a Study of Vibrational Mode Coupling in 2-FLUOROETHANOL and 1,2-DIFLUOROETHANE Using High-Resolution Infrared Spectroscopy.

NASA Astrophysics Data System (ADS)

Mork, Steven Wayne

High resolution infrared spectroscopy was used to examine intramolecular vibrational interactions in 2 -fluoroethanol (2FE) and 1,2-difluoroethane (DFE). A high resolution infrared spectrophotometer capable of better than 10 MHz spectral resolution was designed and constructed. The excitation source consists of three lasers: an argon-ion pumped dye laser which pumps a color -center laser. The infrared beam from the color-center laser is used to excite sample molecules which are rotationally and vibrationally cooled in a supersonic molecular beam. Rovibrational excitation of the sample molecules is detected by monitoring the kinetic energy of the molecular beam with a bolometer. The high resolution infrared spectrum of 2FE was collected and analyzed over the 2977-2990 cm^ {-1}^ectral region. This region contains the asymmetric CH stretch on the fluorinated carbon. The spectrum revealed extensive perturbations in the rotational fine structure. Analysis of these perturbations has provided a quantitative measure of selective vibrational mode coupling between the C-H stretch and its many neighboring dark vibrational modes. Interestingly, excitation of the C-H stretch is known to induce a photoisomerization reaction between 2FE's Gg^' and Tt conformers. Implications of the role of mode coupling in the reaction mechanism are also addressed. Similarly, the high resolution infrared spectrum of DFE was collected and analyzed over the 2978-2996 cm ^{-1}^ectral region. This region contains the symmetric combination of asymmetric C-H stretches in DFE. Perturbations in the rotational fine structure indicate vibrational mode coupling to a single dark vibrational state. The dark state is split by approximately 19 cm^{-1} due to tunneling between two identical gauche conformers. The coupling mechanism is largely anharmonic with a minor component of B/C-plane Coriolis coupling. Effects of centrifugal distortion along the molecular A-axis are also observed. The coupled vibrational mode has been identified as containing C-C torsion, CCF bend and CH_2 rock. As in 2FE, DFE undergoes an isomerization reaction upon excitation of the C-H stretch. Coupling between the C-H stretch and C-C torsion is addressed with respect to the reaction mechanism.

Effects of reagent rotational excitation on the H + CHD{sub 3} → H{sub 2} + CD{sub 3} reaction: A seven dimensional time-dependent wave packet study

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

Zhang, Zhaojun; Zhang, Dong H., E-mail: zhangdh@dicp.ac.cn

Seven-dimensional time-dependent wave packet calculations have been carried out for the title reaction to obtain reaction probabilities and cross sections for CHD{sub 3} in J{sub 0} = 1, 2 rotationally excited initial states with k{sub 0} = 0 − J{sub 0} (the projection of CHD{sub 3} rotational angular momentum on its C{sub 3} axis). Under the centrifugal sudden (CS) approximation, the initial states with the projection of the total angular momentum on the body fixed axis (K{sub 0}) equal to k{sub 0} are found to be much more reactive, indicating strong dependence of reactivity on the orientation of the reagentmore » CHD{sub 3} with respect to the relative velocity between the reagents H and CHD{sub 3}. However, at the coupled-channel (CC) level this dependence becomes much weak although in general the K{sub 0} specified cross sections for the K{sub 0} = k{sub 0} initial states remain primary to the overall cross sections, implying the Coriolis coupling is important to the dynamics of the reaction. The calculated CS and CC integral cross sections obtained after K{sub 0} averaging for the J{sub 0} = 1, 2 initial states with all different k{sub 0} are essentially identical to the corresponding CS and CC results for the J{sub 0} = 0 initial state, meaning that the initial rotational excitation of CHD{sub 3} up to J{sub 0} = 2, regardless of its initial k{sub 0}, does not have any effect on the total cross sections for the title reaction, and the errors introduced by the CS approximation on integral cross sections for the rotationally excited J{sub 0} = 1, 2 initial states are the same as those for the J{sub 0} = 0 initial state.« less

DFT calculations for anharmonic force field and spectroscopic constants of YC2 and its 13C isotopologues

NASA Astrophysics Data System (ADS)

Zhao, Yanliang; Wang, Meishan; Yang, Chuanlu; Ma, Xiaoguang; Li, Jing

2018-02-01

The construction of the complete third and the semi-diagonal quartic force fields including the anharmonicity of the ground state (X˜2A1) for yttrium dicarbide (YC2) is carried out employing the vibrational second-order perturbation theory (VPT2) in combination with the density functional theory (DFT). The equilibrium geometries optimization, anharmonic force field and vibrational spectroscopic constants of YC2 are calculated by B3LYP, B3PW91 and B3P86 methods. Aug-cc-pVnZ (n = D, T, Q) and cc-pVnZ-PP (n = D, T, Q) basis sets are chosen for C and Y atoms, respectively. The calculated geometry parameters of YC2 agree well with the corresponding experimental and previous theoretical results. The bonding characters of Ysbnd C2 or Csbnd C are discussed. Based on the optimized equilibrium geometries, the spectroscopic constants and anharmonic force field of YC2 are calculated. Comparing with the spectroscopic constants of YC2 derived from the experiment, the calculated results show that the B3PW91 and B3P86 methods are superior to B3LYP for YC2. The Coriolis coupling constants, cubic and quartic force constants of YC2 are reasonably predicted. Besides, the spectroscopic constants and anharmonic force field of Y13C2 (X˜2A1) and Y13CC (X˜2A‧) are calculated for the first time, which are expected to guide the high resolution experimental work for YC2 and its 13C isotopologues.

Nonlinear flap-lag-extensional vibrations of rotating, pretwisted, preconed beams including Coriolis effects

NASA Technical Reports Server (NTRS)

Subrahmanyam, K. B.; Kaza, K. R. V.

1985-01-01

The effects of pretwist, precone, setting angle, Coriolis forces and second degree geometric nonlinearities on the natural frequencies, steady state deflections and mode shapes of rotating, torsionally rigid, cantilevered beams were studied. The governing coupled equations of flap lag extensional motion are derived including the effects of large precone and retaining geometric nonlinearities up to second degree. The Galerkin method, with nonrotating normal modes, is used for the solution of both steady state nonlinear equations and linear perturbation equations. Parametric indicating the individual and collective effects of pretwist, precone, Coriolis forces and second degree geometric nonlinearities on the steady state deflection, natural frequencies and mode shapes of rotating blades are presented. It is indicated that the second degree geometric nonlinear terms, which vanish for zero precone, can produce frequency changes of engineering significance. Further confirmation of the validity of including those generated by MSC NASTRAN. It is indicated that the linear and nonlinear Coriolis effects must be included in analyzing thick blades. The Coriolis effects are significant on the first flatwise and the first edgewise modes.

The influence of gravitoinertial force level on oculomotor and perceptual responses to Coriolis, cross-coupling stimulation

NASA Technical Reports Server (NTRS)

Dizio, Paul; Lackner, James R.; Evanoff, John N.

1987-01-01

The goal of the present experiment was to determine whether gravitoinertial force magnitude influences oculomotor and perceptual responses to Coriolis cross-coupling stimulation. Blindfolded subjects who were rotating at constant velocity were asked to make standardized head movements during the free-fall and high-force phases of parabolic flight, and the characteristics of their horizontal nystagmus and the magnitude of their experienced self-motion were measured. Both responses were less intense in the free-fall periods than in the high-force periods. These findings suggest that the response to semicircular canal stimulation depends on the background level of gravitoinertial force.

Nonlinear bending-torsional vibration and stability of rotating, pretwisted, preconed blades including Coriolis effects

NASA Technical Reports Server (NTRS)

Subrahmanyam, K. B.; Kaza, K. R. V.; Brown, G. V.; Lawrence, C.

1986-01-01

The coupled bending-bending-torsional equations of dynamic motion of rotating, linearly pretwisted blades are derived including large precone, second degree geometric nonlinearities and Coriolis effects. The equations are solved by the Galerkin method and a linear perturbation technique. Accuracy of the present method is verified by comparisons of predicted frequencies and steady state deflections with those from MSC/NASTRAN and from experiments. Parametric results are generated to establish where inclusion of only the second degree geometric nonlinearities is adequate. The nonlinear terms causing torsional divergence in thin blades are identified. The effects of Coriolis terms and several other structurally nonlinear terms are studied, and their relative importance is examined.

Nonlinear vibration and stability of rotating, pretwisted, preconed blades including Coriolis effects

NASA Technical Reports Server (NTRS)

Subrahmanyam, K. B.; Kaza, K. R. V.; Brown, G. V.; Lawrence, C.

1987-01-01

The coupled bending-bending-torsional equations of dynamic motion of rotating, linearly pretwisted blades are derived including large precone, second degree geometric nonlinearities and Coriolis effects. The equations are solved by the Galerkin method and a linear perturbation technique. Accuracy of the present method is verified by conparisons of predicted frequencies and steady state deflections with those from MSC/NASTRAN and from experiments. Parametric results are generated to establish where inclusion of only the second degree geometric nonlinearities is adequate. The nonlinear terms causing torsional divergence in thin blades are identified. The effects of Coriolis terms and several other structurally nonlinear terms are studied, and their relative importance is examined.

Coriolis effect and spin Hall effect of light in an inhomogeneous chiral medium.

PubMed

Zhang, Yongliang; Shi, Lina; Xie, Changqing

2016-07-01

We theoretically investigate the spin Hall effect of spinning light in an inhomogeneous chiral medium. The Hamiltonian equations of the photon are analytically obtained within eikonal approximation in the noninertial orthogonal frame. Besides the usual spin curvature coupling, the chiral parameter enters the Hamiltonian as a spin-torsion-like interaction. We reveal that both terms have parallel geometric origins as the Coriolis terms of Maxwell's equations in nontrivial frames.

Visual and vestibular components of motion sickness.

PubMed

Eyeson-Annan, M; Peterken, C; Brown, B; Atchison, D

1996-10-01

The relative importance of visual and vestibular information in the etiology of motion sickness (MS) is not well understood, but these factors can be manipulated by inducing Coriolis and pseudo-Coriolis effects in experimental subjects. We hypothesized that visual and vestibular information are equivalent in producing MS. The experiments reported here aim, in part, to examine the relative influence of Coriolis and pseudo-Coriolis effects in inducing MS. We induced MS symptoms by combinations of whole body rotation and tilt, and environment rotation and tilt, in 22 volunteer subjects. Subjects participated in all of the experiments with at least 2 d between each experiment to dissipate after-effects. We recorded MS signs and symptoms when only visual stimulation was applied, when only vestibular stimulation was applied, and when both visual and vestibular stimulation were applied under specific conditions of whole body and environmental tilt. Visual stimuli produced more symptoms of MS than vestibular stimuli when only visual or vestibular stimuli were used (ANOVA F = 7.94, df = 1, 21 p = 0.01), but there was no significant difference in MS production when combined visual and vestibular stimulation were used to produce the Coriolis effect or pseudo-Coriolis effect (ANOVA: F = 0.40, df = 1, 21 p = 0.53). This was further confirmed by examination of the order in which the symptoms occurred and the lack of a correlation between previous experience and visually induced MS. Visual information is more important than vestibular input in causing MS when these stimuli are presented in isolation. In conditions where both visual and vestibular information are present, cross-coupling appears to occur between the pseudo-Coriolis effect and the Coriolis effect, as these two conditions are not significantly different in producing MS symptoms.

Calculating intensities using effective Hamiltonians in terms of Coriolis-adapted normal modes.

PubMed

Karthikeyan, S; Krishnan, Mangala Sunder; Carrington, Tucker

2005-01-15

The calculation of rovibrational transition energies and intensities is often hampered by the fact that vibrational states are strongly coupled by Coriolis terms. Because it invalidates the use of perturbation theory for the purpose of decoupling these states, the coupling makes it difficult to analyze spectra and to extract information from them. One either ignores the problem and hopes that the effect of the coupling is minimal or one is forced to diagonalize effective rovibrational matrices (rather than diagonalizing effective rotational matrices). In this paper we apply a procedure, based on a quantum mechanical canonical transformation for deriving decoupled effective rotational Hamiltonians. In previous papers we have used this technique to compute energy levels. In this paper we show that it can also be applied to determine intensities. The ideas are applied to the ethylene molecule.

Coriolis effect in optics: unified geometric phase and spin-Hall effect.

PubMed

Bliokh, Konstantin Y; Gorodetski, Yuri; Kleiner, Vladimir; Hasman, Erez

2008-07-18

We examine the spin-orbit coupling effects that appear when a wave carrying intrinsic angular momentum interacts with a medium. The Berry phase is shown to be a manifestation of the Coriolis effect in a noninertial reference frame attached to the wave. In the most general case, when both the direction of propagation and the state of the wave are varied, the phase is given by a simple expression that unifies the spin redirection Berry phase and the Pancharatnam-Berry phase. The theory is supported by the experiment demonstrating the spin-orbit coupling of electromagnetic waves via a surface plasmon nanostructure. The measurements verify the unified geometric phase, demonstrated by the observed polarization-dependent shift (spin-Hall effect) of the waves.

Vestibular coriolis effect differences modeled with three-dimensional linear-angular interactions.

PubMed

Holly, Jan E

2004-01-01

The vestibular coriolis (or "cross-coupling") effect is traditionally explained by cross-coupled angular vectors, which, however, do not explain the differences in perceptual disturbance under different acceleration conditions. For example, during head roll tilt in a rotating chair, the magnitude of perceptual disturbance is affected by a number of factors, including acceleration or deceleration of the chair rotation or a zero-g environment. Therefore, it has been suggested that linear-angular interactions play a role. The present research investigated whether these perceptual differences and others involving linear coriolis accelerations could be explained under one common framework: the laws of motion in three dimensions, which include all linear-angular interactions among all six components of motion (three angular and three linear). The results show that the three-dimensional laws of motion predict the differences in perceptual disturbance. No special properties of the vestibular system or nervous system are required. In addition, simulations were performed with angular, linear, and tilt time constants inserted into the model, giving the same predictions. Three-dimensional graphics were used to highlight the manner in which linear-angular interaction causes perceptual disturbance, and a crucial component is the Stretch Factor, which measures the "unexpected" linear component.

Anomalous torsional tripling in the ν9 and ν10 CH3-deformation modes of ethane 12CH313CH3

NASA Astrophysics Data System (ADS)

Lattanzi, F.; di Lauro, C.

2017-12-01

We have investigated the anomalous torsional behavior in the coupled ν9 and ν10 vibrational fundamentals of 12CH313CH3, both states exhibiting a splitting into three components, instead of two, only in those rotational levels which are very close to resonance. We conclude that the intrinsic additional splitting, which occurs in the E-torsional components, for these two vibrational states is too small to be detected in the high resolution infrared spectrum, but it is substantively enhanced by their coupling. It is shown that this effect requires the simultaneous action of torsion independent operators, such as Fermi-type and z-Coriolis, not allowed in the more symmetric isotopologue 12CH312CH3, and torsion dependent operators, such as torsional-Coriolis, connecting the two vibrational states. Our conclusions lead to a simple model for the coupling of ν9 and ν10, with effective Fermi-type matrix elements W for the A-torsional components, and W ± w for the two pairs of E-torsional components. This causes the additional splitting in the E-pairs. This model is consistent with the mechanism causing the Coriolis-dependent decrease of the A-E torsional splitting in degenerate vibrational states. Exploratory calculations were performed making use of results from a normal mode analysis, showing that the effects predictable by the proposed model are of the correct order of magnitude compared to the observed features, with coupling parameter values reasonably consistent with those determined by the least squares fit of the observed transition wavenumbers.

Toroidal momentum pinch velocity due to the coriolis drift effect on small scale instabilities in a toroidal plasma.

PubMed

Peeters, A G; Angioni, C; Strintzi, D

2007-06-29

In this Letter, the influence of the "Coriolis drift" on small scale instabilities in toroidal plasmas is shown to generate a toroidal momentum pinch velocity. Such a pinch results because the Coriolis drift generates a coupling between the density and temperature perturbations on the one hand and the perturbed parallel flow velocity on the other. A simple fluid model is used to highlight the physics mechanism and gyro-kinetic calculations are performed to accurately assess the magnitude of the pinch. The derived pinch velocity leads to a radial gradient of the toroidal velocity profile even in the absence of a torque on the plasma and is predicted to generate a peaking of the toroidal velocity profile similar to the peaking of the density profile. Finally, the pinch also affects the interpretation of current experiments.

Toroidal Momentum Pinch Velocity due to the Coriolis Drift Effect on Small Scale Instabilities in a Toroidal Plasma

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

Peeters, A. G.; Angioni, C.; Strintzi, D.

In this Letter, the influence of the ''Coriolis drift'' on small scale instabilities in toroidal plasmas is shown to generate a toroidal momentum pinch velocity. Such a pinch results because the Coriolis drift generates a coupling between the density and temperature perturbations on the one hand and the perturbed parallel flow velocity on the other. A simple fluid model is used to highlight the physics mechanism and gyro-kinetic calculations are performed to accurately assess the magnitude of the pinch. The derived pinch velocity leads to a radial gradient of the toroidal velocity profile even in the absence of a torquemore » on the plasma and is predicted to generate a peaking of the toroidal velocity profile similar to the peaking of the density profile. Finally, the pinch also affects the interpretation of current experiment000.« less

MagIC: Fluid dynamics in a spherical shell simulator

NASA Astrophysics Data System (ADS)

Wicht, J.; Gastine, T.; Barik, A.; Putigny, B.; Yadav, R.; Duarte, L.; Dintrans, B.

2017-09-01

MagIC simulates fluid dynamics in a spherical shell. It solves for the Navier-Stokes equation including Coriolis force, optionally coupled with an induction equation for Magneto-Hydro Dynamics (MHD), a temperature (or entropy) equation and an equation for chemical composition under both the anelastic and the Boussinesq approximations. MagIC uses either Chebyshev polynomials or finite differences in the radial direction and spherical harmonic decomposition in the azimuthal and latitudinal directions. The time-stepping scheme relies on a semi-implicit Crank-Nicolson for the linear terms of the MHD equations and a Adams-Bashforth scheme for the non-linear terms and the Coriolis force.

Hyperfine-resolved 3.4-{mu}m spectroscopy of CH{sub 3}I with a widely tunable difference frequency generation source and a cavity-enhanced cell: A case study of a local Coriolis interaction between the v{sub 1}=1 and (v{sub 2},v{sub 6}{sup l})=(1,2{sup 2}) states

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

Okubo, Sho; Nakayama, Hirotaka; Sasada, Hiroyuki

Saturated absorption spectra of the {nu}{sub 1} fundamental band of CH{sub 3}I are recorded with a cavity-enhanced cell and a tunable difference frequency generation source having an 86-cm{sup -1} range. The recorded spectral lines are 250 kHz wide, and most of them are resolved into the individual hyperfine components. The Coriolis interaction between the v{sub 1}=1 and (v{sub 2},v{sub 6}{sup l})=(1,2{sup 2}) states locally perturbing the hyperfine structures is analyzed to yield the Coriolis and hyperfine coupling constants with uncertainties similar to those in typical microwave spectroscopy. The spectrometer has demonstrated the potential for precisely determining the energy structure inmore » the vibrational excited states.« less

High-resolution FTIR spectroscopy of the Coriolis interacting nu3 and nu9 fundamentals of methylene fluoride-d2

NASA Astrophysics Data System (ADS)

Goh, K. L.; Tan, T. L.; Ong, P. P.; Chaw, K. H.; Teo, H. H.

The Fourier transform infrared spectrum of the υ3 and υ9 bands of methylene fluoride-d2 (CD2F2) has been recorded with an unapodized resolution of 0.0024cm-1 in the frequency range 970-1080cm-1. These two bands with band centres approximately 26 cm-1 apart were mutually coupled by Coriolis interactions. By fitting a total of 1639 infrared transitions of both υ3 and υ9 with a standard deviation of 0.00084cm-1 S/S using a Watson's A-reduced Hamiltonian in the Ir representation with the inclusion of a first order c-type Coriolis resonance term, two sets of rovibrational constants for υ3 = 1 and υ9 = 1 states were derived. The υ3 band is B-type while the υ9 band is A-type with band centres at 1030.1573 ± 0.0003 and 1003.7435 ± 0.0001cm-1, respectively.

The Coriolis Interaction between the ν 9 and ν 7 Fundamental Bands of Methylene Fluoride

NASA Astrophysics Data System (ADS)

Goh, K. L.; Tan, T. L.; Ong, P. P.; Teo, H. H.

2000-06-01

The infrared spectrum of the ν7 and ν9 bands of methylene fluoride-d2 (CD2F2) has been recorded with an unapodized resolution of 0.0024 cm-1 in the frequency range of 940-1030 cm-1 using the Fourier transform technique. A weak b-type Coriolis interaction term was found to couple these two vibrational states with band centers about 42 cm-1 apart. By fitting a total of 1031 infrared transitions of both ν7 and ν9 with a standard deviation of 0.0011 cm-1 using a Watson's A-reduced Hamiltonian in the Ir representation with the inclusion of a b-type Coriolis resonance term, two sets of rovibrational constants for ν7 = 1 and ν9 = 1 states up to sextic order were derived. The ν7 band is C type, while the ν9 band is A type with band centers at 961.8958 ± 0.0005 and 1003.7421 ± 0.0001 cm-1, respectively.

Analysis of the coriolis interaction of the ν12 band with 2 ν10 of cis-d 2-ethylene by high-resolution Fourier transform infrared spectroscopy

NASA Astrophysics Data System (ADS)

Goh, K. L.; Tan, T. L.; Ong, P. P.; Teo, H. H.

2000-08-01

The Fourier transform infrared spectrum of the ν12 band of cis-d 2-ethylene ( cis-C 2H 2D 2) has been recorded with an unapodized resolution of 0.0024 cm -1 in the frequency range of 1280-1400 cm -1. This band was found to be mutually coupled by Coriolis interaction with the unobserved 2 ν10 band situated approximately 10 cm -1 below ν12. By fitting a total of 771 infrared transitions of ν12 with a standard deviation of 0.00075 cm -1 using the Watson's Hamiltonian with the inclusion of a c-type Coriolis resonance term, a set of accurate rovibrational constants for V 12=1 state was derived. The ν12 band is A type with a band centre at 1341.1512±0.0001 cm -1. Accurate rovibrational constants for the V 10=2 state were also derived.

Perceptual disturbances predicted in zero-g through three-dimensional modeling.

PubMed

Holly, Jan E

2003-01-01

Perceptual disturbances in zero-g and 1-g differ. For example, the vestibular coriolis (or "cross-coupled") effect is weaker in zero-g. In 1-g, blindfolded subjects rotating on-axis experience perceptual disturbances upon head tilt, but the effects diminish in zero-g. Head tilts during centrifugation in zero-g and 1-g are investigated here by means of three-dimensional modeling, using a model that was previously used to explain the zero-g reduction of the on-axis vestibular coriolis effect. The model's foundation comprises the laws of physics, including linear-angular interactions in three dimensions. Addressed is the question: In zero-g, will the vestibular coriolis effect be as weak during centrifugation as during on-axis rotation? Centrifugation in 1-g was simulated first, with the subject supine, head toward center. The most noticeable result concerned direction of head yaw. For clockwise centrifuge rotation, greater perceptual effects arose in simulations during yaw counterclockwise (as viewed from the top of the head) than for yaw clockwise. Centrifugation in zero-g was then simulated with the same "supine" orientation. The result: In zero-g the simulated vestibular coriolis effect was greater during centrifugation than during on-axis rotation. In addition, clockwise-counterclockwise differences did not appear in zero-g, in contrast to the differences that appear in 1-g.

High-resolution synchrotron FTIR spectroscopic analysis of the Coriolis interaction between the v10 = 1 and v8 = 1 states of ethylene-cis-1,2-d2

NASA Astrophysics Data System (ADS)

Ng, L. L.; Tan, T. L.; Wong, Andy; Appadoo, Dominique R. T.; McNaughton, Don

2016-10-01

The synchrotron Fourier transform infrared (FTIR) spectrum of the b-type ν10 band of ethylene-cis-1,2-d2 (cis-C2H2D2) was recorded at a resolution of 0.00096 cm-1 in the 550-750 cm-1 region. The measured FWHM of the lines was about 0.002 cm-1. The ν10 band, centred at 662.871885(27) cm-1 was found to be perturbed through a b-type Coriolis resonance with the infrared inactive ν8 at 759.9582(20) cm-1. In this work, 1989 infrared transitions of ν10 were assigned for the first time. These perturbed and unperturbed infrared transitions were fitted with an rms deviation of 0.00033 cm-1 using the Watson's A-reduced Hamiltonian in the Ir representation with three Coriolis terms to derive the rovibrational constants for v10 = 1 and v8 = 1 states. Ground state rovibrational constants up to two sextic terms were also derived from a fit of a total of 2532 ground state combination differences with arms deviation of 0.00030 cm-1 from the infrared transitions of the present analysis and those determined previously. The ground state constants compared favourably to the equilibrium state constants from harmonic cc-pVTZ basis set at CCSD(T), MP2 and B3LYP levels. The rotational constants of ν10 and ν8 from this work agree well with those from anharmonic calculations.

High-resolution infrared studies of the v 10, v 11, v 14, and v 18 levels of [1.1.1]propellane

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

Kirkpatrick, Robynne W.; Masiello, Tony; Martin, Matthew A.

2012-11-15

This paper is a continuation of earlier work for which the high resolution infrared spectrum of [1.1.1]propellane was measured and its k and l structure resolved for the first time. Here we present results from an analysis of more than 16,000 transitions involving three fundamental bands v 10 (E'-A1'), v 11 (E'-A1'), v 14 (A2''-A1') and two difference bands (v 10- v 18) (E'-E'') and (v 11-v 18) (E'-E"). Additional information about v18 was also obtained from the difference band (v 15+v 18)-v 18 (E'-E") and the binary combination band (v 15+v 18) (E'-A1'). Through the use of the groundmore » state constants reported in an earlier paper [1], rovibrational constants have been determined for all the vibrational states involved in these bands. The rovibrational parameters for the v 18(E'') state were obtained from combination-differences and showed no need to include interactions with other states. The v 10(E') state analysis was also straight-forward, with only a weak Coriolis interaction with the levels of the v 14(A2'') state. The latter levels are much more affected by a strong Coriolis interaction with the levels of the nearby v 11(E') state and also by a small but significant interaction with another state, presumably the v16(E'') state, that is not directly observed. Gaussian calculations (B3LYP/cc-pVTZ) computed at the anharmonic level aided the analyses by providing initial values for many of the parameters. These theoretical results generally compare favorably with the final parameter values deduced from the spectral analyses. Finally, evidence was obtained for several level crossings between the rotational levels of the v 11 and v 14 states and, using a weak coupling term corresponding to a Δk = ±5, Δl = ∓1 matrix element, it was possible to find transitions from the ground state that, combined with transitions to the same upper state, give a value of C 0 = 0.1936519(4) cm -1. This result, combined with the value of B 0 = 0.28755833(14) cm-1 reported earlier [1], yields a value of 1.586282(3) Å for the length of the novel axial CC bond in propellane.« less

Observation of the seismic anisotropy effects on free oscillations below 4 mHz

NASA Astrophysics Data System (ADS)

Hu, X.; Liu, L.

2009-12-01

We present observations of significant fundamental spheroidal-toroidal mode coupling at frequencies below 4 mHz in the early part of vertical component records from seismic stations on near-equatorial source-receiver propagation paths and in Antarctica after the 26 December 2004 and 28 March 2005 great Sumatra earthquakes. When seismic surface waves propagate along the equator, the particle motion of Love waves runs parallels to the Earth’s rotation axis, and the particle motion of Rayleigh waves runs perpendicular to it, thus the Coriolis force has no vertical deflection effect on Love waves and no transverse deflection effect on the Rayleigh waves. Coriolis coupling can be naturally minimized at a station on a nearequatorial source-receiver propagation path. In Antarctica, especially near the South Pole, the vertical deflection of toroidial motion is very weak but there are lateral gradients in the anisotropic properties of upper mantle. Therefore, we can find a chance to directly observe seismic anisotropy coupling below 4 mHz without the disturbance of Coriolis coupling at Antarctic station, and at the seismic station locate close to the Earth’s equator when the epicenter also locates close to the equator. Our observations of strong anomalous toroidal-spheroidal coupling at these stations provide direct evidence to confirm the theory that the azimuthal anisotropy has pronounced effects on the quasi-toroidal mode excitations at the frequencies below 4 mHz, which can convince the skeptics that anisotropy really is visible in the low-frequency normal mode data. Strong anisotropic coupling is usually observed at stations having the geometric nodes for the spheroidal fundamentals, giving the association of quasi-toroidal excitation with the geometric effect. The presence of significant anisotropy coupling below 4 mHz depends not only on anisotropic depth, anisotropic identities and orientations but also on radiation nodes for Rayleigh waves and geometry nodes for spheroidal fundamentals. The quasi-toroidal modes below 4 mHz have significant sensitivity throughout most of the mantle, extending into the lower mantle, and therefore, it is likely that the resolution of locating the depth of origin of azimuthal anisotropy in the mantle will be improved by joint inversions that take advantage of the partly complementary depth resolution of anisotropy coupling measurements, quasi-Love surface-wave measurements, body wave splitting measurements and surface-wave dispersion measurements.

Copper-catalyzed C(sp3)-OH cleavage with concomitant C-C coupling: synthesis of 3-substituted isoindolinones.

PubMed

Rao, H Surya Prakash; Rao, A Veera Bhadra

2015-02-06

Copper(II) trifluoromethanesulfonate (Cu(OTf)2) efficiently catalyzes the C-C coupling of 3-hydoxyisoindolinones with a variety of aryl-, heteroaryl-, and alkenylboronic acids to furnish C(3) aryl-, heteroaryl-, and alkenyl-substituted isoindolinones. The coupling reactions work smoothly in 1,2-dicholoroethane (DCE) reflux, to effect both inter- and intramolecular versions. This is the first report on C(sp(3))-OH cleavage with concomitant C-C coupling. The photolabile 2-nitrobenzyl protecting group is most appropriate for promotion of the coupling reaction and for deprotection. The tetracyclic ring motif of the alkaloid neuvamine was prepared by applying the newly developed copper-catalyzed C-C coupling.

Shaft flexibility effects on the forced response of a bladed-disk assembly

NASA Technical Reports Server (NTRS)

Khader, N.; Loewy, R. G.

1990-01-01

A model analysis approach is used to study the forced response of an actual flexible bladed-disk-shaft system. Both in-plane and out-of-plane flexible deformations of the bladed-disk assembly are considered, in addition to its rigid-body translations and rotations, resulting from the bending of the supporting flexible shaft in two orthogonal planes. The effects of Coriolis forces and structural coupling between flexible and rigid disk motions on the system's response are investigated. Aerodynamic loads acting on the rotating and vibrating bladed-disk assembly are accounted for through a simple quasi-steady representation, to evaluate their influence, combined with shaft flexibility and Coriolis effects.

First High Resolution Analysis of the ν21 Band of Propane at 921.4 wn: Evidence of Large-Amplitude Tunnelling Effects

NASA Astrophysics Data System (ADS)

Perrin, Agnes; Kwabia Tchana, F.; Flaud, Jean-Marie; Manceron, Laurent; Demaison, Jean; Vogt, Natalja; Groner, Peter; Lafferty, Walter

2015-06-01

A high resolution (0.0015 wn) IR spectrum of propane, C_3H_8, has been recorded with synchrotron radiation at the French light source facility at SOLEIL coupled to a Bruker IFS-125 Fourier transform spectrometer. A preliminary analysis of the ν21 fundamental band (B1, CH3 rock) near 921.4 wn reveals that the rotational energy levels of 211 are split by interactions with the internal rotations of the methyl groups. Conventional analysis of this A-type band yielded band centers at 921.3724(38), 921.3821(33) and 921.3913(44) wn for the AA, EE and AE+EA tunneling splitting components, respectively. These torsional splittings most probably are due to anharmonic and/or Coriolis resonance coupling with nearby highly excited states of both internal rotations of the methyl groups. In addition, several vibrational-rotational resonances were observed that affect the torsional components in different ways. The analysis of the B-type band near 870 wn (ν8, sym. C-C stretch) which also contains split rovibrational transitions due to internal rotation is in progress. It is performed by using the effective rotational Hamiltonian method ERHAM with a code that allows prediction and least-squares fitting of such vibration-rotation spectra. A. Perrin et al., submitted to J. Mol. Spectrosc. P. Groner, J. Chem. Phys. 107 (1997) 4483; J. Mol. Spectrosc. 278 (2012) 52.

Self-induced parametric amplification arising from nonlinear elastic coupling in a micromechanical resonating disk gyroscope

PubMed Central

Nitzan, Sarah H.; Zega, Valentina; Li, Mo; Ahn, Chae H.; Corigliano, Alberto; Kenny, Thomas W.; Horsley, David A.

2015-01-01

Parametric amplification, resulting from intentionally varying a parameter in a resonator at twice its resonant frequency, has been successfully employed to increase the sensitivity of many micro- and nano-scale sensors. Here, we introduce the concept of self-induced parametric amplification, which arises naturally from nonlinear elastic coupling between the degenerate vibration modes in a micromechanical disk-resonator, and is not externally applied. The device functions as a gyroscope wherein angular rotation is detected from Coriolis coupling of elastic vibration energy from a driven vibration mode into a second degenerate sensing mode. While nonlinear elasticity in silicon resonators is extremely weak, in this high quality-factor device, ppm-level nonlinear elastic effects result in an order-of-magnitude increase in the observed sensitivity to Coriolis force relative to linear theory. Perfect degeneracy of the primary and secondary vibration modes is achieved through electrostatic frequency tuning, which also enables the phase and frequency of the parametric coupling to be varied, and we show that the resulting phase and frequency dependence of the amplification follow the theory of parametric resonance. We expect that this phenomenon will be useful for both fundamental studies of dynamic systems with low dissipation and for increasing signal-to-noise ratio in practical applications such as gyroscopes. PMID:25762243

Self-induced parametric amplification arising from nonlinear elastic coupling in a micromechanical resonating disk gyroscope.

PubMed

Nitzan, Sarah H; Zega, Valentina; Li, Mo; Ahn, Chae H; Corigliano, Alberto; Kenny, Thomas W; Horsley, David A

2015-03-12

Parametric amplification, resulting from intentionally varying a parameter in a resonator at twice its resonant frequency, has been successfully employed to increase the sensitivity of many micro- and nano-scale sensors. Here, we introduce the concept of self-induced parametric amplification, which arises naturally from nonlinear elastic coupling between the degenerate vibration modes in a micromechanical disk-resonator, and is not externally applied. The device functions as a gyroscope wherein angular rotation is detected from Coriolis coupling of elastic vibration energy from a driven vibration mode into a second degenerate sensing mode. While nonlinear elasticity in silicon resonators is extremely weak, in this high quality-factor device, ppm-level nonlinear elastic effects result in an order-of-magnitude increase in the observed sensitivity to Coriolis force relative to linear theory. Perfect degeneracy of the primary and secondary vibration modes is achieved through electrostatic frequency tuning, which also enables the phase and frequency of the parametric coupling to be varied, and we show that the resulting phase and frequency dependence of the amplification follow the theory of parametric resonance. We expect that this phenomenon will be useful for both fundamental studies of dynamic systems with low dissipation and for increasing signal-to-noise ratio in practical applications such as gyroscopes.

Adaptation in a rotating artificial gravity environment

NASA Technical Reports Server (NTRS)

Lackner, J. R.; DiZio, P.

1998-01-01

The centripetal force generated by a rotating space vehicle is a potential source of artificial gravity. Minimizing the cost of such a vehicle dictates using the smallest radius and highest rotation rate possible, but head movements made at high rotation rates generate disorienting, nauseogenic cross-coupled semicircular canal stimulation. Early studies suggested 3 or 4 rpm as the highest rate at which humans could adapt to this vestibular stimulus. These studies neglected the concomitant Coriolis force actions on the head/neck system. We assessed non-vestibular Coriolis effects by measuring arm and leg movements made in the center of a rotating room turning at 10 rpm and found that movement endpoints and trajectories are initially deviated; however, subjects readily adapt with 10-20 additional movements, even without seeing their errors. Equilibrium point theories of motor control errantly predict that Coriolis forces will not cause movement endpoint errors so that subjects will not have to adapt their reaching movements during rotation. Adaptation of movement trajectory acquired during Coriolis force perturbations of one arm transfers to the unexposed arm but there is no intermanual transfer of endpoint adaptation indicating that neuromotor representations of movement endpoint and trajectory are separable and can adapt independently, also contradictory to equilibrium point theories. Touching a surface at the end of reaching movements is required for complete endpoint adaptation in darkness but trajectory adapts completely with or without terminal contact. We have also made the first kinematic measurements of unconstrained head movements during rotation, these movements show rapid adaptation to Coriolis force perturbations. Our results point to methods for achieving full compensation for rotation up to 10 rpm. Copyright 1998 Published by Elsevier Science B.V.

Adaptation in a rotating artificial gravity environment.

PubMed

Lackner, J R; DiZio, P

1998-11-01

The centripetal force generated by a rotating space vehicle is a potential source of artificial gravity. Minimizing the cost of such a vehicle dictates using the smallest radius and highest rotation rate possible, but head movements made at high rotation rates generate disorienting, nauseogenic cross-coupled semicircular canal stimulation. Early studies suggested 3 or 4 rpm as the highest rate at which humans could adapt to this vestibular stimulus. These studies neglected the concomitant Coriolis force actions on the head/neck system. We assessed non-vestibular Coriolis effects by measuring arm and leg movements made in the center of a rotating room turning at 10 rpm and found that movement endpoints and trajectories are initially deviated; however, subjects readily adapt with 10-20 additional movements, even without seeing their errors. Equilibrium point theories of motor control errantly predict that Coriolis forces will not cause movement endpoint errors so that subjects will not have to adapt their reaching movements during rotation. Adaptation of movement trajectory acquired during Coriolis force perturbations of one arm transfers to the unexposed arm but there is no intermanual transfer of endpoint adaptation indicating that neuromotor representations of movement endpoint and trajectory are separable and can adapt independently, also contradictory to equilibrium point theories. Touching a surface at the end of reaching movements is required for complete endpoint adaptation in darkness but trajectory adapts completely with or without terminal contact. We have also made the first kinematic measurements of unconstrained head movements during rotation, these movements show rapid adaptation to Coriolis force perturbations. Our results point to methods for achieving full compensation for rotation up to 10 rpm. Copyright 1998 Published by Elsevier Science B.V.

A modified variational method for nonlinear vibration analysis of rotating beams including Coriolis effects

NASA Astrophysics Data System (ADS)

Tian, Jiajin; Su, Jinpeng; Zhou, Kai; Hua, Hongxing

2018-07-01

This paper presents a general formulation for nonlinear vibration analysis of rotating beams. A modified variational method combined with a multi-segment partitioning technique is employed to derive the free and transient vibration behaviors of the rotating beams. The strain energy and kinetic energy functional are formulated based on the order truncation principle of the fully geometrically nonlinear beam theory. The Coriolis effects as well as nonlinear effects due to the coupling of bending-stretching, bending-twist and twist-stretching are taken into account. The present method relaxes the need to explicitly meet the requirements of the boundary conditions for the admissible functions, and allows the use of any linearly independent, complete basis functions as admissible functions for rotating beams. Moreover, the method is readily used to deal with the nonlinear transient vibration problems for rotating beams subjected to dynamic loads. The accuracy, convergence and efficiency of the proposed method are examined by numerical examples. The influences of Coriolis and centrifugal forces on the vibration behaviors of the beams with various hub radiuses and slenderness ratios and rotating at different angular velocities are also investigated.

Three-dimensional numerical simulation of gradual opening in a wave rotor passage

NASA Technical Reports Server (NTRS)

Larosiliere, Louis M.

1993-01-01

The evolution of the contact interface and the propagation of compression waves inside a single wave rotor passage gradually opening to and traversing an inlet port is studied numerically using an inviscid formulation of the governing equations. Insights into the response of the interface and kinematics of the flow field to various opening times are given. Since the opening time is inversely proportional to the rotational speed of the rotor, the effects of passage rotation such as centripetal and Coriolis accelerations are intrinsically coupled to the gradual opening process. Certain three-dimensional features associated with the gradual opening process as a result of centripetal and Coriolis accelerations are illustrated. For the range of opening times or rotational speeds considered, a portion of the interface behaves like a vortex sheet that can degenerate into a complex interfacial structure. The vortices produced along the interface can serve as a stirring mechanism to promote local mixing. Coriolis and centripetal accelerations can introduce three dimensional effects such as interfacial distortions in meridional planes and spanwise migration of fluid elements.

The 2ν6/ν2 + ν3/ν3 + ν5 band system of CH3Br revisited: Modeling anharmonic and Coriolis interactions in a three-level system near 2000 cm-1

NASA Astrophysics Data System (ADS)

Ceausu-Velcescu, Adina; Kwabia Tchana, Fridolin; Landsheere, Xavier

2018-06-01

The 2ν6 (A1 + E)/ν2 + ν3 (A1)/ν3 + ν5 (E) band system of CH3Br, near 2000 cm-1, has been studied, for both 79Br and 81Br isotopologues, using Fourier transform infrared spectroscopy, with a resolution of 0.003 cm-1. This band system, revealing anharmonic (Δk = Δl = 0) and Coriolis (Δk = Δl = ± 1) interactions, has been analyzed through a least-squares fit of more than 3000 transitions, for each isotopologue. More than 600 transitions belonging to the very weak ν3 + ν5 combination band were assigned for the first time, for both CH379Br and CH381Br isotopologues. Assignments of the weak 2 ν60 parallel band, which is Fermi-interacting with ν2 + ν3, were also considerably extended with respect to a previous high-resolution study (Najib et al., 1985), thanks to a more accurate knowledge of the Fermi coupling parameters and of the relative positions of the interacting levels. The least-squares fits provided quantitative reproduction of all data belonging to the four above mentioned bands. Moreover, the Coriolis coupling parameters obtained for the ν2 + ν3/ν3 + ν5 interacting bands show a remarkable consistency with those obtained for the ν2/ν5 'fundamental' system (Kwabia Tchana et al., 2004).

Addition by subtraction in coupled-cluster theory: a reconsideration of the CC and CI interface and the nCC hierarchy.

PubMed

Bartlett, Rodney J; Musiał, Monika

2006-11-28

The nCC hierarchy of coupled-cluster approximations, where n guarantees exactness for n electrons and all products of n electrons are derived and applied to several illustrative problems. The condition of exactness for n=2 defines nCCSD=2CC, with nCCSDT=3CC and nCCSDTQ=4CC being exact for three and four electrons. To achieve this, the minimum number of diagrams is evaluated, which is less than in the corresponding CC model. For all practical purposes, nCC is also the proper definition of a size-extensive CI. 2CC is also an orbitally invariant coupled electron pair approximation. The numerical results of nCC are close to those for the full CC variant, and in some cases are closer to the full CI reference result. As 2CC is exact for separated electron pairs, it is the natural zeroth-order approximation for the correlation problem in molecules with other effects introduced as these units start to interact. The nCC hierarchy of approximations has all the attractive features of CC including its size extensivity, orbital invariance, and orbital insensitivity, but in a conceptually appealing form suited to bond breaking, while being computationally less demanding. Excited states from the equation of motion (EOM-2CC) are also reported, which show results frequently approaching those of EOM-CCSDT.

Effect of microgravity on spatial orientation and posture regulation during Coriolis stimulation.

PubMed

Takahashi, Masahiro; Sekine, Motoki; Ikeda, Takuo; Watanuki, Koichi; Hakuta, Shuzo; Takeoka, Hajime

2004-05-01

To elucidate spatial orientation and posture regulation under conditions of microgravity. Coriolis stimulation was done with five normal subjects on the ground (1 g) and onboard an aircraft (under conditions of microgravity during parabolic flight). Subjects were asked to tilt their heads forward during rotation at speeds of 0, 50, 100 and 150 degrees/s on the ground and 100 degrees/s during flight. Body sway was recorded using a 3D linear accelerometer and eye movements using an infrared charge-coupled device video camera. Flight experiments were performed on 5 consecutive days, and 11-16 parabolic maneuvers were done during each flight. Two subjects boarded each flight and were examined alternately at least five times. Coriolis stimulation at 1 g caused body sway, nystagmus and a movement sensation in accordance with inertial inputs at 1 g. Neither body sway, excepting a minute sway due to the Coriolis force, nor a movement sensation occurred in microgravity, but nystagmus was recorded. Posture, eye movement and sensation at 1 g are controlled with reference to spatial coordinates that represent the external world in the brain. Normal spatial coordinates are not relevant in microgravity because there is no Z-axis, and the posture regulation and sensation that depend on them collapse. The discrepancy in responses between posture and eye movement under conditions of microgravity may be caused by a different constitution of the effectors which adjust posture and gaze.

Advances in copper-catalyzed C-C coupling reactions and related domino reactions based on active methylene compounds.

PubMed

Liu, Yunyun; Wan, Jie-Ping

2012-06-01

Active methylene compounds are a major class of reaction partners for C-C bond formation with sp(2) C-X (X = halide) fragments. As one of the most-classical versions of the Ullmann-type coupling reaction, activated-methylene-based C-C coupling reactions have been efficiently employed in a large number of syntheses. Although this type of reaction has long relied on noble-metal catalysis, the renaissance of copper catalysis at the end of last century has led to dramatic developments in Ullmann C-C coupling reactions. Owing to its low cost, abundance, as well as excellent catalytic activity, the exceptional atom economy of copper catalysis is gaining widespread attention in various organic synthesis. This review summarizes the advances in copper-catalyzed intermolecular and intramolecular C-C coupling reactions that use activated methylene species as well as in tandem reactions that are initiated by this transformation. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Loop Heat Pipe Operation with Thermoelectric Converters and Coupling Blocks

NASA Technical Reports Server (NTRS)

Ku, Jentung; Nagano, Hosei

2007-01-01

This paper presents theoretical and experimental studies on using thermoelectric converters (TECs) and coupling blocks to control the operating temperature of a miniature loop heat pipes (MLHP). The MLHP has two parallel evaporators and two parallel condensers, and each evaporator has its own integral compensation chamber (CC). A TEC is attached to each CC, and connected to the evaporator via a copper thermal strap. The TEC can provide both heating and cooling to the CC, therefore extending the LHP operating temperature over a larger range of the evaporator heat load. A bi-polar power supply is used for the TEC operation. The bipolar power supply automatically changes the direction of the current to the TEC, depending on whether the CC requires heating or cooling, to maintain the CC temperature at the desired set point. The TEC can also enhance the startup success by maintaining a constant CC temperature during the start-up transient. Several aluminum coupling blocks are installed between the vapor line and liquid line. The coupling blocks serve as a heat exchanger which preheats the cold returning liquid so as to reduce the amount of liquid subcooling, and hence the power required to maintain the CC at the desired set point temperature. This paper focuses on the savings of the CC control heater power afforded by the TECs when compared to traditional electric heaters. Tests were conducted by varying the evaporator power, the condenser sink temperature, the CC set point temperature, the number of coupling blocks, and the thermal conductance of the thermal strap. Test results show that the TECs are able to control the CC temperature within k0.5K under all test conditions, and the required TEC heater power is only a fraction of the required electric heater power.

Torsional Splitting in the Degenerate Vibrational States of (70)Ge(2)H(6): Rotation-Torsion Analysis of the nu(7) and nu(9) Fundamentals.

PubMed

Lattanzi; di Lauro C; Bürger; Mkadmi

2000-09-01

The rotational and torsional structure of the nu(7) and nu(9) degenerate fundamentals of (70)Ge(2)H(6) has been analyzed under high resolution. The torsional structure of both v(7) = 1 and v(9) = 1 states can be fitted by a simple one-parameter formula. The x,y-Coriolis interaction with the parallel nu(5) fundamental was accounted for in the analysis of nu(7). A strong perturbation of the J structure of the E(3s) torsional component of the KDeltaK = -2 subbranches of nu(9) can be explained by the resonance with an E(3s) excited level of the pure torsional manifold. The perturber is centered at 361.58 cm(-1), very close to the value estimated with a barrier height of 285 cm(-1). This confirms that the fundamental torsional wavenumber is close to 103 cm(-1), in good agreement with the "ab initio" prediction. The torsional splittings of all the infrared active degenerate fundamentals, nu(7), nu(8), and nu(9), follow the trend predicted by theory, and have been fitted by exploratory calculations accounting only for the torsional Coriolis-coupling mechanism of all degenerate vibrational fundamentals in several torsional states. This confirms that torsional Coriolis coupling is the dominant mechanism responsible for the decrease of the torsional splitting in the degenerate vibrational states. A higher value of the barrier had to be used for the nu(9) mode. Copyright 2000 Academic Press.

Rotation of Giant Stars

NASA Astrophysics Data System (ADS)

Kissin, Yevgeni; Thompson, Christopher

2015-07-01

The internal rotation of post-main sequence stars is investigated, in response to the convective pumping of angular momentum toward the stellar core, combined with a tight magnetic coupling between core and envelope. The spin evolution is calculated using model stars of initial mass 1, 1.5, and 5 {M}⊙ , taking into account mass loss on the giant branches. We also include the deposition of orbital angular momentum from a sub-stellar companion, as influenced by tidal drag along with the excitation of orbital eccentricity by a fluctuating gravitational quadrupole moment. A range of angular velocity profiles {{Ω }}(r) is considered in the envelope, extending from solid rotation to constant specific angular momentum. We focus on the backreaction of the Coriolis force, and the threshold for dynamo action in the inner envelope. Quantitative agreement with measurements of core rotation in subgiants and post-He core flash stars by Kepler is obtained with a two-layer angular velocity profile: uniform specific angular momentum where the Coriolis parameter {Co}\\equiv {{Ω }}{τ }{con}≲ 1 (here {τ }{con} is the convective time), and {{Ω }}(r)\\propto {r}-1 where {Co}≳ 1. The inner profile is interpreted in terms of a balance between the Coriolis force and angular pressure gradients driven by radially extended convective plumes. Inward angular momentum pumping reduces the surface rotation of subgiants, and the need for a rejuvenated magnetic wind torque. The co-evolution of internal magnetic fields and rotation is considered in Kissin & Thompson, along with the breaking of the rotational coupling between core and envelope due to heavy mass loss.

High-resolution FTIR spectroscopy of the ν7 and ν8 bands of 1-phosphapropyne

NASA Astrophysics Data System (ADS)

Bane, Michael K.; Jones, Cameron; Choong, Sam L.; Thompson, Christopher D.; Godfrey, Peter D.; Appadoo, Dominique R. T.; McNaughton, Don

2012-05-01

1-Phosphapropyne has been prepared and high-resolution (0.001 cm-1) spectra have been recorded on the far-infrared beamline at the Australian synchrotron between 1500-700 cm-1 and 400-50 cm-1. Ro-vibrational transitions of the ν8 (308 cm-1) and ν7 (1006 cm-1) fundamentals as well as the 2ν8±2←v8±1 and 2ν80←v8±1 hot-bands have been assigned, and rotational, centrifugal distortion and Coriolis interaction parameters determined. The 2ν8±2←v8±1 hot-band is an example of a particularly complex E ← E transition, for which both states are strongly Coriolis and l(2,2) coupled.

Metastable Autoionizing States of Molecules and Radicals in Highly Energetic Environment

DTIC Science & Technology

2016-03-22

electronic states. The specific aims are to develop and calibrate complex-scaled equation-of-motion coupled cluster (cs-EOM- CC ) and CAP (complex...absorbing potential) augmented EOM- CC methods. We have implemented and benchmarked cs-EOM-CCSD and CAP- augmented EOM-CCSD methods for excitation energies...motion coupled cluster (cs-EOM- CC ) and CAP (complex absorbing potential) augmented EOM- CC methods. We have implemented and benchmarked cs-EOM-CCSD and

An Exploration of Structures in the Transitional Odd-Odd Nucleus Lu-160

DTIC Science & Technology

2015-05-18

25 3.4.1 CSM Quantum Numbers . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 3.4.2 Coriolis Effects ...22 14 Quasiparticle energy levels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 15 Coriolis effect in time-reversed orbits...for various unpaired particles [21]. This notation is summarized in Table 1. 3.4.2 Coriolis Effects The Coriolis effect or the Coriolis force is most

Effect of coriolis force on forced response magnification of intentionally mistuned bladed disk

NASA Astrophysics Data System (ADS)

Kan, Xuanen; Xu, Zili; Zhao, Bo; Zhong, Jize

2017-07-01

Blade manufacturing tolerance and wear in operation may induce mistuning, and mistuning will lead to vibration localization which will result in destruction of bladed disk. Generally, intentional mistuning has been widely investigated to control the maximum forced response. On the other hand, it should be noted that the bladed disk with high rotational speed is obviously subjected to the Coriolis force. However, the Coriolis force is not included in intentionally mistuned bladed disk in previous studies. Therefore, this paper is to study the effect of the Coriolis force on forced response magnification of intentionally mistuned bladed disk. Finite element method is used to calculate the harmonic response of the intentionally mistuned bladed disk with and without the Coriolis force. The effects of intentional mistuning strength and different integer harmonic order on the response magnification factor with the Coriolis force are discussed. It should be pointed out that, when the integer harmonic order is 1, 3 and 5, the response magnification factor with the effect of the Coriolis force increase by 3.9%, 3.53% and 3.76% respectively compared to the system of non-Coriolis force. In addition, forced response magnification factor of intentionally mistuned bladed disk with and without the Coriolis force under different rotational speed is researched in contrast. It shows that, when the rotational speed is 3000 rpm, the response magnification factor with the Coriolis force increases by 0.65% compared to the system of non-Coriolis force, while the response magnification factor with the Coriolis force decreases by 6.28% compared to the system of non-Coriolis force when the rotational speed is 12000 rpm.

Jet-cooled laser-induced fluorescence spectroscopy of cyclohexoxy: rotational and fine structure of molecules in nearly degenerate electronic States.

PubMed

Liu, Jinjun; Miller, Terry A

2014-12-26

The rotational structure of the previously observed B̃(2)A' ← X̃(2)A″ and B̃(2)A' ← Ã(2)A' laser-induced fluorescence spectra of jet-cooled cyclohexoxy radical (c-C6H11O) [ Zu, L.; Liu, J.; Tarczay, G.; Dupré, P; Miller, T. A. Jet-cooled laser spectroscopy of the cyclohexoxy radical. J. Chem. Phys. 2004 , 120 , 10579 ] has been analyzed and simulated using a spectroscopic model that includes the coupling between the nearly degenerate X̃ and à states separated by ΔE. The rotational and fine structure of these two states is reproduced by a 2-fold model using one set of molecular constants including rotational constants, spin-rotation constants (ε's), the Coriolis constant (Aζt), the quenched spin-orbit constant (aζed), and the vibronic energy separation between the two states (ΔE0). The energy level structure of both states can also be reproduced using an isolated-state asymmetric top model with rotational constants and effective spin-rotation constants (ε's) and without involving Coriolis and spin-orbit constants. However, the spin-orbit interaction introduces transitions that have no intensity using the isolated-state model but appear in the observed spectra. The line intensities are well simulated using the 2-fold model with an out-of-plane (b-) transition dipole moment for the B̃ ← X̃ transitions and in-plane (a and c) transition dipole moment for the B̃ ← à transitions, requiring the symmetry for the X̃ (Ã) state to be A″ (A'), which is consistent with a previous determination and opposite to that of isopropoxy, the smallest secondary alkoxy radical. The experimentally determined Ã-X̃ separation and the energy level ordering of these two states with different (A' and A″) symmetries are consistent with quantum chemical calculations. The 2-fold model also enables the independent determination of the two contributions to the Ã-X̃ separation: the relativistic spin-orbit interaction (magnetic effect) and the nonrelativistic vibronic separation between the lowest vibrational energy levels of these two states due to both electrostatic interaction (Coulombic effect) and difference in zero-point energies (kinetic effect).

The KP Approximation Under a Weak Coriolis Forcing

NASA Astrophysics Data System (ADS)

Melinand, Benjamin

2018-02-01

In this paper, we study the asymptotic behavior of weakly transverse water-waves under a weak Coriolis forcing in the long wave regime. We derive the Boussinesq-Coriolis equations in this setting and we provide a rigorous justification of this model. Then, from these equations, we derive two other asymptotic models. When the Coriolis forcing is weak, we fully justify the rotation-modified Kadomtsev-Petviashvili equation (also called Grimshaw-Melville equation). When the Coriolis forcing is very weak, we rigorously justify the Kadomtsev-Petviashvili equation. This work provides the first mathematical justification of the KP approximation under a Coriolis forcing.

The intermolecular vibrations of the water dimer

NASA Astrophysics Data System (ADS)

Braly, Linda Beth

Terahertz laser spectra of water dimer intermolecular vibrations have yielded four (D2O)2 VRT bands (one previously published) and five (H2O)2 VRT bands measured with ca. 1 MHz precision and assigned between 65 and 142 cm-1. The results differ both qualitatively and quantitatively from the predictions of popular, effective pair potentials tested. The spectra also reveal an ordering of the intermolecular vibrations which differs dramatically from that predicted by a normal mode analysis. Strong coupling is indicated between the low barrier tunneling motions and the intermolecular vibrations as well as between different vibrations. In particular the 102.1 cm-1 (H2O) 2 band assigned as the acceptor wag has two types of perturbations. The first perturbation involves coupling of two of the tunneling components between the Ka = 0 and 1 levels similar to that occurring in ground state between Ka = 0 and 1 levels. This is treated with an effective Coriolis coupling constant. These seconded perturbation involves one tunneling component with Ka = 1 coupling with a tunneling component with Ka = 0 of the 108 cm-1 acceptor twist vibration. A more detailed Coriolis coupling scheme is required to deperturb these states. Also it is indicated that the 103.1 cm-1 (H2O) 2 band assigned as the donor in-plane bend is coupled to the acceptor wag resulting in a lowering of the in-plane bend frequency and raising the acceptor wag frequency. In addition the 141 cm-1 (H2O)2 band shows perturbations which could not be. resolved at this time. And the 83 cm-1 (acceptor wag) and 90 cm-1 (D2O)2 (acceptor twist) band are perturbing one another through a Coriolis interaction. A subset of the (D2O)2 data have been used in an ongoing effort to determine an accurate IPS via least-squares fitting to an analytical form. The results from the most recent fit which produced VRT(ASP- W)II are presented and compared with the experimental data. The IPS was used to calculate the eigenstates of the water dimer using the Split Wigner Psuedo Spectral (SWPS) method. The transitions could then be calculated from the eigenstates. This improved IPS reproduces the dominant features of the VRT spectra quite well. The ultimate goal of this water dimer research project is to determine the ``perfect'' water pair potential from the spectroscopic data.

Substrate-Mediated C-C and C-H Coupling after Dehalogenation.

PubMed

Kong, Huihui; Yang, Sha; Gao, Hongying; Timmer, Alexander; Hill, Jonathan P; Díaz Arado, Oscar; Mönig, Harry; Huang, Xinyan; Tang, Qin; Ji, Qingmin; Liu, Wei; Fuchs, Harald

2017-03-15

Intermolecular C-C coupling after cleavage of C-X (mostly, X = Br or I) bonds has been extensively studied for facilitating the synthesis of polymeric nanostructures. However, the accidental appearance of C-H coupling at the terminal carbon atoms would limit the successive extension of covalent polymers. To our knowledge, the selective C-H coupling after dehalogenation has not so far been reported, which may illuminate another interesting field of chemical synthesis on surfaces besides in situ fabrication of polymers, i.e., synthesis of novel organic molecules. By combining STM imaging, XPS analysis, and DFT calculations, we have achieved predominant C-C coupling on Au(111) and more interestingly selective C-H coupling on Ag(111), which in turn leads to selective synthesis of polymeric chains or new organic molecules.

A New Look for Coriolis.

ERIC Educational Resources Information Center

Levi, F. A.

1988-01-01

Describes a demonstration of Coriolis acceleration. Discusses two different meanings of "Coriolis" and two causes of Coriolis acceleration. Gives a set-up method of the demonstration apparatus by using a rotary disk with rubber tubing for tap water, switches, lamps, battery, and counterweight. Provides two pictures with operating method.…

Effect of nonlinear electrostatic forces on the dynamic behaviour of a capacitive ring-based Coriolis Vibrating Gyroscope under severe shock

NASA Astrophysics Data System (ADS)

Chouvion, B.; McWilliam, S.; Popov, A. A.

2018-06-01

This paper investigates the dynamic behaviour of capacitive ring-based Coriolis Vibrating Gyroscopes (CVGs) under severe shock conditions. A general analytical model is developed for a multi-supported ring resonator by describing the in-plane ring response as a finite sum of modes of a perfect ring and the electrostatic force as a Taylor series expansion. It is shown that the supports can induce mode coupling and that mode coupling occurs when the shock is severe and the electrostatic forces are nonlinear. The influence of electrostatic nonlinearity is investigated by numerically simulating the governing equations of motion. For the severe shock cases investigated, when the electrode gap reduces by ∼ 60 % , it is found that three ring modes of vibration (1 θ, 2 θ and 3 θ) and a 9th order force expansion are needed to obtain converged results for the global shock behaviour. Numerical results when the 2 θ mode is driven at resonance indicate that electrostatic nonlinearity introduces mode coupling which has potential to reduce sensor performance under operating conditions. Under some circumstances it is also found that severe shocks can cause the vibrating response to jump to another stable state with much lower vibration amplitude. This behaviour is mainly a function of shock amplitude and rigid-body motion damping.

Response of water temperature to surface wave effects in the Baltic Sea: simulations with the coupled NEMO-WAM model

NASA Astrophysics Data System (ADS)

Alari, Victor; Staneva, Joanna; Breivik, Øyvind; Bidlot, Jean-Raymond; Mogensen, Kristian; Janssen, Peter

2016-04-01

The effects of wind waves on the Baltic Sea water temperature has been studied by coupling the hydrodynamical model NEMO with the wave model WAM. The wave forcing terms that have been taken into consideration are: Stokes-Coriolis force, seastate dependent energy flux and sea-state dependent momentum flux. The combined role of these processes as well as their individual contributions on simulated temperature is analysed. The results indicate a pronounced effect of waves on surface temperature, on the distribution of vertical temperature and on upwellinǵs. In northern parts of the Baltic Sea a warming of the surface layer occurs in the wave included simulations. This in turn reduces the cold bias between simulated and measured data. The warming is primarily caused by sea-state dependent energy flux. Wave induced cooling is mostly observed in near coastal areas and is mainly due to Stokes-Coriolis forcing. The latter triggers effect of intensifying upwellings near the coasts, depending on the direction of the wind. The effect of sea-state dependent momentum flux is predominantly to warm the surface layer. During the summer the wave induced water temperature changes were up to 1 °C.

Comparing the accuracy of perturbative and variational calculations for predicting fundamental vibrational frequencies of dihalomethanes

NASA Astrophysics Data System (ADS)

Krasnoshchekov, Sergey V.; Schutski, Roman S.; Craig, Norman C.; Sibaev, Marat; Crittenden, Deborah L.

2018-02-01

Three dihalogenated methane derivatives (CH2F2, CH2FCl, and CH2Cl2) were used as model systems to compare and assess the accuracy of two different approaches for predicting observed fundamental frequencies: canonical operator Van Vleck vibrational perturbation theory (CVPT) and vibrational configuration interaction (VCI). For convenience and consistency, both methods employ the Watson Hamiltonian in rectilinear normal coordinates, expanding the potential energy surface (PES) as a Taylor series about equilibrium and constructing the wavefunction from a harmonic oscillator product basis. At the highest levels of theory considered here, fourth-order CVPT and VCI in a harmonic oscillator basis with up to 10 quanta of vibrational excitation in conjunction with a 4-mode representation sextic force field (SFF-4MR) computed at MP2/cc-pVTZ with replacement CCSD(T)/aug-cc-pVQZ harmonic force constants, the agreement between computed fundamentals is closer to 0.3 cm-1 on average, with a maximum difference of 1.7 cm-1. The major remaining accuracy-limiting factors are the accuracy of the underlying electronic structure model, followed by the incompleteness of the PES expansion. Nonetheless, computed and experimental fundamentals agree to within 5 cm-1, with an average difference of 2 cm-1, confirming the utility and accuracy of both theoretical models. One exception to this rule is the formally IR-inactive but weakly allowed through Coriolis-coupling H-C-H out-of-plane twisting mode of dichloromethane, whose spectrum we therefore revisit and reassign. We also investigate convergence with respect to order of CVPT, VCI excitation level, and order of PES expansion, concluding that premature truncation substantially decreases accuracy, although VCI(6)/SFF-4MR results are still of acceptable accuracy, and some error cancellation is observed with CVPT2 using a quartic force field.

Synchrotron Infrared Spectroscopy of νb{4}, νb{10}, νb{11} and νb{14} States of Thiirane

NASA Astrophysics Data System (ADS)

Evans, Corey; Carter, Jason P.; McNaughton, Don; Wong, Andy; Appadoo, Dominique

2015-06-01

The high-resolution (0.001 cm-1) spectrum of thiirane has been recorded using the infrared beamline at the Australian synchrotron facility. Spectra have been recorded between 750 cm-1 to 1120 cm-1 and ro-vibrational transitions associated with four bands have been observed and assigned. Coriolis coupling was observed between the νb{4} (1024 cm-1) and the νb{14}(1050 cm-1) fundamentals as well as between νb{11} (825 cm-1) and the νb{8} (895 cm-1) fundamentals. The νb{10} (945 cm-1) fundamental was also observed and was found to have no significant perturbations associated with it. For each of the observed bands rotational, centrifugal distortion and Coriolis interaction parameters have been determined. The ground state constants have also been further refined.

Dealing with chemical reaction pathways and electronic excitations in molecular systems via renormalized and active-space coupled-cluster methods

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

Piecuch, Piotr; Li, Wei; Lutz, Jesse J.

Coupled-cluster (CC) theory has become the de facto standard for high-accuracy molecular calculations, but the widely used CC and equation-of-motion (EOM) CC approaches, such as CCSD(T) and EOMCCSD, have difficulties with capturing stronger electron correlations that characterize multi-reference molecular problems. This presentation demonstrates that many of these difficulties can be addressed by exploiting the completely renormalized (CR) CC and EOMCC approaches, such as CR-CC(2,3), CR-EOMCCSD(T), and CR-EOMCC(2,3), and their local correlation counterparts applicable to systems with hundreds of atoms, and the active-space CC/EOMCC approaches, such as CCSDt and EOMCCSDt, and their extensions to valence systems via the electron-attached and ionizedmore » formalisms.« less

Ultracold Molecules in Optical Lattices: Efficient Production and Application to Molecular Clocks

DTIC Science & Technology

2015-05-03

near the intercombination- line threshold were measured for a variety of states, and explained by considering nonadiabatic effects ( Coriolis coupling) in...Moszynski, T. Zelevinsky. Nonadiabatic Effects in Ultracold Molecules via Anomalous Linear and Quadratic Zeeman Shifts, Physical Review Letters, (12...M. McDonald, G. Reinaudi, W. Skomorowski, R. Moszynski, T. Zelevinsky. Measurement of Nonadiabatic Effects in Ultracold Molecules via Anomalous

C-C cross-coupling reactions of O6-alkyl-2-haloinosine derivatives and a one-pot cross-coupling/O6-deprotection procedure.

PubMed

Gurram, Venkateshwarlu; Pottabathini, Narender; Garlapati, Ramesh; Chaudhary, Avinash B; Patro, Balaram; Lakshman, Mahesh K

2012-08-01

Reaction conditions for the CC cross-coupling of O(6)-alkyl-2-bromo- and 2-chloroinosine derivatives with aryl-, hetaryl-, and alkylboronic acids were studied. Optimization experiments with silyl-protected 2-bromo-O(6)-methylinosine led to the identification of [PdCl(2)(dcpf)]/K(3)PO(4) in 1,4-dioxane as the best conditions for these reactions (dcpf=1,1'-bis(dicyclohexylphosphino)ferrocene). Attempted O(6)-demethylation, as well as the replacement of the C-6 methoxy group by amines, was unsuccessful, which led to the consideration of Pd-cleavable groups such that C-C cross-coupling and O(6)-deprotection could be accomplished in a single step. Thus, inosine 2-chloro-O(6)-allylinosine was chosen as the substrate and, after re-evaluation of the cross-coupling conditions with 2-chloro-O(6)-methylinosine as a model substrate, one-step C-C cross-coupling/deprotection reactions were performed with the O(6)-allyl analogue. These reactions are the first such examples of a one-pot procedure for the modification and deprotection of purine nucleosides under C-C cross-coupling conditions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of the CC(P;Q) Hierarchy of Coupled-Cluster Methods to the Beryllium Dimer.

PubMed

Magoulas, Ilias; Bauman, Nicholas P; Shen, Jun; Piecuch, Piotr

2018-02-08

The performance of coupled-cluster approaches with higher-than-doubly excited clusters, including the CCSD(T), CCSD(2) T , CR-CC(2,3), CCSD(TQ), and CR-CC(2,4) corrections to CCSD, the active-space CCSDt, CCSDtq, and CCSDTq methods, and the CC(t;3), CC(t,q;3), CC(t,q;3,4), and CC(q;4) corrections to CCSDt, CCSDtq, and CCSDTq resulting from the CC(P;Q) formalism, in reproducing the CCSDT and CCSDTQ potential energy curves and vibrational term values characterizing Be 2 in its electronic ground state is assessed. The correlation-consistent aug-cc-pVnZ and aug-cc-pCVnZ (n = T and Q) basis sets are employed. Among the CCSD-based corrections, the completely renormalized CR-CC(2,3) and CR-CC(2,4) approaches perform the best. The CC(t;3), CC(t,q;3), CC(t,q;3,4), and CC(q;4) methods, especially CC(t;3) and CC(q;4), outperform other employed approaches in reproducing the CCSDT and CCSDTQ data. Composite schemes combining the all-electron CCSDT calculations extrapolated to the complete basis set limit with the frozen-core CC(q;4) and CCSDTQ computations using the aug-cc-pVTZ basis to account for connected quadruple excitations reproduce the latest experimental vibrational spectrum of Be 2 to within 4-5 cm -1 , when the vibrational spacings are examined, with typical errors being below 1-2 cm -1 . The resulting binding energies and equilibrium bond lengths agree with their experimentally derived counterparts to within ∼10 cm -1 and 0.01 Å.

PDF turbulence modeling and DNS

NASA Technical Reports Server (NTRS)

Hsu, A. T.

1992-01-01

The problem of time discontinuity (or jump condition) in the coalescence/dispersion (C/D) mixing model is addressed in probability density function (pdf). A C/D mixing model continuous in time is introduced. With the continuous mixing model, the process of chemical reaction can be fully coupled with mixing. In the case of homogeneous turbulence decay, the new model predicts a pdf very close to a Gaussian distribution, with finite higher moments also close to that of a Gaussian distribution. Results from the continuous mixing model are compared with both experimental data and numerical results from conventional C/D models. The effect of Coriolis forces on compressible homogeneous turbulence is studied using direct numerical simulation (DNS). The numerical method used in this study is an eight order compact difference scheme. Contrary to the conclusions reached by previous DNS studies on incompressible isotropic turbulence, the present results show that the Coriolis force increases the dissipation rate of turbulent kinetic energy, and that anisotropy develops as the Coriolis force increases. The Taylor-Proudman theory does apply since the derivatives in the direction of the rotation axis vanishes rapidly. A closer analysis reveals that the dissipation rate of the incompressible component of the turbulent kinetic energy indeed decreases with a higher rotation rate, consistent with incompressible flow simulations (Bardina), while the dissipation rate of the compressible part increases; the net gain is positive. Inertial waves are observed in the simulation results.

Measurement of Coriolis Acceleration with a Smartphone

NASA Astrophysics Data System (ADS)

Shakur, Asif; Kraft, Jakob

2016-05-01

Undergraduate physics laboratories seldom have experiments that measure the Coriolis acceleration. This has traditionally been the case owing to the inherent complexities of making such measurements. Articles on the experimental determination of the Coriolis acceleration are few and far between in the physics literature. However, because modern smartphones come with a raft of built-in sensors, we have a unique opportunity to experimentally determine the Coriolis acceleration conveniently in a pedagogically enlightening environment at modest cost by using student-owned smartphones. Here we employ the gyroscope and accelerometer in a smartphone to verify the dependence of Coriolis acceleration on the angular velocity of a rotatingtrack and the speed of the sliding smartphone.

Critical coupling and coherent perfect absorption for ranges of energies due to a complex gain and loss symmetric system

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

Hasan, Mohammad, E-mail: mohammadhasan786@gmail.com; Ghatak, Ananya, E-mail: gananya04@gmail.com; Mandal, Bhabani Prasad, E-mail: bhabani.mandal@gmail.com

2014-05-15

We consider a non-Hermitian medium with a gain and loss symmetric, exponentially damped potential distribution to demonstrate different scattering features analytically. The condition for critical coupling (CC) for unidirectional wave and coherent perfect absorption (CPA) for bidirectional waves are obtained analytically for this system. The energy points at which total absorption occurs are shown to be the spectral singular points for the time reversed system. The possible energies at which CC occurs for left and right incidence are different. We further obtain periodic intervals with increasing periodicity of energy for CC and CPA to occur in this system. -- Highlights:more » •Energy ranges for CC and CPA are obtained explicitly for complex WS potential. •Analytical conditions for CC and CPA for PT symmetric WS potential are obtained. •Conditions for left and right CC are shown to be different. •Conditions for CC and CPA are shown to be that of SS for the time reversed system. •Our model shows the great flexibility of frequencies for CC and CPA.« less

Quantifying Seasonal Skill In Coupled Sea Ice Models Using Freeboard Measurements From Spaceborne Laser Altimeters

DTIC Science & Technology

2016-06-01

Richter-Menge (2009), (b) Source: Jack Cook, Woods Hole Oceanographic Institute. Four forcing mechanisms, as well as the Coriolis force, influence...changing Arctic environment which is critical to personnel safety, effective use of assets, and operational support (Arctic Roadmap 2014). 18 Canada...Navy to pursue continued Arctic presence, and maximize the effectiveness of the military operations assimilated with civilian science (Showstack 2013

Attenuated coupled cluster: a heuristic polynomial similarity transformation incorporating spin symmetry projection into traditional coupled cluster theory

NASA Astrophysics Data System (ADS)

Gomez, John A.; Henderson, Thomas M.; Scuseria, Gustavo E.

2017-11-01

In electronic structure theory, restricted single-reference coupled cluster (CC) captures weak correlation but fails catastrophically under strong correlation. Spin-projected unrestricted Hartree-Fock (SUHF), on the other hand, misses weak correlation but captures a large portion of strong correlation. The theoretical description of many important processes, e.g. molecular dissociation, requires a method capable of accurately capturing both weak and strong correlation simultaneously, and would likely benefit from a combined CC-SUHF approach. Based on what we have recently learned about SUHF written as particle-hole excitations out of a symmetry-adapted reference determinant, we here propose a heuristic CC doubles model to attenuate the dominant spin collective channel of the quadratic terms in the CC equations. Proof of principle results presented here are encouraging and point to several paths forward for improving the method further.

Omega Design and FEA Based Coriolis Mass Flow Sensor (CMFS) Analysis Using Titanium Material

NASA Astrophysics Data System (ADS)

Patil, Pravin P.; Kumar, Ashwani; Ahmad, Faraz

2018-02-01

The main highlight of this research work is evaluation of resonant frequency for titanium omega type coriolis mass flow sensor. Coriolis mass flow sensor is used for measuring direct mass flow in pipe useful for various industrial applications. It works on the principle of Coriolis effect. Finite Element Analysis (FEA) simulation of omega flow sensor was performed using Ansys 14.5 and Solid Edge, Pro-E was used for modelling of omega tube. Titanium was selected as omega tube material. Experimental setup was prepared for omega tube coriolis flow sensor for performing different test. Experimental setup was used for investigation of different parameters effect on CMFS and validation of simulation results.

The - - and Submm-Wave Spectrum of Allyl Isocyanide and Radioastronomical Observations in Orion KL and the Primos Line Survey

NASA Astrophysics Data System (ADS)

Haykal, I.; Motiyenko, R. A.; Margules, L.; Huet, T. R.; Ecija, P.; Cocinero, E. J.; Basterretxea, F.; Fernandez, J. A.; Castano, F.; Tercero, B.; Cernicharo, J.; Lesarri, A.; Guillemin, J. C.

2013-06-01

Last year we presented the first rotational analysis of the ground state of the two conformers of allyl isocyanide from 4 GHz to 905 GHz. The analysis of the rotational spectrum of the cis conformer of allyl isocyanide was extended. We resolved Coriolis interactions of a and b types between the excited vibrational states ν_1=1 and ν_2=1, calculated to be at 156 cm^{-1} (A^{'}) and 167 cm^{-1} (A^{''}) respectively (MP2/aug-cc-pvtz), from 150 GHz to 600 GHz. Strong perturbations were observed in the 150-310 GHz range for low values of the quantum number K_a starting from K_a = 0, 1. The anharmonicities appeared as well at higher frequencies for larger quantum numbers. The two modes were fitted together with the SPFIT/SPCAT suite of programs and a set of Coriolis parameters was accurately determined. The fit contains more than 3000 lines up to J = 99 and K_a = 12 for both modes. We did not detect these species neither in the IRAM 30-m line survey of Orion KL nor in the PRIMOS survey towards SgrB2. Nevertheless, we provided upper limits to their column density in Orion KL. This work was supported by the CNES and the Action sur Projets de l'INSU, PCMI. I. Haykal et al. manuscript in preparation H. Pickett J. Mol. Spec.{148}, 371-377, 1991.

Estimation of Coriolis Force and Torque Acting on Ares-1

NASA Technical Reports Server (NTRS)

Mackey, Ryan M.; Kulikov, Igor K.; Smelyanskiy, Vadim; Luchinsky, Dmitry; Orr, Jeb

2011-01-01

A document describes work on the origin of Coriolis force and estimating Coriolis force and torque applied to the Ares-1 vehicle during its ascent, based on an internal ballistics model for a multi-segmented solid rocket booster (SRB).

Assessing the distinguishable cluster approximation based on the triple bond-breaking in the nitrogen molecule

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

Rishi, Varun; Perera, Ajith; Bartlett, Rodney J., E-mail: bartlett@qtp.ufl.edu

2016-03-28

Obtaining the correct potential energy curves for the dissociation of multiple bonds is a challenging problem for ab initio methods which are affected by the choice of a spin-restricted reference function. Coupled cluster (CC) methods such as CCSD (coupled cluster singles and doubles model) and CCSD(T) (CCSD + perturbative triples) correctly predict the geometry and properties at equilibrium but the process of bond dissociation, particularly when more than one bond is simultaneously broken, is much more complicated. New modifications of CC theory suggest that the deleterious role of the reference function can be diminished, provided a particular subset of termsmore » is retained in the CC equations. The Distinguishable Cluster (DC) approach of Kats and Manby [J. Chem. Phys. 139, 021102 (2013)], seemingly overcomes the deficiencies for some bond-dissociation problems and might be of use in quasi-degenerate situations in general. DC along with other approximate coupled cluster methods such as ACCD (approximate coupled cluster doubles), ACP-D45, ACP-D14, 2CC, and pCCSD(α, β) (all defined in text) falls under a category of methods that are basically obtained by the deletion of some quadratic terms in the double excitation amplitude equation for CCD/CCSD (coupled cluster doubles model/coupled cluster singles and doubles model). Here these approximate methods, particularly those based on the DC approach, are studied in detail for the nitrogen molecule bond-breaking. The N{sub 2} problem is further addressed with conventional single reference methods but based on spatial symmetry-broken restricted Hartree–Fock (HF) solutions to assess the use of these references for correlated calculations in the situation where CC methods using fully symmetry adapted SCF solutions fail. The distinguishable cluster method is generalized: 1) to different orbitals for different spins (unrestricted HF based DCD and DCSD), 2) by adding triples correction perturbatively (DCSD(T)) and iteratively (DCSDT-n), and 3) via an excited state approximation through the equation of motion (EOM) approach (EOM-DCD, EOM-DCSD). The EOM-CC method is used to identify lower-energy CC solutions to overcome singularities in the CC potential energy curves. It is also shown that UHF based CC and DC methods behave very similarly in bond-breaking of N{sub 2}, and that using spatially broken but spin preserving SCF references makes the CCSD solutions better than those for DCSD.« less

MkMRCC, APUCC and APUBD approaches to 1,n-didehydropolyene diradicals: the nature of through-bond exchange interactions

NASA Astrophysics Data System (ADS)

Nishihara, Satomichi; Saito, Toru; Yamanaka, Shusuke; Kitagawa, Yasutaka; Kawakami, Takashi; Okumura, Mitsutaka; Yamaguchi, Kizashi

2010-10-01

Mukherjee-type (Mk) state specific (SS) multi-reference (MR) coupled-cluster (CC) calculations of 1,n-didehydropolyene diradicals were carried out to elucidate singlet-triplet energy gaps via through-bond coupling between terminal radicals. Spin-unrestricted Hartree-Fock (UHF) based coupled-cluster (CC) computations of these diradicals were also performed. Comparison between symmetry-adapted MkMRCC and broken-symmetry (BS) UHF-CC computational results indicated that spin-contamination error of UHF-CC solutions was left at the SD level, although it had been thought that this error was negligible for the CC scheme in general. In order to eliminate the spin contamination error, approximate spin-projection (AP) scheme was applied for UCC, and the AP procedure indeed eliminated the error to yield good agreement with MRCC in energy. The CCD with spin-unrestricted Brueckner's orbital (UB) was also employed for these polyene diradicals, showing that large spin-contamination errors at UHF solutions are dramatically improved, and therefore AP scheme for UBD removed easily the rest of spin-contaminations. Pure- and hybrid-density functional theory (DFT) calculations of the species were also performed. Three different computational schemes for total spin angular momentums were examined for the AP correction of the hybrid DFT. The AP DFT calculations yielded the singlet-triplet energy gaps that were in good agreement with those of MRCC, AP UHF-CC and AP UB-CC. Chemical indices such as the diradical character were calculated with all these methods. Implications of the present computational results are discussed in relation to previous RMRCC calculations of diradical species and BS calculations of large exchange coupled systems.

Adaptation to vestibular disorientation. VIII, "Coriolis" vestibular stimulation and the influence of different visual surrounds.

DOT National Transportation Integrated Search

1967-08-01

Disorientation caused by 'Coriolis' vestibular reactions has been cited frequently as a significant factor in flying safety. In addition, personnel who maintain rotating radar towers may also be adversely affected by 'Coriolis' problems. In the study...

Rovibrational Constants for the ν 6 and 2ν 9 Bands of HCOOD by Fourier Transform Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Tan, T. L.; Goh, K. L.; Ong, P. P.; Teo, H. H.

1999-11-01

The Fourier transform infrared spectrum of the ν6 and 2ν9 bands of deuterated formic acid (HCOOD) was recorded with an apodized resolution of 0.004 cm-1 in the frequency range of 930-1040 cm-1. These two bands with band centers 40 cm-1 apart were mutually coupled by Coriolis and Fermi interactions. By fitting a total of 1076 infrared transitions of both ν6 and 2ν9 with a standard deviation of 0.00075 cm-1 using a Watson's A-reduced Hamiltonian in the Ir representation with the inclusion of c-type Coriolis and a Fermi-resonance term, two sets of rovibrational constants for v6 = 1, and v9 = 2 states were derived for the first time. Both ν6 and 2ν9 bands are A type with band centers at 972.8520 ± 0.0001 and 1011.6766 ± 0.0001 cm-1, respectively.

Approximate Stokes Drift Profiles and their use in Ocean Modelling

NASA Astrophysics Data System (ADS)

Breivik, O.; Biblot, J.; Janssen, P. A. E. M.

2016-02-01

Deep-water approximations to the Stokes drift velocity profile are explored as alternatives to the monochromatic profile. The alternative profiles investigated rely on the same two quantities required for the monochromatic profile, viz the Stokes transport and the surface Stokes drift velocity. Comparisons with parametric spectra and profiles under wave spectra from the ERA-Interim reanalysis and buoy observations reveal much better agreement than the monochromatic profile even for complex sea states. That the profiles give a closer match and a more correct shear has implications for ocean circulation models since the Coriolis-Stokes force depends on the magnitude and direction of the Stokes drift profile and Langmuir turbulence parameterizations depend sensitively on the shear of the profile. The NEMO general circulation ocean model was recently extended to incorporate the Stokes-Coriolis force along with two other wave-related effects. I will show some results from the coupled atmosphere-wave-ocean ensemble forecast system of ECMWF where these wave effects are now included in the ocean model component.

The US Navy Coupled Ocean-Wave Prediction System

DTIC Science & Technology

2014-09-01

Stokes drift to be the dominant wave effect and that it increased surface drift speeds by 35% and veered the current in the direction of the wind...ocean model has been modified to incorporate the effect of the Stokes drift current, wave radiation stresses due to horizontal gradients of the momentum...for fourth-order differences for horizontal baroclinic pressure gradients and for interpolation of Coriolis terms. There is an option to use the

Properties of coupled-cluster equations originating in excitation sub-algebras

NASA Astrophysics Data System (ADS)

Kowalski, Karol

2018-03-01

In this paper, we discuss properties of single-reference coupled cluster (CC) equations associated with the existence of sub-algebras of excitations that allow one to represent CC equations in a hybrid fashion where the cluster amplitudes associated with these sub-algebras can be obtained by solving the corresponding eigenvalue problem. For closed-shell formulations analyzed in this paper, the hybrid representation of CC equations provides a natural way for extending active-space and seniority number concepts to provide an accurate description of electron correlation effects. Moreover, a new representation can be utilized to re-define iterative algorithms used to solve CC equations, especially for tough cases defined by the presence of strong static and dynamical correlation effects. We will also explore invariance properties associated with excitation sub-algebras to define a new class of CC approximations referred to in this paper as the sub-algebra-flow-based CC methods. We illustrate the performance of these methods on the example of ground- and excited-state calculations for commonly used small benchmark systems.

Measurement of Coriolis Acceleration with a Smartphone

ERIC Educational Resources Information Center

Shaku, Asif; Kraft, Jakob

2016-01-01

Undergraduate physics laboratories seldom have experiments that measure the Coriolis acceleration. This has traditionally been the case owing to the inherent complexities of making such measurements. Articles on the experimental determination of the Coriolis acceleration are few and far between in the physics literature. However, because modern…

Integrability of the coupled cubic-quintic complex Ginzburg-Landau equations and multiple-soliton solutions via mathematical methods

NASA Astrophysics Data System (ADS)

Selima, Ehab S.; Seadawy, Aly R.; Yao, Xiaohua; Essa, F. A.

2018-02-01

This paper is devoted to study the (1+1)-dimensional coupled cubic-quintic complex Ginzburg-Landau equations (cc-qcGLEs) with complex coefficients. This equation can be used to describe the nonlinear evolution of slowly varying envelopes of periodic spatial-temporal patterns in a convective binary fluid. Dispersion relation and properties of cc-qcGLEs are constructed. Painlevé analysis is used to check the integrability of cc-qcGLEs and to establish the Bäcklund transformation form. New traveling wave solutions and a general form of multiple-soliton solutions of cc-qcGLEs are obtained via the Bäcklund transformation and simplest equation method with Bernoulli, Riccati and Burgers’ equations as simplest equations.

Corneal coupling of astigmatism applied to incisional and ablative surgery.

PubMed

Alpins, Noel; Ong, James K Y; Stamatelatos, George

2014-11-01

To redefine measures of corneal coupling for use with incisional and ablation procedures for astigmatism. Private clinics, Melbourne, Victoria, Australia. Retrospective nonrandomized study. The measures known as the coupling ratio (CR) and coupling constant (CC) were redefined to ensure validity in most cases of incisional procedures and laser vision correction procedures. In addition, a new measure--the coupling adjustment (CAdj)--was developed to quantify the amount of spherical adjustment that must be applied to compensate for coupling that occurs as a result of astigmatism treatment. These quantitative measures of coupling were applied to retrospective data to show their applicability. Pure myopic, compound myopic, and compound hyperopic astigmatism excimer laser treatments showed a CR close to zero, a CC close to 0.5, and a CAdj close to zero. Incision LRIs showed a CR close to 1.0 and a CC close to zero. In all cases, the coupling measures were consistent for treatments with a larger astigmatic component (>1.0 diopter) but variable when the astigmatic component of the treatment was smaller. The revised definitions of CR and CC can be used with incisional and ablative surgery. Incorporating the CAdj into the planning of spherocylindrical treatments allows one to factor in the effect of the astigmatic treatment on the spherical component and thus to more accurately target the desired spherical equivalent. Dr. Alpins and Mr. Stamatelatos have a financial interest in the Assort software program. Dr. Ong is an employee of Assort. Copyright © 2014 ASCRS and ESCRS. Published by Elsevier Inc. All rights reserved.

Determinants of Motion Sickness in Tilting Trains: Coriolis/Cross-Coupling Stimuli and Tilt Delay

PubMed Central

Bertolini, Giovanni; Durmaz, Meek Angela; Ferrari, Kim; Küffer, Alexander; Lambert, Charlotte; Straumann, Dominik

2017-01-01

Faster trains require tilting of the cars to counterbalance the centrifugal forces during curves. Motion sensitive passengers, however, complain of discomfort and overt motion sickness. A recent study comparing different control systems in a tilting train, suggested that the delay of car tilts relative to the curve of the track contributes to motion sickness. Other aspects of the motion stimuli, like the lateral accelerations and the car jitters, differed between the tested conditions and prevented a final conclusion on the role of tilt delay. Nineteen subjects were tested on a motorized 3D turntable that simulated the roll tilts during yaw rotations experienced on a tilting train, isolating them from other motion components. Each session was composed of two consecutive series of 12 ideal curves that were defined on the bases of recordings during an actual train ride. The simulated car tilts started either at the beginning of the curve acceleration phase (no-delay condition) or with 3 s of delay (delay condition). Motion sickness was self-assessed by each subject at the end of each series using an analog motion sickness scale. All subjects were tested in both conditions. Significant increases of motion sickness occurred after the first sequence of 12 curves in the delay condition, but not in the no-delay condition. This increase correlated with the sensitivity of motion sickness, which was self-assessed by each subject before the experiment. The second sequence of curve did not lead to a significant further increase of motion sickness in any condition. Our results demonstrate that, even if the speed and amplitude are as low as those experienced on tilting trains, a series of roll tilts with a delay relative to the horizontal rotations, isolated from other motion stimuli occurring during a travel, generate Coriolis/cross-coupling stimulations sufficient to rapidly induce motion sickness in sensitive individuals. The strength and the rapid onset of the motion sickness reported confirm that, even if the angular velocity involved are low, the Coriolis/cross-coupling resulting from the delay is a major factor in causing sickness that can be resolved by improving the tilt timing relative to the horizontal rotation originating from the curve. PMID:28555125

C-C cross-coupling of primary and secondary benzylic alcohols using supported gold-based bimetallic catalysts.

PubMed

Liu, Xiang; Ding, Ran-Sheng; He, Lin; Liu, Yong-Mei; Cao, Yong; He, He-Yong; Fan, Kang-Nian

2013-04-01

Clean alcohol-alcohol cross-coupling: A clean and efficient one-pot direct C-C cross-coupling of equimolar amounts of primary and secondary alcohols by a facile hydrogen autotransfer pathway is achieved over a robust and easily recovered hydrotalcite-supported Au-Pd bimetallic catalyst system. A variety of primary and secondary alcohols have been selectively converted into the corresponding β-alkylated ketones in good yields. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Validation Studies for CHRISTINE-CC Using a Ka-Band Coupled-Cavity TWT

DTIC Science & Technology

2006-04-01

Cavity TWT for 29-31 GHz Figure 3: Output power vs. input power at f=30.0 Communications Systems," I Ith Ka and Broadband GHz for the VTA-6430A1 Ka...Coupled-Cavity TWT DISTRIBUTION: Approved for public release, distribution unlimited This paper is part of the following report: TITLE: 2006 IEEE...Studies for CHRISTINE-CC Using a Ka-Band Coupled-Cavity TWT * D. Chernin, D. Dialetis, T. M. Antonsen, Jr.t, Science Applications International Corp McLean

An Investigation on Ground Electrodes of Capacitive Coupling Human Body Communication.

PubMed

Mao, Jingna; Yang, Huazhong; Zhao, Bo

2017-08-01

Utilizing the body surface as the signal transmission medium, capacitive coupling human body communication (CC-HBC) can achieve a much higher energy efficiency than conventional wireless communications in future wireless body area network (WBAN) applications. Under the CC-HBC scheme, the body surface serves as the forward signal path, whereas the backward path is formed by the capacitive coupling between the ground electrodes (GEs) of transmitter (TX) and receiver (RX). So the type of communication benefits from a low forward loss, while the backward loss depending on the GE coupling strength dominates the total transmission loss. However, none of the previous works have shown a complete research on the effects of GEs. In this paper, all kinds of GE effects on CC-HBC are investigated by both finite element method (FEM) analysis and human body measurement. We set the TX GE and RX GE at different heights, separation distances, and dimensions to study the corresponding influence on the overall signal transmission path loss. In addition, we also investigate the effects of GEs with different shapes and different TX-to-RX relative angles. Based on all the investigations, an analytical model is derived to evaluate the GE related variations of channel loss in CC-HBC.

Closed Loop Adaptive Refinement of Dynamical Models for Complex Chemical Reactions

DTIC Science & Technology

2008-06-26

rotational energy Erot , bond length, or bond angle of the products, the corresponding RS-HDMR component functions, cf. eq. (??), can be constructed from a...rotational energy ∆ Erot , and (3) the H2O vibrational energy ∆Evib. The usually strong Coriolis coupling, for example, between H2O rotational and...averaged vibrational energy) is usually considered after the collision. On the other hand, the corresponding internal energy Eint = Evib+ Erot will remain

Detection of cerebral oxyhaemoglobin changes during vestibular Coriolis cross-coupling stimulation using near infrared spectroscopy.

PubMed

Kobayashi, A; Cheung, B

2006-02-13

Near infrared spectroscopy (NIRS) has been successful in monitoring cerebral haemodynamics when the subject is immobilized during surgery, and when there is a drastic depletion of blood from the cerebral cortex during positive acceleration. In this study, we monitored subtle changes of cerebral oxygen level using NIRS during vestibular stimulation. For the control conditions, cerebral oxygen status was monitored in six stationary subjects sitting upright, and while they executed head movements in the pitch axis with eyes opened and eyes closed. The experimental conditions involved the subjects making a head movement which required a 45 degrees pitch-down followed by a return to upright head movements 12 s later during yaw rotation (Coriolis cross coupling) at 10 and 20 rotations per minute (rpm) in a random order. Oxyhaemoglobin (O(2)Hb), deoxyhaemoglobin (HHb) and total haemoglobin levels were recorded every 0.5 s from both the parietal and the occipital lobe simultaneously. A significant rotation effect was observed in total Hb level changes from baseline in both regions. Occipital O(2)Hb increased significantly after the head movement with eyes opened at 20 rpm. Our findings appear to be consistent with previous vestibular studies that significant changes in brain blood flow occur during caloric stimulation. NIRS can be used to monitor discrete cortical blood flow changes resulting from vestibular and other forms of stimulation.

Stability of gravito-coupled complex gyratory astrofluids

NASA Astrophysics Data System (ADS)

Kumar Karmakar, Pralay; Das, Papari

2017-07-01

We analyze the gravitational instability of complex rotating astrofluids in the presence of dynamic role of dark matter in a homogeneous hydrostatic equilibrium framework. The effects of the lowest-order fluid viscoelasticity, Coriolis force, fluid turbulence and inter-layer frictional coupling dynamics are concurrently considered in spatially-flat geometry. The Coriolis rotation is relative to the center of the entire fluid mass distribution, contributed by both the gyratory bright (visible) and dark (invisible) sectors, conjugated via the mutual gravitational interaction. The turbulence effects are included via the modified Larson equation of state. We use a regular Fourier-based linear perturbation analysis over the rotating fluid field equations to obtain a unique form of quartic dispersion relation with variable coefficients. We numerically carry out the dispersion analysis in two extreme limits: hydrodynamic (low-frequency) and kinetic (high-frequency) regimes. It is demonstrated that, in the former regime, the gas as well as dark matter rotations have stabilizing effects on the Jeans instability of the bi-fluidic admixture. In contrast, in the latter, the rotations play destabilizing roles on the instability. An interesting feature noted here is that the magnitude of the group velocity of the fluctuations throughout increases with both the gas and dark matter rotation frequencies, and vice-versa. We, finally, hope that the obtained results could be helpful in understanding the top-down kinetic mechanisms of bounded structure formation via gravitational collapse dynamics.

Debunking Coriolis Force Myths

ERIC Educational Resources Information Center

Shakur, Asif

2014-01-01

Much has been written and debated about the Coriolis force. Unfortunately, this has done little to demystify the paradoxes surrounding this fictitious force invoked by an observer in a rotating frame of reference. It is the purpose of this article to make another valiant attempt to slay the dragon of the Coriolis force! This will be done without…

Coupled-cluster Green's function: Analysis of properties originating in the exponential parametrization of the ground-state wave function

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

Peng, Bo; Kowalski, Karol

In this paper we derive basic properties of the Green’s function matrix elements stemming from the exponential coupled cluster (CC) parametrization of the ground-state wave function. We demon- strate that all intermediates used to express retarded (or equivalently, ionized) part of the Green’s function in the ω-representation can be expressed through connected diagrams only. Similar proper- ties are also shared by the first order ω-derivatives of the retarded part of the CC Green’s function. This property can be extended to any order ω-derivatives of the Green’s function. Through the Dyson equation of CC Green’s function, the derivatives of corresponding CCmore » self-energy can be evaluated analytically. In analogy to the CC Green’s function, the corresponding CC self-energy is expressed in terms of connected diagrams only. Moreover, the ionized part of the CC Green’s func- tion satisfies the non-homogeneous linear system of ordinary differential equations, whose solution may be represented in the exponential form. Our analysis can be easily generalized to the advanced part of the CC Green’s function.« less

Nested variant of the method of moments of coupled cluster equations for vertical excitation energies and excited-state potential energy surfaces.

PubMed

Kowalski, Karol

2009-05-21

In this article we discuss the problem of proper balancing of the noniterative corrections to the ground- and excited-state energies obtained with approximate coupled cluster (CC) and equation-of-motion CC (EOMCC) approaches. It is demonstrated that for a class of excited states dominated by single excitations and for states with medium doubly excited component, the newly introduced nested variant of the method of moments of CC equations provides mathematically rigorous way of balancing the ground- and excited-state correlation effects. The resulting noniterative methodology accounting for the effect of triples is tested using its parallel implementation on the systems, for which iterative CC/EOMCC calculations with full inclusion of triply excited configurations or their most important subset are numerically feasible.

Ab Initio and Improved Empirical Potentials for the Calculation of the Anharmonic Vibrational States and Intramolecular Mode Coupling of N-Methylacetamide

NASA Technical Reports Server (NTRS)

Gregurick, Susan K.; Chaban, Galina M.; Gerber, R. Benny; Kwak, Dochou (Technical Monitor)

2001-01-01

The second-order Moller-Plesset ab initio electronic structure method is used to compute points for the anharmonic mode-coupled potential energy surface of N-methylacetamide (NMA) in the trans(sub ct) configuration, including all degrees of freedom. The vibrational states and the spectroscopy are directly computed from this potential surface using the Correlation Corrected Vibrational Self-Consistent Field (CC-VSCF) method. The results are compared with CC-VSCF calculations using both the standard and improved empirical Amber-like force fields and available low temperature experimental matrix data. Analysis of our calculated spectroscopic results show that: (1) The excellent agreement between the ab initio CC-VSCF calculated frequencies and the experimental data suggest that the computed anharmonic potentials for N-methylacetamide are of a very high quality; (2) For most transitions, the vibrational frequencies obtained from the ab initio CC-VSCF method are superior to those obtained using the empirical CC-VSCF methods, when compared with experimental data. However, the improved empirical force field yields better agreement with the experimental frequencies as compared with a standard AMBER-type force field; (3) The empirical force field in particular overestimates anharmonic couplings for the amide-2 mode, the methyl asymmetric bending modes, the out-of-plane methyl bending modes, and the methyl distortions; (4) Disagreement between the ab initio and empirical anharmonic couplings is greater than the disagreement between the frequencies, and thus the anharmonic part of the empirical potential seems to be less accurate than the harmonic contribution;and (5) Both the empirical and ab initio CC-VSCF calculations predict a negligible anharmonic coupling between the amide-1 and other internal modes. The implication of this is that the intramolecular energy flow between the amide-1 and the other internal modes may be smaller than anticipated. These results may have important implications for the anharmonic force fields of peptides, for which N-methylacetamide is a model.

Reductive Elimination Leading to C-C Bond Formation in Gold(III) Complexes: A Mechanistic and Computational Study.

PubMed

Rocchigiani, Luca; Fernandez-Cestau, Julio; Budzelaar, Peter H M; Bochmann, Manfred

2018-06-21

The factors affecting the rates of reductive C-C cross-coupling reactions in gold(III) aryls were studied by using complexes that allow easy access to a series of electronically modified aryl ligands, as well as to gold methyl and vinyl complexes, by using the pincer compounds [(C^N^C)AuR] (R=C 6 F 5 , CH=CMe 2 , Me and p-C 6 H 4 X, where X=OMe, F, H, tBu, Cl, CF 3 , or NO 2 ) as starting materials (C^N^C=2,6-(4'-tBuC 6 H 3 ) 2 pyridine dianion). Protodeauration followed by addition of one equivalent SMe 2 leads to the quantitative generation of the thioether complexes [(C^N-CH)AuR(SMe 2 )] + . Upon addition of a second SMe 2 pyridine is displaced, which triggers the reductive aryl-R elimination. The rates for these cross-couplings increase in the sequence k(vinyl)>k(aryl)≫k(C 6 F 5 )>k(Me). Vinyl-aryl coupling is particularly fast, 1.15×10 -3  L mol -1  s -1 at 221 K, whereas both C 6 F 5 and Me couplings encountered higher barriers for the C-C bond forming step. The use of P(p-tol) 3 in place of SMe 2 greatly accelerates the C-C couplings. Computational modelling shows that in the C^N-bonded compounds displacement of N by a donor L is required before the aryl ligands can adopt a conformation suitable for C-C bond formation, so that elimination takes place from a four-coordinate intermediate. The C-C bond formation is the rate-limiting step. In the non-chelating case, reductive C(sp 2 )-C(sp 2 ) elimination from three-coordinate ions [(Ar 1 )(Ar 2 )AuL] + is almost barrier-free, particularly if L=phosphine. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface Structure of Bi(111) from Helium Atom Scattering Measurements. Inelastic Close-Coupling Formalism

PubMed Central

2015-01-01

Elastic and inelastic close-coupling (CC) calculations have been used to extract information about the corrugation amplitude and the surface vibrational atomic displacement by fitting to several experimental diffraction patterns. To model the three-dimensional interaction between the He atom and the Bi(111) surface under investigation, a corrugated Morse potential has been assumed. Two different types of calculations are used to obtain theoretical diffraction intensities at three surface temperatures along the two symmetry directions. Type one consists of solving the elastic CC (eCC) and attenuating the corresponding diffraction intensities by a global Debye–Waller (DW) factor. The second one, within a unitary theory, is derived from merely solving the inelastic CC (iCC) equations, where no DW factor is necessary to include. While both methods arrive at similar predictions for the peak-to-peak corrugation value, the variance of the value obtained by the iCC method is much better. Furthermore, the more extensive calculation is better suited to model the temperature induced signal asymmetries and renders the inclusion for a second Debye temperature for the diffraction peaks futile. PMID:26257838

The Coriolis field

NASA Astrophysics Data System (ADS)

Costa, L. Filipe; Natário, José

2016-05-01

We present a pedagogical discussion of the Coriolis field, emphasizing its not-so-well-understood aspects. We show that this field satisfies the field equations of the so-called Newton-Cartan theory, a generalization of Newtonian gravity that is covariant under changes of arbitrarily rotating and accelerated frames. Examples of solutions of this theory are given, including the Newtonian analogue of the Gödel universe. We discuss how to detect the Coriolis field by its effect on gyroscopes, of which the gyrocompass is an example. Finally, using a similar framework, we discuss the Coriolis field generated by mass currents in general relativity, and its measurement by the gravity probe B and LAGEOS/LARES experiments.

Non-Adiabatic Atomic Transitions: Computational Cross Section Calculations of Alkali Metal-Noble Gas Collisions

DTIC Science & Technology

2011-09-01

there a one time transfer of prob- ability between Coriolis coupled states. One possible way to answer this question would be to literally create and... time -dependent numerical algorithm was developed using FORTRAN 90 to predict S-Matrix elements for alkali metal - noble gas (MNg) collisions. The...committee and the physics department for their time and effort to see me through the completion of my doctorate degree. Charlton D. Lewis, II v Table of

Coupled-cavity surface-emitting lasers: spectral and polarization threshold characteristics and electrooptic switching.

PubMed

Panajotov, Krassimir P; Zujewski, Mateusz; Thienpont, Hugo

2010-12-20

We study spectral and polarization threshold characteristics of coupled-cavity Vertical-Surface-Emitting Lasers (CC-VCSEL) on the base of a simple matrix approach. We show that strong wavelength discrimination can be achieved in CC-VCSELs by slightly detuning the cavities. However, polarization discrimination is not provided by the coupled-cavity design. We also consider the case of reverse-biasing one of the cavities, i.e. using it as a modulator via linear and/or quadratic electrooptic effect. Such a CC-VCSEL can act as a voltage-controlled polarization or wavelength switching device that is decoupled from the laser design and can be optimized for high modulation speed. We also show that using QD stack instead of quantum wells in the top cavity would lead to significant reduction of the driving electrical field.

Dynamics of the G-excess illusion

NASA Technical Reports Server (NTRS)

Baylor, K. A.; Reschke, M.; Guedry, F. E.; Mcgrath, B. J.; Rupert, A. H.

1992-01-01

The G-excess illusion is increasingly recognized as a cause of aviation mishaps especially when pilots perform high-speed, steeply banked turns at low altitudes. Centrifuge studies of this illusion have examined the perception of subject orientation and/or target displacement during maintained hypergravity with the subject's head held stationary. The transient illusory perceptions produced by moving the head in hypergravity are difficult to study onboard centrifuges because the high angular velocity ensures the presence of strong Coriolis cross-coupled semicircular canal effects that mask immediate transient otolith-organ effects. The present study reports perceptions following head movements in hypergravity produced by high-speed aircraft maintaining a banked attitude with low angular velocity to minimize cross-coupled effects. Methods: Fourteen subjects flew on the NASA KC-135 and were exposed to resultant gravity forces of 1.3, 1.5, and 1.8 G for 3 minute periods. On command, seated subjects made controlled head movements in roll, pitch, and yaw at 30 second intervals both in the dark and with faint targets at a distance of 5 feet. Results: head movement produced transient perception of target displacement and velocity at levels as low as 1.3 G. Reports of target velocity without appropriate corresponding displacement were common. At 1.8 G when yaw head movements were made from a face down position, 4 subjects reported oscillatory rotational target displacement with fast and slow alternating components suggestive of torsional nystagmus. Head movements evoked symptoms of nausea in most subjects, with 2 subjects and 1 observer vomiting. Conclusions: The transient percepts present conflicting signals, which introduced confusion in target and subject orientation. Repeated head movements in hypergravity generate nausea by mechanisms distinct from cross-coupled Coriolis effects.

Rovibrational Analysis of ν 2 and 2ν 5 Bands of DCOOH by High Resolution FTIR Spectroscopy

NASA Astrophysics Data System (ADS)

Tan, T. L.; Goh, K. L.; Ong, P. P.; Teo, H. H.

1999-12-01

The infrared absorption spectrum of the ν2 band of deuterated formic acid (DCOOH) was recorded using a Bomem DA3.002 Fourier transform spectrometer in the wavenumber region 2130-2300 cm-1 with an apodized resolution of 0.004 cm-1. A total of 1024 transitions were assigned to this band which is hybrid type A and B, centered at 2219.6896 ± 0.0002 cm-1. As expected, the ν2 band is coupled to 2ν5 by a c-type Coriolis interaction. Both perturbed and unperturbed transitions were assigned and fitted to give seven rovibrational constants for the ν2 = 1 state with a standard deviation of 0.00094 cm-1 using Watson's A-reduced Hamiltonian in the Ir representation. A c-type Coriolis interaction term between ν2 and 2ν5 was derived from the rovibrational analysis. The ratio of the transition moments, ‖μb/μa‖, was found to be 1.42 ± 0.10 for the hybrid band.

Analysis of the Coriolis Interaction between ν 6 and ν 8 Bands of HCOOH

NASA Astrophysics Data System (ADS)

Tan, T. L.; Goh, K. L.; Ong, P. P.; Teo, H. H.

2000-08-01

The Fourier transform infrared (FTIR) spectrum of the ν6 band of formic acid (HCOOH) has been recorded with a resolution of 0.0024 cm-1 in the spectral range 1050-1160 cm-1. The ν6 band was found to be strongly perturbed by the nearby ν8 band centered at about 1033.5 cm-1. Using a Watson's A-reduced Hamiltonian in the Ir representation, and with the inclusion of a-type Coriolis coupling constant, a simultaneous fit of ν6 and ν8 was performed. A total of 2485 infrared transitions including about 700 perturbed transitions of ν6 and 19 transitions of ν8 was fitted with an rms uncertainty of 0.0006 cm-1. Accurate rovibrational constants up to sextic order for both ν6 and ν8 were obtained. The ν6 band was analyzed to be a type AB hybrid with a band center at 1104.852109 ± 0.000050 cm-1. The band center for ν8 was found to be 1033.4647 ± 0.0021 cm-1.

The menstrual cycle and susceptibility to coriolis-induced sickness.

PubMed

Cheung, B; Heskin, R; Hofer, K; Gagnon, M

2001-01-01

Survey studies on motion sickness susceptibility suggest that females tend to report greater severity in illness and higher incidence of vomiting than males. Menstruation is said to be a contributing factor. A recent study suggested that females were least susceptible to seasickness during ovulation in a "round the world" yacht race. Sixteen subjects (18-36 years old) were exposed to Coriolis cross-coupling stimulation in the laboratory. They were tested once during permenstruation (Day 1-5), ovulation (Day 12-15) and premenstruation (Day 24-28), based on a normalized 28-day cycle, in a randomised design. Physiological measurements of motion sickness included forearm and calf cutaneous blood flow. Subjective evaluation of sickness symptoms was based on Graybiel's diagnostic criteria and Golding's rating method. Our results indicated that under controlled laboratory conditions, different phases of the menstrual cycle appear to have no influence on subjective symptoms of motion sickness or on cutaneous blood flow increase in the forearm and calf. The lack of commonality between the types and levels of hormones that are released during motion sickness and those that are involved in different menstrual phases appears to support our findings.

Far-Infrared Spectroscopy of Syn-Vinyl Alcohol

NASA Astrophysics Data System (ADS)

Raston, Paul; Bunn, Hayley

2016-06-01

Vinyl alcohol has been extensively studied in both the microwave and mid-IR spectral regions, where 9 out of 15 vibrational modes have been identified. Here we present the first far-IR spectrum of vinyl alcohol, collected below 700 wn at the Australian Synchrotron. The high resolution (0.001 wn) spectrum reveals the νb{11} and νb{15} fundamentals of syn-vinyl alcohol at 489 wn and 407 wn, in addition to two hot bands of the νb{15} mode at 369 wn and 323 wn. High J transitions in the R-branch of the νb{15} band were found to be perturbed by an a-axis Coriolis interaction with the nearby νb{11} state. The νb{15} torsional mode of syn-vinyl alcohol was fit using a Watson's A-reduced Hamiltonian to yield rotational, centrifugal distortion, and Coriolis coupling parameters. S. Saito, Chem. Phys. Lett. 42, 3 (1976) M. Rodler et al., J. Am. Chem. Soc. 106, 4029 (1948) Y. Koga et al., J. Mol. Spec. 145, 315 (1991) D-L. Joo et al., J. Mol. Spec. 197, 68 (1999)

Renormalized coupled cluster approaches in the cluster-in-molecule framework: predicting vertical electron binding energies of the anionic water clusters (H2O)(n)(-).

PubMed

Xu, Peng; Gordon, Mark S

2014-09-04

Anionic water clusters are generally considered to be extremely challenging to model using fragmentation approaches due to the diffuse nature of the excess electron distribution. The local correlation coupled cluster (CC) framework cluster-in-molecule (CIM) approach combined with the completely renormalized CR-CC(2,3) method [abbreviated CIM/CR-CC(2,3)] is shown to be a viable alternative for computing the vertical electron binding energies (VEBE). CIM/CR-CC(2,3) with the threshold parameter ζ set to 0.001, as a trade-off between accuracy and computational cost, demonstrates the reliability of predicting the VEBE, with an average percentage error of ∼15% compared to the full ab initio calculation at the same level of theory. The errors are predominantly from the electron correlation energy. The CIM/CR-CC(2,3) approach provides the ease of a black-box type calculation with few threshold parameters to manipulate. The cluster sizes that can be studied by high-level ab initio methods are significantly increased in comparison with full CC calculations. Therefore, the VEBE computed by the CIM/CR-CC(2,3) method can be used as benchmarks for testing model potential approaches in small-to-intermediate-sized water clusters.

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

Yamaguchi, Kizashi; Nishihara, Satomichi; Saito, Toru

First principle calculations of effective exchange integrals (J) in the Heisenberg model for diradical species were performed by both symmetry-adapted (SA) multi-reference (MR) and broken-symmetry (BS) single reference (SR) methods. Mukherjee-type (Mk) state specific (SS) MR coupled-cluster (CC) calculations by the use of natural orbital (NO) references of ROHF, UHF, UDFT and CASSCF solutions were carried out to elucidate J values for di- and poly-radical species. Spin-unrestricted Hartree Fock (UHF) based coupled-cluster (CC) computations were also performed to these species. Comparison between UHF-NO(UNO)-MkMRCC and BS UHF-CC computational results indicated that spin-contamination of UHF-CC solutions still remains at the SD level.more » In order to eliminate the spin contamination, approximate spin-projection (AP) scheme was applied for UCC, and the AP procedure indeed corrected the error to yield good agreement with MkMRCC in energy. The CC double with spin-unrestricted Brueckner's orbital (UBD) was furthermore employed for these species, showing that spin-contamination involved in UHF solutions is largely suppressed, and therefore AP scheme for UBCCD removed easily the rest of spin-contamination. We also performed spin-unrestricted pure- and hybrid-density functional theory (UDFT) calculations of diradical and polyradical species. Three different computational schemes for total spin angular momentums were examined for the AP correction of the hybrid (H) UDFT. HUDFT calculations followed by AP, HUDFT(AP), yielded the S-T gaps that were qualitatively in good agreement with those of MkMRCCSD, UHF-CC(AP) and UB-CC(AP). Thus a systematic comparison among MkMRCCSD, UCC(AP) UBD(AP) and UDFT(AP) was performed concerning with the first principle calculations of J values in di- and poly-radical species. It was found that BS (AP) methods reproduce MkMRCCSD results, indicating their applicability to large exchange coupled systems.« less

[Cumulative effect of Coriolis acceleration on coronary hemodynamics].

PubMed

Lapaev, E V; Bednenko, V S

1985-01-01

Time-course variations in coronary circulation and cardiac output were measured in 29 healthy test subjects who performed tests with a continuous cumulation of Coriolis accelerations and in 12 healthy test subjects who were exposed to Coriolis accelerations combined with acute hypoxia. Adaptive changes in coronary circulation were seen. It is recommended to monitor coronary circulation during vestibulometric tests as part of medical expertise of the flying personnel.

Rotational and Fine Structure of Pseudo-Jahn Molecules with C_1 Symmetry

NASA Astrophysics Data System (ADS)

Liu, Jinjun

2016-06-01

It has been found in our previous works that rotational and fine-structure analysis of spectra involving nearly degenerate electronic states may aid in interpretation and analysis of the vibronic structure, specifically in the case of pseudo-Jahn-Teller (pJT) molecules with C_s symmetry. The spectral analysis of pJT derivatives (isopropoxy and cyclohexoxy of a prototypical JT molecule (the methoxy radical) allowed for quantitative determination of various contributions to the energy separation between the nearly degenerate electronic states, including the relativistic spin-orbit (SO) effect, the electrostatic interaction, and their zero-point energy difference. These states are coupled by SO and Coriolis interactions, which can also be determined accurately in rotational and fine structure analysis. Most recently, the spectroscopic model for rotational analysis of pJT molecules has been extended for analysis of molecules with C_1 symmetry, i.e., no symmetry. This model includes the six independently determinable components of the spin-rotation (SR) tensor and the three components of the SO and Coriolis interactions. It has been employed to simulate and fit high-resolution laser-induced fluorescence (LIF) spectra of jet-cooled alkoxy radicals with C_1 symmetry, including the 2-hexoxy and the 2-pentoxy radicals, as well as previously recorded LIF spectrum of the trans-conformer (defined by its OCCC dihedral angle) of the 2-butoxy radical. Although the LIF spectra can be reproduced by using either the SR constants or SO and Coriolis constants, the latter simulation offers results that are physically more meaningful whereas the SR constants have to be regarded as effective constants. Furthermore, we will review the SO and Coriolis constants of alkoxy radicals that have been investigated, starting from the well-studied methoxy radical (CH_3O). J. Liu, D. Melnik, and T. A. Miller, J. Chem. Phys. 139, 094308 (2013) J. Liu and T. A. Miller, J. Phys. Chem. A 118, 11871-11890 (2014) L. Stakhursky, L. Zu, J. Liu, and T. A. Miller, J. Chem. Phys. 125, 094316 (2006)

Quantum-chemical investigation of the structures and electronic spectra of the nucleic acid bases at the coupled cluster CC2 level.

PubMed

Fleig, Timo; Knecht, Stefan; Hättig, Christof

2007-06-28

We study the ground-state structures and singlet- and triplet-excited states of the nucleic acid bases by applying the coupled cluster model CC2 in combination with a resolution-of-the-identity approximation for electron interaction integrals. Both basis set effects and the influence of dynamic electron correlation on the molecular structures are elucidated; the latter by comparing CC2 with Hartree-Fock and Møller-Plesset perturbation theory to second order. Furthermore, we investigate basis set and electron correlation effects on the vertical excitation energies and compare our highest-level results with experiment and other theoretical approaches. It is shown that small basis sets are insufficient for obtaining accurate results for excited states of these molecules and that the CC2 approach to dynamic electron correlation is a reliable and efficient tool for electronic structure calculations on medium-sized molecules.

Analysis of Delayed Sea Breeze Onset for Fort Ord Prescribed Burning Operations

DTIC Science & Technology

2015-12-01

Gahmberg et al. (2009) provided additional detail to the synoptic flow through the Coriolis effect . All directions are as seen from the sea with...ambient flows left of the offshore direction providing the strongest opposing winds as Coriolis effects provide additional support in the offshore...support the development of the sea breeze due to Coriolis effects , the mesoscale flow at the surface is quite different. The 1600 UTC through 1900

CYP96T1 of Narcissus sp. aff. pseudonarcissus Catalyzes Formation of the Para-Para' C-C Phenol Couple in the Amaryllidaceae Alkaloids

PubMed Central

Kilgore, Matthew B.; Augustin, Megan M.; May, Gregory D.; Crow, John A.; Kutchan, Toni M.

2016-01-01

The Amaryllidaceae alkaloids are a family of amino acid derived alkaloids with many biological activities; examples include haemanthamine, haemanthidine, galanthamine, lycorine, and maritidine. Central to the biosynthesis of the majority of these alkaloids is a C-C phenol-coupling reaction that can have para-para', para-ortho', or ortho-para' regiospecificity. Through comparative transcriptomics of Narcissus sp. aff. pseudonarcissus, Galanthus sp., and Galanthus elwesii we have identified a para-para' C-C phenol coupling cytochrome P450, CYP96T1, capable of forming the products (10bR,4aS)-noroxomaritidine and (10bS,4aR)-noroxomaritidine from 4′-O-methylnorbelladine. CYP96T1 was also shown to catalyzed formation of the para-ortho' phenol coupled product, N-demethylnarwedine, as less than 1% of the total product. CYP96T1 co-expresses with the previously characterized norbelladine 4′-O-methyltransferase. The discovery of CYP96T1 is of special interest because it catalyzes the first major branch in Amaryllidaceae alkaloid biosynthesis. CYP96T1 is also the first phenol-coupling enzyme characterized from a monocot. PMID:26941773

Photo-assisted cyanation of transition metal nitrates coupled with room temperature C-C bond cleavage of acetonitrile.

PubMed

Zou, Shihui; Li, Renhong; Kobayashi, Hisayoshi; Liu, Juanjuan; Fan, Jie

2013-03-07

It is a challenge to use acetonitrile as a cyanating agent because of the difficulty in cleaving its C-CN bond. Herein, we report a mild photo-assisted route to conduct the cyanation of transition metal nitrates using acetonitrile as the cyanating agent coupled with room-temperature C-C bond cleavage. DFT calculations and experimental observations suggest a radical-involved reaction mechanism, which excludes toxicity from free cyanide ions.

Pd loaded amphiphilic COF as catalyst for multi-fold Heck reactions, C-C couplings and CO oxidation

PubMed Central

Mullangi, Dinesh; Nandi, Shyamapada; Shalini, Sorout; Sreedhala, Sheshadri; Vinod, Chathakudath P.; Vaidhyanathan, Ramanathan

2015-01-01

COFs represent a class of polymers with designable crystalline structures capable of interacting with active metal nanoparticles to form excellent heterogeneous catalysts. Many valuable ligands/monomers employed in making coordination/organic polymers are prepared via Heck and C-C couplings. Here, we report an amphiphilic triazine COF and the facile single-step loading of Pd0 nanoparticles into it. An 18–20% nano-Pd loading gives highly active composite working in open air at low concentrations (Conc. Pd(0) <0.05 mol%, average TON 1500) catalyzing simultaneous multiple site Heck couplings and C-C couplings using ‘non-boronic acid’ substrates, and exhibits good recyclability with no sign of catalyst leaching. As an oxidation catalyst, it shows 100% conversion of CO to CO2 at 150 °C with no loss of activity with time and between cycles. Both vapor sorptions and contact angle measurements confirm the amphiphilic character of the COF. DFT-TB studies showed the presence of Pd-triazine and Pd-Schiff bond interactions as being favorable. PMID:26057044

Dynamically Consistent Shallow-Atmosphere Equations with a Complete Coriolis force

NASA Astrophysics Data System (ADS)

Tort, Marine; Dubos, Thomas; Bouchut, François; Zeitlin, Vladimir

2014-05-01

Dynamically Consistent Shallow-Atmosphere Equations with a Complete Coriolis force Marine Tort1, Thomas Dubos1, François Bouchut2 & Vladimir Zeitlin1,3 1 Laboratoire of Dynamical Meteorology, Univ. P. and M. Curie, Ecole Normale Supérieure, and Ecole Polytechnique, FRANCE 2 Université Paris-Est, Laboratoire d'Analyse et de Mathématiques Appliquées, FRANCE 3 Institut Universitaire de France Atmospheric and oceanic motion are usually modeled within the shallow-fluid approximation, which simplifies the 3D spherical geometry. For dynamical consistency, i.e. to ensure conservation laws for potential vorticity, energy and angular momentum, the horizontal component of the Coriolis force is neglected. Here new equation sets combining consistently a simplified shallow-fluid geometry with a complete Coriolis force is presented. The derivation invokes Hamilton's principle of least action with an approximate Lagrangian capturing the small increase with height of the solid-body entrainment velocity due to planetary rotation. A three-dimensional compressible model and a one-layer shallow-water model are obtained. The latter extends previous work done on the f-plane and β-plane. Preliminary numerical results confirm the accuracy of the 3D model within the range of parameters for which the equations are relevant. These new models could be useful to incorporate a full Coriolis force into existing numerical models and to disentangle the effects of the shallow-atmosphere approximation from those of the traditional approximation. Related papers: Tort M., Dubos T., Bouchut F. and Zeitlin V. Consistent shallow-water equations on the rotating sphere with complete Coriolis force and topography. J. Fluid Mech. (under revisions) Tort M. and Dubos T. Dynamically consistent shallow-atmosphere equations with a complete Coriolis force. Q.J.R. Meteorol. Soc. (DOI: 10.1002/qj.2274)

The ν8 band of C2HD3 by high-resolution synchrotron FTIR spectroscopy: Coriolis interactions between the v8 = 1 and v6 = 1 states

NASA Astrophysics Data System (ADS)

Ng, L. L.; Tan, T. L.; Akasyah, Luqman; Wong, Andy; Appadoo, Dominique R. T.; McNaughton, Don

2017-10-01

The synchrotron Fourier transform infrared (FTIR) spectrum of the ν8 band of ethylene-d3 (C2HD3) was measured at an unapodized resolution of 0.00096 cm-1 from 830 to 1010 cm-1. Rovibrational constants up to five quartic terms were derived with improved precision for the v8 = 1 state through the fitting of 1566 unperturbed infrared transitions using the Watson's A-reduced Hamiltonian in the Ir representation with a root-mean-square (rms) deviation of 0.00044 cm-1. For the first time, 446 perturbed IR transitions of the ν8 band were fitted together with the 1566 unperturbed infrared transitions to obtain the a- and b-Coriolis resonance parameters from its interaction with the v6 = 1 state, with an rms deviation of 0.00039 cm-1. The IR lines of the ν6 band were too weak for detection. Three rotational constants, a quartic constant and band center of the v6 = 1 state were also derived for the first time in this work. Ground state rovibrational constants of C2HD3 up to five quartic constants were also derived from a fit of 906 ground state combination differences with an rms deviation of 0.00030 cm-1 from infrared transitions of the present analysis. The ground state rotational constants are in close agreement with theoretically calculated values using the cc-pVTZ basis set at CCSD(T), MP2 and B3LYP levels of theory. Alpha constants determined from the rotational constants of the v8 = 1 state derived from the perturbed IR fit compared favourably with those from anharmonic calculations.

On the restricted four-body problem with the effect of small perturbations in the Coriolis and centrifugal forces

NASA Astrophysics Data System (ADS)

Suraj, Md Sanam; Aggarwal, Rajiv; Arora, Monika

2017-09-01

We have studied the restricted four-body problem (R4BP) with the effect of the small perturbation in the Coriolis and centrifugal forces on the libration points and zero velocity curves (ZVCs). Further, we have supposed that all the primaries are set in an equilateral triangle configuration, moving in the circular orbits around their common centre of mass. We have observed that the effect of the small perturbation in centrifugal force has a substantial effect on the location of libration points but a small perturbation in the Coriolis force has no impact on the location of libration points. But the stability of the libration points is highly influenced by the effect of the small perturbation in the Coriolis force. It is observed that as the Coriolis parameter increases, the libration points become stable. Further, it is found that the effect of the small perturbation in the centrifugal force has a substantial influence on the regions of possible motion. Also, when the effect of small perturbation in the centrifugal force increases the forbidden region decreases; here the motion is not possible for the infinitesimal mass. It is observed when the value of the Jacobian constant decreases, the regions of possible motion increase. In addition, we have also discussed how small perturbations in the Coriolis and centrifugal forces influence the Newton-Raphson basins of convergence.

Effect of direction of head movement on motion sickness caused by Coriolis stimulation.

PubMed

Woodman, P D; Griffin, M J

1997-02-01

During constant speed rotation of the body, head rotation about an axis other than the axis of rotation of the body (i.e., Coriolis is stimulation) induces motion sickness. The position of the body relative to the center of rotation will influence the sickness caused by Coriolis stimulation; the direction of head movement will not affect the sickness caused by Coriolis stimulation. There were 24 seated subjects (12 male, 12 female) who made 30 degrees pitch motions of the head every 30 s while rotating about a vertical axis at 10 r.p.m. on a turntable at two separate locations: a) at the center of rotation; and b) 0.75 m from the center of rotation. After each head movement the subjects gave ratings of motion illness. There was no significant difference between illness 0.75 m from the center of rotation and illness at the center of rotation, or between the illness ratings from male and female subjects. Moving the head up from the horizontal caused significantly fewer increases in ratings of motion illness than moving the head back down to the horizontal. Precise location of the body at the center of rotation is not critical during Coriolis stimulation, but the direction of head movement has a large effect on nausea. An influence of somatosensory information on sickness caused by Coriolis stimulation is suggested.

Nonadiabatic effects in ultracold molecules via anomalous linear and quadratic Zeeman shifts.

PubMed

McGuyer, B H; Osborn, C B; McDonald, M; Reinaudi, G; Skomorowski, W; Moszynski, R; Zelevinsky, T

2013-12-13

Anomalously large linear and quadratic Zeeman shifts are measured for weakly bound ultracold 88Sr2 molecules near the intercombination-line asymptote. Nonadiabatic Coriolis coupling and the nature of long-range molecular potentials explain how this effect arises and scales roughly cubically with the size of the molecule. The linear shifts yield nonadiabatic mixing angles of the molecular states. The quadratic shifts are sensitive to nearby opposite f-parity states and exhibit fourth-order corrections, providing a stringent test of a state-of-the-art ab initio model.

Hydraulic forces on a centrifugal impeller undergoing synchronous whirl

NASA Technical Reports Server (NTRS)

Allaire, P. E.; Sato, C. J.; Branagan, L. A.

1984-01-01

High speed centrifugal rotating machinery with large vibrations caused by aerodynamic forces on impellers was examined. A method to calculate forces in a two dimensional orbiting impeller in an unbounded fluid with nonuniform entering flow was developed. A finite element model of the full impeller is employed to solve the inviscid flow equations. Five forces acting on the impeller are: Coriolis forces, centripetal forces, changes in linear momentum, changes in pressure due to rotation and pressure changes due to linear momentum. Both principal and cross coupled stiffness coefficients are calculated for the impeller.

High Resolution Infrared Studies of the v2, v4 Bands of 34S16O3, Including Both Intensity and Wavenumber Perturbations

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

Barber, Jeffrey B.; Masiello, Tony; Chrysostom, Engelene

2003-06-15

The infrared spectrum of the v2, v4 bending mode region of 34S-substituted sulfur trioxide, 34S16O3, has been recorded at a resolution of 0.0025 cm-1. The v2 and v4 levels are coupled by a Coriolis interaction, yielding significant spectral shifts that have been successfully analyzed to obtain rovibrational constants for the ground state and both fundamentals. Comparisons are made with 32S16O3 parameters and the Bo rotational constant is found to be 0.348 556 04(28) cm-1, only very slightly larger than the corresponding value of 0.348 543 33(5) cm-1 for 32S16O3. Coriolis and l-type resonance interactions between the v2 and v4 levelsmore » produce frequency shifts and strong intensity perturbations in the spectra that are considered for both 34S16O3 and 32S16O3. The resulting analysis yields an average value of+0.62(8) for the dipole derivative ratio (?x/?Q4x) (?z/?Q2) and a positive sign for the product of this ratio with the?y2,4 Coriolis constant, for which experiment gives+0.5940(15) . Ab initio calculations indicate that the signs of?x/?Q4x and?z/?Q2 are both positive and hence?y2,4 is also positive, in agreement with earlier calculations. These signs indicate that the effective charge movement in the xz plane has the same sense of rotation as Q2, Q4x atom motion in this plane that produces a py vibrational angular momentum component, correlated motion that is confirmed by ab initio calculations.« less

The Coriolis Program.

ERIC Educational Resources Information Center

Lissaman, P. B. S.

1979-01-01

Detailed are the history, development, and future objectives of the Coriolis program, a project designed to place large turbine units in the Florida Current that would generate large amounts of electric power. (BT)

Short-term depression of gap junctional coupling in reticular thalamic neurons of absence epileptic rats.

PubMed

Kohmann, Denise; Lüttjohann, Annika; Seidenbecher, Thomas; Coulon, Philippe; Pape, Hans-Christian

2016-10-01

Gap junctional electrical coupling between neurons of the reticular thalamic nucleus (RTN) is critical for hypersynchrony in the thalamo-cortical network. This study investigates the role of electrical coupling in pathological rhythmogenesis in RTN neurons in a rat model of absence epilepsy. Rhythmic activation resulted in a Ca(2+) -dependent short-term depression (STD) of electrical coupling between pairs of RTN neurons in epileptic rats, but not in RTN of a non-epileptic control strain. Pharmacological blockade of gap junctions in RTN in vivo induced a depression of seizure activity. The STD of electrical coupling represents a mechanism of Ca(2+) homeostasis in RTN aimed to counteract excessive synchronization. Neurons in the reticular thalamic nucleus (RTN) are coupled by electrical synapses, which play a major role in regulating synchronous activity. This study investigates electrical coupling in RTN neurons from a rat model of childhood absence epilepsy, genetic absence epilepsy rats from Strasbourg (GAERS), compared with a non-epileptic control (NEC) strain, to assess the impact on pathophysiological rhythmogenesis. Whole-cell recordings were obtained from pairs of RTN neurons of GAERS and NEC in vitro. Coupling was determined by injection of hyperpolarizing current steps in one cell and monitoring evoked voltage responses in both activated and coupled cell. The coupling coefficient (cc) was compared under resting condition, during pharmacological interventions and repeated activation using a series of current injections. The effect of gap junctional coupling on seizure expression was investigated by application of gap junctional blockers into RTN of GAERS in vivo. At resting conditions, cc did not differ between GAERS and NEC. During repeated activation, cc declined in GAERS but not in NEC. This depression in cc was restored within 25 s and was prevented by intracellular presence of BAPTA in the activated but not in the coupled cell. Local application of gap junctional blockers into RTN of GAERS in vivo resulted in a decrease of spike wave discharge (SWD) activity. Repeated activation results in a short-term depression (STD) of gap junctional coupling in RTN neurons of GAERS, depending on intracellular Ca(2+) mechanisms in the activated cell. As blockage of gap junctions in vivo results in a decrease of SWD activity, the STD observed in GAERS is considered a compensatory mechanism, aimed to dampen SWD activity. © 2016 The Authors. The Journal of Physiology © 2016 The Physiological Society.

Biorthogonal moment expansions in coupled-cluster theory: Review of key concepts and merging the renormalized and active-space coupled-cluster methods

NASA Astrophysics Data System (ADS)

Shen, Jun; Piecuch, Piotr

2012-06-01

After reviewing recent progress in the area of the development of coupled-cluster (CC) methods for quasi-degenerate electronic states that are characterized by stronger non-dynamical correlation effects, including new generations of single- and multi-reference approaches that can handle bond breaking and excited states dominated by many-electron transitions, and after discussing the key elements of the left-eigenstate completely renormalized (CR) CC and equation-of-motion (EOM) CC methods, and the underlying biorthogonal method of moments of CC (MMCC) equations [P. Piecuch, M. Włoch, J. Chem. Phys. 123 (2005) 224105; P. Piecuch, M. Włoch, J.R. Gour, A. Kinal, Chem. Phys. Lett. 418 (2006) 467; M. Włoch, M.D. Lodriguito, P. Piecuch, J.R. Gour, Mol. Phys. 104 (2006) 2149], it is argued that it is beneficial to merge the CR-CC/EOMCC and active-space CC/EOMCC [P. Piecuch, Mol. Phys. 108 (2010) 2987, and references therein] theories into a single formalism. In order to accomplish this goal, the biorthogonal MMCC theory, which provides compact many-body expansions for the differences between the full configuration interaction and CC or, in the case of excited states, EOMCC energies, obtained using conventional truncation schemes in the cluster operator T and excitation operator Rμ, is generalized, so that one can correct the CC/EOMCC energies obtained with arbitrary truncations in T and Rμ for the selected many-electron correlation effects of interest. The resulting moment expansions, defining the new, Flexible MMCC (Flex-MMCC) formalism, and the ensuing CC(P; Q) hierarchy, proposed in the present work, enable one to correct energies obtained in the active-space CC and EOMCC calculations, in which one selects higher many-body components of T and Rμ via active orbitals and which recover much of the relevant non-dynamical and some dynamical electron correlation effects in applications involving potential energy surfaces (PESs) along bond breaking coordinates, for the effects of higher-order, primarily dynamical, correlations missing in the active-space CC/EOMCC considerations. The Flex-MMCC corrections to the active-space CC/EOMCC energies are mathematically similar to the non-iterative energy corrections defining the existing left-eigenstate CR-CC and CR-EOMCC methods, such as CR-CC(2, 3) and CR-EOMCC(2, 3). The potential advantages of the Flex-MMCC and CC(P; Q) formalisms are illustrated by describing the initial implementation and numerical tests of the novel CC hybrid scheme, abbreviated as CC(t; 3), in which one corrects the results of the CC calculations with singles, doubles, and active-space triples, termed CCSDt, for the remaining effects due to connected triple excitations that are missing in the CCSDt considerations, but are present in the MMCC-based CR-CC(2, 3) approach. By examining bond breaking in the HF, F2, and F2+ molecules, it is demonstrated that the CC(t; 3) method improves the CCSDt and CR-CC(2, 3) results, providing PESs that agree with those obtained with the full CC theory with singles, doubles, and triples (CCSDT) to within small fractions of a millihartree, at the fraction of the computer costs of the CCSDT calculations. Different strategies for defining active-space triples within the CC(t; 3) scheme and the underlying CCSDt method are discussed. When limited to the ground-state problem, the CC(t; 3) approach can be regarded as an improved and rigorously derived extension of the recently proposed CCSD(T)-h method [J. Shen, E. Xu, Z. Kou, S. Li, J. Chem. Phys. 132 (2010) 114115], in which triples corrections of the CCSD(T) type are replaced by their more robust CR-CC(2, 3)-style analogs.

Western North Pacific Monsoon Depressions: Formation, Structure, and Transition to Tropical Cyclones

DTIC Science & Technology

2015-09-01

of the domain (from over Malaysia and western New Guinea; 115°E–135°E) increased, and due to the Coriolis effect the flow became westerlies that...it gains a more westerly component due to the Coriolis effect . If airstream A has a large southerly cross-equatorial component, it can penetrate far...120°E and 130°E (Figure 7b) where the flow began to turn east due to the Coriolis effect . Subsequently, these trajectories began to turn

First principle calculations of effective exchange integrals: Comparison between SR (BS) and MR computational results

NASA Astrophysics Data System (ADS)

Yamaguchi, Kizashi; Nishihara, Satomichi; Saito, Toru; Yamanaka, Shusuke; Kitagawa, Yasutaka; Kawakami, Takashi; Yamada, Satoru; Isobe, Hiroshi; Okumura, Mitsutaka

2015-01-01

First principle calculations of effective exchange integrals (J) in the Heisenberg model for diradical species were performed by both symmetry-adapted (SA) multi-reference (MR) and broken-symmetry (BS) single reference (SR) methods. Mukherjee-type (Mk) state specific (SS) MR coupled-cluster (CC) calculations by the use of natural orbital (NO) references of ROHF, UHF, UDFT and CASSCF solutions were carried out to elucidate J values for di- and poly-radical species. Spin-unrestricted Hartree Fock (UHF) based coupled-cluster (CC) computations were also performed to these species. Comparison between UHF-NO(UNO)-MkMRCC and BS UHF-CC computational results indicated that spin-contamination of UHF-CC solutions still remains at the SD level. In order to eliminate the spin contamination, approximate spin-projection (AP) scheme was applied for UCC, and the AP procedure indeed corrected the error to yield good agreement with MkMRCC in energy. The CC double with spin-unrestricted Brueckner's orbital (UBD) was furthermore employed for these species, showing that spin-contamination involved in UHF solutions is largely suppressed, and therefore AP scheme for UBCCD removed easily the rest of spin-contamination. We also performed spin-unrestricted pure- and hybrid-density functional theory (UDFT) calculations of diradical and polyradical species. Three different computational schemes for total spin angular momentums were examined for the AP correction of the hybrid (H) UDFT. HUDFT calculations followed by AP, HUDFT(AP), yielded the S-T gaps that were qualitatively in good agreement with those of MkMRCCSD, UHF-CC(AP) and UB-CC(AP). Thus a systematic comparison among MkMRCCSD, UCC(AP) UBD(AP) and UDFT(AP) was performed concerning with the first principle calculations of J values in di- and poly-radical species. It was found that BS (AP) methods reproduce MkMRCCSD results, indicating their applicability to large exchange coupled systems.

On the accuracy of explicitly correlated methods to generate potential energy surfaces for scattering calculations and clustering: application to the HCl-He complex.

PubMed

Ajili, Yosra; Hammami, Kamel; Jaidane, Nejm Eddine; Lanza, Mathieu; Kalugina, Yulia N; Lique, François; Hochlaf, Majdi

2013-07-07

We closely compare the accuracy of multidimensional potential energy surfaces (PESs) generated by the recently developed explicitly correlated coupled cluster (CCSD(T)-F12) methods in connection with the cc-pVXZ-F12 (X = D, T) and aug-cc-pVTZ basis sets and those deduced using the well-established orbital-based coupled cluster techniques employing correlation consistent atomic basis sets (aug-cc-pVXZ, X = T, Q, 5) and extrapolated to the complete basis set (CBS) limit. This work is performed on the benchmark rare gas-hydrogen halide interaction (HCl-He) system. These PESs are then incorporated into quantum close-coupling scattering dynamical calculations in order to check the impact of the accuracy of the PES on the scattering calculations. For this system, we deduced inelastic collisional data including (de-)excitation collisional and pressure broadening cross sections. Our work shows that the CCSD(T)-F12/aug-cc-pVTZ PES describes correctly the repulsive wall, the van der Waals minimum and long range internuclear distances whereas cc-pVXZ-F12 (X = D,T) basis sets are not diffuse enough for that purposes. Interestingly, the collision cross sections deduced from the CCSD(T)-F12/aug-cc-pVTZ PES are in excellent agreement with those obtained with CCSD(T)/CBS methodology. The position of the resonances and the general shape of these cross sections almost coincide. Since the cost of the electronic structure computations is reduced by several orders of magnitude when using CCSD(T)-F12/aug-cc-pVTZ compared to CCSD(T)/CBS methodology, this approach can be recommended as an alternative for generation of PESs of molecular clusters and for the interpretation of accurate scattering experiments as well as for a wide production of collisional data to be included in astrophysical and atmospherical models.

Approximate Stokes Drift Profiles and their use in Ocean Modelling

NASA Astrophysics Data System (ADS)

Breivik, Oyvind; Bidlot, Jea-Raymond; Janssen, Peter A. E. M.; Mogensen, Kristian

2016-04-01

Deep-water approximations to the Stokes drift velocity profile are explored as alternatives to the monochromatic profile. The alternative profiles investigated rely on the same two quantities required for the monochromatic profile, viz the Stokes transport and the surface Stokes drift velocity. Comparisons against parametric spectra and profiles under wave spectra from the ERA-Interim reanalysis and buoy observations reveal much better agreement than the monochromatic profile even for complex sea states. That the profiles give a closer match and a more correct shear has implications for ocean circulation models since the Coriolis-Stokes force depends on the magnitude and direction of the Stokes drift profile and Langmuir turbulence parameterizations depend sensitively on the shear of the profile. Of the two Stokes drift profiles explored here, the profile based on the Phillips spectrum is by far the best. In particular, the shear near the surface is almost identical to that influenced by the f-5 tail of spectral wave models. The NEMO general circulation ocean model was recently extended to incorporate the Stokes-Coriolis force along with two other wave-related effects. The ECWMF coupled atmosphere-wave-ocean ensemble forecast system now includes these wave effects in the ocean model component (NEMO).

Iterative reactions of transient boronic acids enable sequential C-C bond formation

NASA Astrophysics Data System (ADS)

Battilocchio, Claudio; Feist, Florian; Hafner, Andreas; Simon, Meike; Tran, Duc N.; Allwood, Daniel M.; Blakemore, David C.; Ley, Steven V.

2016-04-01

The ability to form multiple carbon-carbon bonds in a controlled sequence and thus rapidly build molecular complexity in an iterative fashion is an important goal in modern chemical synthesis. In recent times, transition-metal-catalysed coupling reactions have dominated in the development of C-C bond forming processes. A desire to reduce the reliance on precious metals and a need to obtain products with very low levels of metal impurities has brought a renewed focus on metal-free coupling processes. Here, we report the in situ preparation of reactive allylic and benzylic boronic acids, obtained by reacting flow-generated diazo compounds with boronic acids, and their application in controlled iterative C-C bond forming reactions is described. Thus far we have shown the formation of up to three C-C bonds in a sequence including the final trapping of a reactive boronic acid species with an aldehyde to generate a range of new chemical structures.

C-C Coupling on Single-Atom-Based Heterogeneous Catalyst.

PubMed

Zhang, Xiaoyan; Sun, Zaicheng; Wang, Bin; Tang, Yu; Nguyen, Luan; Li, Yuting; Tao, Franklin Feng

2018-01-24

Compared to homogeneous catalysis, heterogeneous catalysis allows for ready separation of products from the catalyst and thus reuse of the catalyst. C-C coupling is typically performed on a molecular catalyst which is mixed with reactants in liquid phase during catalysis. This homogeneous mixing at a molecular level in the same phase makes separation of the molecular catalyst extremely challenging and costly. Here we demonstrated that a TiO 2 -based nanoparticle catalyst anchoring singly dispersed Pd atoms (Pd 1 /TiO 2 ) is selective and highly active for more than 10 Sonogashira C-C coupling reactions (R≡CH + R'X → R≡R'; X = Br, I; R' = aryl or vinyl). The coupling between iodobenzene and phenylacetylene on Pd 1 /TiO 2 exhibits a turnover rate of 51.0 diphenylacetylene molecules per anchored Pd atom per minute at 60 °C, with a low apparent activation barrier of 28.9 kJ/mol and no cost of catalyst separation. DFT calculations suggest that the single Pd atom bonded to surface lattice oxygen atoms of TiO 2 acts as a site to dissociatively chemisorb iodobenzene to generate an intermediate phenyl, which then couples with phenylacetylenyl bound to a surface oxygen atom. This coupling of phenyl adsorbed on Pd 1 and phenylacetylenyl bound to O ad of TiO 2 forms the product molecule, diphenylacetylene.

Imbalanced functional link between reward circuits and the cognitive control system in patients with obsessive-compulsive disorder.

PubMed

Xie, Chunming; Ma, Lisha; Jiang, Nan; Huang, Ruyan; Li, Li; Gong, Liang; He, Cancan; Xiao, Chaoyong; Liu, Wen; Xu, Shu; Zhang, Zhijun

2017-08-01

Altered reward processing and cognitive deficits are often observed in patients with obsessive-compulsive disorder (OCD); however, whether the imbalance in activity between reward circuits and the cognitive control (CC) system is associated with compulsive behavior remains unknown. Sixty-eight OCD patients and 33 cognitively normal (CN) healthy subjects participated in this resting-state functional magnetic resonance imaging study. Alterations in the functional connectivity between reward circuits and the CC system were quantitatively assessed and compared between the groups. A Granger causality analysis was used to determine the causal informational influence between and within reward circuits and the CC system across all subjects. OCD patients showed a dichotomous pattern of enhanced functional coupling in their reward circuits and a weakened functional coupling in their CC system when compared to CN subjects. Neural correlates of compulsive behavior were primarily located in the reward circuits and CC system in OCD patients. Importantly, the CC system exerted a reduced interregional causal influence over the reward system in OCD patients relative to its effect in CN subjects. The limitations of this study are that it was a cross-sectional study and the potential effects of environmental and genetic factors were not explored. OCD patients showed an imbalance in the functional link between reward circuits and the CC system at rest. This bias toward a loss of control may define a pathological state in which subjects are more vulnerable to engaging in compulsive behaviors.

The role of satellite directional wave spectra for the improvement of the ocean-waves coupling

NASA Astrophysics Data System (ADS)

Aouf, Lotfi; Hauser, Danièle; Chapron, Bertrand

2017-04-01

Swell waves are well captured by the Synthetic Aperture Radar (SAR) which provides the directional wave spectra for waves roughly larger than 200 m. Since the launch of sentinel-1A and 1B SAR directional wave spectra are available to improve the swell wave forecasting and the coupling processes at the air-sea interface. Moreover next year CFOSAT mission will provide directional wave spectra for waves with wavelengths comprised between 70 to 500 m. This study aims to evaluate the assimilation of SAR and synthetic CFOSAT wave spectra on the coupling between the wave model MFWAM and the ocean model NEMO. Three coupling processes as described in Breivik et al. (2014) of Stokes-Coriolis forcing, the ocean side stress and the turbulence injected by the wave breaking in the ocean mixed layer have been used. a coupling run is performed with and without assimilation of directional wave spectra. the impact of SAR wave data on key parameters such as surface sea temperature, currents and salinity is investigated. Particular attention is carried out for ocean areas with swell dominant wave climate.

A CMOS-MEMS clamped–clamped beam displacement amplifier for resonant switch applications

NASA Astrophysics Data System (ADS)

Liu, Jia-Ren; Lu, Shih-Chuan; Tsai, Chun-Pu; Li, Wei-Chang

2018-06-01

This paper presents a micromechanical clamped–clamped beam (CC-beam) displacement amplifier based on a CMOS-MEMS fabrication process platform. In particular, a 2.0 MHz resonant displacement amplifier composed of two identical CC-beams coupled by a mechanical beam at locations where the two beams have mismatched velocities exhibits a larger displacement, up to 9.96×, on one beam than that of the other. The displacement amplification prevents unwanted input impacting—the structure switches only to the output but not the input—required by resonant switch-based mechanical circuits (Kim et al 2009 22nd IEEE Int. Conf. on Micro Electro Mechanical Systems; Lin et al 2009 15th Int. Conf. on Solid-State Sensors, Actuators, & Microsystems (TRANSDUCERS’09) Li et al 2013 17th Int. Conf. on Solid-State Sensors, Actuators, & Microsystems (TRANSDUCERS’13)). Compared to a single CC-beam displacement amplifier, theory predicts that the displacement amplifying CC-beam array yields a larger overall output displacement for displacement gain beyond 1.13 thanks to the preserved input driving force. A complete analytical model predicts the resultant stiffness and displacement gain of the coupled CC-beam displacement amplifier that match well with finite element analysis (FEA) prediction and measured results.

Shaft flexibility effects on aeroelastic stability of a rotating bladed disk

NASA Technical Reports Server (NTRS)

Khader, Naim; Loewy, Robert

1989-01-01

A comprehensive study of Coriolis forces and shaft flexibility effects on the structural dynamics and aeroelastic stability of a rotating bladed-disk assembly attached to a cantilever, massless, flexible shaft is presented. Analyses were performed for an actual bladed-disk assembly, used as the first stage in the fan of the 'E3' engine. In the structural model, both in-plane and out-of-plane elastic deformation of the bladed-disk assembly were considered relative to their hub, in addition to rigid disk translations and rotations introduced by shaft flexibility. Besides structural coupling between blades (through the flexible disk), additional coupling is introduced through quasisteady aerodynamic loads. Rotational effects are accounted for throughout the work, and some mode shapes for the whole structure are presented at a selected rpm.

Magnetic field effects and waves in complex plasmas

NASA Astrophysics Data System (ADS)

Kählert, Hanno; Melzer, André; Puttscher, Marian; Ott, Torben; Bonitz, Michael

2018-05-01

Magnetic fields can modify the physical properties of a complex plasma in various different ways. Weak magnetic fields in the mT range affect only the electrons while strong fields in the Tesla regime also magnetize the ions. In a rotating dusty plasma, the Coriolis force substitutes the Lorentz force and can be used to create an effective magnetization for the strongly coupled dust particles while leaving electrons and ions unaffected. Here, we present a summary of our recent experimental and theoretical work on magnetized complex plasmas. We discuss the dynamics of dust particles in magnetized discharges, the wave spectra of strongly coupled plasmas, and the excitations in confined plasmas. Contribution to the Topical Issue "Fundamentals of Complex Plasmas", edited by Jürgen Meichsner, Michael Bonitz, Holger Fehske, Alexander Piel.

Equation-of-motion coupled-cluster method for doubly ionized states with spin-orbit coupling.

PubMed

Wang, Zhifan; Hu, Shu; Wang, Fan; Guo, Jingwei

2015-04-14

In this work, we report implementation of the equation-of-motion coupled-cluster method for doubly ionized states (EOM-DIP-CC) with spin-orbit coupling (SOC) using a closed-shell reference. Double ionization potentials (DIPs) are calculated in the space spanned by 2h and 3h1p determinants with the EOM-DIP-CC approach at the CC singles and doubles level (CCSD). Time-reversal symmetry together with spatial symmetry is exploited to reduce computational effort. To circumvent the problem of unstable dianion references when diffuse basis functions are included, nuclear charges are scaled. Effect of this stabilization potential on DIPs is estimated based on results from calculations using a small basis set without diffuse basis functions. DIPs and excitation energies of some low-lying states for a series of open-shell atoms and molecules containing heavy elements with two unpaired electrons have been calculated with the EOM-DIP-CCSD approach. Results show that this approach is able to afford a reliable description on SOC splitting. Furthermore, the EOM-DIP-CCSD approach is shown to provide reasonable excitation energies for systems with a dianion reference when diffuse basis functions are not employed.

Equation-of-motion coupled-cluster method for doubly ionized states with spin-orbit coupling

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

Wang, Zhifan; Hu, Shu; Guo, Jingwei

2015-04-14

In this work, we report implementation of the equation-of-motion coupled-cluster method for doubly ionized states (EOM-DIP-CC) with spin-orbit coupling (SOC) using a closed-shell reference. Double ionization potentials (DIPs) are calculated in the space spanned by 2h and 3h1p determinants with the EOM-DIP-CC approach at the CC singles and doubles level (CCSD). Time-reversal symmetry together with spatial symmetry is exploited to reduce computational effort. To circumvent the problem of unstable dianion references when diffuse basis functions are included, nuclear charges are scaled. Effect of this stabilization potential on DIPs is estimated based on results from calculations using a small basis setmore » without diffuse basis functions. DIPs and excitation energies of some low-lying states for a series of open-shell atoms and molecules containing heavy elements with two unpaired electrons have been calculated with the EOM-DIP-CCSD approach. Results show that this approach is able to afford a reliable description on SOC splitting. Furthermore, the EOM-DIP-CCSD approach is shown to provide reasonable excitation energies for systems with a dianion reference when diffuse basis functions are not employed.« less

Metal- and Reagent-Free Anodic C-C Cross-Coupling of Phenols with Benzofurans leading to a Furan Metathesis.

PubMed

Lips, Sebastian; Frontana-Uribe, Bernardo Antonio; Dörr, Maurice; Schollmeyer, Dieter; Franke, Robert; Waldvogel, Siegfried R

2018-04-20

Heterobiaryls consisting of a phenol and a benzofuran motif are of significant importance for pharmaceutical applications. An attractive sustainable, metal- and reagent-free, electrosynthetic, and highly efficient method, that allows access to (2-hydroxyphenyl)benzofurans is presented. Upon the electrochemical dehydrogenative C-C cross-coupling reaction, a metathesis of the benzo moiety at the benzofuran occurs. This gives rise to a substitution pattern at the hydroxyphenyl moiety which would not be compatible by a direct coupling process. The single-step protocol is easy to conduct in an undivided electrolysis cell, therefore scalable, and inherently safe. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copper-catalyzed, C-C coupling-based one-pot tandem reactions for the synthesis of benzofurans using o-iodophenols, acyl chlorides, and phosphorus ylides.

PubMed

Liu, Yunyun; Wang, Hang; Wan, Jie-Ping

2014-11-07

One-pot reactions involving acyl chlorides, phosphorus ylides, and o-iodophenols with copper catalysis have been established for the rapid synthesis of functionalized benzofurans. With all of these easily available and stable reactants, the construction of the target products has been accomplished via tandem transformations involving a key C-C coupling, leading to the formation of one C(sp(2))-C bond, one C(sp(2))-O bond, and one C ═ C bond.

Gravitoinertial force background level affects adaptation to coriolis force perturbations of reaching movements

NASA Technical Reports Server (NTRS)

Lackner, J. R.; Dizio, P.

1998-01-01

We evaluated the combined effects on reaching movements of the transient, movement-dependent Coriolis forces and the static centrifugal forces generated in a rotating environment. Specifically, we assessed the effects of comparable Coriolis force perturbations in different static force backgrounds. Two groups of subjects made reaching movements toward a just-extinguished visual target before rotation began, during 10 rpm counterclockwise rotation, and after rotation ceased. One group was seated on the axis of rotation, the other 2.23 m away. The resultant of gravity and centrifugal force on the hand was 1.0 g for the on-center group during 10 rpm rotation, and 1.031 g for the off-center group because of the 0.25 g centrifugal force present. For both groups, rightward Coriolis forces, approximately 0.2 g peak, were generated during voluntary arm movements. The endpoints and paths of the initial per-rotation movements were deviated rightward for both groups by comparable amounts. Within 10 subsequent reaches, the on-center group regained baseline accuracy and straight-line paths; however, even after 40 movements the off-center group had not resumed baseline endpoint accuracy. Mirror-image aftereffects occurred when rotation stopped. These findings demonstrate that manual control is disrupted by transient Coriolis force perturbations and that adaptation can occur even in the absence of visual feedback. An increase, even a small one, in background force level above normal gravity does not affect the size of the reaching errors induced by Coriolis forces nor does it affect the rate of reacquiring straight reaching paths; however, it does hinder restoration of reaching accuracy.

Particle transport model sensitivity on wave-induced processes

NASA Astrophysics Data System (ADS)

Staneva, Joanna; Ricker, Marcel; Krüger, Oliver; Breivik, Oyvind; Stanev, Emil; Schrum, Corinna

2017-04-01

Different effects of wind waves on the hydrodynamics in the North Sea are investigated using a coupled wave (WAM) and circulation (NEMO) model system. The terms accounting for the wave-current interaction are: the Stokes-Coriolis force, the sea-state dependent momentum and energy flux. The role of the different Stokes drift parameterizations is investigated using a particle-drift model. Those particles can be considered as simple representations of either oil fractions, or fish larvae. In the ocean circulation models the momentum flux from the atmosphere, which is related to the wind speed, is passed directly to the ocean and this is controlled by the drag coefficient. However, in the real ocean, the waves play also the role of a reservoir for momentum and energy because different amounts of the momentum flux from the atmosphere is taken up by the waves. In the coupled model system the momentum transferred into the ocean model is estimated as the fraction of the total flux that goes directly to the currents plus the momentum lost from wave dissipation. Additionally, we demonstrate that the wave-induced Stokes-Coriolis force leads to a deflection of the current. During the extreme events the Stokes velocity is comparable in magnitude to the current velocity. The resulting wave-induced drift is crucial for the transport of particles in the upper ocean. The performed sensitivity analyses demonstrate that the model skill depends on the chosen processes. The results are validated using surface drifters, ADCP, HF radar data and other in-situ measurements in different regions of the North Sea with a focus on the coastal areas. The using of a coupled model system reveals that the newly introduced wave effects are important for the drift-model performance, especially during extremes. Those effects cannot be neglected by search and rescue, oil-spill, transport of biological material, or larva drift modelling.

Ocean-Forced Ice-Shelf Thinning in a Synchronously Coupled Ice-Ocean Model

NASA Astrophysics Data System (ADS)

Jordan, James R.; Holland, Paul R.; Goldberg, Dan; Snow, Kate; Arthern, Robert; Campin, Jean-Michel; Heimbach, Patrick; Jenkins, Adrian

2018-02-01

The first fully synchronous, coupled ice shelf-ocean model with a fixed grounding line and imposed upstream ice velocity has been developed using the MITgcm (Massachusetts Institute of Technology general circulation model). Unlike previous, asynchronous, approaches to coupled modeling our approach is fully conservative of heat, salt, and mass. Synchronous coupling is achieved by continuously updating the ice-shelf thickness on the ocean time step. By simulating an idealized, warm-water ice shelf we show how raising the pycnocline leads to a reduction in both ice-shelf mass and back stress, and hence buttressing. Coupled runs show the formation of a western boundary channel in the ice-shelf base due to increased melting on the western boundary due to Coriolis enhanced flow. Eastern boundary ice thickening is also observed. This is not the case when using a simple depth-dependent parameterized melt, as the ice shelf has relatively thinner sides and a thicker central "bulge" for a given ice-shelf mass. Ice-shelf geometry arising from the parameterized melt rate tends to underestimate backstress (and therefore buttressing) for a given ice-shelf mass due to a thinner ice shelf at the boundaries when compared to coupled model simulations.

Blade mistuning coupled with shaft flexibility effects in rotor aeroelasticity

NASA Technical Reports Server (NTRS)

Khader, Naim; Loewy, Robert G.

1989-01-01

The effect of bladed-disk polar dissymmetry, resulting from variations in mass from one blade to another, on aeroelastic stability boundaries for a fan stage is presented. In addition to both in-plane and out-of-plane deformations of the bladed-disk, bending of the supporting shaft in two planes is considered, and the resulting Coriolis forces and gyroscopic moments are included in the analysis. A quasi-steady aerodynamics approach is combined with the Lagrangian method to develop the governing equations of motion for the flexible bladed-disk-shaft assembly. Calculations are performed for an actual fan stage.

Endoscopy-coupled Raman spectroscopy for in vivo discrimination of inflammatory bowel disease

NASA Astrophysics Data System (ADS)

Pence, I. J.; Nguyen, Q. T.; Bi, X.; Herline, A. J.; Beaulieu, D. M.; Horst, S. N.; Schwartz, D. A.; Mahadevan-Jansen, A.

2014-03-01

Inflammatory bowel disease (IBD), including ulcerative colitis (UC) and Crohn's colitis (CC), affects nearly 2 million Americans, and the incidence is increasing worldwide. It has been established that UC and CC are distinct forms of IBD and require different medical care, however the distinction made between UC and CC is based upon inexact clinical, radiological, endoscopic, and pathologic features. A diagnosis of indeterminate colitis occurs in up to 15% of patients when UC and CC features overlap and cannot be differentiated; in these patients, diagnosis relies on long term followup, success or failure of existing treatment, and recurrence of the disease. Thus, there is need for a tool that can improve the sensitivity and specificity for fast, accurate and automated diagnosis of IBD. Here we present colonoscopy-coupled fiber probe-based Raman spectroscopy as a novel in vivo diagnostic tool for IBD. This in vivo study of both healthy control (NC, N=10) and diagnosed IBD patients with UC (N=15) and CC (N=26) aims to characterize spectral signatures of NC, UC, and CC. Samples are correlated with tissue pathology markers and endoscopic evaluation. Optimal collection parameters for detection have been identified based upon the new, application specific instrument design. The collected spectra are processed and analyzed using multivariate statistical techniques to identify spectral markers and discriminate NC, UC, and CC. Development of spectral markers to discriminate disease type is a necessary first step in the development of real-time, accurate and automated in vivo detection of IBD during colonoscopy procedures.

Thermal Vacuum Test of GLAS Propylene Loop Heat Pipe Development Model

NASA Technical Reports Server (NTRS)

Baker, Charles; Butler, Dan; Ku, Jentung; Kaya, Tarik; Nikitkin, Michael

2000-01-01

This paper presents viewgraphs on Thermal Vacuum Tests of the GLAS (Geoscience Laser Altimeter System) Propylene Loop Heat Pipe Development Model. The topics include: 1) Flight LHP System (Laser); 2) Test Design and Objectives; 3) DM (Development Model) LHP (Loop Heat Pipe) Test Design; 4) Starter Heater and Coupling Blocks; 5) CC Control Heaters and PRT; 6) Heater Plates (Shown in Reflux Mode); 7) Startup Tests; 8) CC Control Heater Power Tests for CC Temperature Control; and 9) Control Temperature Stability.

Airborne ultrasonic inspection in carbon/carbon composite materials

NASA Astrophysics Data System (ADS)

Yang, In-Young; Kim, Young-Hun; Park, Je-Woong; Hsu, David K.; Song, Song-Jin; Cho, Hyun-Jun; Kim, Sun-Kyu; Im, Kwang-Hee

2007-07-01

In this work, a carbon/carbon (C/C) composite material was nondestructively characterized with non-contact ultrasonic methods using automated acquisition scanner as well as contact ultrasonic measurement because (C/C) composite materials have obvious high price over conventional materials. Because of permeation of coupling medium such as water, it is desirable to perform contact-less nondestructive evaluation to assess material properties and part homogeneity. Also through transmission mode was performed because of the main limitation for air-coupled transducers, which is the acoustic impedance mismatch between most materials and air. Especially ultrasonic images and velocities for C/C composite disk brake was measured and found to be consistent to some degree with the non-contact and contact ultrasonic measurement methods. Low frequency through-transmission scans based on both amplitude and time-of-flight of the ultrasonic pulse were used for mapping out the material property inhomogeneity. Measured results were compared with those obtained by the motorized system with using dry-coupling ultrasonics and through transmission method in immersion. Finally, results using a proposed peak-delay measurement method well corresponded to ultrasonic velocities of the pulse overlap method.

Why does MP2 work?

PubMed

Fink, Reinhold F

2016-11-14

We show analytically and numerically that the performance of second order Møller-Plesset (MP) perturbation theory (PT), coupled-cluster (CC) theory, and other perturbation theory approaches can be rationalized by analyzing the wavefunctions of these methods. While rather large deviations for the individual contributions of configurations to the electron correlation energy are found for MP wavefunctions, they profit from an advantageous and robust error cancellation: The absolute contribution to the correlation energy is generally underestimated for the critical excitations with small energy denominators and all other doubly excited configurations where the two excited electrons are coupled to a singlet. This is balanced by an overestimation of the contribution of triplet-coupled double excitations to the correlation energy. The even better performance of spin-component-scaled-MP2 theory is explained by a similar error compensation effect. The wavefunction analysis for the lowest singlet states of H 2 O, CH 2 , CO, and Cu + shows the predicted trends for MP methods, rapid but biased convergence of CC theory as well as the substantial potential of linearized CC, or retaining the excitation-degree (RE)-PT.

Bite angle effects of diphosphines in C-C and C-X bond forming cross coupling reactions.

PubMed

Birkholz, Mandy-Nicole; Freixa, Zoraida; van Leeuwen, Piet W N M

2009-04-01

Catalytic reactions of C-C and C-X bond formation are discussed in this critical review with particular emphasis on cross coupling reactions catalyzed by palladium and wide bite angle bidentate diphosphine ligands. Especially those studies have been collected that allow comparison of the ligand bite angles for the selected ligands: dppp, BINAP, dppf, DPEphos and Xantphos. Similarities with hydrocyanation and CO/ethene/MeOH reactions have been highlighted, while rhodium hydroformylation has been mentioned as a contrasting example, in which predictability is high and steric and electronic effects follow smooth trends. In palladium catalysis wide bite angles and bulkiness of the ligands facilitate generally the reductive elimination thus giving more efficient cross coupling catalysis (174 references).

CC2 oscillator strengths within the local framework for calculating excitation energies (LoFEx).

PubMed

Baudin, Pablo; Kjærgaard, Thomas; Kristensen, Kasper

2017-04-14

In a recent work [P. Baudin and K. Kristensen, J. Chem. Phys. 144, 224106 (2016)], we introduced a local framework for calculating excitation energies (LoFEx), based on second-order approximated coupled cluster (CC2) linear-response theory. LoFEx is a black-box method in which a reduced excitation orbital space (XOS) is optimized to provide coupled cluster (CC) excitation energies at a reduced computational cost. In this article, we present an extension of the LoFEx algorithm to the calculation of CC2 oscillator strengths. Two different strategies are suggested, in which the size of the XOS is determined based on the excitation energy or the oscillator strength of the targeted transitions. The two strategies are applied to a set of medium-sized organic molecules in order to assess both the accuracy and the computational cost of the methods. The results show that CC2 excitation energies and oscillator strengths can be calculated at a reduced computational cost, provided that the targeted transitions are local compared to the size of the molecule. To illustrate the potential of LoFEx for large molecules, both strategies have been successfully applied to the lowest transition of the bivalirudin molecule (4255 basis functions) and compared with time-dependent density functional theory.

Tandem reactions initiated by copper-catalyzed cross-coupling: a new strategy towards heterocycle synthesis.

PubMed

Liu, Yunyun; Wan, Jie-Ping

2011-10-21

Copper-catalyzed cross-coupling reactions which lead to the formation of C-N, C-O, C-S and C-C bonds have been recognized as one of the most useful strategies in synthetic organic chemistry. During past decades, important breakthroughs in the study of Cu-catalyzed coupling processes demonstrated that Cu-catalyzed reactions are broadly applicable to a variety of research fields related to organic synthesis. Representatively, employing these coupling transformations as key steps, a large number of tandem reactions have been developed for the construction of various heterocyclic compounds. These tactics share the advantages of high atom economics of tandem reactions as well as the broad tolerance of Cu-catalyst systems. Therefore, Cu-catalyzed C-X (X = N, O, S, C) coupling transformation-initiated tandem reactions were quickly recognized as a strategy with great potential for synthesizing heterocyclic compounds and gained worldwide attention. In this review, recent research progress in heterocycle syntheses using tandem reactions initiated by copper-catalyzed coupling transformations, including C-N, C-O, C-S as well as C-C coupling processes are summarized.

An approximate closed-form solution for lead lag damping of rotor blades in hover

NASA Technical Reports Server (NTRS)

Peters, D. A.

1975-01-01

Simple stability methods are used to derive an approximate, closed-form expression for the lead-lag damping of rotor blades in hover. Destabilizing terms are shown to be a result of two dynamic mechanisms. First, the destabilizing aerodynamic forces that can occur when blade lift is higher than a critical value are maximized when the blade motion is in a straight line equidistant from the blade chord and the average direction of the air flow velocity. This condition occurs when the Coriolis terms vanish and when the elastic coupling terms align the blade motion with this least stable direction. Second, the nonconservative stiffness terms that result from pitch-flap or pitch-lag coupling can add or subtract energy from the system depending upon whether the motion of the blade tip is clockwise or counterclockwise.

The methylenetetrahydrofolate reductase c.c.677 C>T and c.c.1298 A>C polymorphisms in reproductive failures: Experience from an RSA and RIF study on a Polish population.

PubMed

Nowak, Izabela; Bylińska, Aleksandra; Wilczyńska, Karolina; Wiśniewski, Andrzej; Malinowski, Andrzej; Wilczyński, Jacek R; Radwan, Paweł; Radwan, Michał; Barcz, Ewa; Płoski, Rafał; Motak-Pochrzęst, Hanna; Banasik, Małgorzata; Sobczyński, Maciej; Kuśnierczyk, Piotr

2017-01-01

Almost 1600 individuals from the Polish population were recruited to this study. Among them 319 were fertile couples, 289 were recurrent spontaneous abortion (RSA) couples, and 131 were in the group of recurrent implantation failure (RIF) following in vitro fertilization. The aim of this study was to evaluate the MTHFR c.c.677 C>T and c.c.1298 A>C polymorphisms' association with RSA and RIF. We used PCR-RFLP with HinfI (677 C>T) and MboII (1298 A>C) digestion. We observed a protective effect of the female AC genotype (OR = 0.64, p = 0.01) and the C allele (AC+CC genotypes; OR = 0.65, p = 0.009) against RSA. Moreover, 1298 AA/677 CT women were more frequent in RSA (31.14%) and RIF (25.20%) groups in comparison to fertile women (22.88%), although this difference was significant only in the case of RSA (p = 0.022, OR = 1.52). Male combined genotype analysis revealed no association with reproductive failure of their partners. Nevertheless, the female/male combination AA/AC of the 1298 polymorphism was more frequent in RSA couples (p = 0.049, OR = 1.49). However, the significant results became insignificant after Bonferroni correction. In addition, analysis of haplotypes showed significantly higher frequency of the C/C haplotype (1298 C/677 C) in the female control group than in the female RSA group (p = 0.03, OR = 0.77). Moreover, the association between elevated homocysteine (Hcy) level in plasma of RSA and RIF women and MTHFR polymorphisms was investigated but did not reveal significant differences. In conclusion, for clinical practice, it is better to check the homocysteine level in plasma and, if the Hcy level is increased, to recommend patients to take folic acid supplements rather than undergo screening of MTHFR for 1298 A>C and 677 C>T polymorphisms.

The methylenetetrahydrofolate reductase c.c.677 C>T and c.c.1298 A>C polymorphisms in reproductive failures: Experience from an RSA and RIF study on a Polish population

PubMed Central

Bylińska, Aleksandra; Wilczyńska, Karolina; Wiśniewski, Andrzej; Malinowski, Andrzej; Wilczyński, Jacek R.; Radwan, Paweł; Radwan, Michał; Barcz, Ewa; Płoski, Rafał; Motak-Pochrzęst, Hanna; Banasik, Małgorzata; Sobczyński, Maciej; Kuśnierczyk, Piotr

2017-01-01

Almost 1600 individuals from the Polish population were recruited to this study. Among them 319 were fertile couples, 289 were recurrent spontaneous abortion (RSA) couples, and 131 were in the group of recurrent implantation failure (RIF) following in vitro fertilization. The aim of this study was to evaluate the MTHFR c.c.677 C>T and c.c.1298 A>C polymorphisms’ association with RSA and RIF. We used PCR-RFLP with HinfI (677 C>T) and MboII (1298 A>C) digestion. We observed a protective effect of the female AC genotype (OR = 0.64, p = 0.01) and the C allele (AC+CC genotypes; OR = 0.65, p = 0.009) against RSA. Moreover, 1298 AA/677 CT women were more frequent in RSA (31.14%) and RIF (25.20%) groups in comparison to fertile women (22.88%), although this difference was significant only in the case of RSA (p = 0.022, OR = 1.52). Male combined genotype analysis revealed no association with reproductive failure of their partners. Nevertheless, the female/male combination AA/AC of the 1298 polymorphism was more frequent in RSA couples (p = 0.049, OR = 1.49). However, the significant results became insignificant after Bonferroni correction. In addition, analysis of haplotypes showed significantly higher frequency of the C/C haplotype (1298 C/677 C) in the female control group than in the female RSA group (p = 0.03, OR = 0.77). Moreover, the association between elevated homocysteine (Hcy) level in plasma of RSA and RIF women and MTHFR polymorphisms was investigated but did not reveal significant differences. In conclusion, for clinical practice, it is better to check the homocysteine level in plasma and, if the Hcy level is increased, to recommend patients to take folic acid supplements rather than undergo screening of MTHFR for 1298 A>C and 677 C>T polymorphisms. PMID:29073227

Methods of Controlling the Loop Heat Pipe Operating Temperature

NASA Technical Reports Server (NTRS)

Ku, Jentung

2008-01-01

The operating temperature of a loop heat pipe (LHP) is governed by the saturation temperature of its compensation chamber (CC); the latter is in turn determined by the balance among the heat leak from the evaporator to the CC, the amount of subcooling carried by the liquid returning to the CC, and the amount of heat exchanged between the CC and ambient. The LHP operating temperature can be controlled at a desired set point by actively controlling the CC temperature. The most common method is to cold bias the CC and use electric heater power to maintain the CC set point temperature. The required electric heater power can be large when the condenser sink is very cold. Several methods have been developed to reduce the control heater power, including coupling block, heat exchanger and separate subcooler, variable conductance heat pipe, by-pass valve with pressure regulator, secondary evaporator, and thermoelectric converter. The paper discusses the operating principles, advantages and disadvantages of each method.

Mass perturbation techniques for tuning and decoupling of a Disk Resonator Gyroscope

NASA Astrophysics Data System (ADS)

Schwartz, David

Axisymmetric microelectromechanical (MEM) vibratory rate gyroscopes are designed so that the two Coriolis-coupled modes exploited for rate sensing possess equal modal frequencies and so that the central post which attaches the resonator to the sensor case is a nodal point of the these two modes. The former quality maximizes the signal-to-noise ratio of the sensor, while the latter quality eliminates any coupling of linear acceleration to the modes of interest, which, if present, creates spurious rate signals in response to linear vibration of the sensor case. When the gyro resonators are fabricated, however, small mass and stiffness asymmetries cause the frequencies of the two modes to deviate from each other and couple these modes to linear acceleration. In a resonator post-fabrication step, these effects can be reduced by altering the mass distribution of the resonator. In this dissertation, a scale model of the axisymmetric resonator of the Disk Resonator Gyroscope (DRG) is used to develop and test methods that successfully reduce frequency detuning (Part I) and linear acceleration coupling (Part II) through guided mass perturbations.

Metal-Free Oxidative C-C Bond Formation through C-H Bond Functionalization.

PubMed

Narayan, Rishikesh; Matcha, Kiran; Antonchick, Andrey P

2015-10-12

The formation of C-C bonds embodies the core of organic chemistry because of its fundamental application in generation of molecular diversity and complexity. C-C bond-forming reactions are well-known challenges. To achieve this goal through direct functionalization of C-H bonds in both of the coupling partners represents the state-of-the-art in organic synthesis. Oxidative C-C bond formation obviates the need for prefunctionalization of both substrates. This Minireview is dedicated to the field of C-C bond-forming reactions through direct C-H bond functionalization under completely metal-free oxidative conditions. Selected important developments in this area have been summarized with representative examples and discussions on their reaction mechanisms. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A full-dimensional potential energy surface and quantum dynamics of inelastic collision process for H2-HF

NASA Astrophysics Data System (ADS)

Yang, Dongzheng; Huang, Jing; Zuo, Junxiang; Hu, Xixi; Xie, Daiqian

2018-05-01

A full-dimensional ab initio potential energy surface for the H2-HF van der Waals complex was constructed by employing the coupled-cluster singles and doubles with noniterative inclusion of connected triples with augmented correlation-consistent polarised valence quadruple-zeta basis set plus bond functions. Using the improved coupled-states approximation including the nearest neighbor Coriolis couplings, we calculated the state-to-state scattering dynamics for pure rotational and ro-vibrational energy transfer processes. For pure rotational energy transfer, our results showed a different dynamical behavior for para-H2 and ortho-H2 in collision with hydrogen fluoride (HF), which is consistent with the previous study. Interestingly, some strong resonant peaks were presented in the cross sections for ro-vibrational energy transfer. In addition, the calculated vibrational-resolved rate constant is in agreement with the experimental results reported by Bott et al. These dynamics data can be further applied to the numerical simulation of HF chemical lasers.

The effect of the Coriolis force on the stability of rotating magnetic stars

NASA Technical Reports Server (NTRS)

Sakurai, K.

1972-01-01

The effect of the Coriolis force on the stability of rotating magnetic stars in hydrostatic equilibrium is investigated by using the method of the energy principle. It is shown that this effect is to inhibit the onset of instability.

The effect of the Coriolis force on the stability of rotating magnetic stars.

NASA Technical Reports Server (NTRS)

Sakurai, K.

1972-01-01

The effect of the Coriolis force on the stability of rotating magnetic stars in hydrostatic equilibrium is investigated by using the method of the energy principle. It is shown that this effect is to inhibit the onset of instability.

Effect of Coriolis force on counter-current chromatographic separation by centrifugal partition chromatography.

PubMed

Ikehata, Jun-Ichi; Shinomiya, Kazufusa; Kobayashi, Koji; Ohshima, Hisashi; Kitanaka, Susumu; Ito, Yoichiro

2004-02-06

The effect of Coriolis force on the counter-current chromatographic separation was studied using centrifugal partition chromatography (CPC) with four different two-phase solvent systems including n-hexane-acetonitrile (ACN); tert-butyl methyl ether (MtBE)-aqueous 0.1% trifluoroacetic acid (TFA) (1:1); MtBE-ACN-aqueous 0.1% TFA (2:2:3); and 12.5% (w/w) polyethylene glycol (PEG) 1000-12.5% (w/w) dibasic potassium phosphate. Each separation was performed by eluting either the upper phase in the ascending mode or the lower phase in the descending mode, each in clockwise (CW) and counterclockwise column rotation. Better partition efficiencies were attained by the CW rotation in both mobile phases in all the two-phase solvent systems examined. The mathematical analysis also revealed the Coriolis force works favorably under the CW column rotation for both mobile phases. The overall results demonstrated that the Coriolis force produces substantial effects on CPC separation in both organic-aqueous and aqueous-aqueous two-phase systems.

Wavelength dependence of eddy dissipation and Coriolis force in the dynamics of gravity wave driven fluctuations in the OH nightglow

NASA Technical Reports Server (NTRS)

Hickey, M. P.

1988-01-01

This paper examines the effect of inclusion of Coriolis force and eddy dissipation in the gravity wave dynamics theory of Walterscheid et al. (1987). It was found that the values of the ratio 'eta' (where eta is a complex quantity describing the ralationship between the intensity oscillation about the time-averaged intensity, and the temperature oscillation about the time-averaged temperature) strongly depend on the wave period and the horizontal wavelength; thus, if comparisons are to be made between observations and theory, horizontal wavelengths will need to be measured in conjunction with the OH nightglow measurements. For the waves with horizontal wavelengths up to 1000 km, the eddy dissipation was found to dominate over the Coriolis force in the gravity wave dynamics and also in the associated values of eta. However, for waves with horizontal wavelengths of 10,000 km or more, the Coriolis force cannot be neglected; it has to be taken into account along with the eddy dissipation.

Error Analysis of Magnetohydrodynamic Angular Rate Sensor Combing with Coriolis Effect at Low Frequency.

PubMed

Ji, Yue; Xu, Mengjie; Li, Xingfei; Wu, Tengfei; Tuo, Weixiao; Wu, Jun; Dong, Jiuzhi

2018-06-13

The magnetohydrodynamic (MHD) angular rate sensor (ARS) with low noise level in ultra-wide bandwidth is developed in lasing and imaging applications, especially the line-of-sight (LOS) system. A modified MHD ARS combined with the Coriolis effect was studied in this paper to expand the sensor’s bandwidth at low frequency (<1 Hz), which is essential for precision LOS pointing and wide-bandwidth LOS jitter suppression. The model and the simulation method were constructed and a comprehensive solving method based on the magnetic and electric interaction methods was proposed. The numerical results on the Coriolis effect and the frequency response of the modified MHD ARS were detailed. In addition, according to the experimental results of the designed sensor consistent with the simulation results, an error analysis of model errors was discussed. Our study provides an error analysis method of MHD ARS combined with the Coriolis effect and offers a framework for future studies to minimize the error.

Analysis of High-Resolution Infrared and CARS Spectra of ³⁴S¹⁸O₃

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

Masiello, Tony; Vulpanovici, Nicolae; Barber, Jeffrey B.

2004-09-11

As part of a series of investigations of isotopic forms of sulfur trioxide, high-resolution infrared and coherent anti-Stokes Raman spectroscopies were used to study the fundamental modes and several hot bands of 32S18O3. Hot bands originating from the v2 and v4 bending mode levels have been found to couple strongly to the IR-inactive v1 symmetric stretching mode through indirect Coriolis interactions and Fermi resonances. Coriolis coupling effects are particularly noticeable in 32S18O3 due to the close proximity of the v2 and v4 fundamental vibrations, whose deperturbed wavenumber values are 486.488 13(4) and 504.284 77(4) cm-1. The uncertainties in the lastmore » digits are shown in parentheses and are two standard deviations. From the infrared transitions, accurate rovibrational constants are deduced for all of the mixed states, leading to deperturbed values for v1, and of 1004.68(2), 0.000 713(2), and 0.000 348(2) cm-1, respectively. The Be value is found to be 0.310 820(2) cm-1, yielding an equilibrium bond length re of 141.7333(4) pm that is, within experimental error, identical to the value of 141.7339(3) pm reported previously for 34S18O3. With this work, precise and accurate spectroscopic constants have now been determined in a systematic and consistent manner for all the fundamental vibrational modes of the sulfur trioxide D3h isotopomeric forms 32S16O3, 34S16O3, 32S18O3, and 34S18O3.« less

Surface wave effects on water temperature in the Baltic Sea: simulations with the coupled NEMO-WAM model

NASA Astrophysics Data System (ADS)

Alari, Victor; Staneva, Joanna; Breivik, Øyvind; Bidlot, Jean-Raymond; Mogensen, Kristian; Janssen, Peter

2016-08-01

Coupled circulation (NEMO) and wave model (WAM) system was used to study the effects of surface ocean waves on water temperature distribution and heat exchange at regional scale (the Baltic Sea). Four scenarios—including Stokes-Coriolis force, sea-state dependent energy flux (additional turbulent kinetic energy due to breaking waves), sea-state dependent momentum flux and the combination these forcings—were simulated to test the impact of different terms on simulated temperature distribution. The scenario simulations were compared to a control simulation, which included a constant wave-breaking coefficient, but otherwise was without any wave effects. The results indicate a pronounced effect of waves on surface temperature, on the distribution of vertical temperature and on upwelling's. Overall, when all three wave effects were accounted for, did the estimates of temperature improve compared to control simulation. During the summer, the wave-induced water temperature changes were up to 1 °C. In northern parts of the Baltic Sea, a warming of the surface layer occurs in the wave included simulations in summer months. This in turn reduces the cold bias between simulated and measured data, e.g. the control simulation was too cold compared to measurements. The warming is related to sea-state dependent energy flux. This implies that a spatio-temporally varying wave-breaking coefficient is necessary, because it depends on actual sea state. Wave-induced cooling is mostly observed in near-coastal areas and is the result of intensified upwelling in the scenario, when Stokes-Coriolis forcing is accounted for. Accounting for sea-state dependent momentum flux results in modified heat exchange at the water-air boundary which consequently leads to warming of surface water compared to control simulation.

LoFEx - A local framework for calculating excitation energies: Illustrations using RI-CC2 linear response theory.

PubMed

Baudin, Pablo; Kristensen, Kasper

2016-06-14

We present a local framework for the calculation of coupled cluster excitation energies of large molecules (LoFEx). The method utilizes time-dependent Hartree-Fock information about the transitions of interest through the concept of natural transition orbitals (NTOs). The NTOs are used in combination with localized occupied and virtual Hartree-Fock orbitals to generate a reduced excitation orbital space (XOS) specific to each transition where a standard coupled cluster calculation is carried out. Each XOS is optimized to ensure that the excitation energies are determined to a predefined precision. We apply LoFEx in combination with the RI-CC2 model to calculate the lowest excitation energies of a set of medium-sized organic molecules. The results demonstrate the black-box nature of the LoFEx approach and show that significant computational savings can be gained without affecting the accuracy of CC2 excitation energies.

Oscillator strengths, first-order properties, and nuclear gradients for local ADC(2).

PubMed

Schütz, Martin

2015-06-07

We describe theory and implementation of oscillator strengths, orbital-relaxed first-order properties, and nuclear gradients for the local algebraic diagrammatic construction scheme through second order. The formalism is derived via time-dependent linear response theory based on a second-order unitary coupled cluster model. The implementation presented here is a modification of our previously developed algorithms for Laplace transform based local time-dependent coupled cluster linear response (CC2LR); the local approximations thus are state specific and adaptive. The symmetry of the Jacobian leads to considerable simplifications relative to the local CC2LR method; as a result, a gradient evaluation is about four times less expensive. Test calculations show that in geometry optimizations, usually very similar geometries are obtained as with the local CC2LR method (provided that a second-order method is applicable). As an exemplary application, we performed geometry optimizations on the low-lying singlet states of chlorophyllide a.

Novel strategy to implement active-space coupled-cluster methods

NASA Astrophysics Data System (ADS)

Rolik, Zoltán; Kállay, Mihály

2018-03-01

A new approach is presented for the efficient implementation of coupled-cluster (CC) methods including higher excitations based on a molecular orbital space partitioned into active and inactive orbitals. In the new framework, the string representation of amplitudes and intermediates is used as long as it is beneficial, but the contractions are evaluated as matrix products. Using a new diagrammatic technique, the CC equations are represented in a compact form due to the string notations we introduced. As an application of these ideas, a new automated implementation of the single-reference-based multi-reference CC equations is presented for arbitrary excitation levels. The new program can be considered as an improvement over the previous implementations in many respects; e.g., diagram contributions are evaluated by efficient vectorized subroutines. Timings for test calculations for various complete active-space problems are presented. As an application of the new code, the weak interactions in the Be dimer were studied.

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

NASA Astrophysics Data System (ADS)

Shamasundar, K. R.

2018-06-01

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

Enhanced Sensitivity of Novel Surface Acoustic Wave Microelectromechanical System-Interdigital Transducer Gyroscope

NASA Astrophysics Data System (ADS)

Wang, Wen; Oh, Haekwan; Lee, Keekeun; Yoon, Sungjin; Yang, Sangsik

2009-06-01

In this paper, we present a novel microelectromechanical system-interdigital transducer (MEMS-IDT) surface acoustic wave (SAW) gyroscope with an 80 MHz central frequency on a 128° YX LiNbO3 wafer. The developed MEMS-IDT gyroscope is composed of a two-port SAW resonator, a dual delay line oscillator, and metallic dots. The SAW resonator provides a stable standing wave, and the vibrating metallic dot at an antinode of the standing wave induces the second SAW in the normal direction of its vibrating axis. The dual delay line oscillator detects the Coriolis force by comparing the resonant frequencies between two oscillators through the interference effect. The coupling of mode (COM) modeling was used to extract the optimal design parameters prior to fabrication. In the electrical testing by the network analyzer, the fabricated SAW resonator and delay lines showed low insertion loss and similar operation frequencies between a resonator and delay lines. When the device was rotated, the resonant frequency differences between two oscillators linearly varied owing to the Coriolis force. The obtained sensitivity was approximately 119 Hz deg-1 s-1 in the angular rate range of 0-1000 deg/s. Satisfactory linearity and superior directivity were also observed in the test.

A view on coupled cluster perturbation theory using a bivariational Lagrangian formulation.

PubMed

Kristensen, Kasper; Eriksen, Janus J; Matthews, Devin A; Olsen, Jeppe; Jørgensen, Poul

2016-02-14

We consider two distinct coupled cluster (CC) perturbation series that both expand the difference between the energies of the CCSD (CC with single and double excitations) and CCSDT (CC with single, double, and triple excitations) models in orders of the Møller-Plesset fluctuation potential. We initially introduce the E-CCSD(T-n) series, in which the CCSD amplitude equations are satisfied at the expansion point, and compare it to the recently developed CCSD(T-n) series [J. J. Eriksen et al., J. Chem. Phys. 140, 064108 (2014)], in which not only the CCSD amplitude, but also the CCSD multiplier equations are satisfied at the expansion point. The computational scaling is similar for the two series, and both are term-wise size extensive with a formal convergence towards the CCSDT target energy. However, the two series are different, and the CCSD(T-n) series is found to exhibit a more rapid convergence up through the series, which we trace back to the fact that more information at the expansion point is utilized than for the E-CCSD(T-n) series. The present analysis can be generalized to any perturbation expansion representing the difference between a parent CC model and a higher-level target CC model. In general, we demonstrate that, whenever the parent parameters depend upon the perturbation operator, a perturbation expansion of the CC energy (where only parent amplitudes are used) differs from a perturbation expansion of the CC Lagrangian (where both parent amplitudes and parent multipliers are used). For the latter case, the bivariational Lagrangian formulation becomes more than a convenient mathematical tool, since it facilitates a different and faster convergent perturbation series than the simpler energy-based expansion.

Determination of the structure of the X(3872) in p¯A collisions

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

Larionov, A. B.; Strikman, M.; Bleicher, M.

2015-07-22

The structure of the X(3872) meson is unknown. Different competing models of the cc¯ exotic state X(3872) exist, including the possibilities that this state is either a mesonic molecule with dominating D 0D¯* 0 + c.c. composition, a cc¯qq¯ tetraquark, or a cc¯-gluon hybrid state. It is expected that the X(3872) state is rather strongly coupled to the pp¯ channel and, therefore, can be produced in pp¯ and p¯A collisions at PANDA. We propose to test the hypothetical molecular structure of X(3872) by studying the D or D¯* source stripping reactions on a nuclear residue.

Regioselective Cu(I)-catalyzed tandem A3-coupling/decarboxylative coupling to 3-amino-1,4-enynes.

PubMed

Feng, Huangdi; Ermolat'ev, Denis S; Song, Gonghua; Van der Eycken, Erik V

2012-04-06

An efficient and novel copper-mediated protocol for the synthesis of 3-amino-1,4-enynes from glyoxylic acid, an amine, and an alkyne was developed. This new reaction involving two sequential C-C bond formations is air and moisture tolerant and proceeds via a tandem A(3)-coupling and a selective decarboxylative coupling.

A Randomized Clinical Trial to Determine Optimal Infertility Treatment in Older Couples: The Forty and Over Treatment Trial (FORT-T)

PubMed Central

Goldman, Marlene B.; Thornton, Kim L.; Ryley, David; Alper, Michael M.; Fung, June L.; Hornstein, Mark D.; Reindollar, Richard H.

2014-01-01

Objective To determine optimal infertility therapy in women at the end of their reproductive potential. Design Randomized clinical trial. Setting Academic medical centers and private infertility center in a state with mandated insurance coverage. Patients Couples with ≥ 6 months of unexplained infertility; female partner aged 38–42. Interventions Randomized to treatment with 2 cycles of clomiphene citrate (CC) and intrauterine insemination (IUI), follicle stimulating hormone (FSH)/IUI, or immediate IVF, followed by IVF if not pregnant. Main Outcome Measures Proportion with a clinically recognized pregnancy, number of treatment cycles, and time to conception after 2 treatment cycles and at the end of treatment. Results 154 couples were randomized to receive CC/IUI (N=51), FSH/IUI (N=52), or immediate IVF (N=51); 140 (90.9%) couples initiated treatment. Cumulative clinical pregnancy rates per couple after the first 2 cycles of CC/IUI, FSH/IUI, or immediate IVF were 21.6%, 17.3%, and 49.0%, respectively. After all treatment, 71.4% (110/154) of couples conceived a clinically recognized pregnancy and 46.1% delivered at least one live-born baby. 84.2% of all live born infants resulting from treatment were achieved from IVF. There were 36% fewer treatment cycles in the IVF arm compared to either COH/IUI arm and couples conceived a pregnancy leading to a live birth after fewer treatment cycles. Conclusions An RCT to compare treatment initiated with 2 cycles of COH/IUI to immediate IVF in older women with unexplained infertility demonstrated superior pregnancy rates with fewer treatment cycles in the immediate IVF group. PMID:24796764

The Coriolis Effect: A Model for Student Involvement

ERIC Educational Resources Information Center

Exline, Joseph D.

1977-01-01

Lists materials and procedures for constructing a model that demonstrates certain aspects of the Coriolis effect. Materials include an electric drill motor, voltage control, toy dart gun and darts, wood blocks of varying dimensions. Includes description of an experiment illustrating relationship between speed of rotation and amount of apparent…

The influence of gravitoinertial force level on oculomotor and perceptual responses to sudden stop stimulation

NASA Technical Reports Server (NTRS)

Dizio, Paul; Lackner, James R.; Evanoff, John N.

1987-01-01

The goal of this investigation was to determine whether the vestibular response to vertical, z-axis body rotation in the dark is influenced by the magnitude of gravitoinertial force. The parameters measured were the nystagmus and the duration of illusory self-motion elicited in blindfolded subjects by cessation of such rotation during the free-fall, high, and terrestrial force phases of parabolic flight maneuvers. The pattern of findings is consistent with the responses that were observed earlier to constant levels of Coriolis cross-coupled stimulation during parabolic flight maneuvers both in terms of the mode of nystagmus suppression and the effect of G-level.

Flow shear stabilization of rotating plasmas due to the Coriolis effect.

PubMed

Haverkort, J W; de Blank, H J

2012-07-01

A radially decreasing toroidal rotation frequency can have a stabilizing effect on nonaxisymmetric magnetohydrodynamic (MHD) instabilities. We show that this is a consequence of the Coriolis effect that induces a restoring pressure gradient force when plasma is perturbed radially. In a rotating cylindrical plasma, this Coriolis-pressure effect is canceled by the centrifugal effect responsible for the magnetorotational instability. In a magnetically confined toroidal plasma, a large aspect ratio expansion shows that only half of the effect is canceled. This analytical result is confirmed by numerical computations. When the plasma rotates faster toroidally in the core than near the edge, the effect can contribute to the formation of transport barriers by stabilizing MHD instabilities.

[Pharmacological correction of central nervous system function in exposure to Coriolis acceleration].

PubMed

Karkishchenko, N N; Dimitriadi, N A; Molchanovskiĭ, V V

1986-01-01

Healthy volunteers with a low vestibular tolerance were exposed to Coriolis acceleration. Potassium orotate, pyracetame and riboxine were used as prophylactic measures against disorders in the function of the vestibular apparatus and higher compartments of the higher nervous system. The central nervous function was assessed with respect to the spectral power of electroencephalograms, short-term memory and mental performance. Potassium orotate given at a dose of 40 mg/kg body weight/day during 12-14 days as well as pyracetame given at a dose of 30 mg/kg body weight/day during 3 or 7 days increased significantly statokinetic tolerance and produced a protective effect on the central nervous function against Coriolis acceleration.

Distributed Cooperative Control of Multiple Nonlinear Systems with Nonholonomic Constraints and Uncertainty

DTIC Science & Technology

2015-04-04

system j, Mj(q∗j) is a 3×3 positive- definite symmetric matrix, Cj(q∗j , q̇∗j)q̇∗j represents centripetal and Coriolis force, Gj(q∗j) is the...states of system j, Mj(q∗j) is a 3×3 positive- definite symmetric matrix, Cj(q∗j , q̇∗j)q̇∗j represents centripetal and Coriolis force, Gj(q∗j) is the...positive- definite symmetric matrix, Cj(q∗j , q̇∗j)q̇∗j is cen- tripetal and Coriolis force, Gj(q∗j) is gravitational force, Bj(q∗j) is an 4 × 2 input

Reducing motion sickness - A comparison of autogenic-feedback training and an alternative cognitive task

NASA Technical Reports Server (NTRS)

Toscano, W. B.; Cowings, P. S.

1982-01-01

Eighteen men were randomly assigned to three groups matched for susceptibility to Coriolis motion sickness. All subjects were given six Coriolis Sickness Susceptibility Index (CSSI) tests separated by 5-d intervals. Treatment Group I subjects were taught to control their own autonomic responses before the third, fourth, and fifth CSSI tests (6 h total training). Group II subjects were given 'sham' training in an alternative cognitive task under conditions otherwise identical to those of Group I. Group III subjects received no treatment. Results showed that Group I subjects could withstand the stress of Coriolis acceleration significantly longer after training. Neither of the other two groups changed significantly.

Vibration and buckling of rotating, pretwisted, preconed beams including Coriolis effects

NASA Technical Reports Server (NTRS)

Subrahmanyam, K. B.; Kaza, K. R. V.

1985-01-01

The effects of pretwist, precone, setting angle and Coriolis forces on the vibration and buckling behavior of rotating, torsionally rigid, cantilevered beams were studied. The beam is considered to be clamped on the axis of rotation in one case, and off the axis of rotation in the other. Two methods are employed for the solution of the vibration problem: (1) one based upon a finite-difference approach using second order central differences for solution of the equations of motion, and (2) based upon the minimum of the total potential energy functional with a Ritz type of solution procedure making use of complex forms of shape functions for the dependent variables. The individual and collective effects of pretwist, precone, setting angle, thickness ratio and Coriolis forces on the natural frequencies and the buckling boundaries are presented. It is shown that the inclusion of Coriolis effects is necessary for blades of moderate to large thickness ratios while these effects are not so important for small thickness ratio blades. The possibility of buckling due to centrifugal softening terms for large values of precone and rotation is shown.

Hypoxia and Coriolis Illusion in Pilots During Simulated Flight.

PubMed

Kowalczuk, Krzysztof P; Gazdzinski, Stefan P; Janewicz, Michał; Gąsik, Marek; Lewkowicz, Rafał; Wyleżoł, Mariusz

2016-02-01

Pilots' vision and flight performance may be impeded by spatial disorientation and high altitude hypoxia. The Coriolis illusion affects both orientation and vision. However, the combined effect of simultaneous Coriolis illusion and hypoxia on saccadic eye movement has not been evaluated. A simulated flight was performed by 14 experienced pilots under 3 conditions: once under normal oxygen partial pressure and twice under reduced oxygen partial pressures, reflecting conditions at 5000 m and 6000 m (16,404 and 19,685 ft), respectively. Eye movements were evaluated with a saccadometer. At normal oxygen pressure, Coriolis illusion resulted in 55% and 31% increases in mean saccade amplitude and duration, respectively, but a 32% increase in mean saccade frequency was only noted for saccades smaller than the angular distance between cockpit instruments, suggesting an increase in the number of correction saccades. At lower oxygen pressures a pronounced increase in the standard deviation of all measures was noticed; however, the pattern of changes remained unchanged. Simple measures of saccadic movement are not affected by short-term hypoxia, most likely due to compensatory mechanisms.

Cu/Mn bimetallic catalysis enables carbonylative Suzuki-Miyaura coupling with unactivated alkyl electrophiles.

PubMed

Pye, Dominic R; Cheng, Li-Jie; Mankad, Neal P

2017-07-01

A bimetallic system consisting of Cu-carbene and Mn-carbonyl co-catalysts was employed for carbonylative C-C coupling of arylboronic esters with alkyl halides, allowing for the convergent synthesis of ketones. The system operates under mild conditions and exhibits complementary reactivity to Pd catalysis. The method is compatible with a wide range of arylboronic ester nucleophiles and proceeds smoothly for both primary and secondary alkyl iodide electrophiles. Preliminary mechanistic experiments corroborate a hypothetical catalytic mechanism consisting of co-dependent cycles wherein the Cu-carbene co-catalyst engages in transmetallation to generate an organocopper nucleophile, while the Mn-carbonyl co-catalyst activates the alkyl halide electrophile by single-electron transfer and then undergoes reversible carbonylation to generate an acylmanganese electrophile. The two cycles then intersect with a heterobimetallic, product-releasing C-C coupling step.

O-Acetyl Side-Chains in Monosaccharides: Redundant NMR Spin-Couplings and Statistical Models for Acetate Ester Conformational Analysis.

PubMed

Turney, Toby; Pan, Qingfeng; Sernau, Luke; Carmichael, Ian; Zhang, Wenhui; Wang, Xiaocong; Woods, Robert J; Serianni, Anthony S

2017-01-12

α- and β-d-glucopyranose monoacetates 1-3 were prepared with selective 13 C enrichment in the O-acetyl side-chain, and ensembles of 13 C- 1 H and 13 C- 13 C NMR spin-couplings (J-couplings) were measured involving the labeled carbons. Density functional theory (DFT) was applied to a set of model structures to determine which J-couplings are sensitive to rotation of the ester bond θ. Eight J-couplings ( 1 J CC , 2 J CH , 2 J CC , 3 J CH , and 3 J CC ) were found to be sensitive to θ, and four equations were parametrized to allow quantitative interpretations of experimental J-values. Inspection of J-coupling ensembles in 1-3 showed that O-acetyl side-chain conformation depends on molecular context, with flanking groups playing a dominant role in determining the properties of θ in solution. To quantify these effects, ensembles of J-couplings containing four values were used to determine the precision and accuracy of several 2-parameter statistical models of rotamer distributions across θ in 1-3. The statistical method used to generate these models has been encoded in a newly developed program, MA'AT, which is available for public use. These models were compared to O-acetyl side-chain behavior observed in a representative sample of crystal structures, and in molecular dynamics (MD) simulations of O-acetylated model structures. While the functional form of the model had little effect on the precision of the calculated mean of θ in 1-3, platykurtic models were found to give more precise estimates of the width of the distribution about the mean (expressed as circular standard deviations). Validation of these 2-parameter models to interpret ensembles of redundant J-couplings using the O-acetyl system as a test case enables future extension of the approach to other flexible elements in saccharides, such as glycosidic linkage conformation.

Angular velocities, angular accelerations, and coriolis accelerations

NASA Technical Reports Server (NTRS)

Graybiel, A.

1975-01-01

Weightlessness, rotating environment, and mathematical analysis of Coriolis acceleration is described for man's biological effective force environments. Effects on the vestibular system are summarized, including the end organs, functional neurology, and input-output relations. Ground-based studies in preparation for space missions are examined, including functional tests, provocative tests, adaptive capacity tests, simulation studies, and antimotion sickness.

Myths, Misconceptions, and Misunderstandings: A Different Spin on Coriolis--Applying Frame of Reference

ERIC Educational Resources Information Center

DiSpezio, Michael A.

2011-01-01

This article addresses misconceptions surrounding the Coriolis force and describes how it should be presented as a function within inertial and noninertial frames of reference. Not only does this demonstrate the nature of science as it strives to best interpret the natural world (and presents alternative explanations), but it offers a rich…

Microgyroscope with closed loop output

NASA Technical Reports Server (NTRS)

Challoner, A. Dorian (Inventor); Gutierrez, Roman C. (Inventor); Tang, Tony K. (Inventor); Cargille, Donald R. (Inventor)

2002-01-01

A micro-gyroscope (10) having closed loop operation by a control voltage (V.sub.TY), that is demodulated by an output signal of the sense electrodes (S1, S2), providing Coriolis torque rebalance to prevent displacement of the micro-gyroscope (10) on the output axis (y-axis). The present invention provides wide-band, closed-loop operation for a micro-gyroscope (10) and allows the drive frequency to be closely tuned to a high Q sense axis resonance. A differential sense signal (S1-S2) is compensated and fed back by differentially changing the voltage on the drive electrodes to rebalance Coriolis torque. The feedback signal is demodulated in phase with the drive axis signal (K.sub..omega..crclbar..sub.x) to produce a measure of the Coriolis force.

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.

Nonlinear vibrations analysis of rotating drum-disk coupling structure

NASA Astrophysics Data System (ADS)

Chaofeng, Li; Boqing, Miao; Qiansheng, Tang; Chenyang, Xi; Bangchun, Wen

2018-04-01

A dynamic model of a coupled rotating drum-disk system with elastic support is developed in this paper. By considering the effects of centrifugal and Coriolis forces as well as rotation-induced hoop stress, the governing differential equation of the drum-disk is derived by Donnell's shell theory. The nonlinear amplitude-frequency characteristics of coupled structure are studied. The results indicate that the natural characteristics of the coupling structure are sensitive to the supporting stiffness of the disk, and the sensitive range is affected by rotating speeds. The circumferential wave numbers can affect the characteristics of the drum-disk structure. If the circumferential wave number n = 1 , the vibration response of the drum keeps a stable value under an unbalanced load of the disk, there is no coupling effect if n ≠ 1 . Under the excitation, the nonlinear hardening characteristics of the forward traveling wave are more evident than that of the backward traveling wave. Moreover, because of the coupling effect of the drum and the disk, the supporting stiffness of the disk has certain effect on the nonlinear characteristics of the forward and backward traveling waves. In addition, small length-radius and thickness-radius ratios have a significant effect on the nonlinear characteristics of the coupled structure, which means nonlinear shell theory should be adopted to design rotating drum's parameter for its specific structural parameters.

Torsion-rotation structure and quasi-symmetric-rotor behaviour for the CH3SH asymmetric CH3-bending and C-H stretching bands of E parentage

NASA Astrophysics Data System (ADS)

Lees, R. M.; Xu, Li-Hong; Guislain, B. G.; Reid, E. M.; Twagirayezu, S.; Perry, D. S.; Dawadi, M. B.; Thapaliya, B. P.; Billinghurst, B. E.

2018-01-01

High-resolution Fourier transform spectra of the asymmetric methyl-bending and methyl-stretching bands of CH3SH have been recorded employing synchrotron radiation at the FIR beamline of the Canadian Light Source. Analysis of the torsion-rotation structure and relative intensities has revealed the novel feature that for both bend and stretch the in-plane and out-of-plane modes behave much like a Coriolis-coupled l-doublet pair originating from degenerate E modes of a symmetric top. As the axial angular momentum K increases, the energies of the coupled "l = ±1" modes diverge linearly, with effective Coriolis ζ constants typical for symmetric tops. For the methyl-stretching states, separated at K = 0 by only about 1 cm-1, the assigned sub-bands follow a symmetric top Δ(K - l) = 0 selection rule, with only ΔK = -1 transitions observed to the upper l = -1 in-plane A‧ component and only ΔK = +1 transitions to the lower l = +1 out-of-plane A″ component. The K = 0 separation of the CH3-bending states is larger at 9.1 cm-1 with the l-ordering reversed. Here, both ΔK = +1 and ΔK = -1 transitions are seen for each l-component but with a large difference in relative intensity. Term values for the excited state levels have been fitted to J(J + 1) power-series expansions to obtain substate origins. These have then been fitted to a Fourier model to characterize the torsion-K-rotation energy patterns. For both pairs of vibrational states, the torsional energies display the customary oscillatory behaviour as a function of K and have inverted torsional splittings relative to the ground state. The spectra show numerous perturbations, indicating local resonances with the underlying bath of high torsional levels and vibrational combination and overtone states. The overall structure of the two pairs of bands represents a new regime in which the vibrational energy separations, torsional splittings and shifts due to molecular asymmetry are all of the same order, creating a challenging and complex vibration-torsion-rotation coupling environment.

Two-photon absorption cross sections within equation-of-motion coupled-cluster formalism using resolution-of-the-identity and Cholesky decomposition representations: Theory, implementation, and benchmarks

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

Nanda, Kaushik D.; Krylov, Anna I.

The equation-of-motion coupled-cluster (EOM-CC) methods provide a robust description of electronically excited states and their properties. Here, we present a formalism for two-photon absorption (2PA) cross sections for the equation-of-motion for excitation energies CC with single and double substitutions (EOM-CC for electronically excited states with single and double substitutions) wave functions. Rather than the response theory formulation, we employ the expectation-value approach which is commonly used within EOM-CC, configuration interaction, and algebraic diagrammatic construction frameworks. In addition to canonical implementation, we also exploit resolution-of-the-identity (RI) and Cholesky decomposition (CD) for the electron-repulsion integrals to reduce memory requirements and to increasemore » parallel efficiency. The new methods are benchmarked against the CCSD and CC3 response theories for several small molecules. We found that the expectation-value 2PA cross sections are within 5% from the quadratic response CCSD values. The RI and CD approximations lead to small errors relative to the canonical implementation (less than 4%) while affording computational savings. RI/CD successfully address the well-known issue of large basis set requirements for 2PA cross sections calculations. The capabilities of the new code are illustrated by calculations of the 2PA cross sections for model chromophores of the photoactive yellow and green fluorescent proteins.« less

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.

Coriolis effects on nonlinear oscillations of rotating cylinders and rings

NASA Technical Reports Server (NTRS)

Padovan, J.

1976-01-01

The effects which moderately large deflections have on the frequency spectrum of rotating rings and cylinders are considered. To develop the requisite solution, a variationally constrained version of the Lindstedt-Poincare procedure is employed. Based on the solution developed, in addition to considering the effects of displacement induced nonlinearity, the role of Coriolis forces is also given special consideration.

The etiology and drug therapy of kinesia: investigations by means of the coriolis effect under cyclizine.

PubMed

Reicke, N

1976-01-01

The typical symptoms of kinesia were produced in 30 healthy test subjects by means of the Coriolis effect and the effect of cyclizine upon them was investigated in a single blind trial. The drug showed a clear effect on the autonomic symptoms (nausea) while there was no evidence of inhibition of the peripheral vestibular function.

Geostrophic balance with a full Coriolis Force: implications for low latitutde studies

NASA Technical Reports Server (NTRS)

Juarez, M. de la Torre

2002-01-01

In its standard form, geostrophic balance uses a partial representation of the Coriolis force. The resulting formation has a singularity at the equator, and violates mass and momentum conservation. When the horizontal projection of the planetary rotation vector is considered, the singularity at the equator disappears, continuity can be preserved, and quasigeostrophy can be formulated at planetary scale.

Congenitally blind individuals rapidly adapt to coriolis force perturbations of their reaching movements

NASA Technical Reports Server (NTRS)

DiZio, P.; Lackner, J. R.

2000-01-01

Reaching movements made to visual targets in a rotating room are initially deviated in path and endpoint in the direction of transient Coriolis forces generated by the motion of the arm relative to the rotating environment. With additional reaches, movements become progressively straighter and more accurate. Such adaptation can occur even in the absence of visual feedback about movement progression or terminus. Here we examined whether congenitally blind and sighted subjects without visual feedback would demonstrate adaptation to Coriolis forces when they pointed to a haptically specified target location. Subjects were tested pre-, per-, and postrotation at 10 rpm counterclockwise. Reaching to straight ahead targets prerotation, both groups exhibited slightly curved paths. Per-rotation, both groups showed large initial deviations of movement path and curvature but within 12 reaches on average had returned to prerotation curvature levels and endpoints. Postrotation, both groups showed mirror image patterns of curvature and endpoint to the per-rotation pattern. The groups did not differ significantly on any of the performance measures. These results provide compelling evidence that motor adaptation to Coriolis perturbations can be achieved on the basis of proprioceptive, somatosensory, and motor information in the complete absence of visual experience.

The influence of the self-consistent mode structure on the Coriolis pinch effect

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

Peeters, A. G.; Camenen, Y.; Casson, F. J.

This paper discusses the effect of the mode structure on the Coriolis pinch effect [A. G. Peeters, C. Angioni, and D. Strintzi, Phys. Rev. Lett. 98, 265003 (2007)]. It is shown that the Coriolis drift effect can be compensated for by a finite parallel wave vector, resulting in a reduced momentum pinch velocity. Gyrokinetic simulations in full toroidal geometry reveal that parallel dynamics effectively removes the Coriolis pinch for the case of adiabatic electrons, while the compensation due to the parallel dynamics is incomplete for the case of kinetic electrons, resulting in a finite pinch velocity. The finite flux inmore » the case of kinetic electrons is interpreted to be related to the electron trapping, which prevents a strong asymmetry in the electrostatic potential with respect to the low field side position. The physics picture developed here leads to the discovery and explanation of two unexpected effects: First the pinch velocity scales with the trapped particle fraction (root of the inverse aspect ratio), and second there is no strong collisionality dependence. The latter is related to the role of the trapped electrons, which retain some symmetry in the eigenmode, but play no role in the perturbed parallel velocity.« less

Pyridine group assisted addition of diazo-compounds to imines in the 3-CC reaction of 2-aminopyridines, aldehydes, and diazo-compounds.

PubMed

Gulevich, Anton V; Helan, Victoria; Wink, Donald J; Gevorgyan, Vladimir

2013-02-15

A novel three-component coupling (3-CC) reaction of 2-aminoazines, aromatic aldehydes, and diazo-compounds producing polyfunctional β-amino-α-diazo-compounds has been developed. The reaction features an unprecedented heterocycle-assisted addition of a diazo-compound to an imine. The obtained diazoesters were efficiently converted into valuable heterocycles as well as β-amino acid derivatives.

Effect of channel coupling on the elastic scattering of lithium isotopes

NASA Astrophysics Data System (ADS)

Furumoto, T.; Suhara, T.; Itagaki, N.

2018-04-01

Herein, we investigated the channel coupling (CC) effect on the elastic scatterings of lithium (Li) isotopes (A =6 -9) for 12C and 28Si targets at E /A =50 -60 MeV. The wave functions of the Li isotopes were obtained using the stochastic multi-configuration mixing method based on the microscopic-cluster model. The proton radii of the 7Li, 8Li, and 9Li nuclei became smaller as the number of valence neutrons increased. The valence neutrons in the 8Li and 9Li nuclei exhibited a glue-like behavior, thereby attracting the α and t clusters. Based on the transition densities derived from these microscopic wave functions, the elastic-scattering cross section was calculated using a microscopic coupled-channel method with a complex G -matrix interaction. The existing experimental data for the elastic scatterings of the Li isotopes and 10Be nuclei were well reproduced. The Li isotope elastic cross sections were demonstrated for the 12C and 28Si targets at E /A =53 MeV. The glue-like effect of the valence neutrons on the Li isotope was clearly demonstrated by the CC effect on elastic scattering. Finally, we realize that the valence neutrons stabilized the bindings of the core parts and the CC effect related to core excitation was indeed reduced.

Sensitivities of Tropical Cyclones to Surface Friction and the Coriolis Parameter in a 2-D Cloud-Resolving Model

NASA Technical Reports Server (NTRS)

Chao, Winston C.; Chen, Baode; Tao, Wei-Kuo; Lau, William K. M. (Technical Monitor)

2002-01-01

The sensitivities to surface friction and the Coriolis parameter in tropical cyclogenesis are studied using an axisymmetric version of the Goddard cloud ensemble model. Our experiments demonstrate that tropical cyclogenesis can still occur without surface friction. However, the resulting tropical cyclone has very unrealistic structure. Surface friction plays an important role of giving the tropical cyclones their observed smaller size and diminished intensity. Sensitivity of the cyclogenesis process to surface friction. in terms of kinetic energy growth, has different signs in different phases of the tropical cyclone. Contrary to the notion of Ekman pumping efficiency, which implies a preference for the highest Coriolis parameter in the growth rate if all other parameters are unchanged, our experiments show no such preference.

Amide-Directed Photoredox Catalyzed C-C Bond Formation at Unactivated sp3 C-H Bonds

PubMed Central

Chu, John C. K.; Rovis, Tomislav

2017-01-01

Carbon-carbon (C-C) bond formation is paramount in the synthesis of biologically relevant molecules, modern synthetic materials and commodity chemicals such as fuels and lubricants. Traditionally, the presence of a functional group is required at the site of C-C bond formation. Strategies that allow C-C bond formation at inert carbon-hydrogen (C-H) bonds allow scientists to access molecules which would otherwise be inaccessible and to develop more efficient syntheses of complex molecules.1,2 Herein we report a method for the formation of C-C bonds by directed cleavage of traditionally non-reactive C-H bonds and their subsequent coupling with readily available alkenes. Our methodology allows for the selective C-C bond formation at single C-H bonds in molecules that contain a multitude of seemingly indifferentiable such bonds. Selectivity arises through a relayed photoredox catalyzed oxidation of an N-H bond. We anticipate our findings to serve as a starting point for functionalization at inert C-H bonds through a hydrogen atom transfer strategy. PMID:27732580

Correlated natural transition orbital framework for low-scaling excitation energy calculations (CorNFLEx).

PubMed

Baudin, Pablo; Kristensen, Kasper

2017-06-07

We present a new framework for calculating coupled cluster (CC) excitation energies at a reduced computational cost. It relies on correlated natural transition orbitals (NTOs), denoted CIS(D')-NTOs, which are obtained by diagonalizing generalized hole and particle density matrices determined from configuration interaction singles (CIS) information and additional terms that represent correlation effects. A transition-specific reduced orbital space is determined based on the eigenvalues of the CIS(D')-NTOs, and a standard CC excitation energy calculation is then performed in that reduced orbital space. The new method is denoted CorNFLEx (Correlated Natural transition orbital Framework for Low-scaling Excitation energy calculations). We calculate second-order approximate CC singles and doubles (CC2) excitation energies for a test set of organic molecules and demonstrate that CorNFLEx yields excitation energies of CC2 quality at a significantly reduced computational cost, even for relatively small systems and delocalized electronic transitions. In order to illustrate the potential of the method for large molecules, we also apply CorNFLEx to calculate CC2 excitation energies for a series of solvated formamide clusters (up to 4836 basis functions).

Synthesis and anti-obesity effects in vivo of Crotadihydrofuran C as a novel PPARγ antagonist from Crotalaria albida

NASA Astrophysics Data System (ADS)

Sun, Qin-Hu; Zhang, Yu; Chou, Gui-Xin

2017-04-01

Crotadihydrofuran C (CC) from the herbs of Crotalaria albida is able to inhibit adipocyte differentiation and lipid accumulation. However, the effects of CC on obesity and metabolic disorders have not yet been elucidated. In our study, the first enantioselective synthesis of the 2-isopropenyl dihydrofuran isoflavone skeleton (CC) is described. The convenient and efficient synthetic protocols developed skilfully solve the problems of the ortho-para directing group and Suzuki coupling reaction using a boronic acid pinacol ester that was more stable and easy to obtain. Furthermore, CC treatment of high-fat diet (HFD)-fed obese mice remarkably reduced their body weight, fat mass, and lipid level as well as improved insulin resistance and non-alcoholic fatty liver disease (NAFLD). A TR-FRET assay showed that CC was specifically bound to PPARγ LBD, which was further confirmed by the molecular docking study. These results suggest that CC could be a useful and potential natural product for treating metabolic diseases, including obesity, hyperlipidemia insulin resistance and NAFLD, without toxic side-effects.

Integrated metabolism in sponge-microbe symbiosis revealed by genome-centered metatranscriptomics.

PubMed

Moitinho-Silva, Lucas; Díez-Vives, Cristina; Batani, Giampiero; Esteves, Ana Is; Jahn, Martin T; Thomas, Torsten

2017-07-01

Despite an increased understanding of functions in sponge microbiomes, the interactions among the symbionts and between symbionts and host are not well characterized. Here we reconstructed the metabolic interactions within the sponge Cymbastela concentrica microbiome in the context of functional features of symbiotic diatoms and the host. Three genome bins (CcPhy, CcNi and CcThau) were recovered from metagenomic data of C. concentrica, belonging to the proteobacterial family Phyllobacteriaceae, the Nitrospira genus and the thaumarchaeal order Nitrosopumilales. Gene expression was estimated by mapping C. concentrica metatranscriptomic reads. Our analyses indicated that CcPhy is heterotrophic, while CcNi and CcThau are chemolithoautotrophs. CcPhy expressed many transporters for the acquisition of dissolved organic compounds, likely available through the sponge's filtration activity and symbiotic carbon fixation. Coupled nitrification by CcThau and CcNi was reconstructed, supported by the observed close proximity of the cells in fluorescence in situ hybridization. CcPhy facultative anaerobic respiration and assimilation by diatoms may consume the resulting nitrate. Transcriptional analysis of diatom and sponge functions indicated that these organisms are likely sources of organic compounds, for example, creatine/creatinine and dissolved organic carbon, for other members of the symbiosis. Our results suggest that organic nitrogen compounds, for example, creatine, creatinine, urea and cyanate, fuel the nitrogen cycle within the sponge. This study provides an unprecedented view of the metabolic interactions within sponge-microbe symbiosis, bridging the gap between cell- and community-level knowledge.

Pd-N-Heterocyclic Carbene (NHC) Organic Silica: Synthesis and Application in Carbon-Carbon Coupling Reactions

EPA Science Inventory

The first Pd-N-heterocyclic carbene (NHC) complex in the form of organic silica was prepared using sol-gel method and its application in Heck and Suzuki reaction were demonstrated. These C-C coupling reactions proceeded efficiently under the influence of microwave irradiation, wi...

Massively parallel implementations of coupled-cluster methods for electron spin resonance spectra. I. Isotropic hyperfine coupling tensors in large radicals

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

Verma, Prakash; Morales, Jorge A., E-mail: jorge.morales@ttu.edu; Perera, Ajith

2013-11-07

Coupled cluster (CC) methods provide highly accurate predictions of molecular properties, but their high computational cost has precluded their routine application to large systems. Fortunately, recent computational developments in the ACES III program by the Bartlett group [the OED/ERD atomic integral package, the super instruction processor, and the super instruction architecture language] permit overcoming that limitation by providing a framework for massively parallel CC implementations. In that scheme, we are further extending those parallel CC efforts to systematically predict the three main electron spin resonance (ESR) tensors (A-, g-, and D-tensors) to be reported in a series of papers. Inmore » this paper inaugurating that series, we report our new ACES III parallel capabilities that calculate isotropic hyperfine coupling constants in 38 neutral, cationic, and anionic radicals that include the {sup 11}B, {sup 17}O, {sup 9}Be, {sup 19}F, {sup 1}H, {sup 13}C, {sup 35}Cl, {sup 33}S,{sup 14}N, {sup 31}P, and {sup 67}Zn nuclei. Present parallel calculations are conducted at the Hartree-Fock (HF), second-order many-body perturbation theory [MBPT(2)], CC singles and doubles (CCSD), and CCSD with perturbative triples [CCSD(T)] levels using Roos augmented double- and triple-zeta atomic natural orbitals basis sets. HF results consistently overestimate isotropic hyperfine coupling constants. However, inclusion of electron correlation effects in the simplest way via MBPT(2) provides significant improvements in the predictions, but not without occasional failures. In contrast, CCSD results are consistently in very good agreement with experimental results. Inclusion of perturbative triples to CCSD via CCSD(T) leads to small improvements in the predictions, which might not compensate for the extra computational effort at a non-iterative N{sup 7}-scaling in CCSD(T). The importance of these accurate computations of isotropic hyperfine coupling constants to elucidate experimental ESR spectra, to interpret spin-density distributions, and to characterize and identify radical species is illustrated with our results from large organic radicals. Those include species relevant for organic chemistry, petroleum industry, and biochemistry, such as the cyclo-hexyl, 1-adamatyl, and Zn-porphycene anion radicals, inter alia.« less

Non-inertial calibration of vibratory gyroscopes

NASA Technical Reports Server (NTRS)

Gutierrez, Roman C. (Inventor); Tang, Tony K. (Inventor)

2003-01-01

The electrostatic elements already present in a vibratory gyroscope are used to simulate the Coriolis forces. An artificial electrostatic rotation signal is added to the closed-loop force rebalance system. Because the Coriolis force is at the same frequency as the artificial electrostatic force, the simulated force may be introduced into the system to perform an inertial test on MEMS vibratory gyroscopes without the use of a rotation table.

Long-term Morphological Modeling at Coastal Inlets

DTIC Science & Technology

2015-05-15

the Coriolis effect which in this case deflects the ebb jet towards the north. a. Initial b. 10 years Figure 3. Idealized inlet representing...In order to quantify the physical effects of long-term, regional climactic changes in the environment, numerical morphodynamic models must be able...atmospheric pressure, wave, river, and tidal forcing; and Coriolis -Stokes force. The sediment transport model simulates nonequilibrium total-load

Do Practical Standard Coupled Cluster Calculations Agree Better than Kohn–Sham Calculations with Currently Available Functionals When Compared to the Best Available Experimental Data for Dissociation Energies of Bonds to 3d Transition Metals?

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

Xu, Xuefei; Zhang, Wenjing; Tang, Mingsheng

2015-05-12

Coupled-cluster (CC) methods have been extensively used as the high-level approach in quantum electronic structure theory to predict various properties of molecules when experimental results are unavailable. It is often assumed that CC methods, if they include at least up to connected-triple-excitation quasiperturbative corrections to a full treatment of single and double excitations (in particular, CCSD(T)), and a very large basis set, are more accurate than Kohn–Sham (KS) density functional theory (DFT). In the present work, we tested and compared the performance of standard CC and KS methods on bond energy calculations of 20 3d transition metal-containing diatomic molecules againstmore » the most reliable experimental data available, as collected in a database called 3dMLBE20. It is found that, although the CCSD(T) and higher levels CC methods have mean unsigned deviations from experiment that are smaller than most exchange-correlation functionals for metal–ligand bond energies of transition metals, the improvement is less than one standard deviation of the mean unsigned deviation. Furthermore, on average, almost half of the 42 exchange-correlation functionals that we tested are closer to experiment than CCSD(T) with the same extended basis set for the same molecule. The results show that, when both relativistic and core–valence correlation effects are considered, even the very high-level (expensive) CC method with single, double, triple, and perturbative quadruple cluster operators, namely, CCSDT(2)Q, averaged over 20 bond energies, gives a mean unsigned deviation (MUD(20) = 4.7 kcal/mol when one correlates only valence, 3p, and 3s electrons of transition metals and only valence electrons of ligands, or 4.6 kcal/mol when one correlates all core electrons except for 1s shells of transition metals, S, and Cl); and that is similar to some good xc functionals (e.g., B97-1 (MUD(20) = 4.5 kcal/mol) and PW6B95 (MUD(20) = 4.9 kcal/mol)) when the same basis set is used. We found that, for both coupled cluster calculations and KS calculations, the T1 diagnostics correlate the errors better than either the M diagnostics or the B1 DFT-based diagnostics. The potential use of practical standard CC methods as a benchmark theory is further confounded by the finding that CC and DFT methods usually have different signs of the error. We conclude that the available experimental data do not provide a justification for using conventional single-reference CC theory calculations to validate or test xc functionals for systems involving 3d transition metals.« less

Alkali metal mediated C-C bond coupling reaction

NASA Astrophysics Data System (ADS)

Tachikawa, Hiroto

2015-02-01

Metal catalyzed carbon-carbon (C-C) bond formation is one of the important reactions in pharmacy and in organic chemistry. In the present study, the electron and hole capture dynamics of a lithium-benzene sandwich complex, expressed by Li(Bz)2, have been investigated by means of direct ab-initio molecular dynamics method. Following the electron capture of Li(Bz)2, the structure of [Li(Bz)2]- was drastically changed: Bz-Bz parallel form was rapidly fluctuated as a function of time, and a new C-C single bond was formed in the C1-C1' position of Bz-Bz interaction system. In the hole capture, the intermolecular vibration between Bz-Bz rings was only enhanced. The mechanism of C-C bond formation in the electron capture was discussed on the basis of theoretical results.

Pyridine Group-Assisted Addition of Diazo-Compounds to Imines in the 3-CC Reaction of 2-Aminopyridines, Aldehydes, and Diazo-Compounds

PubMed Central

Gulevich, Anton V.; Helan, Victoria; Wink, Donald J.

2013-01-01

A novel three-component (3-CC) coupling reaction of 2-aminoazines, aromatic aldehydes and diazo-compounds producing polyfunctional β-amino-α-diazo-compounds has been developed. The reaction features an unprecedented heterocycle-assisted addition of a diazo-compound to an imine. The obtained diazoesters were efficiently converted into valuable heterocycles, as well as to β-amino acid derivatives. PMID:23373731

Switching on elusive organometallic mechanisms with photoredox catalysis

NASA Astrophysics Data System (ADS)

Terrett, Jack A.; Cuthbertson, James D.; Shurtleff, Valerie W.; MacMillan, David W. C.

2015-08-01

Transition-metal-catalysed cross-coupling reactions have become one of the most used carbon-carbon and carbon-heteroatom bond-forming reactions in chemical synthesis. Recently, nickel catalysis has been shown to participate in a wide variety of C-C bond-forming reactions, most notably Negishi, Suzuki-Miyaura, Stille, Kumada and Hiyama couplings. Despite the tremendous advances in C-C fragment couplings, the ability to forge C-O bonds in a general fashion via nickel catalysis has been largely unsuccessful. The challenge for nickel-mediated alcohol couplings has been the mechanistic requirement for the critical C-O bond-forming step (formally known as the reductive elimination step) to occur via a Ni(III) alkoxide intermediate. Here we demonstrate that visible-light-excited photoredox catalysts can modulate the preferred oxidation states of nickel alkoxides in an operative catalytic cycle, thereby providing transient access to Ni(III) species that readily participate in reductive elimination. Using this synergistic merger of photoredox and nickel catalysis, we have developed a highly efficient and general carbon-oxygen coupling reaction using abundant alcohols and aryl bromides. More notably, we have developed a general strategy to `switch on' important yet elusive organometallic mechanisms via oxidation state modulations using only weak light and single-electron-transfer catalysts.

Switching on elusive organometallic mechanisms with photoredox catalysis.

PubMed

Terrett, Jack A; Cuthbertson, James D; Shurtleff, Valerie W; MacMillan, David W C

2015-08-20

Transition-metal-catalysed cross-coupling reactions have become one of the most used carbon-carbon and carbon-heteroatom bond-forming reactions in chemical synthesis. Recently, nickel catalysis has been shown to participate in a wide variety of C-C bond-forming reactions, most notably Negishi, Suzuki-Miyaura, Stille, Kumada and Hiyama couplings. Despite the tremendous advances in C-C fragment couplings, the ability to forge C-O bonds in a general fashion via nickel catalysis has been largely unsuccessful. The challenge for nickel-mediated alcohol couplings has been the mechanistic requirement for the critical C-O bond-forming step (formally known as the reductive elimination step) to occur via a Ni(III) alkoxide intermediate. Here we demonstrate that visible-light-excited photoredox catalysts can modulate the preferred oxidation states of nickel alkoxides in an operative catalytic cycle, thereby providing transient access to Ni(III) species that readily participate in reductive elimination. Using this synergistic merger of photoredox and nickel catalysis, we have developed a highly efficient and general carbon-oxygen coupling reaction using abundant alcohols and aryl bromides. More notably, we have developed a general strategy to 'switch on' important yet elusive organometallic mechanisms via oxidation state modulations using only weak light and single-electron-transfer catalysts.

Motion of a Point Mass in a Rotating Disc: A Quantitative Analysis of the Coriolis and Centrifugal Force

NASA Astrophysics Data System (ADS)

Haddout, Soufiane

2016-06-01

In Newtonian mechanics, the non-inertial reference frames is a generalization of Newton's laws to any reference frames. While this approach simplifies some problems, there is often little physical insight into the motion, in particular into the effects of the Coriolis force. The fictitious Coriolis force can be used by anyone in that frame of reference to explain why objects follow curved paths. In this paper, a mathematical solution based on differential equations in non-inertial reference is used to study different types of motion in rotating system. In addition, the experimental data measured on a turntable device, using a video camera in a mechanics laboratory was conducted to compare with mathematical solution in case of parabolically curved, solving non-linear least-squares problems, based on Levenberg-Marquardt's and Gauss-Newton algorithms.

The triaxiality and Coriolis effects on the fission barrier in isovolumic nuclei with mass number A = 256 based on multidimensional total Routhian surface calculations

NASA Astrophysics Data System (ADS)

Chai, Qing-Zhen; Zhao, Wei-Juan; Wang, Hua-Lei; Liu, Min-Liang; Xu, Fu-Rong

2018-05-01

The triaxiality and Coriolis effects on the first fission barrier in even-even nuclei with A=256 have been studied in terms of the approach of multidimensional total Routhian surface calculations. The present results are compared with available data and other theories, showing a good agreement. Based on the deformation energy or Routhian curves, the first fission barriers are analyzed, focusing on their shapes, heights, and evolution with rotation. It is found that, relative to the effect on the ground-state minimum, the saddle point, at least the first one, can be strongly affected by the triaxial deformation degree of freedom and Coriolis force. The evolution trends of the macroscopic and microscopic (shell and pairing) contributions as well as the triaxial fission barriers are briefly discussed.

Reducing the data: Analysis of the role of vascular geometry on blood flow patterns in curved vessels

NASA Astrophysics Data System (ADS)

Alastruey, Jordi; Siggers, Jennifer H.; Peiffer, Véronique; Doorly, Denis J.; Sherwin, Spencer J.

2012-03-01

Three-dimensional simulations of blood flow usually produce such large quantities of data that they are unlikely to be of clinical use unless methods are available to simplify our understanding of the flow dynamics. We present a new method to investigate the mechanisms by which vascular curvature and torsion affect blood flow, and we apply it to the steady-state flow in single bends, helices, double bends, and a rabbit thoracic aorta based on image data. By calculating forces and accelerations in an orthogonal coordinate system following the centreline of each vessel, we obtain the inertial forces (centrifugal, Coriolis, and torsional) explicitly, which directly depend on vascular curvature and torsion. We then analyse the individual roles of the inertial, pressure gradient, and viscous forces on the patterns of primary and secondary velocities, vortical structures, and wall stresses in each cross section. We also consider cross-sectional averages of the in-plane components of these forces, which can be thought of as reducing the dynamics of secondary flows onto the vessel centreline. At Reynolds numbers between 50 and 500, secondary motions in the directions of the local normals and binormals behave as two underdamped oscillators. These oscillate around the fully developed state and are coupled by torsional forces that break the symmetry of the flow. Secondary flows are driven by the centrifugal and torsional forces, and these are counterbalanced by the in-plane pressure gradients generated by the wall reaction. The viscous force primarily opposes the pressure gradient, rather than the inertial forces. In the axial direction, and depending on the secondary motion, the curvature-dependent Coriolis force can either enhance or oppose the bulk of the axial flow, and this shapes the velocity profile. For bends with little or no torsion, the Coriolis force tends to restore flow axisymmetry. The maximum circumferential and axial wall shear stresses along the centreline correlate well with the averaged in-plane pressure gradient and the radial displacement of the peak axial velocity, respectively. We conclude with a discussion of the physiological implications of these results.

The rotation-vibration structure of the SO 2 C 1B 2 state explained by a new internal coordinate force field

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

Jiang, Jun; Park, G. Barratt; Field, Robert W.

A new quartic force field for the SO 2 C ~ 1B 2 state has been derived, based on high resolution data from S 16O 2 and S 18O 2. Included are eight b 2 symmetry vibrational levels of S 16O 2 reported in the first paper of this series [G. B. Park, et al., J. Chem. Phys. 144, 144311 (2016)]. Many of the experimental observables not included in the fit, such as the Franck-Condon intensities and the Coriolis-perturbed effective C rotational constants of highly anharmonic C ~ state vibrational levels, are well reproduced using our force field. Because themore » two stretching modes of the C ~ state are strongly coupled via Fermi-133 interaction, the vibrational structure of the C state is analyzed in a Fermi-system basis set, constructed explicitly in this work via partial diagonalization of the vibrational Hamiltonian. The physical significance of the Fermi-system basis is discussed in terms of semiclassical dynamics, based on study of Fermi-resonance systems by Kellman and coworkers [M. E. Kellman and L. Xiao, J. Chem. Phys. 93, 5821 (1990)]. By diagonalizing the vibrational Hamiltonian in the Fermi-system basis, the vibrational characters of all vibrational levels can be determined unambiguously. It is shown that the bending mode cannot be treated separately from the coupled stretching modes, particularly at vibrational energies of more than 2000 cm –1. Based on our force field, the structure of the Coriolis interactions in the C ~ state of SO 2 is also discussed. As a result, we identify the origin of the alternating patterns in the effective C rotational constants of levels in the vibrational progressions of the symmetry-breaking mode, ν β (which correlates with the antisymmetric stretching mode in our assignment scheme).« less

The rotation-vibration structure of the SO 2 C 1B 2 state explained by a new internal coordinate force field

DOE PAGES

Jiang, Jun; Park, G. Barratt; Field, Robert W.

2016-04-14

A new quartic force field for the SO 2 C ~ 1B 2 state has been derived, based on high resolution data from S 16O 2 and S 18O 2. Included are eight b 2 symmetry vibrational levels of S 16O 2 reported in the first paper of this series [G. B. Park, et al., J. Chem. Phys. 144, 144311 (2016)]. Many of the experimental observables not included in the fit, such as the Franck-Condon intensities and the Coriolis-perturbed effective C rotational constants of highly anharmonic C ~ state vibrational levels, are well reproduced using our force field. Because themore » two stretching modes of the C ~ state are strongly coupled via Fermi-133 interaction, the vibrational structure of the C state is analyzed in a Fermi-system basis set, constructed explicitly in this work via partial diagonalization of the vibrational Hamiltonian. The physical significance of the Fermi-system basis is discussed in terms of semiclassical dynamics, based on study of Fermi-resonance systems by Kellman and coworkers [M. E. Kellman and L. Xiao, J. Chem. Phys. 93, 5821 (1990)]. By diagonalizing the vibrational Hamiltonian in the Fermi-system basis, the vibrational characters of all vibrational levels can be determined unambiguously. It is shown that the bending mode cannot be treated separately from the coupled stretching modes, particularly at vibrational energies of more than 2000 cm –1. Based on our force field, the structure of the Coriolis interactions in the C ~ state of SO 2 is also discussed. As a result, we identify the origin of the alternating patterns in the effective C rotational constants of levels in the vibrational progressions of the symmetry-breaking mode, ν β (which correlates with the antisymmetric stretching mode in our assignment scheme).« less

Rovibrational Interactions in the Ground and Two Lowest Excited Vibrational States of Methoxy Isocyanate

NASA Astrophysics Data System (ADS)

Pienkina, A.; Margulès, L.; Motiyenko, R. A.; Guillemin, J.-C.

2017-06-01

Recent detection of methyl isocyanate (CH_3NCO) in the Orion, towards Sgr B2(N) and on the surface of the comet 67P/Churyumov-Gerasimenko motivated us to study another isocyanate, methoxy isocyanate (CH_3ONCO) as a possible candidate molecule for searches in the interstellar clouds. Neither identification or laboratory rotational spectra of CH_3ONCO has been reported up to now. Methoxy isocyanate was synthesized by the flash vacuum pyrolysis of N-Methoxycarbonyl-O-methyl-hydroxylamine (MeOC(O)NHOMe) at a temperature of 800 K. Experimental spectrum of CH_3ONCO was recorded in situ in the millimeter-wave range (75-105 GHz and 150-330 GHz) using Lille's fast-scan fully solid-state DDS spectrometer. The recorded spectrum is strongly perturbed due to the interaction between the overall rotation and the skeletal torsion. Perturbations affect even rotational transitions with low K_a levels of the ground vibrational state, appearing in shifting frequency predictions and intensities distortions of the lines. The interactions are significant due to the relatively small vibrational energy difference (≈50 \\wn) between the states and different representations of the C_s symmetry point group for the ground (A'), ν_{18}=1 (A'') and ν_{18}=2 (A') vibrational states, thus leading to a "ladder" of multiple resonances by means of a-, and b-type Coriolis coupling. The global fit analysis of the rotational spectrum of methoxy isocyanate using Coriolis coupling terms in the ground and two lowest vibrational states (ν_{18}=1 and ν_{18}=2) will be presented. J. Cernicharo, N. Marcelino, E. Roueff et al. 2012, ApJ, 759, L43 D. T. Halfen, V. V. Ilyushin, & L. M. Ziurys, 2015, ApJ, 812, L5 F. Goesmann, H. Rosenbauer, J. H. Bredehöft et al. 2015, Science, 349.6247, aab0689 This work was funded by the French ANR under the Contract No. ANR-13-BS05-0008-02 IMOLABS.

Linear response coupled cluster theory with the polarizable continuum model within the singles approximation for the solvent response.

PubMed

Caricato, Marco

2018-04-07

We report the theory and the implementation of the linear response function of the coupled cluster (CC) with the single and double excitations method combined with the polarizable continuum model of solvation, where the correlation solvent response is approximated with the perturbation theory with energy and singles density (PTES) scheme. The singles name is derived from retaining only the contribution of the CC single excitation amplitudes to the correlation density. We compare the PTES working equations with those of the full-density (PTED) method. We then test the PTES scheme on the evaluation of excitation energies and transition dipoles of solvated molecules, as well as of the isotropic polarizability and specific rotation. Our results show a negligible difference between the PTED and PTES schemes, while the latter affords a significantly reduced computational cost. This scheme is general and can be applied to any solvation model that includes mutual solute-solvent polarization, including explicit models. Therefore, the PTES scheme is a competitive approach to compute response properties of solvated systems using CC methods.

Linear response coupled cluster theory with the polarizable continuum model within the singles approximation for the solvent response

NASA Astrophysics Data System (ADS)

Caricato, Marco

2018-04-01

We report the theory and the implementation of the linear response function of the coupled cluster (CC) with the single and double excitations method combined with the polarizable continuum model of solvation, where the correlation solvent response is approximated with the perturbation theory with energy and singles density (PTES) scheme. The singles name is derived from retaining only the contribution of the CC single excitation amplitudes to the correlation density. We compare the PTES working equations with those of the full-density (PTED) method. We then test the PTES scheme on the evaluation of excitation energies and transition dipoles of solvated molecules, as well as of the isotropic polarizability and specific rotation. Our results show a negligible difference between the PTED and PTES schemes, while the latter affords a significantly reduced computational cost. This scheme is general and can be applied to any solvation model that includes mutual solute-solvent polarization, including explicit models. Therefore, the PTES scheme is a competitive approach to compute response properties of solvated systems using CC methods.

Palladium complexes of N-heterocyclic carbenes as catalysts for cross-coupling reactions--a synthetic chemist's perspective.

PubMed

Kantchev, Eric Assen B; O'Brien, Christopher J; Organ, Michael G

2007-01-01

Palladium-catalyzed C-C and C-N bond-forming reactions are among the most versatile and powerful synthetic methods. For the last 15 years, N-heterocyclic carbenes (NHCs) have enjoyed increasing popularity as ligands in Pd-mediated cross-coupling and related transformations because of their superior performance compared to the more traditional tertiary phosphanes. The strong sigma-electron-donating ability of NHCs renders oxidative insertion even in challenging substrates facile, while their steric bulk and particular topology is responsible for fast reductive elimination. The strong Pd-NHC bonds contribute to the high stability of the active species, even at low ligand/Pd ratios and high temperatures. With a number of commercially available, stable, user-friendly, and powerful NHC-Pd precatalysts, the goal of a universal cross-coupling catalyst is within reach. This Review discusses the basics of Pd-NHC chemistry to understand the peculiarities of these catalysts and then gives a critical discussion on their application in C-C and C-N cross-coupling as well as carbopalladation reactions.

Prototype Design and Mission Analysis for a Small Satellite Exploiting Environmental Disturbances for Attitude Stabilization

DTIC Science & Technology

2016-03-01

acceleration of the shifting masses experiences a Coriolis Effect due to the angular velocity of the spacecraft. However, the perpendicular component of...angular velocity. If we neglect the Coriolis Effect in absolute acceleration, both terms become zero. Then, Equation 4.22 becomes ( )0 0 0 0 0...METHOD ......................................................83  C.  EXPLORATION OF THE ALTITUDE AND INCLINATION EFFECTS ON THE CONTROL

Coriolis effect on dynamic stall in a vertical axis wind turbine

NASA Astrophysics Data System (ADS)

Tsai, Hsieh-Chen; Colonius, Tim

2013-11-01

The immersed boundary method is used to simulate the flow around a two-dimensional rotating NACA 0018 airfoil at moderate (sub-scale) Reynolds number in order to investigate separated flow occurring on a vertical-axis wind turbine (VAWT). The influence of dynamic stall on the forces is characterized as a function of tip-speed ratio. The influence of the Coriolis effect is also investigated by comparing the rotating airfoil to one undergoing a surging and pitching motion that produces an equivalent speed and angle-of-attack variation over the cycle. While the Coriolis force produces only small differences in the averaged forces, it plays an important role during dynamic stall. Due to the fact that the Coriolis force deflects the fluid and propagates the vortices differently, the wake-capturing phenomenon of the trailing edge vortex is observed in the flow around the rotating airfoil during a certain range of azimuthal angle. This wake-capturing of the trailing edge vortex leads to a large decrease in lift. However, because of the phase difference between each wake-capturing, there are only small differences in the average forces. The simulations are also compared to results from companion water-tunnel experiments at Caltech. This project is supported by the Gordon and Betty Moore Foundation.

Evidence of Paternal N5, N10 - Methylenetetrahydrofolate Reductase (MTHFR) C677T Gene Polymorphism in Couples with Recurrent Spontaneous Abortions (RSAs) in Kolar District- A South West of India

PubMed Central

Vanilla, Shiny; Kotur, Pushpa F; Kutty, Moideen A; Vegi, Pradeep Kumar

2015-01-01

Introduction: Recurrent spontaneous abortion (RSA) is a multifactorial clinical obstetrics complication commonly occurring in pregnancy. Many research studies have noted the mutations such as C677T in N5, N10 - Methylenetetrahydrofolate reductase (MTHFR)gene which is regarded as RSA risk factor. This study was carried out to determine the occurrence of frequency of C677T of the MTHFR gene mutations with RSA. Aim: The purpose of present study is to determine the frequency of MTHFR C677T polymorphisms in couples with recurrent pregnancy loss and the impact of paternal polymorphisms of MTHFR C677T in recurrent pregnancy loss in population of couples living in Kolar district of Karnataka with RSA. Design: A total of 15 couples with a history of two or more unexplained RSA were enrolled as subjects in the study and a total of 15 couples with normal reproductive history, having two or more children and no history of miscarriages were enrolled as controls. Materials and Methods: DNA extraction from samples case and control group couples and its quantification by Agarose gel electrophoresis, assessment of DNA purity, MTHFR C 677T gene mutation detection by PCR-RFLP method. Statistical analysis: Carried out by web based online SPSS tool. Results: The frequency of C677T genotype showed homozygous wild type CC (80%), heterozygous CT type (13.3%) and homozygous mutation TT type (6.67%) observed in males. Similarly from female’s homozygous wild type CC (86.6%), heterozygous type (13.3%), and homozygous type mutations TT (0%) was recorded. In couple control groups, we observed homozygous wild type CC (86.6%), heterozygous CT type (13.3%) and homozygous type mutations TT type (0%). Conclusion: We noticed a high frequency of MTHFR specifically T allele associated with paternal side.Therefore, the present study indicated the impact of paternal gene polymorphism of MTHFR C677T on screening in couples with recurrent pregnancy loss. PMID:25859445

The influence of FLiNaK salt impregnation on the mechanical properties of a 2D woven C/C composite

NASA Astrophysics Data System (ADS)

Zhang, Dongsheng; Xia, Huihao; Yang, Xinmei; Feng, Shanglei; Song, Jinliang; Zhou, Xingtai

2017-03-01

Impregnating of molten LiF-NaF-KF salt (LiF-NaF-KF: 46.5-11.5-42 mol%, FLiNaK) into a 2D woven C/C composite was performed at 650 °C under different pressure. The weight gain and mechanical properties change of the 2D woven C/C composite after FLiNaK salt impregnation were measured. The FLiNaK salt distribution into the 2D woven C/C composite was observed by X-ray computed tomography (X-ray CT) and scanning electron microscopy. The results showed that the weight gain of the 2D woven C/C composite increased with increasing impregnating pressure. In X-ray CT images, FLiNaK salt was distributed into the open pores and fissures among fiber bundles and neighboring plies. The interlaminar shear strength, compressive strength, and flexural strength of the 2D woven C/C composite increased with the increase of weight gain. The influence of FLiNaK salt impregnation on the mechanical properties was attributed to the coupling effect of re-densification of FLiNaK salt impregnation and residual stress formed in 2D woven C/C composite.

Airborne asbestos in Colorado public schools.

PubMed

Chadwick, D A; Buchan, R M; Beaulieu, H J

1985-02-01

Levels of airborne asbestos for six Colorado public school facilities with sprayed-on asbestos materials were documented using three analytical techniques. Phase contrast microscopy showed levels up to the thousandths of a fiber per cubic centimeter (f/cc), scanning electron microscopy (SEM) up to the hundredths of a f/cc, and transmission electron microscopy coupled to selected area electron diffraction and energy dispersive X-ray analysis (TEM-SAED-EDXA) up to the tenths of an asbestos f/cc. Phase contrast microscopy was found to be an inadequate analytical technique for documenting the levels of airborne asbestos fibers in the schools: only large fibers which were not embedded in the filter were counted, and asbestos fibers were not distinguished from nonasbestos.

Carbon X-ray absorption spectra of fluoroethenes and acetone: A study at the coupled cluster, density functional, and static-exchange levels of theory

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

Fransson, Thomas; Norman, Patrick; Coriani, Sonia

2013-03-28

Near carbon K-edge X-ray absorption fine structure spectra of a series of fluorine-substituted ethenes and acetone have been studied using coupled cluster and density functional theory (DFT) polarization propagator methods, as well as the static-exchange (STEX) approach. With the complex polarization propagator (CPP) implemented in coupled cluster theory, relaxation effects following the excitation of core electrons are accounted for in terms of electron correlation, enabling a systematic convergence of these effects with respect to electron excitations in the cluster operator. Coupled cluster results have been used as benchmarks for the assessment of propagator methods in DFT as well as themore » state-specific static-exchange approach. Calculations on ethene and 1,1-difluoroethene illustrate the possibility of using nonrelativistic coupled cluster singles and doubles (CCSD) with additional effects of electron correlation and relativity added as scalar shifts in energetics. It has been demonstrated that CPP spectra obtained with coupled cluster singles and approximate doubles (CC2), CCSD, and DFT (with a Coulomb attenuated exchange-correlation functional) yield excellent predictions of chemical shifts for vinylfluoride, 1,1-difluoroethene, trifluoroethene, as well as good spectral features for acetone in the case of CCSD and DFT. Following this, CPP-DFT is considered to be a viable option for the calculation of X-ray absorption spectra of larger {pi}-conjugated systems, and CC2 is deemed applicable for chemical shifts but not for studies of fine structure features. The CCSD method as well as the more approximate CC2 method are shown to yield spectral features relating to {pi}*-resonances in good agreement with experiment, not only for the aforementioned molecules but also for ethene, cis-1,2-difluoroethene, and tetrafluoroethene. The STEX approach is shown to underestimate {pi}*-peak separations due to spectral compressions, a characteristic which is inherent to this method.« less

Carbon X-ray absorption spectra of fluoroethenes and acetone: a study at the coupled cluster, density functional, and static-exchange levels of theory.

PubMed

Fransson, Thomas; Coriani, Sonia; Christiansen, Ove; Norman, Patrick

2013-03-28

Near carbon K-edge X-ray absorption fine structure spectra of a series of fluorine-substituted ethenes and acetone have been studied using coupled cluster and density functional theory (DFT) polarization propagator methods, as well as the static-exchange (STEX) approach. With the complex polarization propagator (CPP) implemented in coupled cluster theory, relaxation effects following the excitation of core electrons are accounted for in terms of electron correlation, enabling a systematic convergence of these effects with respect to electron excitations in the cluster operator. Coupled cluster results have been used as benchmarks for the assessment of propagator methods in DFT as well as the state-specific static-exchange approach. Calculations on ethene and 1,1-difluoroethene illustrate the possibility of using nonrelativistic coupled cluster singles and doubles (CCSD) with additional effects of electron correlation and relativity added as scalar shifts in energetics. It has been demonstrated that CPP spectra obtained with coupled cluster singles and approximate doubles (CC2), CCSD, and DFT (with a Coulomb attenuated exchange-correlation functional) yield excellent predictions of chemical shifts for vinylfluoride, 1,1-difluoroethene, trifluoroethene, as well as good spectral features for acetone in the case of CCSD and DFT. Following this, CPP-DFT is considered to be a viable option for the calculation of X-ray absorption spectra of larger π-conjugated systems, and CC2 is deemed applicable for chemical shifts but not for studies of fine structure features. The CCSD method as well as the more approximate CC2 method are shown to yield spectral features relating to π∗-resonances in good agreement with experiment, not only for the aforementioned molecules but also for ethene, cis-1,2-difluoroethene, and tetrafluoroethene. The STEX approach is shown to underestimate π∗-peak separations due to spectral compressions, a characteristic which is inherent to this method.

Quantifying the Performances of DFT for Predicting Vibrationally Resolved Optical Spectra: Asymmetric Fluoroborate Dyes as Working Examples.

PubMed

Bednarska, Joanna; Zaleśny, Robert; Bartkowiak, Wojciech; Ośmiałowski, Borys; Medved', Miroslav; Jacquemin, Denis

2017-09-12

This article aims at a quantitative assessment of the performances of a panel of exchange-correlation functionals, including semilocal (BLYP and PBE), global hybrids (B3LYP, PBE0, M06, BHandHLYP, M06-2X, and M06-HF), and range-separated hybrids (CAM-B3LYP, LC-ωPBE, LC-BLYP, ωB97X, and ωB97X-D), in predicting the vibrationally resolved absorption spectra of BF 2 -carrying compounds. To this end, for 19 difluoroborates as examples, we use, as a metric, the vibrational reorganization energy (λ vib ) that can be determined based on the computationally efficient linear coupling model (a.k.a. vertical gradient method). The reference values of λ vib were determined by employing the CC2 method combined with the cc-pVTZ basis set for a representative subset of molecules. To validate the performances of CC2, comparisons with experimental data have been carried out as well. This study shows that the vibrational reorganization energy, involving Huang-Rhys factors and normal-mode frequencies, can indeed be used to quantify the reliability of functionals in the calculations of the vibrational fine structure of absorption bands, i.e., an accurate prediction of the vibrational reorganization energy leads to absorption band shapes better fitting the selected reference. The CAM-B3LYP, M06-2X, ωB97X-D, ωB97X, and BHandHLYP functionals all deliver vibrational reorganization energies with absolute relative errors smaller than 20% compared to CC2, whereas 10% accuracy can be achieved with the first three functionals. Indeed, the set of examined exchange-correlation functionals can be divided into three groups: (i) BLYP, B3LYP, PBE, PBE0, and M06 yield inaccurate band shapes (λ vib,TDDFT < λ vib,CC2 ), (ii) BHandHLYP, CAM-B3LYP, M06-2X, ωB97X, and ωB97X-D provide accurate band shapes (λ vib,TDDFT ≈ λ vib,CC2 ), and (iii) LC-ωPBE, LC-BLYP, and M06-HF deliver rather poor band topologies (λ vib,TDDFT > λ vib,CC2 ). This study also demonstrates that λ vib can be reliably estimated using the CC2 model and the relatively small cc-pVDZ basis set. Therefore, the linear coupling model combined with the CC2/cc-pVDZ level of theory can be used as a very efficient approach to determine λ vib values that can be used to select the most adequate functional for more accurate vibronic calculations, e.g., including more refined models and environmental effects.

The Experiment and Numerical Simulation of Composite Countersunk-head Fasteners Pull-through Mechanical Behavior

NASA Astrophysics Data System (ADS)

Mu, Junwu; Guan, Zhidong; Bian, Tianya; Li, Zengshan; Wang, Kailun; Liu, Sui

2014-10-01

Fasteners made of the anisotropic carbon/carbon (C/C) composite material have been developed for joining C/C composite material components in the high-temperature environment. The fastener specimens are fabricated from the C/C composites which are made from laminated carbon cloths with Z-direction carbon fibers being punctured as perform. Densification process cycles such as the thermal gradient chemical vapor infiltration (CVI) technology were repeated to obtain high density C/C composites fastener. The fasteners were machined parallel to the carbon cloths (X-Y direction). A method was proposed to test pull-through mechanical behavior of the countersunk-head C/C composite material fasteners. The damage morphologies of the fasteners were observed through the charge coupled device (CCD) and the scanning electron microscope (SEM). The internal micro-structure were observed through the high-resolution Mirco-CT systems. Finally, an excellent simulation of the C/C composite countersunk-head fasteners were performed with the finite element method (FEM), in which the damage evolution model of the fastener was established based on continuum damage mechanics. The simulation is correspond well with the test result . The damage evolution process and the relation between the countersunk depth and the ultimate load was investigated.

Symplastic isolation of the sieve element-companion cell complex in the phloem of Ricinus communis and Salix alba stems.

PubMed

van Bel, A J; Kempers, R

1991-12-01

The anatomical and physiological isolation of the sieve element-companion cell complex (se-cc complex) was investigated in stems of Ricinus communis L. and Salix alba L. In Ricinus, the plasmodesmatal frequencies were in the proportions 8∶1∶2∶30, in the order given, at the interfaces between sieve tube-companion cell, sieve tube-phloem parenchyma cell, companion cellphloem parenchyma cell, and phloem parenchyma cellphloem parenchyma cell. The membrane potentials of the se-cc complex and the surrounding phloem-parenchyma cells sharply contrasted: the membrane potential of the se-cc complex was about twice as negative as that of the phloem parenchyma. Lucifer Yellow CH injected into the sieve element or into the companion cell remained within the se-cc complex. Dye introduced into phloem parenchyma only moved (mostly poorly) to other phloem-parenchyma cells. The distribution of the plasmodesmatal frequencies, the differential dye-coupling and the sharp discontinuities in membrane potentials indicate that the se-cc complexes constitute symplast domains in the stem phloem. Symplastic autonomy is discussed as a basic necessity for the functioning of the se-cc complex in the stem.

Quantum cluster theory for the polarizable continuum model. I. The CCSD level with analytical first and second derivatives.

PubMed

Cammi, R

2009-10-28

We present a general formulation of the coupled-cluster (CC) theory for a molecular solute described within the framework of the polarizable continuum model (PCM). The PCM-CC theory is derived in its complete form, called PTDE scheme, in which the correlated electronic density is used to have a self-consistent reaction field, and in an approximate form, called PTE scheme, in which the PCM-CC equations are solved assuming the fixed Hartree-Fock solvent reaction field. Explicit forms for the PCM-CC-PTDE equations are derived at the single and double (CCSD) excitation level of the cluster operator. At the same level, explicit equations for the analytical first derivatives of the PCM basic energy functional are presented, and analytical second derivatives are also discussed. The corresponding PCM-CCSD-PTE equations are given as a special case of the full theory.

Sub-Doppler rotationally resolved spectroscopy of lower vibronic bands of benzene with Zeeman effects

NASA Astrophysics Data System (ADS)

Doi, Atsushi; Kasahara, Shunji; Katô, Hajime; Baba, Masaaki

2004-04-01

Sub-Doppler high-resolution excitation spectra and the Zeeman effects of the 601, 101601, and 102601 bands of the S1 1B2u←S0 1A1g transition of benzene were measured by crossing laser beam perpendicular to a collimated molecular beam. 1593 rotational lines of the 101601 band and 928 lines of the 102601 band were assigned, and the molecular constants of the excited states were determined. Energy shifts were observed for the S1 1B2u(v1=1,v6=1,J,Kl=-11) levels, and those were identified as originating from a perpendicular Coriolis interaction. Many energy shifts were observed for the S1 1B2u(v1=2,v6=1,J,Kl) levels. The Zeeman splitting of a given J level was observed to increase with K and reach the maximum at K=J, which demonstrates that the magnetic moment lies perpendicular to the molecular plane. The Zeeman splittings of the K=J levels were observed to increase linearly with J. From the analysis, the magnetic moment is shown to be originating mostly from mixing of the S1 1B2u and S2 1B1u states by the J-L coupling (electronic Coriolis interaction). The number of perturbations was observed to increase as the excess energy increases, and all the perturbing levels were found to be a singlet state from the Zeeman spectra.

Implementation of a Balance Operator in NCOM

DTIC Science & Technology

2016-04-07

the background temperature Tb and salinity Sb fields do), f is the Coriolis parameter, k is the vertical unit vector, ∇ is the horizontal gradient, p... effectively used as a natural metric in the space of cost function gradients. The associated geometry inhibits descent in the unbalanced directions...28) where f is the local Coriolis parameter, ∆yv is the local grid spacing in the y direction at a v point, and the overbars indicates horizontal

Three Dimensional Dynamics of Freshwater Lenses in the Oceans Near Surface Layer

DTIC Science & Technology

2016-09-14

a third new front appeared…” However, this striking effect was observed only when the following con- ditions for the Froude number (Fr) and the... Coriolis forces and, strictly speaking, is valid only for the equatorial region. CONCLUSIONS Convective rains within the ITCZ pro- duce localized...freshwater plumes under the influence of both ambient stratification and wind stress and how they interact to affect plume dynam- ics. The Coriolis

Effects of eddy viscosity and thermal conduction and Coriolis force in the dynamics of gravity wave driven fluctuations in the OH nightglow

NASA Technical Reports Server (NTRS)

Hickey, M. P.

1988-01-01

The chemical-dynamical model of Walterscheid et al. (1987), which describes wave-driven fluctuations in OH nightglow, was modified to include the effects of both eddy thermal conduction and viscosity, as well as the Coriolis force (with the shallow atmosphere approximation). Using the new model, calculations were performed for the same nominal case as used by Walterscheid et al. but with only wave periods considered. For this case, the Coriolis force was found to be unimportant at any wave period. For wave periods greater than 2 or 3 hours, the inclusion of thermal conduction alone greatly modified the results (in terms of a complex ratio 'eta' which expresses the relationship between the intensity oscillation about the time-averaged intensity and the temperature oscillation about the time-averaged temperature); this effect was reduced with the further inclusion of the eddy viscosity.

Dual-mass vibratory rate gyroscope with suppressed translational acceleration response and quadrature-error correction capability

NASA Technical Reports Server (NTRS)

Clark, William A. (Inventor); Juneau, Thor N. (Inventor); Lemkin, Mark A. (Inventor); Roessig, Allen W. (Inventor)

2001-01-01

A microfabricated vibratory rate gyroscope to measure rotation includes two proof-masses mounted in a suspension system anchored to a substrate. The suspension has two principal modes of compliance, one of which is driven into oscillation. The driven oscillation combined with rotation of the substrate about an axis perpendicular to the substrate results in Coriolis acceleration along the other mode of compliance, the sense-mode. The sense-mode is designed to respond to Coriolis accelerationwhile suppressing the response to translational acceleration. This is accomplished using one or more rigid levers connecting the two proof-masses. The lever allows the proof-masses to move in opposite directions in response to Coriolis acceleration. The invention includes a means for canceling errors, termed quadrature error, due to imperfections in implementation of the sensor. Quadrature-error cancellation utilizes electrostatic forces to cancel out undesired sense-axis motion in phase with drive-mode position.

Three-dimensional dynamics of scientific balloon systems in response to sudden gust loadings. [including a computer program user manual

NASA Technical Reports Server (NTRS)

Dorsey, D. R., Jr.

1975-01-01

A mathematical model was developed of the three-dimensional dynamics of a high-altitude scientific research balloon system perturbed from its equilibrium configuration by an arbitrary gust loading. The platform is modelled as a system of four coupled pendula, and the equations of motion were developed in the Lagrangian formalism assuming a small-angle approximation. Three-dimensional pendulation, torsion, and precessional motion due to Coriolis forces are considered. Aerodynamic and viscous damping effects on the pendulatory and torsional motions are included. A general model of the gust field incident upon the balloon system was developed. The digital computer simulation program is described, and a guide to its use is given.

Bridging single and multireference coupled cluster theories with universal state selective formalism

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

Bhaskaran-Nair, Kiran; Kowalski, Karol

2013-05-28

The universal state selective (USS) multireference approach is used to construct new energy functionals which offers a unique possibility of bridging single and multireference coupled cluster theories (SR/MRCC). These functionals, which can be used to develop iterative and non-iterative approaches, utilize a special form of the trial wavefunctions, which assure additive separability (or size-consistency) of the USS energies in the non-interacting subsystem limit. When the USS formalism is combined with approximate SRCC theories, the resulting formalism can be viewed as a size-consistent version of the method of moments of coupled cluster equations (MMCC) employing a MRCC trial wavefunction. Special casesmore » of the USS formulations, which utilize single reference state specific CC (V.V. Ivanov, D.I. Lyakh, L. Adamowicz, Phys. Chem. Chem. Phys. 11, 2355 (2009)) and tailored CC (T. Kinoshita, O. Hino, R.J. Bartlett, J. Chem. Phys. 123, 074106 (2005)) expansions are also discussed.« less

Microwave-Assisted Synthesis of 5-Phenyl-2-Hydroxyacetophenone Derivatives by a Green Suzuki Coupling Reaction

ERIC Educational Resources Information Center

Soares, Pedro; Fernandes, Carlos; Chavarria, Daniel; Borges, Fernanda

2015-01-01

In recent years, the use of boron-containing reagents in palladium-assisted C-C coupling reactions (the Suzuki reaction) has gained prominence due to the vast array of reagents commercially available. Consequently, the generation of carbon-carbon bonds, namely of functionalized biphenyl systems, is at present considered the backbone of organic…

Analytic energy derivatives for the calculation of the first-order molecular properties using the domain-based local pair-natural orbital coupled-cluster theory

NASA Astrophysics Data System (ADS)

Datta, Dipayan; Kossmann, Simone; Neese, Frank

2016-09-01

The domain-based local pair-natural orbital coupled-cluster (DLPNO-CC) theory has recently emerged as an efficient and powerful quantum-chemical method for the calculation of energies of molecules comprised of several hundred atoms. It has been demonstrated that the DLPNO-CC approach attains the accuracy of a standard canonical coupled-cluster calculation to about 99.9% of the basis set correlation energy while realizing linear scaling of the computational cost with respect to system size. This is achieved by combining (a) localized occupied orbitals, (b) large virtual orbital correlation domains spanned by the projected atomic orbitals (PAOs), and (c) compaction of the virtual space through a truncated pair natural orbital (PNO) basis. In this paper, we report on the implementation of an analytic scheme for the calculation of the first derivatives of the DLPNO-CC energy for basis set independent perturbations within the singles and doubles approximation (DLPNO-CCSD) for closed-shell molecules. Perturbation-independent one-particle density matrices have been implemented in order to account for the response of the CC wave function to the external perturbation. Orbital-relaxation effects due to external perturbation are not taken into account in the current implementation. We investigate in detail the dependence of the computed first-order electrical properties (e.g., dipole moment) on the three major truncation parameters used in a DLPNO-CC calculation, namely, the natural orbital occupation number cutoff used for the construction of the PNOs, the weak electron-pair cutoff, and the domain size cutoff. No additional truncation parameter has been introduced for property calculation. We present benchmark calculations on dipole moments for a set of 10 molecules consisting of 20-40 atoms. We demonstrate that 98%-99% accuracy relative to the canonical CCSD results can be consistently achieved in these calculations. However, this comes with the price of tightening the threshold for the natural orbital occupation number cutoff by an order of magnitude compared to the DLPNO-CCSD energy calculations.

Electron correlation in the interacting quantum atoms partition via coupled-cluster lagrangian densities.

PubMed

Holguín-Gallego, Fernando José; Chávez-Calvillo, Rodrigo; García-Revilla, Marco; Francisco, Evelio; Pendás, Ángel Martín; Rocha-Rinza, Tomás

2016-07-15

The electronic energy partition established by the Interacting Quantum Atoms (IQA) approach is an important method of wavefunction analyses which has yielded valuable insights about different phenomena in physical chemistry. Most of the IQA applications have relied upon approximations, which do not include either dynamical correlation (DC) such as Hartree-Fock (HF) or external DC like CASSCF theory. Recently, DC was included in the IQA method by means of HF/Coupled-Cluster (CC) transition densities (Chávez-Calvillo et al., Comput. Theory Chem. 2015, 1053, 90). Despite the potential utility of this approach, it has a few drawbacks, for example, it is not consistent with the calculation of CC properties different from the total electronic energy. To improve this situation, we have implemented the IQA energy partition based on CC Lagrangian one- and two-electron orbital density matrices. The development presented in this article is tested and illustrated with the H2 , LiH, H2 O, H2 S, N2 , and CO molecules for which the IQA results obtained under the consideration of (i) the CC Lagrangian, (ii) HF/CC transition densities, and (iii) HF are critically analyzed and compared. Additionally, the effect of the DC in the different components of the electronic energy in the formation of the T-shaped (H2 )2 van der Waals cluster and the bimolecular nucleophilic substitution between F(-) and CH3 F is examined. We anticipate that the approach put forward in this article will provide new understandings on subjects in physical chemistry wherein DC plays a crucial role like molecular interactions along with chemical bonding and reactivity. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Proton-pumping mechanism of cytochrome c oxidase: A kinetic master-equation approach

PubMed Central

Kim, Young C.; Hummer, Gerhard

2011-01-01

Cytochrome c oxidase (CcO) is an efficient energy transducer that reduces oxygen to water and converts the released chemical energy into an electrochemical membrane potential. As a true proton pump, CcO translocates protons across the membrane against this potential. Based on a wealth of experiments and calculations, an increasingly detailed picture of the reaction intermediates in the redox cycle has emerged. However, the fundamental mechanism of proton pumping coupled to redox chemistry remains largely unresolved. Here we examine and extend a kinetic master-equation approach to gain insight into redox-coupled proton pumping in CcO. Basic principles of the CcO proton pump emerge from an analysis of the simplest kinetic models that retain essential elements of the experimentally determined structure, energetics, and kinetics, and that satisfy fundamental physical principles. The master-equation models allow us to address the question of how pumping can be achieved in a system in which all reaction steps are reversible. Whereas proton pumping does not require the direct modulation of microscopic reaction barriers, such kinetic gating greatly increases the pumping efficiency. Further efficiency gains can be achieved by partially decoupling the proton uptake pathway from the ative-site region. Such a mechanism is consistent with the proposed Glu valve, in which the side chain of a key glutamic acid shuttles between the D channel and the active-site region. We also show that the models predict only small proton leaks even in the absence of turnover. The design principles identified here for CcO provide a blueprint for novel biology-inspired fuel cells, and the master-equation formulation should prove useful also for other molecular machines. PMID:21946020

Calculation of excitation energies from the CC2 linear response theory using Cholesky decomposition

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

Baudin, Pablo, E-mail: baudin.pablo@gmail.com; qLEAP – Center for Theoretical Chemistry, Department of Chemistry, Aarhus University, Langelandsgade 140, DK-8000 Aarhus C; Marín, José Sánchez

2014-03-14

A new implementation of the approximate coupled cluster singles and doubles CC2 linear response model is reported. It employs a Cholesky decomposition of the two-electron integrals that significantly reduces the computational cost and the storage requirements of the method compared to standard implementations. Our algorithm also exploits a partitioning form of the CC2 equations which reduces the dimension of the problem and avoids the storage of doubles amplitudes. We present calculation of excitation energies of benzene using a hierarchy of basis sets and compare the results with conventional CC2 calculations. The reduction of the scaling is evaluated as well asmore » the effect of the Cholesky decomposition parameter on the quality of the results. The new algorithm is used to perform an extrapolation to complete basis set investigation on the spectroscopically interesting benzylallene conformers. A set of calculations on medium-sized molecules is carried out to check the dependence of the accuracy of the results on the decomposition thresholds. Moreover, CC2 singlet excitation energies of the free base porphin are also presented.« less

The Coupling between Earth's Inertial and Rotational Eigenmodes

NASA Astrophysics Data System (ADS)

Triana, S. A.; Rekier, J.; Trinh, A.; Laguerre, R.; Zhu, P.; Dehant, V. M. A.

2017-12-01

Wave motions in the Earth's fluid core, supported by the restoring action of both buoyancy (within the stably stratified top layer) and the Coriolis force, lead to the existence of global oscillation modes, the so-called gravito-inertial modes. These fluid modes can couple with the rotational modes of the Earth by exerting torques on the mantle and the inner core. Viscous shear stresses at the fluid boundaries, along with pressure and gravitation, contribute to the overall torque balance. Previous research by Rogister & Valette (2009) suggests that indeed rotational and gravito-inertial modes are coupled, thus shifting the frequencies of the Chandler Wobble (CW), the Free Core Nutation (FCN) and the Free Inner Core Nutation (FICN). Here we present the first results from a numerical model of the Earth's fluid core and its interaction with the rotational eigenmodes. In this first step we consider a fluid core without a solid inner core and we restrict to ellipticities of the same order as the Ekman number. We formulate the problem as a generalised eigenvalue problem that solves simultaneously the Liouville equation for the rotational modes (the torque balance), and the Navier-Stokes equation for the inertial modes.

Time-dependent quantum wave packet calculation for nonadiabatic F(2P3/2,2P1/2)+H2 reaction

NASA Astrophysics Data System (ADS)

Zhang, Yan; Xie, Ting-Xian; Han, Ke-Li; Zhang, John Z. H.

2003-12-01

In this paper we present a time-dependent quantum wave packet calculation for the reaction of F(2P3/2,2P1/2)+H2 on the Alexander-Stark-Werner potential energy surface. The reaction probabilities and the integral cross sections for the reaction of F(2P3/2,2P1/2)+H2 (v=j=0) are computed using time-dependent quantum methods with the centrifugal sudden approximate. The results are compared with recent time-independent quantum calculations. The two-surface reaction probability for the initial ground spin-orbit state of J=0.5 is similar to the time-independent result obtained by Alexander et al. [J. Chem. Phys. 113, 11084 (2000)]. Our calculation also shows that electronic coupling has a relatively minor effect on the reactivity from the 2P3/2 state but a non-negligible one from the 2P1/2 state. By comparison with exact time-independent calculations, it is found that the Coriolis coupling plays a relatively minor role. In addition, most of the reactivity of the excited state of fluorine atom results from the spin-orbit coupling.

Understanding the insight into the mechanisms and dynamics of the Cl-initiated oxidation of (CH3)3CC(O)X and the subsequent reactions in the presence of NO and O2 (X = F, Cl, and Br).

PubMed

Bai, Feng-Yang; Lv, Shuang; Ma, Yuan; Liu, Chun-Yu; He, Chun-Fang; Pan, Xiu-Mei

2017-03-01

In this work, the density functional and high-level ab initio theories are adopted to investigate the mechanisms and kinetics of reaction of (CH 3 ) 3 CC(O)X (X = F, Cl, and Br) with atomic chlorine. Rate coefficients for the reactions of chlorine atom with (CH 3 ) 3 CC(O)F (k 1 ), (CH 3 ) 3 CC(O)Cl (k 2 ), and (CH 3 ) 3 CC(O)Br (k 3 ) are calculated using canonical variational transition state theory coupled with small curvature tunneling method over a wide range of temperatures from 250 to 1000 K. The dynamic calculations are performed by the variational transition state theory with the interpolated single-point energies method at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-311++G(d,p) level of theory. Computed rate constant is in good line with the available experimental value. The rate constants for the title reactions are in this order: k 1

Dependence of vestibular reactions on frequency of action of sign-variable accelerations

NASA Technical Reports Server (NTRS)

Lapayev, E. V.; Vorobyev, O. A.; Ivanov, V. V.

1980-01-01

It was revealed that during the tests with continuous action of sign variable Coriolis acceleration the development of kinetosis was proportionate to the time of head inclinations in the range of 1 to 4 seconds while illusions of rocking in sagittal plane was more expressed in fast inclinations. The obtained data provided the evidence of sufficient dependence of vestibulovegetative and vestibulosensory reactions on the period of repetition of sign variable Coriolis acceleration.

Implementation of a Balance Operator in NCOM

DTIC Science & Technology

2016-04-07

the background temperature Tb and salinity Sb fields do), f is the Coriolis parameter, k is the vertical unit vector, ∇ is the horizontal gradient, p... effectively used as a natural metric in the space of cost function gradients. The associated geometry inhibits descent in the unbalanced directions and...28) where f is the local Coriolis parameter, ∆yv is the local grid spacing in the y direction at a v point, and the overbars indicates horizontal

Filtering Drifter Trajectories Sampled at Submesoscale Resolution

DTIC Science & Technology

2015-07-10

interval 5 min and a positioning error 1.5 m, the acceleration error is 4 10 m/s , a value comparable with the typical Coriolis acceleration of a water...10 ms , corresponding to the Coriolis acceleration experi- enced by a water parcel traveling at a speed of 2.2 m/s. This value corresponds to the...computed by integrating the NCOM velocity field contaminated by a random walk process whose effective dispersion coefficient (150 m /s) was specified as the

The "RA" Expeditions: The Archaeological and Anthropological Background. The "RA" Expeditions: The Coriolis Effect. The "RA" Expeditions: The Papyrus Reed. Learning Experiences for Coastal and Oceanic Awareness Studies, Nos. 211, 212, 213. [Project COAST].

ERIC Educational Resources Information Center

Delaware Univ., Newark. Coll. of Education.

Included are three units related to coastal and oceanic awareness. These are: (1) The "RA" Expeditions: The Archaeological and Anthropological Background; (2) The "RA" Expeditions: The Coriolis Effect; and (3) The "RA" Expeditions: The Papyrus Reed. Each of the three units are designed for students in grades 6-12.…

An Adaptive Approach for Precise Underwater Vehicle Control in Combined Robot-Diver Operations

DTIC Science & Technology

2015-03-01

addressing rigid body and added mass, Coriolis effects , damping and restoring forces. 3. System Modeling for THAUS-like Platforms Yuh [3] presents...term, ( )C  is the rigid body and added mass Coriolis effects , ( )D  is the damping term, and )(g  is the reactionary force term. The second...operations potentially increase the efficiency, effectiveness and safety of the tasks they perfonn. The utilization of an autonomous unde1water vehicle

What you thought you knew about motion sickness isn't necessarily so

NASA Technical Reports Server (NTRS)

Cowings, P. S.; Malmstrom, F. V.

1984-01-01

Motion sickness symptoms, stimuli, and drug therapy are discussed. Autogenic feedback training (AFT) methods of preventing motion sickness are explained. Research with AFT indicates that participants who had AFT could withstand longer periods of Coriolis acceleration, participants with high or low susceptibility to motion sickness could control their symptoms with AFT, AFT for Coriolis acceleration is transferable to other motion sickness stimuli, and most people can learn AFT, though with varying rates of learning.

The parity-adapted basis set in the formulation of the photofragment angular momentum polarization problem: The role of the Coriolis interaction

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

Shternin, Peter S.; Vasyutinskii, Oleg S.

We present a theoretical framework for calculating the recoil-angle dependence of the photofragment angular momentum polarization taking into account both radial and Coriolis nonadiabatic interactions in the diatomic/linear photodissociating molecules. The parity-adapted representation of the total molecular wave function has been used throughout the paper. The obtained full quantum-mechanical expressions for the photofragment state multipoles have been simplified by using the semiclassical approximation in the high-J limit and then analyzed for the cases of direct photodissociation and slow predissociation in terms of the anisotropy parameters. In both cases, each anisotropy parameter can be presented as a linear combination of themore » generalized dynamical functions f{sub K}(q,q{sup '},q-tilde,q-tilde{sup '}) of the rank K representing contribution from different dissociation mechanisms including possible radial and Coriolis nonadiabatic transitions, coherent effects, and the rotation of the recoil axis. In the absence of the Coriolis interactions, the obtained results are equivalent to the earlier published ones. The angle-recoil dependence of the photofragment state multipoles for an arbitrary photolysis reaction is derived. As shown, the polarization of the photofragments in the photolysis of a diatomic or a polyatomic molecule can be described in terms of the anisotropy parameters irrespective of the photodissociation mechanism.« less

Cinnamomum cassia Essential Oil Inhibits α-MSH-Induced Melanin Production and Oxidative Stress in Murine B16 Melanoma Cells

PubMed Central

Chou, Su-Tze; Chang, Wen-Lun; Chang, Chen-Tien; Hsu, Shih-Lan; Lin, Yu-Che; Shih, Ying

2013-01-01

Essential oils extracted from aromatic plants exhibit important biological activities and have become increasingly important for the development of aromatherapy for complementary and alternative medicine. The essential oil extracted from Cinnamomum cassia Presl (CC-EO) has various functional properties; however, little information is available regarding its anti-tyrosinase and anti-melanogenic activities. In this study, 16 compounds in the CC-EO have been identified; the major components of this oil are cis-2-methoxycinnamic acid (43.06%) and cinnamaldehyde (42.37%). CC-EO and cinnamaldehyde exhibited anti-tyrosinase activities; however, cis-2-methoxycinnamic acid did not demonstrate tyrosinase inhibitory activity. In murine B16 melanoma cells stimulated with α-melanocyte-stimulating hormone (α-MSH), CC-EO and cinnamaldehyde not only reduced the melanin content and tyrosinase activity of the cells but also down-regulated tyrosinase expression without exhibiting cytotoxicity. Moreover, CC-EO and cinnamaldehyde decreased thiobarbituric acid-reactive substance (TBARS) levels and restored glutathione (GSH) and catalase activity in the α-MSH-stimulated B16 cells. These results demonstrate that CC-EO and its major component, cinnamaldehyde, possess potent anti-tyrosinase and anti-melanogenic activities that are coupled with antioxidant properties. Therefore, CC-EO may be a good source of skin-whitening agents and may have potential as an antioxidant in the future development of complementary and alternative medicine-based aromatherapy. PMID:24051402

The role of the complete Coriolis force in weakly stratified oceanic flows

NASA Astrophysics Data System (ADS)

Tort, M.; Winters, K. B.; Ribstein, B.; Zeitlin, V.

2016-02-01

Ocean dynamics is usually described using the primitive equations based on the so-called traditional approximation (TA), where the Coriolis force associated with the horizontal component of the planetary rotation is neglected (also called non-traditional (NT) part proportional to cosΦ, see Fig 1.). However, recent studies have shown that the NT part of the Coriolis force plays a non-negligible dynamical role in some particular oceanic flows (see Gerkema et al., 2008 for an extensive review of NT effects for geophysical and astrophysical flows). Here we explore the relevance of including the NT component of the Coriolis force in ocean models, by presenting particular results regarding two different mid-latitude flow configurations after relaxing the TA: Propagation of wind-induced near-inertial waves (NIWs). Under the TA, NIWs propagate toward the equator, the inertially poleward propagation being internally reflected at a depth-independent critical latitude. The combined effects of the NT Coriolis force and weak stratification in the deep ocean leads to the existence of waveguides for sub-inertial waves, which get trapped and propagate further poleward (Winters et al., 2011). Here we consider storm-induced NIWs and their evolution in a non-linear Boussinesq model on the β-plane in the NT approximation. Preliminary results are presented concerning the behavior of the waves in a weakly stratified mixed-layer, where NT effects are expected to be significant. Inertial instability. A detailed linear stability analysis of the Bickley jet at large Rossby numbers in the NT approximation on the f-plane is performed for long waves in a continuously stratified Boussinesq model. For a sufficiently weak stratification, both symmetric and asymmetric inertial instabilities have substantially higher growth rates than in the TA while no discernible differences between the two approximations are observed for strong enough stratifications (Tort et al., 2015).

Covalent coupling via dehalogenation on Ni(111) supported boron nitride and graphene.

PubMed

Morchutt, Claudius; Björk, Jonas; Krotzky, Sören; Gutzler, Rico; Kern, Klaus

2015-02-11

Polymerization of 1,3,5-tris(4-bromophenyl)benzene via dehalogenation on graphene and hexagonal boron nitride is investigated by scanning tunneling microscopy experiments and density functional theory calculations. This work reveals how the interactions between molecules and graphene or h-BN grown on Ni(111) govern the surface-confined synthesis of polymers through C-C coupling.

Solvatochromic shifts from coupled-cluster theory embedded in density functional theory

NASA Astrophysics Data System (ADS)

Höfener, Sebastian; Gomes, André Severo Pereira; Visscher, Lucas

2013-09-01

Building on the framework recently reported for determining general response properties for frozen-density embedding [S. Höfener, A. S. P. Gomes, and L. Visscher, J. Chem. Phys. 136, 044104 (2012)], 10.1063/1.3675845, in this work we report a first implementation of an embedded coupled-cluster in density-functional theory (CC-in-DFT) scheme for electronic excitations, where only the response of the active subsystem is taken into account. The formalism is applied to the calculation of coupled-cluster excitation energies of water and uracil in aqueous solution. We find that the CC-in-DFT results are in good agreement with reference calculations and experimental results. The accuracy of calculations is mainly sensitive to factors influencing the correlation treatment (basis set quality, truncation of the cluster operator) and to the embedding treatment of the ground-state (choice of density functionals). This allows for efficient approximations at the excited state calculation step without compromising the accuracy. This approximate scheme makes it possible to use a first principles approach to investigate environment effects with specific interactions at coupled-cluster level of theory at a cost comparable to that of calculations of the individual subsystems in vacuum.

Extensive regularization of the coupled cluster methods based on the generating functional formalism: application to gas-phase benchmarks and to the S(N)2 reaction of CHCl3 and OH- in water

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

Kowalski, Karol; Valiev, Marat

2009-12-21

The recently introduced energy expansion based on the use of generating functional (GF) [K. Kowalski, P.D. Fan, J. Chem. Phys. 130, 084112 (2009)] provides a way of constructing size-consistent non-iterative coupled-cluster (CC) corrections in terms of moments of the CC equations. To take advantage of this expansion in a strongly interacting regime, the regularization of the cluster amplitudes is required in order to counteract the effect of excessive growth of the norm of the CC wavefunction. Although proven to be effcient, the previously discussed form of the regularization does not lead to rigorously size-consistent corrections. In this paper we addressmore » the issue of size-consistent regularization of the GF expansion by redefning the equations for the cluster amplitudes. The performance and basic features of proposed methodology is illustrated on several gas-phase benchmark systems. Moreover, the regularized GF approaches are combined with QM/MM module and applied to describe the SN2 reaction of CHCl3 and OH- in aqueous solution.« less

The equation-of-motion coupled cluster method for triple electron attached states

NASA Astrophysics Data System (ADS)

Musiał, Monika; Olszówka, Marta; Lyakh, Dmitry I.; Bartlett, Rodney J.

2012-11-01

The initial implementation of the triple electron attachment (TEA) equation-of-motion (EOM) coupled cluster (CC) method is presented, aiming at the description of electronic states with three open shell electrons outside a suitably chosen closed shell vacuum. In particular, such an approach can be used for describing dissociation of chemical bonds predominantly formed by three valence electrons, for example, in LiC and NaC molecules. Both ground and excited states are considered while rigorously maintaining the correct spin value. The preliminary results show a correct asymptotic behavior of the dissociation curves. At the same time, we emphasize that a chemically accurate description will require an extension of the minimal TEA-EOM-CC model introduced here, analogous to those already used in the double ionization potential and double electron attachment methods.

Latex-protein complexes from an acute phase recombinant antigen of Toxoplasma gondii for the diagnosis of recently acquired toxoplasmosis.

PubMed

Peretti, Leandro E; Gonzalez, Verónica D G; Marcipar, Iván S; Gugliotta, Luis M

2014-08-01

The synthesis and characterization of latex-protein complexes (LPC), from the acute phase recombinant antigen P35 (P35Ag) of Toxoplasma gondii and "core-shell" carboxylated or polystyrene (PS) latexes (of different sizes and charge densities) are considered, with the aim of producing immunoagglutination reagents able to detect recently acquired toxoplasmosis. Physical adsorption (PA) and chemical coupling (CC) of P35Ag onto latex particles at different pH were investigated. Greater amounts of adsorbed protein were obtained on PS latexes than on carboxylated latexes, indicating that hydrophobic forces govern the interactions between the protein and the particle surface. In the CC experiments, the highest amount of bound protein was obtained at pH 6, near the isoelectric point of the protein (IP=6.27). At this pH, it decreased both the repulsion between particle surface and protein, and the repulsion between neighboring molecules. The LPC were characterized and the antigenicity of the P35Ag protein coupled on the particles surface was evaluated by Enzyme-Linked ImmunoSorbent Assay (ELISA). Results from ELISA showed that the P35Ag coupled to the latex particles surface was not affected during the particles sensitization by PA and CC and the produced LPC were able to recognize specific anti-P35Ag antibodies present in the acute phase of the disease. Copyright © 2014 Elsevier B.V. All rights reserved.

Feasibility on Ultrasonic Velocity using Contact and Non-Contact Nondestructive Techniques for Carbon/Carbon Composites

NASA Astrophysics Data System (ADS)

Im, K. H.; Chang, M.; Hsu, D. K.; Song, S. J.; Cho, H.; Park, J. W.; Kweon, Y. S.; Sim, J. K.; Yang, I. Y.

2007-03-01

Advanced materials are to be required to have specific functions associated with extremely environments. One of them is carbon/carbon(C/C) composite material, which has obvious advantages over conventional materials. The C/Cs have become to be utilized as parts of aerospace applications and its low density, high thermal conductivity and excellent mechanical properties at elevated temperatures make it an ideal material for aircraft brake disks. Because of permeation of coupling medium such as water, it is desirable to perform contact-less nondestructive evaluation to assess material properties and part homogeneity. In this work, a C/C composite material was characterized with non-contact and contact ultrasonic methods using a scanner with automatic-data acquisition function. Also through transmission mode was performed because of the main limitation for air-coupled transducers, which is the acoustic impedance mismatch between most materials and air. Especially ultrasonic images and velocities for C/C composite disk brake were compared and found to be consistent to some degree with the non-contact and contact ultrasonic measurement methods. Low frequency through-transmission scans based on both amplitude of the ultrasonic pulse was used for mapping out the material property inhomogeneity. Measured results were compared with those obtained by the dry-coupling ultrasonic UT system and through transmission method in immersion. Finally, feasibility has been found to measure and compare ultrasonic velocities of C/C composites with using the contact/noncontact peak-delay measurement method based on the pulse overlap method.

Multiscale Asymptotics for the Skeleton of the Madden-Julian Oscillation and Tropical-Extratropical Interactions (Open Access)

DTIC Science & Technology

2015-11-30

equatorial baroclinic dynamics, and (iii) the interactive effects of moisture and convection. More specifically, the model integrates the dry...interactions 5 Par. Derivation Dim. val. Description β 2.3× 10−11 m−1s−1 Variation of Coriolis parameter with latitude θ0 300 K Potential temperature...tropical Coriolis force, and x and y denote the zonal and meridional coordinates. Without the moisture q and convection envelope a, system (1) is the two

Salient features of solitary waves in dusty plasma under the influence of Coriolis force

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

Das, G. C.; Nag, Apratim; Department of Physics, G. C. College, Silchar-788004

The main interest is to study the nonlinear acoustic wave in rotating dusty plasma augmented through the derivation of a modified Sagdeev potential equation. Small rotation causes the interaction of Coriolis force in the dynamical system, and leads to the complexity in the derivation of the nonlinear wave equation. As a result, the finding of solitary wave propagation in dusty plasma ought to be of merit. However, the nonlinear wave equation has been successfully solved by the use of the hyperbolic method. Main emphasis has been given to the changes on the evolution and propagation of soliton, and the variationmore » caused by the dusty plasma constituents as well as by the Coriolis force have been highlighted. Some interesting nonlinear wave behavior has been found which can be elaborately studied for the interest of laboratory and space plasmas. Further, to support the theoretical investigations, numeric plasma parameters have been taken for finding the inherent features of solitons.« less

75 FR 31791 - Government-Owned Inventions; Availability for Licensing

Federal Register 2010, 2011, 2012, 2013, 2014

2010-06-04

... reveal the genetic processes occurring in ccRCC tissues that may contribute to advanced disease. Positive... transformed into blood brain barrier permeable forms by the coupling of an Inter-Cellular Adhesion Molecule-1...

A study of human performance in a rotating environment

NASA Technical Reports Server (NTRS)

Green, J. A.; Peacock, J. L.; Holm, A. P.

1971-01-01

Consideration is given to the lack of sufficient data relative to the response of man to the attendant oculovestibular stimulations induced by multi-directional movement of an individual within the rotating environment to provide the required design criteria. This was done to determine the overall impact of artificial gravity simulations on potential design configurations and crew operational procedures. Gross locomotion and fine motor performance were evaluated. Results indicate that crew orientation, rotational rates, vehicle design configurations, and operational procedures may be used to reduce the severity of the adverse effects of the Coriolis and cross-coupled angular accelerations acting on masses moving within a rotating environment. Results further indicate that crew selection, motivation, and short-term exposures to the rotating environment may be important considerations for future crew indoctrination and training programs.

A coupled subsurface-boundary layer model of water on Mars

NASA Astrophysics Data System (ADS)

Zent, A. P.; Haberle, R. M.; Houben, H. C.; Jakosky, B. M.

1993-02-01

A 1D numerical model of the exchange of H2O between the atmosphere and subsurface of Mars through the PBL is employed to explore the mechanisms of H2O exchange and to elucidate the role played by the regolith in the local H2O budget. The atmospheric model includes effects of Coriolis, pressure gradient, and frictional forces for momentum: radiation, sensible heat flux, and advection for heat. It is suggested that in most cases, the flux through the Martian surface reverses twice in the course of each sol. The effects of surface albedo, thermal inertia, solar declination, atmospheric optical depth, and regolith pore structure are explored. It is proposed that higher thermal inertia forces more H2O into the atmosphere because the regolith is warmer at depth.

Photoionization cross section by Stieltjes imaging applied to coupled cluster Lanczos pseudo-spectra

NASA Astrophysics Data System (ADS)

Cukras, Janusz; Coriani, Sonia; Decleva, Piero; Christiansen, Ove; Norman, Patrick

2013-09-01

A recently implemented asymmetric Lanczos algorithm for computing (complex) linear response functions within the coupled cluster singles (CCS), coupled cluster singles and iterative approximate doubles (CC2), and coupled cluster singles and doubles (CCSD) is coupled to a Stieltjes imaging technique in order to describe the photoionization cross section of atoms and molecules, in the spirit of a similar procedure recently proposed by Averbukh and co-workers within the Algebraic Diagrammatic Construction approach. Pilot results are reported for the atoms He, Ne, and Ar and for the molecules H2, H2O, NH3, HF, CO, and CO2.

Photoionization cross section by Stieltjes imaging applied to coupled cluster Lanczos pseudo-spectra.

PubMed

Cukras, Janusz; Coriani, Sonia; Decleva, Piero; Christiansen, Ove; Norman, Patrick

2013-09-07

A recently implemented asymmetric Lanczos algorithm for computing (complex) linear response functions within the coupled cluster singles (CCS), coupled cluster singles and iterative approximate doubles (CC2), and coupled cluster singles and doubles (CCSD) is coupled to a Stieltjes imaging technique in order to describe the photoionization cross section of atoms and molecules, in the spirit of a similar procedure recently proposed by Averbukh and co-workers within the Algebraic Diagrammatic Construction approach. Pilot results are reported for the atoms He, Ne, and Ar and for the molecules H2, H2O, NH3, HF, CO, and CO2.

A novel Laccase Biosensor based on Laccase immobilized Graphene-Cellulose Microfiber Composite modified Screen-Printed Carbon Electrode for Sensitive Determination of Catechol

PubMed Central

Palanisamy, Selvakumar; Ramaraj, Sayee Kannan; Chen, Shen-Ming; Yang, Thomas C. K.; Yi-Fan, Pan; Chen, Tse-Wei; Velusamy, Vijayalakshmi; Selvam, Sonadevi

2017-01-01

In the present work, we demonstrate the fabrication of laccase biosensor to detect the catechol (CC) using laccase immobilized on graphene-cellulose microfibers (GR-CMF) composite modified screen printed carbon electrode (SPCE). The direct electrochemical behavior of laccase was investigated using laccase immobilized different modified SPCEs, such as GR/SPCE, CMF/SPCE and GR-CMF/SPCE. Compared with laccase immobilized GR and CMF modified SPCEs, a well-defined redox couple of CuI/CuII for laccase was observed at laccase immobilized GR-CMF composite modified SPCE. Cyclic voltammetry results show that the as-prepared biosensor has 7 folds higher catalytic activity with lower oxidation potential towards CC than SPCE modified with GR-CMF composite. Under optimized conditions, amperometric i-t method was used for the quantification of CC, and the amperometric response of the biosensor was linear over the concertation of CC ranging from 0.2 to 209.7 μM. The sensitivity, response time and the detection limit of the biosensor for CC is 0.932 μMμA−1 cm−2, 2 s and 0.085 μM, respectively. The biosensor has high selectivity towards CC in the presence of potentially active biomolecules and phenolic compounds. The biosensor also accessed for the detection of CC in different water samples and shows good practicality with an appropriate repea. PMID:28117357

Search for heavy vector-like quarks coupling to light quarks in proton–proton collisions at s = 7   TeV with the ATLAS detector

DOE PAGES

Aad, G.; Abbott, B.; Abdallah, J.; ...

2012-05-01

This Letter presents a search for singly produced vector-like quarks, Q, coupling to light quarks, q. The search is sensitive to both charged current (CC) and neutral current (NC) processes, pp→Qq→Wqq' and pp→Qq→Zqq' with a leptonic decay of the vector gauge boson. In 1.04fb -1 of data taken in 2011 by the ATLAS experiment at a center-of-mass energy √s=7TeV, no evidence of such heavy vector-like quarks is observed above the expected Standard Model background. Limits on the heavy vector-like quark production cross section times branching ratio as a function of mass m Q are obtained. For a coupling κ qQ=v/mmore » Q, where v is the Higgs vacuum expectation value, 95% C.L. lower limits on the mass of a vector-like quark are set at 900 GeV and 760 GeV from CC and NC processes, respectively.« less

X(3872), IG(JPC) = 0+(1++), as the χc1(2P) charmonium

NASA Astrophysics Data System (ADS)

Achasov, N. N.; Rogozina, E. V.

2015-09-01

Contrary to almost standard opinion that the X(3872) resonance is the D∗0D¯0 + c.c. molecule or the qcq¯c¯ four-quark state, we discuss the scenario where the X(3872) resonance is the cc¯ = χc1(2P) charmonium which “sits on” the D∗0D¯0 threshold. We explain the shift of the mass of the X(3872) resonance with respect to the prediction of a potential model for the mass of the χc1(2P) charmonium by the contribution of the virtual D∗D¯ + c.c. intermediate states into the self energy of the X(3872) resonance. This allows us to estimate the coupling constant of the X(7872) resonance with the D∗0D¯0 channel, the branching ratio of the X(3872) → D∗0D¯0 + c.c. decay, and the branching ratio of the X(3872) decay into all non-D∗0D¯0 + c.c. states. We predict a significant number of unknown decays of X(3872) via two gluon: X(3872) →gluon gluon →hadrons. We suggest a physically clear program of experimental researches for verification of our assumption.

An Overview of A Perturbation Analysis for Uni-directionally Coupled Vibratory Gyroscopes

NASA Astrophysics Data System (ADS)

Vu, Huy; Palacios, Antonio; In, Visarath; Longhini, Patrick; Neff, Joseph

2011-04-01

The complex behaviours of gyroscope systems have been scientifically researched and thoroughly studied for decades. Most of scientific research involving gyroscopes specifically concentrates on studying the designs and fabrications at the circuitry level. Although gaining a recent popularity with the low cost of MEMS device that offers an attractive approach for gyroscope fabrications, its performance is far from meeting the requirements for an inertial grade guidance system. To improve the performance, our current research is theoretically focusing upon investigating the dynamics of vibratory gyroscopes coupled in a ring configuration. Particularly, a certain topology of arrangements among coupled gyroscopes can be designed and studied to enhance robustness. The main operation depends mostly on an external source for a stable oscillation in the drive axis, while an oscillatory motion in the sense axis, which is used to detect an angular rate of rotation, is enabled through the transfers of energy from the drive via the Coriolis force. With the mathematical model depicted as Duffing oscillators, however, by adding a certain coupling among gyroscopes, a similar behavior to a Duffing oscillator is expected, only with more complicated dynamics at a higher dimension. A number of Perturbation methods have popularly been carried out, to seek for a general asymptotic solution of typical Duffing oscillators. In this work as an overview, the two-time scale Perturbation expansion is asymptotically applied on the uni-directionally coupled vibratory gyroscopes to find an analytical solution which is then compared to the numerical one.

Traveling wave electrode design of electro-optically modulated coupled-cavity surface-emitting lasers.

PubMed

Zujewski, Mateusz; Thienpont, Hugo; Panajotov, Krassimir

2012-11-19

We present a novel design of an electro-optically modulated coupled-cavity vertical-cavity surface-emitting laser (CC-VCSEL) with traveling wave electrodes of the modulator cavity, which allows to overcome the RC time constant of a traditional lumped electrode structures. The CC-VCSEL optical design is based on longitudinal mode switching which has recently experimentally demonstrated a record modulation speed. We carry out segmented transmission line electrical design of the modulator cavity in order to compensate for the low impedance of the modulator section and to match the 50 Ω electrical network. We have optimized two types of highly efficient modulator structures reaching -3 dB electrical cut-off frequency of f(cut-off) = 330 GHz with maximum reflection of -22 dB in the range from f(LF) = 100 MHz to f(cut-off) and 77 - 89% modulation efficiency.

A new approach to construct a fused 2-ylidene chromene ring: highly regioselective synthesis of novel chromeno quinoxalines.

PubMed

Kumar, K Shiva; Rambabu, D; Prasad, Bagineni; Mujahid, Mohammad; Krishna, G Rama; Rao, M V Basaveswara; Reddy, C Malla; Vanaja, G R; Kalle, Arunasree M; Pal, Manojit

2012-06-28

Regioselective construction of a fused 2-ylidene chromene ring was achieved for the first time by using AlCl(3)-induced C-C bond formation followed by Pd/C-Cu mediate coupling-cyclization strategy. A number of chromeno[4,3-b]quinoxaline derivatives were prepared by using this strategy. Single crystal X-ray diffraction study of a representative compound e.g. 6-(2,2-dimethylpropylidene)-4-methyl-6H-chromeno[4,3-b]quinoxalin-3-ol confirmed the presence of an exocyclic C-C double bond with Z-geometry. The crystal structure analysis and hydrogen bonding patterns of the same compound along with its structure elaboration via propargylation followed by Sonogashira coupling of the resulting terminal alkyne is presented. A probable mechanism for the formation of 2-ylidene chromene ring is discussed. Some of the compounds synthesized showed anticancer properties when tested in vitro.

Coupled Cluster Method with Single and Double Excitations Tailored by Matrix Product State Wave Functions.

PubMed

Veis, Libor; Antalík, Andrej; Brabec, Jiří; Neese, Frank; Legeza, Örs; Pittner, Jiří

2016-10-03

In the past decade, the quantum chemical version of the density matrix renormalization group (DMRG) method has established itself as the method of choice for calculations of strongly correlated molecular systems. Despite its favorable scaling, it is in practice not suitable for computations of dynamic correlation. We present a novel method for accurate "post-DMRG" treatment of dynamic correlation based on the tailored coupled cluster (CC) theory in which the DMRG method is responsible for the proper description of nondynamic correlation, whereas dynamic correlation is incorporated through the framework of the CC theory. We illustrate the potential of this method on prominent multireference systems, in particular, N 2 and Cr 2 molecules and also oxo-Mn(Salen), for which we have performed the first post-DMRG computations in order to shed light on the energy ordering of the lowest spin states.

CACA-TOCSY with alternate 13C-12C labeling: a 13Calpha direct detection experiment for mainchain resonance assignment, dihedral angle information, and amino acid type identification.

PubMed

Takeuchi, Koh; Frueh, Dominique P; Sun, Zhen-Yu J; Hiller, Sebastian; Wagner, Gerhard

2010-05-01

We present a (13)C direct detection CACA-TOCSY experiment for samples with alternate (13)C-(12)C labeling. It provides inter-residue correlations between (13)C(alpha) resonances of residue i and adjacent C(alpha)s at positions i - 1 and i + 1. Furthermore, longer mixing times yield correlations to C(alpha) nuclei separated by more than one residue. The experiment also provides C(alpha)-to-sidechain correlations, some amino acid type identifications and estimates for psi dihedral angles. The power of the experiment derives from the alternate (13)C-(12)C labeling with [1,3-(13)C] glycerol or [2-(13)C] glycerol, which allows utilizing the small scalar (3)J(CC) couplings that are masked by strong (1)J(CC) couplings in uniformly (13)C labeled samples.

Diagnosis of dynamic process over rainband of landfall typhoon

NASA Astrophysics Data System (ADS)

Ran, Ling-Kun; Yang, Wen-Xia; Chu, Yan-Li

2010-07-01

This paper introduces a new physical parameter — thermodynamic shear advection parameter combining the perturbation vertical component of convective vorticity vector with the coupling of horizontal divergence perturbation and vertical gradient of general potential temperature perturbation. For a heavy-rainfall event resulting from the landfall typhoon 'Wipha', the parameter is calculated by using National Centres for Enviromental Prediction/National Centre for Atmospheric Research global final analysis data. The results showed that the parameter corresponds to the observed 6 h accumulative rainband since it is capable of catching hold of the dynamic and thermodynamic disturbance in the lower troposphere over the observed rainband. Before the typhoon landed, the advection of the parameter by basic-state flow and the coupling of general potential temperature perturbation with curl of Coriolis force perturbation are the primary dynamic processes which are responsible for the local change of the parameter. After the typhoon landed, the disturbance is mainly driven by the combination of five primary dynamic processes. The advection of the parameter by basic-state flow was weakened after the typhoon landed.

[Human tolerance to Coriolis acceleration during exertion of different muscle groups].

PubMed

Aĭzikov, G S; Emel'ianov, M D; Ovechkin, V G

1975-01-01

The effect of an arbitrary loading of different muscle groups (shoulder, back, legs) and motor acts on the tolerance to Coriolis accelerations was investigated in 140 experiments in which 40 test subjects participated. The accelerations were cumulated and simulated by the Bryanov scheme. Muscle tension was accompanied by a less expressed vestibulo-vegetative reaction and shortening of the recovery period after the development of motion sickness symptoms. The greatest changes were observed during the performance of complex motor acts and tension of shoulder muscles. Possible mechanisms of these effects are discussed.

Modeling the detailed kinetics of mitochondrial cytochrome c oxidase: Catalytic mechanism and nitric oxide inhibition

PubMed Central

Pannala, Venkat R.; Camara, Amadou K. S.

2016-01-01

Cytochrome c oxidase (CcO) catalyzes the exothermic reduction of O2 to H2O by using electrons from cytochrome c, and hence plays a crucial role in ATP production. Although details on the enzyme structure and redox centers involved in O2 reduction have been known, there still remains a considerable ambiguity on its mechanism of action, e.g., the number of sequential electrons donated to O2 in each catalytic step, the sites of protonation and proton pumping, and nitric oxide (NO) inhibition mechanism. In this work, we developed a thermodynamically constrained mechanistic mathematical model for the catalytic action of CcO based on available kinetic data. The model considers a minimal number of redox centers on CcO and couples electron transfer and proton pumping driven by proton motive force (PMF), and accounts for the inhibitory effects of NO on the reaction kinetics. The model is able to fit well all the available kinetic data under diverse experimental conditions with a physiologically realistic unique parameter set. The model predictions show that: 1) the apparent Km of O2 varies considerably and increases from fully reduced to fully oxidized cytochrome c depending on pH and the energy state of mitochondria, and 2) the intermediate enzyme states depend on pH and cytochrome c redox fraction and play a central role in coupling mitochondrial respiration to PMF. The developed CcO model can easily be integrated into existing mitochondrial bioenergetics models to understand the role of the enzyme in controlling oxidative phosphorylation in normal and disease conditions. PMID:27633738

Systematically convergent basis sets for transition metals. I. All-electron correlation consistent basis sets for the 3d elements Sc-Zn

NASA Astrophysics Data System (ADS)

Balabanov, Nikolai B.; Peterson, Kirk A.

2005-08-01

Sequences of basis sets that systematically converge towards the complete basis set (CBS) limit have been developed for the first-row transition metal elements Sc-Zn. Two families of basis sets, nonrelativistic and Douglas-Kroll-Hess (-DK) relativistic, are presented that range in quality from triple-ζ to quintuple-ζ. Separate sets are developed for the description of valence (3d4s) electron correlation (cc-pVnZ and cc-pVnZ-DK; n =T,Q, 5) and valence plus outer-core (3s3p3d4s) correlation (cc-pwCVnZ and cc-pwCVnZ-DK; n =T,Q, 5), as well as these sets augmented by additional diffuse functions for the description of negative ions and weak interactions (aug-cc-pVnZ and aug-cc-pVnZ-DK). Extensive benchmark calculations at the coupled cluster level of theory are presented for atomic excitation energies, ionization potentials, and electron affinities, as well as molecular calculations on selected hydrides (TiH, MnH, CuH) and other diatomics (TiF, Cu2). In addition to observing systematic convergence towards the CBS limits, both 3s3p electron correlation and scalar relativity are calculated to strongly impact many of the atomic and molecular properties investigated for these first-row transition metal species.

Effect of a pH Gradient on the Protonation States of Cytochrome c Oxidase: A Continuum Electrostatics Study.

PubMed

Magalhães, Pedro R; Oliveira, A Sofia F; Campos, Sara R R; Soares, Cláudio M; Baptista, António M

2017-02-27

Cytochrome c oxidase (CcO) couples the reduction of dioxygen to water with transmembrane proton pumping, which leads to the generation of an electrochemical gradient. In this study we analyze how one of the components of the electrochemical gradient, the difference in pH across the membrane, or ΔpH, influences the protonation states of residues in CcO. We modified our continuum electrostatics/Monte Carlo (CE/MC) method in order to include the ΔpH and applied it to the study of CcO, in what is, to our best knowledge, the first CE/MC study of CcO in the presence of a pH gradient. The inclusion of a transmembrane pH gradient allows for the identification of residues whose titration behavior depends on the pH on both sides of the membrane. Among the several residues with unusual titration profiles, three are well-known key residues in the proton transfer process of CcO: E286 I , Y288 I , and K362 I . All three residues have been previously identified as being critical for the catalytic or proton pumping functions of CcO. Our results suggest that when the pH gradient increases, these residues may be part of a regulatory mechanism to stem the proton flow.

Joint experimental-theoretical investigation of the lower bound states of the NO(X2Pi)-Kr complex.

PubMed

Wen, Bo; Meyer, Henning; Kłos, Jacek; Alexander, Millard H

2009-07-02

We describe the first measurement of the near IR spectrum of the NO-Kr van der Waals complex. A variant of IR-REMPI double-resonance spectroscopy is employed in which the IR and UV lasers are scanned simultaneously in such a way that throughout the scan the sum of the two photon energies is kept constant, matching a UV resonance of the system. In the region of the first overtone vibration of the NO monomer, we observe several rotationally resolved bands for the NO-Kr complex. In addition to the origin band located at 3723.046 cm(-1), we observe excited as well as hot bands involving the excitation of one or two quanta of z-axis rotation. Another band is assigned to the excitation of one quantum of bending vibration. The experimental spectra are compared with results of bound-state calculations for a new set of potential energy surfaces calculated at the spin-restricted coupled cluster level. For the average vibration-rotation energies, there is excellent agreement between the theoretical results based on the coupled states (CS) approximation and the full close-coupling (CC) treatment. Finer details like the electrostatic splitting and the P-type doubling of the rotational levels are accounted for only within the CC formalism. The comparison of the CC results with the measured spectra confirms the high quality of the PESs. However, the high resolution of the experiments is sufficient to identify some inaccuracies in the difference between the potential energy surfaces of A' and A'' reflection symmetry.

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

PubMed

Zhang, Shiyang; Mo, Yuxiang

2009-10-15

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

Comparison of the quadratic configuration interaction and coupled cluster approaches to electron correlation including the effect of triple excitations

NASA Technical Reports Server (NTRS)

Taylor, Peter R.; Lee, Timothy J.; Rendell, Alistair P.

1990-01-01

The recently proposed quadratic configuration interaction (QCI) method is compared with the more rigorous coupled cluster (CC) approach for a variety of chemical systems. Some of these systems are well represented by a single-determinant reference function and others are not. The finite order singles and doubles correlation energy, the perturbational triples correlation energy, and a recently devised diagnostic for estimating the importance of multireference effects are considered. The spectroscopic constants of CuH, the equilibrium structure of cis-(NO)2 and the binding energies of Be3, Be4, Mg3, and Mg4 were calculated using both approaches. The diagnostic for estimating multireference character clearly demonstrates that the QCI method becomes less satisfactory than the CC approach as non-dynamical correlation becomes more important, in agreement with a perturbational analysis of the two methods and the numerical estimates of the triple excitation energies they yield. The results for CuH show that the differences between the two methods become more apparent as the chemical systems under investigation becomes more multireference in nature and the QCI results consequently become less reliable. Nonetheless, when the system of interest is dominated by a single reference determinant both QCI and CC give very similar results.

Client-centered counseling improves client satisfaction with family planning visits: evidence from Irbid, Jordan

PubMed Central

Kamhawi, Sarah; Underwood, Carol; Murad, Huda; Jabre, Bushra

2013-01-01

ABSTRACT Background: High levels of unmet need for family planning and high contraceptive discontinuation rates persist in Jordan, prompting the Jordan Health Communication Partnership (JHCP) to initiate a client-centered family planning service program called “Consult and Choose” (CC), together with community-based activities to encourage women with unmet need to visit health centers. Methods: We held exit interviews with 461 family planning clients between November–December 2011 to assess, from the clients' perspective, whether trained providers followed the CC protocol and used the CC tools, as well as to measure client satisfaction. We also tracked referral card information from community-based activities to health centers and examined service statistics to explore trends in family planning use. Results: On average, clients reported that providers performed 5.6 of the 7 steps outlined in the CC protocol. Nearly 83% of respondents were very satisfied with their clinic visits. Logistic regression analysis found that the odds of being “very satisfied” increases by 20% with each additional counseling protocol step performed and by 70% with each increase in the number of CC materials used. Between June 2011 and August 2012, 14,490 referral cards from community-based activities were collected in health centers, 59% of which were for family planning services. Service statistic trends indicate an increase in the number of new family planning users and in couple-years of protection after starting the CC program. Conclusions: Implementation of the CC program at health centers nationally, in tandem with community-based interventions, could play a key role in attaining Jordan's goal of reducing its total fertility rate to 2.1 by 2030. Although this initiative would likely be replicated most readily in other middle-income countries, lower-resource countries could also adapt the tested CC approach. PMID:25276531

Seismic waves and earthquakes in a global monolithic model

NASA Astrophysics Data System (ADS)

Roubíček, Tomáš

2018-03-01

The philosophy that a single "monolithic" model can "asymptotically" replace and couple in a simple elegant way several specialized models relevant on various Earth layers is presented and, in special situations, also rigorously justified. In particular, global seismicity and tectonics is coupled to capture, e.g., (here by a simplified model) ruptures of lithospheric faults generating seismic waves which then propagate through the solid-like mantle and inner core both as shear (S) or pressure (P) waves, while S-waves are suppressed in the fluidic outer core and also in the oceans. The "monolithic-type" models have the capacity to describe all the mentioned features globally in a unified way together with corresponding interfacial conditions implicitly involved, only when scaling its parameters appropriately in different Earth's layers. Coupling of seismic waves with seismic sources due to tectonic events is thus an automatic side effect. The global ansatz is here based, rather for an illustration, only on a relatively simple Jeffreys' viscoelastic damageable material at small strains whose various scaling (limits) can lead to Boger's viscoelastic fluid or even to purely elastic (inviscid) fluid. Self-induced gravity field, Coriolis, centrifugal, and tidal forces are counted in our global model, as well. The rigorous mathematical analysis as far as the existence of solutions, convergence of the mentioned scalings, and energy conservation is briefly presented.

ONIOM Study of Chemical Reactions in Microsolvation Clusters: (H2O)(n)CH3Cl+OH-(H2O)(m) (n+m = 1 and 2)

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

Re, Suyong; Morokuma, Keiji

2001-07-07

The reliability of the two-layered ONIOM (our own N-layered molecular orbital + molecular mechanics) method was examined for the investigation of the SN2 reaction pathway (reactants, reactant complexes, transition states, product complexes, and products) between CH3Cl and an OH- ion in microsolvation clusters with one or two water molecules. Only the solute part, CH3Cl and OH-, was treated at a high level of molecular orbital (MO) theory, and all solvent water molecules were treated at a low MO level. The ONIOM calculation at the MP2 (Moller-Plesset second order perturbation)/aug-cc-pVDZ (augmented correlation-consistent polarized valence double-zeta basis set) level of theory asmore » the high level coupled with the B3LYP (Becke 3 parameter-Lee-Yag-Parr)/6-31+G(d) as the low level was found to reasonably reproduce the "target"geometries at the MP2/aug-cc-pVDZ level of theory. The energetics can be further improved to an average absolute error of <1.0 kcal/mol per solvent water molecule relative to the target CCSD(T) (coupled cluster singles and doubles with triples by perturbation)/aug-cc-pVDZ level by using the ONIOM method in which the high level was CCSD(T)/aug-cc-pVDZ level with the low level of MP2/aug-cc-pVDZ. The present results indicate that the ONIOM method would be a powerful tool for obtaining reliable geometries and energetics for chemical reactions in larger microsolvated clusters with a fraction of cost of the full high level calculation, when an appropriate combination of high and low level methods is used. The importance of a careful test is emphasized.« less

Computerized implementation of higher-order electron-correlation methods and their linear-scaling divide-and-conquer extensions.

PubMed

Nakano, Masahiko; Yoshikawa, Takeshi; Hirata, So; Seino, Junji; Nakai, Hiromi

2017-11-05

We have implemented a linear-scaling divide-and-conquer (DC)-based higher-order coupled-cluster (CC) and Møller-Plesset perturbation theories (MPPT) as well as their combinations automatically by means of the tensor contraction engine, which is a computerized symbolic algebra system. The DC-based energy expressions of the standard CC and MPPT methods and the CC methods augmented with a perturbation correction were proposed for up to high excitation orders [e.g., CCSDTQ, MP4, and CCSD(2) TQ ]. The numerical assessment for hydrogen halide chains, polyene chains, and first coordination sphere (C1) model of photoactive yellow protein has revealed that the DC-based correlation methods provide reliable correlation energies with significantly less computational cost than that of the conventional implementations. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

A rodent model for artificial gravity: VOR adaptation and Fos expression.

PubMed

Kaufman, Galen; Weng, Tianxiang; Ruttley, Tara

2005-01-01

Vestibulo-ocular reflex (VOR) adaptation and brainstem Fos expression as a result of short radius cross-coupling stimuli were investigated to find neural correlates of the inherent Coriolis force asymmetry from an artificial gravity (AG) environment. Head-fixed gerbils (Meriones unguiculatus, N=79) were exposed, in the dark, to 60--90 minutes of cross-coupled rotations, combinations of pitch (or roll) and yaw rotation, while binocular horizontal, vertical, and torsional eye position were determined using infrared video-oculography. Centripetal acceleration in combination with angular cross-coupling was also studied. Simultaneous sinusoidal rotations in two planes (yaw with roll or pitch) provided a net symmetrical stimulus for the right and left labyrinths. In contrast, a constant velocity yaw rotation during sinusoidal roll or pitch provided the asymmetric stimulus model for AG. We found orthogonally oriented half-cycle VOR gain changes. The results depended on the direction of horizontal rotation during asymmetrical cross-coupling, and other aspects of the stimulus, including the phase relationship between the two rotational inputs, the symmetry of the stimulus, and training. Fos expression also revealed laterality differences in the prepositus and inferior olivary C subnucleus. In contrast the inferior olivary beta and ventrolateral outgrowth were labeled bilaterally. Additional cross-coupling dependent labeling was found in the flocculus, hippocampus, and several cortical regions, including the perirhinal and temporal association cortices. Analyses showed significant differences across the brain regions for several factors (symmetry, rotation velocity and direction, the presence of centripetal acceleration or a visual surround, and training). Finally, animals compensating from a unilateral surgical labyrinthectomy who received multiple cross-coupling training sessions had improved half-cycle VOR gain in the ipsilateral eye with head rotation toward the intact side. We hypothesize that cross-coupling vestibular training can benefit aspects of motor recovery or performance.

CC, CS, and IOS generalized phenomenological cross sections for atom--diatom mixtures

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

Fitz, D.E.; Kouri, D.J.; Evans, D.

1981-05-01

Close coupled expressions for phenomenological cross sections which describe transport properties of atom--diatom mixtures are obtained in the total-J coupling scheme and are related to the bracket integrals of kinetic theory. Coupled states and infinite order sudden expressions for the generalized phenomenological cross sections using initial, final, and average l-labeling are also given. Particular care is taken to use a phase convention for the CS and IOS approximations which is consistent with the Arthurs--Dalgarno formalism and which gives the correct behavior of degeneracy averaged differential cross sections.

Quasi-linear gyrokinetic predictions of the Coriolis momentum pinch in NSTX

DOE Data Explorer

Guttenfelder, W. [Princeton Plasma Physics Lab. (PPPL), Princeton, NJ (United States); Kaye, S. M. [Princeton Plasma Physics Lab. (PPPL), Princeton, NJ (United States); Ren, Y. [Princeton Plasma Physics Lab. (PPPL), Princeton, NJ (United States); Solomon, W. [Princeton Plasma Physics Lab. (PPPL), Princeton, NJ (United States); Bell, R. E. [Princeton Plasma Physics Lab. (PPPL), Princeton, NJ (United States); Candy, J. [Princeton Plasma Physics Lab. (PPPL), Princeton, NJ (United States); Gerhardt, S. P. [Princeton Plasma Physics Lab. (PPPL), Princeton, NJ (United States); LeBlanc, B. P. [Princeton Plasma Physics Lab. (PPPL), Princeton, NJ (United States); Yuh, H. [Princeton Plasma Physics Lab. (PPPL), Princeton, NJ (United States)

2016-04-01

This paper presents quasi-linear gyrokinetic predictions of the Coriolis momentum pinch for low aspect-ratio NSTX H-modes where previous experimental measurements were focused. Local, linear calculations predict that in the region of interest (just outside the mid-radius) of these relatively high-beta plasmas, profiles are most unstable to microtearing modes that are only effective in transporting electron energy. However, sub-dominant electromagnetic and electrostatic ballooning modes are also unstable, which are effective at transporting energy, particles and momentum. The quasi-linear prediction of transport from these weaker ballooning modes, assuming they contribute transport in addition to that from microtearing modes in a nonlinear turbulent state, leads to a very small or outward convection of momentum, inconsistent with the experimentally measured inward pinch, and opposite to predictions in conventional aspect ratio tokamaks. Additional predictions of a low beta L-mode plasma, unstable to more traditional electrostatic ion temperature gradient-trapped electron mode instability, show that the Coriolis pinch is inward but remains relatively weak and insensitive to many parameter variations. The weak or outward pinch predicted in NSTX plasmas appears to be at least partially correlated to changes in the parallel mode structure that occur at finite beta and low aspect ratio, as discussed in previous theories. The only conditions identified where a stronger inward pinch is predicted occur either in the purely electrostatic limit or if the aspect ratio is increased. As the Coriolis pinch cannot explain the measured momentum pinch, additional theoretical momentum transport mechanisms are discussed that may be potentially important.

On the origin of the angular momentum of galaxies: cosmological tidal torques supplemented by the Coriolis force

NASA Astrophysics Data System (ADS)

Casuso, E.; Beckman, J. E.

2015-05-01

We present here a theoretical model which can at least contribute to the observed relation between the specific angular momenta of galaxies and their masses. This study offers prima facie evidence that the origin of an angular momentum of galaxies could be somewhat more complex than previously proposed. The most recent observations point to a scenario in which, after recombination, matter was organized around bubbles (commonly termed voids), which acquired rotation by tidal torque interaction. Subsequently, a combination of the effects of the gravitational collapse of gas in protogalaxies and the Coriolis force due to the rotation of the voids could produce the rotation of spiral galaxies. Thereafter, the tidal interaction between the objects populating the quasi-spherical voids, in which the galaxies far away from the rotation axes (populating the sheet forming the surface of a void) interact with higher probability with others similarly situated in a neighbouring void, offers a mechanism for transforming some of the galaxies into ellipticals, breaking their spin and yielding galaxies with low net angular momentum, as observed. This model gives an explanation for those observations which suggest a tendency of galactic spins to align along the radius vectors pointing towards the centres of the voids for ellipticals/SO and parallel to filaments and sheets for the spirals. Furthermore, while in simple tidal torque theory the angular momentum supplied to galaxies diminishes drastically with the cosmic expansion, in our approximation for which the Coriolis force acts in addition to tidal torques, the Coriolis force due to void rotation ensures almost continuous angular momentum supply.

Rotational spectrum and conformational composition of cyanoacetaldehyde, a compound of potential prebiotic and astrochemical interest.

PubMed

Møllendal, Harald; Margulès, Laurent; Motiyenko, Roman A; Larsen, Niels Wessel; Guillemin, Jean-Claude

2012-04-26

The rotational spectrum of cyanoacetaldehyde (NCCH(2)CHO) has been investigated in the 19.5-80.5 and 150-500 GHz spectral regions. It is found that cyanoacetaldehyde is strongly preferred over its tautomer cyanovinylalcohol (NCCH═CHOH) in the gas phase. The spectra of two rotameric forms of cyanoacetaldehyde produced by rotation about the central C-C bond have been assigned. The C-C-C-O dihedral angle has an unusual value of 151(3)° from the synperiplanar (0°) position in one of the conformers denoted I, while this dihedral angle is exactly synperiplanar in the second rotamer called II, which therefore has C(s) symmetry. Conformer I is found to be preferred over II by 2.9(8) kJ/mol from relative intensity measurements. A double minimum potential for rotation about the central C-C bond with a small barrier maximum at the exact antiperiplanar (180°) position leads to Coriolis perturbations in the rotational spectrum of conformer I. Selected transitions of I were fitted to a Hamiltonian allowing for this sort of interaction, and the separation between the two lowest vibrational states was determined to be 58794(14) MHz [1.96112(5) cm(-1)]. Attempts to include additional transitions in the fits using this Hamiltonian failed, and it is concluded that it lacks interaction terms to account satisfactorily for all the observed transitions. The situation was different for II. More than 2000 transitions were assigned and fitted to the usual Watson Hamiltonian, which allowed very accurate values to be determined not only for the rotational constants, but for many centrifugal distortion constants as well. Two vibrationally excited states were also assigned for this form. Theoretical calculations were performed at the B3LYP, MP2, and CCSD levels of theory using large basis sets to augment the experimental work. The predictions of these calculations turned out to be in good agreement with most experimental results.

Novel members of the adipokinetic hormone family in beetles of the superfamily Scarabaeoidea.

PubMed

Gäde, Gerd; Šimek, Petr; Marco, Heather G

2016-12-01

Eight beetle species of the superfamily Scarabaeoidea were investigated with respect to peptides belonging to the adipokinetic hormone (AKH) family in their neurohemal organs, the corpora cardiaca (CC). The following beetle families are represented: Scarabaeidae, Lucanidae, and Geotrupidae. AKH peptides were identified through a heterospecific trehalose-mobilizing bioassay and by sequence analyses, using liquid chromatography coupled to positive electrospray mass spectrometry (LC-ESI-MS) and analysis of the tandem MS 2 spectra obtained by collision-induced dissociation. All the beetle species have octapeptide AKHs; some have two AKHs, while others have only one. Novel AKH members were found in Euoniticellus intermedius and Circellium bacchus (family Scarabaeidae), as well as in Dorcus parallelipipedus (family Lucanidae). Two species of the family Geotrupidae and two species of the Scarabaeidae subfamily Cetoniinae contain one known AKH peptide, Melme-CC, while E. intermedius produces a novel peptide code named Euoin-AKH: pEINFTTGWamide. Two AKH peptides were each identified in CC of C. bacchus and D. parallelipipedus: the novel Cirba-AKH: pEFNFSAGWamide and the known peptide, Scade-CC-I in the former, and the novel Dorpa-AKH: pEVNYSPVW amide and the known peptide, Melme-CC in the latter. Kheper bonelli (subfamily Scarabaeinae) also has two AKHs, the known Scade-CC-I and Scade-CC-II. All the novel peptides were synthesized and the amino acid sequence assignments were unequivocally confirmed by co-elution of the synthetic peptides with their natural equivalent, and identical MS parameters of the two forms. The novel synthetic peptides are all active in inducing hypertrehalosemia in cockroaches.

Catalytic Carbonyl Allylation, Propargylation and Vinylation from the Alcohol or Aldehyde Oxidation Level via C-C Bond Forming Hydrogenation and Transfer Hydrogenation: A Departure from Preformed Organometallic Reagents**

PubMed Central

Bower, John F.; Kim, In Su; Patman, Ryan L.; Krische, Michael J.

2009-01-01

Classical protocols for carbonyl allylation, propargylation and vinylation typically rely upon the use of preformed allyl metal, allenyl metal and vinyl metal reagents, respectively, mandating stoichiometric generation of metallic byproducts. Through transfer hydrogenative C-C coupling, carbonyl addition may be achieved from the aldehyde or alcohol oxidation level in the absence of stoichiometric organometallic reagents or metallic reductants. Here, we review transfer hydrogenative methods for carbonyl addition, which encompass the first cataltyic protocols enabling direct C–H functionalization of alcohols. PMID:19040235

Dependence of Tropical Cyclone Intensification on the Latitude under Vertical Shear

NASA Astrophysics Data System (ADS)

Bi, Mingyu; Ge, Xuyang; Li, Tim

2018-02-01

The sensitivity of tropical cyclone (TC) intensification to the ambient rotation effect under vertical shear is investigated. The results show that the vortices develop more rapidly with intermediate planetary vorticity, which suggests an optimal latitude for the TC development in the presence of vertical shear. This is different from the previous studies in which no mean flow is considered. It is found that the ambient rotation has two main effects. On the one hand, the boundary layer imbalance is largely controlled by the Coriolis parameter. For TCs at lower latitudes, due to the weaker inertial instability, the boundary inflow is promptly established, which results in a stronger moisture convergence and thus greater diabatic heating in the inner core region. On the other hand, the Coriolis parameter modulates the vertical realignment of the vortex with a higher Coriolis parameter, favoring a quicker vertical realignment and thus a greater potential for TC development. The combination of these two effects results in an optimal latitude for TC intensification in the presence of a vertical shear investigated.

Vibration and buckling of rotating, pretwisted, preconed beams including Cooriolis effects

NASA Technical Reports Server (NTRS)

Subrahmanyam, K. B.; Kaza, K. R. V.

1985-01-01

The effects of pretwist, precone, setting angle and Coriolis forces on the vibration and buckling behavior of rotating, torsionally rigid, cantilevered beams were studied. The beam is considered to be clamped on the axis of rotation in one case, and off the axis of rotation in the other. Two methods are employed for the solution of the vibration problem: (1) one based upon a finite-difference approach using second order central differences for solution of the equations of motion, and (2) based upon the minimum of the total potential energy functional with a Ritz type of solution procedure making use of complex forms of shape functions for the dependent variables. The individual and collective effects of pretwist, precone, setting angle, thickness ratio and Coriolis forces on the natural frequencies and the buckling boundaries are presented. It is shown that the inclusion of Coriolis effects is necessary for blades of moderate to large thickness ratios while these effects are not so important for small thickness ratio blades. The possibility of buckling due to centrifugal softening terms for large values of precone and rotation is shown.

Dependence of tropical cyclone development on coriolis parameter: A theoretical model

NASA Astrophysics Data System (ADS)

Deng, Liyuan; Li, Tim; Bi, Mingyu; Liu, Jia; Peng, Melinda

2018-03-01

A simple theoretical model was formulated to investigate how tropical cyclone (TC) intensification depends on the Coriolis parameter. The theoretical framework includes a two-layer free atmosphere and an Ekman boundary layer at the bottom. The linkage between the free atmosphere and the boundary layer is through the Ekman pumping vertical velocity in proportion to the vorticity at the top of the boundary layer. The closure of this linear system assumes a simple relationship between the free atmosphere diabatic heating and the boundary layer moisture convergence. Under a set of realistic atmospheric parameter values, the model suggests that the most preferred latitude for TC development is around 5° without considering other factors. The theoretical result is confirmed by high-resolution WRF model simulations in a zero-mean flow and a constant SST environment on an f -plane with different Coriolis parameters. Given an initially balanced weak vortex, the TC-like vortex intensifies most rapidly at the reference latitude of 5°. Thus, the WRF model simulations confirm the f-dependent characteristics of TC intensification rate as suggested by the theoretical model.

The Effect of Temperature on Kinetics and Diffusion Coefficients of Metallocene Derivatives in Polyol-Based Deep Eutectic Solvents

PubMed Central

Bahadori, Laleh; Chakrabarti, Mohammed Harun; Manan, Ninie Suhana Abdul; Hashim, Mohd Ali; Mjalli, Farouq Sabri; AlNashef, Inas Muen; Brandon, Nigel

2015-01-01

The temperature dependence of the density, dynamic viscosity and ionic conductivity of several deep eutectic solvents (DESs) containing ammonium-based salts and hydrogen bond donvnors (polyol type) are investigated. The temperature-dependent electrolyte viscosity as a function of molar conductivity is correlated by means of Walden’s rule. The oxidation of ferrocene (Fc/Fc+) and reduction of cobaltocenium (Cc+/Cc) at different temperatures are studied by cyclic voltammetry and potential-step chronoamperometry in DESs. For most DESs, chronoamperometric transients are demonstrated to fit an Arrhenius-type relation to give activation energies for the diffusion of redox couples at different temperatures. The temperature dependence of the measured conductivities of DES1 and DES2 are better correlated with the Vogel-Tamman-Fulcher equation. The kinetics of the Fc/Fc+ and Cc+/Cc electrochemical systems have been investigated over a temperature range from 298 to 338 K. The heterogeneous electron transfer rate constant is then calculated at different temperatures by means of a logarithmic analysis. The glycerol-based DES (DES5) appears suitable for further testing in electrochemical energy storage devices. PMID:26642045

Higher symmetries of the Schrödinger operator in Newton-Cartan geometry

NASA Astrophysics Data System (ADS)

Gundry, James

2017-03-01

We establish several relationships between the non-relativistic conformal symmetries of Newton-Cartan geometry and the Schrödinger equation. In particular we discuss the algebra sch(d) of vector fields conformally-preserving a flat Newton-Cartan spacetime, and we prove that its curved generalisation generates the symmetry group of the covariant Schrödinger equation coupled to a Newtonian potential and generalised Coriolis force. We provide intrinsic Newton-Cartan definitions of Killing tensors and conformal Schrödinger-Killing tensors, and we discuss their respective links to conserved quantities and to the higher symmetries of the Schrödinger equation. Finally we consider the role of conformal symmetries in Newtonian twistor theory, where the infinite-dimensional algebra of holomorphic vector fields on twistor space corresponds to the symmetry algebra cnc(3) on the Newton-Cartan spacetime.

Millimeter-wave and Submillimeter-wave Spectra of Aminoacetonitrile in the Three Lowest Vibrational Excited States

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

Esposti, Claudio Degli; Dore, Luca; Melosso, Mattia

It is important to study possible precursors of amino acids such as glycine to enable future searches in interstellar space. Aminoacetonitrile (NH{sub 2}CH{sub 2}CN) is one of the most feasible molecules for this purpose. This molecule was already detected toward Sgr B2(N). Aminoacetonitrile has a few low-lying vibrational excited states, and transitions within these states may be found in space. In this study, the pure-rotational transitions in the three lowest vibrational states in the 80–450 GHz range have been assigned and analyzed. It was found to be very important to include Coriolis coupling between the two lowest vibrational fundamentals, whilemore » the third one was unperturbed. The partition function was evaluated considering these new results.« less

Millimetre Wave Rotational Spectrum of Glycolic Acid

NASA Technical Reports Server (NTRS)

Kisiel, Zbigniew; Pszczolkowski, Lech; Bialkowska-Jaworska, Ewa; Charnley, Steven B.

2016-01-01

The pure rotational spectrum of glycolic acid, CH2OHCOOH, was studied in the region 115-318 GHz. For the most stable SSC conformer, transitions in all vibrational states up to 400 cm(exp -1) have been measured and their analysis is reported. The data sets for the ground state, v21 = 1, and v21 = 2 have been considerably extended. Immediately higher in vibrational energy are two triads of interacting vibrational states and their rotational transitions have been assigned and successfully fitted with coupled Hamiltonians accounting for Fermi and Coriolis resonances. The derived energy level spacings establish that the vibrational frequency of the v21 mode is close to 100 cm(exp -1). The existence of the less stable AAT conformer in the near 50 C sample used in our experiment was also confirmed and additional transitions have been measured.

Thermal decomposition of 1,3,3-trinitroazetidine (TNAZ): A density functional theory and ab initio study

NASA Astrophysics Data System (ADS)

Veals, Jeffrey D.; Thompson, Donald L.

2014-04-01

Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO2 or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO2 elimination by N-N and C-N bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO2 group elimination or by a concerted H-atom and nitroalkyl NO2 group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO2 elimination by N-N bond fission, HONO elimination involving the nitramine NO2 group, HONO elimination involving a nitroalkyl NO2 group, and finally NO2 elimination by C-N bond fission.

Effect of the Earth's rotation on subduction processes

NASA Astrophysics Data System (ADS)

Levin, B. W.; Rodkin, M. V.; Sasorova, E. V.

2017-09-01

The role played by the Earth's rotation is very important in problems of physics of the atmosphere and ocean. The importance of inertia forces is traditionally estimated by the value of the Rossby number: if this parameter is small, the Coriolis force considerably affects the character of movements. In the case of convection in the Earth's mantle and movements of lithospheric plates, the Rossby number is quite small; therefore, the effect of the Coriolis force is reflected in the character of movements of the lithospheric plates. Analysis of statistical data on subduction zones verifies this suggestion.

Letter: Symmetric instability drastically changes upon inclusion of the full Coriolis force

NASA Astrophysics Data System (ADS)

Zeitlin, V.

2018-06-01

It is shown that the classical symmetric instability drastically changes, if the usually neglected vertical component of the Coriolis force and the contribution of the vertical velocity into its horizontal components are taken into account. The influence of these "non-traditional" terms is different for flows with positive and negative horizontal relative vorticities. A critical value of the Richardson number appears in the second case, with the instability changing its character across it. Major differences appear between hydrostatic and non-hydrostatic versions of the instability. All these features are absent in the traditional approximation.

Colliding Stellar Wind Models with Orbital Motion

NASA Astrophysics Data System (ADS)

Wilkin, Francis P.; O'Connor, Brendan

2018-01-01

We present thin-shell models for the collision between two ballistic stellar winds, including orbital motion.The stellar orbits are assumed circular, so that steady-state solutions exist in the rotating frame, where we include centrifugal and Coriolis forces. Exact solutions for the pre-shock winds are incorporated. Here we discuss 2-D model results for equal wind momentum-loss rates, although we allow for the winds to have distinct speeds and mass loss rates. For these unequal wind conditions, we obtain a clear violation of skew-symmetry, despite equal momentum loss rates, due to the Coriolis force.

Quantum chemical calculations and analysis of FTIR, FT-Raman and UV-Vis spectra of temozolomide molecule

NASA Astrophysics Data System (ADS)

Bhat, Sheeraz Ahmad; Ahmad, Shabbir

2015-11-01

A combined experimental and theoretical study of the structure, vibrational and electronic spectra of temozolomide molecule, which is largely used in the treatment of brain tumours, is presented. FTIR (4000-400 cm-1) and FT-Raman spectra (4000‒50 cm-1) have been recorded and analysed using anharmonic frequency calculations using VPT2, VSCF and CC-VSCF levels of theory within B3LYP/6-311++G(d,p) framework. Anharmonic methods give accurate frequencies of fundamental modes, overtones as well as Fermi resonances and account for coupling of different modes. The anharmonic frequencies calculated using VPT2 and CC-VSCF methods show better agreement with the experimental data. Harmonic frequencies including solvent effects are also computed using IEF-PCM model. The magnitudes of coupling between pair of modes have been calculated using coupling integral based on 2MR-QFF approximation. Intermolecular interactions are discussed for three possible dimers of temozolomide. UV-Vis spectrum, examined in ethanol solvent, is compared with the calculated spectrum at TD-DFT/6-311++G(d,p) level of theory. The electronic properties, such as excitation energy, frontier molecular orbital energies and the assignments of the absorption bands are also discussed.

Plasmonic Control of Multi-Electron Transfer and C-C Coupling in Visible-Light-Driven CO2 Reduction on Au Nanoparticles.

PubMed

Yu, Sungju; Wilson, Andrew J; Heo, Jaeyoung; Jain, Prashant K

2018-04-11

Artificial photosynthesis relies on the availability of synthetic photocatalysts that can drive CO 2 reduction in the presence of water and light. From the standpoint of solar fuel production, it is desirable that these photocatalysts perform under visible light and produce energy-rich hydrocarbons from CO 2 reduction. However, the multistep nature of CO 2 -to-hydrocarbon conversion poses a significant kinetic bottleneck when compared to CO production and H 2 evolution. Here, we show that plasmonic Au nanoparticle photocatalysts can harvest visible light for multielectron, multiproton reduction of CO 2 to yield C 1 (methane) and C 2 (ethane) hydrocarbons. The light-excitation attributes influence the C 2 and C 1 selectivity. The observed trends in activity and selectivity follow Poisson statistics of electron harvesting. Higher photon energies and flux favor simultaneous harvesting of more than one electron from the photocharged Au nanoparticle catalyst, inducing the C-C coupling required for C 2 production. These findings elucidate the nature of plasmonic photocatalysis, which involves strong light-matter coupling, and set the stage for the controlled chemical bond formation by light excitation.

From D-sorbitol to five-membered bis(cyclo-carbonate) as a platform molecule for the synthesis of different original biobased chemicals and polymers.

PubMed

Furtwengler, Pierre; Avérous, Luc

2018-06-14

Bis(cyclo-carbonate) was successfully synthesized from D-sorbitol (Sorb-BisCC) through an environmentally friendly process with dimethyl carbonate (DMC) as a reactant. In agreement with green chemistry principles, solvent free reactions were catalyzed and took place at low temperature. The reaction yield was increased until 50%, with the use of 1.3.5-triazabicyclo[4.4.0]dec-5-ene as catalyst and a continuous DMC feed to limit the side-reactions or the loss of reactant by azeotropic flux with a reactional subsidiary product. The obtained Sorb-BisCC is a remarkable platform molecule which could compete with others polycyclic platform molecules (isosorbide). Sorb-BisCC can be e.g., used to synthesize different chemicals such as short and long polyols, or novel biobased non-isocyanate polyurethanes (NIPU). Two Sorb-BisCC molecules have been coupled to obtain novel cyclic diols with pendant side chains. Polyether polyols were also obtained by anionic ring opening polymerization. According to the synthesis conditions, these synthetized polyether polyols range from partially to highly cross-linked materials. Finally, NIPU were synthesized with short and biobased fatty diamines. These different modifications and synthesis highlight the versatility of the Sorb-BisCC and demonstrated its high potential as building block. Sorb-BisCC can be considered as a platform molecule to open the way to different original and biobased chemical architectures.

Approximations to complete basis set-extrapolated, highly correlated non-covalent interaction energies.

PubMed

Mackie, Iain D; DiLabio, Gino A

2011-10-07

The first-principles calculation of non-covalent (particularly dispersion) interactions between molecules is a considerable challenge. In this work we studied the binding energies for ten small non-covalently bonded dimers with several combinations of correlation methods (MP2, coupled-cluster single double, coupled-cluster single double (triple) (CCSD(T))), correlation-consistent basis sets (aug-cc-pVXZ, X = D, T, Q), two-point complete basis set energy extrapolations, and counterpoise corrections. For this work, complete basis set results were estimated from averaged counterpoise and non-counterpoise-corrected CCSD(T) binding energies obtained from extrapolations with aug-cc-pVQZ and aug-cc-pVTZ basis sets. It is demonstrated that, in almost all cases, binding energies converge more rapidly to the basis set limit by averaging the counterpoise and non-counterpoise corrected values than by using either counterpoise or non-counterpoise methods alone. Examination of the effect of basis set size and electron correlation shows that the triples contribution to the CCSD(T) binding energies is fairly constant with the basis set size, with a slight underestimation with CCSD(T)∕aug-cc-pVDZ compared to the value at the (estimated) complete basis set limit, and that contributions to the binding energies obtained by MP2 generally overestimate the analogous CCSD(T) contributions. Taking these factors together, we conclude that the binding energies for non-covalently bonded systems can be accurately determined using a composite method that combines CCSD(T)∕aug-cc-pVDZ with energy corrections obtained using basis set extrapolated MP2 (utilizing aug-cc-pVQZ and aug-cc-pVTZ basis sets), if all of the components are obtained by averaging the counterpoise and non-counterpoise energies. With such an approach, binding energies for the set of ten dimers are predicted with a mean absolute deviation of 0.02 kcal/mol, a maximum absolute deviation of 0.05 kcal/mol, and a mean percent absolute deviation of only 1.7%, relative to the (estimated) complete basis set CCSD(T) results. Use of this composite approach to an additional set of eight dimers gave binding energies to within 1% of previously published high-level data. It is also shown that binding within parallel and parallel-crossed conformations of naphthalene dimer is predicted by the composite approach to be 9% greater than that previously reported in the literature. The ability of some recently developed dispersion-corrected density-functional theory methods to predict the binding energies of the set of ten small dimers was also examined. © 2011 American Institute of Physics

High-Resolution Study of the C-D Stretching Bands of 12C 6D 6 and 13C 6D 6

NASA Astrophysics Data System (ADS)

Pliva, J.; Johns, J. W. C.; Goodman, L.

1994-01-01

The perpendicular C-D stretching bands ν 12 (species E1 u) were measured for two isotopomers of benzene with D6 h symmetry. 12C 6D 6 and 13C 6D 6, on a high-resolution Fourier transform spectrometer. Both bands show effects of fairly strong perturbations by states resulting from combinations of low-frequency vibrations. The ν 12 state of 12C 6D 6 is in Fermi resonance with the combination ν 2 + ν 3 whose pP lines, enhanced by the resonance, are observed just below the pP branches of ν 12. An x, y-type Coriolis interaction with an unidentified state of symmetry E2 u, and another anharmonic interaction with an unknown E1 u state, have also been detected in the spectrum. These interactions were included, along with the Fermi resonance and the rotational l-resonance and -doubling, in the Hamiltonian used in the analysis of this band. For the ν 12 band of the 13C 6D 6 isotopomer, a strong perturbation by an anharmonic resonance with the E1 u state ν 7 + ν 11 + ν 14 and a much weaker perturbation. presumably by a z-type Coriolis interaction with an unidentified perturber, have been observed and taken into account in the analysis. Spectroscopic constants are reported for the ν 12 states of the two isotopic species, and parameters obtained for the various perturbers and coupling constants are also listed. It is found that the ζ sum for the E1 u vibrations of all D6 h isotopomers of benzene differs slightly from the theoretical value of ∑ζ t = -1.

Eckart frame vibration-rotation Hamiltonians: Contravariant metric tensor

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

Pesonen, Janne, E-mail: janne.pesonen@helsinki.fi

2014-02-21

Eckart frame is a unique embedding in the theory of molecular vibrations and rotations. It is defined by the condition that the Coriolis coupling of the reference structure of the molecule is zero for every choice of the shape coordinates. It is far from trivial to set up Eckart kinetic energy operators (KEOs), when the shape of the molecule is described by curvilinear coordinates. In order to obtain the KEO, one needs to set up the corresponding contravariant metric tensor. Here, I derive explicitly the Eckart frame rotational measuring vectors. Their inner products with themselves give the rotational elements, andmore » their inner products with the vibrational measuring vectors (which, in the absence of constraints, are the mass-weighted gradients of the shape coordinates) give the Coriolis elements of the contravariant metric tensor. The vibrational elements are given as the inner products of the vibrational measuring vectors with themselves, and these elements do not depend on the choice of the body-frame. The present approach has the advantage that it does not depend on any particular choice of the shape coordinates, but it can be used in conjunction with all shape coordinates. Furthermore, it does not involve evaluation of covariant metric tensors, chain rules of derivation, or numerical differentiation, and it can be easily modified if there are constraints on the shape of the molecule. Both the planar and non-planar reference structures are accounted for. The present method is particular suitable for numerical work. Its computational implementation is outlined in an example, where I discuss how to evaluate vibration-rotation energies and eigenfunctions of a general N-atomic molecule, the shape of which is described by a set of local polyspherical coordinates.« less

High-resolution infrared study of vinyl fluoride in the 750-1050 cm(-1) region: rovibrational analysis and resonances involving the nu8, nu10, and nu11 fundamentals.

PubMed

Tasinato, Nicola; Stoppa, Paolo; Charmet, A Pietropolli; Giorgianni, Santi; Gambi, Alberto

2006-12-21

The FTIR spectra of CH2[double bond]CHF have been investigated in the nu(8), nu(10), and nu(11) region between 750 and 1050 cm(-1) at a resolution of about 0.002 cm(-1). The nu(8) vibration of symmetry species A' gives rise to an a/b-type hybrid band, while the nu(10) and nu(11) modes of A' ' symmetry produce c-type absorptions. Due to the proximity of their band origins, the three vibrations perturb each other by Coriolis and high-order anharmonic resonances. In particular, the interactions between the nu(8) and nu(10) modes are very strong and widespread with band origins separated by only 1.37 cm(-1). Besides the expected c-type characteristics, the nu(10) band shows a very intense pseudo a-type component caused by the strong first-order Coriolis resonances with the nu(8) state. Furthermore, the 2nu(9) "dark state" was found to be involved in the interacting band systems. The spectral analysis resulted in the identification of 3144, 3235, and 3577 transitions of the nu(8), nu(10), and nu(11) vibrations, respectively. Almost all the assigned data were simultaneously fitted using the Watson's A-reduction Hamiltonian in the Ir representation and the perturbation operators. The model employed includes nine types of resonances within the tetrad nu(8)/nu(10)/nu(11)/2nu(9) and a set of spectroscopic constants for the nu(8), nu(10), and nu(11) fundamentals as well as parameters for the "dark state" 2nu(9), and fourteen coupling terms have been determined.

Far-infrared vibration--rotation-tunneling spectroscopy of Ar--NH sub 3 : Intermolecular vibrations and effective angular potential energy surface

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

Schmuttenmaer, C.A.; Cohen, R.C.; Loeser, J.G.

Two new intermolecular vibration--rotation-tunneling (VRT) bands of Ar--NH{sub 3} have been measured using tunable far infrared laser spectroscopy. We have unambiguously assigned these and a previously measured FIR band (Gwo {ital et} {ital al}., Mol. Phys. {bold 71}, 453 (1990)) as {Pi}(1{sub 0}, {ital n}=0){l arrow}{Sigma}(0{sub 0}, {ital n}=0), {Sigma}(1{sub 0}, {ital n}=0){l arrow}{Sigma}(0{sub 0}, {ital n}=0), and {Sigma}(0{sub 0}, {ital n}=1){l arrow}{Sigma}(0{sub 0}, {ital n}=0). The three upper states of these are found to be strongly mixed by anisotropy and Coriolis effects. A simultaneous least squares fit of all transitions has yielded vibrational frequencies, rotational and centrifugal distortion constants,more » and a Coriolis parameter as well as quadrupole hyperfine coupling constants for the upper states. An effective angular potential energy surface for Ar--NH{sub 3} in its lowest stretching state has been determined from these data, after explicitly accounting for the effects of bend stretch interactions. Features of the surface include a global minimum at the near T-shaped configuration ({theta}=90{degree}), a 30 cm{sup {minus}1} to 60 cm{sup {minus}1} barrier to rotation at {theta}=180{degree} (or 0{degree}), and a very low barrier or possibly a secondary minimum at {theta}=0{degree} (or 180{degree}). Both attractive and repulsive interactions are shown to contribute significantly to the anisotropic forces in the complex. Comparison with {ital ab} {ital initio} calculations are presented.« less

"Outer-sphere to inner-sphere" redox cycling for ultrasensitive immunosensors.

PubMed

Akanda, Md Rajibul; Choe, Yu-Lim; Yang, Haesik

2012-01-17

This paper reports chemical-chemical (CC) and electrochemical-chemical-chemical (ECC) redox cycling, for use in ultrasensitive biosensor applications. A triple chemical amplification approach using an enzymatic reaction, CC redox cycling, and ECC redox cycling is applied toward electrochemical immunosensors of cardiac troponin I. An enzymatic reaction, in which alkaline phosphatase converts 4-aminophenyl phosphate to 4-aminophenol (AP), triggers CC redox cycling in the presence of an oxidant and a reductant, and electrochemical signals are measured with ECC redox cycling after an incubation period of time in an air-saturated solution. To obtain high, selective, and reproducible redox cycling without using redox enzymes, two redox reactions [the reaction between AP and the oxidant and the reaction between the oxidized form of AP (4-quinone imine, QI) and the reductant] should be fast, but an unwanted reaction between the oxidant and reductant should be very slow. Because species that undergo outer-sphere reactions (OSR-philic species) react slowly with species that undergo inner-sphere reactions (ISR-philic species), highly OSR-philic Ru(NH(3))(6)(3+) and highly ISR-philic tris(2-carboxyethyl)phosphine (TCEP) are chosen as the oxidant and reductant, respectively. The OSR- and ISR-philic QI/AP couple allows fast redox reactions with both the OSR-philic Ru(NH(3))(6)(3+) and the ISR-philic TCEP. Highly OSR-philic indium-tin oxide (ITO) electrodes minimize unwanted electrochemical reactions with highly ISR-philic species. Although the formal potential of the Ru(NH(3))(6)(3+)/Ru(NH(3))(6)(2+) couple is lower than that of the QI/AP couple, the endergonic reaction between Ru(NH(3))(6)(3+) and AP is driven by the highly exergonic reaction between TCEP and QI (via a coupled reaction mechanism). Overall, the "outer-sphere to inner-sphere" redox cycling in the order of highly OSR-philic ITO, highly OSR-philic Ru(NH(3))(6)(3+)/Ru(NH(3))(6)(2+) couple, OSR- and ISR-philic QI/AP couple, and highly ISR-philic TCEP allows high, selective, and reproducible signal amplification. The electrochemical data obtained by chronocoulometry permit a lower detection limits than those obtained by cyclic voltammetry. The detection limit of an immunosensor for troponin I in serum, calculated from the anodic charges in chronocoulometry, is ca. 10 fg/mL.

Continuous Catalytic Production of Methyl Acrylates from Unsaturated Alcohols by Gold: The Strong Effect of C=C Unsaturation on Reaction Selectivity

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

Zugic, Branko; Karakalos, Stavros; Stowers, Kara J.

2016-03-04

Here we demonstrate the gas-phase catalytic production of methyl acrylates by oxygen-assisted coupling of methanol with the unsaturated alcohols allyl alcohol and methylallyl alcohol over nanoporous gold (npAu) at atmospheric pressure. Analogous investigations on O-activated Au(110) exhibit the same pattern of reactivity and are used to establish that the competition between methoxy and allyloxy (or methallyloxy) reaction intermediates for adsorption sites, mediated by the reactants themselves, determines the selectivity of reaction. Our results clearly show that the C=C bond substantially increases the binding efficacy of the allyloxy (or methallyloxy), thus requiring extremely high methanol mole fractions (>0.99) in order tomore » achieve comparable surface concentrations of methoxy and produce optimum yields of either methacrylate or methyl methacrylate. Allyloxy and methallyloxy were favored by factors of ~100 and ~450, respectively, vs methoxy. These values are more than 1 order of magnitude greater than those measured for competitive binding of ethoxy and 1-butoxy vs methoxy, demonstrating the strong effect of the carbon–carbon bond unsaturation. The 4.5-fold increase due to the addition of the methyl group in methylallyl alcohol vs allyl alcohol indicates the significant effect of the additional van der Waals interactions between the methyl group and the surface. Gas-phase acidity is also shown to be a good qualitative indicator for the relative binding strength of the alkoxides. This work provides insight into the control of reaction selectivity for coupling reactions and demonstrates the value of fundamental studies on single crystals for establishing key principles governing reaction selectivity. Notably, these oxygen-assisted coupling reactions occur without oxidation of the C=C bond.« less

Reduction of the virtual space for coupled-cluster excitation energies of large molecules and embedded systems

PubMed Central

Send, Robert; Kaila, Ville R. I.; Sundholm, Dage

2011-01-01

We investigate how the reduction of the virtual space affects coupled-cluster excitation energies at the approximate singles and doubles coupled-cluster level (CC2). In this reduced-virtual-space (RVS) approach, all virtual orbitals above a certain energy threshold are omitted in the correlation calculation. The effects of the RVS approach are assessed by calculations on the two lowest excitation energies of 11 biochromophores using different sizes of the virtual space. Our set of biochromophores consists of common model systems for the chromophores of the photoactive yellow protein, the green fluorescent protein, and rhodopsin. The RVS calculations show that most of the high-lying virtual orbitals can be neglected without significantly affecting the accuracy of the obtained excitation energies. Omitting all virtual orbitals above 50 eV in the correlation calculation introduces errors in the excitation energies that are smaller than 0.1 eV . By using a RVS energy threshold of 50 eV , the CC2 calculations using triple-ζ basis sets (TZVP) on protonated Schiff base retinal are accelerated by a factor of 6. We demonstrate the applicability of the RVS approach by performing CC2∕TZVP calculations on the lowest singlet excitation energy of a rhodopsin model consisting of 165 atoms using RVS thresholds between 20 eV and 120 eV. The calculations on the rhodopsin model show that the RVS errors determined in the gas-phase are a very good approximation to the RVS errors in the protein environment. The RVS approach thus renders purely quantum mechanical treatments of chromophores in protein environments feasible and offers an ab initio alternative to quantum mechanics∕molecular mechanics separation schemes. PMID:21663351

Continuous Catalytic Production of Methyl Acrylates from Unsaturated Alcohols by Gold: The Strong Effect of C=C Unsaturation on Reaction Selectivity

DOE PAGES

Zugic, Branko; Karakalos, Stavros; Stowers, Kara J.; ...

2016-02-02

We demonstrate the gas-phase catalytic production of methyl acrylates by oxygen-assisted coupling of methanol with the unsaturated alcohols allyl alcohol and methylallyl alcohol over nanoporous gold (npAu) at atmospheric pressure. Analogous investigations on O-activated Au(110) exhibit the same pattern of reactivity and are used to establish that the competition between methoxy and allyloxy (or methallyloxy) reaction intermediates for adsorption sites, mediated by the reactants themselves, determines the selectivity of reaction. These results clearly show that the C=C bond substantially increases the binding efficacy of the allyloxy (or methallyloxy), thus requiring extremely high methanol mole fractions (>0.99) in order to achievemore » comparable surface concentrations of methoxy and produce optimum yields of either methacrylate or methyl methacrylate. Allyloxy and methallyloxy were favored by factors of ~100 and ~450, respectively, vs methoxy. These values are more than 1 order of magnitude greater than those measured for competitive binding of ethoxy and 1-butoxy vs methoxy, demonstrating the strong effect of the carbon–carbon bond unsaturation. The 4.5-fold increase due to the addition of the methyl group in methylallyl alcohol vs allyl alcohol indicates the significant effect of the additional van der Waals interactions between the methyl group and the surface. Gas-phase acidity is also shown to be a good qualitative indicator for the relative binding strength of the alkoxides. This work then provides insight into the control of reaction selectivity for coupling reactions and demonstrates the value of fundamental studies on single crystals for establishing key principles governing reaction selectivity. Notably, these oxygen-assisted coupling reactions occur without oxidation of the C=C bond.« less

Structure of CC chemokine receptor 2 with orthosteric and allosteric antagonists

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

Zheng, Yi; Qin, Ling; Zacarías, Natalia V. Ortiz

CC chemokine receptor 2 (CCR2) is one of 19 members of the chemokine receptor subfamily of human class A G-protein-coupled receptors. CCR2 is expressed on monocytes, immature dendritic cells, and T-cell subpopulations, and mediates their migration towards endogenous CC chemokine ligands such as CCL2 (ref. 1). CCR2 and its ligands are implicated in numerous inflammatory and neurodegenerative diseases2 including atherosclerosis, multiple sclerosis, asthma, neuropathic pain, and diabetic nephropathy, as well as cancer3. These disease associations have motivated numerous preclinical studies and clinical trials4 (see http://www.clinicaltrials.gov) in search of therapies that target the CCR2–chemokine axis. To aid drug discovery efforts5, heremore » we solve a structure of CCR2 in a ternary complex with an orthosteric (BMS-681 (ref. 6)) and allosteric (CCR2-RA-[R]7) antagonist. BMS-681 inhibits chemokine binding by occupying the orthosteric pocket of the receptor in a previously unseen binding mode. CCR2-RA-[R] binds in a novel, highly druggable pocket that is the most intracellular allosteric site observed in class A G-protein-coupled receptors so far; this site spatially overlaps the G-protein-binding site in homologous receptors. CCR2-RA-[R] inhibits CCR2 non-competitively by blocking activation-associated conformational changes and formation of the G-protein-binding interface. The conformational signature of the conserved microswitch residues observed in double-antagonist-bound CCR2 resembles the most inactive G-protein-coupled receptor structures solved so far. Like other protein–protein interactions, receptor–chemokine complexes are considered challenging therapeutic targets for small molecules, and the present structure suggests diverse pocket epitopes that can be exploited to overcome obstacles in drug design.« less

Reduction of the virtual space for coupled-cluster excitation energies of large molecules and embedded systems.

PubMed

Send, Robert; Kaila, Ville R I; Sundholm, Dage

2011-06-07

We investigate how the reduction of the virtual space affects coupled-cluster excitation energies at the approximate singles and doubles coupled-cluster level (CC2). In this reduced-virtual-space (RVS) approach, all virtual orbitals above a certain energy threshold are omitted in the correlation calculation. The effects of the RVS approach are assessed by calculations on the two lowest excitation energies of 11 biochromophores using different sizes of the virtual space. Our set of biochromophores consists of common model systems for the chromophores of the photoactive yellow protein, the green fluorescent protein, and rhodopsin. The RVS calculations show that most of the high-lying virtual orbitals can be neglected without significantly affecting the accuracy of the obtained excitation energies. Omitting all virtual orbitals above 50 eV in the correlation calculation introduces errors in the excitation energies that are smaller than 0.1 eV. By using a RVS energy threshold of 50 eV, the CC2 calculations using triple-ζ basis sets (TZVP) on protonated Schiff base retinal are accelerated by a factor of 6. We demonstrate the applicability of the RVS approach by performing CC2/TZVP calculations on the lowest singlet excitation energy of a rhodopsin model consisting of 165 atoms using RVS thresholds between 20 eV and 120 eV. The calculations on the rhodopsin model show that the RVS errors determined in the gas-phase are a very good approximation to the RVS errors in the protein environment. The RVS approach thus renders purely quantum mechanical treatments of chromophores in protein environments feasible and offers an ab initio alternative to quantum mechanics/molecular mechanics separation schemes. © 2011 American Institute of Physics

Quasi-linear gyrokinetic predictions of the Coriolis momentum pinch in National Spherical Torus Experiment

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

Guttenfelder, W.; Kaye, S. M.; Ren, Y.

This paper presents quasi-linear gyrokinetic predictions of the Coriolis momentum pinch for low aspect-ratio National Spherical Torus Experiment (NSTX) H-modes where previous experimental measurements were focused. Local, linear calculations predict that in the region of interest (just outside the mid-radius) of these relatively high-beta plasmas, profiles are most unstable to microtearing modes that are only effective in transporting electron energy. However, sub-dominant electromagnetic and electrostaticballooning modes are also unstable, which are effective at transporting energy, particles, and momentum. The quasi-linear prediction of transport from these weaker ballooning modes, assuming they contribute transport in addition to that from microtearing modes inmore » a nonlinear turbulent state, leads to a very small or outward convection of momentum, inconsistent with the experimentally measured inward pinch, and opposite to predictions in conventional aspect ratio tokamaks. Additional predictions of a low beta L-mode plasma, unstable to more traditional electrostatic ion temperature gradient-trapped electron mode instability, show that the Coriolis pinch is inward but remains relatively weak and insensitive to many parameter variations. The weak or outward pinch predicted in NSTX plasmas appears to be at least partially correlated to changes in the parallel mode structure that occur at a finite beta and low aspect ratio, as discussed in previous theories. The only conditions identified where a stronger inward pinch is predicted occur either in the purely electrostatic limit or if the aspect ratio is increased. Lastly, as the Coriolis pinch cannot explain the measured momentum pinch, additional theoretical momentum transport mechanisms are discussed that may be potentially important.« less

Quasi-linear gyrokinetic predictions of the Coriolis momentum pinch in National Spherical Torus Experiment

DOE PAGES

Guttenfelder, W.; Kaye, S. M.; Ren, Y.; ...

2016-05-11

This paper presents quasi-linear gyrokinetic predictions of the Coriolis momentum pinch for low aspect-ratio National Spherical Torus Experiment (NSTX) H-modes where previous experimental measurements were focused. Local, linear calculations predict that in the region of interest (just outside the mid-radius) of these relatively high-beta plasmas, profiles are most unstable to microtearing modes that are only effective in transporting electron energy. However, sub-dominant electromagnetic and electrostaticballooning modes are also unstable, which are effective at transporting energy, particles, and momentum. The quasi-linear prediction of transport from these weaker ballooning modes, assuming they contribute transport in addition to that from microtearing modes inmore » a nonlinear turbulent state, leads to a very small or outward convection of momentum, inconsistent with the experimentally measured inward pinch, and opposite to predictions in conventional aspect ratio tokamaks. Additional predictions of a low beta L-mode plasma, unstable to more traditional electrostatic ion temperature gradient-trapped electron mode instability, show that the Coriolis pinch is inward but remains relatively weak and insensitive to many parameter variations. The weak or outward pinch predicted in NSTX plasmas appears to be at least partially correlated to changes in the parallel mode structure that occur at a finite beta and low aspect ratio, as discussed in previous theories. The only conditions identified where a stronger inward pinch is predicted occur either in the purely electrostatic limit or if the aspect ratio is increased. Lastly, as the Coriolis pinch cannot explain the measured momentum pinch, additional theoretical momentum transport mechanisms are discussed that may be potentially important.« less

Evaluation of Legionella Air Contamination in Healthcare Facilities by Different Sampling Methods: An Italian Multicenter Study.

PubMed

Montagna, Maria Teresa; De Giglio, Osvalda; Cristina, Maria Luisa; Napoli, Christian; Pacifico, Claudia; Agodi, Antonella; Baldovin, Tatjana; Casini, Beatrice; Coniglio, Maria Anna; D'Errico, Marcello Mario; Delia, Santi Antonino; Deriu, Maria Grazia; Guida, Marco; Laganà, Pasqualina; Liguori, Giorgio; Moro, Matteo; Mura, Ida; Pennino, Francesca; Privitera, Gaetano; Romano Spica, Vincenzo; Sembeni, Silvia; Spagnolo, Anna Maria; Tardivo, Stefano; Torre, Ida; Valeriani, Federica; Albertini, Roberto; Pasquarella, Cesira

2017-06-22

Healthcare facilities (HF) represent an at-risk environment for legionellosis transmission occurring after inhalation of contaminated aerosols. In general, the control of water is preferred to that of air because, to date, there are no standardized sampling protocols. Legionella air contamination was investigated in the bathrooms of 11 HF by active sampling (Surface Air System and Coriolis ® μ) and passive sampling using settling plates. During the 8-hour sampling, hot tap water was sampled three times. All air samples were evaluated using culture-based methods, whereas liquid samples collected using the Coriolis ® μ were also analyzed by real-time PCR. Legionella presence in the air and water was then compared by sequence-based typing (SBT) methods. Air contamination was found in four HF (36.4%) by at least one of the culturable methods. The culturable investigation by Coriolis ® μ did not yield Legionella in any enrolled HF. However, molecular investigation using Coriolis ® μ resulted in eight HF testing positive for Legionella in the air. Comparison of Legionella air and water contamination indicated that Legionella water concentration could be predictive of its presence in the air. Furthermore, a molecular study of 12 L. pneumophila strains confirmed a match between the Legionella strains from air and water samples by SBT for three out of four HF that tested positive for Legionella by at least one of the culturable methods. Overall, our study shows that Legionella air detection cannot replace water sampling because the absence of microorganisms from the air does not necessarily represent their absence from water; nevertheless, air sampling may provide useful information for risk assessment. The liquid impingement technique appears to have the greatest capacity for collecting airborne Legionella if combined with molecular investigations.

Evaluation of Legionella Air Contamination in Healthcare Facilities by Different Sampling Methods: An Italian Multicenter Study

PubMed Central

Montagna, Maria Teresa; De Giglio, Osvalda; Cristina, Maria Luisa; Napoli, Christian; Pacifico, Claudia; Agodi, Antonella; Baldovin, Tatjana; Casini, Beatrice; Coniglio, Maria Anna; D’Errico, Marcello Mario; Delia, Santi Antonino; Deriu, Maria Grazia; Guida, Marco; Laganà, Pasqualina; Liguori, Giorgio; Moro, Matteo; Mura, Ida; Pennino, Francesca; Privitera, Gaetano; Romano Spica, Vincenzo; Sembeni, Silvia; Spagnolo, Anna Maria; Tardivo, Stefano; Torre, Ida; Valeriani, Federica; Albertini, Roberto; Pasquarella, Cesira

2017-01-01

Healthcare facilities (HF) represent an at-risk environment for legionellosis transmission occurring after inhalation of contaminated aerosols. In general, the control of water is preferred to that of air because, to date, there are no standardized sampling protocols. Legionella air contamination was investigated in the bathrooms of 11 HF by active sampling (Surface Air System and Coriolis®μ) and passive sampling using settling plates. During the 8-hour sampling, hot tap water was sampled three times. All air samples were evaluated using culture-based methods, whereas liquid samples collected using the Coriolis®μ were also analyzed by real-time PCR. Legionella presence in the air and water was then compared by sequence-based typing (SBT) methods. Air contamination was found in four HF (36.4%) by at least one of the culturable methods. The culturable investigation by Coriolis®μ did not yield Legionella in any enrolled HF. However, molecular investigation using Coriolis®μ resulted in eight HF testing positive for Legionella in the air. Comparison of Legionella air and water contamination indicated that Legionella water concentration could be predictive of its presence in the air. Furthermore, a molecular study of 12 L. pneumophila strains confirmed a match between the Legionella strains from air and water samples by SBT for three out of four HF that tested positive for Legionella by at least one of the culturable methods. Overall, our study shows that Legionella air detection cannot replace water sampling because the absence of microorganisms from the air does not necessarily represent their absence from water; nevertheless, air sampling may provide useful information for risk assessment. The liquid impingement technique appears to have the greatest capacity for collecting airborne Legionella if combined with molecular investigations. PMID:28640202

Analytical Energy Gradients for Excited-State Coupled-Cluster Methods

NASA Astrophysics Data System (ADS)

Wladyslawski, Mark; Nooijen, Marcel

The equation-of-motion coupled-cluster (EOM-CC) and similarity transformed equation-of-motion coupled-cluster (STEOM-CC) methods have been firmly established as accurate and routinely applicable extensions of single-reference coupled-cluster theory to describe electronically excited states. An overview of these methods is provided, with emphasis on the many-body similarity transform concept that is the key to a rationalization of their accuracy. The main topic of the paper is the derivation of analytical energy gradients for such non-variational electronic structure approaches, with an ultimate focus on obtaining their detailed algebraic working equations. A general theoretical framework using Lagrange's method of undetermined multipliers is presented, and the method is applied to formulate the EOM-CC and STEOM-CC gradients in abstract operator terms, following the previous work in [P.G. Szalay, Int. J. Quantum Chem. 55 (1995) 151] and [S.R. Gwaltney, R.J. Bartlett, M. Nooijen, J. Chem. Phys. 111 (1999) 58]. Moreover, the systematics of the Lagrange multiplier approach is suitable for automation by computer, enabling the derivation of the detailed derivative equations through a standardized and direct procedure. To this end, we have developed the SMART (Symbolic Manipulation and Regrouping of Tensors) package of automated symbolic algebra routines, written in the Mathematica programming language. The SMART toolkit provides the means to expand, differentiate, and simplify equations by manipulation of the detailed algebraic tensor expressions directly. The Lagrangian multiplier formulation establishes a uniform strategy to perform the automated derivation in a standardized manner: A Lagrange multiplier functional is constructed from the explicit algebraic equations that define the energy in the electronic method; the energy functional is then made fully variational with respect to all of its parameters, and the symbolic differentiations directly yield the explicit equations for the wavefunction amplitudes, the Lagrange multipliers, and the analytical gradient via the perturbation-independent generalized Hellmann-Feynman effective density matrix. This systematic automated derivation procedure is applied to obtain the detailed gradient equations for the excitation energy (EE-), double ionization potential (DIP-), and double electron affinity (DEA-) similarity transformed equation-of-motion coupled-cluster singles-and-doubles (STEOM-CCSD) methods. In addition, the derivatives of the closed-shell-reference excitation energy (EE-), ionization potential (IP-), and electron affinity (EA-) equation-of-motion coupled-cluster singles-and-doubles (EOM-CCSD) methods are derived. Furthermore, the perturbative EOM-PT and STEOM-PT gradients are obtained. The algebraic derivative expressions for these dozen methods are all derived here uniformly through the automated Lagrange multiplier process and are expressed compactly in a chain-rule/intermediate-density formulation, which facilitates a unified modular implementation of analytic energy gradients for CCSD/PT-based electronic methods. The working equations for these analytical gradients are presented in full detail, and their factorization and implementation into an efficient computer code are discussed.

Coupled-channel analyses on 16O + 147,148,150,152,154Sm heavy-ion fusion reactions

NASA Astrophysics Data System (ADS)

Erol, Burcu; Yılmaz, Ahmet Hakan

2018-02-01

Heavy-ion collisons are typically characterized by the presence of many open reaction channels. In the energies around the Coulomb barrier, the main processes are elastic scattering, inelastic excitations of low-lying modes and fusion operations of one or two nuclei. The fusion process is generally defined as the effect of one-dimensional barrier penetration model, taking scattering potential as the sum of Coulomb and proximity potential. We have performed heay-ion fusion reactions with coupled-channel (CC) calculations. Coupled-channel formalism is carried out under barrier energy in heavy-ion fusion reactions. In this work fusion cross sections have been calculated and analyzed in detail for the five systems 16O + 147,148,150,152,154sm in the framework of coupled-channel approach (using the codes CCFUS and CCDEF) and Wong Formula. Calculated results are compared with experimental data, CC calculations using code CCFULL and with the cross section datas taken from `nrv'. CCDEF, CCFULL and Wong Formula explains the fusion reactions of heavy-ions very well, while using the scattering potential as WOODS-SAXON volume potential with Akyuz-Winther parameters. It was observed that AW potential parameters are able to reproduce the experimentally observed fusion cross sections reasonably well for these systems. There is a good agreement between the calculated results with the experimental and nrv[8] results.

Systematic investigations of deep sub-barrier fusion reactions using an adiabatic approach

NASA Astrophysics Data System (ADS)

Ichikawa, Takatoshi

2015-12-01

Background: At extremely low incident energies, unexpected decreases in fusion cross sections, compared to the standard coupled-channels (CC) calculations, have been observed in a wide range of fusion reactions. These significant reductions of the fusion cross sections are often referred to as the fusion hindrance. However, the physical origin of the fusion hindrance is still unclear. Purpose: To describe the fusion hindrance based on an adiabatic approach, I propose a novel extension of the standard CC model by introducing a damping factor that describes a smooth transition from sudden to adiabatic processes, that is, the transition from the separated two-body to the united dinuclear system. I demonstrate the performance of this model by systematically investigating various deep sub-barrier fusion reactions. Method: I extend the standard CC model by introducing a damping factor into the coupling matrix elements in the standard CC model. This avoids double counting of the CC effects, when two colliding nuclei overlap one another. I adopt the Yukawa-plus-exponential (YPE) model as a basic heavy ion-ion potential, which is advantageous for a unified description of the one- and two-body potentials. For the purpose of these systematic investigations, I approximate the one-body potential with a third-order polynomial function based on the YPE model. Results: Calculated fusion cross sections for the medium-heavy mass systems of 64Ni+64Ni , 58Ni+58Ni , and 58Ni+54Fe , the medium-light mass systems of 40Ca+40Ca , 48Ca+48Ca , and 24Mg+30Si , and the mass-asymmetric systems of 48Ca+96Zr and 16O+208Pb are consistent with the experimental data. The astrophysical S factor and logarithmic derivative representations of these are also in good agreement with the experimental data. The values obtained for the individual radius and diffuseness parameters in the damping factor, which reproduce the fusion cross sections well, are nearly equal to the average value for all the systems. Conclusions: Since the results calculated with the damping factor are in excellent agreement with the experimental data in all systems, I conclude that a coordinate-dependent coupling strength is responsible for the fusion hindrance. In all systems, the potential energies at the touching point VTouch strongly correlate with the incident threshold energies for which the fusion hindrance starts to emerge, except for the medium-light mass systems.

Sub-barrier fusion of Si+Si systems

NASA Astrophysics Data System (ADS)

Colucci, G.; Montagnoli, G.; Stefanini, A. M.; Bourgin, D.; Čolović, P.; Corradi, L.; Courtin, S.; Faggian, M.; Fioretto, E.; Galtarossa, F.; Goasduff, A.; Haas, F.; Mazzocco, M.; Scarlassara, F.; Stefanini, C.; Strano, E.; Urbani, M.; Szilner, S.; Zhang, G. L.

2017-11-01

The near- and sub-barrier fusion excitation function has been measured for the system 30Si+30Si at the Laboratori Nazionali di Legnaro of INFN, using the 30Si beam of the XTU Tandem accelerator in the energy range 47 - 90 MeV. A set-up based on a beam electrostatic deflector was used for detecting fusion evaporation residues. The measured cross sections have been compared to previous data on 28Si+28Si and Coupled Channels (CC) calculations have been performed using M3Y+repulsion and Woods-Saxon potentials, where the lowlying 2+ and 3- excitations have been included. A weak imaginary potential was found to be necessary to reproduce the low energy 28Si+28Si data. This probably simulates the effect of the oblate deformation of this nucleus. On the contrary, 30Si is a spherical nucleus, 30Si+30Si is nicely fit by CC calculations and no imaginary potential is needed. For this system, no maximum shows up for the astrophysical S-factor so that we have no evidence for hindrance, as confirmed by the comparison with CC calculations. The logarithmic derivative of the two symmetric systems highlights their different low energy trend. A difference can also be noted in the two barrier distributions, where the high-energy peak present in 28Si+28Si is not observed for 30Si+30Si, probably due to the weaker couplings in last case.

Roebel assembled coated conductor cables (RACC): Ac-Losses and current carrying potential

NASA Astrophysics Data System (ADS)

Frank, A.; Heller, R.; Goldacker, W.; Kling, A.; Schmidt, C.

2008-02-01

Low ac-loss HTS cables for transport currents well above 1 kA are required for application in transformers and generators and are taken into consideration for future generations of fusion reactor coils. Coated conductors (CC) are suitable candidates for high field application at an operation temperature in the range 50-77 K. Ac-field applications require cables with low ac-losses and hence twisting of the individual strands. We solved this problem using the Roebel technique. Short lengths of Roebel bar cables were prepared from industrial DyBCO and YBCO-CC. Meander shaped tapes of 4 or 5 mm width with twist pitches of 123 or 127 mm were cut from the 10 or 12 mm wide CC tapes using a specially designed tool. Eleven or twelve of these strands were assembled to a cable. The electrical and mechanical connection of the tapes was achieved using a silver powder filled conductive epoxy resin. Ac-losses of a short sample in an external ac-field were measured as a function of frequency and field amplitude as well as the coupling current decay time constant. We discuss the results in terms of available theories and compare measured time constants in transverse field with measured coupling losses. Finally the potential of this cable type for ac-use is discussed with respect to ac-losses and current carrying capability.

A Self-Adaptive Capacitive Compensation Technique for Body Channel Communication.

PubMed

Mao, Jingna; Yang, Huazhong; Lian, Yong; Zhao, Bo

2017-10-01

In wireless body area network, capacitive-coupling body channel communication (CC-BCC) has the potential to attain better energy efficiency over conventional wireless communication schemes. The CC-BCC scheme utilizes the human body as the forward signal transmission medium, reducing the path loss in wireless body-centric communications. However, the backward path is formed by the coupling capacitance between the ground electrodes (GEs) of transmitter (Tx) and receiver (Rx), which increases the path loss and results in a body posture dependent backward impedance. Conventional methods use a fixed inductor to resonate with the backward capacitor to compensate the path loss, while it's not effective in compensating the variable backward impedance induced by the body movements. In this paper, we propose a self-adaptive capacitive compensation (SACC) technique to address such a problem. A backward distance detector is introduced to estimate the distance between two GEs of Tx and Rx, and a backward capacitance model is built to calculate the backward capacitance. The calculated backward capacitance at varying body posture is compensated by a digitally controlled tunable inductor (DCTI). The proposed SACC technique is validated by a prototype CC-BCC system, and measurements are taken on human subjects. The measurement results show that 9dB-16 dB channel enhancement can be achieved at a backward path distance of 1 cm-10 cm.

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

Xiao, Hai; Cheng, Tao; Goddard, William A.

Energy and environmental concerns demand development of more efficient and selective electrodes for electrochemical reduction of CO 2 to form fuels and chemicals. Since Cu is the only pure metal exhibiting reduction to form hydrocarbon chemicals, we focus here on the Cu (111) electrode. We present a methodology for density functional theory calculations to obtain accurate onset electrochemical potentials with explicit constant electrochemical potential and pH effects using implicit solvation. We predict the atomistic mechanisms underlying electrochemical reduction of CO, finding that (1) at acidic pH, the C 1 pathway proceeds through COH to CHOH to form CH 4 whilemore » C 2 (C 3) pathways are kinetically blocked; (2) at neutral pH, the C 1 and C 2 (C 3) pathways share the COH common intermediate, where the branch to C-C coupling is realized by a novel CO-COH pathway; and (3) at high pH, early C-C coupling through adsorbed CO dimerization dominates, suppressing the C 1 pathways by kinetics, thereby boosting selectivity for multi-carbon products.« less

Synthesis of palladium nanoparticles with leaf extract of Chrysophyllum cainito (Star apple) and their applications as efficient catalyst for C-C coupling and reduction reactions

NASA Astrophysics Data System (ADS)

Majumdar, Rakhi; Tantayanon, Supawan; Bag, Braja Gopal

2017-10-01

A simple green chemical method for the one-step synthesis of palladium nanoparticles (PdNPs) has been described by reducing palladium (II) chloride with the leaf extract of Chrysophyllum cainito in aqueous medium. The synthesis of the palladium nanoparticles completed within 2-3 h at room temperature, whereas on heat treatment (70-80 °C), the synthesis of colloidal PdNPs completed almost instantly. The stabilized PdNPs have been characterized in detail by spectroscopic, electron microscopic and light scattering measurements. The synthesized PdNPs have been utilized as a green catalyst for C-C coupling reactions under aerobic and phosphine-free conditions in aqueous medium. In addition, the synthesized PdNPs have also been utilized as a catalyst for a very efficient sodium borohydride reduction of 3- and 4-nitrophenols. The synthesized PdNPs can retain their catalytic activity for several months.

Fine-structure resolved rotational transitions and database for CN+H2 collisions

NASA Astrophysics Data System (ADS)

Burton, Hannah; Mysliwiec, Ryan; Forrey, Robert C.; Yang, B. H.; Stancil, P. C.; Balakrishnan, N.

2018-06-01

Cross sections and rate coefficients for CN+H2 collisions are calculated using the coupled states (CS) approximation. The calculations are benchmarked against more accurate close-coupling (CC) calculations for transitions between low-lying rotational states. Comparisons are made between the two formulations for collision energies greater than 10 cm-1. The CS approximation is used to construct a database which includes highly excited rotational states that are beyond the practical limitations of the CC method. The database includes fine-structure resolved rotational quenching transitions for v = 0 and j ≤ 40, where v and j are the vibrational and rotational quantum numbers of the initial state of the CN molecule. Rate coefficients are computed for both para-H2 and ortho-H2 colliders. The results are shown to be in good agreement with previous calculations, however, the rates are substantially different from mass-scaled CN+He rates that are often used in astrophysical models.

Equation-of-motion coupled cluster method for the description of the high spin excited states

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

Musiał, Monika, E-mail: musial@ich.us.edu.pl; Lupa, Łukasz; Kucharski, Stanisław A.

2016-04-21

The equation-of-motion (EOM) coupled cluster (CC) approach in the version applicable for the excitation energy (EE) calculations has been formulated for high spin components. The EE-EOM-CC scheme based on the restricted Hartree-Fock reference and standard amplitude equations as used in the Davidson diagonalization procedure yields the singlet states. The triplet and higher spin components require separate amplitude equations. In the case of quintets, the relevant equations are much simpler and easier to solve. Out of 26 diagrammatic terms contributing to the R{sub 1} and R{sub 2} singlet equations in the case of quintets, only R{sub 2} operator survives with 5more » diagrammatic terms present. In addition all terms engaging three body elements of the similarity transformed Hamiltonian disappear. This indicates a substantial simplification of the theory. The implemented method has been applied to the pilot study of the excited states of the C{sub 2} molecule and quintet states of C and Si atoms.« less

Green heterogeneous Pd(II) catalyst produced from chitosan-cellulose micro beads for green synthesis of biaryls.

PubMed

Baran, Talat; Sargin, Idris; Kaya, Murat; Menteş, Ayfer

2016-11-05

In green catalyst systems, both the catalyst and the technique should be environmentally safe. In this study we designed a green palladium(II) catalyst for microwave-assisted Suzuki CC coupling reactions. The catalyst support was produced from biopolymers; chitosan and cellulose. The catalytic activity of the catalyst was tested on 16 substrates in solvent-free media and compared with those of commercial palladium salts. Reusability tests were done. The catalyst was also used in conventional reflux-heating system to demonstrate the efficiency of microwave heating method. We recorded high activity, selectivity and excellent TONs (6600) and TOFs (82500) just using a small catalyst loading (1.5×10(-3)mol%) in short reaction time (5min). The catalyst exhibited a long lifetime (9 runs). The findings indicated that both green chitosan/cellulose-Pd(II) catalyst and the microwave heating are suitable for synthesis of biaryl compounds by using Suzuki CC coupling reactions. Copyright © 2016 Elsevier Ltd. All rights reserved.

A simple microfluidic Coriolis effect flowmeter for operation at high pressure and high temperature.

PubMed

Harrison, Christopher; Jundt, Jacques

2016-08-01

We describe a microfluidic Coriolis effect flowmeter that is simple to assemble, operates at elevated temperature and pressure, and can be operated with a lock-in amplifier. The sensor has a flow rate sensitivity greater than 2° of phase shift per 1 g/min of mass flow and is benchmarked with flow rates ranging from 0.05 to 2.0 g/min. The internal volume is 15 μl and uses off-the-shelf optical components to measure the tube motion. We demonstrate that fluid density can be calculated from the frequency of the resonating element with proper calibration.

Comment on ``Turbulent equipartition theory of toroidal momentum pinch'' [Phys. Plasmas 15, 055902 (2008)

NASA Astrophysics Data System (ADS)

Peeters, A. G.; Angioni, C.; Strintzi, D.

2009-03-01

The comment addresses questions raised on the derivation of the momentum pinch velocity due to the Coriolis drift effect [A. G. Peeters et al., Phys. Rev. Lett. 98, 265003 (2007)]. These concern the definition of the gradient, and the scaling with the density gradient length. It will be shown that the turbulent equipartition mechanism is included within the derivation using the Coriolis drift, with the density gradient scaling being the consequence of drift terms not considered in [T. S. Hahm et al., Phys. Plasmas 15, 055902 (2008)]. Finally the accuracy of the analytic models is assessed through a comparison with the full gyrokinetic solution.

Atmospheric stability and complex terrain: comparing measurements and CFD

NASA Astrophysics Data System (ADS)

Koblitz, T.; Bechmann, A.; Berg, J.; Sogachev, A.; Sørensen, N.; Réthoré, P.-E.

2014-12-01

For wind resource assessment, the wind industry is increasingly relying on Computational Fluid Dynamics models that focus on modeling the airflow in a neutrally stratified surface layer. So far, physical processes that are specific to the atmospheric boundary layer, for example the Coriolis force, buoyancy forces and heat transport, are mostly ignored in state-of-the-art flow solvers. In order to decrease the uncertainty of wind resource assessment, the effect of thermal stratification on the atmospheric boundary layer should be included in such models. The present work focuses on non-neutral atmospheric flow over complex terrain including physical processes like stability and Coriolis force. We examine the influence of these effects on the whole atmospheric boundary layer using the DTU Wind Energy flow solver EllipSys3D. To validate the flow solver, measurements from Benakanahalli hill, a field experiment that took place in India in early 2010, are used. The experiment was specifically designed to address the combined effects of stability and Coriolis force over complex terrain, and provides a dataset to validate flow solvers. Including those effects into EllipSys3D significantly improves the predicted flow field when compared against the measurements.

A New Continuous Rotation IMU Alignment Algorithm Based on Stochastic Modeling for Cost Effective North-Finding Applications

PubMed Central

Li, Yun; Wu, Wenqi; Jiang, Qingan; Wang, Jinling

2016-01-01

Based on stochastic modeling of Coriolis vibration gyros by the Allan variance technique, this paper discusses Angle Random Walk (ARW), Rate Random Walk (RRW) and Markov process gyroscope noises which have significant impacts on the North-finding accuracy. A new continuous rotation alignment algorithm for a Coriolis vibration gyroscope Inertial Measurement Unit (IMU) is proposed in this paper, in which the extended observation equations are used for the Kalman filter to enhance the estimation of gyro drift errors, thus improving the north-finding accuracy. Theoretical and numerical comparisons between the proposed algorithm and the traditional ones are presented. The experimental results show that the new continuous rotation alignment algorithm using the extended observation equations in the Kalman filter is more efficient than the traditional two-position alignment method. Using Coriolis vibration gyros with bias instability of 0.1°/h, a north-finding accuracy of 0.1° (1σ) is achieved by the new continuous rotation alignment algorithm, compared with 0.6° (1σ) north-finding accuracy for the two-position alignment and 1° (1σ) for the fixed-position alignment. PMID:27983585

Dynamic Characteristics of Regional Flows around the Pyrénées in View of the PYREX Experiment. Part I: Analysis of the Pressure and Wind Fields and Experimental Assessment of the Applicability of the Linear Theory.

NASA Astrophysics Data System (ADS)

Bénech, B.; Koffi, E.; Druilhet, A.; Durand, P.; Bessemoulin, P.; Campins, J.; Jansa, A.; Terliuc, B.

1998-01-01

regarding (a) the perturbation of the surface pressure field, which resembles the predicted bipolar distribution; (b) the dependence of the drag on Fr1, which enables the assessment of the linear theory and the definition of the conditions of applicability of two models [(i) a two-dimensional model, for which it was possible to define quantitatively the effective blocked area, and (ii) a three-dimensional model, for which a scaling function that combines the direction of incidence, the mountain shape, and the Coriolis effect was found almost constant, with an average value of 0.2 for all the cases under study]; (c) the extension of the area affected by the blocking effect, estimated to be 4.5-5 times the width of the barrier and the drift of the strong deceleration point due to the Coriolis effect; (d) the dependence of the wind velocities on Fr1 at the edges of the barrier; and (e) the asymmetric flow deviation induced by the Coriolis effect and biased by the departure of the flow from normal incidence.

Development of Coriolis mass flowmeter with digital drive and signal processing technology.

PubMed

Hou, Qi-Li; Xu, Ke-Jun; Fang, Min; Liu, Cui; Xiong, Wen-Jun

2013-09-01

Coriolis mass flowmeter (CMF) often suffers from two-phase flowrate which may cause flowtube stalling. To solve this problem, a digital drive method and a digital signal processing method of CMF is studied and implemented in this paper. A positive-negative step signal is used to initiate the flowtube oscillation without knowing the natural frequency of the flowtube. A digital zero-crossing detection method based on Lagrange interpolation is adopted to calculate the frequency and phase difference of the sensor output signals in order to synthesize the digital drive signal. The digital drive approach is implemented by a multiplying digital to analog converter (MDAC) and a direct digital synthesizer (DDS). A digital Coriolis mass flow transmitter is developed with a digital signal processor (DSP) to control the digital drive, and realize the signal processing. Water flow calibrations and gas-liquid two-phase flowrate experiments are conducted to examine the performance of the transmitter. The experimental results show that the transmitter shortens the start-up time and can maintain the oscillation of flowtube in two-phase flowrate condition. Copyright © 2013 ISA. Published by Elsevier Ltd. All rights reserved.

Subgrid-scale models for large-eddy simulation of rotating turbulent channel flows

NASA Astrophysics Data System (ADS)

Silvis, Maurits H.; Bae, Hyunji Jane; Trias, F. Xavier; Abkar, Mahdi; Moin, Parviz; Verstappen, Roel

2017-11-01

We aim to design subgrid-scale models for large-eddy simulation of rotating turbulent flows. Rotating turbulent flows form a challenging test case for large-eddy simulation due to the presence of the Coriolis force. The Coriolis force conserves the total kinetic energy while transporting it from small to large scales of motion, leading to the formation of large-scale anisotropic flow structures. The Coriolis force may also cause partial flow laminarization and the occurrence of turbulent bursts. Many subgrid-scale models for large-eddy simulation are, however, primarily designed to parametrize the dissipative nature of turbulent flows, ignoring the specific characteristics of transport processes. We, therefore, propose a new subgrid-scale model that, in addition to the usual dissipative eddy viscosity term, contains a nondissipative nonlinear model term designed to capture transport processes, such as those due to rotation. We show that the addition of this nonlinear model term leads to improved predictions of the energy spectra of rotating homogeneous isotropic turbulence as well as of the Reynolds stress anisotropy in spanwise-rotating plane-channel flows. This work is financed by the Netherlands Organisation for Scientific Research (NWO) under Project Number 613.001.212.

Clomiphene Citrate versus Letrozole for Ovarian Stimulation in Therapeutic Donor Sperm Insemination.

PubMed

El Hachem, Hady; Antaki, Roland; Sylvestre, Camille; Kadoch, Isaac-Jacques; Lapensée, Louise; Bouet, Pierre Emmanuel

2017-01-01

To compare clomiphene citrate (CC) and letrozole for ovarian stimulation (OS) in therapeutic donor sperm insemination (TDI) cycles. Retrospective cohort study between January 2011 and June 2014 at a University-affiliated private IVF clinic in Montreal, Canada. 257 normo-ovulatory women ≤40 years of age with no history of infertility undergoing 590 TDI cycles in the absence of a male partner (single women and same-sex couples) or azoospermia were included. Patients received 100 mg CC daily (145 women, 321 cycles) or letrozole 5 mg daily (112 women, 269 cycles), from days 3 to 7. Only the first 3 cycles were included per patient. Our main outcome measure was cumulative live birth rates (LBR). Baseline characteristics were comparable between the 2 groups. There were no differences in LBR per cycle (16.5% (53/321) vs. 11.5% (31/269), p = 0.08) and cumulative LBR (36.6% (53/145) vs. 27.7% (31/112), p = 0.13), between CC and letrozole, respectively. Multiple pregnancy rate (11.6% (8/69) vs. 8.7% (4/46), p = 0.6) and miscarriage rate (21.7 vs. 21.7%, p = 1) were also comparable between CC and letrozole, respectively. In normo-ovulatory women undergoing TDI, OS with CC or letrozole resulted in similar live birth and twin pregnancy rates. © 2016 S. Karger AG, Basel.

Immune response CC chemokines CCL2 and CCL5 are associated with pulmonary sarcoidosis

PubMed Central

2011-01-01

Background Pulmonary sarcoidosis involves an intense leukocyte infiltration of the lung with the formation of non-necrotizing granulomas. CC chemokines (chemokine (C-C motif) ligand 2 (CCL2)-CCL5) are chemoattractants of mononuclear cells and act through seven transmembrane G-coupled receptors. Previous studies have demonstrated conflicting results with regard to the associations of these chemokines with sarcoidosis. In an effort to clarify previous discrepancies, we performed the largest observational study to date of CC chemokines in bronchoalveolar lavage fluid (BALF) from patients with pulmonary sarcoidosis. Results BALF chemokine levels from 72 patients affected by pulmonary sarcoidosis were analyzed by enzyme-linked immunosorbent assay (ELISA) and compared to 8 healthy volunteers. BALF CCL3 and CCL4 levels from pulmonary sarcoidosis patients were not increased compared to controls. However, CCL2 and CCL5 levels were elevated, and subgroup analysis showed higher levels of both chemokines in all stages of pulmonary sarcoidosis. CCL2, CCL5, CC chemokine receptor type 1 (CCR1), CCR2 and CCR3 were expressed from mononuclear cells forming the lung granulomas, while CCR5 was only found on mast cells. Conclusions These data suggest that CCL2 and CCL5 are important mediators in recruiting CCR1, CCR2, and CCR3 expressing mononuclear cells as well as CCR5-expressing mast cells during all stages of pulmonary sarcoidosis. PMID:21463523

Immune response CC chemokines CCL2 and CCL5 are associated with pulmonary sarcoidosis.

PubMed

Palchevskiy, Vyacheslav; Hashemi, Nastran; Weigt, Stephen S; Xue, Ying Ying; Derhovanessian, Ariss; Keane, Michael P; Strieter, Robert M; Fishbein, Michael C; Deng, Jane C; Lynch, Joseph P; Elashoff, Robert; Belperio, John A

2011-04-04

Pulmonary sarcoidosis involves an intense leukocyte infiltration of the lung with the formation of non-necrotizing granulomas. CC chemokines (chemokine (C-C motif) ligand 2 (CCL2)-CCL5) are chemoattractants of mononuclear cells and act through seven transmembrane G-coupled receptors. Previous studies have demonstrated conflicting results with regard to the associations of these chemokines with sarcoidosis. In an effort to clarify previous discrepancies, we performed the largest observational study to date of CC chemokines in bronchoalveolar lavage fluid (BALF) from patients with pulmonary sarcoidosis. BALF chemokine levels from 72 patients affected by pulmonary sarcoidosis were analyzed by enzyme-linked immunosorbent assay (ELISA) and compared to 8 healthy volunteers. BALF CCL3 and CCL4 levels from pulmonary sarcoidosis patients were not increased compared to controls. However, CCL2 and CCL5 levels were elevated, and subgroup analysis showed higher levels of both chemokines in all stages of pulmonary sarcoidosis. CCL2, CCL5, CC chemokine receptor type 1 (CCR1), CCR2 and CCR3 were expressed from mononuclear cells forming the lung granulomas, while CCR5 was only found on mast cells. These data suggest that CCL2 and CCL5 are important mediators in recruiting CCR1, CCR2, and CCR3 expressing mononuclear cells as well as CCR5-expressing mast cells during all stages of pulmonary sarcoidosis.

Suggestion for search of cyclopropenone (c-C3H2O) in a cosmic object

NASA Astrophysics Data System (ADS)

Sharma, M. K.; Sharma, M.; Chandra, S.

2017-03-01

Following Minimum Energy Principle, out of the three isomers of chemical formula C3H2O, the cyclopropenone (c-C3H2O) is the most stable and therefore may be the most abundant and easily detectable in a cosmic object. The cyclopropenone is detected in Sgr B2(N). Owing to half-spin of each of two hydrogen atoms, the c-C3H2O has two distinct ortho and para species. Using the rotational and centrifugal distortion constants along with the electric dipole moment, we have calculated energies of 100 rotational levels of each of the ortho and para species of c-C3H2O and the Einstein A-coefficients for radiative transitions between the levels. The values of Einstein A-coefficients along with the scaled values for collisional rate coefficients are used for solving a set of statistical equilibrium equations coupled with the equations of radiative transfer. Brightness temperatures of seven rotational transitions of each of the ortho and para species of c-C3H2O are investigated. Out of fourteen transitions, seven are found to show anomalous absorption and rest seven are found to show emission feature. We find that the transitions 110 -111 (1.544 GHz) may play important role in identification of cyclopropenone in a cosmic object.

Coupling with ocean mixed layer leads to intraseasonal variability in tropical deep convection: Evidence from cloud-resolving simulations

NASA Astrophysics Data System (ADS)

Anber, Usama; Wang, Shuguang; Sobel, Adam

2017-03-01

The effect of coupling a slab ocean mixed layer to atmospheric convection is examined in cloud-resolving model (CRM) simulations in vertically sheared and unsheared environments without Coriolis force, with the large-scale circulation parameterized using the Weak Temperature Gradient (WTG) approximation. Surface fluxes of heat and moisture as well as radiative fluxes are fully interactive, and the vertical profile of domain-averaged horizontal wind is strongly relaxed toward specified profiles with vertical shear that varies from one simulation to the next. Vertical wind shear is found to play a critical role in the simulated behavior. There exists a threshold value of the shear strength above which the coupled system develops regular oscillations between deep convection and dry nonprecipitating states, similar to those found earlier in a much more idealized model which did not consider wind shear. The threshold value of the vertical shear found here varies with the depth of the ocean mixed layer. The time scale of the spontaneously generated oscillations also varies with mixed layer depth, from 10 days with a 1 m deep mixed layer to 50 days with a 10 m deep mixed layer. The results suggest the importance of the interplay between convection organized by vertical wind shear, radiative feedbacks, large-scale dynamics, and ocean mixed layer heat storage in real intraseasonal oscillations.

Ab Initio Effective Rovibrational Hamiltonians for Non-Rigid Molecules via Curvilinear VMP2

NASA Astrophysics Data System (ADS)

Changala, Bryan; Baraban, Joshua H.

2017-06-01

Accurate predictions of spectroscopic constants for non-rigid molecules are particularly challenging for ab initio theory. For all but the smallest systems, ``brute force'' diagonalization of the full rovibrational Hamiltonian is computationally prohibitive, leaving us at the mercy of perturbative approaches. However, standard perturbative techniques, such as second order vibrational perturbation theory (VPT2), are based on the approximation that a molecule makes small amplitude vibrations about a well defined equilibrium structure. Such assumptions are physically inappropriate for non-rigid systems. In this talk, we will describe extensions to curvilinear vibrational Møller-Plesset perturbation theory (VMP2) that account for rotational and rovibrational effects in the molecular Hamiltonian. Through several examples, we will show that this approach provides predictions to nearly microwave accuracy of molecular constants including rotational and centrifugal distortion parameters, Coriolis coupling constants, and anharmonic vibrational and tunneling frequencies.

Silicon bulk micromachined, symmetric, degenerate vibratorygyroscope, accelerometer and sensor and method for using the same

NASA Technical Reports Server (NTRS)

Tang, Tony K. (Inventor); Kaiser, William J. (Inventor); Bartman, Randall K. (Inventor); Wilcox, Jaroslava Z. (Inventor); Gutierrez, Roman C. (Inventor); Calvet, Robert J. (Inventor)

1999-01-01

When embodied in a microgyroscope, the invention is comprised of a silicon, four-leaf clover structure with a post attached to the center. The whole structure is suspended by four silicon cantilevers or springs. The device is electrostatically actuated and capacitively detects Coriolis induced motions of the leaves of the leaf clover structure. In the case where the post is not symmetric with the plane of the clover leaves, the device can is usable as an accelerometer. If the post is provided in the shape of a dumb bell or an asymmetric post, the center of gravity is moved out of the plane of clover leaf structure and a hybrid device is provided. When the clover leaf structure is used without a center mass, it performs as a high Q resonator usable as a sensor of any physical phenomena which can be coupled to the resonant performance.

Efficacy of phosphatidylcholine in the modulation of motion sickness susceptibility

NASA Technical Reports Server (NTRS)

Kohl, R. L.; Ryan, P.; Homick, J. L.

1985-01-01

This study evaluated the efficacy of pharmacological doses of phosphatidylcholine (lecithin) in the modulation of motion sickness induced by exposure to coriolis stimulation in a rotating chair. Subjects received daily dietary supplements of 25 grams of lecithin (90 percent phosphatidylcholine) and were tested for their susceptibility to motion sickness after 4 h, 2 d, and 21 d. A small but statistically significant increase in susceptibility (+15 percent) was noted 4 h after supplemental phosphatidylcholine, with four of nine subjects demonstrating a marked increase in susceptibility. This finding was attributed to choline's stimulatory action on cholinergic systems, an action which opposes that of the classical antimotion sickness drug scopolamine. Chronic lecithin loading revealed a trend towards reduced susceptibility, possibly indicating the occurrence of adaptive mechanisms such as receptor down-regulation. Withdrawal from lecithin loading, perhaps coupled with anticholinergic treatment, might prove to be a potent prophylactic regimen and ought to be tested.

High resolution FTIR spectrum of the ν 6 band of deuterated formic acid (DCOOH)

NASA Astrophysics Data System (ADS)

Goh, K. L.; Ong, P. P.; Tan, T. L.; Teo, H. H.

1999-07-01

The high resolution FTIR spectrum of the ν 6 band of DCOOH has been measured with a resolution of 0.004 cm -1 in the spectral range of 920-1020 cm -1. The ν 6 band was found to be perturbed by the neighbouring ν 8 band situated at about 100 cm -1 lower. Using a Watson's A-reduced Hamiltonian in the Ir representation, and with the inclusion of a-, and b-Coriolis coupling constants, a simultaneous fit of ν 6 and ν 8 was performed, fitting a total of 1656 infrared transitions of ν 6 with an rms uncertainty of 0.00038 cm -1. A set of accurate rovibrational constants for ν 6 were obtained. The ν 6 band was analysed to be primarily A-typed with a band centre at 970.88931±0.00003 cm -1.

Terahertz laser spectroscopy of the water dimer intermolecular vibrations. I. (D2O)2

NASA Astrophysics Data System (ADS)

Braly, L. B.; Cruzan, J. D.; Liu, K.; Fellers, R. S.; Saykally, R. J.

2000-06-01

Terahertz laser VRT spectra of the water dimer consisting of 731 transitions measured with an average precision of 2 MHz and involving four (D2O)2 intermolecular vibrations (one previously published) have been measured between 65 and 104 cm-1. The precisely determined energy level patterns differ both qualitatively and quantitatively from the predictions of several dimer potentials tested, and reveal an ordering of the intermolecular vibrations which differs dramatically from that predicted by standard normal mode analysis. Strong coupling is indicated between the low barrier tunneling motions and the intermolecular vibrations as well as among different vibrations. Particularly, the 83 cm-1 (acceptor wag) and 90 cm-1 (D2O)2 (acceptor twist) vibrations interact through a Coriolis perturbation. These spectra provide the basis for our recent determination of the water pair potential. The corresponding data set for (H2O)2 is presented in an accompanying paper.

Synchrotron-based far-infrared spectroscopy of furan: Rotational analysis of the ν 14 , ν 11 , ν 18 and ν 19 vibrational levels

NASA Astrophysics Data System (ADS)

Tokaryk, D. W.; Culligan, S. D.; Billinghurst, B. E.; van Wijngaarden, J. A.

2011-11-01

Four vibrational levels of the five-membered ring molecule furan (C 4H 4O) have been rotationally analyzed from far-infrared Fourier transform spectra obtained at the Canadian Light Source synchrotron. We found that the low-lying ν14 and ν11 levels at 602.9 and 599.6 cm -1 interact through a second-order Coriolis resonance. This perturbation was characterized through a coupled analysis of the ν14 and ν18 fundamental spectra and the ν18- ν11 band. The ν19 fundamental spectrum was analyzed as well, and the data for all observed bands were combined with previously reported microwave transitions to produce the final fit. The spectra are an excellent demonstration of the high quality of data that can be obtained when far-infrared synchrotron radiation is used as the radiation source in Fourier transform spectroscopy experiments.

Coupled Research in Ocean Acoustics and Signal Processing for the Next Generation of Underwater Acoustic Communication Systems

DTIC Science & Technology

2016-08-05

JPAnalytics LLC CC: DCMA Boston DTIC Director, NRL Progress Report #8 Coupled Research in Ocean Acoustics and Signal Processing for the Next...Generation of Underwater Acoustic Communication Systems Principal Investigator’s Name: Dr. James Preisig Period Covered By Report: 1/20/2016 to 4/19/2016...Technical work this period has spanned two areas. The first of these is VHF Acoustics . During this time period, the Principle Investigator worked with Dr

Ruthenium-catalyzed insertion of adjacent diol carbon atoms into C-C bonds: Entry to type II polyketides.

PubMed

Bender, Matthias; Turnbull, Ben W H; Ambler, Brett R; Krische, Michael J

2017-08-25

Current catalytic processes involving carbon-carbon bond activation rely on π-unsaturated coupling partners. Exploiting the concept of transfer hydrogenative coupling, we report a ruthenium(0)-catalyzed cycloaddition of benzocyclobutenones that functionalizes two adjacent saturated diol carbon-hydrogen bonds. These regio- and diastereoselective processes enable convergent construction of type II polyketide substructures. Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Copper-facilitated Suzuki reactions: application to 2-heterocyclic boronates.

PubMed

Deng, James Z; Paone, Daniel V; Ginnetti, Anthony T; Kurihara, Hideki; Dreher, Spencer D; Weissman, Steven A; Stauffer, Shaun R; Burgey, Christopher S

2009-01-15

The palladium-catalyzed Suzuki-Miyaura reaction has been utilized as one of the most powerful methods for C-C bond formation. However, Suzuki reactions of electron-deficient 2-heterocyclic boronates generally give low conversions and remain challenging. The successful copper(I) facilitated Suzuki coupling of 2-heterocyclic boronates that is broad in scope is reported. Use of this methodology affords greatly enhanced yields of these notoriously difficult couplings. Furthermore, mechanistic investigations suggest a possible role of copper in the catalytic cycle.

Palladium-catalyzed Heck-type cross-couplings of unactivated alkyl iodides.

PubMed

McMahon, Caitlin M; Alexanian, Erik J

2014-06-02

A palladium-catalyzed, intermolecular Heck-type coupling of alkyl iodides and alkenes is described. This process is successful with a variety of primary and secondary unactivated alkyl iodides as reaction partners, including those with hydrogen atoms in the β position. The mild catalytic conditions enable intermolecular C-C bond formations with a diverse set of alkyl iodides and alkenes, including substrates containing base- or nucleophile-sensitive functionality. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Positive anodic poised potential regulates microbial fuel cell performance with the function of open and closed circuitry.

PubMed

Srikanth, S; Venkata Mohan, S; Sarma, P N

2010-07-01

Positive influence of poised potential on microbial fuel cell (MFC) performance was observed with increase in the applied potential up to 600 mV and decreased thereafter. Higher power output (79.33 mW/m(2)) was observed at 600 mV poised potential under open circuit operation (OC). Closed circuit operation (CC) showed almost negligible power output due to continuous electron discharge against an external load (100 Omega). However, CC operation resulted in the higher substrate (chemical oxygen demand (COD)) degradation [61.23% (control); 70.46% (OC; 600 mV); 74.15% (CC; 600 mV)] and total dissolved solids (TDS) removal [29.17% (control); 43.75% (OC; 600 mV); 72.92% (CC; 600 mV)] efficiencies compared to OC. Electron discharge and energy conversion efficiency was also observed to be higher with 600 mV poised potential. Poising potential showed additional redox couples (-0.29+/-0.05 mV) on cyclic voltammetry. Application of poised potential during startup phase will help to enrich electrochemically active consortia on anode resulting in improved performance of MFC. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

A Gene Module-Based eQTL Analysis Prioritizing Disease Genes and Pathways in Kidney Cancer.

PubMed

Yang, Mary Qu; Li, Dan; Yang, William; Zhang, Yifan; Liu, Jun; Tong, Weida

2017-01-01

Clear cell renal cell carcinoma (ccRCC) is the most common and most aggressive form of renal cell cancer (RCC). The incidence of RCC has increased steadily in recent years. The pathogenesis of renal cell cancer remains poorly understood. Many of the tumor suppressor genes, oncogenes, and dysregulated pathways in ccRCC need to be revealed for improvement of the overall clinical outlook of the disease. Here, we developed a systems biology approach to prioritize the somatic mutated genes that lead to dysregulation of pathways in ccRCC. The method integrated multi-layer information to infer causative mutations and disease genes. First, we identified differential gene modules in ccRCC by coupling transcriptome and protein-protein interactions. Each of these modules consisted of interacting genes that were involved in similar biological processes and their combined expression alterations were significantly associated with disease type. Then, subsequent gene module-based eQTL analysis revealed somatic mutated genes that had driven the expression alterations of differential gene modules. Our study yielded a list of candidate disease genes, including several known ccRCC causative genes such as BAP1 and PBRM1 , as well as novel genes such as NOD2, RRM1, CSRNP1, SLC4A2, TTLL1 and CNTN1. The differential gene modules and their driver genes revealed by our study provided a new perspective for understanding the molecular mechanisms underlying the disease. Moreover, we validated the results in independent ccRCC patient datasets. Our study provided a new method for prioritizing disease genes and pathways.

Design of improved ceramic/polymeric composites

NASA Astrophysics Data System (ADS)

Seghi, Steven Monte

This thesis describes an optimized approach for fabrication of boron nitride matrix composites reinforced with carbon fibers. The boron nitride was introduced via liquid infiltration of borazine oligomer to obtain high density (rho ˜ 1.75g/cc) composites and d002 spacings of 3.35A, which afforded excellent hydrolytic stability. The friction and wear properties were explored using an inertial dynamometer for potential replacement of current C/C in aircraft brakes. One set of tested composites provided outstanding wear resistance, incurring nearly zero wear across the entire range tested. In contrast to C/C, the coefficient of friction (COF) was relatively stable with respect to energy level, varying only 0.2 to 0.3. The wear surface morphologies were examined and it was found that low volume BN composites wore by a mechanism similar to C/C. The wear rates were controlled by the formation of a friction film from the wear debris. In the case of BN composites, this film incurred wear via an abrasive and brittle fracture mechanism while C/C exhibited only abrasive wear. As the BN content increased, a film still formed from the debris but large particles of BN emerged that limited direct contact of the surfaces thus effectively eliminating abrasive wear so the underlying film wore via brittle fracture. The removed wear debris was easily reincorporated into the film, with the suspected aid of boron oxide, thus keeping the wear rates low. The last chapter deals with the design, fabrication, and evaluation of a new coupling agent for glass fiber/epoxy matrix composites. This interface consisted of a thin coating of activated carbon (ACI) with high surface area to take advantage of mechanical interlocking. Furthermore, the surface chemistry was modified to provide varying degrees of bonding to the resin. These ACI provided equivalent moduli when compared to similar composites using commercial coupling agents. Hygrothermal aging showed the basic surface chemistry ACI to be extremely resistant to mechanical property degradation. The ACI systems displayed two distinct failure modes, fiber/matrix fracture and fiber debonding, controlled by the interface strength and thus the surface chemistry. These different failure modes led to a damage evolution study via thermoelastic stress analysis.

33 CFR 156.120 - Requirements for transfer.

Code of Federal Regulations, 2010 CFR

2010-07-01

... prevent kinking or other damage to the hose and strain on its coupling. (d) Each part of the transfer.... (cc) Smoking is not permitted in the facilities marine transfer area except in designated smoking areas. (dd) Welding, hot work operations and smoking are prohibited on vessels during the transfer of...

High-Resolution Infrared Studies of Perdeutero-Spiropentane, C 5D 8

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

Erickson, Blake A.; Ju, X.; Nibler, Joseph W.

Perdeutero-spiropentane (C 5D 8) has been synthesized and infrared and Raman spectra are reported for the first time. Wavenumber assignments are made for most of the fundamental vibrational modes. Gas phase infrared spectra were recorded at a resolution (0.002 cm -1) sufficient to resolve individual rovibrational lines and show evidence of strong Coriolis and/or Fermi resonance interactions for most bands. However a detailed rovibrational analysis of the fundamental v 15 (b 2) parallel band proved possible and a fit of more than 1600 lines yielded a band origin of 1053.84465(10) cm -1 and ground state constants (in units of cmmore » -1): B 0 = 0.1120700(9), D J = 1.51(3) x10 -8, D JK = 3.42(15) x10 -8. We note that the B 0 value is significantly less than a value of Ba = 0.1140 cm-1 calculated using structural parameters from an earlier electron diffraction (ED) study, whereas one expects B a to be lower than B 0 because of thermal averaging over higher vibrational levels. A similar discrepancy was noted in an earlier study of C 5H 8 [1]. The structural and spectroscopic results are in good accord with values computed at the anharmonic level using the B3LYP density functional method with a cc-pVTZ basis set.« less

An Energy Efficient Technique Using Electric Active Shielding for Capacitive Coupling Intra-Body Communication

PubMed Central

Ma, Chao; Huang, Zhonghua; Wang, Zhiqi; Zhou, Linxuan; Li, Yinlin

2017-01-01

Capacitive coupling intra-body communication (CC-IBC) has become one of the candidates for healthcare sensor networks due to its positive prevailing features of energy efficiency, transmission rate and security. Under the CC-IBC scheme, some of the electric field emitted from signal (SIG) electrode of the transmitter will couple directly to the ground (GND) electrode, acting equivalently as an internal impedance of the signal source and inducing considerable energy losses. However, none of the previous works have fully studied the problem. In this paper, the underlying theory of such energy loss is investigated and quantitatively evaluated using conventional parameters. Accordingly, a method of electric active shielding is proposed to reduce the displacement current across the SIG-GND electrodes, leading to less power loss. In addition, the variation of such loss in regard to frequency range and positions on human body was also considered. The theory was validated by finite element method simulation and experimental measurement. The prototype result shows that the receiving power has been improved by approximate 5.5 dBm while the total power consumption is maximally 9 mW less using the proposed technique, providing an energy efficient option in physical layer for wearable and implantable healthcare sensor networks. PMID:28885546

Analytic first derivatives for a spin-adapted open-shell coupled cluster theory: Evaluation of first-order electrical properties

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

Datta, Dipayan, E-mail: datta@uni-mainz.de; Gauss, Jürgen, E-mail: gauss@uni-mainz.de

2014-09-14

An analytic scheme is presented for the evaluation of first derivatives of the energy for a unitary group based spin-adapted coupled cluster (CC) theory, namely, the combinatoric open-shell CC (COSCC) approach within the singles and doubles approximation. The widely used Lagrange multiplier approach is employed for the derivation of an analytical expression for the first derivative of the energy, which in combination with the well-established density-matrix formulation, is used for the computation of first-order electrical properties. Derivations of the spin-adapted lambda equations for determining the Lagrange multipliers and the expressions for the spin-free effective density matrices for the COSCC approachmore » are presented. Orbital-relaxation effects due to the electric-field perturbation are treated via the Z-vector technique. We present calculations of the dipole moments for a number of doublet radicals in their ground states using restricted open-shell Hartree-Fock (ROHF) and quasi-restricted HF (QRHF) orbitals in order to demonstrate the applicability of our analytic scheme for computing energy derivatives. We also report calculations of the chlorine electric-field gradients and nuclear quadrupole-coupling constants for the CCl, CH{sub 2}Cl, ClO{sub 2}, and SiCl radicals.« less

Modeling Photoelectron Spectra of CuO, Cu2O, and CuO2 Anions with Equation-of-Motion Coupled-Cluster Methods: An Adventure in Fock Space.

PubMed

Orms, Natalie; Krylov, Anna I

2018-04-12

The experimental photoelectron spectra of di- and triatomic copper oxide anions have been reported previously. We present an analysis of the experimental spectra of the CuO - , Cu 2 O - , and CuO 2 - anions using equation-of-motion coupled-cluster (EOM-CC) methods. The open-shell electronic structure of each molecule demands a unique combination of EOM-CC methods to achieve an accurate and balanced representation of the multiconfigurational anionic- and neutral-state manifolds. Analysis of the Dyson orbitals associated with photodetachment from CuO - reveals the strong non-Koopmans character of the CuO states. For the lowest detachment energy, a good agreement between theoretical and experimental values is obtained with CCSD(T) (coupled-cluster with single and double excitations and perturbative account of triple excitations). The (T) correction is particularly important for Cu 2 O - . Use of a relativistic pseudopotential and matching basis set improves the quality of results in most cases. EOM-DIP-CCSD analysis of the low-lying states of CuO 2 - reveals multiple singlet and triplet anionic states near the triplet ground state, adding an extra layer of complexity to the interpretation of the experimental CuO 2 - photoelectron spectrum.

Exposure to 137Cs deposited in soil – A Monte Carlo study

NASA Astrophysics Data System (ADS)

da Silveira, Lucas M.; Pereira, Marco A. M.; Neves, Lucio P.; Perini, Ana P.; Belinato, Walmir; Caldas, Linda V. E.; Santos, William S.

2018-03-01

In the event of an environmental contamination with radioactive materials, one of the most dangerous materials is 137Cs. In order to evaluate the radiation doses involved in an environmental contamination of soil, with 137Cs, we carried out a computational dosimetric study. We determined the radiation conversion coefficients (CC) for effective (E) and equivalent (H T) doses, using a male and a female anthropomorphic phantoms. These phantoms were coupled with the MCNPX (2.7.0) Monte Carlo simulation software, for three different types of soil. The highest CC[H T] values were for the gonads and skin (male) and bone marrow and skin (female). We found no difference for the different types of soil.

Biodegradation of thermoplastic starch/eggshell powder composites.

PubMed

Bootklad, Munlika; Kaewtatip, Kaewta

2013-09-12

Thermoplastic starch (TPS) was prepared using compression molding and chicken eggshell was used as a filler. The effect of the eggshell powder (EP) on the properties of TPS was compared with the effect of commercial calcium carbonate (CC). The organic compound on the surface of the eggshell powder acted as a coupling agent that resulted in a strong adhesion between the eggshell powder and the TPS matrix, as confirmed by SEM micrographs. The biodegradation was determined by the soil burial test. The TPS/EP composites were more rapidly degraded than the TPS/CC composites. In addition, the eggshell powder improved the water resistance and thermal stability of the TPS. Copyright © 2013 Elsevier Ltd. All rights reserved.

A MRCC study of the isomerisation of cyclopropane

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

Lang, Jakub; Švaňa, Matej; Demel, Ondřej

2017-01-19

Mukherjee’s and Brillouin-Wigner multi-reference coupled cluster methods were used to study the isomerization of cyclopropane to propene through a trimethylene/propylidene diradicals. Main aim was to obtain high quality ab-initio data using advanced methods that treat both static and dynamic correlation in the involved species. The MkCCSD(T)/cc-pVQZ activation energy of cyclopropane isomerization via trimethylene is 65.6 kcal/mol, in a good agreement with experimental values in the range 60-65 kcal/mol. The MkCCSD(T)/cc-pV5Z adiabatic singlet-triplet gap in trimethylene is 0.6 kcal/mol, slightly higher than previous CASPT2 result -0.7 kcal/mol by Skancke et al.

Centrifugal and Coriolis Effects on Thermal Convection in a Rotating Vertical Cylinder

NASA Astrophysics Data System (ADS)

Lee, Hanjie; Pearlstein, Arne J.

1997-11-01

For a rotating vertical circular cylinder, we compute steady axisymmetric flows driven by heating from below, accounting for both centrifugal and Coriolis effects. We discuss the dependence of the flow and heat transfer on Rayleigh number and Ekman number for selected values of the Prandtl number and aspect ratio. For the case where the sidewall temperature varies linearly, the computed solutions include single- and multi-cell flows. We pay particular attention to deviations from rigid-body rotation, with emphasis on topological division of the flow by surfaces on which the azimuthal velocity is equal to the product of the angular velocity and the radius, or by surfaces on which the meridional flow vanishes.

Nonmodal phenomena in differentially rotating dusty plasmas

NASA Astrophysics Data System (ADS)

Poedts, Stefaan; Rogava, Andria D.

2000-10-01

In this paper the foundation is layed for the nonmodal investigation of velocity shear induced phenomena in a differentially rotating flow of a dusty plasma. The simplest case of nonmagnetized flow is considered. It is shown that, together with the innate properties of the dusty plasma, the presence of differential rotation, Coriolis forces, and self-gravity casts a considerable richness on the nonmodal dynamics of linear perturbations in the flow. In particular: (i) dust-acoustic waves acquire the ability to extract energy from the mean flow and (ii) shear-induced, nonperiodic modes of collective plasma behavior-shear-dust-acoustic vortices-are generated. The presence of self-gravity and the nonzero Coriolis parameter (``epicyclic shaking'') makes these collective modes transiently unstable. .

Pendulum rides, rotations and the Coriolis effect

NASA Astrophysics Data System (ADS)

Pendrill, Ann-Marie; Modig, Conny

2018-07-01

An amusement park is full of examples that can be made into challenging problems for students, combining mathematical modelling with video analysis, as well as measurements in the rides. Traditional amusement ride related textbook problems include free-fall, circular motion, pendula and energy conservation in roller coasters, where the moving bodies are typically considered point-like. However, an amusement park can offer many more examples that are useful in physics and engineering education, many of them with strong mathematical content. This paper analyses forces on riders in a large rotating pendulum ride, where the Coriolis effect is sufficiently large to be visible in accelerometer data from the rides and leads to different ride experiences in different positions.

Magnetic Flux Concentrations in Stratified Turbulent Plasma Due to Negative Effective Magnetic Pressure Instability

NASA Astrophysics Data System (ADS)

Jabbari, S.; Brandenburg, A.

2014-12-01

Recent studies have suggested a new mechanism that can be used to explain the formation of magnetic spots or bipolar regions in highly stratified turbulent plasmas. According to this model, a large-scale magnetic field suppresses the turbulent pressure, which leads to a negative contribution of turbulence to the effective magnetic pressure. Direct numerical simulations (DNS) have confirmed that the negative contribution is large enough so that the effective magnetic pressure becomes negative and leads to a large-scale instability, which we refer to as negative effective magnetic pressure Instability (NEMPI). NEMPI was used to explain the formation of active regions and sunspots on the solar surface. One step toward improving this model was to combine dynamo in- stability with NEMPI. The dynamo is known to be responsible for the solar large-scale magnetic field and to play a role in solar activity. In this context, we studied stratified turbulent plasmas in spherical geometry, where the background field was generated by alpha squared dynamo. For NEMPI to be excited, the initial magnetic field should be in a proper range, so we used quenching function for alpha. Using the Pencil Code and mean field simulations (MFS), we showed that in the presence of dynamo-generated magnetic fields, we deal with a coupled system, where both instabilities, dynamo and NEMPI, work together and lead to the formation of magnetic structures (Jabbari et al. 2013). We also studied a similar system in plane geometry in the presence of rotation and confirmed that for slow rotation NEMPI works, but as the Coriolis number increases, the rotation suppresses NEMPI. By increasing the Coriolis number even further, the combination of fast rotation and high stratification excites a dynamo, which leads again to a coupled system of dynamo and NEMPI (Jabbari et al. 2014). Another important finding concerning NEMPI is the case where the instability is excited by a vertical magnetic field (Brandenburg et al. 2013). When the field is vertical, the resulting magnetic flux concentrations lead to the magnetic spots and can be of equipartition field strength. DNS, MFS, and implicit large eddy simulations (ILES) confirm that in a proper parameter regime, vertical imposed fields lead to the formation of circular magnetic spots (Brandenburg et al. 2014).

Benchmark studies on the building blocks of DNA. 3. Watson-Crick and stacked base pairs.

PubMed

Szalay, Péter G; Watson, Thomas; Perera, Ajith; Lotrich, Victor; Bartlett, Rodney J

2013-04-18

Excited states of stacked adenine-thymine and guanine-cytosine pairs as well as the Watson-Crick pair of guanine-thymine have been investigated using the equation of motion coupled-cluster (EOM-CC) method with single and double as well as approximate triple excitations. Transitions have been assigned, and the form of the excitations has been analyzed. The majority of the excitations could be classified as localized on the nucleobases, but for all three studied systems, charge-transfer (CT) transitions could also be identified. The main aim of this study was to compare the performance of lower-level methods (ADC(2) and TDDFT) to the high-level EOM-CC ones. It was shown that both ADC(2) and TDDFT with long-range correction have nonsystematic error in excitation energies, causing alternation of the energetic ordering of the excitations. Considering the high costs of the EOM-CC calculations, there is a need for reliable new approximate methods.

Structure of bovine cytochrome c oxidase crystallized at a neutral pH using a fluorinated detergent.

PubMed

Luo, Fangjia; Shinzawa-Itoh, Kyoko; Hagimoto, Kaede; Shimada, Atsuhiro; Shimada, Satoru; Yamashita, Eiki; Yoshikawa, Shinya; Tsukihara, Tomitake

2017-07-01

Cytochrome c oxidase (CcO) couples proton pumping to O 2 reduction. Its enzymatic activity depends sensitively on pH over a wide range. However, owing to difficulty in crystallizing this protein, X-ray structure analyses of bovine CcO aimed at understanding its reaction mechanism have been conducted using crystals prepared at pH 5.7, which is significantly lower than that in the cell. Here, oxidized CcO at pH 7.3 was crystallized using a fluorinated octyl-maltoside derivative, and the structure was determined at 1.77 Å resolution. No structural differences between crystals obtained at the neutral pH and the acidic pH were detected within the molecules. On the other hand, some differences in intermolecular interactions were detected between the two types of crystal. The influence of pH on the molecular surface is likely to contribute to the pH dependency of the aerobic oxidation of ferrocytochrome c.

Closely related, yet unique: Distinct homo- and heterodimerization patterns of G protein coupled chemokine receptors and their fine-tuning by cholesterol

PubMed Central

Gahbauer, Stefan; Pluhackova, Kristyna

2018-01-01

Chemokine receptors, a subclass of G protein coupled receptors (GPCRs), play essential roles in the human immune system, they are involved in cancer metastasis as well as in HIV-infection. A plethora of studies show that homo- and heterodimers or even higher order oligomers of the chemokine receptors CXCR4, CCR5, and CCR2 modulate receptor function. In addition, membrane cholesterol affects chemokine receptor activity. However, structural information about homo- and heterodimers formed by chemokine receptors and their interplay with cholesterol is limited. Here, we report homo- and heterodimer configurations of the chemokine receptors CXCR4, CCR5, and CCR2 at atomistic detail, as obtained from thousands of molecular dynamics simulations. The observed homodimerization patterns were similar for the closely related CC chemokine receptors, yet they differed significantly between the CC receptors and CXCR4. Despite their high sequence identity, cholesterol modulated the CC homodimer interfaces in a subtype-specific manner. Chemokine receptor heterodimers display distinct dimerization patterns for CXCR4/CCR5 and CXCR4/CCR2. Furthermore, associations between CXCR4 and CCR5 reveal an increased cholesterol-sensitivity as compared to CXCR4/CCR2 heterodimerization patterns. This work provides a first comprehensive structural overview over the complex interaction network between chemokine receptors and indicates how heterodimerization and the interaction with the membrane environment diversifies the function of closely related GPCRs. PMID:29529028

Coupled-cluster based basis sets for valence correlation calculations

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

Claudino, Daniel; Bartlett, Rodney J., E-mail: bartlett@qtp.ufl.edu; Gargano, Ricardo

Novel basis sets are generated that target the description of valence correlation in atoms H through Ar. The new contraction coefficients are obtained according to the Atomic Natural Orbital (ANO) procedure from CCSD(T) (coupled-cluster singles and doubles with perturbative triples correction) density matrices starting from the primitive functions of Dunning et al. [J. Chem. Phys. 90, 1007 (1989); ibid. 98, 1358 (1993); ibid. 100, 2975 (1993)] (correlation consistent polarized valence X-tuple zeta, cc-pVXZ). The exponents of the primitive Gaussian functions are subject to uniform scaling in order to ensure satisfaction of the virial theorem for the corresponding atoms. These newmore » sets, named ANO-VT-XZ (Atomic Natural Orbital Virial Theorem X-tuple Zeta), have the same number of contracted functions as their cc-pVXZ counterparts in each subshell. The performance of these basis sets is assessed by the evaluation of the contraction errors in four distinct computations: correlation energies in atoms, probing the density in different regions of space via 〈r{sup n}〉 (−3 ≤ n ≤ 3) in atoms, correlation energies in diatomic molecules, and the quality of fitting potential energy curves as measured by spectroscopic constants. All energy calculations with ANO-VT-QZ have contraction errors within “chemical accuracy” of 1 kcal/mol, which is not true for cc-pVQZ, suggesting some improvement compared to the correlation consistent series of Dunning and co-workers.« less

Surface wave effects in the NEMO ocean model: Forced and coupled experiments

NASA Astrophysics Data System (ADS)

Breivik, Øyvind; Mogensen, Kristian; Bidlot, Jean-Raymond; Balmaseda, Magdalena Alonso; Janssen, Peter A. E. M.

2015-04-01

The NEMO general circulation ocean model is extended to incorporate three physical processes related to ocean surface waves, namely the surface stress (modified by growth and dissipation of the oceanic wavefield), the turbulent kinetic energy flux from breaking waves, and the Stokes-Coriolis force. Experiments are done with NEMO in ocean-only (forced) mode and coupled to the ECMWF atmospheric and wave models. Ocean-only integrations are forced with fields from the ERA-Interim reanalysis. All three effects are noticeable in the extratropics, but the sea-state-dependent turbulent kinetic energy flux yields by far the largest difference. This is partly because the control run has too vigorous deep mixing due to an empirical mixing term in NEMO. We investigate the relation between this ad hoc mixing and Langmuir turbulence and find that it is much more effective than the Langmuir parameterization used in NEMO. The biases in sea surface temperature as well as subsurface temperature are reduced, and the total ocean heat content exhibits a trend closer to that observed in a recent ocean reanalysis (ORAS4) when wave effects are included. Seasonal integrations of the coupled atmosphere-wave-ocean model consisting of NEMO, the wave model ECWAM, and the atmospheric model of ECMWF similarly show that the sea surface temperature biases are greatly reduced when the mixing is controlled by the sea state and properly weighted by the thickness of the uppermost level of the ocean model. These wave-related physical processes were recently implemented in the operational coupled ensemble forecast system of ECMWF.

Higher-order equation-of-motion coupled-cluster methods for ionization processes.

PubMed

Kamiya, Muneaki; Hirata, So

2006-08-21

Compact algebraic equations defining the equation-of-motion coupled-cluster (EOM-CC) methods for ionization potentials (IP-EOM-CC) have been derived and computer implemented by virtue of a symbolic algebra system largely automating these processes. Models with connected cluster excitation operators truncated after double, triple, or quadruple level and with linear ionization operators truncated after two-hole-one-particle (2h1p), three-hole-two-particle (3h2p), or four-hole-three-particle (4h3p) level (abbreviated as IP-EOM-CCSD, CCSDT, and CCSDTQ, respectively) have been realized into parallel algorithms taking advantage of spin, spatial, and permutation symmetries with optimal size dependence of the computational costs. They are based on spin-orbital formalisms and can describe both alpha and beta ionizations from open-shell (doublet, triplet, etc.) reference states into ionized states with various spin magnetic quantum numbers. The application of these methods to Koopmans and satellite ionizations of N2 and CO (with the ambiguity due to finite basis sets eliminated by extrapolation) has shown that IP-EOM-CCSD frequently accounts for orbital relaxation inadequately and displays errors exceeding a couple of eV. However, these errors can be systematically reduced to tenths or even hundredths of an eV by IP-EOM-CCSDT or CCSDTQ. Comparison of spectroscopic parameters of the FH+ and NH+ radicals between IP-EOM-CC and experiments has also underscored the importance of higher-order IP-EOM-CC treatments. For instance, the harmonic frequencies of the A 2Sigma- state of NH+ are predicted to be 1285, 1723, and 1705 cm(-1) by IP-EOM-CCSD, CCSDT, and CCSDTQ, respectively, as compared to the observed value of 1707 cm(-1). The small adiabatic energy separation (observed 0.04 eV) between the X 2Pi and a 4Sigma- states of NH+ also requires IP-EOM-CCSDTQ for a quantitative prediction (0.06 eV) when the a 4Sigma- state has the low-spin magnetic quantum number (s(z) = 1/2). When the state with s(z) = 3/2 is sought, the energy separations converge much more rapidly with the IP-EOM-CCSD value (0.03 eV) already being close to the observed (0.04 eV).

Interference of fission amplitudes of neutron resonances and T-odd asymmetry for various prescission third particles in the ternary fission of nuclei

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

Kadmensky, S. G., E-mail: kadmensky@phys.vsu.ru; Bunakov, V. E.; Kadmensky, S. S.

Differential cross sections for reactions of the true ternary fission of nuclei that was induced by cold polarized neutrons were constructed with allowance of the effect that Coriolis interaction and the interference between fission amplitudes of neutron resonances excited in fissile nuclei upon incidentneutron capture by target nuclei exerted on angular distributions of prescission third particles (alpha particles, neutrons, or photons). It is shown that T -odd TRI- and ROT-type asymmetries for prescission alpha particles are associated with, respectively, the odd and even components of the Coriolis interaction-perturbed amplitude of angular distributions of particles belonging to the types indicated above.more » These asymmetries have angular distributions differing from each other and stemming from a nontrivial dependence of these components on the neutron-resonance spins J{sub s} and their projections K{sub s} onto the symmetry axis of the nucleus involved. It is shown that angular distributions of prescission photons and neutrons from reactions of the ternary fission of nuclei that is induced by cold polarized neutrons are determined by the effect of Coriolis forces exclusively. Therefore, the emerging T-odd asymmetries have a character of a ROT-type asymmetry and are universal for all target nuclei.« less

Sensorimotor adaptation to inertial forces in a multi-force environment does not depend on the number of targets: indirect validation of the altered-proprioception hypothesis.

PubMed

Bourdin, C; Bock, O

2006-11-20

The ability of our sensorimotor system to adapt to changing and complex environmental demands has been under experimental scrutiny for more than a century. Previous works have shown that aimed arm movements adapt quickly and completely to Coriolis force, but incompletely to the combination of Coriolis and centrifugal forces without visual cues. Two hypotheses may be advanced to explain this discrepancy: the workspace-exploration hypothesis, and the degraded-proprioception hypothesis. The aim of this study was to distinguish between the above two alternatives by comparing adaptive improvement during off-axis rotation in subjects pointing at one, three or seven different targets in complete darkness. Two main results emerge: (a) off-axis rotation led initially to errors in the direction of Coriolis force and in the opposite direction of the centrifugal force; (b) the size of the visited workspace has no effect on the way the subjects adapt to a multi-force environment. The lack of a target-number effect and the persistence of lateral errors in the pointing movements performed during rotation of the platform, support the degraded-proprioception rather than the workspace-exploration hypothesis of adaptation to a multi-force environment.

Support of gas flowmeter upgrade

NASA Technical Reports Server (NTRS)

Waugaman, Dennis

1996-01-01

A project history review, literature review, and vendor search were conducted to identify a flowmeter that would improve the accuracy of gaseous flow measurements in the White Sands Test Facility (WSTF) Calibration Laboratory and the Hydrogen High Flow Facility. Both facilities currently use sonic flow nozzles to measure flowrates. The flow nozzle pressure drops combined with corresponding pressure and temperature measurements have been estimated to produce uncertainties in flowrate measurements of 2 to 5 percent. This study investigated the state of flowmeter technology to make recommendations that would reduce those uncertainties. Most flowmeters measure velocity and volume, therefore mass flow measurement must be calculated based on additional pressures and temperature measurement which contribute to the error. The two exceptions are thermal dispersion meters and Coriolis mass flowmeters. The thermal dispersion meters are accurate to 1 to 5 percent. The Coriolis meters are significantly more accurate, at least for liquids. For gases, there is evidence they may be accurate to within 0.5 percent or better of the flowrate, but there may be limitations due to inappropriate velocity, pressure, Mach number and vibration disturbances. In this report, a comparison of flowmeters is presented. Candidate Coriolis meters and a methodology to qualify the meter with tests both at WSTF and Southwest Research Institute are recommended and outlined.

Altered metabolic pathways in clear cell renal cell carcinoma: A meta-analysis and validation study focused on the deregulated genes and their associated networks

PubMed Central

Zaravinos, Apostolos; Pieri, Myrtani; Mourmouras, Nikos; Anastasiadou, Natassa; Zouvani, Ioanna; Delakas, Dimitris; Deltas, Constantinos

2014-01-01

Clear cell renal cell carcinoma (ccRCC) is the predominant subtype of renal cell carcinoma (RCC). It is one of the most therapy-resistant carcinomas, responding very poorly or not at all to radiotherapy, hormonal therapy and chemotherapy. A more comprehensive understanding of the deregulated pathways in ccRCC can lead to the development of new therapies and prognostic markers. We performed a meta- analysis of 5 publicly available gene expression datasets and identified a list of co- deregulated genes, for which we performed extensive bioinformatic analysis coupled with experimental validation on the mRNA level. Gene ontology enrichment showed that many proteins are involved in response to hypoxia/oxygen levels and positive regulation of the VEGFR signaling pathway. KEGG analysis revealed that metabolic pathways are mostly altered in ccRCC. Similarly, Ingenuity Pathway Analysis showed that the antigen presentation, inositol metabolism, pentose phosphate, glycolysis/gluconeogenesis and fructose/mannose metabolism pathways are altered in the disease. Cellular growth, proliferation and carbohydrate metabolism, were among the top molecular and cellular functions of the co-deregulated genes. qRT-PCR validated the deregulated expression of several genes in Caki-2 and ACHN cell lines and in a cohort of ccRCC tissues. NNMT and NR3C1 increased expression was evident in ccRCC biopsies from patients using immunohistochemistry. ROC curves evaluated the diagnostic performance of the top deregulated genes in each dataset. We show that metabolic pathways are mostly deregulated in ccRCC and we highlight those being most responsible in its formation. We suggest that these genes are candidate predictive markers of the disease. PMID:25594006

An expanded calibration study of the explicitly correlated CCSD(T)-F12b method using large basis set standard CCSD(T) atomization energies.

PubMed

Feller, David; Peterson, Kirk A

2013-08-28

The effectiveness of the recently developed, explicitly correlated coupled cluster method CCSD(T)-F12b is examined in terms of its ability to reproduce atomization energies derived from complete basis set extrapolations of standard CCSD(T). Most of the standard method findings were obtained with aug-cc-pV7Z or aug-cc-pV8Z basis sets. For a few homonuclear diatomic molecules it was possible to push the basis set to the aug-cc-pV9Z level. F12b calculations were performed with the cc-pVnZ-F12 (n = D, T, Q) basis set sequence and were also extrapolated to the basis set limit using a Schwenke-style, parameterized formula. A systematic bias was observed in the F12b method with the (VTZ-F12/VQZ-F12) basis set combination. This bias resulted in the underestimation of reference values associated with small molecules (valence correlation energies <0.5 E(h)) and an even larger overestimation of atomization energies for bigger systems. Consequently, caution should be exercised in the use of F12b for high accuracy studies. Root mean square and mean absolute deviation error metrics for this basis set combination were comparable to complete basis set values obtained with standard CCSD(T) and the aug-cc-pVDZ through aug-cc-pVQZ basis set sequence. However, the mean signed deviation was an order of magnitude larger. Problems partially due to basis set superposition error were identified with second row compounds which resulted in a weak performance for the smaller VDZ-F12/VTZ-F12 combination of basis sets.

Molecular cloning and biochemical characterization of two cation chloride cotransporter subfamily members of Hydra vulgaris.

PubMed

Hartmann, Anna-Maria; Pisella, Lucie I; Medina, Igor; Nothwang, Hans Gerd

2017-01-01

Cation Chloride Cotransporters (CCCs) comprise secondary active membrane proteins mainly mediating the symport of cations (Na+, K+) coupled with chloride (Cl-). They are divided into K+-Cl- outward transporters (KCCs), the Na+-K+-Cl- (NKCCs) and Na+-Cl- (NCCs) inward transporters, the cation chloride cotransporter interacting protein CIP1, and the polyamine transporter CCC9. KCCs and N(K)CCs are established in the genome since eukaryotes and metazoans, respectively. Most of the physiological and functional data were obtained from vertebrate species. To get insights into the basal functional properties of KCCs and N(K)CCs in the metazoan lineage, we cloned and characterized KCC and N(K)CC from the cnidarian Hydra vulgaris. HvKCC is composed of 1,032 amino-acid residues. Functional analyses revealed that hvKCC mediates a Na+-independent, Cl- and K+ (Tl+)-dependent cotransport. The classification of hvKCC as a functional K-Cl cotransporter is furthermore supported by phylogenetic analyses and a similar structural organization. Interestingly, recently obtained physiological analyses indicate a role of cnidarian KCCs in hyposmotic volume regulation of nematocytes. HvN(K)CC is composed of 965 amino-acid residues. Phylogenetic analyses and structural organization suggest that hvN(K)CC is a member of the N(K)CC subfamily. However, no inorganic ion cotransport function could be detected using different buffer conditions. Thus, hvN(K)CC is a N(K)CC subfamily member without a detectable inorganic ion cotransporter function. Taken together, the data identify two non-bilaterian solute carrier 12 (SLC12) gene family members, thereby paving the way for a better understanding of the evolutionary paths of this important cotransporter family.

Fluorescence spectroscopy for diagnostic differentiation in uteri's cervix biopsies with cervical/vaginal atypical cytology.

PubMed

Rodero, Ademir Barianni; Silveira, Landulfo; Rodero, David Augusto; Racanicchi, Roberto; Pacheco, Marcos Tadeu T

2008-09-01

This work aims the diagnostic differentiation of chronic inflammation (CC), low-grade Intraepithelial squamous lesions (LGSIL) and high-grade intraepithelial squamous lesions (HGSIL) in biopsies of cervix of uterus from patients with atypias (ASC-US and ASC-H) and lesions (LGSIL and HGSIL), traced in the cervical/vaginal cytology by using Laser-Induced Fluorescence Spectroscopy (LIFS), with 488 nm excitation wavelength. Ninety seven biopsies from 32 patients with atypical cervical/vaginal cytology were collected. The biopsies were guided by colposcopy and taken at the squamous-columnar junction. Fluorescence emission spectra of each biopsy were collected by means of an optical fiber cable coupled to an argon laser at 488 nm as excitation source and addressed to a spectrograph and CCD camera/controller. Spectra were separated into three groups, CC, LGSIL and HGSIL, based on the cytopathology. It was detected similar mean spectra profiles for CC and LGSIL, and differences for HGSIL. An algorithm was developed for tissue classification based on the intensity of the multiplication of each spectrum by the mean spectrum of each group, searching for a discriminator that would address this spectral difference. The sensitivity and specificity of HGSIL identification, compared to CC and LGSIL was 89% and 100%, respectively. The LIFS using excitation wavelength of 488 nm could be used to differentiate HGSIL lesions from LGSIL and CC inflammation, and could help a precocious and less invasive diagnosis of cervix lesions.

Rhodium-Catalyzed Boron Arylation of 1,2-Azaborines**

PubMed Central

Rudebusch, Gabriel E.; Zakharov, Lev N.; Liu, Shih-Yuan

2013-01-01

A Sn-phony in B! BN isosteres of biphenyl compounds are prepared through Rh-catalyzed cross-coupling between 2-chloro-1,2-azaborines and arylstannanes (see scheme). The synthetic method should enable investigations of structure–activity relationships (SARs) by expanding the chemical space of the pharmaceutically relevant biphenyl structure through BN/CC isosterism. PMID:23832871

Synthesis of Pd-N-heterocyclic carbene Pd-catalyst and its application in MW-assisted Heck and Suzuki reaction

EPA Science Inventory

The first Pd-N-heterocyclic carbene (NHC) complex in the form of organic silica is prepared using sol-gel method and its application in Heck and Suzuki reactions are demonstrated. These C-C coupling reactions proceeded efficiently under the influence of microwave irradiation, wit...

Electromagnetic Wave Propagation through Circular Waveguides Containing Radially Inhomogeneous Lossy Media

DTIC Science & Technology

1989-08-01

where the slope becomes infinite. This point could represent a cutoff frequency of the two coupled complex modes as a/b increases and the cutin ...a good example of attenuation near the cutin for each mode. A common characteristic throughout these plots, and also very similar to the cc versus a/b

Direct conversion of CO2 into liquid fuels with high selectivity over a bifunctional catalyst.

PubMed

Gao, Peng; Li, Shenggang; Bu, Xianni; Dang, Shanshan; Liu, Ziyu; Wang, Hui; Zhong, Liangshu; Qiu, Minghuang; Yang, Chengguang; Cai, Jun; Wei, Wei; Sun, Yuhan

2017-10-01

Although considerable progress has been made in carbon dioxide (CO 2 ) hydrogenation to various C 1 chemicals, it is still a great challenge to synthesize value-added products with two or more carbons, such as gasoline, directly from CO 2 because of the extreme inertness of CO 2 and a high C-C coupling barrier. Here we present a bifunctional catalyst composed of reducible indium oxides (In 2 O 3 ) and zeolites that yields a high selectivity to gasoline-range hydrocarbons (78.6%) with a very low methane selectivity (1%). The oxygen vacancies on the In 2 O 3 surfaces activate CO 2 and hydrogen to form methanol, and C-C coupling subsequently occurs inside zeolite pores to produce gasoline-range hydrocarbons with a high octane number. The proximity of these two components plays a crucial role in suppressing the undesired reverse water gas shift reaction and giving a high selectivity for gasoline-range hydrocarbons. Moreover, the pellet catalyst exhibits a much better performance during an industry-relevant test, which suggests promising prospects for industrial applications.

Activity of convective coupled equatorial wave in tropical Tropopause layer in reanalysis and high-top CMIP5 models

NASA Astrophysics Data System (ADS)

Harza, Alia; Lubis, Sandro W.; Setiawan, Sonni

2018-05-01

The activity of convectively coupled equatorial waves (CCEWs), including Kelvin waves, Mixed Rossby-Gravity (MRG), and Equatorial Rossby (ER), in the tropical tropopause layer (TTL) is investigated in the Reanalysis and nine high-top CMIP5 models using the zonal wave number-frequency spectral analysis with equatorially symmetric-antisymmetric decomposition. We found that the TTL activities in the high-top CMIP5 models show significant difference among the high-top CMIP5 models with respect to the observation. The MIROC and HadGEM2-CC models work best in simulating Kelvin wave in the TTL, while the HadGEM2-CC and MPI-ESM-LR models work best in simulating MRG waves. The ER waves in TTL are best simulated in the MRI-CGCM model. None of the models are good in simulating all waves at once. It is concluded that the broad range of wave activity found in the different CMIP5 models depend on the convective parameterization used by each model and the representation of the tropical stratosphere variability, including the QBO.

Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111)

DOE PAGES

Xiao, Hai; Cheng, Tao; Goddard, William A.; ...

2015-12-30

Energy and environmental concerns demand development of more efficient and selective electrodes for electrochemical reduction of CO 2 to form fuels and chemicals. Since Cu is the only pure metal exhibiting reduction to form hydrocarbon chemicals, we focus here on the Cu (111) electrode. We present a methodology for density functional theory calculations to obtain accurate onset electrochemical potentials with explicit constant electrochemical potential and pH effects using implicit solvation. We predict the atomistic mechanisms underlying electrochemical reduction of CO, finding that (1) at acidic pH, the C 1 pathway proceeds through COH to CHOH to form CH 4 whilemore » C 2 (C 3) pathways are kinetically blocked; (2) at neutral pH, the C 1 and C 2 (C 3) pathways share the COH common intermediate, where the branch to C-C coupling is realized by a novel CO-COH pathway; and (3) at high pH, early C-C coupling through adsorbed CO dimerization dominates, suppressing the C 1 pathways by kinetics, thereby boosting selectivity for multi-carbon products.« less

Hybrid Correlation Energy (HyCE): An Approach Based on Separate Evaluations of Internal and External Components.

PubMed

Ivanic, Joseph; Schmidt, Michael W

2018-06-04

A novel hybrid correlation energy (HyCE) approach is proposed that determines the total correlation energy via distinct computation of its internal and external components. This approach evolved from two related studies. First, rigorous assessment of the accuracies and size extensivities of a number of electron correlation methods, that include perturbation theory (PT2), coupled-cluster (CC), configuration interaction (CI), and coupled electron pair approximation (CEPA), shows that the CEPA(0) variant of the latter and triples-corrected CC methods consistently perform very similarly. These findings were obtained by comparison to near full CI results for four small molecules and by charting recovered correlation energies for six steadily growing chain systems. Second, by generating valence virtual orbitals (VVOs) and utilizing the CEPA(0) method, we were able to partition total correlation energies into internal (or nondynamic) and external (or dynamic) parts for the aforementioned six chain systems and a benchmark test bed of 36 molecules. When using triple-ζ basis sets it was found that per orbital internal correlation energies were appreciably larger than per orbital external energies and that the former showed far more chemical variation than the latter. Additionally, accumulations of external correlation energies were seen to proceed smoothly, and somewhat linearly, as the virtual space is gradually increased. Combination of these two studies led to development of the HyCE approach, whereby the internal and external correlation energies are determined separately by CEPA(0)/VVO and PT2/external calculations, respectively. When applied to the six chain systems and the 36-molecule benchmark test set it was found that HyCE energies followed closely those of triples-corrected CC and CEPA(0) while easily outperforming MP2 and CCSD. The success of the HyCE approach is more notable when considering that its cost is only slightly more than MP2 and significantly cheaper than the CC approaches.

Construction Costs and Physico-chemical Properties of the Assimilatory Organs of Nepenthes Species in Northern Borneo

PubMed Central

Osunkoya, Olusegun O.; Daud, Siti Dayanawati; Di-Giusto, Bruno; Wimmer, Franz L.; Holige, Thippeswamy M.

2007-01-01

Background and Aims Species of the Nepenthaceae family are under-represented in studies of leaf traits and the consequent view of mineral nutrition and limitation in carnivorous plants. This study is aimed to complement existing data on leaf traits of carnivorous plants. Methods Physico-chemical properties, including construction costs (CC), of the assimilatory organs (leaf and pitcher) of a guild of lowland Nepenthes species inhabiting heath and/or peat swamp forests of Brunei, Northern Borneo were determined. Key Results Stoichiometry analyses indicate that Nepenthes species are nitrogen limited. Most traits vary appreciably across species, but greater variations exist between the assimilatory organs. Organ mass per unit area, dry matter tissue concentration (density), nitrogen (N), phosphorus (P), carbon, heat of combustion (Hc) and CC values were higher in the leaf relative to the pitcher, while organ thickness, potassium (K) and ash showed the opposite trend. Cross-species correlations indicate that joint rather than individual consideration of the leaf and the pitcher give better predictive relationships between variables, signalling tight coupling and functional interdependence of the two assimilatory organs. Across species, mass-based CC did not vary with N or P, but increases significantly with tissue density, carbon and Hc, and decreases with K and ash contents. Area-based CC gave the same trends (though weaker in strength) in addition to a significant positive correlation with tissue mass per unit area. Conclusions The lower CC value for the pitcher is in agreement with the concept of low marginal cost for carnivory relative to conventional autotrophy. The poor explanatory power of N, P or N : P ratio with CC suggests that factors other than production of expensive photosynthetic machinery (which calls for a high N input), including concentrations of lignin, wax/lipids or osmoregulatory ions like K+, may give a better explanation of the CC variation across Nepenthes species. PMID:17452380

Silver-catalyzed double-decarboxylative cross-coupling of α-keto acids with cinnamic acids in water: a strategy for the preparation of chalcones.

PubMed

Zhang, Ning; Yang, Daoshan; Wei, Wei; Yuan, Li; Nie, Fafa; Tian, Laijin; Wang, Hua

2015-03-20

A silver-catalyzed double-decarboxylative protocol has been proposed for the construction of chalcone derivatives via cascade coupling of substituted α-keto acids with cinnamic acids under the mild aqueous conditions. The developed method for constructing C-C bonds via double-decarboxylative reactions is efficient, practical, and environmentally benign by using the readily available starting materials. It should provide a promising synthesis candidate for the formation of diverse and useful chalcone derivatives in the fields of synthetic and pharmaceutical chemistry.

The electronic structure of vanadium monochloride cation (VCl+): Tackling the complexities of transition metal species

NASA Astrophysics Data System (ADS)

DeYonker, Nathan J.; Halfen, DeWayne T.; Allen, Wesley D.; Ziurys, Lucy M.

2014-11-01

Six electronic states (X 4Σ-, A 4Π, B 4Δ, 2Φ, 2Δ, 2Σ+) of the vanadium monochloride cation (VCl+) are described using large basis set coupled cluster theory. For the two lowest quartet states (X 4Σ- and A 4Π), a focal point analysis (FPA) approach was used that conjoined a correlation-consistent family of basis sets up to aug-cc-pwCV5Z-DK with high-order coupled cluster theory through pentuple (CCSDTQP) excitations. FPA adiabatic excitation energies (T0) and spectroscopic constants (re, r0, Be, B0, bar De, He, ωe, v0, αe, ωexe) were extrapolated to the valence complete basis set Douglas-Kroll (DK) aug-cc-pV∞Z-DK CCSDT level of theory, and additional treatments accounted for higher-order valence electron correlation, core correlation, and spin-orbit coupling. Due to the delicate interplay between dynamical and static electronic correlation, single reference coupled cluster theory is able to provide the correct ground electronic state (X 4Σ-), while multireference configuration interaction theory cannot. Perturbations from the first- and second-order spin orbit coupling of low-lying states with quartet spin multiplicity reveal an immensely complex rotational spectrum relative to the isovalent species VO, VS, and TiCl. Computational data on the doublet manifold suggest that the lowest-lying doublet state (2Γ) has a Te of ˜11 200 cm-1. Overall, this study shows that laboratory and theoretical rotational spectroscopists must work more closely in tandem to better understand the bonding and structure of molecules containing transition metals.

Low-lying excited states of model proteins: Performances of the CC2 method versus multireference methods

NASA Astrophysics Data System (ADS)

Ben Amor, Nadia; Hoyau, Sophie; Maynau, Daniel; Brenner, Valérie

2018-05-01

A benchmark set of relevant geometries of a model protein, the N-acetylphenylalanylamide, is presented to assess the validity of the approximate second-order coupled cluster (CC2) method in studying low-lying excited states of such bio-relevant systems. The studies comprise investigations of basis-set dependence as well as comparison with two multireference methods, the multistate complete active space 2nd order perturbation theory (MS-CASPT2) and the multireference difference dedicated configuration interaction (DDCI) methods. First of all, the applicability and the accuracy of the quasi-linear multireference difference dedicated configuration interaction method have been demonstrated on bio-relevant systems by comparison with the results obtained by the standard MS-CASPT2. Second, both the nature and excitation energy of the first low-lying excited state obtained at the CC2 level are very close to the Davidson corrected CAS+DDCI ones, the mean absolute deviation on the excitation energy being equal to 0.1 eV with a maximum of less than 0.2 eV. Finally, for the following low-lying excited states, if the nature is always well reproduced at the CC2 level, the differences on excitation energies become more important and can depend on the geometry.

Low-lying excited states of model proteins: Performances of the CC2 method versus multireference methods.

PubMed

Ben Amor, Nadia; Hoyau, Sophie; Maynau, Daniel; Brenner, Valérie

2018-05-14

A benchmark set of relevant geometries of a model protein, the N-acetylphenylalanylamide, is presented to assess the validity of the approximate second-order coupled cluster (CC2) method in studying low-lying excited states of such bio-relevant systems. The studies comprise investigations of basis-set dependence as well as comparison with two multireference methods, the multistate complete active space 2nd order perturbation theory (MS-CASPT2) and the multireference difference dedicated configuration interaction (DDCI) methods. First of all, the applicability and the accuracy of the quasi-linear multireference difference dedicated configuration interaction method have been demonstrated on bio-relevant systems by comparison with the results obtained by the standard MS-CASPT2. Second, both the nature and excitation energy of the first low-lying excited state obtained at the CC2 level are very close to the Davidson corrected CAS+DDCI ones, the mean absolute deviation on the excitation energy being equal to 0.1 eV with a maximum of less than 0.2 eV. Finally, for the following low-lying excited states, if the nature is always well reproduced at the CC2 level, the differences on excitation energies become more important and can depend on the geometry.

Quantification and visualization of glutathione S-transferase omega 1 in cells using inductively coupled plasma mass spectrometry (ICP-MS) and fluorescence microscopy.

PubMed

Liang, Yong; Jiang, Xin; Tang, Nannan; Yang, Limin; Chen, Haifeng; Wang, Qiuquan

2015-03-01

We report a novel activity-based and Cu-free click chemistry (CC) mediated methodology for glutathione S-transferase omega 1 (GSTO1) quantification using species-unspecific isotope dilution inductively coupled plasma mass spectrometry (SUID ICP-MS), in which dibenzylcyclooctyne-modified 2-chloroacetamide (DBCO-ChAcA) was designed and synthesized, meanwhile, as a navigator towards GSTO1 for subsequent N3-DOTA-Eu-tagging via Cu-free CC. Using (153)Eu-SUID ICP-MS coupled with size exclusion chromatography (SEC), the LOD (3σ) of GSTO1 reached 6.9 fmol with an RSD of 2.4% at the 0.1 μM level (n = 5) considering the recovery of GSTO1 on the SEC was 96.5 ± 2.4%. The GSTO1 contents in the cells of human hepatocellular carcinoma C7721 and breast carcinoma MCF-7 as well as normal hepatic C7701 without or with cis-platin administration were quantified to be from 1.2 μg/10,000 cells (n = 3, RSD = 4.5%) corresponding to 1.2 × 10(-2) ng per cell to 4.76 μg/10,000 cells (n = 3, RSD = 2.9%) corresponding to 4.76 × 10(-2) ng per cell. For a comparative study, DBCO-ChAcA-fluor 488-based fluorescence microscopy could not alone visualize GSTO1 in the cells but could together with those from the small SH-containing molecules such as GSH and that from extra N3-fluor 488 in the cells. This activity-based CC-mediated tagging/labeling strategy provided an opportunity for ICP-MS-based targeted protein quantification, and is very much expected to find its applications in biological mechanism study and the subsequent drug design.

Communication: Time-dependent optimized coupled-cluster method for multielectron dynamics

NASA Astrophysics Data System (ADS)

Sato, Takeshi; Pathak, Himadri; Orimo, Yuki; Ishikawa, Kenichi L.

2018-02-01

Time-dependent coupled-cluster method with time-varying orbital functions, called time-dependent optimized coupled-cluster (TD-OCC) method, is formulated for multielectron dynamics in an intense laser field. We have successfully derived the equations of motion for CC amplitudes and orthonormal orbital functions based on the real action functional, and implemented the method including double excitations (TD-OCCD) and double and triple excitations (TD-OCCDT) within the optimized active orbitals. The present method is size extensive and gauge invariant, a polynomial cost-scaling alternative to the time-dependent multiconfiguration self-consistent-field method. The first application of the TD-OCC method of intense-laser driven correlated electron dynamics in Ar atom is reported.

Communication: Time-dependent optimized coupled-cluster method for multielectron dynamics.

PubMed

Sato, Takeshi; Pathak, Himadri; Orimo, Yuki; Ishikawa, Kenichi L

2018-02-07

Time-dependent coupled-cluster method with time-varying orbital functions, called time-dependent optimized coupled-cluster (TD-OCC) method, is formulated for multielectron dynamics in an intense laser field. We have successfully derived the equations of motion for CC amplitudes and orthonormal orbital functions based on the real action functional, and implemented the method including double excitations (TD-OCCD) and double and triple excitations (TD-OCCDT) within the optimized active orbitals. The present method is size extensive and gauge invariant, a polynomial cost-scaling alternative to the time-dependent multiconfiguration self-consistent-field method. The first application of the TD-OCC method of intense-laser driven correlated electron dynamics in Ar atom is reported.

A theoretical and experimental benchmark study of core-excited states in nitrogen

NASA Astrophysics Data System (ADS)

Myhre, Rolf H.; Wolf, Thomas J. A.; Cheng, Lan; Nandi, Saikat; Coriani, Sonia; Gühr, Markus; Koch, Henrik

2018-02-01

The high resolution near edge X-ray absorption fine structure spectrum of nitrogen displays the vibrational structure of the core-excited states. This makes nitrogen well suited for assessing the accuracy of different electronic structure methods for core excitations. We report high resolution experimental measurements performed at the SOLEIL synchrotron facility. These are compared with theoretical spectra calculated using coupled cluster theory and algebraic diagrammatic construction theory. The coupled cluster singles and doubles with perturbative triples model known as CC3 is shown to accurately reproduce the experimental excitation energies as well as the spacing of the vibrational transitions. The computational results are also shown to be systematically improved within the coupled cluster hierarchy, with the coupled cluster singles, doubles, triples, and quadruples method faithfully reproducing the experimental vibrational structure.

The onset of chaos in orbital pilot-wave dynamics.

PubMed

Tambasco, Lucas D; Harris, Daniel M; Oza, Anand U; Rosales, Rodolfo R; Bush, John W M

2016-10-01

We present the results of a numerical investigation of the emergence of chaos in the orbital dynamics of droplets walking on a vertically vibrating fluid bath and acted upon by one of the three different external forces, specifically, Coriolis, Coulomb, or linear spring forces. As the vibrational forcing of the bath is increased progressively, circular orbits destabilize into wobbling orbits and eventually chaotic trajectories. We demonstrate that the route to chaos depends on the form of the external force. When acted upon by Coriolis or Coulomb forces, the droplet's orbital motion becomes chaotic through a period-doubling cascade. In the presence of a central harmonic potential, the transition to chaos follows a path reminiscent of the Ruelle-Takens-Newhouse scenario.

The onset of convection in a binary fluid mixture with temperature dependent viscosity and Coriolis force with Soret presence

NASA Astrophysics Data System (ADS)

Abidin, Nurul Hafizah Zainal; Mokhtar, Nor Fadzillah Mohd; Majid, Zanariah Abdul; Ghani, Siti Salwa Abd

2017-11-01

Temperature dependent viscosity and Coriolis force were applied to the steady Benard-Marangoni convection where the lower boundary of a horizontal layer of the binary mixture is heated from below and cooled from above. The purpose of this paper is to study in detail the onset of convection with these effects. Few cases of boundary conditions are studied which are rigid-rigid, rigid-free and free-free representing the lower-upper boundaries. A detailed numerical calculation of the marginal stability curves was performed by using the Galerkin method and it is showed that temperature dependent viscosity and Soret number destabilize the binary fluid layer system and Taylor number act oppositely.

Acoustic nonreciprocity in Coriolis mean flow systems.

PubMed

Naghdi, Masoud; Farzbod, Farhad

2018-01-01

One way to break acoustic reciprocity is to have a moving wave propagation medium. If the acoustic wave vector and the moving fluid velocity are collinear, the wave vector shift caused by the fluid flow can be used to break. In this paper, an alternative approach is investigated in which the fluid velocity enters the differential equation of the system as a cross product term with the wave vector. A circular field where the fluid velocity increases radially has a Coriolis acceleration term. In such a system, the acoustic wave enters from the central wall and exits from the perimeter wall. In this paper, the differential equation is solved numerically and the effect of fluid velocity on the nonreciprocity factor is examined.

Complex strain fields

NASA Astrophysics Data System (ADS)

Bradshaw, P.

Computational techniques for accounting for extra strain rates, abnormal distributions of delta-U/delta-y, fluctuating strain rates, and the effects of body forces in modeling shear flows are discussed. Consideration is given to simple shears where the extra strain rate does not affect turbulence, thin shear layers, moderately thin shear layers, and strongly distorted flows. Attention is given to formulations based on the exact transport equations for Reynolds stress as derived from the time-averaged Navier-Stokes equations. Extra strain rates arise from curvature, lateral divergence, and bulk compression, with Coriolis forces accounting for the first, intensification of the spanwise vorticity for the second, and compression or dilation of the shear layer producing the third. The curvature forces, e.g., buoyancy and Coriolis forces, are responsible for hurricanes and tornadoes.

Chemoselective Radical Dehalogenation and C-C Bond Formation on Aryl Halide Substrates Using Organic Photoredox Catalysts.

PubMed

Poelma, Saemi O; Burnett, G Leslie; Discekici, Emre H; Mattson, Kaila M; Treat, Nicolas J; Luo, Yingdong; Hudson, Zachary M; Shankel, Shelby L; Clark, Paul G; Kramer, John W; Hawker, Craig J; Read de Alaniz, Javier

2016-08-19

Despite the number of methods available for dehalogenation and carbon-carbon bond formation using aryl halides, strategies that provide chemoselectivity for systems bearing multiple carbon-halogen bonds are still needed. Herein, we report the ability to tune the reduction potential of metal-free phenothiazine-based photoredox catalysts and demonstrate the application of these catalysts for chemoselective carbon-halogen bond activation to achieve C-C cross-coupling reactions as well as reductive dehalogenations. This procedure works both for conjugated polyhalides as well as unconjugated substrates. We further illustrate the usefulness of this protocol by intramolecular cyclization of a pyrrole substrate, an advanced building block for a family of natural products known to exhibit biological activity.

VizieR Online Data Catalog: Protonated oxirane characterization (Puzzarini+, 2014)

NASA Astrophysics Data System (ADS)

Puzzarini, C.; Ali, A.; Biczysko, M.; Barone, V.

2017-04-01

The coupled-cluster (CC) singles and doubles approximation augmented by a perturbative treatment of triple excitations (CCSD(T); Raghavachari et al., 1989, ChPhL, 157, 479) was employed in molecular structure and anharmonic force-field calculations. Harmonic force fields were also computed using the less expensive and less accurate second-order Moller-Plesset perturbation theory (MP2; Moller & Plesset, 1934, PhRv, 46, 618). CCSD(T) and MP2 calculations were carried out in conjunction with the correlation-consistent basis sets, (aug)-cc-p(C)VnZ (n = T, Q) (Dunning, 1989, JChPh, 90, 1007; Kendall et al., 1992, JChPh, 96, 6796; Woon & Dunning, 1995, JChPh, 103, 4572), with the quantum-chemical CFour program package employed throughout. (4 data files).

Three-wave and four-wave interactions in gravity wave turbulence

NASA Astrophysics Data System (ADS)

Aubourg, Quentin; Campagne, Antoine; Peureux, Charles; Ardhuin, Fabrice; Sommeria, Joel; Viboud, Samuel; Mordant, Nicolas

2017-11-01

Weak-turbulence theory is a statistical framework to describe a large ensemble of nonlinearly interacting waves. The archetypal example of such system is the ocean surface that is made of interacting surface gravity waves. Here we describe a laboratory experiment dedicated to probe the statistical properties of turbulent gravity waves. We set up an isotropic state of interacting gravity waves in the Coriolis facility (13-m-diam circular wave tank) by exciting waves at 1 Hz by wedge wave makers. We implement a stereoscopic technique to obtain a measurement of the surface elevation that is resolved in both space and time. Fourier analysis shows that the laboratory spectra are systematically steeper than the theoretical predictions and the field observations in the Black Sea by Leckler et al. [F. Leckler et al., J. Phys. Oceanogr. 45, 2484 (2015), 10.1175/JPO-D-14-0237.1]. We identify a strong impact of surface dissipation on the scaling of the Fourier spectrum at the scales that are accessible in the experiments. We use bicoherence and tricoherence statistical tools in frequency and/or wave-vector space to identify the active nonlinear coupling. These analyses are also performed on the field data by Leckler et al. for comparison with the laboratory data. Three-wave coupling is characterized by and shown to involve mostly quasiresonances of waves with second- or higher-order harmonics. Four-wave coupling is not observed in the laboratory but is evidenced in the field data. We discuss temporal scale separation to explain our observations.

Anionic water pentamer and hexamer clusters: An extensive study of structures and energetics

NASA Astrophysics Data System (ADS)

Ünal, Aslı; Bozkaya, Uǧur

2018-03-01

An extensive study of structures and energetics for anionic pentamer and hexamer clusters is performed employing high level ab initio quantum chemical methods, such as the density-fitted orbital-optimized linearized coupled-cluster doubles (DF-OLCCD), coupled-cluster singles and doubles (CCSD), and coupled-cluster singles and doubles with perturbative triples [CCSD(T)] methods. In this study, sixteen anionic pentamer clusters and eighteen anionic hexamer clusters are reported. Relative, binding, and vertical detachment energies (VDE) are presented at the complete basis set limit (CBS), extrapolating energies of aug4-cc-pVTZ and aug4-cc-pVQZ custom basis sets. The largest VDE values obtained at the CCSD(T)/CBS level are 9.9 and 11.2 kcal mol-1 for pentamers and hexamers, respectively, which are in very good agreement with the experimental values of 9.5 and 11.1 kcal mol-1. Our binding energy results, at the CCSD(T)/CBS level, indicate strong bindings in anionic clusters due to hydrogen bond interactions. The average binding energy per water molecules is -5.0 and -5.3 kcal mol-1 for pentamers and hexamers, respectively. Furthermore, our results demonstrate that the DF-OLCCD method approaches to the CCSD(T) quality for anionic clusters. The inexpensive analytic gradients of DF-OLCCD compared to CCSD or CCSD(T) make it very attractive for high-accuracy studies.

Anionic water pentamer and hexamer clusters: An extensive study of structures and energetics.

PubMed

Ünal, Aslı; Bozkaya, Uğur

2018-03-28

An extensive study of structures and energetics for anionic pentamer and hexamer clusters is performed employing high level ab initio quantum chemical methods, such as the density-fitted orbital-optimized linearized coupled-cluster doubles (DF-OLCCD), coupled-cluster singles and doubles (CCSD), and coupled-cluster singles and doubles with perturbative triples [CCSD(T)] methods. In this study, sixteen anionic pentamer clusters and eighteen anionic hexamer clusters are reported. Relative, binding, and vertical detachment energies (VDE) are presented at the complete basis set limit (CBS), extrapolating energies of aug4-cc-pVTZ and aug4-cc-pVQZ custom basis sets. The largest VDE values obtained at the CCSD(T)/CBS level are 9.9 and 11.2 kcal mol -1 for pentamers and hexamers, respectively, which are in very good agreement with the experimental values of 9.5 and 11.1 kcal mol -1 . Our binding energy results, at the CCSD(T)/CBS level, indicate strong bindings in anionic clusters due to hydrogen bond interactions. The average binding energy per water molecules is -5.0 and -5.3 kcal mol -1 for pentamers and hexamers, respectively. Furthermore, our results demonstrate that the DF-OLCCD method approaches to the CCSD(T) quality for anionic clusters. The inexpensive analytic gradients of DF-OLCCD compared to CCSD or CCSD(T) make it very attractive for high-accuracy studies.

Ruthenium Catalyzed Diastereo- and Enantioselective Coupling of Propargyl Ethers with Alcohols: Siloxy-Crotylation via Hydride Shift Enabled Conversion of Alkynes to π-Allyls

PubMed Central

Liang, Tao; Zhang, Wandi; Chen, Te-Yu; Nguyen, Khoa D.; Krische, Michael J.

2015-01-01

The first enantioselective carbonyl crotylations through direct use of alkynes as chiral allylmetal equivalents are described. Chiral ruthenium(II) complexes modified by Josiphos (SL-J009-1) catalyze the C-C coupling of TIPS-protected propargyl ether 1a with primary alcohols 2a-2o to form products of carbonyl siloxy-crotylation 3a-3o, which upon silyl deprotection-reduction deliver 1,4-diols 5a-5o with excellent control of regio-, anti-diastereo- and enantioselectivity. Structurally related propargyl ethers 1b and 1c bearing ethyl- and phenyl-substituents engage in diastereo- and enantioselective coupling, as illustrated in the formation of adducts 5p and 5q, respectively. Selective mono-tosylation of diols 5a, 5c, 5e, 5f, 5k and 5m is accompanied by spontaneous cyclization to deliver the trans-2,3-disubstituted furans 6a, 6c, 6e, 6f, 6k and 6m, respectively. Primary alcohols 2a, 2l and 2p were converted to the siloxy-crotylation products 3a, 3l and 3p, which upon silyl deprotection-lactol oxidation were transformed to the trans-4,5-disubstituted γ-butyrolactones 7a, 7l and 7p. The formation of 7p represents a total synthesis of (+)-trans-whisky lactone. Unlike closely related ruthenium catalyzed alkyne-alcohol C-C couplings, deuterium labeling studies provide clear evidence of a novel 1,2-hydride shift mechanism that converts metal-bound alkynes to π-allyls in the absence of intervening allenes. PMID:26418572

The Effect of Sub-Auroral Polarization Streams (SAPS) on Ionosphere and Thermosphere during 2015 St. Patrick's Day storm: Global Ionosphere-Thermosphere Model (GITM) Simulations

NASA Astrophysics Data System (ADS)

Guo, J.; Deng, Y.; Zhang, D.; Lu, Y.; Sheng, C.

2017-12-01

Sub-Auroral Polarization Streams (SAPS) are incorporated into the non-hydrostatic Global Ionosphere-Thermosphere Model (GITM), revealing the complex effects on neutral dynamics and ion-neutral coupling processes. The intense westward ion stream could enhance the neutral zonal wind within the SAPS channel. Through neutral dynamics the neutrals then divide into two streams, one turns poleward and the other turns equatorward, forming a two-cell pattern in the SAPS-changed wind. The significant Joule heating induced by SAPS also leads to traveling atmospheric disturbances (TAD) accompanied by traveling ionospheric disturbances (TID), increasing the total electron content (TEC) by 2-8 TECu in the mid-latitude ionosphere. We investigate the potential causes of the reported poleward wind surge during the St. Patrick's Day storm in 2015. It is confirmed that Coriolis force on the westward zonal wind can contribute the poleward wind during post-SAPS interval. In addition, the simulations imply that the sudden decrease of heating rate within auroral oval could result in a TAD propagating equatorward, which could also be responsible for the sudden poleward wind surge. This study highlights the complicated effects of SAPS on ion-neutral coupling and neutral dynamics.

High resolution FTIR spectroscopic study of the ν4 band of CH 3CHF 2 enclosed in a flow of cold N 2 gas

NASA Astrophysics Data System (ADS)

Appadoo, Dominique R. T.; Robertson, Evan G.; McNaughton, Don

2003-01-01

An enclosive flow cooling (EFC) cell has been constructed, and coupled to a Brüker IFS 120HR high resolution Fourier transform spectrometer to record rotationally cold absorption spectra of gases of atmospheric interest at high spectral resolution. The new system has been characterized using N 2O, revealing that rotational temperatures as cold as 110 K are readily attainable using liquid nitrogen as a cryogen. Infrared spectra of the ν4 band of 1,1-difluoroethane (R152a), CH 3CHF 2, cooled in the EFC cell have been measured at a resolution of 0.0019 cm-1. Eight hundred and twenty rovibrational transitions of the weak ν4 band with 2⩽ J'⩽46 and Kc'⩽16 were assigned and fitted to Watson's A-reduced Hamiltonian. The ν4 CH 3 symmetric deformation ( a/c-type) was found to be coupled to the ν13 asymmetric deformation ( b-type) via an a-axis Coriolis interaction. In the ensuing analysis, values of spectroscopic constants were obtained for both the ν4 and dark ν13 states. Supporting ab initio calculations up to the MP2/TZV+(3 df,3 p) level are presented.

Unusual subauroral neutral wind disturbances during geomagnetic storms

NASA Astrophysics Data System (ADS)

Zhang, S.; Erickson, P. J.; Holt, J. M.

2016-12-01

Under the influence of geomagnetic storms, general circulation of the global thermosphere undergoes substantial changes that vary with latitudes. High latitude heating processes establish pressure gradients both vertically and horizontally. The equatorward wind surge and the associated westward wind enhancement are a typical disturbance wind characteristic that affacts ionosphere and thermosphere dynamics at mid-, low, and equatorial latitudes. At subauroral latitudes, however, new observations of neutral wind disturbances show some "abnormal" (unusual) behaviors in responding to complicated ion-neutral coupling processes. During the 2015 St. Patrick's Day great geomagnetic storm, incoherent scatter radar measurements at Millstone Hill show the following salient variations: (1) oscillating meridional wind disturbances with the Traveling Atmosphere Disturbance (TAD) feature; (2) vertical wind signature; (3) pre-mindnight poleward wind surges. The latter two variations appear to be associated with strong ion-neutral interaction developed during the subauroral polarization streams (SAPS) presence. Strong frictional heating caused by the relative velocity between the ions with SAPS speed and the neutrals leads to appreciable thermospheric upperwelling. Strong westward ion drifts shown as SAPS also enhance the wseward neutral flow, which subsequently causes a poleward component of the meridional wind due to the Coriolis force. This paper will present these observations of the wind and discuss ion-neutral coupling effects associated with SAPS.

ARM-microcontroller based portable nitrite electrochemical analyzer using cytochrome c reductase biofunctionalized onto screen printed carbon electrode.

PubMed

Santharaman, Paulraj; Venkatesh, Krishna Arun; Vairamani, Kanagavel; Benjamin, Alby Robson; Sethy, Niroj K; Bhargava, Kalpana; Karunakaran, Chandran

2017-04-15

Nitrite (NO 2 - ) supplementation limits hypoxia-induced oxidative stress and activates the alternate NO pathway which may partially account for the nitrite-mediated cardioprotection. So, sensitive and selective biosensors with point-of-care devices need to be explored to detect the physiological nitrite level due to its important role in human pathophysiology. In this work, cytochrome c reductase (CcR) biofunctionalized self assembled monolayer (SAM) functionalized on gold nanoparticles (GNPs) in polypyrrole (PPy) nanocomposite onto the screen printed carbon electrode (SPCE) was investigated as a biosensor for the detection of nitrite based on its electrochemical and catalytic properties. CcR was covalently coupled with SAM layers on GNPs by using EDC and NHS. Direct electrochemical response of CcR biofunctionalized electrodes showed a couple of well-defined and nearly reversible cyclic voltammetric peaks at -0.34 and -0.45 vs. Ag/AgCl. Under optimal conditions, the biosensor could be used for the determination of NO 2 - with a linear range from 0.1-1600µm and a detection limit of 60nM with a sensitivity of 0.172µAµM -1 cm -2 . Further, we have designed and developed a novel and cost effective portable electrochemical analyzer for the measurement of NO 2 - in hypoxia induced H9c2 cardiac cells using ARM microcontroller. The results obtained here using the developed portable electrochemical nitrite analyzer were also compared with the standard cyclic voltammetry instrument and found in agreement with each other. Copyright © 2016 Elsevier B.V. All rights reserved.

The direct arylation of allylic sp3 C-H bonds via organic and photoredox catalysis

NASA Astrophysics Data System (ADS)

Cuthbertson, James D.; MacMillan, David W. C.

2015-03-01

The direct functionalization of unactivated sp3 C-H bonds is still one of the most challenging problems facing synthetic organic chemists. The appeal of such transformations derives from their capacity to facilitate the construction of complex organic molecules via the coupling of simple and otherwise inert building blocks, without introducing extraneous functional groups. Despite notable recent efforts, the establishment of general and mild strategies for the engagement of sp3 C-H bonds in C-C bond forming reactions has proved difficult. Within this context, the discovery of chemical transformations that are able to directly functionalize allylic methyl, methylene and methine carbons in a catalytic manner is a priority. Although protocols for direct oxidation and amination of allylic C-H bonds (that is, C-H bonds where an adjacent carbon is involved in a C = C bond) have become widely established, the engagement of allylic substrates in C-C bond forming reactions has thus far required the use of pre-functionalized coupling partners. In particular, the direct arylation of non-functionalized allylic systems would enable access to a series of known pharmacophores (molecular features responsible for a drug's action), though a general solution to this long-standing challenge remains elusive. Here we report the use of both photoredox and organic catalysis to accomplish a mild, broadly effective direct allylic C-H arylation. This C-C bond forming reaction readily accommodates a broad range of alkene and electron-deficient arene reactants, and has been used in the direct arylation of benzylic C-H bonds.

The direct arylation of allylic sp(3) C-H bonds via organic and photoredox catalysis.

PubMed

Cuthbertson, James D; MacMillan, David W C

2015-03-05

The direct functionalization of unactivated sp(3) C-H bonds is still one of the most challenging problems facing synthetic organic chemists. The appeal of such transformations derives from their capacity to facilitate the construction of complex organic molecules via the coupling of simple and otherwise inert building blocks, without introducing extraneous functional groups. Despite notable recent efforts, the establishment of general and mild strategies for the engagement of sp(3) C-H bonds in C-C bond forming reactions has proved difficult. Within this context, the discovery of chemical transformations that are able to directly functionalize allylic methyl, methylene and methine carbons in a catalytic manner is a priority. Although protocols for direct oxidation and amination of allylic C-H bonds (that is, C-H bonds where an adjacent carbon is involved in a C = C bond) have become widely established, the engagement of allylic substrates in C-C bond forming reactions has thus far required the use of pre-functionalized coupling partners. In particular, the direct arylation of non-functionalized allylic systems would enable access to a series of known pharmacophores (molecular features responsible for a drug's action), though a general solution to this long-standing challenge remains elusive. Here we report the use of both photoredox and organic catalysis to accomplish a mild, broadly effective direct allylic C-H arylation. This C-C bond forming reaction readily accommodates a broad range of alkene and electron-deficient arene reactants, and has been used in the direct arylation of benzylic C-H bonds.

Scope and Mechanistic Investigations on the Solvent-Controlled Regio- and Stereoselective Formation of Enol Esters from the Ruthenium-Catalyzed Coupling Reaction of Terminal Alkynes and Carboxylic Acids

PubMed Central

Yi, Chae S.; Gao, Ruili

2009-01-01

The ruthenium-hydride complex (PCy3)2(CO)RuHCl was found to be a highly effective catalyst for the alkyne-to-carboxylic acid coupling reaction to give synthetically useful enol ester products. Strong solvent effect was observed for the ruthenium catalyst in modulating the activity and selectivity; the coupling reaction in CH2Cl2 led to the regioselective formation of gem-enol ester products, while the stereoselective formation of (Z)-enol esters was obtained in THF. The coupling reaction was found to be strongly inhibited by PCy3. The coupling reaction of both PhCO2H/PhC≡CD and PhCO2D/PhC≡CH led to the extensive deuterium incorporation on the vinyl positions of the enol ester products. An opposite Hammett value was observed when the correlation of a series of para-substituted p-X-C6H4CO2H (X = OMe, CH3, H, CF3, CN) with phenylacetylene was examined in CDCl3 (ρ = +0.30) and THF (ρ = −0.68). Catalytically relevant Ru-carboxylate and –vinylidene-carboxylate complexes, (PCy3)2(CO)(Cl)Ru(κ2-O2CC6H4-p-OMe) and (PCy3)2(CO)(Cl)RuC(=CHPh)O2CC6H4-p-OMe, were isolated, and the structure of both complexes was completely established by X-ray crystallography. A detailed mechanism of the coupling reaction involving a rate-limiting C-O bond formation step was proposed on the basis of these kinetic and structural studies. The regioselective formation of the gem-enol ester products in CH2Cl2 was rationalized by a direct migratory insertion of the terminal alkyne via a Ru-carboxylate species, whereas the stereoselective formation of (Z)-enol ester products in THF was explained by invoking a Ru-vinylidene species. PMID:20161379

Tidal dissipation in rotating fluid bodies: the presence of a magnetic field

NASA Astrophysics Data System (ADS)

Lin, Yufeng; Ogilvie, Gordon I.

2018-02-01

We investigate effects of the presence of a magnetic field on tidal dissipation in rotating fluid bodies. We consider a simplified model consisting of a rigid core and a fluid envelope, permeated by a background magnetic field (either a dipolar field or a uniform axial field). The wave-like tidal responses in the fluid layer are in the form of magnetic Coriolis waves, which are restored by both the Coriolis force and the Lorentz force. Energy dissipation occurs through viscous damping and Ohmic damping of these waves. Our numerical results show that the tidal dissipation can be dominated by Ohmic damping even with a weak magnetic field. The presence of a magnetic field smooths out the complicated frequency dependence of the dissipation rate, and broadens the frequency spectrum of the dissipation rate, depending on the strength of the background magnetic field. However, the frequency-averaged dissipation is independent of the strength and structure of the magnetic field, and of the dissipative parameters in the approximation that the wave-like response is driven only by the Coriolis force acting on the non-wavelike tidal flow. Indeed, the frequency-averaged dissipation quantity is in good agreement with previous analytical results in the absence of magnetic fields. Our results suggest that the frequency-averaged tidal dissipation of the wave-like perturbations is insensitive to detailed damping mechanisms and dissipative properties.

Posturography of ataxia induced by Coriolis- and Purkinje-effects.

PubMed

Fitger, C; Brandt, T

1982-02-01

Vestibular Coriolis- and Purkinje-effect, which are known to induce vertigo, were investigated with respect to body posture. One aim of this investigation was to provide information concerning clinical vertigo symptoms. Standing on a rotatable stabilometer, 25 healthy subjects had to execute lateral head tilts during (Coriolis), or after (Purkinje), rotation varied with different constant velocities. The conditions were varied with respect to eyes open vs. eyes closed, head upright vs. head tilt to the right and left, direction of rotation clockwise vs. counterclockwise, active vs. passive head tilt, and active vs. passive body rotation. The results supported the expectation that destabilization was less severe with open than with closed eyes and that sway amplitudes were increased after head tilt as well as with a higher velocity of rotation. The direction of the induced body shift was, as expected, opposite to the initial vestibular stimulus. A forward shift after stop without head tilt was frequently found, being independent of the previous direction of rotation. Reported perceptions coincided mostly not with the initial vestibular signal but rather with the actual movement of compensation. Active instead of passive movements did not produce clearly different effects. The Purkinje experiment appeared to be equivalent to the situation when a patient with an acute lesion of a horizontal vestibular canal bends his head. The stabilogram under this condition may allow a prediction of the side of the lesion.

An assessment of the deflecting effect on human movement due to the Coriolis inertial forces in a space vehicle.

PubMed

Hennion, P Y; Mollard, R

1993-01-01

Under conditions of prolonged space flight, it may be feasible to restore gravity artificially using centrifugal inertial forces in a spinning vehicle. As a result, the motion of the passengers relative to the vehicle is affected by Coriolis forces. The aim of this study is to propose a theoretical method to evaluate the extent of these effects compared to other inertial or motor forces affecting movement. We investigated typical right upper limb movement in a numerical model with a two-solid-links mechanism, including a spherical joint for the shoulder and a hinge joint for the elbow. The inertial and dimensional characteristics of this model derive from measurements and computations obtained on laboratory subjects. The same is true for the movements assigned to the model. These were inferred from actual recordings of arm movement when the subject presses a button placed in front of him with his index finger. From these relative velocities, the resulting forces and moments applied to the elbow and the shoulder were computed for a 1 rad s-1 rotational speed of transport motion, using classical kinetic relations. The result is that the Coriolis moments are of the same order of magnitude as the corresponding inertial moments and one-tenth of the value of a typical elbow flexion moment. Thus, they should cause a significant disturbance in movement.

Non-Adiabatic Effects on Excited States of Vinylidene Observed with Slow Photoelectron Velocity-Map Imaging.

PubMed

DeVine, Jessalyn A; Weichman, Marissa L; Zhou, Xueyao; Ma, Jianyi; Jiang, Bin; Guo, Hua; Neumark, Daniel M

2016-12-21

High-resolution slow photoelectron velocity-map imaging spectra of cryogenically cooled X̃ 2 B 2 H 2 CC - and D 2 CC - in the region of the vinylidene triplet excited states are reported. Three electronic bands are observed and, with the assistance of electronic structure calculations and quantum dynamics on ab initio-based near-equilibrium potential energy surfaces, are assigned as detachment to the [Formula: see text] 3 B 2 (T 1 ), b̃ 3 A 2 (T 2 ), and à 1 A 2 (S 1 ) excited states of neutral vinylidene. This work provides the first experimental observation of the à singlet excited state of H 2 CC. While regular vibrational structure is observed for the ã and à electronic bands, a number of irregular features are resolved in the vicinity of the b̃ band vibrational origin. High-level ab initio calculations suggest that this anomalous structure arises from a conical intersection between the ã and b̃ triplet states near the b̃ state minimum, which strongly perturbs the vibrational levels in the two electronic states through nonadiabatic coupling. Using the adiabatic electron affinity of H 2 CC previously measured to be 0.490(6) eV by Ervin and co-workers [J. Chem. Phys. 1989, 91, 5974], term energies for the excited neutral states of H 2 CC are found to be T 0 (ã 3 B 2 ) = 2.064(6), T 0 (b̃ 3 A 2 ) = 2.738(6), and T 0 (à 1 A 2 ) = 2.991(6) eV.

Motion in a modified Chermnykh's restricted three-body problem with oblateness

NASA Astrophysics Data System (ADS)

Singh, Jagadish; Leke, Oni

2014-03-01

In this paper, the restricted problem of three bodies is generalized to include a case when the passively gravitating test particle is an oblate spheroid under effect of small perturbations in the Coriolis and centrifugal forces when the first primary is a source of radiation and the second one an oblate spheroid, coupled with the influence of the gravitational potential from the belt. The equilibrium points are found and it is seen that, in addition to the usual three collinear equilibrium points, there appear two new ones due to the potential from the belt and the mass ratio. Two triangular equilibrium points exist. These equilibria are affected by radiation of the first primary, small perturbation in the centrifugal force, oblateness of both the test particle and second primary and the effect arising from the mass of the belt. The linear stability of the equilibrium points is explored and the stability outcome of the collinear equilibrium points remains unstable. In the case of the triangular points, motion is stable with respect to some conditions which depend on the critical mass parameter; influenced by the small perturbations, radiating effect of the first primary, oblateness of the test body and second primary and the gravitational potential from the belt. The effects of each of the imposed free parameters are analyzed. The potential from the belt and small perturbation in the Coriolis force are stabilizing parameters while radiation, small perturbation in the centrifugal force and oblateness reduce the stable regions. The overall effect is that the region of stable motion increases under the combine action of these parameters. We have also found the frequencies of the long and short periodic motion around stable triangular points. Illustrative numerical exploration is rendered in the Sun-Jupiter and Sun-Earth systems where we show that in reality, for some values of the system parameters, the additional equilibrium points do not in general exist even when there is a belt to interact with.

A theoretical investigation of one-dimensional lithium-bonded chain: enhanced first hyperpolarizability and little red-shift.

PubMed

Ma, Fang; Bai, Dongsheng; Xu, Hongliang

2014-12-01

We present a theoretical investigation of the electric properties of two kinds of one-dimensional lithium bonded chains: (NC-Li)n and (NC-CC-Li)n (n = 1-8). The resulting (NC-Li)n and (NC-CC-Li)n were found to exhibit enhanced first hyperpolarizabilities (β 0) with increasing n, and a slight change in the absorption maximum wavelength λmax at the crucial transition. Comparing with (NC-Li)n, (NC-CC-Li)n exhibited particularly drastically enhanced β 0 values due to clearly enhanced coupled oscillators and double-degenerated charge transitions. β 0 is known to be the microscopic origin of the second-order non-linear optical (NLO) property, and λmax is an approximate measure of the transparency achievable, thus both are important indices of high-performance NLO molecules. Therefore, our investigations into one-dimensional lithium bond chains will be beneficial to understanding the relationship between β 0 and λmax, thus aiding the design of one-dimensional NLO materials with excellent transparence-efficiency.

Renner-Teller quantum dynamics of NH(a(1)Delta) + H reactions on the NH(2) A(2)A(1) and X(2)B(1) coupled surfaces.

PubMed

Defazio, P; Gamallo, P; González, M; Petrongolo, C

2010-09-16

Four reactions NH(a1Delta) + H′(2S) are investigated by the quantum mechanical real wavepacket method, taking into account nonadiabatic Renner-Teller (RT) and rovibronic Coriolis couplings between the involved states. We consider depletion (d) to N(2D) + H2(X1Sigmag+), exchange (e) to NH′(a1Delta) + H(2S), quenching (q) to NH(X3Sigma-) + H′(2S), and exchange-quenching (eq) to NH′(X3Sigma-) + H(2S). We extend our RT theory to a general AB + C collision using a geometry-dependent but very simple and empirical RT matrix element. Reaction probabilities, cross sections, and rate constants are presented, and RT results are compared with Born-Oppenheimer (BO), experimental, and semiclassical data. The nonadiabatic couplings open two new channels, (q) and (eq), and increase the (d) and (e) reactivity with respect to the BO one, when NH(a1Delta) is rotationally excited. In this case, the quantum cross sections are larger than the semiclassical ones at low collision energies. The calculated rate constants at 300 K are k(d) = 3.06, k(e) = 3.32, k(q) = 1.44, and k(eq) = 1.70 in 10(-11) cm3 s(-1) compared with the measured values k(d) = (3.2 =/- 1.7), k(q + eq) = (1.7 +/- 0.3), and k(total) = (4.8 +/- 1.7). The theoretical depletion rate is thus in good agreement with the experimental value, but the quenching and total rates are overestimated, because the present RT couplings are too large. This discrepancy is probably due to our simple and empirical RT matrix element.

Quantum scattering studies of spin-orbit effects in the Cl({sup 2}P) + HCl {yields} ClH + Cl({sup 2}P) reaction

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

Schatz, G.C.; McCabe, P.; Connor, J.N.L.

1998-07-01

The authors present quantum scattering calculations for the Cl + HCl {yields} ClH + Cl reaction in which they include the three electronic states that correlate asymptotically to the ground state of Cl({sup 2}P) + HCl(X{sup 1}{Sigma}{sup +}). The potential surfaces and couplings are taken from the recent work of C.S. Maierle, G.C. Schatz, M.S. Gordon, P. McCabe and J.N.L. Connor, J. Chem. Soc. Farad. Trans. (1997). They are based on extensive ab initio calculations for geometries in the vicinity of the lowest energy saddle point, and on an electrostatic expansion (plus empirical dispersion and repulsion) for long range geometriesmore » including the van der Waals wells. Spin-orbit coupling has been included using a spin-orbit coupling parameter {lambda} that is assumed to be independent of nuclear geometry, and Coriolis interactions are incorporated accurately. The scattering calculations use a hyperspherical coordinate coupled channel method in full dimensionality. AJ-shifting approximation is employed to convert cumulative reaction probabilities for total angular momentum quantum number J = 1/2 into state selected and thermal rate coefficients. Two issues have been studied: (a) the influence of the magnitude of {lambda} on the fine-structure resolved cumulative probabilities and rate coefficients (the authors consider {lambda}`s that vary from 0 to {+-}100% of the true Cl value), and (b) the transition state resonance spectrum, and its variation with {lambda} and with other parameters in the calculations. Cl + HCl is a simple hydrogen transfer reaction which serves as a canonical model both for heavy-light-heavy atom reactions, and for the reactions of halogen atoms with closed shell molecules.« less

Multidimensional intermolecular dynamics from tunable far-infrared laser spectroscopy: Angular-radial coupling in the intermolecular potential of argon--H sub 2 O

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

Cohen, R.C.; Saykally, R.J.

1991-12-01

Five new vibration--rotation tunneling states of Ar--H{sub 2}O (the {Sigma} and {Pi}(1{sub 11}) and the {Sigma} and {Pi}(2{sub 12}) internal rotor states and the {ital n}=1, {Pi}(1{sub 01}) stretching-internal rotor combination level) have been accessed by tunable far-infrared laser spectroscopy. The measured vibrational band origins of transitions to these states are within 2% of predictions made from an anisotropic three-dimensional intermolecular potential surface (denoted AW1) derived from a nonlinear least-squares fit to previous far-infrared spectral data (J. Phys. Chem. {bold 94}, 7991(1990)). This provides strong evidence that the AW1 intermolecular potential surface incorporates much of the essential physics of themore » intermolecular forces which bind the cluster. However, larger deviations from the predictions are found in the observed rotational term values. A detailed analysis of these deviations clearly demonstrates the need for even stronger angular-radial coupling in the Ar--H{sub 2}O intermolecular potential than the already substantial coupling present in the AW1 surface. Specifically, the presently observed {Sigma}(1{sub 11}) state and the {ital n}=1, {Sigma}(0{sub 00}) state are found to be approximately 65:35 mixtures of the basis states which represent pure stretching and internal rotation. The {Sigma}(2{sub 12}) level is found to be mixed just as strongly with {ital n}=2, {Sigma}(1{sub 01}). The formalism for accurately deperturbing vibration--rotation--tunneling states coupled by Coriolis interactions used in the above analysis is presented.« less

Computational fluid dynamics modeling of rope-guided conveyances in two typical kinds of shaft layouts.

PubMed

Wu, Renyuan; Zhu, Zhencai; Cao, Guohua

2015-01-01

The behavior of rope-guided conveyances is so complicated that the rope-guided hoisting system hasn't been understood thoroughly so far. In this paper, with user-defined functions loaded, ANSYS FLUENT 14.5 was employed to simulate lateral motion of rope-guided conveyances in two typical kinds of shaft layouts. With rope-guided mine elevator and mine cages taken into account, results show that the lateral aerodynamic buffeting force is much larger than the Coriolis force, and the side aerodynamic force have the same order of magnitude as the Coriolis force. The lateral aerodynamic buffeting forces should also be considered especially when the conveyance moves along the ventilation air direction. The simulation shows that the closer size of the conveyances can weaken the transverse aerodynamic buffeting effect.

Spectroscopic studies of ozone in cryosolutions: FT-IR spectra of 16O3 in liquid nitrogen, oxygen, argon and krypton

NASA Astrophysics Data System (ADS)

Bulanin, Kirill M.; Bulanin, Michael O.; Rudakova, Aida V.; Kolomijtsova, Tatiana D.; Shchepkin, Dmitrij N.

2018-03-01

We have measured and interpreted the IR spectra of ozone dissolved in liquid nitrogen, oxygen, argon, and krypton in the 650-4700 cm-1 spectral region at 79-117 K. Frequency shifts, band intensities and bandshapes of 22 spectral features of soluted ozone were analyzed. The bands of the A1 symmetry have a complex contour and possess an excess intensity with respect to the value of the purely vibrational transition moment. It was found that this effect is related to the manifestation of the Coriolis interaction. The bandshape distortion manifests itself as an additional intensity from the side of the B1 symmetry band being an intensity source in the case of the Coriolis interaction.

Adaptation to Coriolis force perturbation of movement trajectory; role of proprioceptive and cutaneous somatosensory feedback

NASA Technical Reports Server (NTRS)

Lackner, James R.; DiZio, Paul

2002-01-01

Subjects exposed to constant velocity rotation in a large fully-enclosed room that rotates initially make large reaching errors in pointing to targets. The paths and endpoints of their reaches are deviated in the direction of the transient lateral Coriolis forces generated by the forward velocity of their reaches. With additional reaches, subjects soon reach in straighter paths and become more accurate at landing on target even in the absence of visual feedback about their movements. Two factors contribute to this adaptation: first, muscle spindle and golgi tendon organ feedback interpreted in relation to efferent commands provide information about movement trajectory, and second, somatosensory stimulation of the fingertip at the completion of a reach provides information about the location of the fingertip relative to the torso.

A theoretical and experimental benchmark study of core-excited states in nitrogen

DOE PAGES

Myhre, Rolf H.; Wolf, Thomas J. A.; Cheng, Lan; ...

2018-02-14

The high resolution near edge X-ray absorption fine structure spectrum of nitrogen displays the vibrational structure of the core-excited states. This makes nitrogen well suited for assessing the accuracy of different electronic structure methods for core excitations. We report high resolution experimental measurements performed at the SOLEIL synchrotron facility. These are compared with theoretical spectra calculated using coupled cluster theory and algebraic diagrammatic construction theory. The coupled cluster singles and doubles with perturbative triples model known as CC3 is shown to accurately reproduce the experimental excitation energies as well as the spacing of the vibrational transitions. In conclusion, the computationalmore » results are also shown to be systematically improved within the coupled cluster hierarchy, with the coupled cluster singles, doubles, triples, and quadruples method faithfully reproducing the experimental vibrational structure.« less

A theoretical and experimental benchmark study of core-excited states in nitrogen

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

Myhre, Rolf H.; Wolf, Thomas J. A.; Cheng, Lan

The high resolution near edge X-ray absorption fine structure spectrum of nitrogen displays the vibrational structure of the core-excited states. This makes nitrogen well suited for assessing the accuracy of different electronic structure methods for core excitations. We report high resolution experimental measurements performed at the SOLEIL synchrotron facility. These are compared with theoretical spectra calculated using coupled cluster theory and algebraic diagrammatic construction theory. The coupled cluster singles and doubles with perturbative triples model known as CC3 is shown to accurately reproduce the experimental excitation energies as well as the spacing of the vibrational transitions. In conclusion, the computationalmore » results are also shown to be systematically improved within the coupled cluster hierarchy, with the coupled cluster singles, doubles, triples, and quadruples method faithfully reproducing the experimental vibrational structure.« less

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.

Influence of toroidal rotation on tearing modes

NASA Astrophysics Data System (ADS)

Cai, Huishan; Cao, Jintao; Li, Ding

2017-10-01

Tearing modes stability analysis including toroidal rotation is studied. It is found that rotation affects the stability of tearing modes mainly through the interaction with resistive inner region of tearing mode. The coupling of magnetic curvature with centrifugal force and Coriolis force provides a perturbed perpendicular current, and a return parallel current is induced to affect the stability of tearing modes. Toroidal rotation plays a stable role, which depends on the magnitude of Mach number and adiabatic index Γ, and is independent on the direction of toroidal rotation. For Γ >1, the scaling of growth rate is changed for typical Mach number in present tokamaks. For Γ = 1 , the scaling keeps unchanged, and the effect of toroidal rotation is much less significant, compared with that for Γ >1. National Magnetic Confinement Fusion Science Program and National Science Foundation of China under Grants No. 2014GB106004, No. 2013GB111000, No. 11375189, No. 11075161 and No. 11275260, and Youth Innovation Promotion Association CAS.

Fine structure of α decay from the variational principle

NASA Astrophysics Data System (ADS)

Mirea, M.

2017-12-01

Starting from the variational principle, the time-dependent pairing equations are generalized by including the Landau-Zener effect and the Coriolis coupling. A system of microscopic equations of motion for configuration mixing is deduced, allowing the determination of quantities that have the same meaning as the preformation factors of the α particle. These equations are solved in order to reproduce the hindrance factors of the α decay of an odd-A mass nucleus. The α decay of 211Po is treated as a superasymmetric fission process, by following the rearrangement of the nuclear orbitals from the parent ground state up to the scission configuration. The probabilities of finding the excited states of the daughter at scission are obtained from the microscopic equations of motion. The intensities of the transitions to the excited states of the daughter were evaluated theoretically. The experimental data were compared with the theoretical findings. A very good agreement was obtained. A mean value of the tunneling velocity of about 2 ×104 fm/fs was extracted.

PyVCI: A flexible open-source code for calculating accurate molecular infrared spectra

NASA Astrophysics Data System (ADS)

Sibaev, Marat; Crittenden, Deborah L.

2016-06-01

The PyVCI program package is a general purpose open-source code for simulating accurate molecular spectra, based upon force field expansions of the potential energy surface in normal mode coordinates. It includes harmonic normal coordinate analysis and vibrational configuration interaction (VCI) algorithms, implemented primarily in Python for accessibility but with time-consuming routines written in C. Coriolis coupling terms may be optionally included in the vibrational Hamiltonian. Non-negligible VCI matrix elements are stored in sparse matrix format to alleviate the diagonalization problem. CPU and memory requirements may be further controlled by algorithmic choices and/or numerical screening procedures, and recommended values are established by benchmarking using a test set of 44 molecules for which accurate analytical potential energy surfaces are available. Force fields in normal mode coordinates are obtained from the PyPES library of high quality analytical potential energy surfaces (to 6th order) or by numerical differentiation of analytic second derivatives generated using the GAMESS quantum chemical program package (to 4th order).

Design and control of rotating soil-like substrate plant-growing facility based on plant water requirement and computational fluid dynamics simulation

NASA Astrophysics Data System (ADS)

Hu, Dawei; Li, Leyuan; Liu, Hui; Zhang, Houkai; Fu, Yuming; Sun, Yi; Li, Liang

It is necessary to process inedible plant biomass into soil-like substrate (SLS) by bio-compost to realize biological resource sustainable utilization. Although similar to natural soil in structure and function, SLS often has uneven water distribution adversely affecting the plant growth due to unsatisfactory porosity, permeability and gravity distribution. In this article, SLS plant-growing facility (SLS-PGF) were therefore rotated properly for cultivating lettuce, and the Brinkman equations coupled with laminar flow equations were taken as governing equations, and boundary conditions were specified by actual operating characteristics of rotating SLS-PGF. Optimal open-control law of the angular and inflow velocity was determined by lettuce water requirement and CFD simulations. The experimental result clearly showed that water content was more uniformly distributed in SLS under the action of centrifugal and Coriolis force, rotating SLS-PGF with the optimal open-control law could meet lettuce water requirement at every growth stage and achieve precise irrigation.

Infrared spectroscopy of the ν1 + ν4 and 3ν4 bands of the nitrate radical

NASA Astrophysics Data System (ADS)

Kawaguchi, Kentarou; Fujimori, Ryuji; Ishiwata, Takashi

2018-05-01

High-resolution Fourier transform infrared spectra of the ν1 + ν4 and 3ν4 bands of 14NO3 were observed in the 1414 and 1174 cm-1 regions, respectively, and the corresponding ones of 15NO3 in the 1407 and 1159 cm-1 regions, respectively, and analyzed as E‧-A2‧ bands. The rotational constants of the upper states of 14NO3 are determined to be 0.457584 and 0.46089 cm-1 for ν1 + ν4 and 3ν4, respectively, consistent with the vibrational assignment. Effective Coriolis coupling constants of the ground electronic state are partly explained by vibronic interaction from the B2E‧ state, and a large change (37% decrease) in the value of the ν1 + ν4 state compared with that of the ν4 state is attributed to a mixing with the ν3 + ν4 state (1492 cm-1) through vibrational anharmonicity.

The rotating spectrometer: Biotechnology for cell separations

NASA Technical Reports Server (NTRS)

Noever, David A.

1991-01-01

An instrument for biochemical studies, called the rotating spectrometer, separates previously inseparable cell cultures. The rotating spectrometer is intended for use in pharmacological studies which require fractional splitting of heterogeneous cell cultures based on cell morphology and swimming behavior. As a method to separate and concentrate cells in free solution, the rotating method requires active organism participation and can effectively split the large class of organisms known to form spontaneous patterns. Examples include the biochemical star, an organism called Tetrahymena pyriformis. Following focusing in a rotating frame, the separation is accomplished using different radial dependencies of concentrated algal and protozoan species. The focusing itself appears as concentric rings and arises from the coupling between swimming direction and Coriolis forces. A dense cut is taken at varying radii, and extraction is replenished at an inlet. Unlike standard separation and concentrating techniques such as filtration or centrifugation, the instrument is able to separate motile from immotile fractions. For a single pass, typical split efficiencies can reach 200 to 300 percent compared to the inlet concentration.

The rotating spectrometer: New biotechnology for cell separations

NASA Technical Reports Server (NTRS)

Noever, David A.; Matsos, Helen C.

1990-01-01

An instrument for biochemical studies, called the rotating spectrometer, separates previously inseparable cell cultures. The rotating spectrometer is intended for use in pharmacological studies which require fractional splitting of heterogeneous cell cultures based on cell morphology and swimming behavior. As a method to separate and concentrate cells in free solution, the rotating method requires active organism participation and can effectively split the large class of organisms known to form spontaneous patterns. Examples include the biochemical star, an organism called Tetrahymena pyriformis. Following focusing in a rotated frame, the separation is accomplished using different radial dependencies of concentrated algal and protozoan species. The focusing itself appears as concentric rings and arises from the coupling between swimming direction and Coriolis forces. A dense cut is taken at varying radii and extraction is replenished at an inlet. Unlike standard separation and concentrating techniques such as filtration or centrifugation, the instrument is able to separate motile from immotile fractions. For a single pass, typical split efficiencies can reach 200 to 300 percent compared to the inlet concentration.

Substorm-related thermospheric density and wind disturbances

NASA Astrophysics Data System (ADS)

Ritter, P.; Luhr, H.; Doornbos, E. N.

2009-12-01

The input of energy and momentum from the magnetosphere is most efficiently coupled into the high latitude ionosphere-thermosphere. The phenomenon we are focusing on here is the magnetospheric substorm. This paper presents substorm related observations of the thermosphere derived from the CHAMP satellite. With its sensitive accelerometer the satellite can measure the air density and zonal winds. Based on a large number of substorm events the average high and low latitude thermosphere response to substorm onsets was deduced. During magnetic substorms the thermospheric density is enhanced first at high latitudes. Then the disturbance travels at sonic speed to lower latitudes, and 3-4 hours later the bulge reaches the equator on the night side. Under the influence of the Coriolis force the traveling atmospheric disturbance (TAD) is deflected westward. In accordance with present-day atmospheric models the disturbance zonal wind velocities during substorms are close to zero near the equator before midnight and attain moderate westward velocities after midnight. In general, the wind system is only weakly perturbed by substorms.

Immediate compensation for variations in self-generated Coriolis torques related to body dynamics and carried objects

PubMed Central

DiZio, Paul; Lackner, James R.

2013-01-01

We have previously shown that the Coriolis torques that result when an arm movement is performed during torso rotation do not affect movement trajectory. Our purpose in the present study was to examine whether torso motion-induced Coriolis and other interaction torques are counteracted during a turn and reach (T&R) movement when the effective mass of the hand is augmented, and whether the dominant arm has an advantage in coordinating intersegmental dynamics as predicted by the dynamic dominance hypothesis (Sainburg RL. Exp Brain Res 142: 241–258, 2002). Subjects made slow and fast T&R movements in the dark to just extinguished targets with either arm, while holding or not holding a 454-g object. Movement endpoints were equally accurate at both speeds, with either hand, and in both weight conditions, but subjects tended to angularly undershoot and produce more variable endpoints for targets requiring greater torso rotation. There were no changes in endpoint accuracy or trajectory deviation over repeated movements. The dominant right arm was more stable in its control of trajectory direction across targets, whereas the nondominant left arm had an improved ability to stop accurately on the target for higher levels of interaction torques. The trajectories to more eccentric targets were straighter when performed at higher speeds but slightly more deviated when subjects held the weight. Subjects did not slow their torso velocity or change the timing of the arm and torso velocities when holding the weight, although there was a slight decrease in their hand velocity relative to the torso. The delay between the onsets of torso and finger movements was almost twice as large for the right arm than the left, suggesting the right arm was better able to account for torso rotation in the arm movement. Holding the weight increased the peak Coriolis torque by 40% at the shoulder and 45% at the elbow and, for the most eccentric target, increased the peak net torque by 12% at the shoulder and 34% at the elbow. In accordance with Sainburg's dynamic dominance hypothesis, the right arm exhibited an advantage for coordinating intersegmental dynamics, showing a more stable finger velocity in relation to the torso across targets, decreasing error variability with movement speed, and more synchronized peaks of finger relative and torso angular velocities in conditions with greater joint torque requirements. The arm used had little effect on the movement path and the magnitude of the joint torques in any of the conditions. These results indicate that compensations for forthcoming Coriolis torque variations take into account the dynamic properties of the body and of external objects, as well as the planned velocities of the torso and arm. PMID:23803330

Immediate compensation for variations in self-generated Coriolis torques related to body dynamics and carried objects.

PubMed

Pigeon, Pascale; Dizio, Paul; Lackner, James R

2013-09-01

We have previously shown that the Coriolis torques that result when an arm movement is performed during torso rotation do not affect movement trajectory. Our purpose in the present study was to examine whether torso motion-induced Coriolis and other interaction torques are counteracted during a turn and reach (T&R) movement when the effective mass of the hand is augmented, and whether the dominant arm has an advantage in coordinating intersegmental dynamics as predicted by the dynamic dominance hypothesis (Sainburg RL. Exp Brain Res 142: 241-258, 2002). Subjects made slow and fast T&R movements in the dark to just extinguished targets with either arm, while holding or not holding a 454-g object. Movement endpoints were equally accurate at both speeds, with either hand, and in both weight conditions, but subjects tended to angularly undershoot and produce more variable endpoints for targets requiring greater torso rotation. There were no changes in endpoint accuracy or trajectory deviation over repeated movements. The dominant right arm was more stable in its control of trajectory direction across targets, whereas the nondominant left arm had an improved ability to stop accurately on the target for higher levels of interaction torques. The trajectories to more eccentric targets were straighter when performed at higher speeds but slightly more deviated when subjects held the weight. Subjects did not slow their torso velocity or change the timing of the arm and torso velocities when holding the weight, although there was a slight decrease in their hand velocity relative to the torso. The delay between the onsets of torso and finger movements was almost twice as large for the right arm than the left, suggesting the right arm was better able to account for torso rotation in the arm movement. Holding the weight increased the peak Coriolis torque by 40% at the shoulder and 45% at the elbow and, for the most eccentric target, increased the peak net torque by 12% at the shoulder and 34% at the elbow. In accordance with Sainburg's dynamic dominance hypothesis, the right arm exhibited an advantage for coordinating intersegmental dynamics, showing a more stable finger velocity in relation to the torso across targets, decreasing error variability with movement speed, and more synchronized peaks of finger relative and torso angular velocities in conditions with greater joint torque requirements. The arm used had little effect on the movement path and the magnitude of the joint torques in any of the conditions. These results indicate that compensations for forthcoming Coriolis torque variations take into account the dynamic properties of the body and of external objects, as well as the planned velocities of the torso and arm.

Human Leukocyte Antigen Class I and Class II Polymorphisms and Serum Cytokine Profiles in Cervical Cancer.

PubMed

Bahls, Larissa; Yamakawa, Roger; Zanão, Karina; Alfieri, Daniela; Flauzino, Tamires; Delongui, Francieli; de Abreu, André; Souza, Raquel; Gimenes, Fabrícia; Reiche, Edna; Borelli, Sueli; Consolaro, Marcia

2017-08-31

Only a small proportion of women who are exposed to infection with high-risk human papillomavirus (HR-HPV) progress to persistent infection and develop cervical cancer (CC). The immune response and genetic background of the host may affect the risk of progression from a HR-HPV infection to lesions and cancer. However, to our knowledge, no studies has been conducted to evaluate the relationship between variability of human leukocyte antigens ( HLA ) genes and serum cytokine expression in this pathology. In the current study, we examined the associations of HLA alleles and haplotypes including Class I ( HLA-A , -B and -C ) and II ( HLA-DRB1 , -DQA1 and -DQB1 ) with serum levels of cytokines interleukin (IL)-6, tumor necrosis factor-α (TNF-α), IL-10 and IL-17 as well as risks of HPV infections, lesions and CC among admixed Brazilian women. HLA polymorphisms were associated with an increased risk or protection from HPV, lesions and CC. Additionally, we demonstrated a potential association of a HLA class I haplotype ( HLA-B*14-C*08 ) with higher IL-10 cytokine serum levels in cervical disease, suggesting an association between HLA class I and specific cytokines in cervical carcinogenesis. However, larger studies with detailed HPV types coupled with genetic data are needed to further evaluate the effects of HLA and CC by HPV genotype.

Human Leukocyte Antigen Class I and Class II Polymorphisms and Serum Cytokine Profiles in Cervical Cancer

PubMed Central

Bahls, Larissa; Yamakawa, Roger; Zanão, Karina; Alfieri, Daniela; Flauzino, Tamires; Delongui, Francieli; de Abreu, André; Souza, Raquel; Gimenes, Fabrícia; Reiche, Edna; Borelli, Sueli; Consolaro, Marcia

2017-01-01

Only a small proportion of women who are exposed to infection with high-risk human papillomavirus (HR-HPV) progress to persistent infection and develop cervical cancer (CC). The immune response and genetic background of the host may affect the risk of progression from a HR-HPV infection to lesions and cancer. However, to our knowledge, no studies has been conducted to evaluate the relationship between variability of human leukocyte antigens (HLA) genes and serum cytokine expression in this pathology. In the current study, we examined the associations of HLA alleles and haplotypes including Class I (HLA-A, -B and -C) and II (HLA-DRB1, -DQA1 and -DQB1) with serum levels of cytokines interleukin (IL)-6, tumor necrosis factor-α (TNF-α), IL-10 and IL-17 as well as risks of HPV infections, lesions and CC among admixed Brazilian women. HLA polymorphisms were associated with an increased risk or protection from HPV, lesions and CC. Additionally, we demonstrated a potential association of a HLA class I haplotype (HLA-B*14-C*08) with higher IL-10 cytokine serum levels in cervical disease, suggesting an association between HLA class I and specific cytokines in cervical carcinogenesis. However, larger studies with detailed HPV types coupled with genetic data are needed to further evaluate the effects of HLA and CC by HPV genotype. PMID:28858203

An Accurate ab initio Quartic Force Field and Vibrational Frequencies for CH4 and Isotopomers

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Martin, Jan M. L.; Taylor, Peter R.

1995-01-01

A very accurate ab initio quartic force field for CH4 and its isotopomers is presented. The quartic force field was determined with the singles and doubles coupled-cluster procedure that includes a quasiperturbative estimate of the effects of connected triple excitations, CCSD(T), using the correlation consistent polarized valence triple zeta, cc-pVTZ, basis set. Improved quadratic force constants were evaluated with the correlation consistent polarized valence quadruple zeta, cc-pVQZ, basis set. Fundamental vibrational frequencies are determined using second-order perturbation theory anharmonic analyses. All fundamentals of CH4 and isotopomers for which accurate experimental values exist and for which there is not a large Fermi resonance, are predicted to within +/- 6 cm(exp -1). It is thus concluded that our predictions for the harmonic frequencies and the anharmonic constants are the most accurate estimates available. It is also shown that using cubic and quartic force constants determined with the correlation consistent polarized double zeta, cc-pVDZ, basis set in conjunction with the cc-pVQZ quadratic force constants and equilibrium geometry leads to accurate predictions for the fundamental vibrational frequencies of methane, suggesting that this approach may be a viable alternative for larger molecules. Using CCSD(T), core correlation is found to reduce the CH4 r(e), by 0.0015 A. Our best estimate for r, is 1.0862 +/- 0.0005 A.

Accurate energetics of small molecules containing third-row atoms Ga-Kr: A comparison of advanced ab initio and density functional theory

NASA Astrophysics Data System (ADS)

Yockel, Scott; Mintz, Benjamin; Wilson, Angela K.

2004-07-01

Advanced ab initio [coupled cluster theory through quasiperturbative triple excitations (CCSD(T))] and density functional (B3LYP) computational chemistry approaches were used in combination with the standard and augmented correlation consistent polarized valence basis sets [cc-pVnZ and aug-cc-pVnZ, where n=D(2), T(3), Q(4), and 5] to investigate the energetic and structural properties of small molecules containing third-row (Ga-Kr) atoms. These molecules were taken from the Gaussian-2 (G2) extended test set for third-row atoms. Several different schemes were used to extrapolate the calculated energies to the complete basis set (CBS) limit for CCSD(T) and the Kohn-Sham (KS) limit for B3LYP. Zero point energy and spin orbital corrections were included in the results. Overall, CCSD(T) atomization energies, ionization energies, proton affinities, and electron affinities are in good agreement with experiment, within 1.1 kcal/mol when the CBS limit has been determined using a series of two basis sets of at least triple zeta quality. For B3LYP, the overall mean absolute deviation from experiment for the three properties and the series of molecules is more significant at the KS limit, within 2.3 and 2.6 kcal/mol for the cc-pVnZ and aug-cc-pVnZ basis set series, respectively.

Thermochemistry analyses for transformation of C6 glucose compound into C9, C12 and C15 alkanes using density functional theory

NASA Astrophysics Data System (ADS)

Verma, Anand Mohan; Kishore, Nanda

2017-02-01

The hydrolysis of cellulose fraction of biomass yields C6 glucose which further can be transformed into long-chain hydrocarbons by C-C coupling. In this study, C6 glucose is transformed into three chain alkanes, namely, C9, C12 and C15 using C-C coupling reactions under the gas and aqueous phase milieus. The geometry optimisation and vibrational frequency calculations are carried out at well-known hybrid-GGA functional, B3LYP with the basis set of 6-31+g(d,p) under the density functional theory framework. The single point energetics are calculated at M05-2X/6-311+g(3df,2p) level of theory. All thermochemical properties are calculated over a wide range of temperature between 300 and 900 K at an interval of 100 K. The thermochemistry suggested that the aqueous phase behaviour is suitable for the hydrolysis of sugar into long-chain alkanes compared to gas-phase environment. The hydrodeoxygenation reactions under each reaction pathway are found as most favourable reactions in both phases; however, aqueous phase dominates over gas phase in all discussed thermodynamic parameters.

Stereoselective Synthesis of Methylene Oxindoles via Palladium(II)-Catalyzed Intramolecular Cross-Coupling of Carbamoyl Chlorides.

PubMed

Le, Christine M; Sperger, Theresa; Fu, Rui; Hou, Xiao; Lim, Yong Hwan; Schoenebeck, Franziska; Lautens, Mark

2016-11-02

We report a highly robust, general and stereoselective method for the synthesis of 3-(chloromethylene)oxindoles from alkyne-tethered carbamoyl chlorides using PdCl 2 (PhCN) 2 as the catalyst. The transformation involves a stereo- and regioselective chloropalladation of an internal alkyne to generate a nucleophilic vinyl Pd II species, which then undergoes an intramolecular cross-coupling with a carbamoyl chloride. The reaction proceeds under mild conditions, is insensitive to the presence of moisture and air, and is readily scalable. The products obtained from this reaction are formed with >95:5 Z:E selectivity in nearly all cases and can be used to access biologically relevant oxindole cores. Through combined experimental and computational studies, we provide insight into stereo- and regioselectivity of the chloropalladation step, as well as the mechanism for the C-C bond forming process. Calculations provide support for a mechanism involving oxidative addition into the carbamoyl chloride bond to generate a high valent Pd IV species, which then undergoes facile C-C reductive elimination to form the final product. Overall, the transformation constitutes a formal Pd II -catalyzed intramolecular alkyne chlorocarbamoylation reaction.

Collisional excitation of ArH+ by hydrogen atoms

NASA Astrophysics Data System (ADS)

Dagdigian, Paul J.

2018-06-01

The rotational excitation of the 36ArH+ ion in collisions with hydrogen atoms is investigated in this work. The potential energy surface (PES) describing the 36ArH+-H interaction, with the ion bond length r fixed at the average of r over the radial v = 0 vibrational state distribution, was obtained with a coupled cluster method that included single, double, and (perturbatively) triple excitations [RCCSD(T)]. A deep minimum (De = 3135 cm-1) in the PES was found in linear H-ArH+ geometry at an ion-atom separation Re = 4.80a0. Energy-dependent cross-sections and rate coefficients as a function of temperature for this collision pair were computed in close-coupling (CC) calculations. Since the PES possesses a deep well, this is a good system to test the performance of the quantum statistical (QS) method developed by Manolopoulos and co-workers as a more efficient method to compute the cross-sections. Good agreement was found between rate coefficients obtained by the CC and QS methods at several temperatures. In a simple application, the excitation of ArH+ is simulated for conditions under which this ion is observed in absorption.

Collisional rates based on the first potential energy surface of the NeH+ -He system

NASA Astrophysics Data System (ADS)

Bop, Cheikh T.; Hammami, K.; Faye, N. A. B.

2017-09-01

The potential energy surface is computed at the explicitly correlated coupled cluster with simple, second and perturbative triple excitation method (CCSD(T)-F12) in connection with the augmented-correlation consistent-polarized valence triple zeta (aug-cc-pVTZ) Gaussian basis set for the NeH+ -He system. The calculations were performed by first taking into account the vibration of the molecule and then averaging the so-obtained three-dimensional potential. From this average interaction potential, cross-sections among the 11 first rotational levels of NeH+ induced by collision with He are calculated for energies up to 4000 cm-1 using the quantum mechanical close coupling (CC) approach. Collisional rate coefficients are obtained by thermally averaging these cross-sections at low temperature (T ≤ 300 K). The propensity rules of the rotational transitions obtained in this paper are discussed and compared with those of HeH+ and ArH+ in collision with electron. This work may be helpful for the eventual investigations, both theoretical and experimental, focused to detect the key cationic noble gas hydride NeH+ in the interstellar and circumstellar media as well as in laboratory experiments.

Disrupted inter-hemispheric functional and structural coupling in Internet addiction adolescents.

PubMed

Bi, Yanzhi; Yuan, Kai; Feng, Dan; Xing, Lihong; Li, Yangding; Wang, Hongmei; Yu, Dahua; Xue, Ting; Jin, Chenwang; Qin, Wei; Tian, Jie

2015-11-30

Rapid progress had been made towards the effect of Internet addiction (IA) on the adolescents brain, relatively little is known about the alterations in inter-hemispheric resting state functional connectivity (RSFC) changes. In the current study, voxel-mirrored homotopic connectivity (VMHC) was used to examine inter-hemispheric RSFC in IA adolescents (n=21) and controls (n=21). The integrity of the fibers connecting the regions, which showed aberrant inter-hemispheric functional connectivity, was assessed by fiber tractography analysis. In addition, the coupling of inter-hemispheric functional and structural connectivity was investigated. Relative to controls, IA adolescents showed decreased VMHC of dorsolateral prefrontal cortex (DLPFC) and reduced fractional anisotropy (FA) values in the genu of corpus callosum (CC). The decreased VMHC of DLPFC was significantly negative correlated with the duration of IA. Moreover, the VMHC of DLPFC showed significant correlations with the FA of CC in healthy controls, which was disrupted in IA. Our findings provided more scientific evidence for the involvement of DLPFC in IA. It is hoped that multimodal imaging methods can provide deeper insights into the IA effects on the brain. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Complementary velocity and heat transfer measurements in a rotating turbine cooling passage

NASA Astrophysics Data System (ADS)

Bons, Jeffrey Peter

An experimental investigation was conducted on the internal flowfield of a simulated turbine blade cooling passage. The passage is of a square cross-section and was manufactured from quartz for optical accessibility. Velocity measurements were taken using Particle Image Velocimetry for both heated and non-heated cases. Thin film resistive heaters on the four passage walls allow heat to be added to the coolant flow without obstructing laser access. Under the same conditions, an infrared detector with associated optics collected wall temperature data for use in calculating local Nusselt number. The test section was operated with radial outward flow and at values of Reynolds number, Rotation number, and density ratio typical of applications. Velocity data for the non-heated case document the evolution of the Coriolis-induced double vortex. The vortex has the effect of increasing the leading side boundary layer thickness while decreasing the trailing side boundary layer thickness. Also, the streamwise component of the Coriolis acceleration creates a thinned side wall boundary layer. These data reveal an unsteady, turbulent flowfield in the cooling passage. Velocity data for the heated case show a strongly distorted streamwise profile indicative of a buoyancy effect on the leading side. The Coriolis vortex is the mechanism for the accumulation of stagnant flow on the leading side of the passage. Heat transfer data show a maximum factor of two difference in the Nusselt number from trailing side to leading side. An estimate of this heat transfer disparity based on the measured boundary layer edge velocity yields approximately the same factor of two. A momentum integral model was developed for data interpretation which accounts for Coriolis and buoyancy effects. Calculated streamwise profiles and secondary flows match the experimental data well. The model, the velocity data, and the heat transfer data combine to suggest the presence of separated flow on the leading wall starting at about five passage widths for the conditions studied. (Copies available exclusively from MIT Libraries, Rm. 14-0551, Cambridge, MA 02139-4307. Ph. 617-253-5668; Fax 617-253-1690.)

Coriolis-force-induced trajectory and endpoint deviations in the reaching movements of labyrinthine-defective subjects

NASA Technical Reports Server (NTRS)

DiZio, P.; Lackner, J. R.

2001-01-01

When reaching movements are made during passive constant velocity body rotation, inertial Coriolis accelerations are generated that displace both movement paths and endpoints in their direction. These findings directly contradict equilibrium point theories of movement control. However, it has been argued that these movement errors relate to subjects sensing their body rotation through continuing vestibular activity and making corrective movements. In the present study, we evaluated the reaching movements of five labyrinthine-defective subjects (lacking both semicircular canal and otolith function) who cannot sense passive body rotation in the dark and five age-matched, normal control subjects. Each pointed 40 times in complete darkness to the location of a just extinguished visual target before, during, and after constant velocity rotation at 10 rpm in the center of a fully enclosed slow rotation room. All subjects, including the normal controls, always felt completely stationary when making their movements. During rotation, both groups initially showed large deviations of their movement paths and endpoints in the direction of the transient Coriolis forces generated by their movements. With additional per-rotation movements, both groups showed complete adaptation of movement curvature (restoration of straight-line reaches) during rotation. The labyrinthine-defective subjects, however, failed to regain fully accurate movement endpoints after 40 reaches, unlike the control subjects who did so within 11 reaches. Postrotation, both groups' movements initially had mirror image curvatures to their initial per-rotation reaches; the endpoint aftereffects were significantly different from prerotation baseline for the control subjects but not for the labyrinthine-defective subjects reflecting the smaller amount of endpoint adaptation they achieved during rotation. The labyrinthine-defective subjects' movements had significantly lower peak velocity, higher peak elevation, lower terminal velocity, and a more vertical touchdown than those of the control subjects. Thus the way their reaches terminated denied them the somatosensory contact cues necessary for full endpoint adaptation. These findings fully contradict equilibrium point theories of movement control. They emphasize the importance of contact cues in adaptive movement control and indicate that movement errors generated by Coriolis perturbations of limb movements reveal characteristics of motor planning and adaptation in both healthy and clinical populations.

The Role of Corpus Callosum Development in Functional Connectivity and Cognitive Processing

PubMed Central

Findlay, Anne M.; Honma, Susanne; Jeremy, Rita J.; Strominger, Zoe; Bukshpun, Polina; Wakahiro, Mari; Brown, Warren S.; Paul, Lynn K.; Barkovich, A. James; Mukherjee, Pratik; Nagarajan, Srikantan S.; Sherr, Elliott H.

2012-01-01

The corpus callosum is hypothesized to play a fundamental role in integrating information and mediating complex behaviors. Here, we demonstrate that lack of normal callosal development can lead to deficits in functional connectivity that are related to impairments in specific cognitive domains. We examined resting-state functional connectivity in individuals with agenesis of the corpus callosum (AgCC) and matched controls using magnetoencephalographic imaging (MEG-I) of coherence in the alpha (8–12 Hz), beta (12–30 Hz) and gamma (30–55 Hz) bands. Global connectivity (GC) was defined as synchronization between a region and the rest of the brain. In AgCC individuals, alpha band GC was significantly reduced in the dorsolateral pre-frontal (DLPFC), posterior parietal (PPC) and parieto-occipital cortices (PO). No significant differences in GC were seen in either the beta or gamma bands. We also explored the hypothesis that, in AgCC, this regional reduction in functional connectivity is explained primarily by a specific reduction in interhemispheric connectivity. However, our data suggest that reduced connectivity in these regions is driven by faulty coupling in both inter- and intrahemispheric connectivity. We also assessed whether the degree of connectivity correlated with behavioral performance, focusing on cognitive measures known to be impaired in AgCC individuals. Neuropsychological measures of verbal processing speed were significantly correlated with resting-state functional connectivity of the left medial and superior temporal lobe in AgCC participants. Connectivity of DLPFC correlated strongly with performance on the Tower of London in the AgCC cohort. These findings indicate that the abnormal callosal development produces salient but selective (alpha band only) resting-state functional connectivity disruptions that correlate with cognitive impairment. Understanding the relationship between impoverished functional connectivity and cognition is a key step in identifying the neural mechanisms of language and executive dysfunction in common neurodevelopmental and psychiatric disorders where disruptions of callosal development are consistently identified. PMID:22870191

Physics that Textbook Writers Usually Get Wrong: III.

ERIC Educational Resources Information Center

Bauman, Robert P.

1992-01-01

Examines inconsistencies in science textbook discussions of vector quantities and force. Provides illustrations of textbook inconsistencies related to Newton's laws of motion and the concepts of centrifugal and coriolis force. (MDH)

14N Quadrupole Coupling in the Microwave Spectra of N-Vinylformamide

NASA Astrophysics Data System (ADS)

Kannengießer, Raphaela; Stahl, Wolfgang; Nguyen, Ha Vinh Lam; Bailey, William C.

2016-06-01

The microwave spectra of two conformers, trans and cis, of the title compound were recorded using two molecular beam Fourier transform microwave spectrometers operating in the frequency range 2 GHz to 40 GHz, and aimed at analysis of their 14N quadrupole hyperfine structures. Rotational constants, centrifugal distortion constants, and nuclear quadrupole coupling constants (NQCCs) χaa and χbb - χcc, were all determined with very high accuracy. Two fits including 176 and 117 hyperfine transitions were performed for the trans and cis conformers, respectively. Standard deviations of both fits are close to the measurement accuracy of 2 kHz. The NQCCs of the two conformers are almost exactly the same, and are compared with values found for other saturated and unsaturated formamides. Complementary quantum chemical calculations - MP2/6-311++G(d,p) rotational constants, MP2/cc-pVTZ centrifugal distortion constants, and B3PW91/6-311+G(d,p)//MP2/6-311++G(d,p) nuclear quadrupole coupling constants - give spectroscopic parameters in excellent agreement with the experimental parameters. B3PW91/6-311+G(d,p) calculated electric field gradients, in conjunction with eQ/h = 4.599(12) MHz/a.u., yields more reliable NQCCs for formamides possessing conjugated π-electron systems than does the B3PW91/6-311+G(df,pd) model recommended in Ref., whereas this latter performs better for aliphatic formamides. We conclude from this that f-polarization functions on heavy atoms hinder rather than help with modeling of conjugated π-electron systems. W. C. Bailey, Chem. Phys., 2000, 252, 57 W. C. Bailey, Calculation of Nuclear Quadrupole Coupling Constants in Gaseous State Molecules, http://nqcc.wcbailey.net/index.html.

The Role of Infertility Etiology in Success Rate of Intrauterine Insemination Cycles: An Evaluation of Predictive Factors for Pregnancy Rate

PubMed Central

Ashrafi, Mahnaz; Rashidi, Mandana; Ghasemi, Afsaneh; Arabipoor, Arezoo; Daghighi, Sara; Pourasghari, Parisa; Zolfaghari, Zahra

2013-01-01

Background: The objective of this study was to identify the prognostic factors that influence the outcome of ovarian stimulation with intrauterine insemination (IUI) cycles in couples with different infertility etiology. Materials and Methods: This retrospective study was performed in data of 1348 IUI cycles with ovarian stimulation by clomiphene citrate (CC) and/or gonadotropins in 632 women with five different infertility etiology subgroups at Akbarabbadi Hospital, Tehran, Iran. Results: The pregnancy rate (PR)/ cycle was highest (19.9%) among couples with unexplained infertility and lowest (10.6%) in couples with multiple factors infertility. In cases of unexplained infertility, the best PRs were seen after CC plus gonadotropins stimulation (26.3%) and with inseminated motile sperm count>30×106 (21.9%), but the tendency didn’t reach statistical significant. In the ovarian factor group, the best PRs were observed in women aged between 30 and 34 years (20.8%), with 2-3 preovulatory follicles (37.8%) and infertility duration between 1and 3 years (20.8%), while only infertility duration (p=0.03) and number of preovulatory follicles (p=0.01) were statistically significant. Multiple logistic regression analysis determined that number of preovulatory follicles (p=0.02), duration of infertility (p=0.015), age (p=0.019), infertility etiology (p=0.05) and stimulation regimen (p=0.01) were significant independent factors in order to predict overall clinical PR. Conclusion: The etiology of infertility is important to achieve remarkable IUI success. It is worth mentioning that within different etiologies of infertility, the demographic and cycles characteristics of couples did not show the same effect. Favorable variables for treatment success are as follows: age <40, duration of infertility ≤5 years and a cause of infertility except of multiple factors. PMID:24520471

The application of remote sensing for climate change adaptation in Sahel region

NASA Astrophysics Data System (ADS)

Deafalla, Taisser H. H.; Csaplovics, Elmar; El-Abbas, Mustafa M.

2014-10-01

In recent years, there is no doubt that global climate change (CC) has observable development impacts, which seriously threatens the ability of individuals and communities at all levels. During this process, the clear degradation in the situation of ecosystems has produced a global concern of the urgency to mitigate climate threats and related effects. Assessing the impacts and vulnerability of CC requires accurate, up-to-date and improved information. Coupled with the ready availability of historical remote sensing (RS) data, the reduction in data cost and increased resolution from satellite platforms, RS technology appears poised to make a great impact on planning agencies and providing better understanding the dynamics of the climate system, predict and mitigate the expected global changes and the effects on human civilization involved in mapping Land Use Land Cover (LU/LC) at a variety of spatial scales. This research was designed to study the impact of CC in conflict zones and potential flashpoints in Sudan namely Nuba Mountains, where the community in this area living in fragile and unstable conditions, which making them more vulnerable to the risk of violent conflict and CC effects. And to determine the factors that exacerbate vulnerability in the study area as well as to map and assess the LU/LC change during the period 1984 to 2011 covered the years (1999, 2002 and 2009). Multispectral satellite data (i.e. LANDSAT TM and TERRA ASTER) were used. Change detection techniques were applied to analyze the rate of changes, causal factors as well as the drivers of changes. Recent study showed the importance of spatial variables in tackling CC which promoted the use of maps made within a RS. In addition to provide an input for climate models; and thus plan adaptation strategies.

Reduced-cost linear-response CC2 method based on natural orbitals and natural auxiliary functions

PubMed Central

Mester, Dávid

2017-01-01

A reduced-cost density fitting (DF) linear-response second-order coupled-cluster (CC2) method has been developed for the evaluation of excitation energies. The method is based on the simultaneous truncation of the molecular orbital (MO) basis and the auxiliary basis set used for the DF approximation. For the reduction of the size of the MO basis, state-specific natural orbitals (NOs) are constructed for each excited state using the average of the second-order Møller–Plesset (MP2) and the corresponding configuration interaction singles with perturbative doubles [CIS(D)] density matrices. After removing the NOs of low occupation number, natural auxiliary functions (NAFs) are constructed [M. Kállay, J. Chem. Phys. 141, 244113 (2014)], and the NAF basis is also truncated. Our results show that, for a triple-zeta basis set, about 60% of the virtual MOs can be dropped, while the size of the fitting basis can be reduced by a factor of five. This results in a dramatic reduction of the computational costs of the solution of the CC2 equations, which are in our approach about as expensive as the evaluation of the MP2 and CIS(D) density matrices. All in all, an average speedup of more than an order of magnitude can be achieved at the expense of a mean absolute error of 0.02 eV in the calculated excitation energies compared to the canonical CC2 results. Our benchmark calculations demonstrate that the new approach enables the efficient computation of CC2 excitation energies for excited states of all types of medium-sized molecules composed of up to 100 atoms with triple-zeta quality basis sets. PMID:28527453

Suggestion for search of ethylene oxide (c-C2H4O) in a cosmic object

NASA Astrophysics Data System (ADS)

Sharma, M. K.; Sharma, M.; Chandra, S.

2018-05-01

Ethylene oxide (c-C2H4O) and its isomer acetaldehyde (CH3CHO) are important organic molecules because of their potential role in the formation of amino acids. The c-C2H4O molecule is a b-type asymmetric top molecule and owing to half-spin of each of the four hydrogen atoms, it has two distinct ortho (nuclear spin one) and para (nuclear spin zero and two) species. It has been detected in the Sgr B2N. Using the rotational and centrifugal distortion constants along with the electric dipole moment, we have calculated energies of 100 rotational levels of each of the ortho and para species of c-C2H4O molecule and the Einstein A-coefficients for radiative transitions between the levels. The values of Einstein A-coefficients along with the scaled values for the collisional rate coefficients are used for solving a set of statistical equilibrium equations coupled with the equations of radiative transfer. Brightness-temperatures of five rotational transitions of each of the ortho and para species of c-C2H4O molecule are investigated. Out of these ten transitions, three transitions are found to show the anomalous absorption and rest seven are found to show the emission feature. We have also investigated seven transitions observed unblended in the Sgr B2(N). We have found that the transitions 3_{3 0} - 3_{2 1} (23.134 GHz), 2_{2 0} - 2_{1 1} (15.603 GHz), 3_{3 1} - 3_{2 2} (39.680 GHz) and 1_{1 1} - 0_{0 0} (39.582 GHz) may play important role for the identification of ethylene oxide in a cosmic object.

Defect detection in slab surface: a novel dual Charge-coupled Device imaging-based fuzzy connectedness strategy.

PubMed

Zhao, Liming; Ouyang, Qi; Chen, Dengfu; Udupa, Jayaram K; Wang, Huiqian; Zeng, Yuebin

2014-11-01

To provide an accurate surface defects inspection system and make the automation of robust image segmentation method a reality in routine production line, a general approach is presented for continuous casting slab (CC-slab) surface defects extraction and delineation. The applicability of the system is not tied to CC-slab exclusively. We combined the line array CCD (Charge-coupled Device) traditional scanning imaging (LS-imaging) and area array CCD laser three-dimensional (3D) scanning imaging (AL-imaging) strategies in designing the system. Its aim is to suppress the respective imaging system's limitations. In the system, the images acquired from the two CCD sensors are carefully aligned in space and in time by maximum mutual information-based full-fledged registration schema. Subsequently, the image information is fused from these two subsystems such as the unbroken 2D information in LS-imaging and 3D depressed information in AL-imaging. Finally, on the basis of the established dual scanning imaging system the region of interest (ROI) localization by seed specification was designed, and the delineation for ROI by iterative relative fuzzy connectedness (IRFC) algorithm was utilized to get a precise inspection result. Our method takes into account the complementary advantages in the two common machine vision (MV) systems and it performs competitively with the state-of-the-art as seen from the comparison of experimental results. For the first time, a joint imaging scanning strategy is proposed for CC-slab surface defect inspection that allows a feasible way of powerful ROI delineation strategies to be applied to the MV inspection field. Multi-ROI delineation by using IRFC in this research field may further improve the results.

Correlation consistent basis sets for actinides. I. The Th and U atoms.

PubMed

Peterson, Kirk A

2015-02-21

New correlation consistent basis sets based on both pseudopotential (PP) and all-electron Douglas-Kroll-Hess (DKH) Hamiltonians have been developed from double- to quadruple-zeta quality for the actinide atoms thorium and uranium. Sets for valence electron correlation (5f6s6p6d), cc - pV nZ - PP and cc - pV nZ - DK3, as well as outer-core correlation (valence + 5s5p5d), cc - pwCV nZ - PP and cc - pwCV nZ - DK3, are reported (n = D, T, Q). The -PP sets are constructed in conjunction with small-core, 60-electron PPs, while the -DK3 sets utilized the 3rd-order Douglas-Kroll-Hess scalar relativistic Hamiltonian. Both series of basis sets show systematic convergence towards the complete basis set limit, both at the Hartree-Fock and correlated levels of theory, making them amenable to standard basis set extrapolation techniques. To assess the utility of the new basis sets, extensive coupled cluster composite thermochemistry calculations of ThFn (n = 2 - 4), ThO2, and UFn (n = 4 - 6) have been carried out. After accurately accounting for valence and outer-core correlation, spin-orbit coupling, and even Lamb shift effects, the final 298 K atomization enthalpies of ThF4, ThF3, ThF2, and ThO2 are all within their experimental uncertainties. Bond dissociation energies of ThF4 and ThF3, as well as UF6 and UF5, were similarly accurate. The derived enthalpies of formation for these species also showed a very satisfactory agreement with experiment, demonstrating that the new basis sets allow for the use of accurate composite schemes just as in molecular systems composed only of lighter atoms. The differences between the PP and DK3 approaches were found to increase with the change in formal oxidation state on the actinide atom, approaching 5-6 kcal/mol for the atomization enthalpies of ThF4 and ThO2. The DKH3 atomization energy of ThO2 was calculated to be smaller than the DKH2 value by ∼1 kcal/mol.

Histaminergic response to Coriolis stimulation: implication for transdermal scopolamine therapy of motion sickness.

PubMed

Wang, E T; Zhou, D R; He, L H

1992-07-01

The blood levels of histamine and 5-hydroxytryptamine (5-HT) in 10 subjects, with or without administration of the transdermal therapeutic system of scopolamine (TTS-S), were measured following motion sickness (MS) induced by Coriolis stimulation. Histamine and 5-HT were assayed using the fluorometric method. The results demonstrated that the blood levels of histamine increased significantly following MS and were even higher in the subjects using TTS-S, but we found neither significant changes in the blood levels of 5-HT following MS nor any effect of TTS-S on it. The results suggest that histamine contributes to the development of MS, and scopolamine may exert its anti-MS action by affecting the histaminergic system as well as the acetylcholinergic system; there may not be a definite relation between 5-HT and the development of MS.

Computational Fluid Dynamics Modeling of Rope-Guided Conveyances in Two Typical Kinds of Shaft Layouts

PubMed Central

Wu, Renyuan; Zhu, Zhencai; Cao, Guohua

2015-01-01

The behavior of rope-guided conveyances is so complicated that the rope-guided hoisting system hasn’t been understood thoroughly so far. In this paper, with user-defined functions loaded, ANSYS FLUENT 14.5 was employed to simulate lateral motion of rope-guided conveyances in two typical kinds of shaft layouts. With rope-guided mine elevator and mine cages taken into account, results show that the lateral aerodynamic buffeting force is much larger than the Coriolis force, and the side aerodynamic force have the same order of magnitude as the Coriolis force. The lateral aerodynamic buffeting forces should also be considered especially when the conveyance moves along the ventilation air direction. The simulation shows that the closer size of the conveyances can weaken the transverse aerodynamic buffeting effect. PMID:25679522

Spectroscopic studies of ozone in cryosolutions: FT-IR spectra of 16O3 in liquid nitrogen, oxygen, argon and krypton.

PubMed

Bulanin, Kirill M; Bulanin, Michael O; Rudakova, Aida V; Kolomijtsova, Tatiana D; Shchepkin, Dmitrij N

2018-03-15

We have measured and interpreted the IR spectra of ozone dissolved in liquid nitrogen, oxygen, argon, and krypton in the 650-4700cm -1 spectral region at 79-117K. Frequency shifts, band intensities and bandshapes of 22 spectral features of soluted ozone were analyzed. The bands of the А 1 symmetry have a complex contour and possess an excess intensity with respect to the value of the purely vibrational transition moment. It was found that this effect is related to the manifestation of the Coriolis interaction. The bandshape distortion manifests itself as an additional intensity from the side of the В 1 symmetry band being an intensity source in the case of the Coriolis interaction. Copyright © 2017. Published by Elsevier B.V.

High Reynolds number turbulence model of rotating shear flows

NASA Astrophysics Data System (ADS)

Masuda, S.; Ariga, I.; Koyama, H. S.

1983-09-01

A Reynolds stress closure model for rotating turbulent shear flows is developed. Special attention is paid to keeping the model constants independent of rotation. First, general forms of the model of a Reynolds stress equation and a dissipation rate equation are derived, the only restrictions of which are high Reynolds number and incompressibility. The model equations are then applied to two-dimensional equilibrium boundary layers and the effects of Coriolis acceleration on turbulence structures are discussed. Comparisons with the experimental data and with previous results in other external force fields show that there exists a very close analogy between centrifugal, buoyancy and Coriolis force fields. Finally, the model is applied to predict the two-dimensional boundary layers on rotating plane walls. Comparisons with existing data confirmed its capability of predicting mean and turbulent quantities without employing any empirical relations in rotating fields.

Approaching a realistic force balance in geodynamo simulations

PubMed Central

Yadav, Rakesh K.; Gastine, Thomas; Christensen, Ulrich R.; Wolk, Scott J.; Poppenhaeger, Katja

2016-01-01

Earth sustains its magnetic field by a dynamo process driven by convection in the liquid outer core. Geodynamo simulations have been successful in reproducing many observed properties of the geomagnetic field. However, although theoretical considerations suggest that flow in the core is governed by a balance between Lorentz force, rotational force, and buoyancy (called MAC balance for Magnetic, Archimedean, Coriolis) with only minute roles for viscous and inertial forces, dynamo simulations must use viscosity values that are many orders of magnitude larger than in the core, due to computational constraints. In typical geodynamo models, viscous and inertial forces are not much smaller than the Coriolis force, and the Lorentz force plays a subdominant role; this has led to conclusions that these simulations are viscously controlled and do not represent the physics of the geodynamo. Here we show, by a direct analysis of the relevant forces, that a MAC balance can be achieved when the viscosity is reduced to values close to the current practical limit. Lorentz force, buoyancy, and the uncompensated (by pressure) part of the Coriolis force are of very similar strength, whereas viscous and inertial forces are smaller by a factor of at least 20 in the bulk of the fluid volume. Compared with nonmagnetic convection at otherwise identical parameters, the dynamo flow is of larger scale and is less invariant parallel to the rotation axis (less geostrophic), and convection transports twice as much heat, all of which is expected when the Lorentz force strongly influences the convection properties. PMID:27790991

Morphodynamic modeling of a large inside sandbar and its dextral morphology in a convergent estuary: Qiantang Estuary, China

NASA Astrophysics Data System (ADS)

Xie, Dongfeng; Gao, Shu; Wang, Zheng Bing; Pan, Cunhong; Wu, Xiuguang; Wang, Qiushun

2017-08-01

We investigate the evolution of a large-scale sand body, a unique type of sandbars in a convergent estuary. Specifically, we analyze and simulate the sand deposition system (defined as an inside bar) in the Qiantang Estuary (QE) in China. The deposit is 130 km long and up to 10 m thick and is characterized by a dextral morphology in the lower QE. Numerical simulation is carried out using an idealized horizontal 2-D morphodynamic model mimicking the present QE settings. Our results indicate that the morphological evolution is controlled by the combination of river discharge and tides. The seasonal and interannual cycles of river discharges play a major role on the inside bar evolution. The bar is eroding during high river discharge periods, but accretion prevails during low river discharge periods. Meanwhile, the highest part of the sand body can move downstream or upstream by several kilometers, modifying the seasonal sediment exchange patterns. We also show that the Coriolis force plays an important role on the dextral morphology patterns in wide, convergent estuaries. It induces a significant lateral water level difference and a large-scale gyre of residual sediment transport. Subsequently, the seaward tail of the inside bar shifts southward to help create a condition for the development of tidal flats in the lower reach of the estuary. The lateral bed level differences induced by Coriolis force are up to several meters. Coriolis effects also modify the behavior of flood and ebb tidal channels.

Substitution and protonation effects on spin-spin coupling constants in prototypical aromatic rings: C6H6, C5H5N and C5H5P.

PubMed

Del Bene, Janet E; Elguero, José

2006-08-01

Ab initio equation-of-motion coupled cluster calculations have been carried out to evaluate one-, two-, and three-bond 13C-13C, 15N-13C, 31P-13C coupling constants in benzene, pyridine, pyridinium, phosphinine, and phosphininium. The introduction of N or P heteroatoms into the aromatic ring not only changes the magnitudes of the corresponding X-C coupling constants (J, for X = C, N, or P) but also the signs and magnitudes of corresponding reduced coupling constants (K). Protonation of the heteroatoms also produces dramatic changes in coupling constants and, by removing the lone pair of electrons from the sigma-electron framework, leads to the same signs for corresponding reduced coupling constants for benzene, pyridinium, and phosphininium. C-C coupling constants are rather insensitive to the presence of the heteroatoms and protonation. All terms that contribute to the total coupling constant (except for the diamagnetic spin-orbit (DSO) term) must be computed if good agreement with experimental data is to be obtained. Copyright 2006 John Wiley & Sons, Ltd.

A new efficient method for calculation of Frenkel exciton parameters in molecular aggregates

NASA Astrophysics Data System (ADS)

Plötz, Per-Arno; Niehaus, Thomas; Kühn, Oliver

2014-05-01

The Frenkel exciton Hamiltonian is at the heart of many simulations of excitation energy transfer in molecular aggregates. It separates the aggregate into Coulomb-coupled monomers. Here it is shown that the respective parameters, i.e., monomeric excitation energies and Coulomb couplings between transition densities can be efficiently calculated using time-dependent tight-binding-based density functional theory (TD-DFTB). Specifically, Coulomb couplings are expressed in terms of self-consistently determined Mulliken transition charges. The approach is applied to two dimer systems. First, formaldehyde oxime for which a detailed comparison with standard DFT using the B3LYP and the PBE functionals as well as with SCS-CC2 is provided. Second, the Coulomb coupling is explored in dependence on the intermolecular coordinates for a perylene bisimide dimer. This provides structural evidence for the previously observed biphasic aggregation behavior of this dye.

Multi-body dynamic coupling mechanism for generating throwing arm velocity during baseball pitching.

PubMed

Naito, Kozo; Takagi, Tokio; Kubota, Hideaki; Maruyama, Takeo

2017-08-01

The purpose of this study was to identify the detailed mechanism how the maximum throwing arm endpoint velocity is determined by the muscular torques and non-muscular interactive torques from the perspective of the dynamic coupling among the trunk, thorax and throwing and non-throwing arm segments. The pitching movements of ten male collegiate baseball pitchers were measured by a three-dimensional motion capture system. Using the induced-segmental velocity analysis (IVA) developed in this study, the maximum fingertip velocity of the throwing arm (MFV) was decomposed into each contribution of the muscular torques, passive motion-dependent torques due to gyroscopic moment, Coriolis force and centrifugal force, and other interactive torque components. The results showed that MFV (31.6±1.7m/s) was mainly attributed to two different mechanisms. The first is the passive motion-dependent effect on increasing the angular velocities of three joints (thorax rotation, elbow extension and wrist flexion). The second is the muscular torque effect of the shoulder internal rotation (IR) torque on generating IR angular velocity. In particular, the centrifugal force-induced elbow extension motion, which was the greatest contributor among individual joint contributions, was caused primarily by the angular velocity-dependent forces associated with the humerus, thorax, and trunk rotations. Our study also found that a compensatory mechanism was achieved by the negative and positive contributions of the muscular torque components. The current IVA is helpful to understand how the rapid throwing arm movement is determined by the dynamic coupling mechanism. Copyright © 2017 Elsevier B.V. All rights reserved.

The electronic structure of vanadium monochloride cation (VCl{sup +}): Tackling the complexities of transition metal species

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

DeYonker, Nathan J., E-mail: ndyonker@memphis.edu; Halfen, DeWayne T.; Ziurys, Lucy M.

Six electronic states (X {sup 4}Σ{sup −}, A {sup 4}Π, B {sup 4}Δ, {sup 2}Φ, {sup 2}Δ, {sup 2}Σ{sup +}) of the vanadium monochloride cation (VCl{sup +}) are described using large basis set coupled cluster theory. For the two lowest quartet states (X {sup 4}Σ{sup −} and A {sup 4}Π), a focal point analysis (FPA) approach was used that conjoined a correlation-consistent family of basis sets up to aug-cc-pwCV5Z-DK with high-order coupled cluster theory through pentuple (CCSDTQP) excitations. FPA adiabatic excitation energies (T{sub 0}) and spectroscopic constants (r{sub e}, r{sub 0}, B{sub e}, B{sub 0}, D{sup ¯}{sub e}, H{sub e},more » ω{sub e}, v{sub 0}, α{sub e}, ω{sub e}x{sub e}) were extrapolated to the valence complete basis set Douglas-Kroll (DK) aug-cc-pV∞Z-DK CCSDT level of theory, and additional treatments accounted for higher-order valence electron correlation, core correlation, and spin-orbit coupling. Due to the delicate interplay between dynamical and static electronic correlation, single reference coupled cluster theory is able to provide the correct ground electronic state (X {sup 4}Σ{sup −}), while multireference configuration interaction theory cannot. Perturbations from the first- and second-order spin orbit coupling of low-lying states with quartet spin multiplicity reveal an immensely complex rotational spectrum relative to the isovalent species VO, VS, and TiCl. Computational data on the doublet manifold suggest that the lowest-lying doublet state ({sup 2}Γ) has a T{sub e} of ∼11 200 cm{sup −1}. Overall, this study shows that laboratory and theoretical rotational spectroscopists must work more closely in tandem to better understand the bonding and structure of molecules containing transition metals.« less

Synthesis of polycyclic molecules by double C(sp2)-H/C(sp3)-H arylations with a single palladium catalyst.

PubMed

Pierre, Cathleen; Baudoin, Olivier

2011-04-01

Polycyclic molecules were obtained in good yields by double C(sp(2))-H/C(sp(3))-H arylations mediated by a single palladium/phosphine catalyst. Both double intermolecular/intramolecular and intramolecular/intramolecular C-C couplings were performed successfully, which indicates that this concept has a broad applicability for the rapid construction of molecular complexity.

Ab initio study of Fe(+)-benzyne

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.

1993-01-01

The interaction of Fe(+) with benzyne is studied using the self-consistent-field (SCF), complete active space SCF, and modified-coupled-pair functional levels of theory. The most stable structure is planar, where the Fe(+) has inserted into the in-plane pi bond, although the C-C bond distance suggests that some in-plane pi bonding remains. This system is compared with Sc(+) bonding to benzyne and other ligands.

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.

Geminal-spanning orbitals make explicitly correlated reduced-scaling coupled-cluster methods robust, yet simple

NASA Astrophysics Data System (ADS)

Pavošević, Fabijan; Neese, Frank; Valeev, Edward F.

2014-08-01

We present a production implementation of reduced-scaling explicitly correlated (F12) coupled-cluster singles and doubles (CCSD) method based on pair-natural orbitals (PNOs). A key feature is the reformulation of the explicitly correlated terms using geminal-spanning orbitals that greatly reduce the truncation errors of the F12 contribution. For the standard S66 benchmark of weak intermolecular interactions, the cc-pVDZ-F12 PNO CCSD F12 interaction energies reproduce the complete basis set CCSD limit with mean absolute error <0.1 kcal/mol, and at a greatly reduced cost compared to the conventional CCSD F12.

Construction of new biopolymer (chitosan)-based pincer-type Pd(II) complex and its catalytic application in Suzuki cross coupling reactions

NASA Astrophysics Data System (ADS)

Baran, Talat; Menteş, Ayfer

2017-04-01

In this paper we described the fabrication, characterization and application of a new biopolymer (chitosan)-based pincer-type Pd(II) catalyst in Suzuki cross coupling reactions using a non-toxic, cheap, eco-friendly and practical method. The catalytic activity tests showed remarkable product yields as well as TON (19800) and TOF (330000) values with a small catalyst loading. In addition, the catalyst indicated good recyclability in the Suzuki C-C reaction. This biopolymer supported catalyst can be used with various catalyst systems due to its unique properties, such as being inert, green in nature, low cost and chemically durable.

Physics in the laundromat

NASA Astrophysics Data System (ADS)

McDonald, Kirk T.

1998-03-01

The spin cycle of a washing machine involves motion that is stabilized by the Coriolis force, similar to the case of the motion of shafts of large turbines. This system is an example of a stable inverted pendulum.

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

Moore, II, Barry; Schrader, Robert L.; Kowalski, Karol

The longest-wavelength π-to-π* electronic excitations of rhodamine-like dyes (RDs) with different group16 heteroatoms (O, S, Se, Te) have been investigated. Time-dependent Kohn–Sham theory (TDKST) calculations were compared with coupled-cluster (CC) and equations-of-motion (EOM) CC results for π-to-π* singlet and triplet excitations. The RDs exhibit characteristics in the TDKST calculations that are very similar to previously investigated cyanine dyes, in the sense that the singlet energies obtained with nonhybrid functionals are too high compared with the CC results at the SD(T) level. The errors became increasingly larger for functionals with increasing amounts of exact exchange. TDKST with all tested functionals ledmore » to severe underestimations of the corresponding triplet excitations and overestimations of the singlet--triplet gaps. Long-range-corrected range-separated exchange and "optimal tuning" of the range separation parameter did not significantly improve the TDKST results. A detailed analysis suggests that the problem is differential electron correlation between the ground and excited states, which is not treated sufficiently by the relatively small integrals over the exchange-correlation response kernel that enters the excitation energy expression. As a result, numerical criteria are suggested that may help identify "cyanine-like" problems in TDKST calculations of excitation spectra.« less

Effect of cocoa's theobromine on intestinal microbiota of rats.

PubMed

Martín-Peláez, Sandra; Camps-Bossacoma, Mariona; Massot-Cladera, Malen; Rigo-Adrover, Mar; Franch, Àngels; Pérez-Cano, Francisco J; Castell, Margarida

2017-10-01

To establish the role of cocoa theobromine on gut microbiota composition and fermentation products after cocoa consumption in rats. Lewis rats were fed either a standard diet (RF diet), a diet containing 10% cocoa (CC diet) or a diet including 0.25% theobromine (TB diet) for 15 days. Gut microbiota (fluorescence in situ hybridization coupled to flow cytometry and metagenomics analysis), SCFA and IgA-coated bacteria were analyzed in fecal samples. CC and TB diets induced lower counts of E. coli whereas TB diet led to lower counts of Bifidobacterium spp., Streptococcus spp. and Clostridium histolyticum-C. perfingens group compared to RF diet. Metagenomics analysis also revealed a different microbiota pattern among the studied groups. The SCFA content was higher after both CC and TB diets, which was mainly due to enhanced butyric acid production. Furthermore, both diets decreased the proportion of IgA-coated bacteria. Cocoa's theobromine plays a relevant role in some effects related to cocoa intake, such as the lower proportion of IgA-coated bacteria. Moreover, theobromine modifies gut microbiota although other cocoa compounds could also act on intestinal bacteria, attenuating or enhancing the theobromine effects. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of cobalt doping level of ferrites in enhancing sensitivity of analytical performances of carbon paste electrode for simultaneous determination of catechol and hydroquinone.

PubMed

Lakić, Mladen; Vukadinović, Aleksandar; Kalcher, Kurt; Nikolić, Aleksandar S; Stanković, Dalibor M

2016-12-01

This work presents the simultaneous determination of catechol (CC) and hydroquinone (HQ), employing a modified carbon paste electrode (CPE) with ferrite nanomaterial. Ferrite nanomaterial was doped with different amount of cobalt and this was investigated toward simultaneous oxidation of CC and HQ. It was shown that this modification strongly increases electrochemical characteristics of the CPE. Also, electrocatalytic activity of such materials strongly depends on the level of substituted Co in the ferrite nanoparticles. The modified electrodes, labeled as CoFerrite/CPE, showed two pairs of well-defined redox peaks for the electrochemical processes of catechol and hydroquinone. Involving of ferrite material in the structure of CPE, cause increase in the potentials differences between redox couples of the investigated compounds, accompanied with increases in peaks currents. Several important parameters were optimized and calibration curves, with limits of detection (LOD) of 0.15 and 0.3µM for catechol and hydroquinone, respectively, were constructed by employing amperometric detection. Effect of possible interfering compounds was also studied, and proposed method was successfully applied for CC and HQ quantification in real samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Role of a Ubiquitously Expressed Receptor in the Vertebrate Olfactory System

PubMed Central

DeMaria, Shannon; Berke, Allison P.; Van Name, Eric; Heravian, Anisa; Ferreira, Todd

2013-01-01

Odorant cues are recognized by receptors expressed on olfactory sensory neurons, the primary sensory neurons of the olfactory epithelium. Odorant receptors typically obey the “one receptor, one neuron” rule, in which the receptive field of the olfactory neuron is determined by the singular odorant receptor that it expresses. Odor-evoked receptor activity across the population of olfactory neurons is then interpreted by the brain to identify the molecular nature of the odorant stimulus. In the present study, we characterized the properties of a C family G-protein-coupled receptor that, unlike most other odorant receptors, is expressed in a large population of microvillous sensory neurons in the zebrafish olfactory epithelium and the mouse vomeronasal organ. We found that this receptor, OlfCc1 in zebrafish and its murine ortholog Vmn2r1, is a calcium-dependent, low-sensitivity receptor specific for the hydrophobic amino acids isoleucine, leucine, and valine. Loss-of-function experiments in zebrafish embryos demonstrate that OlfCc1 is required for olfactory responses to a diverse mixture of polar, nonpolar, acidic, and basic amino acids. OlfCc1 was also found to promote localization of other OlfC receptor family members to the plasma membrane in heterologous cells. Together, these results suggest that the broadly expressed OlfCc1 is required for amino acid detection by the olfactory system and suggest that it plays a role in the function and/or intracellular trafficking of other olfactory and vomeronasal receptors with which it is coexpressed. PMID:24048853

Trace analysis of glyphosate in water by capillary electrophoresis on a chip with high sample volume loadability.

PubMed

Horčičiak, Michal; Masár, Marián; Bodor, Róbert; Danč, Ladislav; Bel, Peter

2012-03-01

A new method for the determination of trace glyphosate (GLYP), non-selective pesticide, by CZE with online ITP pre-treatment of drinking waters on a column-coupling (CC) chip has been developed. CC chip was equipped with two injection channels of 0.9 and 9.9 μL volumes, two separation channels of 9.3 μL total volume and a pair of conductivity detectors. A very effective ITP sample clean-up performed in the first channel at low pH (3.2) was introduced for quick CZE resolution and detection of GLYP carried out at higher pH (6.1) in the second channel on the CC chip. The LOD for GLYP was estimated at 2.5 μg/L (15 nmol/L) using a 9.9 |mL volume of the injection channel. ITP-CZE analyses of model and real samples have provided very favorable intra-day (0.1-1.2% RSD) and inter-day (2.9% RSD) repeatabilities of the migration time for GLYP while 0.2-6.9% RSD values were typical for the peak area data. Recoveries of GLYP in spiked drinking water varied in the range of 99-109%. A minimum pre-treatment of drinking water (degassing and dilution) and a short analysis time (ca. 10 min) were distinctive features of ITP-CZE determinations of GLYP on the CC chip with high sample volume loaded, as well. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gaussian basis sets for use in correlated molecular calculations. XI. Pseudopotential-based and all-electron relativistic basis sets for alkali metal (K-Fr) and alkaline earth (Ca-Ra) elements

NASA Astrophysics Data System (ADS)

Hill, J. Grant; Peterson, Kirk A.

2017-12-01

New correlation consistent basis sets based on pseudopotential (PP) Hamiltonians have been developed from double- to quintuple-zeta quality for the late alkali (K-Fr) and alkaline earth (Ca-Ra) metals. These are accompanied by new all-electron basis sets of double- to quadruple-zeta quality that have been contracted for use with both Douglas-Kroll-Hess (DKH) and eXact 2-Component (X2C) scalar relativistic Hamiltonians. Sets for valence correlation (ms), cc-pVnZ-PP and cc-pVnZ-(DK,DK3/X2C), in addition to outer-core correlation [valence + (m-1)sp], cc-p(w)CVnZ-PP and cc-pwCVnZ-(DK,DK3/X2C), are reported. The -PP sets have been developed for use with small-core PPs [I. S. Lim et al., J. Chem. Phys. 122, 104103 (2005) and I. S. Lim et al., J. Chem. Phys. 124, 034107 (2006)], while the all-electron sets utilized second-order DKH Hamiltonians for 4s and 5s elements and third-order DKH for 6s and 7s. The accuracy of the basis sets is assessed through benchmark calculations at the coupled-cluster level of theory for both atomic and molecular properties. Not surprisingly, it is found that outer-core correlation is vital for accurate calculation of the thermodynamic and spectroscopic properties of diatomic molecules containing these elements.

Unraveling torsional bath interactions with the CO stretching state in methanol

NASA Astrophysics Data System (ADS)

Pearson, John C.; Daly, Adam M.; Lees, Ronald M.

2015-12-01

Quantum mechanical models describing the effects of a C3 internal rotor have been successful in modeling all the torsional manifolds of isolated vibrational states. However, modeling the coupling between nearly degenerate small amplitude vibrations in the C3 internal rotation case remains far from satisfactory and a variety of practical and fundamental questions persist on basis sets, the relative importance of effects and how the problem should be approached. The ν8 C-O stretching state of methanol has been well studied with infrared techniques and has the potential to serve as an experimental reference data set for the development of models for the coupled large and small amplitude motion case. A combined infrared-microwave study of the lowest K A-states of vt = 3, vt = 4 and ν8 has been performed to understand the nature of the interactions between ν8 the excited torsional states. The interaction between vt = 4 and ν8 at K = 0+ has been confirmed to be Fermi type with magnitude of 2.5 cm-1. Additionally, the fundamental a-symmetry and b-symmetry Coriolis interactions between vt = 3 and ν8 have been estimated to be 8900 MHz and -360 MHz, respectively. The magnitude of these interactions suggests that modeling the ν8 state, the vt = 3 state, and the vt = 4 states will have to carefully account for these interactions.

Reynolds Stress Closure for Inertial Frames and Rotating Frames

NASA Astrophysics Data System (ADS)

Petty, Charles; Benard, Andre

2017-11-01

In a rotating frame-of-reference, the Coriolis acceleration and the mean vorticity field have a profound impact on the redistribution of kinetic energy among the three components of the fluctuating velocity. Consequently, the normalized Reynolds (NR) stress is not objective. Furthermore, because the Reynolds stress is defined as an ensemble average of a product of fluctuating velocity vector fields, its eigenvalues must be non-negative for all turbulent flows. These fundamental properties (realizability and non-objectivity) of the NR-stress cannot be compromised in computational fluid dynamic (CFD) simulations of turbulent flows in either inertial frames or in rotating frames. The recently developed universal realizable anisotropic prestress (URAPS) closure for the NR-stress depends explicitly on the local mean velocity gradient and the Coriolis operator. The URAPS-closure is a significant paradigm shift from turbulent closure models that assume that dyadic-valued operators associated with turbulent fluctuations are objective.

Automated centrifugal-microfluidic platform for DNA purification using laser burst valve and coriolis effect.

PubMed

Choi, Min-Seong; Yoo, Jae-Chern

2015-04-01

We report a fully automated DNA purification platform with a micropored membrane in the channel utilizing centrifugal microfluidics on a lab-on-a-disc (LOD). The microfluidic flow in the LOD, into which the reagents are injected for DNA purification, is controlled by a single motor and laser burst valve. The sample and reagents pass successively through the micropored membrane in the channel when each laser burst valve is opened. The Coriolis effect is used by rotating the LOD bi-directionally to increase the purity of the DNA, thereby preventing the mixing of the waste and elution solutions. The total process from the lysed sample injection into the LOD to obtaining the purified DNA was finished within 7 min with only one manual step. The experimental result for Salmonella shows that the proposed microfluidic platform is comparable to the existing devices in terms of the purity and yield of DNA.