited in the gas or liquid phase to proceed efficiently when the reactions are confined on a surface. Over the past decade, dozens of well-known "textbook" coupling reactions have been shown to proceed as surface-confined coupling reactions. In most cases, the surface-confined coupling reactions were discovered by trial and error, and the reaction pathways are largely unknown. It is thus highly desirable to unravel the mechanisms, mechanisms of surface activation in particular, of the surface-confined coupling reactions. Because the reactions take place on surfaces, advanced surface science techniques can be applied to study the surface-confined coupling reactions. Among them, scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) are the two most extensively used experimental tools. The former resolves submolecular structures of individual reactants, intermediates, and products in real space, while the latter monitors the chemical states during the reactions in real time. Combination of the two methods provides unprecedented spatial and temporal information on the reaction pathways. The experimental findings are complemented by theoretical modeling. In particular, density-functional theory (DFT) transition-state calculations have been used to shed light on reaction mechanisms and to unravel the trends of different surface materials. In this Account, we discuss recent progress made in two widely studied surface-confined coupling reactions, aryl-aryl (Ullmann-type) coupling and alkyne-alkyne (Glaser-type) coupling, and focus on surface activation effects. Combined experimental and theoretical studies on the same reactions taking place on different metal surfaces have clearly demonstrated that different surfaces not only reduce the reaction barrier differently and render different reaction pathways but also control the morphology of the reaction products and, to some degree, select the reaction products. We end the Account with a list of questions to be addressed in the future. Satisfactorily answering these questions may lead to using the surface-confined coupling reactions to synthesize predefined products with high yield.

Vibration Damping Circuit Card Assembly

NASA Technical Reports Server (NTRS)

Hunt, Ronald Allen (Inventor)

2016-01-01

A vibration damping circuit card assembly includes a populated circuit card having a mass M. A closed metal container is coupled to a surface of the populated circuit card at approximately a geometric center of the populated circuit card. Tungsten balls fill approximately 90% of the metal container with a collective mass of the tungsten balls being approximately (0.07) M.

Self-consistency in the phonon space of the particle-phonon coupling model

NASA Astrophysics Data System (ADS)

Tselyaev, V.; Lyutorovich, N.; Speth, J.; Reinhard, P.-G.

2018-04-01

In the paper the nonlinear generalization of the time blocking approximation (TBA) is presented. The TBA is one of the versions of the extended random-phase approximation (RPA) developed within the Green-function method and the particle-phonon coupling model. In the generalized version of the TBA the self-consistency principle is extended onto the phonon space of the model. The numerical examples show that this nonlinear version of the TBA leads to the convergence of results with respect to enlarging the phonon space of the model.

Rotational-vibrational coupling in the theory of electron-molecule scattering

NASA Technical Reports Server (NTRS)

Temkin, A.; Sullivan, E. C.

1974-01-01

The adiabatic-nuclei approximation of vibrational-rotational excitation of homonuclear diatomic molecules can be simply augmented to describe the vibrational-rotational coupling by including the dependence of the vibrational wave function on j. Appropriate formulas are given, and the theory, is applied to e-H2 excitation, whereby it is shown that deviations from the simple Born-Oppenheimer approximation measured by Wong and Schultz can be explained. More important, it can be seen that the inclusion of the j-dependent centrifugal term is essential for transitions involving high-rotational quantum numbers.

Intermediate band formation in a δ-doped like QW superlattices of GaAs/AlxGa1-xAs for solar cell design

NASA Astrophysics Data System (ADS)

Del Río-De Santiago, A.; Martínez-Orozco, J. C.; Rodríguez-Magdaleno, K. A.; Contreras-Solorio, D. A.; Rodríguez-Vargas, I.; Ungan, F.

2018-03-01

It is reported a numerical computation of the local density of states for a δ-doped like QW superlattices of AlxGa1-xAs, as a possible heterostructure that, being integrated into a solar cell device design, can provide an intermediate band of allowed states to assist the absorption of photons with lower energies than that of the energy gap of the solar-cell constituent materials. This work was performed using the nearest neighbors sp3s* tight-binding model including spin. The confining potential caused by the ionized donor impurities in δ-doped impurities seeding that was obtained analytically within the lines of the Thomas-Fermi approximation was reproduced here by the Al concentration x variation. This potential is considered as an external perturbation in the tight-binding methodology and it is included in the diagonal terms of the tight-binding Hamiltonian. Special attention is paid to the width of the intermediate band caused by the change in the considered aluminium concentration x, the inter-well distance between δ-doped like QW wells and the number of them in the superlattice. In general we can conclude that this kind of superlattices can be suitable for intermediate band formation for possible intermediate-band solar cell design.

Gravitropism in roots of intermediate-starch mutants of Arabidopsis

NASA Technical Reports Server (NTRS)

Kiss, J. Z.; Wright, J. B.; Caspar, T.

1996-01-01

Gravitropism was studied in roots of wild type (WT) Arabidopsis thaliana (L.) Heynh. (strain Wassilewskija) and three starch-deficient mutants that were generated by T-DNA insertional mutagenesis. One of these mutants was starchless while the other two were intermediate mutants, which had 51% and 60%, respectively, of the WT amount of starch as determined by light and electron microscopy. The four parameters used to assay gravitropism were: orientation during vertical growth, time course of curvature, induction, and intermittent stimulation experiments. WT roots were much more responsive to gravity than were roots of the starchless mutant, and the intermediate starch mutants exhibited an intermediate graviresponse. Our data suggest that lowered starch content in the mutants primarily affects gravitropism rather than differential growth because both phototropic curvature and growth rates were approximately equal among all four genotypes. Since responses of intermediate-starch mutants were closer to the WT response than to the starchless mutant, it appears that 51-60% of the WT level of starch is near the threshold amount needed for full gravitropic sensitivity. While other interpretations are possible, the data are consistent with the starch statolith hypothesis for gravity perception in that the degree of graviresponsiveness is proportional to the total mass of plastids per cell.

Sensitivity of Precipitation in Coupled Land-Atmosphere Models

NASA Technical Reports Server (NTRS)

Neelin, David; Zeng, N.; Suarez, M.; Koster, R.

2004-01-01

The project objective was to understand mechanisms by which atmosphere-land-ocean processes impact precipitation in the mean climate and interannual variations, focusing on tropical and subtropical regions. A combination of modeling tools was used: an intermediate complexity land-atmosphere model developed at UCLA known as the QTCM and the NASA Seasonal-to-Interannual Prediction Program general circulation model (NSIPP GCM). The intermediate complexity model was used to develop hypotheses regarding the physical mechanisms and theory for the interplay of large-scale dynamics, convective heating, cloud radiative effects and land surface feedbacks. The theoretical developments were to be confronted with diagnostics from the more complex GCM to validate or modify the theory.

Palladium-catalyzed Suzuki-Miyaura coupling of amides by carbon-nitrogen cleavage: general strategy for amide N-C bond activation.

PubMed

Meng, Guangrong; Szostak, Michal

2016-06-15

The first palladium-catalyzed Suzuki-Miyaura cross-coupling of amides with boronic acids for the synthesis of ketones by sterically-controlled N-C bond activation is reported. The transformation is characterized by operational simplicity using bench-stable, commercial reagents and catalysts, and a broad substrate scope, including substrates with electron-donating and withdrawing groups on both coupling partners, steric-hindrance, heterocycles, halides, esters and ketones. The scope and limitations are presented in the synthesis of >60 functionalized ketones. Mechanistic studies provide insight into the catalytic cycle of the cross-coupling, including the first experimental evidence for Pd insertion into the amide N-C bond. The synthetic utility is showcased by a gram-scale cross-coupling and cross-coupling at room temperature. Most importantly, this process provides a blueprint for the development of a plethora of metal catalyzed reactions of typically inert amide bonds via acyl-metal intermediates. A unified strategy for amide bond activation to enable metal insertion into N-C amide bond is outlined ().

Oxidative coupling of sp 2 and sp 3 carbon-hydrogen bonds to construct dihydrobenzofurans.

PubMed

Shi, Jiang-Ling; Wang, Ding; Zhang, Xi-Sha; Li, Xiao-Lei; Chen, Yu-Qin; Li, Yu-Xue; Shi, Zhang-Jie

2017-08-10

Metal-catalyzed cross-couplings provide powerful, concise, and accurate methods to construct carbon-carbon bonds from organohalides and organometallic reagents. Recent developments extended cross-couplings to reactions where one of the two partners connects with an aryl or alkyl carbon-hydrogen bond. From an economic and environmental point of view, oxidative couplings between two carbon-hydrogen bonds would be ideal. Oxidative coupling between phenyl and "inert" alkyl carbon-hydrogen bonds still awaits realization. It is very difficult to develop successful strategies for oxidative coupling of two carbon-hydrogen bonds owning different chemical properties. This article provides a solution to this challenge in a convenient preparation of dihydrobenzofurans from substituted phenyl alkyl ethers. For the phenyl carbon-hydrogen bond activation, our choice falls on the carboxylic acid fragment to form the palladacycle as a key intermediate. Through careful manipulation of an additional ligand, the second "inert" alkyl carbon-hydrogen bond activation takes place to facilitate the formation of structurally diversified dihydrobenzofurans.Cross-dehydrogenative coupling is finding increasing application in synthesis, but coupling two chemically distinct sites remains a challenge. Here, the authors report an oxidative coupling between sp 2 and sp 3 carbons by sequentially activating the more active aryl site followed by the alkyl position.

Analytic model for the long-term evolution of circular Earth satellite orbits including lunar node regression

NASA Astrophysics Data System (ADS)

Zhu, Ting-Lei; Zhao, Chang-Yin; Zhang, Ming-Jiang

2017-04-01

This paper aims to obtain an analytic approximation to the evolution of circular orbits governed by the Earth's J2 and the luni-solar gravitational perturbations. Assuming that the lunar orbital plane coincides with the ecliptic plane, Allan and Cook (Proc. R. Soc. A, Math. Phys. Eng. Sci. 280(1380):97, 1964) derived an analytic solution to the orbital plane evolution of circular orbits. Using their result as an intermediate solution, we establish an approximate analytic model with lunar orbital inclination and its node regression be taken into account. Finally, an approximate analytic expression is derived, which is accurate compared to the numerical results except for the resonant cases when the period of the reference orbit approximately equals the integer multiples (especially 1 or 2 times) of lunar node regression period.

Investigating the two-moment characterisation of subcellular biochemical networks.

PubMed

Ullah, Mukhtar; Wolkenhauer, Olaf

2009-10-07

While ordinary differential equations (ODEs) form the conceptual framework for modelling many cellular processes, specific situations demand stochastic models to capture the influence of noise. The most common formulation of stochastic models for biochemical networks is the chemical master equation (CME). While stochastic simulations are a practical way to realise the CME, analytical approximations offer more insight into the influence of noise. Towards that end, the two-moment approximation (2MA) is a promising addition to the established analytical approaches including the chemical Langevin equation (CLE) and the related linear noise approximation (LNA). The 2MA approach directly tracks the mean and (co)variance which are coupled in general. This coupling is not obvious in CME and CLE and ignored by LNA and conventional ODE models. We extend previous derivations of 2MA by allowing (a) non-elementary reactions and (b) relative concentrations. Often, several elementary reactions are approximated by a single step. Furthermore, practical situations often require the use of relative concentrations. We investigate the applicability of the 2MA approach to the well-established fission yeast cell cycle model. Our analytical model reproduces the clustering of cycle times observed in experiments. This is explained through multiple resettings of M-phase promoting factor (MPF), caused by the coupling between mean and (co)variance, near the G2/M transition.

NHC-catalyzed cleavage of vicinal diketones and triketones followed by insertion of enones and ynones.

PubMed

Takaki, Ken; Hino, Makoto; Ohno, Akira; Komeyama, Kimihiro; Yoshida, Hiroto; Fukuoka, Hiroshi

2017-01-01

Thiazolium carbene-catalyzed reactions of 1,2-diketones and 1,2,3-triketones with enones and ynones have been investigated. The diketones gave α,β-double acylation products via unique Breslow intermediates isolable as acid salts, whereas the triketones formed stable adducts with the NHC instead of the coupling products.

Coupling Binding to Catalysis: Using Yeast Cell Surface Display to Select Enzymatic Activities.

PubMed

Zhang, Keya; Bhuripanyo, Karan; Wang, Yiyang; Yin, Jun

2015-01-01

We find yeast cell surface display can be used to engineer enzymes by selecting the enzyme library for high affinity binding to reaction intermediates. Here we cover key steps of enzyme engineering on the yeast cell surface including library design, construction, and selection based on magnetic and fluorescence-activated cell sorting.

The use of complete sets of orthogonal operators in spectroscopic studies

NASA Astrophysics Data System (ADS)

Raassen, A. J. J.; Uylings, P. H. M.

1996-01-01

Complete sets of orthogonal operators are used to calculate eigenvalues and eigenvector compositions in complex spectra. The latter are used to transform the LS-transition matrix into realistic intermediate coupling transition probabilities. Calculated transition probabilities for some close lying levels in Ni V and Fe III illustrate the power of the complete orthogonal operator approach.

On-Line Synthesis and Analysis by Mass Spectrometry

ERIC Educational Resources Information Center

Bain, Ryan M.; Pulliam, Christopher J.; Raab, Shannon A.; Cooks, R. Graham

2015-01-01

In this laboratory experiment, students learn how to use ESI to accelerate chemical synthesis and to couple it with on-line mass spectrometry for structural analysis. The Hantzsch synthesis of symmetric 1,4-dihydropyridines is a classic example of a one-pot reaction in which multiple intermediates can serve to indicate the progress of the reaction…

NHC-catalyzed cleavage of vicinal diketones and triketones followed by insertion of enones and ynones

PubMed Central

Hino, Makoto; Ohno, Akira; Komeyama, Kimihiro; Yoshida, Hiroto; Fukuoka, Hiroshi

2017-01-01

Thiazolium carbene-catalyzed reactions of 1,2-diketones and 1,2,3-triketones with enones and ynones have been investigated. The diketones gave α,β-double acylation products via unique Breslow intermediates isolable as acid salts, whereas the triketones formed stable adducts with the NHC instead of the coupling products. PMID:28904625

Guanosine radical reactivity explored by pulse radiolysis coupled with transient electrochemistry.

PubMed

Latus, A; Alam, M S; Mostafavi, M; Marignier, J-L; Maisonhaute, E

2015-06-04

We follow the reactivity of a guanosine radical created by a radiolytic electron pulse both by spectroscopic and electrochemical methods. This original approach allows us to demonstrate that there is a competition between oxidation and reduction of these intermediates, an important result to further analyse the degradation or repair pathways of DNA bases.

A coupling method for a cardiovascular simulation model which includes the Kalman filter.

PubMed

Hasegawa, Yuki; Shimayoshi, Takao; Amano, Akira; Matsuda, Tetsuya

2012-01-01

Multi-scale models of the cardiovascular system provide new insight that was unavailable with in vivo and in vitro experiments. For the cardiovascular system, multi-scale simulations provide a valuable perspective in analyzing the interaction of three phenomenons occurring at different spatial scales: circulatory hemodynamics, ventricular structural dynamics, and myocardial excitation-contraction. In order to simulate these interactions, multiscale cardiovascular simulation systems couple models that simulate different phenomena. However, coupling methods require a significant amount of calculation, since a system of non-linear equations must be solved for each timestep. Therefore, we proposed a coupling method which decreases the amount of calculation by using the Kalman filter. In our method, the Kalman filter calculates approximations for the solution to the system of non-linear equations at each timestep. The approximations are then used as initial values for solving the system of non-linear equations. The proposed method decreases the number of iterations required by 94.0% compared to the conventional strong coupling method. When compared with a smoothing spline predictor, the proposed method required 49.4% fewer iterations.

Structural intermediates and directionality of the swiveling motion of Pyruvate Phosphate Dikinase

NASA Astrophysics Data System (ADS)

Minges, Alexander; Ciupka, Daniel; Winkler, Christian; Höppner, Astrid; Gohlke, Holger; Groth, Georg

2017-03-01

Pyruvate phosphate dikinase (PPDK) is a vital enzyme in cellular energy metabolism catalyzing the ATP- and Pi-dependent formation of phosphoenolpyruvate from pyruvate in C4 -plants, but the reverse reaction forming ATP in bacteria and protozoa. The multi-domain enzyme is considered an efficient molecular machine that performs one of the largest single domain movements in proteins. However, a comprehensive understanding of the proposed swiveling domain motion has been limited by not knowing structural intermediates or molecular dynamics of the catalytic process. Here, we present crystal structures of PPDKs from Flaveria, a model genus for studying the evolution of C4 -enzymes from phylogenetic ancestors. These structures resolve yet unknown conformational intermediates and provide the first detailed view on the large conformational transitions of the protein in the catalytic cycle. Independently performed unrestrained MD simulations and configurational free energy calculations also identified these intermediates. In all, our experimental and computational data reveal strict coupling of the CD swiveling motion to the conformational state of the NBD. Moreover, structural asymmetries and nucleotide binding states in the PPDK dimer support an alternate binding change mechanism for this intriguing bioenergetic enzyme.

Cleave and couple: toward fully sustainable catalytic conversion of lignocellulose to value added building blocks and fuels.

PubMed

Sun, Zhuohua; Barta, Katalin

2018-06-21

The structural complexity of lignocellulose offers unique opportunities for the development of entirely new, energy efficient and waste-free pathways in order to obtain valuable bio-based building blocks. Such sustainable catalytic methods - specifically tailored to address the efficient conversion of abundant renewable starting materials - are necessary to successfully compete, in the future, with fossil-based multi-step processes. In this contribution we give a summary of recent developments in this field and describe our "cleave and couple" strategy, where "cleave" refers to the catalytic deconstruction of lignocellulose to aromatic and aliphatic alcohol intermediates, and "couple" involves the development of novel, sustainable transformations for the formation of C-C and C-N bonds in order to obtain a range of attractive products from lignocellulose.

Sensitivity of the Tropical Ocean-Atmosphere to Seasonal and Long-Term Climate Forcing

NASA Technical Reports Server (NTRS)

Kim, K.-M.; Lau, K.-M.

1999-01-01

Since the pioneer works of Bjerknes (1966,1969) many studies have been conducted to understand the El Nino and Southern Oscillation (ENSO) phenomenon. These studies have led to a basic understanding of the dynamics of El Nino. Central to the couple dynamics of ENSO is the delayed action oscillator theory (Suarez and Schopf 1988), which successfully describes the cyclic feature of El Nino. While the oscillatory feature of El Nino is reasonably well understood, the irregularity of El Nino, the effect of monsoon on ENSO, and the response of coupled system to the global warming are still under debate. In the present study, we attempt to provide some theoretical understanding of possible impacts of seasonal cycle, monsoon, and climate changes on ENSO using intermediate coupled model.

Indirect measurement of N-14 quadrupolar coupling for NH3 intercalated in potassium graphite

NASA Technical Reports Server (NTRS)

Tsang, T.; Fronko, R. M.; Resing, H. A.

1987-01-01

A method for indirect measurement of the nuclear quadrupolar coupling was developed and applied to NH3 molecules in the graphite intercalation compound K(NH3)4.3C24, which has a layered structure with alternating carbon and intercalant layers. Three triplets were observed in the H-1 NMR spectra of the compound. The value of the N-14 quadrupolar coupling constant of NH3 (3.7 MHz), determined indirectly from the H-1 NMR spectra, was intermediate between the gas value of 4.1 MHz and the solid-state value of 3.2 MHz. The method was also used to deduce the (H-1)-(H-1) and (N-14)-(H-1) dipolar interactions, the H-1 chemical shifts, and the molecular orientations and motions of NH3.

Coherent destruction of tunneling in chaotic microcavities via three-state anti-crossings

PubMed Central

Song, Qinghai; Gu, Zhiyuan; Liu, Shuai; Xiao, Shumin

2014-01-01

Coherent destruction of tunneling (CDT) has been one seminal result of quantum dynamics control. Traditionally, CDT is understood as destructive interference between two intermediate transition paths near the level crossing. CDT near the level anti-crossings, especially the “locking”, has not been thoroughly explored so far. Taking chaotic microcavity as an example, here we study the inhibition of the tunneling via the strong couplings of three resonances. While the tunneling rate is only slightly affected by each strong coupling between two modes, the destructive interference between two strong couplings can dramatically improve the inhibition of the tunneling. A “locking” point, where dynamical tunneling is completely suppressed, has even been observed. We believe our finding will shed light on researches on micro- & nano-photonics. PMID:24781881

Effect of Electrical Stimulation on Beta-Adrenergic Receptor Population and Coupling Efficiency in Chicken and Rat Skeleton Muscle Cell Cultures

NASA Technical Reports Server (NTRS)

Young, Ronald B.; Bridge, Kristin Y.; Strietzel, Catherine J.

1999-01-01

Expression of the beta-adrenergic receptor (bAR) and its coupling to cyclic AMP (cAMP) synthesis are important components of the signaling system that controls muscle atrophy and hypertrophy, and the goal of this study was to determine if electrical stimulation in a pattern simulating slow muscle contraction would alter the bAR response in primary cultures of avian and mammalian skeletal muscle cells. Specifically, chicken skeletal muscle cells and rat skeletal muscle cells that had been grown for seven days in culture were subjected to electrical stimulation for an additional two days at a pulse frequency of 0.5 pulses/sec and a pulse duration of 200 msec. In chicken skeletal muscle cells, the bAR population was not significantly affected by electrical stimulation; however, the ability of these cells to synthesize cyclic AMP was reduced by approximately one-half. Thus, in chicken muscle cells an enhanced level of contraction reduced the coupling efficiency of bAR for cyclic AMP production by approximately 55% compared to controls. In contrast, the bAR population in rat muscle cells was increased by approximately 25% by electrical stimulation, and the ability of these cells to synthesize cyclic AMP was also increased by almost two-fold. Thus, in rat muscle cells an enhanced level of contraction increased the coupling efficiency of bAR for cyclic AMP production by approximately 50% compared to controls. The basal levels of intracellular cyclic AMP in both rat muscle cells and chicken muscle cells were not affected by electrical stimulation.

Millimeter-wave active probe

DOEpatents

Majidi-Ahy, Gholamreza; Bloom, David M.

1991-01-01

A millimeter-wave active probe for use in injecting signals with frequencies above 50GHz to millimeter-wave and ultrafast devices and integrated circuits including a substrate upon which a frequency multiplier consisting of filter sections and impedance matching sections are fabricated in uniplanar transmission line format. A coaxial input and uniplanar 50 ohm transmission line couple an approximately 20 GHz input signal to a low pass filter which rolls off at approximately 25 GHz. An input impedance matching section couples the energy from the low pass filter to a pair of matched, antiparallel beam lead diodes. These diodes generate odd-numberd harmonics which are coupled out of the diodes by an output impedance matching network and bandpass filter which suppresses the fundamental and third harmonics and selects the fifth harmonic for presentation at an output.

Costs of Epilepsy in an Intermediate Care Facility for Persons with Mental Retardation.

ERIC Educational Resources Information Center

Burke, Thomas A.; McKee, Jerry R.; Pathak, Dev S.; Donahue, Rafe M. J.; Parasuraman, T. V.; Batenhorst, Alice S.

1999-01-01

A study compared the cost of caring for 50 institutionalized persons with developmental disabilities and epilepsy with 50 individuals with developmental disabilities. Costs attributable to epilepsy were found to be approximately $825.00 and $918.00 per person over a six-month period. Personnel, drugs, hospitalization, and laboratories/procures…

Competencia Comunicativa em Portuges (Communicative Competence in Portuguese).

ERIC Educational Resources Information Center

Paiva, Ricardo

A textbook designed to give speech and writing practice to intermediate and advanced students of Portuguese as a second language includes 14 units intended to cover two semesters' work with approximately five hours per week of instruction. The units typically include: a text forming the basis for free conversation and practice of language…

Quasiclassical description of the nearest-neighbor hopping dc conduction via hydrogen-like donors in intermediately compensated GaAs crystals

NASA Astrophysics Data System (ADS)

Poklonski, N. A.; Vyrko, S. A.; Zabrodskii, A. G.

2010-08-01

Expressions for the pre-exponential factor σ3 and the thermal activation energy ɛ3 of hopping electric conductivity of electrons via hydrogen-like donors in n-type gallium arsenide are obtained in the quasiclassical approximation. Crystals with the donor concentration N and the acceptor concentration KN at the intermediate compensation ratio K (approximately from 0.25 to 0.75) are considered. We assume that the donors in the charge states (0) and (+1) and the acceptors in the charge state (-1) form a joint nonstoichiometric simple cubic 'sublattice' within the crystalline matrix. In such sublattice the distance between nearest impurity atoms is Rh = [(1 + K)N]-1/3 which is also the length of an electron hop between donors. To take into account orientational disorder of hops we assume that the impurity sublattice randomly and smoothly changes orientation inside a macroscopic sample. Values of σ3(N) and ɛ3(N) calculated for the temperature of 2.5 K agree with known experimental data at the insulator side of the insulator-metal phase transition.

Column-coupling strategies for multidimensional electrophoretic separation techniques.

PubMed

Kler, Pablo A; Sydes, Daniel; Huhn, Carolin

2015-01-01

Multidimensional electrophoretic separations represent one of the most common strategies for dealing with the analysis of complex samples. In recent years we have been witnessing the explosive growth of separation techniques for the analysis of complex samples in applications ranging from life sciences to industry. In this sense, electrophoretic separations offer several strategic advantages such as excellent separation efficiency, different methods with a broad range of separation mechanisms, and low liquid consumption generating less waste effluents and lower costs per analysis, among others. Despite their impressive separation efficiency, multidimensional electrophoretic separations present some drawbacks that have delayed their extensive use: the volumes of the columns, and consequently of the injected sample, are significantly smaller compared to other analytical techniques, thus the coupling interfaces between two separations components must be very efficient in terms of providing geometrical precision with low dead volume. Likewise, very sensitive detection systems are required. Additionally, in electrophoretic separation techniques, the surface properties of the columns play a fundamental role for electroosmosis as well as the unwanted adsorption of proteins or other complex biomolecules. In this sense the requirements for an efficient coupling for electrophoretic separation techniques involve several aspects related to microfluidics and physicochemical interactions of the electrolyte solutions and the solid capillary walls. It is interesting to see how these multidimensional electrophoretic separation techniques have been used jointly with different detection techniques, for intermediate detection as well as for final identification and quantification, particularly important in the case of mass spectrometry. In this work we present a critical review about the different strategies for coupling two or more electrophoretic separation techniques and the different intermediate and final detection methods implemented for such separations.

Bimolecular Coupling as a Vector for Decomposition of Fast-Initiating Olefin Metathesis Catalysts.

PubMed

Bailey, Gwendolyn A; Foscato, Marco; Higman, Carolyn S; Day, Craig S; Jensen, Vidar R; Fogg, Deryn E

2018-06-06

The correlation between rapid initiation and rapid decomposition in olefin metathesis is probed for a series of fast-initiating, phosphine-free Ru catalysts: the Hoveyda catalyst HII, RuCl 2 (L)(═CHC 6 H 4 - o-O i Pr); the Grela catalyst nG (a derivative of HII with a nitro group para to O i Pr); the Piers catalyst PII, [RuCl 2 (L)(═CHPCy 3 )]OTf; the third-generation Grubbs catalyst GIII, RuCl 2 (L)(py) 2 (═CHPh); and dianiline catalyst DA, RuCl 2 (L)( o-dianiline)(═CHPh), in all of which L = H 2 IMes = N,N'-bis(mesityl)imidazolin-2-ylidene. Prior studies of ethylene metathesis have established that various Ru metathesis catalysts can decompose by β-elimination of propene from the metallacyclobutane intermediate RuCl 2 (H 2 IMes)(κ 2 -C 3 H 6 ), Ru-2. The present work demonstrates that in metathesis of terminal olefins, β-elimination yields only ca. 25-40% propenes for HII, nG, PII, or DA, and none for GIII. The discrepancy is attributed to competing decomposition via bimolecular coupling of methylidene intermediate RuCl 2 (H 2 IMes)(═CH 2 ), Ru-1. Direct evidence for methylidene coupling is presented, via the controlled decomposition of transiently stabilized adducts of Ru-1, RuCl 2 (H 2 IMes)L n (═CH 2 ) (L n = py n' ; n' = 1, 2, or o-dianiline). These adducts were synthesized by treating in situ-generated metallacyclobutane Ru-2 with pyridine or o-dianiline, and were isolated by precipitating at low temperature (-116 or -78 °C, respectively). On warming, both undergo methylidene coupling, liberating ethylene and forming RuCl 2 (H 2 IMes)L n . A mechanism is proposed based on kinetic studies and molecular-level computational analysis. Bimolecular coupling emerges as an important contributor to the instability of Ru-1, and a potentially major pathway for decomposition of fast-initiating, phosphine-free metathesis catalysts.

Utility of the CS and IOS approximations for calculating generalized phenomenological cross sections in atom-diatom systems

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

Fitz, D.E.; Kouri, D.J.; Liu, W.K.

1982-04-01

The calculation of shear viscosity and thermal conductivity coefficients in the presence of a magnetic field requires the accurate calculation of several types of generalized phenomenological cross sections in which velocity and angular momentum tensors are coupled with the orbital and rotational motion of the system. These cross sections are then averaged over energy in a fashion appropriate for the phenomenon of interest. The coupled states (CS) and/or infinite order sudden (IOS) approximations have been used to calculate several such cross sections for systems such as He-HCl, He-CO, He-H/sub 2/, HD-Ne, Ar-N/sub 2/, and Ne-H/sub 2/. Excellent results are obtainedmore » compared with close-coupled methods for cross sections which are symmetric in tensor index, especially in the CS approximation, and these results are not very sensitive to the choice of orbital wave parameter. On the other hand, the cross sections which are asymmetric in tensor index are much more sensitive to interference effects and are unsatisfactory in many cases.« less

Asymptotic safety of quantum gravity beyond Ricci scalars

NASA Astrophysics Data System (ADS)

Falls, Kevin; King, Callum R.; Litim, Daniel F.; Nikolakopoulos, Kostas; Rahmede, Christoph

2018-04-01

We investigate the asymptotic safety conjecture for quantum gravity including curvature invariants beyond Ricci scalars. Our strategy is put to work for families of gravitational actions which depend on functions of the Ricci scalar, the Ricci tensor, and products thereof. Combining functional renormalization with high order polynomial approximations and full numerical integration we derive the renormalization group flow for all couplings and analyse their fixed points, scaling exponents, and the fixed point effective action as a function of the background Ricci curvature. The theory is characterized by three relevant couplings. Higher-dimensional couplings show near-Gaussian scaling with increasing canonical mass dimension. We find that Ricci tensor invariants stabilize the UV fixed point and lead to a rapid convergence of polynomial approximations. We apply our results to models for cosmology and establish that the gravitational fixed point admits inflationary solutions. We also compare findings with those from f (R ) -type theories in the same approximation and pin-point the key new effects due to Ricci tensor interactions. Implications for the asymptotic safety conjecture of gravity are indicated.

Wet chemical synthesis of zinc-iron oxide nanocomposite

NASA Astrophysics Data System (ADS)

Ito, Honami; Amagasa, Shota; Nishida, Naoki; Kobayashi, Yoshio; Yamada, Yasuhiro

2017-11-01

Zinc-iron oxide nanoparticles (ZnxFe3-xO4 and δ-ZnxFe1-xOOH) were successfully synthesized by room temperature chemical reaction of a solution containing ZnCl2 and FeCl2 in the presence of gelatin. The composition of products could be controlled by variation of the Zn/Fe mixture ratio of the starting material. ZnxFe3-xO4 nanoparticles were obtained from a solution with a high Zn/Fe ratio, whereas Zn-doped feroxyhyte ( δ-ZnxFe1-xOOH) nanoparticles were obtained from a solution with a low Zn/Fe ratio. The ZnxFe3-xO4 nanoparticles were spherical with diameters of approximately 10 nm, and the δ-ZnxFe1-xOOH particles were needle-like with lengths of approximately 100 nm. Mössbauer spectra measured at room temperature indicated superparamagnetic behavior of the nanoparticles, whereas the magnetic components were observed at low temperature. The Zn content of the intermediate species (( {Zn}^{ {II}}x {Fe}^{ {II}}_{1-x} {Fe}^{ {III}}2O4)) plays an important role in the oxidation process. When the Zn concentration was high, the content of Fe2+ in the intermediate species was small, and Zn2+ prevented further oxidation of the nanoparticles. When the starting material had low Zn concentration, the amount of Fe2+ in the intermediate species became large and was rapidly oxidized into δ-ZnxFe1-xOOH while rinsing under the ambient atmosphere.

Calculation of light delay for coupled microrings by FDTD technique and Padé approximation.

PubMed

Huang, Yong-Zhen; Yang, Yue-De

2009-11-01

The Padé approximation with Baker's algorithm is compared with the least-squares Prony method and the generalized pencil-of-functions (GPOF) method for calculating mode frequencies and mode Q factors for coupled optical microdisks by FDTD technique. Comparisons of intensity spectra and the corresponding mode frequencies and Q factors show that the Padé approximation can yield more stable results than the Prony and the GPOF methods, especially the intensity spectrum. The results of the Prony method and the GPOF method are greatly influenced by the selected number of resonant modes, which need to be optimized during the data processing, in addition to the length of the time response signal. Furthermore, the Padé approximation is applied to calculate light delay for embedded microring resonators from complex transmission spectra obtained by the Padé approximation from a FDTD output. The Prony and the GPOF methods cannot be applied to calculate the transmission spectra, because the transmission signal obtained by the FDTD simulation cannot be expressed as a sum of damped complex exponentials.

An asymptotically consistent approximant for the equatorial bending angle of light due to Kerr black holes

NASA Astrophysics Data System (ADS)

Barlow, Nathaniel S.; Weinstein, Steven J.; Faber, Joshua A.

2017-07-01

An accurate closed-form expression is provided to predict the bending angle of light as a function of impact parameter for equatorial orbits around Kerr black holes of arbitrary spin. This expression is constructed by assuring that the weak- and strong-deflection limits are explicitly satisfied while maintaining accuracy at intermediate values of impact parameter via the method of asymptotic approximants (Barlow et al 2017 Q. J. Mech. Appl. Math. 70 21-48). To this end, the strong deflection limit for a prograde orbit around an extremal black hole is examined, and the full non-vanishing asymptotic behavior is determined. The derived approximant may be an attractive alternative to computationally expensive elliptical integrals used in black hole simulations.

Analysis and experimental study of wireless power transfer with HTS coil and copper coil as the intermediate resonators system

NASA Astrophysics Data System (ADS)

Wang, Xiufang; Nie, Xinyi; Liang, Yilang; Lu, Falong; Yan, Zhongming; Wang, Yu

2017-01-01

Intermediate resonator (repeater) between transmitter and receiver can significantly increase the distance of wireless power transfer (WPT) and the efficiency of wireless power transfer. The wireless power transfer via strongly coupled magnetic resonances with an high temperature superconducting (HTS) coil and copper coil as intermediate resonators was presented in this paper. The electromagnetic experiment system under different conditions with different repeating coils were simulated by finite element software. The spatial distribution patterns of magnetic induction intensity at different distances were plotted. In this paper, we examined transfer characteristics with HTS repeating coil and copper repeating coil at 77 K and 300 K, respectively. Simulation and experimental results show that HTS and copper repeating coil can effectively enhance the space magnetic induction intensity, which has significant effect on improving the transmission efficiency and lengthening transmission distance. We found that the efficiency and the distance of wireless power transfer system with an HTS coil as repeater is much higher by using of copper coil as repeater.

The theory of maximally and minimally even sets, the one- dimensional antiferromagnetic Ising model, and the continued fraction compromise of musical scales

NASA Astrophysics Data System (ADS)

Douthett, Elwood (Jack) Moser, Jr.

1999-10-01

Cyclic configurations of white and black sites, together with convex (concave) functions used to weight path length, are investigated. The weights of the white set and black set are the sums of the weights of the paths connecting the white sites and black sites, respectively, and the weight between sets is the sum of the weights of the paths that connect sites opposite in color. It is shown that when the weights of all configurations of a fixed number of white and a fixed number of black sites are compared, minimum (maximum) weight of a white set, minimum (maximum) weight of the a black set, and maximum (minimum) weight between sets occur simultaneously. Such configurations are called maximally even configurations. Similarly, the configurations whose weights are the opposite extremes occur simultaneously and are called minimally even configurations. Algorithms that generate these configurations are constructed and applied to the one- dimensional antiferromagnetic spin-1/2 Ising model. Next the goodness of continued fractions as applied to musical intervals (frequency ratios and their base 2 logarithms) is explored. It is shown that, for the intermediate convergents between two consecutive principal convergents of an irrational number, the first half of the intermediate convergents are poorer approximations than the preceding principal convergent while the second half are better approximations; the goodness of a middle intermediate convergent can only be determined by calculation. These convergents are used to determine what equal-tempered systems have intervals that most closely approximate the musical fifth (pn/ qn = log2(3/2)). The goodness of exponentiated convergents ( 2pn/qn~3/2 ) is also investigated. It is shown that, with the exception of a middle convergent, the goodness of the exponential form agrees with that of its logarithmic Counterpart As in the case of the logarithmic form, the goodness of a middle intermediate convergent in the exponential form can only be determined by calculation. A Desirability Function is constructed that simultaneously measures how well multiple intervals fit in a given equal-tempered system. These measurements are made for octave (base 2) and tritave systems (base 3). Combinatorial properties important to music modulation are considered. These considerations lead These considerations lead to the construction of maximally even scales as partitions of an equal-tempered system.

Theory of electron capture from a hydrogen-like ion by a bare ion with extensions to inner-shell capture

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

Alston, S.G.

1982-01-01

A complete systematic derivation is given of a new approximation for the calculation of the cross section for electron capture from a hydrogen-like ion of large nuclear charge Z/sub T/e by a bare ion of charge Z/sub p/e moving with speed v. The amplitude in the wave treatment is obtained through consistent expansion in the small parameters Z/sub p//Z/sub T/ and Z/sub p/e/sup 2//hv; however, the ratio Z/sub T/e/sup 2//hv is not assumed small. Electron-target nucleus interactions are included to all orders and electron-projectile interactions were included consistently to first order so that the theory is called the strong potentialmore » Born (SPB). Following a careful analysis of the approach to the energy shell, an off-shell factor is seen to arise which does not appear in the impulse approximation (IA). The effects of this factor on the capture amplitude are explored. It is shown that, in comparison with the IA, the correct weighting of the target spectrum of intermediate states in the SPB significantly alters the 1s ..-->.. ns cross section and at the same time makes peaking approximations to the amplitude more realistic, even for intermediate velocity Z/sub p/e/sup 2//h<« less

Strong-potential Born calculations for 1s-1s electron capture from atoms by protons

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

McGuire, J.H.; Kletke, R.E.; Sil, N.C.

1985-08-01

The strong-potential Born (SPB) approximation is examined by comparing various SPB calculations of high-velocity 1s-1s electron capture cross sections with one another and with experimental data. Above about 1 MeV, calculations using the SPB method of McGuire and Sil (SPMS) (Phys. Rev. A 28, 3679 (1983)) are in good agreement with total-cross-section observations for protons on H, He, C, Ne, and Ar as expected. For p+H and p+He, the SPB full-peaking (SPB-FP) approximation of Macek and Alston (Phys. Rev. A 26, 250 (1982)) and the SPB transverse-peaking (SPB-TP) approximation of Alston (Phys. Rev. A 27, 2342 (1982)) differ from ourmore » SPMS total cross sections by typically a factor of 2, as expected from general validity criteria. However, the differential cross sections at very forward angles (well within the Thomas angle) are the same in SPMS, SPB-FP, and SPB-TP methods in all cases. Below 1 MeV, cross sections obtained with use of various SPB methods differ considerably from one another, placing a limit of validity for these SPB calculations. We also suggest that in the gap between those energies where continuum intermediate states simply dominate, and above those energies where bound intermediate states simply dominate, detailed conceptual understanding of electron capture is incomplete.« less

GMX approximation for the linear E ⊗ ɛ Jahn-Teller effect

NASA Astrophysics Data System (ADS)

Mancini, Jay D.; Fessatidis, Vassilios; Bowen, Samuel P.

2006-02-01

A newly developed generalized moments expansion (GMX) based on the t-expansion of Horn and Weinstein is applied to a linear E ⊗ ɛ Jahn-Teller system. Comparisons are made with other moments schemes as well a coupled cluster approximation.

A coupled-cluster study of photodetachment cross sections of closed-shell anions

NASA Astrophysics Data System (ADS)

Cukras, Janusz; Decleva, Piero; Coriani, Sonia

2014-11-01

We investigate the performance of Stieltjes Imaging applied to Lanczos pseudo-spectra generated at the coupled cluster singles and doubles, coupled cluster singles and approximate iterative doubles and coupled cluster singles levels of theory in modeling the photodetachment cross sections of the closed shell anions H-, Li-, Na-, F-, Cl-, and OH-. The accurate description of double excitations is found to play a much more important role than in the case of photoionization of neutral species.

A coupled-cluster study of photodetachment cross sections of closed-shell anions.

PubMed

Cukras, Janusz; Decleva, Piero; Coriani, Sonia

2014-11-07

We investigate the performance of Stieltjes Imaging applied to Lanczos pseudo-spectra generated at the coupled cluster singles and doubles, coupled cluster singles and approximate iterative doubles and coupled cluster singles levels of theory in modeling the photodetachment cross sections of the closed shell anions H(-), Li(-), Na(-), F(-), Cl(-), and OH(-). The accurate description of double excitations is found to play a much more important role than in the case of photoionization of neutral species.

Soil Moisture Dynamics in the Shallow Subsurface Near the Land/Atmospheric Interface- Challenges and New Research Approaches (Invited)

NASA Astrophysics Data System (ADS)

Illangasekare, T. H.; Smits, K. M.; Trautz, A.; Rice, A. K.; Cihan, A.; Davarzani, H.

2013-12-01

SSoil moisture processes in the subsurface/near-land-surface, play a crucial role in the hydrologic cycle and global water budget. This zone is subject to both natural and human induced disturbances, resulting in continually changing soil structure and hydraulic, thermal, and mechanical properties. Understanding of the dynamics of soil moisture distribution in this zone is of interest in various applications in hydrology such as land-atmospheric interaction, soil evaporation and evapotranspiration, as well as emerging problems on assessing the risk of leakage of sequestrated CO2 from deep geologic formations to the shallow subsurface, and potential leakage of methane to the atmosphere in shale gas development that contributes to global warming. Shallow subsurface soil moisture is highly influenced by diurnal temperature variations, evaporation/condensation, precipitation and liquid water and water vapor flow, all of which are strongly coupled. Modeling studies, have shown that soil moisture in this zone is highly sensitive to the heat and mass flux boundary conditions at the land surface. Hence, approximation of these boundary conditions without properly incorporating complex feedback between the land and the atmospheric boundary layer are expected to result in significant errors. Even though considerable knowledge exists on how soil moisture changes in response to the flux and energy boundary conditions, emerging problems involving land atmospheric interactions require the quantification of soil moisture variability at higher spatial and temporal resolutions than what is needed in traditional applications in soil physics and vadose zone hydrology. These factors lead to many modeling challenges, primarily of which is the issue of up-scaling. It is our contention that knowledge that will contribute to both improving our understanding of the fundamental processes and practical problem solutions cannot be obtained using only field data. Basic to this limitation is the inability to make field measurements at very fine scales at high temporal resolutions. Also, as the natural boundary conditions at the land/atmospheric interface are not controllable in the field, even in pilot scale studies, the developed theories and models cannot be validated for a diversity of conditions that could be expected. As an alternative, we propose an innovative testing approach that couples a low velocity boundary layer climate wind tunnel to intermediate scale porous media tanks. Intermediate scale testing using soil tanks packed to represent different heterogeneous test configurations provides an attractive and cost effective alternative to investigate a class of problems involving the shallow unsaturated zone. In this talk, we will present examples of studies we have conducted in a hierarchy of test systems, including the intermediate scale. The advantages and limitations of testing at this scale are discussed using these examples. The features and capabilities of newly developed test systems are presented with the goal of exploring opportunities to use them to study some of the challenging multi-scale problems in the near surface unsaturated zone.

Accidental Predissociation: A Special Case of Photo-Induced Isotope Fractionation Effect and Possible Occurrence in Nature

NASA Astrophysics Data System (ADS)

Chakraborty, S.; Thiemens, M. H.

2009-12-01

Photo-Induced Isotope Fractionation Effects (PHIFE) are known to produce isotopic frac-tionation in some photo-dissociating molecules (1-2). The PHIFE formalism is based on the Born-Oppenheimer approximation and the Reflection Principle. The isotopic fractionation arises principally from the spectral shift induced by the small difference in zero point energy between isotopologues and the contraction of the wave function due to isotopic substitution, consequently, the associated isotopic fractionations depends on the reduced mass of the isotopically substi-tuted species. The PHIFE formalism is only applicable to the molecules which undergo direct photo-dissociation that possess continuous absorption spectra. Simple molecules (N2, O2, CO) however do not follow a direct dissociation pathway and dissociate through an indirect process termed predissociation, which occurs when the molecule is excited to a quasi-bound state energetically above the dissociation continuum. The PHIFE formalism is not applicable when the absorption spectra are discrete. The assumption that the lightest isotopologues are preferentially predissociated is only valid for restricted predissociation cases. There is a special case of predissociation known as ‘accidental predissociation’ (3), which takes place through an intermediate bound state in two steps (i) leakage to an intermediate bound state (coupled through spin orbit interaction) and, (ii) predissociation to a third quasi-bound state from the intermediate state. Line broadening at an accidental predissociation is a function of the magnitude of coupling matrix elements and the linewidths are strongly influenced by isotopic substitution (4). An anomalous isotopic effect in accidental predissociation was spectroscopically observed in CO (5), N2 (4) and BeH (6). We measured the isotopic fractionation for the first time in two accidental predissociating states of CO through VUV photodissociation using the 9.0.2 beamline at ALS (7-8). In light of these data, anomalous isotopic fractionations associated with accidental predissociation will be discussed for the CO and N2. These fractionations are important as VUV-photodissociation of CO and N2 have been invoked in solar nebula (self-shielding, (9-10)) to explain the observed iso-topic signatures in different solar system objects neglecting these isotope effects during photo-dissociation. References: 1. Y. L. Yung, C. E. Miller, Science 278, 1778 (1997). 2. S. Chakraborty, S. K. Bhattacharya, J. Chem. Phys. 118, 2164 (2003). 3. H. Lefebvre-Brion, R. W. Field, The Spectra and Dynamics of Diatomic Molecules. (Elsevier Academic Press, 2004). 4. A. J. Lorquet, J. C. Lorquet, Chem. Phys. Lett. 26, 138 (1974). 5. W. Ubachs, I. Velchev, P. Cacciani, J. Chem. Phys. 113, 547 (2000). 6. H. Lefebvre-Brion, R. Colin, J. Mol. Spectrosc. 65, 33 (1977). 7. S. Chakraborty, M. Ahmed, T. L. Jackson, M. H. Thiemens, Science 321, 1328 (2008). 8. S. Chakraborty, M. Ahmed, T. L. Jackson, M. H. Thiemens, Science 324, 4 (2009). 9. R. N. Clayton, Nature 415, 860 (2002). 10. J. R. Lyons, E. D. Young, Nature 435, 317 (2005).

Unification of Gauge Couplings in the E{sub 6}SSM

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

Athron, P.; King, S. F.; Luo, R.

2010-02-10

We argue that in the two--loop approximation gauge coupling unification in the exceptional supersymmetric standard model (E{sub 6}SSM) can be achieved for any phenomenologically reasonable value of alpha{sub 3}(M{sub Z}) consistent with the experimentally measured central value.

State-selective charge exchange in slow collisions of Si3+ ions with H atoms: A molecular state close coupling treatment*)

NASA Astrophysics Data System (ADS)

Joseph, Dwayne C.; Saha, Bidhan C.

2012-11-01

Charge transfer cross sections are calculated by employing both the quantal and semiclassical ɛ(R) molecular orbital close coupling (MOCC) approximations in the adiabatic representation and compared with other theoretical and experimental results

Analytical Solution for the Anisotropic Rabi Model: Effects of Counter-Rotating Terms

NASA Astrophysics Data System (ADS)

Zhang, Guofeng; Zhu, Hanjie

2015-03-01

The anisotropic Rabi model, which was proposed recently, differs from the original Rabi model: the rotating and counter-rotating terms are governed by two different coupling constants. This feature allows us to vary the counter-rotating interaction independently and explore the effects of it on some quantum properties. In this paper, we eliminate the counter-rotating terms approximately and obtain the analytical energy spectrums and wavefunctions. These analytical results agree well with the numerical calculations in a wide range of the parameters including the ultrastrong coupling regime. In the weak counter-rotating coupling limit we find out that the counter-rotating terms can be considered as the shifts to the parameters of the Jaynes-Cummings model. This modification shows the validness of the rotating-wave approximation on the assumption of near-resonance and relatively weak coupling. Moreover, the analytical expressions of several physics quantities are also derived, and the results show the break-down of the U(1)-symmetry and the deviation from the Jaynes-Cummings model.

Analytical solution for the anisotropic Rabi model: effects of counter-rotating terms.

PubMed

Zhang, Guofeng; Zhu, Hanjie

2015-03-04

The anisotropic Rabi model, which was proposed recently, differs from the original Rabi model: the rotating and counter-rotating terms are governed by two different coupling constants. This feature allows us to vary the counter-rotating interaction independently and explore the effects of it on some quantum properties. In this paper, we eliminate the counter-rotating terms approximately and obtain the analytical energy spectrums and wavefunctions. These analytical results agree well with the numerical calculations in a wide range of the parameters including the ultrastrong coupling regime. In the weak counter-rotating coupling limit we find out that the counter-rotating terms can be considered as the shifts to the parameters of the Jaynes-Cummings model. This modification shows the validness of the rotating-wave approximation on the assumption of near-resonance and relatively weak coupling. Moreover, the analytical expressions of several physics quantities are also derived, and the results show the break-down of the U(1)-symmetry and the deviation from the Jaynes-Cummings model.

Regional seismic wavefield computation on a 3-D heterogeneous Earth model by means of coupled traveling wave synthesis

USGS Publications Warehouse

Pollitz, F.F.

2002-01-01

I present a new algorithm for calculating seismic wave propagation through a three-dimensional heterogeneous medium using the framework of mode coupling theory originally developed to perform very low frequency (f < ???0.01-0.05 Hz) seismic wavefield computation. It is a Greens function approach for multiple scattering within a defined volume and employs a truncated traveling wave basis set using the locked mode approximation. Interactions between incident and scattered wavefields are prescribed by mode coupling theory and account for the coupling among surface waves, body waves, and evanescent waves. The described algorithm is, in principle, applicable to global and regional wave propagation problems, but I focus on higher frequency (typically f ??????0.25 Hz) applications at regional and local distances where the locked mode approximation is best utilized and which involve wavefields strongly shaped by propagation through a highly heterogeneous crust. Synthetic examples are shown for P-SV-wave propagation through a semi-ellipsoidal basin and SH-wave propagation through a fault zone.

Artificial dispersion via high-order homogenization: magnetoelectric coupling and magnetism from dielectric layers

PubMed Central

Liu, Yan; Guenneau, Sébastien; Gralak, Boris

2013-01-01

We investigate a high-order homogenization (HOH) algorithm for periodic multi-layered stacks. The mathematical tool of choice is a transfer matrix method. Expressions for effective permeability, permittivity and magnetoelectric coupling are explored by frequency power expansions. On the physical side, this HOH uncovers a magnetoelectric coupling effect (odd-order approximation) and artificial magnetism (even-order approximation) in moderate contrast photonic crystals. Comparing the effective parameters' expressions of a stack with three layers against that of a stack with two layers, we note that the magnetoelectric coupling effect vanishes while the artificial magnetism can still be achieved in a centre-symmetric periodic structure. Furthermore, we numerically check the effective parameters through the dispersion law and transmission property of a stack with two dielectric layers against that of an effective bianisotropic medium: they are in good agreement throughout the low-frequency (acoustic) band until the first stop band, where the analyticity of the logarithm function of the transfer matrix () breaks down. PMID:24101891

Transition properties from the Hermitian formulation of the coupled cluster polarization propagator

NASA Astrophysics Data System (ADS)

Tucholska, Aleksandra M.; Modrzejewski, Marcin; Moszynski, Robert

2014-09-01

Theory of one-electron transition density matrices has been formulated within the time-independent coupled cluster method for the polarization propagator [R. Moszynski, P. S. Żuchowski, and B. Jeziorski, Coll. Czech. Chem. Commun. 70, 1109 (2005)]. Working expressions have been obtained and implemented with the coupled cluster method limited to single, double, and linear triple excitations (CC3). Selected dipole and quadrupole transition probabilities of the alkali earth atoms, computed with the new transition density matrices are compared to the experimental data. Good agreement between theory and experiment is found. The results obtained with the new approach are of the same quality as the results obtained with the linear response coupled cluster theory. The one-electron density matrices for the ground state in the CC3 approximation have also been implemented. The dipole moments for a few representative diatomic molecules have been computed with several variants of the new approach, and the results are discussed to choose the approximation with the best balance between the accuracy and computational efficiency.

Analytical Solution for the Anisotropic Rabi Model: Effects of Counter-Rotating Terms

PubMed Central

Zhang, Guofeng; Zhu, Hanjie

2015-01-01

The anisotropic Rabi model, which was proposed recently, differs from the original Rabi model: the rotating and counter-rotating terms are governed by two different coupling constants. This feature allows us to vary the counter-rotating interaction independently and explore the effects of it on some quantum properties. In this paper, we eliminate the counter-rotating terms approximately and obtain the analytical energy spectrums and wavefunctions. These analytical results agree well with the numerical calculations in a wide range of the parameters including the ultrastrong coupling regime. In the weak counter-rotating coupling limit we find out that the counter-rotating terms can be considered as the shifts to the parameters of the Jaynes-Cummings model. This modification shows the validness of the rotating-wave approximation on the assumption of near-resonance and relatively weak coupling. Moreover, the analytical expressions of several physics quantities are also derived, and the results show the break-down of the U(1)-symmetry and the deviation from the Jaynes-Cummings model. PMID:25736827

Numerical approximation of the electromechanical coupling in the left ventricle with inclusion of the Purkinje network.

PubMed

Landajuela, Mikel; Vergara, Christian; Gerbi, Antonello; Dedé, Luca; Formaggia, Luca; Quarteroni, Alfio

2018-03-25

In this work, we consider the numerical approximation of the electromechanical coupling in the left ventricle with inclusion of the Purkinje network. The mathematical model couples the 3D elastodynamics and bidomain equations for the electrophysiology in the myocardium with the 1D monodomain equation in the Purkinje network. For the numerical solution of the coupled problem, we consider a fixed-point iterative algorithm that enables a partitioned solution of the myocardium and Purkinje network problems. Different levels of myocardium-Purkinje network splitting are considered and analyzed. The results are compared with those obtained using standard strategies proposed in the literature to trigger the electrical activation. Finally, we present a numerical study that, although performed in an idealized computational domain, features all the physiological issues that characterize a heartbeat simulation, including the initiation of the signal in the Purkinje network and the systolic and diastolic phases. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Cascadia Subduction Zone

USGS Publications Warehouse

Frankel, Arthur D.; Petersen, Mark D.

2008-01-01

The geometry and recurrence times of large earthquakes associated with the Cascadia Subduction Zone (CSZ) were discussed and debated at a March 28-29, 2006 Pacific Northwest workshop for the USGS National Seismic Hazard Maps. The CSZ is modeled from Cape Mendocino in California to Vancouver Island in British Columbia. We include the same geometry and weighting scheme as was used in the 2002 model (Frankel and others, 2002) based on thermal constraints (Fig. 1; Fluck and others, 1997 and a reexamination by Wang et al., 2003, Fig. 11, eastern edge of intermediate shading). This scheme includes four possibilities for the lower (eastern) limit of seismic rupture: the base of elastic zone (weight 0.1), the base of transition zone (weight 0.2), the midpoint of the transition zone (weight 0.2), and a model with a long north-south segment at 123.8? W in the southern and central portions of the CSZ, with a dogleg to the northwest in the northern portion of the zone (weight 0.5). The latter model was derived from the approximate average longitude of the contour of the 30 km depth of the CSZ as modeled by Fluck et al. (1997). A global study of the maximum depth of thrust earthquakes on subduction zones by Tichelaar and Ruff (1993) indicated maximum depths of about 40 km for most of the subduction zones studied, although the Mexican subduction zone had a maximum depth of about 25 km (R. LaForge, pers. comm., 2006). The recent inversion of GPS data by McCaffrey et al. (2007) shows a significant amount of coupling (a coupling factor of 0.2-0.3) as far east as 123.8? West in some portions of the CSZ. Both of these lines of evidence lend support to the model with a north-south segment at 123.8? W.

The Potential Feasibility of Chlorinic Photosynthesis on Extrasolar Planets

NASA Astrophysics Data System (ADS)

Haas, Johnson

2009-09-01

It is highly likely that the first convincing evidence of extrasolar life will arrive in the form of atmospheric absorption spectra. The modern search for life-bearing extrasolar planets emphasizes the potential detection of O2 and O3 absorption spectra in exoplanetary atmospheres as archetypal signatures of biology. However, oxygenic photosynthesis apparently failed to evolve independently more than once on Earth, and is thus unlikely to be reliably ubiquitous throughout the universe. Alternative evolutionary paths may yield planetary atmospheres tinted with the waste products of other dominant metabolisms, including potentially exotic biochemistries. This study examines the potential feasibility of one such exotic metabolism: chlorinic photosynthesis (CPS), defined as biologically-mediated halogenation of aqueous chloride to HClO, Cl2 or partially-oxidized intermediates (e.g. haloalkanes, haloacids, haloaromatics), coupled with photosynthetic CO2 fixation. This metabolic couple is feasible thermodynamically and appears to be geochemically plausible under approximately terrestrial conditions. This study hypothesizes that planetary biospheres dominated by CPS would develop atmospheres enriched with dihalogens and other halogenated compounds, evolve a highly oxidizing surface geochemical environment, and foster biological selection pressures favoring halogen resistance and eventual metazoan heterotrophy based on dihalogen and halocarbon respiration. Planets favoring the evolution of CPS would probably receive equivalent or greater surface UV flux than Earth did in the Paleoarchean (promoting abiotic photo-oxidation of aqueous halides, and establishing a strong biological selective pressure toward their accommodation), and would orbit stars having equivalent or greater bulk metallicities (promoting greater planetary halide abundances) relative to the Sun. Directed searches for such worlds should probably focus on A, F and G0 spectral class stars having bulk metallicities of +0.0 Dex or greater.

A pair natural orbital implementation of the coupled cluster model CC2 for excitation energies.

PubMed

Helmich, Benjamin; Hättig, Christof

2013-08-28

We demonstrate how to extend the pair natural orbital (PNO) methodology for excited states, presented in a previous work for the perturbative doubles correction to configuration interaction singles (CIS(D)), to iterative coupled cluster methods such as the approximate singles and doubles model CC2. The original O(N(5)) scaling of the PNO construction is reduced by using orbital-specific virtuals (OSVs) as an intermediate step without spoiling the initial accuracy of the PNO method. Furthermore, a slower error convergence for charge-transfer states is analyzed and resolved by a numerical Laplace transformation during the PNO construction, so that an equally accurate treatment of local and charge-transfer excitations is achieved. With state-specific truncated PNO expansions, the eigenvalue problem is solved by combining the Davidson algorithm with deflation to project out roots that have already been determined and an automated refresh with a generation of new PNOs to achieve self-consistency of the PNO space. For a large test set, we found that truncation errors for PNO-CC2 excitation energies are only slightly larger than for PNO-CIS(D). The computational efficiency of PNO-CC2 is demonstrated for a large organic dye, where a reduction of the doubles space by a factor of more than 1000 is obtained compared to the canonical calculation. A compression of the doubles space by a factor 30 is achieved by a unified OSV space only. Moreover, calculations with the still preliminary PNO-CC2 implementation on a series of glycine oligomers revealed an early break even point with a canonical RI-CC2 implementation between 100 and 300 basis functions.

Pseudotachylyte in the Tananao Metamorphic Complex, Taiwan: Occurrence and dynamic phase changes of fossil earthquakes

NASA Astrophysics Data System (ADS)

Chu, Hao-Tsu; Hwang, Shyh-Lung; Shen, Pouyan; Yui, Tzen-Fu

2012-12-01

Pseudotachylyte veins and cataclasites were studied in the mylonitized granitic gneiss of the Tananao Metamorphic Complex at Hoping, Eastern Taiwan. The aphanitic pseudotachylyte veins vary in thickness, ranging from millimeters to about 1 cm. Field and optical microscopic observations show that such pseudotachylyte veins cut across cataclasites, which, in turn, transect the mylonitized granitic gneiss. Scanning electron microscopic images also show that both the pseudotachylyte veins and the cataclasites have been metasomatized by a K-rich fluid, resulting in the replacement of Na-plagioclase by K-feldspar (veins). Analytical electron microscopic observations reveal further details of physical and chemical changes (mainly fragmentation, dislocations, cleaving-healing with inclusions and relic voids, and retention of high-temperature albite) of quartz and feldspar in crushed grains. Pseudotachylytes occur as dark veins having a higher content of chlorite-biotite, clinozoisite-epidote and titanite fragments than cataclasites. These veins, coupled with hematite/jarosite-Fe-rich amorphous shell/carbonaceous material, indicate that crushing, healing/sintering, and inhomogeneous melt/fluid infiltration involving incipient and intermediate/high temperature melt patches, before and/or contemporaneous with the metasomatic K-rich fluid, prevailed in a coupled or sequential manner in the faulting event to form nonequilibrium phase assemblage. The chlorite-biotite, carbonaceous material and other nanoscale minerals could be vulnerable in future earthquakes under the influence of water. The timing of the formation of these pseudotachylyte veins should be later than the area's age of mylonitization of granitic gneiss of approximately 4.1-3.0 Ma (Wang et al., 1998). The formation of pseudotachylytes registers the fossil earthquakes during early stages in the exhumation history of the uplifting Taiwan Mountain belt since the Plio-Pleistocene Arc-Continent collision.

Cross sections for electron scattering by carbon disulfide in the low- and intermediate-energy range

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

Brescansin, L. M.; Iga, I.; Lee, M.-T.

2010-01-15

In this work, we report a theoretical study on e{sup -}-CS{sub 2} collisions in the low- and intermediate-energy ranges. Elastic differential, integral, and momentum-transfer cross sections, as well as grand total (elastic + inelastic) and absorption cross sections, are reported in the 1-1000 eV range. A recently proposed complex optical potential composed of static, exchange, and correlation-polarization plus absorption contributions is used to describe the electron-molecule interaction. The Schwinger variational iterative method combined with the distorted-wave approximation is applied to calculate the scattering amplitudes. The comparison between our calculated results and the existing experimental and/or theoretical results is encouraging.

Low-mass black holes as the remnants of primordial black hole formation.

PubMed

Greene, Jenny E

2012-01-01

Bridging the gap between the approximately ten solar mass 'stellar mass' black holes and the 'supermassive' black holes of millions to billions of solar masses are the elusive 'intermediate-mass' black holes. Their discovery is key to understanding whether supermassive black holes can grow from stellar-mass black holes or whether a more exotic process accelerated their growth soon after the Big Bang. Currently, tentative evidence suggests that the progenitors of supermassive black holes were formed as ∼10(4)-10(5) M(⊙) black holes via the direct collapse of gas. Ongoing searches for intermediate-mass black holes at galaxy centres will help shed light on this formation mechanism.

Equations for normal-mode statistics of sound scattering by a rough elastic boundary in an underwater waveguide, including backscattering.

PubMed

Morozov, Andrey K; Colosi, John A

2017-09-01

Underwater sound scattering by a rough sea surface, ice, or a rough elastic bottom is studied. The study includes both the scattering from the rough boundary and the elastic effects in the solid layer. A coupled mode matrix is approximated by a linear function of one random perturbation parameter such as the ice-thickness or a perturbation of the surface position. A full two-way coupled mode solution is used to derive the stochastic differential equation for the second order statistics in a Markov approximation.

Accelerating the coupled-cluster singles and doubles method using the chain-of-sphere approximation

NASA Astrophysics Data System (ADS)

Dutta, Achintya Kumar; Neese, Frank; Izsák, Róbert

2018-06-01

In this paper, we present a chain-of-sphere implementation of the external exchange term, the computational bottleneck of coupled-cluster calculations at the singles and doubles level. This implementation is compared to standard molecular orbital, atomic orbital and resolution of identity implementations of the same term within the ORCA package and turns out to be the most efficient one for larger molecules, with a better accuracy than the resolution-of-identity approximation. Furthermore, it becomes possible to perform a canonical CC calculation on a tetramer of nucleobases in 17 days, 20 hours.

The Magnetospheric Constellation Mission. Dynamic Response and Coupling Observatory (DRACO): Understanding the Global Dynamics of the Structured Magnetotail

NASA Technical Reports Server (NTRS)

2001-01-01

Magnetospheric Constellation Dynamic Response and Coupling Observatory (DRACO) is the Solar Terrestrial Probe (STP) designed to understand the nonlinear dynamics, responses, and connections within the Earth's structured magnetotail, using a constellation of approximately 50 to 100 distributed vector measurement spacecraft. DRACO will reveal magnetotail processes operating within a domain extending 20 Earth radii (R(sub E)) across the tail and 40 R(sub E)down the tail, on spatial and time scales accessible to global circulation models, i.e., approximately 2 R(sub E) and 10 seconds.

Complex-valued derivative propagation method with approximate Bohmian trajectories: Application to electronic nonadiabatic dynamics

NASA Astrophysics Data System (ADS)

Wang, Yu; Chou, Chia-Chun

2018-05-01

The coupled complex quantum Hamilton-Jacobi equations for electronic nonadiabatic transitions are approximately solved by propagating individual quantum trajectories in real space. Equations of motion are derived through use of the derivative propagation method for the complex actions and their spatial derivatives for wave packets moving on each of the coupled electronic potential surfaces. These equations for two surfaces are converted into the moving frame with the same grid point velocities. Excellent wave functions can be obtained by making use of the superposition principle even when nodes develop in wave packet scattering.

Understanding transient uncoupling induced synchronization through modified dynamic coupling

NASA Astrophysics Data System (ADS)

Ghosh, Anupam; Godara, Prakhar; Chakraborty, Sagar

2018-05-01

An important aspect of the recently introduced transient uncoupling scheme is that it induces synchronization for large values of coupling strength at which the coupled chaotic systems resist synchronization when continuously coupled. However, why this is so is an open problem? To answer this question, we recall the conventional wisdom that the eigenvalues of the Jacobian of the transverse dynamics measure whether a trajectory at a phase point is locally contracting or diverging with respect to another nearby trajectory. Subsequently, we go on to highlight a lesser appreciated fact that even when, under the corresponding linearised flow, the nearby trajectory asymptotically diverges away, its distance from the reference trajectory may still be contracting for some intermediate period. We term this phenomenon transient decay in line with the phenomenon of the transient growth. Using these facts, we show that an optimal coupling region, i.e., a region of the phase space where coupling is on, should ideally be such that at any of the constituent phase point either the maximum of the real parts of the eigenvalues is negative or the magnitude of the positive maximum is lesser than that of the negative minimum. We also invent and employ a modified dynamics coupling scheme—a significant improvement over the well-known dynamic coupling scheme—as a decisive tool to justify our results.

Long-term outcomes of children with intermediate sweat chloride values in infancy.

PubMed

Groves, Tyler; Robinson, Paul; Wiley, Veronica; Fitzgerald, Dominic A

2015-06-01

To describe the clinical course of children who have intermediate sweat chloride values on initial screening for cystic fibrosis (CF). We performed a retrospective review of children with intermediate sweat chloride values (raised immunoreactive trypsinogen/1 copy of p.F508del CF mutation on newborn screening (NBS)/sweat chloride value of 30-59 mmol/L) presenting to The Children's Hospital at Westmead over 15 years. Patients with an intermediate sweat chloride evolving to a formal diagnosis of CF (termed "delayed CF") were matched (2:1) with NBS positive patients with CF (termed "NBS positive CF"). Clinical outcomes were compared. Fourteen of 29 (48%, 95% CI 0.3-0.66) patients with intermediate sweat chloride value evolved to a diagnosis of CF and were matched with 28 NBS positive patients with CF. Delayed CF had less pancreatic insufficiency (OR 0.06, 95% CI 0.01-0.44, P = .006), less colonization with nonmucoid Pseudomonas aeruginosa (OR 0.04, 95% CI 0.01-0.38, P = .005), milder obstructive lung disease (forced expiratory volume in 1 second/forced vital capacity ratio), and overall disease severity (Shwachman scores) at 10 years (mean difference 5.93, 95% CI 0.39-11.46, P = .04; mean difference 4.72, 95% CI 0.9-8.53, P = .015, respectively). Nutritional outcomes were better at 2 years for delayed CF but did not persist to later ages. In this cohort, approximately one-half of infants with intermediate sweat chloride value were later diagnosed with CF. The clinical course of delayed CF was milder in some aspects compared with NBS positive CF. These results emphasize the importance of ongoing follow-up of infants with intermediate sweat chloride values. Crown Copyright © 2015. Published by Elsevier Inc. All rights reserved.

Dynein-ADP as a force-generating intermediate revealed by a rapid reactivation of flagellar axoneme.

PubMed Central

Tani, T; Kamimura, S

1999-01-01

Fragmented flagellar axonemes of sand dollar spermatozoa were reactivated by rapid photolysis of caged ATP. After a time lag of 10 ms, axonemes treated with protease started sliding disintegration. Axonemes without protease digestion started nanometer-scale high-frequency oscillation after a similar time lag. Force development in the sliding disintegration was measured with a flexible glass needle and its time course was corresponded well to that of the dynein-ADP intermediate production estimated using kinetic rates previously reported. However, with a high concentration ( approximately 80 microM) of vanadate, which binds to the dynein-ADP intermediate and forms a stable complex of dynein-ADP-vanadate, the time course of force development in sliding disintegration was not affected at all. In the case of high frequency oscillation, the time lag to start the oscillation, the initial amplitude, and the initial frequency were not affected by vanadate, though the oscillation once started was damped more quickly at higher concentrations of vanadate. These results suggest that during the initial turnover of ATP hydrolysis, force generation of dynein is not blocked by vanadate. A vanadate-insensitive dynein-ADP is postulated as a force-generating intermediate. PMID:10465762

Simulation of ground-water flow in the Intermediate and Floridan aquifer systems in Peninsular Florida

USGS Publications Warehouse

Sepúlveda, Nicasio

2002-01-01

A numerical model of the intermediate and Floridan aquifer systems in peninsular Florida was used to (1) test and refine the conceptual understanding of the regional ground-water flow system; (2) develop a data base to support subregional ground-water flow modeling; and (3) evaluate effects of projected 2020 ground-water withdrawals on ground-water levels. The four-layer model was based on the computer code MODFLOW-96, developed by the U.S. Geological Survey. The top layer consists of specified-head cells simulating the surficial aquifer system as a source-sink layer. The second layer simulates the intermediate aquifer system in southwest Florida and the intermediate confining unit where it is present. The third and fourth layers simulate the Upper and Lower Floridan aquifers, respectively. Steady-state ground-water flow conditions were approximated for time-averaged hydrologic conditions from August 1993 through July 1994 (1993-94). This period was selected based on data from Upper Floridan a quifer wells equipped with continuous water-level recorders. The grid used for the ground-water flow model was uniform and composed of square 5,000-foot cells, with 210 columns and 300 rows.

Concentration of small ring structures in vitreous silica from a first-principles analysis of the Raman spectrum.

PubMed

Umari, P; Gonze, Xavier; Pasquarello, Alfredo

2003-01-17

Using a first-principles approach, we calculate Raman spectra for a model structure of vitreous silica. We develop a perturbational method for calculating the dielectric tensor in an ultrasoft pseudopotential scheme and obtain Raman coupling tensors by finite differences with respect to atomic displacements. For frequencies below 1000 cm(-1), the parallel-polarized Raman spectrum of vitreous silica is dominated by oxygen bending motions, showing a strong sensitivity to the intermediate range structure. By modeling the Raman coupling, we derive estimates for the concentrations of three- and four-membered rings from the experimental intensities of the Raman defect lines.

X-ray microprobe of orbital alignment in strong-field ionized atoms.

PubMed

Young, L; Arms, D A; Dufresne, E M; Dunford, R W; Ederer, D L; Höhr, C; Kanter, E P; Krässig, B; Landahl, E C; Peterson, E R; Rudati, J; Santra, R; Southworth, S H

2006-08-25

We have developed a synchrotron-based, time-resolved x-ray microprobe to investigate optical strong-field processes at intermediate intensities (10(14) - 10(15) W/cm2). This quantum-state specific probe has enabled the direct observation of orbital alignment in the residual ion produced by strong-field ionization of krypton atoms via resonant, polarized x-ray absorption. We found strong alignment to persist for a period long compared to the spin-orbit coupling time scale (6.2 fs). The observed degree of alignment can be explained by models that incorporate spin-orbit coupling. The methodology is applicable to a wide range of problems.