Stochastic many-body perturbation theory for anharmonic molecular vibrations

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

Hermes, Matthew R.; Hirata, So, E-mail: sohirata@illinois.edu; CREST, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012

2014-08-28

A new quantum Monte Carlo (QMC) method for anharmonic vibrational zero-point energies and transition frequencies is developed, which combines the diagrammatic vibrational many-body perturbation theory based on the Dyson equation with Monte Carlo integration. The infinite sums of the diagrammatic and thus size-consistent first- and second-order anharmonic corrections to the energy and self-energy are expressed as sums of a few m- or 2m-dimensional integrals of wave functions and a potential energy surface (PES) (m is the vibrational degrees of freedom). Each of these integrals is computed as the integrand (including the value of the PES) divided by the value ofmore » a judiciously chosen weight function evaluated on demand at geometries distributed randomly but according to the weight function via the Metropolis algorithm. In this way, the method completely avoids cumbersome evaluation and storage of high-order force constants necessary in the original formulation of the vibrational perturbation theory; it furthermore allows even higher-order force constants essentially up to an infinite order to be taken into account in a scalable, memory-efficient algorithm. The diagrammatic contributions to the frequency-dependent self-energies that are stochastically evaluated at discrete frequencies can be reliably interpolated, allowing the self-consistent solutions to the Dyson equation to be obtained. This method, therefore, can compute directly and stochastically the transition frequencies of fundamentals and overtones as well as their relative intensities as pole strengths, without fixed-node errors that plague some QMC. It is shown that, for an identical PES, the new method reproduces the correct deterministic values of the energies and frequencies within a few cm{sup −1} and pole strengths within a few thousandths. With the values of a PES evaluated on the fly at random geometries, the new method captures a noticeably greater proportion of anharmonic effects.« less

Towards an automated and efficient calculation of resonating vibrational states based on state-averaged multiconfigurational approaches

NASA Astrophysics Data System (ADS)

Meier, Patrick; Oschetzki, Dominik; Pfeiffer, Florian; Rauhut, Guntram

2015-12-01

Resonating vibrational states cannot consistently be described by single-reference vibrational self-consistent field methods but request the use of multiconfigurational approaches. Strategies are presented to accelerate vibrational multiconfiguration self-consistent field theory and subsequent multireference configuration interaction calculations in order to allow for routine calculations at this enhanced level of theory. State-averaged vibrational complete active space self-consistent field calculations using mode-specific and state-tailored active spaces were found to be very fast and superior to state-specific calculations or calculations with a uniform active space. Benchmark calculations are presented for trans-diazene and bromoform, which show strong resonances in their vibrational spectra.

Towards an automated and efficient calculation of resonating vibrational states based on state-averaged multiconfigurational approaches

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

Meier, Patrick; Oschetzki, Dominik; Pfeiffer, Florian

Resonating vibrational states cannot consistently be described by single-reference vibrational self-consistent field methods but request the use of multiconfigurational approaches. Strategies are presented to accelerate vibrational multiconfiguration self-consistent field theory and subsequent multireference configuration interaction calculations in order to allow for routine calculations at this enhanced level of theory. State-averaged vibrational complete active space self-consistent field calculations using mode-specific and state-tailored active spaces were found to be very fast and superior to state-specific calculations or calculations with a uniform active space. Benchmark calculations are presented for trans-diazene and bromoform, which show strong resonances in their vibrational spectra.

Vibration monitoring via nano-composite piezoelectric foam bushings

NASA Astrophysics Data System (ADS)

Bird, Evan T.; Merrell, A. Jake; Anderson, Brady K.; Newton, Cory N.; Rosquist, Parker G.; Fullwood, David T.; Bowden, Anton E.; Seeley, Matthew K.

2016-11-01

Most mechanical systems produce vibrations as an inherent side effect of operation. Though some vibrations are acceptable in operation, others can cause damage or signal a machine’s imminent failure. These vibrations would optimally be monitored in real-time, without human supervision to prevent failure and excessive wear in machinery. This paper explores a new alternative to currently-used machine-monitoring equipment, namely a piezoelectric foam sensor system. These sensors are made of a silicone-based foam embedded with nano- and micro-scale conductive particles. Upon impact, they emit an electric response that is directly correlated with impact energy, with no electrical power input. In the present work, we investigated their utility as self-sensing bushings on machinery. These sensors were found to accurately detect both the amplitude and frequency of typical machine vibrations. The bushings could potentially save time and money over other vibration sensing mechanisms, while simultaneously providing a potential control input that could be utilized for correcting vibrational imbalance.

A new compound control method for sine-on-random mixed vibration test

NASA Astrophysics Data System (ADS)

Zhang, Buyun; Wang, Ruochen; Zeng, Falin

2017-09-01

Vibration environmental test (VET) is one of the important and effective methods to provide supports for the strength design, reliability and durability test of mechanical products. A new separation control strategy was proposed to apply in multiple-input multiple-output (MIMO) sine on random (SOR) mixed mode vibration test, which is the advanced and intensive test type of VET. As the key problem of the strategy, correlation integral method was applied to separate the mixed signals which included random and sinusoidal components. The feedback control formula of MIMO linear random vibration system was systematically deduced in frequency domain, and Jacobi control algorithm was proposed in view of the elements, such as self-spectrum, coherence, and phase of power spectral density (PSD) matrix. Based on the excessive correction of excitation in sine vibration test, compression factor was introduced to reduce the excitation correction, avoiding the destruction to vibration table or other devices. The two methods were synthesized to be applied in MIMO SOR vibration test system. In the final, verification test system with the vibration of a cantilever beam as the control object was established to verify the reliability and effectiveness of the methods proposed in the paper. The test results show that the exceeding values can be controlled in the tolerance range of references accurately, and the method can supply theory and application supports for mechanical engineering.

Vibrational multiconfiguration self-consistent field theory: implementation and test calculations.

PubMed

Heislbetz, Sandra; Rauhut, Guntram

2010-03-28

A state-specific vibrational multiconfiguration self-consistent field (VMCSCF) approach based on a multimode expansion of the potential energy surface is presented for the accurate calculation of anharmonic vibrational spectra. As a special case of this general approach vibrational complete active space self-consistent field calculations will be discussed. The latter method shows better convergence than the general VMCSCF approach and must be considered the preferred choice within the multiconfigurational framework. Benchmark calculations are provided for a small set of test molecules.

Understanding the Origins of Dipolar Couplings and Correlated Motion in the Vibrational Spectrum of Water.

PubMed

Heyden, Matthias; Sun, Jian; Forbert, Harald; Mathias, Gerald; Havenith, Martina; Marx, Dominik

2012-08-16

The combination of vibrational spectroscopy and molecular dynamics simulations provides a powerful tool to obtain insights into the molecular details of water structure and dynamics in the bulk and in aqueous solutions. Applying newly developed approaches to analyze correlations of charge currents, molecular dipole fluctuations, and vibrational motion in real and k-space, we compare results from nonpolarizable water models, widely used in biomolecular modeling, to ab initio molecular dynamics. For the first time, we unfold the infrared response of bulk water into contributions from correlated fluctuations in the three-dimensional, anisotropic environment of an average water molecule, from the OH-stretching region down to the THz regime. Our findings show that the absence of electronic polarizability in the force field model not only results in differences in dipolar couplings and infrared absorption but also induces artifacts into the correlated vibrational motion between hydrogen-bonded water molecules, specifically at the intramolecular bending frequency. Consequently, vibrational motion is partially ill-described with implications for the accuracy of non-self-consistent, a posteriori methods to add polarizability.

Bonding in the first-row diatomic molecules within the local spin-density approximation

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

Painter, G.S.; Averill, F.W.

1982-08-15

The Hohenberg-Kohn-Sham density-functional equations in the local spin-density approximation (LSDA) have been solved with essentially no loss of accuracy for dimers of the first row of the Periodic Table with the use of a fully-self-consistent spin-polarized Gaussian-orbital approach. Spectroscopic constants (binding energies, equilibrium separations, and ground-state vibrational frequencies) have been derived from the calculated potential-energy curves. Intercomparison of results obtained using the exchange-correlation functionals of Slater (scaled exchange or X..cap alpha..), Gunnarsson and Lundqvist (GL), and Vosko, Wilk, and Nusair (VWN) permits assessment of the relative merits of each and serves to identify general shortcomings in the LSDA. Basic trendsmore » are similar for each functional, but the treatment of the spin dependence of the exchange-correlation energy in the GL and VWN functionals yields a variation of the binding energy across the series which is more systematic than that in the X..cap alpha.. approximation. Agreement between the present results and those of Dunlap, Connolly, and Sabin in the X..cap alpha.., approximation confirms the accuracy of the variational charge-density-fit procedure used in the latter work. The refinements in correlation treatment within the VWN functional are reflected in improvements in binding energies which are only slight for most dimers in the series. This behavior is attributed to the error remaining in the exchange channel within the LSDA and demonstrates the necessity for self-interaction corrections for more accurate binding-energy determinations. Within the current LSDA, absolute accuracies of the VWN functional for the first-row dimers are within 2.3 eV for binding energies, 0.07 a.u. for bond lengths, and approx.200 cm/sup -1/ for vibrational frequencies.« less

Hybrid configuration mixing model for odd nuclei

NASA Astrophysics Data System (ADS)

Colò, G.; Bortignon, P. F.; Bocchi, G.

2017-03-01

In this work, we introduce a new approach which is meant to be a first step towards complete self-consistent low-lying spectroscopy of odd nuclei. So far, we essentially limit ourselves to the description of a double-magic core plus an extra nucleon. The model does not contain any free adjustable parameter and is instead based on a Hartree-Fock (HF) description of the particle states in the core, together with self-consistent random-phase approximation (RPA) calculations for the core excitations. We include both collective and noncollective excitations, with proper care of the corrections due to the overlap between them (i.e., due to the nonorthonormality of the basis). As a consequence, with respect to traditional particle-vibration coupling calculations in which one can only address single-nucleon states and particle-vibration multiplets, we can also describe states of shell-model types like 2 particle-1 hole. We will report results for 49Ca and 133Sb and discuss future perspectives.

Rigorous Model Reduction for a Damped-Forced Nonlinear Beam Model: An Infinite-Dimensional Analysis

NASA Astrophysics Data System (ADS)

Kogelbauer, Florian; Haller, George

2018-06-01

We use invariant manifold results on Banach spaces to conclude the existence of spectral submanifolds (SSMs) in a class of nonlinear, externally forced beam oscillations. SSMs are the smoothest nonlinear extensions of spectral subspaces of the linearized beam equation. Reduction in the governing PDE to SSMs provides an explicit low-dimensional model which captures the correct asymptotics of the full, infinite-dimensional dynamics. Our approach is general enough to admit extensions to other types of continuum vibrations. The model-reduction procedure we employ also gives guidelines for a mathematically self-consistent modeling of damping in PDEs describing structural vibrations.

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

Bleiziffer, Patrick, E-mail: patrick.bleiziffer@fau.de; Krug, Marcel; Görling, Andreas

A self-consistent Kohn-Sham method based on the adiabatic-connection fluctuation-dissipation (ACFD) theorem, employing the frequency-dependent exact exchange kernel f{sub x} is presented. The resulting SC-exact-exchange-only (EXX)-ACFD method leads to even more accurate correlation potentials than those obtained within the direct random phase approximation (dRPA). In contrast to dRPA methods, not only the Coulomb kernel but also the exact exchange kernel f{sub x} is taken into account in the EXX-ACFD correlation which results in a method that, unlike dRPA methods, is free of self-correlations, i.e., a method that treats exactly all one-electron systems, like, e.g., the hydrogen atom. The self-consistent evaluation ofmore » EXX-ACFD total energies improves the accuracy compared to EXX-ACFD total energies evaluated non-self-consistently with EXX or dRPA orbitals and eigenvalues. Reaction energies of a set of small molecules, for which highly accurate experimental reference data are available, are calculated and compared to quantum chemistry methods like Møller-Plesset perturbation theory of second order (MP2) or coupled cluster methods [CCSD, coupled cluster singles, doubles, and perturbative triples (CCSD(T))]. Moreover, we compare our methods to other ACFD variants like dRPA combined with perturbative corrections such as the second order screened exchange corrections or a renormalized singles correction. Similarly, the performance of our EXX-ACFD methods is investigated for the non-covalently bonded dimers of the S22 reference set and for potential energy curves of noble gas, water, and benzene dimers. The computational effort of the SC-EXX-ACFD method exhibits the same scaling of N{sup 5} with respect to the system size N as the non-self-consistent evaluation of only the EXX-ACFD correlation energy; however, the prefactor increases significantly. Reaction energies from the SC-EXX-ACFD method deviate quite little from EXX-ACFD energies obtained non-self-consistently with dRPA orbitals and eigenvalues, and the deviation reduces even further if the Coulomb kernel is scaled by a factor of 0.75 in the dRPA to reduce self-correlations in the dRPA correlation potential. For larger systems, such a non-self-consistent EXX-ACFD method is a competitive alternative to high-level wave-function-based methods, yielding higher accuracy than MP2 and CCSD methods while exhibiting a better scaling of the computational effort than CCSD or CCSD(T) methods. Moreover, EXX-ACFD methods were shown to be applicable in situation characterized by static correlation.« less

Experiences with nonsynchronous forced vibration in centrifugal compressors

NASA Technical Reports Server (NTRS)

Smith, D. R.; Wachel, J. C.

1984-01-01

The high subsynchronous vibrations which are often forced vibrations caused by flow instabilities, such as stage stall were examined. Modifications to improve the rotor stability by changing the bearings or seals have little effects on the subsynchronous vibrations. Understanding of the differences between forced vibrations and self excited vibrations to properly diagnose the problem and to correct it, is recommended. A list of characteristics of the two types of subsynchronous vibration is presented.

First-row diatomics: Calculation of the geometry and energetics using self-consistent gradient-functional approximations

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

Kutzler, F.W.; Painter, G.S.

1992-02-15

A fully self-consistent series of nonlocal (gradient) density-functional calculations has been carried out using the augmented-Gaussian-orbital method to determine the magnitude of gradient corrections to the potential-energy curves of the first-row diatomics, Li{sub 2} through F{sub 2}. Both the Langreth-Mehl-Hu and the Perdew-Wang gradient-density functionals were used in calculations of the binding energy, bond length, and vibrational frequency for each dimer. Comparison with results obtained in the local-spin-density approximation (LSDA) using the Vosko-Wilk-Nusair functional, and with experiment, reveals that bond lengths and vibrational frequencies are rather insensitive to details of the gradient functionals, including self-consistency effects, but the gradient correctionsmore » reduce the overbinding commonly observed in the LSDA calculations of first-row diatomics (with the exception of Li{sub 2}, the gradient-functional binding-energy error is only 50--12 % of the LSDA error). The improved binding energies result from a large differential energy lowering, which occurs in open-shell atoms relative to the diatomics. The stabilization of the atom arises from the use of nonspherical charge and spin densities in the gradient-functional calculations. This stabilization is negligibly small in LSDA calculations performed with nonspherical densities.« less

Spectroscopic properties of nuclear skyrme energy density functionals.

PubMed

Tarpanov, D; Dobaczewski, J; Toivanen, J; Carlsson, B G

2014-12-19

We address the question of how to improve the agreement between theoretical nuclear single-particle energies (SPEs) and observations. Empirically, in doubly magic nuclei, the SPEs can be deduced from spectroscopic properties of odd nuclei that have one more or one less neutron or proton. Theoretically, bare SPEs, before being confronted with observations, must be corrected for the effects of the particle vibration coupling (PVC). In the present work, we determine the PVC corrections in a fully self-consistent way. Then, we adjust the SPEs, with PVC corrections included, to empirical data. In this way, the agreement with observations, on average, improves; nevertheless, large discrepancies still remain. We conclude that the main source of disagreement is still in the underlying mean fields, and not in including or neglecting the PVC corrections.

Study on the spectroscopic parameters and transition probabilities of 25 low-lying states of the AlC+ cation

NASA Astrophysics Data System (ADS)

Zhang, Jicai; Shi, Deheng; Xing, Wei; Sun, Jinfeng; Zhu, Zunlue

2017-11-01

This paper investigates the spectroscopic parameters and transition probabilities of 25 low-lying states, which come from the first five dissociation channels of AlC+ cation. The potential energy curves are calculated with the complete active space self-consistent field method, which is followed by the valence internally contracted multireference configuration interaction approach with Davidson correction. Of these 25 states, only the 35Σ-state is repulsive; the c1Σ+, f1Π, and 15Π states have the double well; the first well of c1Σ+ state and the second well of 15Π state are very weakly bound; the first well of c1Σ+ state has no vibrational levels; the 25Π state and the double well of f1Π state have only several vibrational states; the B3Σ-, E3Σ+, D3Π, 15Σ+, 25Σ-, and 15Π states are inverted when the spin-orbit coupling effect is included. The avoided crossings exist between the B3Σ- and 33Σ- states, the c1Σ+ and d1Σ+ states, the f1Π and 31Π states, the 15Π and 25Π states, as well as the 25Π and 35Π states. Core-valence correlation and scalar relativistic corrections are considered. The extrapolation of potential energies to the complete basis set limit is done. The spectroscopic parameters and vibrational levels are determined for all the Λ-S and Ω bound states. The transition dipole moments are calculated. Franck-Condon factors of a great number of electronic transitions are evaluated. On the whole, the spin-orbit coupling effect on the spectroscopic parameters and vibrational levels is small except for very few states. The results determined in this paper could provide some powerful guidelines to observe these states in a spectroscopy experiment.

An ab initio global potential-energy surface for NH2(A(2)A') and vibrational spectrum of the Renner-Teller A(2)A'-X(2)A" system.

PubMed

Zhou, Shulan; Li, Zheng; Xie, Daiqian; Lin, Shi Ying; Guo, Hua

2009-05-14

A global potential-energy surface for the first excited electronic state of NH(2)(A(2)A(')) has been constructed by three-dimensional cubic spline interpolation of more than 20,000 ab initio points, which were calculated at the multireference configuration-interaction level with the Davidson correction using the augmented correlation-consistent polarized valence quadruple-zeta basis set. The (J=0) vibrational energy levels for the ground (X(2)A(")) and excited (A(2)A(')) electronic states of NH(2) were calculated on our potential-energy surfaces with the diagonal Renner-Teller terms. The results show a good agreement with the experimental vibrational frequencies of NH(2) and its isotopomers.

Self-consistent Non-LTE Model of Infrared Molecular Emissions and Oxygen Dayglows in the Mesosphere and Lower Thermosphere

NASA Technical Reports Server (NTRS)

Feofilov, Artem G.; Yankovsky, Valentine A.; Pesnell, William D.; Kutepov, Alexander A.; Goldberg, Richard A.; Mauilova, Rada O.

2007-01-01

We present the new version of the ALI-ARMS (for Accelerated Lambda Iterations for Atmospheric Radiation and Molecular Spectra) model. The model allows simultaneous self-consistent calculating the non-LTE populations of the electronic-vibrational levels of the O3 and O2 photolysis products and vibrational level populations of CO2, N2,O2, O3, H2O, CO and other molecules with detailed accounting for the variety of the electronic-vibrational, vibrational-vibrational and vibrational-translational energy exchange processes. The model was used as the reference one for modeling the O2 dayglows and infrared molecular emissions for self-consistent diagnostics of the multi-channel space observations of MLT in the SABER experiment It also allows reevaluating the thermalization efficiency of the absorbed solar ultraviolet energy and infrared radiative cooling/heating of MLT by detailed accounting of the electronic-vibrational relaxation of excited photolysis products via the complex chain of collisional energy conversion processes down to the vibrational energy of optically active trace gas molecules.

Application of least mean square algorithm to suppression of maglev track-induced self-excited vibration

NASA Astrophysics Data System (ADS)

Zhou, D. F.; Li, J.; Hansen, C. H.

2011-11-01

Track-induced self-excited vibration is commonly encountered in EMS (electromagnetic suspension) maglev systems, and a solution to this problem is important in enabling the commercial widespread implementation of maglev systems. Here, the coupled model of the steel track and the magnetic levitation system is developed, and its stability is investigated using the Nyquist criterion. The harmonic balance method is employed to investigate the stability and amplitude of the self-excited vibration, which provides an explanation of the phenomenon that track-induced self-excited vibration generally occurs at a specified amplitude and frequency. To eliminate the self-excited vibration, an improved LMS (Least Mean Square) cancellation algorithm with phase correction (C-LMS) is employed. The harmonic balance analysis shows that the C-LMS cancellation algorithm can completely suppress the self-excited vibration. To achieve adaptive cancellation, a frequency estimator similar to the tuner of a TV receiver is employed to provide the C-LMS algorithm with a roughly estimated reference frequency. Numerical simulation and experiments undertaken on the CMS-04 vehicle show that the proposed adaptive C-LMS algorithm can effectively eliminate the self-excited vibration over a wide frequency range, and that the robustness of the algorithm suggests excellent potential for application to EMS maglev systems.

The GaOH-HGaO potential energy hypersurface and the necessity of correlating the 3d electrons

NASA Astrophysics Data System (ADS)

Richards, Claude A., Jr.; Yamaguchi, Yukio; Kim, Seung-Joon; Schaefer, Henry F., III

1996-06-01

The ground state potential energy hypersurface of the GaOH-HGaO system has been investigated using high level ab initio molecular electronic structure theory. The geometries and physical properties of two equilibrium structures, one isomerization transition state and one inversion transition state were determined at the self-consistent field (SCF), configuration interaction with single and double excitations (CISD), coupled cluster with single and double excitations (CCSD), and CCSD with perturbative triple excitations [CCSD(T)] levels of theory with four sets of basis functions. It has been found that freezing the 3d electrons of the Ga atom in the correlation procedures is not appropriate for this system. For the energy difference ΔE (GaOH-HGaO) the freezing of the 3d electrons results in an error of 25 kcal/mol! The dipole moments, harmonic vibrational frequencies, and infrared (IR) intensities are predicted for the four stationary points. At the highest level of theory employed in this study, CCSD(T) using triple zeta plus double polarization with higher angular momentum and diffuse functions [TZ2P(f,d)+diff] basis set, the bent GaOH was found to be 41.9 kcal/mol more stable than the linear HGaO species; with the zero-point vibrational energy (ZPVE) correction, the energy separation becomes 40.4 kcal/mol. The classical barrier height for the exothermic isomerization (1,2 hydrogen shift) reaction HGaO→GaOH is determined to be 44.5 kcal/mol and the barrier height with the ZPVE correction 42.3 kcal/mol. The classical barrier to linearity for the bent GaOH molecule is determined to be 1.7 kcal/mol and the barrier height with the ZPVE correction to be 1.2 kcal/mol. The predicted dipole moments of GaOH and HGaO are 1.41 and 4.45 Debye, respectively. The effects of electron correlation reduce the dipole moment of HGaO by the sizable amount of 1.2 Debye. The two equilibrium species may be suitable for microwave spectroscopic investigation. Furthermore, they may also be detectable by IR techniques due to the relatively large intensities of their vibrational modes. The geometrical and energetic features are compared with those of the valence isoelectronic HXO-XOH systems, where X is a group IIIA atom and the HXO+-XOH+ systems, where X is a group IVA atom.

Theoretical study on the dissociation energies, ionization potentials and electron affinities of three perfluoroalkyl iodides

NASA Astrophysics Data System (ADS)

Cheng, Li; Shen, Zuochun; Lu, Jianye; Gao, Huide; Lü, Zhiwei

2005-11-01

Dissociation energies, ionization potentials and electron affinities of three perfluoroalkyl iodides, CF 3I, C 2F 5I, and i-C 3F 7I are calculated accurately with B3LYP, MP n ( n = 2-4), QCISD, QCISD(T), CCSD, and CCSD(T) methods. Calculations are performed by using large-core correlation-consistent pseudopotential basis set (SDB-aug-cc-pVTZ) for iodine atom. In all energy calculations, the zero point vibration energy is corrected. And the basis set superposition error is corrected by counterpoise method in the calculation of dissociation energy. Theoretical results are compared with the experimental values.

Self-Consistent Optimization of Excited States within Density-Functional Tight-Binding.

PubMed

Kowalczyk, Tim; Le, Khoa; Irle, Stephan

2016-01-12

We present an implementation of energies and gradients for the ΔDFTB method, an analogue of Δ-self-consistent-field density functional theory (ΔSCF) within density-functional tight-binding, for the lowest singlet excited state of closed-shell molecules. Benchmarks of ΔDFTB excitation energies, optimized geometries, Stokes shifts, and vibrational frequencies reveal that ΔDFTB provides a qualitatively correct description of changes in molecular geometries and vibrational frequencies due to excited-state relaxation. The accuracy of ΔDFTB Stokes shifts is comparable to that of ΔSCF-DFT, and ΔDFTB performs similarly to ΔSCF with the PBE functional for vertical excitation energies of larger chromophores where the need for efficient excited-state methods is most urgent. We provide some justification for the use of an excited-state reference density in the DFTB expansion of the electronic energy and demonstrate that ΔDFTB preserves many of the properties of its parent ΔSCF approach. This implementation fills an important gap in the extended framework of DFTB, where access to excited states has been limited to the time-dependent linear-response approach, and affords access to rapid exploration of a valuable class of excited-state potential energy surfaces.

Self-Injurious Behavior in Correctional and Noncorrectional Psychiatric Patients.

ERIC Educational Resources Information Center

Hillbrand, Marc

1993-01-01

Examined prevalence and selected correlates of self-injurious behavior (SIB) among inmates (n=23) referred for treatment to maximum-security forensic hospital, non-SIB inmates (n=23), and noncorrections SIB patients (n=30). Found two distinct patterns of SIB: pattern consistent with conceptualization of SIB as expression of generalized behavioral…

The Influence of Solvent on the Structural Properties of trans-(NHC)PtI2Py Complex: A Platinum-Based Anticancer Drug

NASA Astrophysics Data System (ADS)

Sadigh Vishkaee, Teherh; Fazaeli, Reza

2018-06-01

Quantum chemical calculations using MPW1PW91 method were applied to analyze the solvent effect on the structural, spectral, and thermochemical parameters for a platinum-based anticancer drug trans-(NHC)PtI2Py complex. The solvent effects were examined by the self-consistent reaction field theory (SCRF) based on Polarizable Continuum Model (PCM). The linear correlations between the solvation energies, HOMO-LUMO gaps, IR-active stretching vibration of Pt-N bonds and N-H of NHC ligand with dielectric constants of solvents were studied. The wave numbers of these IR-active stretching vibrations in different solvents were correlated with the Kirkwood-Bauer-Magat equation (KBM). The thermodynamic activation parameter such free energy of solvation, enthalpy of solvation were also calculated.

A full-dimensional ab initio potential energy surface and rovibrational energies of the Ar–HF complex

NASA Astrophysics Data System (ADS)

Huang, Jing; Zhou, Yanzi; Xie, Daiqian

2018-04-01

We report a new full-dimensional ab initio potential energy surface for the Ar-HF van der Waals complex at the level of coupled-cluster singles and doubles with noniterative inclusion of connected triples levels [CCSD(T)] using augmented correlation-consistent quintuple-zeta basis set (aV5Z) plus bond functions. Full counterpoise correction was employed to correct the basis-set superposition error. The hypersurface was fitted using artificial neural network method with a root mean square error of 0.1085 cm-1 for more than 8000 ab initio points. The complex was found to prefer a linear Ar-H-F equilibrium structure. The three-dimensional discrete variable representation method and the Lanczos propagation algorithm were then employed to calculate the rovibrational states without separating inter- and intra- molecular nuclear motions. The calculated vibrational energies of Ar-HF differ from the experiment values within about 1 cm-1 on the first four HF vibrational states, and the predicted pure rotational energies on (0000) and (1000) vibrational states are deviated from the observed value by about 1%, which shows the accuracy of our new PES.

First-principles anharmonic quantum calculations for peptide spectroscopy: VSCF calculations and comparison with experiments.

PubMed

Roy, Tapta Kanchan; Sharma, Rahul; Gerber, R Benny

2016-01-21

First-principles quantum calculations for anharmonic vibrational spectroscopy of three protected dipeptides are carried out and compared with experimental data. Using hybrid HF/MP2 potentials, the Vibrational Self-Consistent Field with Second-Order Perturbation Correction (VSCF-PT2) algorithm is used to compute the spectra without any ad hoc scaling or fitting. All of the vibrational modes (135 for the largest system) are treated quantum mechanically and anharmonically using full pair-wise coupling potentials to represent the interaction between different modes. In the hybrid potential scheme the MP2 method is used for the harmonic part of the potential and a modified HF method is used for the anharmonic part. The overall agreement between computed spectra and experiment is very good and reveals different signatures for different conformers. This study shows that first-principles spectroscopic calculations of good accuracy are possible for dipeptides hence it opens possibilities for determination of dipeptide conformer structures by comparison of spectroscopic calculations with experiment.

Full self-consistency versus quasiparticle self-consistency in diagrammatic approaches: Exactly solvable two-site Hubbard model

DOE PAGES

Kutepov, A. L.

2015-07-22

Self-consistent solutions of Hedin's equations (HE) for the two-site Hubbard model (HM) have been studied. They have been found for three-point vertices of increasing complexity (Γ = 1 (GW approximation), Γ₁ from the first-order perturbation theory, and the exact vertex Γ E). Comparison is made between the cases when an additional quasiparticle (QP) approximation for Green's functions is applied during the self-consistent iterative solving of HE and when QP approximation is not applied. Results obtained with the exact vertex are directly related to the present open question—which approximation is more advantageous for future implementations, GW + DMFT or QPGW +more » DMFT. It is shown that in a regime of strong correlations only the originally proposed GW + DMFT scheme is able to provide reliable results. Vertex corrections based on Perturbation Theory systematically improve the GW results when full self-consistency is applied. The application of QP self-consistency combined with PT vertex corrections shows similar problems to the case when the exact vertex is applied combined with QP sc. An analysis of Ward Identity violation is performed for all studied in this work's approximations and its relation to the general accuracy of the schemes used is provided.« less

Full self-consistency versus quasiparticle self-consistency in diagrammatic approaches: exactly solvable two-site Hubbard model.

PubMed

Kutepov, A L

2015-08-12

Self-consistent solutions of Hedin's equations (HE) for the two-site Hubbard model (HM) have been studied. They have been found for three-point vertices of increasing complexity (Γ = 1 (GW approximation), Γ1 from the first-order perturbation theory, and the exact vertex Γ(E)). Comparison is made between the cases when an additional quasiparticle (QP) approximation for Green's functions is applied during the self-consistent iterative solving of HE and when QP approximation is not applied. The results obtained with the exact vertex are directly related to the present open question-which approximation is more advantageous for future implementations, GW + DMFT or QPGW + DMFT. It is shown that in a regime of strong correlations only the originally proposed GW + DMFT scheme is able to provide reliable results. Vertex corrections based on perturbation theory (PT) systematically improve the GW results when full self-consistency is applied. The application of QP self-consistency combined with PT vertex corrections shows similar problems to the case when the exact vertex is applied combined with QP sc. An analysis of Ward Identity violation is performed for all studied in this work's approximations and its relation to the general accuracy of the schemes used is provided.

The Transition from Hydrogen Bonding to Ionization in (HCI)n(NH3)n and (HCI)n(H2O)n Clusters: Consequences for Anharmonic Vibrational Spectroscopy

NASA Technical Reports Server (NTRS)

Chaban, Galina M.; Gerber, R. Benny; Janda, Kenneth C.; Kwak, Dochan (Technical Monitor)

2001-01-01

Anharmonic vibrational frequencies and intensities are calculated for 1:1 and 2:2 (HCl)(sub n)(NH3)(sub n) and (HCl)(sub n)(H2O)(sub n) complexes, employing the correlation-corrected vibrational self-consistent field method with ab initio potential surfaces at the MP2/TZP computational level. In this method, the anharmonic coupling between all vibrational modes is included, which is found to be important for the systems studied. For the 4:4 (HCl)(sub n)(H2O)(sub n) complex, the vibrational spectra are calculated at the harmonic level, and anharmonic effects are estimated. Just as the (HCl)(sub n)(NH3)(sub n) structure switches from hydrogen-bonded to ionic for n=2, the (HCl)(sub n)(H2O)(sub n) switches to ionic structure for n=4. For (HCl)2(H2O)2, the lowest energy structure corresponds to the hydrogen-bonded form. However, configurations of the ionic form are separated from this minimum by a barrier of less than an O-H stretching quantum. This suggests the possibility of experiments on ionization dynamics using infrared excitation of the hydrogen-bonded form. The strong cooperative effects on the hydrogen bonding, and concomitant transition to ionic bonding, makes an accurate estimate of the large anharmonicity crucial for understanding the infrared spectra of these systems. The anharmonicity is typically of the order of several hundred wave numbers for the proton stretching motions involved in hydrogen or ionic bonding, and can also be quite large for the intramolecular modes. In addition, the large cooperative effects in the 2:2 and higher order (HCl(sub n)(H2O)(sub n) complexes may have interesting implications for solvation of hydrogen halides at ice surfaces.

Structural and vibrational properties of transition-metal oxides from first-principles calculations

NASA Astrophysics Data System (ADS)

Cococcioni, M.; Floris, A.; Himmetoglu, B.

2010-12-01

The calculation of the vibrational spectrum of minerals is of fundamental importance to assess their behavior (e.g. their elastic properties, or possible structural phase transitions) under the high-temperature, high-pressure conditions of the Earth’s interior. The ubiquitous presence of transition metals and the consequent importance of electronic correlations make the study of these materials quite difficult to approach with approximate DFT functionals (as LDA or GGA). The DFT+U, consisting in a Hubbard-modeled correction to the DFT energy functionals, has been successfully used to study the electronic, structural, and magnetic properties of several Fe-bearing minerals. However, the vibrational spectrum of these systems has never been determined entirely (frozen- phonon techniques are overly expensive except for zone-center phonons). In this work we introduce the extension of Density-Functional-Perturbation-Theory to DFT+U, that allows to efficiently compute the phonon spectrum of transition-metal compounds from their correlated ground states. A comparative analysis between the vibrational properties of MnO, FeO, CoO, and NiO (in the undistorted cubic cell) highlights a marked dependence of several features of their phonon spectrum on the occupancy of localized d orbitals and thus, on elec- tronic correlation. The new computational tool is also employed to evaluate the rhombohedral distortion of FeO (particularly abundant in the Earth’s lower mantle) and to assess the stability of its B1 phase in different conditions of pressure and temperature.

Beyond the random-phase approximation for the electron correlation energy: the importance of single excitations.

PubMed

Ren, Xinguo; Tkatchenko, Alexandre; Rinke, Patrick; Scheffler, Matthias

2011-04-15

The random-phase approximation (RPA) for the electron correlation energy, combined with the exact-exchange (EX) energy, represents the state-of-the-art exchange-correlation functional within density-functional theory. However, the standard RPA practice--evaluating both the EX and the RPA correlation energies using Kohn-Sham (KS) orbitals from local or semilocal exchange-correlation functionals--leads to a systematic underbinding of molecules and solids. Here we demonstrate that this behavior can be corrected by adding a "single excitation" contribution, so far not included in the standard RPA scheme. A similar improvement can also be achieved by replacing the non-self-consistent EX total energy by the corresponding self-consistent Hartree-Fock total energy, while retaining the RPA correlation energy evaluated using KS orbitals. Both schemes achieve chemical accuracy for a standard benchmark set of noncovalent intermolecular interactions.

Internal vibrations of a molecule consisting of rigid segments. I - Non-interacting internal vibrations

NASA Technical Reports Server (NTRS)

He, X. M.; Craven, B. M.

1993-01-01

For molecular crystals, a procedure is proposed for interpreting experimentally determined atomic mean square anisotropic displacement parameters (ADPs) in terms of the overall molecular vibration together with internal vibrations with the assumption that the molecule consists of a set of linked rigid segments. The internal librations (molecular torsional or bending modes) are described using the variable internal coordinates of the segmented body. With this procedure, the experimental ADPs obtained from crystal structure determinations involving six small molecules (sym-trinitrobenzene, adenosine, tetra-cyanoquinodimethane, benzamide, alpha-cyanoacetic acid hydrazide and N-acetyl-L-tryptophan methylamide) have been analyzed. As a consequence, vibrational corrections to the bond lengths and angles of the molecule are calculated as well as the frequencies and force constants for each internal torsional or bending vibration.

On basis set superposition error corrected stabilization energies for large n-body clusters.

PubMed

Walczak, Katarzyna; Friedrich, Joachim; Dolg, Michael

2011-10-07

In this contribution, we propose an approximate basis set superposition error (BSSE) correction scheme for the site-site function counterpoise and for the Valiron-Mayer function counterpoise correction of second order to account for the basis set superposition error in clusters with a large number of subunits. The accuracy of the proposed scheme has been investigated for a water cluster series at the CCSD(T), CCSD, MP2, and self-consistent field levels of theory using Dunning's correlation consistent basis sets. The BSSE corrected stabilization energies for a series of water clusters are presented. A study regarding the possible savings with respect to computational resources has been carried out as well as a monitoring of the basis set dependence of the approximate BSSE corrections. © 2011 American Institute of Physics

Collision dynamics of H+ + N2 at low energies based on time-dependent density-functional theory

NASA Astrophysics Data System (ADS)

Yu, W.; Zhang, Y.; Zhang, F. S.; Hutton, R.; Zou, Y.; Gao, C.-Z.; Wei, B.

2018-02-01

Using time-dependent density-functional theory at the level of local density approximation augmented by a self-interaction correction and coupled non-adiabatically to molecular dynamics, we study, from a theoretical perspective, scattering dynamics of the proton in collisions with the N2 molecule at 30 eV. Nine different collision configurations are employed to analyze the proton energy loss spectra, electron depletion, scattering angles and self-interaction effects. Our results agree qualitatively with the experimental data and previous theoretical calculations. The discrepancies are ascribed to the limitation of the theoretical models in use. We find that self-interaction effects can significantly influence the electron capture and the excited diatomic vibrational motion, which is in consistent with other calculations. In addition, it is found that the molecular structure can be readily retrieved from the proton energy loss spectra due to a significant momentum transfer in head-on collisions.

Subsychronous vibration of multistage centrifugal compressors forced by rotating stall

NASA Technical Reports Server (NTRS)

Fulton, J. W.

1987-01-01

A multistage centrifugal compressor, in natural gas re-injection service on an offshore petroleum production platform, experienced subsynchronous vibrations which caused excessive bearing wear. Field performance testing correlated the subsynchronous amplitude with the discharge flow coefficient, demonstrating the excitation to be aerodynamic. Adding two impellers allowed an increase in the diffuser flow angle (with respect to tangential) to meet the diffuser stability criteria based on factory and field tests correlated using the theory of Senoo (for rotating stall in a vaneless diffuser). This modification eliminated all significant subsynchronous vibrations in field service, thus confirming the correctness of the solution. Other possible sources of aerodynamically induced vibrations were considered, but the judgment that those are unlikely has been confirmed by subsequent experience with other similar compressors.

Providing Agility in C2 Environments Through Networked Information Processing: A Model of Expertise

DTIC Science & Technology

2014-06-01

personal benefits promoting self-esteem, pride, self-efficacy, personal identification with colleagues and organizations, obtaining a better...studies based on staged-event methods with “target-present” and “target-absent” lineups . The results show that when choosers make positive... identification , the correlation between confidence and accuracy was consistently high. Besides correct choosers have a higher mean confidence level than

The study of molecular spectroscopy by ab initio methods

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

1991-01-01

This review illustrates the potential of theory for solving spectroscopic problems. The accuracy of approximate techniques for including electron correlation have been calibrated by comparison with full configuration-interaction calculations. Examples of the application of ab initio calculations to vibrational, rotational, and electronic spectroscopy are given. It is shown that the state-averaged, complete active space self-consistent field, multireference configuration-interaction procedure provides a good approach for treating several electronic states accurately in a common molecular orbital basis.

Spin-orbit ZORA and four-component Dirac-Coulomb estimation of relativistic corrections to isotropic nuclear shieldings and chemical shifts of noble gas dimers.

PubMed

Jankowska, Marzena; Kupka, Teobald; Stobiński, Leszek; Faber, Rasmus; Lacerda, Evanildo G; Sauer, Stephan P A

2016-02-05

Hartree-Fock and density functional theory with the hybrid B3LYP and general gradient KT2 exchange-correlation functionals were used for nonrelativistic and relativistic nuclear magnetic shielding calculations of helium, neon, argon, krypton, and xenon dimers and free atoms. Relativistic corrections were calculated with the scalar and spin-orbit zeroth-order regular approximation Hamiltonian in combination with the large Slater-type basis set QZ4P as well as with the four-component Dirac-Coulomb Hamiltonian using Dyall's acv4z basis sets. The relativistic corrections to the nuclear magnetic shieldings and chemical shifts are combined with nonrelativistic coupled cluster singles and doubles with noniterative triple excitations [CCSD(T)] calculations using the very large polarization-consistent basis sets aug-pcSseg-4 for He, Ne and Ar, aug-pcSseg-3 for Kr, and the AQZP basis set for Xe. For the dimers also, zero-point vibrational (ZPV) corrections are obtained at the CCSD(T) level with the same basis sets were added. Best estimates of the dimer chemical shifts are generated from these nuclear magnetic shieldings and the relative importance of electron correlation, ZPV, and relativistic corrections for the shieldings and chemical shifts is analyzed. © 2015 Wiley Periodicals, Inc.

Full self-consistency in the Fermi-orbital self-interaction correction

NASA Astrophysics Data System (ADS)

Yang, Zeng-hui; Pederson, Mark R.; Perdew, John P.

2017-05-01

The Perdew-Zunger self-interaction correction cures many common problems associated with semilocal density functionals, but suffers from a size-extensivity problem when Kohn-Sham orbitals are used in the correction. Fermi-Löwdin-orbital self-interaction correction (FLOSIC) solves the size-extensivity problem, allowing its use in periodic systems and resulting in better accuracy in finite systems. Although the previously published FLOSIC algorithm Pederson et al., J. Chem. Phys. 140, 121103 (2014)., 10.1063/1.4869581 appears to work well in many cases, it is not fully self-consistent. This would be particularly problematic for systems where the occupied manifold is strongly changed by the correction. In this paper, we demonstrate a different algorithm for FLOSIC to achieve full self-consistency with only marginal increase of computational cost. The resulting total energies are found to be lower than previously reported non-self-consistent results.

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.

Preliminary recognition of whole body vibration risk in private farmers' working environment.

PubMed

Solecki, Leszek

2007-01-01

The objective of the study was the preliminary recognition of whole body mechanical vibration risk among farmers in the rural work environment. The study covered 15 farms using cultivated land of the size of over 10 ha, carrying out mixed production (plant-animal), equipped with agricultural tractors, and a basic set of tractor-mounted agricultural machinery, with a partial contribution of self-propelled agricultural machines. The scope of the study covered the measurements of effective vibration RMS acceleration (equivalent, maximum, minimum, peak) frequency corrected on the seats of agricultural vehicles in the three spatial directions of vibration (X, Y, Z). These measurements were realized while performing various field and transport work activities during the period of the whole year. A analysis of the peak, maximum and minimum vibration accelerations confirms that in the agricultural occupational environment there occurs a considerable variation of the vibration values registered. This is also evidenced by high values of the Crest Factor, sometimes exceeding a score of 10. Analysis of the registered equivalent values of vibration acceleration (frequency corrected) from the hygienic aspect showed that vibration occurring on the seats may create risk for farmers' health while performing such work activities as: tending and raking of hay, fertilizers spreading, soil aggregation, grass mowing and cultivation. Analysis of the spatial distribution of the measured, frequency corrected vibration accelerations indicates that considerably the highest acceleration values occur in the vertical plane (direction-Z). Literature data clearly confirm an unfavourable effect of whole body vibration present in agricultural vehicles on discomfort and the occurrence of back pain in the operators, especially in the low back region (lumbar spine), as well as degenerative changes in the spine.

Anharmonic effects in IR, Raman, and Raman optical activity spectra of alanine and proline zwitterions.

PubMed

Danecek, Petr; Kapitán, Josef; Baumruk, Vladimír; Bednárová, Lucie; Kopecký, Vladimír; Bour, Petr

2007-06-14

The difference spectroscopy of the Raman optical activity (ROA) provides extended information about molecular structure. However, interpretation of the spectra is based on complex and often inaccurate simulations. Previously, the authors attempted to make the calculations more robust by including the solvent and exploring the role of molecular flexibility for alanine and proline zwitterions. In the current study, they analyze the IR, Raman, and ROA spectra of these molecules with the emphasis on the force field modeling. Vibrational harmonic frequencies obtained with 25 ab initio methods are compared to experimental band positions. The role of anharmonic terms in the potential and intensity tensors is also systematically explored using the vibrational self-consistent field, vibrational configuration interaction (VCI), and degeneracy-corrected perturbation calculations. The harmonic approach appeared satisfactory for most of the lower-wavelength (200-1800 cm(-1)) vibrations. Modern generalized gradient approximation and hybrid density functionals, such as the common B3LYP method, provided a very good statistical agreement with the experiment. Although the inclusion of the anharmonic corrections still did not lead to complete agreement between the simulations and the experiment, occasional enhancements were achieved across the entire region of wave numbers. Not only the transitional frequencies of the C-H stretching modes were significantly improved but also Raman and ROA spectral profiles including N-H and C-H lower-frequency bending modes were more realistic after application of the VCI correction. A limited Boltzmann averaging for the lowest-frequency modes that could not be included directly in the anharmonic calculus provided a realistic inhomogeneous band broadening. The anharmonic parts of the intensity tensors (second dipole and polarizability derivatives) were found less important for the entire spectral profiles than the force field anharmonicities (third and fourth energy derivatives), except for a few weak combination bands which were dominated by the anharmonic tensor contributions.

Anharmonic effects in IR, Raman, and Raman optical activity spectra of alanine and proline zwitterions

NASA Astrophysics Data System (ADS)

Daněček, Petr; Kapitán, Josef; Baumruk, Vladimír; Bednárová, Lucie; Kopecký, Vladimír; Bouř, Petr

2007-06-01

The difference spectroscopy of the Raman optical activity (ROA) provides extended information about molecular structure. However, interpretation of the spectra is based on complex and often inaccurate simulations. Previously, the authors attempted to make the calculations more robust by including the solvent and exploring the role of molecular flexibility for alanine and proline zwitterions. In the current study, they analyze the IR, Raman, and ROA spectra of these molecules with the emphasis on the force field modeling. Vibrational harmonic frequencies obtained with 25 ab initio methods are compared to experimental band positions. The role of anharmonic terms in the potential and intensity tensors is also systematically explored using the vibrational self-consistent field, vibrational configuration interaction (VCI), and degeneracy-corrected perturbation calculations. The harmonic approach appeared satisfactory for most of the lower-wavelength (200-1800cm-1) vibrations. Modern generalized gradient approximation and hybrid density functionals, such as the common B3LYP method, provided a very good statistical agreement with the experiment. Although the inclusion of the anharmonic corrections still did not lead to complete agreement between the simulations and the experiment, occasional enhancements were achieved across the entire region of wave numbers. Not only the transitional frequencies of the C-H stretching modes were significantly improved but also Raman and ROA spectral profiles including N-H and C-H lower-frequency bending modes were more realistic after application of the VCI correction. A limited Boltzmann averaging for the lowest-frequency modes that could not be included directly in the anharmonic calculus provided a realistic inhomogeneous band broadening. The anharmonic parts of the intensity tensors (second dipole and polarizability derivatives) were found less important for the entire spectral profiles than the force field anharmonicities (third and fourth energy derivatives), except for a few weak combination bands which were dominated by the anharmonic tensor contributions.

Ab initio and DFT study of hydrogen bond interactions between ascorbic acid and dimethylsulfoxide based on FT-IR and FT-Raman spectra

NASA Astrophysics Data System (ADS)

Niazazari, Naser; Zatikyan, Ashkhen L.; Markarian, Shiraz A.

2013-06-01

The hydrogen bonding of 1:1 complexes formed between L-ascorbic acid (LAA) and dimethylsulfoxide (DMSO) has been studied by means of ab initio and density functional theory (DFT) calculations. Solutions of L-ascorbic acid (AA) in dimethylsulfoxide (DMSO) have been studied by means of both FT-IR (4000-220 cm-1) and FT-Raman spectroscopy. Ab initio Hartree-Fock (HF) and DFT methods have been used to determine the structure and energies of stable conformers of various types of L-AA/DMSO complexes in gas phase and solution. The basis sets 6-31++G∗∗ and 6-311+G∗ were used to describe the structure, energy, charges and vibrational frequencies of interacting complexes in the gas phase. The optimized geometric parameters and interaction energies for various complexes at different theories have been estimated. Binding energies have been corrected for basis set superposition error (BSSE) and harmonic vibrational frequencies of the structures have been calculated to obtain the stable forms of the complexes. The self-consistent reaction field (SCRF) has been used to calculate the effect of DMSO as the solvent on the geometry, energy and charges of complexes. The solvent effect has been studied using the Onsager models. It is shown that the polarity of the solvent plays an important role on the structures and relative stabilities of different complexes. The results obtained show that there is a satisfactory correlation between experimental and theoretical predictions.

Double counting in the density functional plus dynamical mean-field theory of transition metal oxides

NASA Astrophysics Data System (ADS)

Dang, Hung

2015-03-01

Recently, the combination of density functional theory (DFT) and dynamical mean-field theory (DMFT) has become a widely-used beyond-mean-field approach for strongly correlated materials. However, not only is the correlation treated in DMFT but also in DFT to some extent, a problem arises as the correlation is counted twice in the DFT+DMFT framework. The correction for this problem is still not well-understood. To gain more understanding of this ``double counting'' problem, I provide a detailed study of the metal-insulator transition in transition metal oxides in the subspace of oxygen p and transition metal correlated d orbitals using DFT+DMFT. I will show that the fully charge self-consistent DFT+DMFT calculations with the standard ``fully-localized limit'' (FLL) double counting correction fail to predict correctly materials such as LaTiO3, LaVO3, YTiO3 and SrMnO3 as insulators. Investigations in a wide range of the p- d splitting, the d occupancy, the lattice structure and the double counting correction itself will be presented to understand the reason behind this failure. I will also show that if the double counting correction is chosen to reproduce the p- d splitting consistent with experimental data, the DFT+DMFT approach can still give reasonable results in comparison with experiments.

Extension and Application of High-Speed Digital Imaging Analysis Via Spatiotemporal Correlation and Eigenmode Analysis of Vocal Fold Vibration Before and After Polyp Excision.

PubMed

Wang, Jun-Sheng; Olszewski, Emily; Devine, Erin E; Hoffman, Matthew R; Zhang, Yu; Shao, Jun; Jiang, Jack J

2016-08-01

To evaluate the spatiotemporal correlation of vocal fold vibration using eigenmode analysis before and after polyp removal and explore the potential clinical relevance of spatiotemporal analysis of correlation length and entropy as quantitative voice parameters. We hypothesized that increased order in the vibrating signal after surgical intervention would decrease the eigenmode-based entropy and increase correlation length. Prospective case series. Forty subjects (23 males, 17 females) with unilateral (n = 24) or bilateral (n = 16) polyps underwent polyp removal. High-speed videoendoscopy was performed preoperatively and 2 weeks postoperatively. Spatiotemporal analysis was performed to determine entropy, quantification of signal disorder, correlation length, size, and spatially ordered structure of vocal fold vibration in comparison to full spatial consistency. The signal analyzed consists of the vibratory pattern in space and time derived from the high-speed video glottal area contour. Entropy decreased (Z = -3.871, P < .001) and correlation length increased (t = -8.913, P < .001) following polyp excision. The intraclass correlation coefficients (ICC) for correlation length and entropy were 0.84 and 0.93. Correlation length and entropy are sensitive to mass lesions. These parameters could potentially be used to augment subjective visualization after polyp excision when evaluating procedural efficacy. © The Author(s) 2016.

Rotor internal friction instability

NASA Technical Reports Server (NTRS)

Bently, D. E.; Muszynska, A.

1985-01-01

Two aspects of internal friction affecting stability of rotating machines are discussed. The first role of internal friction consists of decreasing the level of effective damping during rotor subsynchronous and backward precessional vibrations caused by some other instability mechanisms. The second role of internal frication consists of creating rotor instability, i.e., causing self-excited subsynchronous vibrations. Experimental test results document both of these aspects.

Rocksalt or cesium chloride: Investigating the relative stability of the cesium halide structures with random phase approximation based methods

NASA Astrophysics Data System (ADS)

Nepal, Niraj K.; Ruzsinszky, Adrienn; Bates, Jefferson E.

2018-03-01

The ground state structural and energetic properties for rocksalt and cesium chloride phases of the cesium halides were explored using the random phase approximation (RPA) and beyond-RPA methods to benchmark the nonempirical SCAN meta-GGA and its empirical dispersion corrections. The importance of nonadditivity and higher-order multipole moments of dispersion in these systems is discussed. RPA generally predicts the equilibrium volume for these halides within 2.4% of the experimental value, while beyond-RPA methods utilizing the renormalized adiabatic LDA (rALDA) exchange-correlation kernel are typically within 1.8%. The zero-point vibrational energy is small and shows that the stability of these halides is purely due to electronic correlation effects. The rAPBE kernel as a correction to RPA overestimates the equilibrium volume and could not predict the correct phase ordering in the case of cesium chloride, while the rALDA kernel consistently predicted results in agreement with the experiment for all of the halides. However, due to its reasonable accuracy with lower computational cost, SCAN+rVV10 proved to be a good alternative to the RPA-like methods for describing the properties of these ionic solids.

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.

Magnetic Exchange Couplings from Semilocal Functionals Evaluated Nonself-Consistently on Hybrid Densities: Insights on Relative Importance of Exchange, Correlation, and Delocalization.

PubMed

Phillips, Jordan J; Peralta, Juan E

2012-09-11

Semilocal functionals generally yield poor magnetic exchange couplings for transition-metal complexes, typically overpredicting in magnitude the experimental values. Here we show that semilocal functionals evaluated nonself-consistently on densities from hybrid functionals can yield magnetic exchange couplings that are greatly improved with respect to their self-consistent semilocal values. Furthermore, when semilocal functionals are evaluated nonself-consistently on densities from a "half-and-half" hybrid, their errors with respect to experimental values can actually be lower than those from self-consistent calculations with standard hybrid functionals such as PBEh or TPSSh. This illustrates that despite their notoriously poor performance for exchange couplings, for many systems semilocal functionals are capable of delivering accurate relative energies for magnetic states provided that their electron delocalization error is corrected. However, while self-consistent calculations with hybrids uniformly improve results for all complexes, evaluating nonself-consistently with semilocal functionals does not give a balanced improvement for both ferro- and antiferromagnetically coupled complexes, indicating that there is more at play with the overestimation problem than simply the delocalization error. Additionally, we show that for some systems the conventional wisdom of choice of exchange functional mattering more than correlation does not hold. This combined with results from the nonself-consistent calculations provide insight on clarifying the relative roles of exchange, correlation, and delocalization in calculating magnetic exchange coupling parameters in Kohn-Sham Density Functional Theory.

Electronic Transitions of Tungsten Monosulfide

NASA Astrophysics Data System (ADS)

Tsang, L. F.; Chan, Man-Chor; Zou, Wenli; Cheung, Allan S. C.

2017-06-01

Electronic transition spectrum of the tungsten monosulfide (WS) molecule in the near infrared region between 725 nm and 885 nm has been recorded using laser ablation/reaction free-jet expansion and laser induced fluorescence spectroscopy. The WS molecule was produced by reacting laser - ablated tungsten atoms with 1% CS_{2} seeded in argon. Fifteen vibrational bands with resolved rotational structure have been recorded and analyzed, which were organized into seven electronic transition systems. The ground state has been identified to be the X^{3}Σ^{-}(0^{+}) state, and the determined vibrational frequency, ΔG_{1/2} and bond length, r_{0}, are respectively 556.7 cm^{-1} and 2.0676 Å. In addition, vibrational bands belong to another transition system involving lower state with Ω = 1 component have also been analyzed. Least-squares fit of the measured line positions yielded molecular constants for the electronic states involved. The low-lying Λ-S states and Ω sub-states of WS have been calculated using state-averaged complete active space self-consistent field (SA-CASSCF) and followed by MRCISD+Q (internally contracted multi-reference configuration interaction with singles and doubles plus Davidson's cluster correction). The active space consists of 10 electrons in 9 orbitals corresponding to the W 5d6s and S 3p shells. The lower molecular orbitals from W 5s5p and S 3s are inactive but are also correlated, and relativistic effective core potential (RECPs) are adopted to replace the core orbitals with 60 (W) and 10 (S) core electrons, respectively. Spin-orbit coupling (SOC) is calculated via the state-interaction (SI) approach with RECP spin-orbit operators using SA-CASSCF wavefunctions, where the diagonal elements in the SOC matrix are replaced by the corresponding MRCISD+Q energies calculated above. Spectroscopic constants and potential energy curves of the ground and many low-lying Λ-S states and Ω sub-states of the WS molecule are obtained. The calculated spectroscopic constants of the ground and low-lying states are generally in good agreement with our experimental determination. This work represents the first experimental investigation of the electronic and molecular structure of the WS molecule.

The influence of anharmonic and solvent effects on the theoretical vibrational spectra of the guanine-cytosine base pairs in Watson-Crick and Hoogsteen configurations.

PubMed

Bende, Attila; Muntean, Cristina M

2014-03-01

The theoretical IR and Raman spectra of the guanine-cytosine DNA base pairs in Watson-Crick and Hoogsteen configurations were computed using DFT method with M06-2X meta-hybrid GGA exchange-correlation functional, including the anharmonic corrections and solvent effects. The results for harmonic frequencies and their anharmonic corrections were compared with our previously calculated values obtained with the B3PW91 hybrid GGA functional. Significant differences were obtained for the anharmonic corrections calculated with the two different DFT functionals, especially for the stretching modes, while the corresponding harmonic frequencies did not differ considerable. For the Hoogtseen case the H⁺ vibration between the G-C base pair can be characterized as an asymmetric Duffing oscillator and therefore unrealistic anharmonic corrections for normal modes where this proton vibration is involved have been obtained. The spectral modification due to the anharmonic corrections, solvent effects and the influence of sugar-phosphate group for the Watson-Crick and Hoogsteen base pair configurations, respectively, were also discussed. For the Watson-Crick case also the influence of the stacking interaction on the theoretical IR and Raman spectra was analyzed. Including the anharmonic correction in our normal mode analysis is essential if one wants to obtain correct assignments of the theoretical frequency values as compared with the experimental spectra.

Self-consistent expansion for the molecular beam epitaxy equation

NASA Astrophysics Data System (ADS)

Katzav, Eytan

2002-03-01

Motivated by a controversy over the correct results derived from the dynamic renormalization group (DRG) analysis of the nonlinear molecular beam epitaxy (MBE) equation, a self-consistent expansion for the nonlinear MBE theory is considered. The scaling exponents are obtained for spatially correlated noise of the general form D(r-->-r',t-t')=2D0\\|r-->- r'\\|2ρ-dδ(t-t'). I find a lower critical dimension dc(ρ)=4+2ρ, above which the linear MBE solution appears. Below the lower critical dimension a ρ-dependent strong-coupling solution is found. These results help to resolve the controversy over the correct exponents that describe nonlinear MBE, using a reliable method that proved itself in the past by giving reasonable results for the strong-coupling regime of the Kardar-Parisi-Zhang system (for d>1), where DRG failed to do so.

Self-consistent expansion for the molecular beam epitaxy equation.

PubMed

Katzav, Eytan

2002-03-01

Motivated by a controversy over the correct results derived from the dynamic renormalization group (DRG) analysis of the nonlinear molecular beam epitaxy (MBE) equation, a self-consistent expansion for the nonlinear MBE theory is considered. The scaling exponents are obtained for spatially correlated noise of the general form D(r-r('),t-t('))=2D(0)[r-->-r(')](2rho-d)delta(t-t(')). I find a lower critical dimension d(c)(rho)=4+2rho, above which the linear MBE solution appears. Below the lower critical dimension a rho-dependent strong-coupling solution is found. These results help to resolve the controversy over the correct exponents that describe nonlinear MBE, using a reliable method that proved itself in the past by giving reasonable results for the strong-coupling regime of the Kardar-Parisi-Zhang system (for d>1), where DRG failed to do so.

Structure and vibrational spectra of pyridine betaine hydrochloride

NASA Astrophysics Data System (ADS)

Szafran, Mirosław; Koput, Jacek; Baran, Jan; Głowiak, Tadeusz

1997-12-01

The crystal structure of pyridine betaine hydrochloride (PBET·HCl) was determined by X-ray diffraction to be monoclinic, space group {P2 1}/{c} with a = 8.533(2) Å, b = 9.548(2) Å, c = 10.781(2) Å, β = 107.228(3)° and Z = 4. Betaine is protonated and the carboxyl group forms a hydrogen bond with the chloride ion: O·Cl - distance is 2.928(3) Å. The interaction of pyridine betaine (PBET) with HCl was examined by ab initio self-consistent field (SCF), second-order Møller-Plesset (MP2) and density functional theory (DFT) methods using the 6-31G(d,p) basis set. Two minima are located in the potential surface at the SCF level (PBETH +·Cl - and PBET·HCl, with the latter being 1.2 kcal mol -1 lower in energy) and only one minimum (PBET·HCl) at the MP2 and DFT levels. The molecular parameters of PBETH +·Cl -, computed by the SCF method, reproduce the corresponding experimental data. The computed vibrational frequencies of PBETH +·Cl - resemble correctly the experimental vibrational spectrum in the solid state. The root-mean-square (r.m.s.) deviations between the experimental and calculated SCF frequencies are 65 cm -1 for all bands and 15 cm -1 without the νClH band. All measured IR bands were interpreted in terms of the calculated vibrational models.

Bayesian power spectrum inference with foreground and target contamination treatment

NASA Astrophysics Data System (ADS)

Jasche, J.; Lavaux, G.

2017-10-01

This work presents a joint and self-consistent Bayesian treatment of various foreground and target contaminations when inferring cosmological power spectra and three-dimensional density fields from galaxy redshift surveys. This is achieved by introducing additional block-sampling procedures for unknown coefficients of foreground and target contamination templates to the previously presented ARES framework for Bayesian large-scale structure analyses. As a result, the method infers jointly and fully self-consistently three-dimensional density fields, cosmological power spectra, luminosity-dependent galaxy biases, noise levels of the respective galaxy distributions, and coefficients for a set of a priori specified foreground templates. In addition, this fully Bayesian approach permits detailed quantification of correlated uncertainties amongst all inferred quantities and correctly marginalizes over observational systematic effects. We demonstrate the validity and efficiency of our approach in obtaining unbiased estimates of power spectra via applications to realistic mock galaxy observations that are subject to stellar contamination and dust extinction. While simultaneously accounting for galaxy biases and unknown noise levels, our method reliably and robustly infers three-dimensional density fields and corresponding cosmological power spectra from deep galaxy surveys. Furthermore, our approach correctly accounts for joint and correlated uncertainties between unknown coefficients of foreground templates and the amplitudes of the power spectrum. This effect amounts to correlations and anti-correlations of up to 10 per cent across wide ranges in Fourier space.

Proton affinity and enthalpy of formation of formaldehyde

NASA Astrophysics Data System (ADS)

Czakó, Gábor; Nagy, Balázs; Tasi, Gyula; Somogyi, Árpád; Šimunek, Ján; Noga, Jozef; Braams, Bastiaan J.; Bowman, Joel M.; Császár; , Attila G.

The proton affinity and the enthalpy of formation of the prototypical carbonyl, formaldehyde, have been determined by the first-principles composite focal-point analysis (FPA) approach. The electronic structure computations employed the all-electron coupled-cluster method with up to single, double, triple, quadruple, and even pentuple excitations. In these computations the aug-cc-p(C)VXZ [X = 2(D), 3(T), 4(Q), 5, and 6] correlation-consistent Gaussian basis sets for C and O were used in conjunction with the corresponding aug-cc-pVXZ (X = 2-6) sets for H. The basis set limit values have been confirmed via explicitly correlated computations. Our FPA study supersedes previous computational work for the proton affinity and to some extent the enthalpy of formation of formaldehyde by accounting for (a) electron correlation beyond the "gold standard" CCSD(T) level; (b) the non-additivity of core electron correlation effects; (c) scalar relativity; (d) diagonal Born-Oppenheimer corrections computed at a correlated level; (e) anharmonicity of zero-point vibrational energies, based on global potential energy surfaces and variational vibrational computations; and (f) thermal corrections to enthalpies by direct summation over rovibrational energy levels. Our final proton affinities at 298.15 (0.0) K are ΔpaHo (H2CO) = 711.02 (704.98) ± 0.39 kJ mol-1. Our final enthalpies of formation at 298.15 (0.0) K are ΔfHo (H2CO) = -109.23 (-105.42) ± 0.33 kJ mol-1. The latter values are based on the enthalpy of the H2 + CO → H2CO reaction but supported by two further reaction schemes, H2O + C → H2CO and 2H + C + O → H2CO. These values, especially ΔpaHo (H2CO), have better accuracy and considerably lower uncertainty than the best previous recommendations and thus should be employed in future studies.

First-principles calculations on anharmonic vibrational frequencies of polyethylene and polyacetylene in the Gamma approximation.

PubMed

Keçeli, Murat; Hirata, So; Yagi, Kiyoshi

2010-07-21

The frequencies of the infrared- and/or Raman-active (k=0) vibrations of polyethylene and polyacetylene are computed by taking account of the anharmonicity in the potential energy surfaces (PESs) and the resulting phonon-phonon couplings explicitly. The electronic part of the calculations is based on Gaussian-basis-set crystalline orbital theory at the Hartree-Fock and second-order Møller-Plesset (MP2) perturbation levels, providing one-, two-, and/or three-dimensional slices of the PES (namely, using the so-called n-mode coupling approximation with n=3), which are in turn expanded in the fourth-order Taylor series with respect to the normal coordinates. The vibrational part uses the vibrational self-consistent field, vibrational MP2, and vibrational truncated configuration-interaction (VCI) methods within the Gamma approximation, which amounts to including only k=0 phonons. It is shown that accounting for both electron correlation and anharmonicity is essential in achieving good agreement (the mean and maximum absolute deviations less than 50 and 90 cm(-1), respectively, for polyethylene and polyacetylene) between computed and observed frequencies. The corresponding values for the calculations including only one of such effects are in excess of 120 and 300 cm(-1), respectively. The VCI calculations also reproduce semiquantitatively the frequency separation and intensity ratio of the Fermi doublet involving the nu(2)(0) fundamental and nu(8)(pi) first overtone in polyethylene.

Two-dimensional vibrational spectroscopy of the amide I band of crystalline acetanilide: Fermi resonance, conformational substates, or vibrational self-trapping?

NASA Astrophysics Data System (ADS)

Edler, J.; Hamm, P.

2003-08-01

Two-dimensional infrared (2D-IR) spectroscopy is applied to investigate acetanilide, a molecular crystal consisting of quasi-one-dimensional hydrogen bonded peptide units. The amide-I band exhibits a double peak structure, which has been attributed to different mechanisms including vibrational self-trapping, a Fermi resonance, or the existence of two conformational substates. The 2D-IR spectrum of crystalline acetanilide is compared with that of two different molecular systems: (i) benzoylchloride, which exhibits a strong symmetric Fermi resonance and (ii) N-methylacetamide dissolved in methanol which occurs in two spectroscopically distinguishable conformations. Both 2D-IR spectra differ significantly from that of crystalline acetanilide, proving that these two alternative mechanisms cannot account for the anomalous spectroscopy of crystalline acetanilide. On the other hand, vibrational self-trapping of the amide-I band can naturally explain the 2D-IR response.

Coupled rotor/airframe vibration analysis

NASA Technical Reports Server (NTRS)

Sopher, R.; Studwell, R. E.; Cassarino, S.; Kottapalli, S. B. R.

1982-01-01

A coupled rotor/airframe vibration analysis developed as a design tool for predicting helicopter vibrations and a research tool to quantify the effects of structural properties, aerodynamic interactions, and vibration reduction devices on vehicle vibration levels is described. The analysis consists of a base program utilizing an impedance matching technique to represent the coupled rotor/airframe dynamics of the system supported by inputs from several external programs supplying sophisticated rotor and airframe aerodynamic and structural dynamic representation. The theoretical background, computer program capabilities and limited correlation results are presented in this report. Correlation results using scale model wind tunnel results show that the analysis can adequately predict trends of vibration variations with airspeed and higher harmonic control effects. Predictions of absolute values of vibration levels were found to be very sensitive to modal characteristics and results were not representative of measured values.

On the contribution of vibrational anharmonicity to the binding energies of water clusters.

PubMed

Diri, Kadir; Myshakin, Evgeniy M; Jordan, Kenneth D

2005-05-05

The second-order vibrational perturbation theory method has been used together with the B3LYP and MP2 electronic structure methods to investigate the effects of anharmonicity on the vibrational zero-point energy (ZPE) contributions to the binding energies of (H2O)n, n = 2-6, clusters. For the low-lying isomers of (H2O)6, the anharmonicity correction to the binding energy is calculated to range from -248 to -355 cm(-1). It is also demonstrated that although high-order electron correlation effects are important for the individual vibrational frequencies, they are relatively unimportant for the net ZPE contributions to the binding energies of water clusters.

Precision measurements and computations of transition energies in rotationally cold triatomic hydrogen ions up to the midvisible spectral range.

PubMed

Pavanello, Michele; Adamowicz, Ludwik; Alijah, Alexander; Zobov, Nikolai F; Mizus, Irina I; Polyansky, Oleg L; Tennyson, Jonathan; Szidarovszky, Tamás; Császár, Attila G; Berg, Max; Petrignani, Annemieke; Wolf, Andreas

2012-01-13

First-principles computations and experimental measurements of transition energies are carried out for vibrational overtone lines of the triatomic hydrogen ion H(3)(+) corresponding to floppy vibrations high above the barrier to linearity. Action spectroscopy is improved to detect extremely weak visible-light spectral lines on cold trapped H(3)(+) ions. A highly accurate potential surface is obtained from variational calculations using explicitly correlated Gaussian wave function expansions. After nonadiabatic corrections, the floppy H(3)(+) vibrational spectrum is reproduced at the 0.1 cm(-1) level up to 16600 cm(-1).

Calculation of binary magnetic properties and potential energy curve in xenon dimer: second virial coefficient of (129)Xe nuclear shielding.

PubMed

Hanni, Matti; Lantto, Perttu; Runeberg, Nino; Jokisaari, Jukka; Vaara, Juha

2004-09-22

Quantum chemical calculations of the nuclear shielding tensor, the nuclear quadrupole coupling tensor, and the spin-rotation tensor are reported for the Xe dimer using ab initio quantum chemical methods. The binary chemical shift delta, the anisotropy of the shielding tensor Delta sigma, the nuclear quadrupole coupling tensor component along the internuclear axis chi( parallel ), and the spin-rotation constant C( perpendicular ) are presented as a function of internuclear distance. The basis set superposition error is approximately corrected for by using the counterpoise correction (CP) method. Electron correlation effects are systematically studied via the Hartree-Fock, complete active space self-consistent field, second-order Møller-Plesset many-body perturbation, and coupled-cluster singles and doubles (CCSD) theories, the last one without and with noniterative triples, at the nonrelativistic all-electron level. We also report a high-quality theoretical interatomic potential for the Xe dimer, gained using the relativistic effective potential/core polarization potential scheme. These calculations used valence basis set of cc-pVQZ quality supplemented with a set of midbond functions. The second virial coefficient of Xe nuclear shielding, which is probably the experimentally best-characterized intermolecular interaction effect in nuclear magnetic resonance spectroscopy, is computed as a function of temperature, and compared to experiment and earlier theoretical results. The best results for the second virial coefficient, obtained using the CCSD(CP) binary chemical shift curve and either our best theoretical potential or the empirical potentials from the literature, are in good agreement with experiment. Zero-point vibrational corrections of delta, Delta sigma, chi (parallel), and C (perpendicular) in the nu=0, J=0 rovibrational ground state of the xenon dimer are also reported.

Semiclassical theory of the self-consistent vibration-rotation fields and its application to the bending-rotation interaction in the H{sub 2}O molecule

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

Skalozub, A.S.; Tsaune, A.Ya.

1994-12-01

A new approach for analyzing the highly excited vibration-rotation (VR) states of nonrigid molecules is suggested. It is based on the separation of the vibrational and rotational terms in the molecular VR Hamiltonian by introducing periodic auxiliary fields. These fields transfer different interactions within a molecule and are treated in terms of the mean-field approximation. As a result, the solution of the stationary Schroedinger equation with the VR Hamiltonian amounts to a quantization of the Berry phase in a problem of the molecular angular-momentum motion in a certain periodic VR field (rotational problem). The quantization procedure takes into account themore » motion of the collective vibrational variables in the appropriate VR potentials (vibrational problem). The quantization rules, the mean-field configurations of auxiliary interactions, and the solutions to the Schrodinger equations for the vibrational and rotational problems are self-consistently connected with one another. The potentialities of the theory are demonstrated by the bending-rotation interaction modeled by the Bunker-Landsberg potential function in the H{sub 2} molecule. The calculations are compared with both the results of the exact computations and those of other approximate methods. 32 refs., 4 tabs.« less

MRCI study on the spectroscopic parameters, transition dipole moments and transition probabilities of 16 low-lying states of the BeB radical

NASA Astrophysics Data System (ADS)

Zhou, Dan; Shi, Deheng; Sun, Jinfeng; Zhu, Zunlue

2018-03-01

In this work, we calculate the potential energy curves of 16 Λ-S and 36 Ω states of beryllium boride (BeB) radical using the complete active space self-consistent field method, followed by the valence internally contracted multireference configuration interaction approach with Davidson correction. The 16 Λ-S states are the X2Π, A2Σ+, B2Π, C2Δ, D2Ʃ-, E2Σ+, G2Π, I2Σ+, a4Σ-, b4Π, c4Σ-, d4Δ, e4Σ+, g4Π, h4Π, and 24Σ+, which are obtained from the first three dissociation channels of the BeB radical. The Ω states are obtained from the Λ-S states. Of the Λ-S states, the G2Π, I2Σ+, and h4Π states exhibit double well curves. The G2Π, b4Π, and g4Π states are inverted with the spin-orbit coupling effect included. The d4Δ, e4Σ+, and g4Π states as well as the second well of the h4Π state are very weakly bound. Avoided crossings exist between the G2Π and H2Π states, the A2Σ+ and E2Σ+ states, the c4Σ- and f4Σ- states, the g4Π and h4Π states, the I2Σ+ and 42Σ+ states, as well as the 24Σ+ and 34Σ+ states. To improve the quality of the potential energy curves, core-valence correlation and scalar relativistic corrections, as well as the extrapolation of the potential energies to the complete basis set limit, are included. The transition dipole moments are computed. Spectroscopic parameters and vibrational levels are determined along with Franck-Condon factors, Einstein coefficients, and radiative lifetimes of many electronic transitions. The transition probabilities are evaluated. The spin-orbit coupling effect on the spectroscopic parameters and vibrational levels is discussed. The spectroscopic parameters, vibrational levels, and transition probabilities reported in this paper can be considered very reliable and can be employed to predict these states in an appropriate spectroscopy experiment.

OVMS: the optical path difference and vibration monitoring system for the LBT and its interferometers

NASA Astrophysics Data System (ADS)

Kürster, M.; Bertram, T.; Borelli, J. L.; Brix, M.; Gässler, W.; Herbst, T. M.; Naranjo, V.; Pott, J.-U.; Trowitzsch, J.; Connors, T. E.; Hinz, P. M.; McMahon, T. J.; Ashby, D. S.; Brynnel, J. G.; Cushing, N. J.; Edgin, T.; Esguerra, J. D.; Green, R. F.; Kraus, J.; Little, J.; Beckmann, U.; Weigelt, G. P.

2010-07-01

Characterisation, mitigation and correction of telescope vibrations have proven to be crucial for the performance of astronomical infrared interferometers. The project teams of the interferometers for the LBT, LINC-NIRVANA and LBTI, and LBT Observatory (LBTO) have embarked on a joint effort to implement an accelerometer-based vibration measurement system distributed over the optical elements of the LBT. OVMS, the Optical Path Difference and Vibration Monitoring System will serve to (i) ensure conditions suitable for adaptive optics (AO) and interferometric (IF) observations and (ii) utilize vibration information, converted into tip-tilt and optical path difference data, in the control strategies of the LBT adaptive secondary mirrors and the beam combining interferometers. The system hardware is mainly developed by Steward Observatory's LBTI team and its installation at the LBT is underway. The OVMS software development and associated computer infrastructure is the responsibility of the LINC-NIRVANA team at MPIA Heidelberg. Initially, the OVMS will fill a data archive provided by LBTO that will be used to study vibration data and correlate them with telescope movements and environmental parameters thereby identifiying sources of vibrations and to eliminate or mitigate them. Data display tools will help LBTO staff to keep vibrations within predefined thresholds for quiet conditions for AO and IF observations. Later-on real-time data from the OVMS will be fed into the control loops of the AO systems and IF instruments in order to permit the correction of vibration signals with frequencies up to 450 Hz.

Largely reduced grid densities in a vibrational self-consistent field treatment do not significantly impact the resultingwavenumbers.

PubMed

Lutz, Oliver M D; Rode, Bernd M; Bonn, Günther K; Huck, Christian W

2014-12-17

Especially for larger molecules relevant to life sciences, vibrational self-consistent field (VSCF) calculations can become unmanageably demanding even when only first and second order potential coupling terms are considered. This paper investigates to what extent the grid density of the VSCF's underlying potential energy surface can be reduced without sacrificing accuracy of the resulting wavenumbers. Including single-mode and pair contributions, a reduction to eight points per mode did not introduce a significant deviation but improved the computational efficiency by a factor of four. A mean unsigned deviation of 1.3% from the experiment could be maintained for the fifteen molecules under investigation and the approach was found to be applicable to rigid, semi-rigid and soft vibrational problems likewise. Deprotonated phosphoserine, stabilized by two intramolecular hydrogen bonds, was investigated as an exemplary application.

A microscopic derivation of nuclear collective rotation-vibration model and its application to nuclei

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

Gulshani, P., E-mail: matlap@bell.net

We derive a microscopic version of the successful phenomenological hydrodynamic model of Bohr-Davydov-Faessler-Greiner for collective rotation-vibration motion of an axially symmetric deformed nucleus. The derivation is not limited to small oscillation amplitude. The nuclear Schrodinger equation is canonically transformed to collective co-ordinates, which is then linearized using a constrained variational method. The associated constraints are imposed on the wavefunction rather than on the particle co-ordinates. The approach yields three self-consistent, time-reversal invariant, cranking-type Schrodinger equations for the rotation-vibration and intrinsic motions, and a self-consistency equation. For harmonic oscillator mean-field potentials, these equations are solved in closed forms for excitation energy,more » cut-off angular momentum, and other nuclear properties for the ground-state rotational band in some deformed nuclei. The results are compared with measured data.« less

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. II. 1D spectra for a dimer.

PubMed

Tiwari, Vivek; Jonas, David M

2018-02-28

Vibrational-electronic resonance in photosynthetic pigment-protein complexes invalidates Förster's adiabatic framework for interpreting spectra and energy transfer, thus complicating determination of how the surrounding protein affects pigment properties. This paper considers the combined effects of vibrational-electronic resonance and inhomogeneous variations in the electronic excitation energies of pigments at different sites on absorption, emission, circular dichroism, and hole-burning spectra for a non-degenerate homodimer. The non-degenerate homodimer has identical pigments in different sites that generate differences in electronic energies, with parameters loosely based on bacteriochlorophyll a pigments in the Fenna-Matthews-Olson antenna protein. To explain the intensity borrowing, the excited state vibrational-electronic eigenvectors are discussed in terms of the vibrational basis localized on the individual pigments, as well as the correlated/anti-correlated vibrational basis delocalized over both pigments. Compared to those in the isolated pigment, vibrational satellites for the correlated vibration have the same frequency and precisely a factor of 2 intensity reduction through vibrational delocalization in both absorption and emission. Vibrational satellites for anti-correlated vibrations have their relaxed emission intensity reduced by over a factor 2 through vibrational and excitonic delocalization. In absorption, anti-correlated vibrational satellites borrow excitonic intensity but can be broadened away by the combination of vibronic resonance and site inhomogeneity; in parallel, their vibronically resonant excitonic partners are also broadened away. These considerations are consistent with photosynthetic antenna hole-burning spectra, where sharp vibrational and excitonic satellites are absent. Vibrational-excitonic resonance barely alters the inhomogeneously broadened linear absorption, emission, and circular dichroism spectra from those for a purely electronic excitonic coupling model. Energy transfer can leave excess energy behind as vibration on the electronic ground state of the donor, allowing vibrational relaxation on the donor's ground electronic state to make energy transfer permanent by removing excess energy from the excited electronic state of the dimer.

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. II. 1D spectra for a dimer

NASA Astrophysics Data System (ADS)

Tiwari, Vivek; Jonas, David M.

2018-02-01

Vibrational-electronic resonance in photosynthetic pigment-protein complexes invalidates Förster's adiabatic framework for interpreting spectra and energy transfer, thus complicating determination of how the surrounding protein affects pigment properties. This paper considers the combined effects of vibrational-electronic resonance and inhomogeneous variations in the electronic excitation energies of pigments at different sites on absorption, emission, circular dichroism, and hole-burning spectra for a non-degenerate homodimer. The non-degenerate homodimer has identical pigments in different sites that generate differences in electronic energies, with parameters loosely based on bacteriochlorophyll a pigments in the Fenna-Matthews-Olson antenna protein. To explain the intensity borrowing, the excited state vibrational-electronic eigenvectors are discussed in terms of the vibrational basis localized on the individual pigments, as well as the correlated/anti-correlated vibrational basis delocalized over both pigments. Compared to those in the isolated pigment, vibrational satellites for the correlated vibration have the same frequency and precisely a factor of 2 intensity reduction through vibrational delocalization in both absorption and emission. Vibrational satellites for anti-correlated vibrations have their relaxed emission intensity reduced by over a factor 2 through vibrational and excitonic delocalization. In absorption, anti-correlated vibrational satellites borrow excitonic intensity but can be broadened away by the combination of vibronic resonance and site inhomogeneity; in parallel, their vibronically resonant excitonic partners are also broadened away. These considerations are consistent with photosynthetic antenna hole-burning spectra, where sharp vibrational and excitonic satellites are absent. Vibrational-excitonic resonance barely alters the inhomogeneously broadened linear absorption, emission, and circular dichroism spectra from those for a purely electronic excitonic coupling model. Energy transfer can leave excess energy behind as vibration on the electronic ground state of the donor, allowing vibrational relaxation on the donor's ground electronic state to make energy transfer permanent by removing excess energy from the excited electronic state of the dimer.

Reliability of perceived neighbourhood conditions and the effects of measurement error on self-rated health across urban and rural neighbourhoods.

PubMed

Pruitt, Sandi L; Jeffe, Donna B; Yan, Yan; Schootman, Mario

2012-04-01

Limited psychometric research has examined the reliability of self-reported measures of neighbourhood conditions, the effect of measurement error on associations between neighbourhood conditions and health, and potential differences in the reliabilities between neighbourhood strata (urban vs rural and low vs high poverty). We assessed overall and stratified reliability of self-reported perceived neighbourhood conditions using five scales (social and physical disorder, social control, social cohesion, fear) and four single items (multidimensional neighbouring). We also assessed measurement error-corrected associations of these conditions with self-rated health. Using random-digit dialling, 367 women without breast cancer (matched controls from a larger study) were interviewed twice, 2-3 weeks apart. Test-retest (intraclass correlation coefficients (ICC)/weighted κ) and internal consistency reliability (Cronbach's α) were assessed. Differences in reliability across neighbourhood strata were tested using bootstrap methods. Regression calibration corrected estimates for measurement error. All measures demonstrated satisfactory internal consistency (α ≥ 0.70) and either moderate (ICC/κ=0.41-0.60) or substantial (ICC/κ=0.61-0.80) test-retest reliability in the full sample. Internal consistency did not differ by neighbourhood strata. Test-retest reliability was significantly lower among rural (vs urban) residents for two scales (social control, physical disorder) and two multidimensional neighbouring items; test-retest reliability was higher for physical disorder and lower for one multidimensional neighbouring item among the high (vs low) poverty strata. After measurement error correction, the magnitude of associations between neighbourhood conditions and self-rated health were larger, particularly in the rural population. Research is needed to develop and test reliable measures of perceived neighbourhood conditions relevant to the health of rural populations.

Self-consistent implementation of ensemble density functional theory method for multiple strongly correlated electron pairs

DOE PAGES

Filatov, Michael; Liu, Fang; Kim, Kwang S.; ...

2016-12-22

Here, the spin-restricted ensemble-referenced Kohn-Sham (REKS) method is based on an ensemble representation of the density and is capable of correctly describing the non-dynamic electron correlation stemming from (near-)degeneracy of several electronic configurations. The existing REKS methodology describes systems with two electrons in two fractionally occupied orbitals. In this work, the REKS methodology is extended to treat systems with four fractionally occupied orbitals accommodating four electrons and self-consistent implementation of the REKS(4,4) method with simultaneous optimization of the orbitals and their fractional occupation numbers is reported. The new method is applied to a number of molecular systems where simultaneous dissociationmore » of several chemical bonds takes place, as well as to the singlet ground states of organic tetraradicals 2,4-didehydrometaxylylene and 1,4,6,9-spiro[4.4]nonatetrayl.« less

Theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis-, and trans-1,2-difluoroethylenes

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

Nozirov, Farhod, E-mail: teobaldk@gmail.com, E-mail: farhod.nozirov@gmail.com; Stachów, Michał, E-mail: michal.stachow@gmail.com; Kupka, Teobald, E-mail: teobaldk@gmail.com, E-mail: farhod.nozirov@gmail.com

2014-04-14

A theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis- and trans-1,2-difluoroethylenes is reported. The results obtained using density functional theory (DFT) combined with large basis sets and gauge-independent atomic orbital calculations were critically compared with experiment and conventional, higher level correlated electronic structure methods. Accurate structural, vibrational, and NMR parameters of difluoroethylenes were obtained using several density functionals combined with dedicated basis sets. B3LYP/6-311++G(3df,2pd) optimized structures of difluoroethylenes closely reproduced experimental geometries and earlier reported benchmark coupled cluster results, while BLYP/6-311++G(3df,2pd) produced accurate harmonic vibrational frequencies. The most accurate vibrations were obtained using B3LYP/6-311++G(3df,2pd)more » with correction for anharmonicity. Becke half and half (BHandH) density functional predicted more accurate {sup 19}F isotropic shieldings and van Voorhis and Scuseria's τ-dependent gradient-corrected correlation functional yielded better carbon shieldings than B3LYP. A surprisingly good performance of Hartree-Fock (HF) method in predicting nuclear shieldings in these molecules was observed. Inclusion of zero-point vibrational correction markedly improved agreement with experiment for nuclear shieldings calculated by HF, MP2, CCSD, and CCSD(T) methods but worsened the DFT results. The threefold improvement in accuracy when predicting {sup 2}J(FF) in 1,1-difluoroethylene for BHandH density functional compared to B3LYP was observed (the deviations from experiment were −46 vs. −115 Hz)« less

Estimating the intrinsic limit of the Feller-Peterson-Dixon composite approach when applied to adiabatic ionization potentials in atoms and small molecules

NASA Astrophysics Data System (ADS)

Feller, David

2017-07-01

Benchmark adiabatic ionization potentials were obtained with the Feller-Peterson-Dixon (FPD) theoretical method for a collection of 48 atoms and small molecules. In previous studies, the FPD method demonstrated an ability to predict atomization energies (heats of formation) and electron affinities well within a 95% confidence level of ±1 kcal/mol. Large 1-particle expansions involving correlation consistent basis sets (up to aug-cc-pV8Z in many cases and aug-cc-pV9Z for some atoms) were chosen for the valence CCSD(T) starting point calculations. Despite their cost, these large basis sets were chosen in order to help minimize the residual basis set truncation error and reduce dependence on approximate basis set limit extrapolation formulas. The complementary n-particle expansion included higher order CCSDT, CCSDTQ, or CCSDTQ5 (coupled cluster theory with iterative triple, quadruple, and quintuple excitations) corrections. For all of the chemical systems examined here, it was also possible to either perform explicit full configuration interaction (CI) calculations or to otherwise estimate the full CI limit. Additionally, corrections associated with core/valence correlation, scalar relativity, anharmonic zero point vibrational energies, non-adiabatic effects, and other minor factors were considered. The root mean square deviation with respect to experiment for the ionization potentials was 0.21 kcal/mol (0.009 eV). The corresponding level of agreement for molecular enthalpies of formation was 0.37 kcal/mol and for electron affinities 0.20 kcal/mol. Similar good agreement with experiment was found in the case of molecular structures and harmonic frequencies. Overall, the combination of energetic, structural, and vibrational data (655 comparisons) reflects the consistent ability of the FPD method to achieve close agreement with experiment for small molecules using the level of theory applied in this study.

Breaking through the glass ceiling: The correlation between the self-diffusivity in and krypton permeation through deeply supercooled liquid nanoscale methanol films

NASA Astrophysics Data System (ADS)

Smith, R. Scott; Matthiesen, Jesper; Kay, Bruce D.

2010-03-01

Molecular beam techniques, temperature-programmed desorption (TPD), and reflection absorption infrared spectroscopy (RAIRS) are used to explore the relationship between krypton permeation through and the self-diffusivity of supercooled liquid methanol at temperatures (100-115 K) near the glass transition temperature, Tg (103 K). Layered films, consisting of CH3OH and CD3OH, are deposited on top of a monolayer of Kr on a graphene covered Pt(111) substrate at 25 K. Concurrent Kr TPD and RAIRS spectra are acquired during the heating of the composite film to temperatures above Tg. The CO vibrational stretch is sensitive to the local molecular environment and is used to determine the supercooled liquid diffusivity from the intermixing of the isotopic layers. We find that the Kr permeation and the diffusivity of the supercooled liquid are directly and quantitatively correlated. These results validate the rare-gas permeation technique as a tool for probing the diffusivity of supercooled liquids.

Breaking through the glass ceiling: the correlation between the self-diffusivity in and krypton permeation through deeply supercooled liquid nanoscale methanol films.

PubMed

Smith, R Scott; Matthiesen, Jesper; Kay, Bruce D

2010-03-28

Molecular beam techniques, temperature-programmed desorption (TPD), and reflection absorption infrared spectroscopy (RAIRS) are used to explore the relationship between krypton permeation through and the self-diffusivity of supercooled liquid methanol at temperatures (100-115 K) near the glass transition temperature, T(g) (103 K). Layered films, consisting of CH(3)OH and CD(3)OH, are deposited on top of a monolayer of Kr on a graphene covered Pt(111) substrate at 25 K. Concurrent Kr TPD and RAIRS spectra are acquired during the heating of the composite film to temperatures above T(g). The CO vibrational stretch is sensitive to the local molecular environment and is used to determine the supercooled liquid diffusivity from the intermixing of the isotopic layers. We find that the Kr permeation and the diffusivity of the supercooled liquid are directly and quantitatively correlated. These results validate the rare-gas permeation technique as a tool for probing the diffusivity of supercooled liquids.

Short-range second order screened exchange correction to RPA correlation energies

NASA Astrophysics Data System (ADS)

Beuerle, Matthias; Ochsenfeld, Christian

2017-11-01

Direct random phase approximation (RPA) correlation energies have become increasingly popular as a post-Kohn-Sham correction, due to significant improvements over DFT calculations for properties such as long-range dispersion effects, which are problematic in conventional density functional theory. On the other hand, RPA still has various weaknesses, such as unsatisfactory results for non-isogyric processes. This can in parts be attributed to the self-correlation present in RPA correlation energies, leading to significant self-interaction errors. Therefore a variety of schemes have been devised to include exchange in the calculation of RPA correlation energies in order to correct this shortcoming. One of the most popular RPA plus exchange schemes is the second order screened exchange (SOSEX) correction. RPA + SOSEX delivers more accurate absolute correlation energies and also improves upon RPA for non-isogyric processes. On the other hand, RPA + SOSEX barrier heights are worse than those obtained from plain RPA calculations. To combine the benefits of RPA correlation energies and the SOSEX correction, we introduce a short-range RPA + SOSEX correction. Proof of concept calculations and benchmarks showing the advantages of our method are presented.

Short-range second order screened exchange correction to RPA correlation energies.

PubMed

Beuerle, Matthias; Ochsenfeld, Christian

2017-11-28

Direct random phase approximation (RPA) correlation energies have become increasingly popular as a post-Kohn-Sham correction, due to significant improvements over DFT calculations for properties such as long-range dispersion effects, which are problematic in conventional density functional theory. On the other hand, RPA still has various weaknesses, such as unsatisfactory results for non-isogyric processes. This can in parts be attributed to the self-correlation present in RPA correlation energies, leading to significant self-interaction errors. Therefore a variety of schemes have been devised to include exchange in the calculation of RPA correlation energies in order to correct this shortcoming. One of the most popular RPA plus exchange schemes is the second order screened exchange (SOSEX) correction. RPA + SOSEX delivers more accurate absolute correlation energies and also improves upon RPA for non-isogyric processes. On the other hand, RPA + SOSEX barrier heights are worse than those obtained from plain RPA calculations. To combine the benefits of RPA correlation energies and the SOSEX correction, we introduce a short-range RPA + SOSEX correction. Proof of concept calculations and benchmarks showing the advantages of our method are presented.

Accounting for the exact degeneracy and quasidegeneracy in the automerization of cyclobutadiene via multireference coupled-cluster methods.

PubMed

Li, Xiangzhu; Paldus, Josef

2009-09-21

The automerization of cyclobutadiene (CBD) is employed to test the performance of the reduced multireference (RMR) coupled-cluster (CC) method with singles and doubles (RMR CCSD) that employs a modest-size MR CISD wave function as an external source for the most important (primary) triples and quadruples in order to account for the nondynamic correlation effects in the presence of quasidegeneracy, as well as of its perturbatively corrected version accounting for the remaining (secondary) triples [RMR CCSD(T)]. The experimental results are compared with those obtained by the standard CCSD and CCSD(T) methods, by the state universal (SU) MR CCSD and its state selective or state specific (SS) version as formulated by Mukherjee et al. (SS MRCC or MkMRCC) and, wherever available, by the Brillouin-Wigner MRCC [MR BWCCSD(T)] method. Both restricted Hartree-Fock (RHF) and multiconfigurational self-consistent field (MCSCF) molecular orbitals are employed. For a smaller STO-3G basis set we also make a comparison with the exact full configuration interaction (FCI) results. Both fundamental vibrational energies-as obtained via the integral averaging method (IAM) that can handle anomalous potentials and automatically accounts for anharmonicity- and the CBD automerization barrier for the interconversion of the two rectangular structures are considered. It is shown that the RMR CCSD(T) potential has the smallest nonparallelism error relative to the FCI potential and the corresponding fundamental vibrational frequencies compare reasonably well with the experimental ones and are very close to those recently obtained by other authors. The effect of anharmonicity is assessed using the second-order perturbation theory (MP2). Finally, the invariance of the RMR CC methods with respect to orbital rotations is also examined.

Theoretical studies for excited-state tautomerization in the 7-azaindole-(CH3OH)n (n = 1 and 2) complexes in the gas phase.

PubMed

Fang, Hua; Kim, Yongho

2011-12-01

The excited-state tautomerization of 7-azaindole (7AI) complexes bonded with either one or two methanol molecule(s) was studied by systematic quantum mechanical calculations in the gas phases. Electronic structures and energies for the reactant, transition state (TS), and product were computed at the complete active space self-consistent field (CASSCF) levels with the second-order multireference perturbation theory (MRPT2) to consider the dynamic electron correlation. The time-dependent density functional theory (TDDFT) was also used for comparison. The excited-state double proton transfer (ESDPT) in 7AI-CH(3)OH occurs in a concerted but asynchronous mechanism. Similarly, such paths are also found in the two transition states during the excited-state triple proton transfer (ESTPT) of the 7AI-(CH(3)OH)(2) complex. In the first TS, the pyrrole ring proton first migrated to methanol, while in the second the methanol proton moved first to the pyridine ring. The CASSCF level with the MRPT2 correction showed that the former path was much preferable to the latter, and the ESDPT is much slower than the ESTPT. Additionally, the vibrational-mode enhanced tautomerization in the 7AI-(CH(3)OH)(2) complex was also studied. We found that the excitation of the low-frequency mode shortens the reaction path to increase the tautomerization rate. Overall, most TDDFT methods used in this study predicted different TS structures and barriers from the CASSCF methods with MRPT2 corrections. © 2011 American Chemical Society

Consistent Correlations for Parameterised Boolean Equation Systems with Applications in Correctness Proofs for Manipulations

NASA Astrophysics Data System (ADS)

Willemse, Tim A. C.

We introduce the concept of consistent correlations for parameterised Boolean equation systems (PBESs), motivated largely by the laborious proofs of correctness required for most manipulations in this setting. Consistent correlations focus on relating the equations that occur in PBESs, rather than their solutions. For a fragment of PBESs, consistent correlations are shown to coincide with a recently introduced form of bisimulation. Finally, we show that bisimilarity on processes induces consistent correlations on PBESs encoding model checking problems. We apply our theory to two example manipulations from the literature.

Non-orthogonal internally contracted multi-configurational perturbation theory (NICPT): Dynamic electron correlation for large, compact active spaces

NASA Astrophysics Data System (ADS)

Kähler, Sven; Olsen, Jeppe

2017-11-01

A computational method is presented for systems that require high-level treatments of static and dynamic electron correlation but cannot be treated using conventional complete active space self-consistent field-based methods due to the required size of the active space. Our method introduces an efficient algorithm for perturbative dynamic correlation corrections for compact non-orthogonal MCSCF calculations. In the algorithm, biorthonormal expansions of orbitals and CI-wave functions are used to reduce the scaling of the performance determining step from quadratic to linear in the number of configurations. We describe a hierarchy of configuration spaces that can be chosen for the active space. Potential curves for the nitrogen molecule and the chromium dimer are compared for different configuration spaces. Already the most compact spaces yield qualitatively correct potentials that with increasing size of configuration spaces systematically approach complete active space results.

Bottom-up coarse-grained models with predictive accuracy and transferability for both structural and thermodynamic properties of heptane-toluene mixtures

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

Dunn, Nicholas J. H.; Noid, W. G., E-mail: wnoid@chem.psu.edu

This work investigates the promise of a “bottom-up” extended ensemble framework for developing coarse-grained (CG) models that provide predictive accuracy and transferability for describing both structural and thermodynamic properties. We employ a force-matching variational principle to determine system-independent, i.e., transferable, interaction potentials that optimally model the interactions in five distinct heptane-toluene mixtures. Similarly, we employ a self-consistent pressure-matching approach to determine a system-specific pressure correction for each mixture. The resulting CG potentials accurately reproduce the site-site rdfs, the volume fluctuations, and the pressure equations of state that are determined by all-atom (AA) models for the five mixtures. Furthermore, we demonstratemore » that these CG potentials provide similar accuracy for additional heptane-toluene mixtures that were not included their parameterization. Surprisingly, the extended ensemble approach improves not only the transferability but also the accuracy of the calculated potentials. Additionally, we observe that the required pressure corrections strongly correlate with the intermolecular cohesion of the system-specific CG potentials. Moreover, this cohesion correlates with the relative “structure” within the corresponding mapped AA ensemble. Finally, the appendix demonstrates that the self-consistent pressure-matching approach corresponds to minimizing an appropriate relative entropy.« less

Bottom-up coarse-grained models with predictive accuracy and transferability for both structural and thermodynamic properties of heptane-toluene mixtures.

PubMed

Dunn, Nicholas J H; Noid, W G

2016-05-28

This work investigates the promise of a "bottom-up" extended ensemble framework for developing coarse-grained (CG) models that provide predictive accuracy and transferability for describing both structural and thermodynamic properties. We employ a force-matching variational principle to determine system-independent, i.e., transferable, interaction potentials that optimally model the interactions in five distinct heptane-toluene mixtures. Similarly, we employ a self-consistent pressure-matching approach to determine a system-specific pressure correction for each mixture. The resulting CG potentials accurately reproduce the site-site rdfs, the volume fluctuations, and the pressure equations of state that are determined by all-atom (AA) models for the five mixtures. Furthermore, we demonstrate that these CG potentials provide similar accuracy for additional heptane-toluene mixtures that were not included their parameterization. Surprisingly, the extended ensemble approach improves not only the transferability but also the accuracy of the calculated potentials. Additionally, we observe that the required pressure corrections strongly correlate with the intermolecular cohesion of the system-specific CG potentials. Moreover, this cohesion correlates with the relative "structure" within the corresponding mapped AA ensemble. Finally, the appendix demonstrates that the self-consistent pressure-matching approach corresponds to minimizing an appropriate relative entropy.

Skyrme RPA description of γ-vibrational states in rare-earth nuclei

NASA Astrophysics Data System (ADS)

Nesterenko, V. O.; Kartavenko, V. G.; Kleinig, W.; Kvasil, J.; Repko, A.; Jolos, R. V.; Reinhard, P.-G.

2016-01-01

The lowest γ-vibrational states with Kπ = 2+γ in well-deformed Dy, Er and Yb isotopes are investigated within the self-consistent separable quasiparticle random-phase-approximation (QRPA) approach based on the Skyrme functional. The energies Eγ and reduced transition probabilities B(E2)γ of the states are calculated with the Skyrme force SV-mas10. We demonstrate the strong effect of the pairing blocking on the energies of γ-vibrational states. It is also shown that collectivity of γ-vibrational states is strictly determined by keeping the Nilsson selection rules in the corresponding lowest 2qp configurations.

Time-varying output performances of piezoelectric vibration energy harvesting under nonstationary random vibrations

NASA Astrophysics Data System (ADS)

Yoon, Heonjun; Kim, Miso; Park, Choon-Su; Youn, Byeng D.

2018-01-01

Piezoelectric vibration energy harvesting (PVEH) has received much attention as a potential solution that could ultimately realize self-powered wireless sensor networks. Since most ambient vibrations in nature are inherently random and nonstationary, the output performances of PVEH devices also randomly change with time. However, little attention has been paid to investigating the randomly time-varying electroelastic behaviors of PVEH systems both analytically and experimentally. The objective of this study is thus to make a step forward towards a deep understanding of the time-varying performances of PVEH devices under nonstationary random vibrations. Two typical cases of nonstationary random vibration signals are considered: (1) randomly-varying amplitude (amplitude modulation; AM) and (2) randomly-varying amplitude with randomly-varying instantaneous frequency (amplitude and frequency modulation; AM-FM). In both cases, this study pursues well-balanced correlations of analytical predictions and experimental observations to deduce the relationships between the time-varying output performances of the PVEH device and two primary input parameters, such as a central frequency and an external electrical resistance. We introduce three correlation metrics to quantitatively compare analytical prediction and experimental observation, including the normalized root mean square error, the correlation coefficient, and the weighted integrated factor. Analytical predictions are in an excellent agreement with experimental observations both mechanically and electrically. This study provides insightful guidelines for designing PVEH devices to reliably generate electric power under nonstationary random vibrations.

Development of an unsteady aerodynamics model to improve correlation of computed blade stresses with test data

NASA Technical Reports Server (NTRS)

Gangwani, S. T.

1985-01-01

A reliable rotor aeroelastic analysis operational that correctly predicts the vibration levels for a helicopter is utilized to test various unsteady aerodynamics models with the objective of improving the correlation between test and theory. This analysis called Rotor Aeroelastic Vibration (RAVIB) computer program is based on a frequency domain forced response analysis which utilizes the transfer matrix techniques to model helicopter/rotor dynamic systems of varying degrees of complexity. The results for the AH-1G helicopter rotor were compared with the flight test data during high speed operation and they indicated a reasonably good correlation for the beamwise and chordwise blade bending moments, but for torsional moments the correlation was poor. As a result, a new aerodynamics model based on unstalled synthesized data derived from the large amplitude oscillating airfoil experiments was developed and tested.

Accurate ab initio binding energies of the benzene dimer.

PubMed

Park, Young Choon; Lee, Jae Shin

2006-04-20

Accurate binding energies of the benzene dimer at the T and parallel displaced (PD) configurations were determined using the single- and double-coupled cluster method with perturbative triple correction (CCSD(T)) with correlation-consistent basis sets and an effective basis set extrapolation scheme recently devised. The difference between the estimated CCSD(T) basis set limit electronic binding energies for the T and PD shapes appears to amount to more than 0.3 kcal/mol, indicating the PD shape is a more stable configuration than the T shape for this dimer in the gas phase. This conclusion is further strengthened when a vibrational zero-point correction to the electronic binding energies of this dimer is made, which increases the difference between the two configurations to 0.4-0.5 kcal/mol. The binding energies of 2.4 and 2.8 kcal/mol for the T and PD configurations are in good accord with the previous experimental result from ionization potential measurement.

Theoretical investigation of the structural, electronic, and thermodynamic properties of CdS1-xSex alloys

NASA Astrophysics Data System (ADS)

Long, Debing; Li, Mingkai; Meng, Dongxue; Ahuja, Rajeev; He, Yunbin

2018-03-01

In this work, the structural, electronic, and thermodynamic properties of wurtzite (WZ) and zincblende (ZB) CdS1-xSex alloys are investigated using the density functional theory (DFT) and the cluster expansion method. A special quasirandom structure containing 16 atoms is constructed to calculate the band structures of random alloys. The band gaps of CdS1-xSex alloys are direct and decrease as the Se content increases. The delta self-consistent-field method is applied to correct band gaps that are underestimated by DFT. The band offsets clearly reflect the variation in valence band maxima and conduction band minima, thus providing information useful to the design of relevant quantum well structures. The positive formation enthalpies of both phases imply that CdS1-xSex is an immiscible system and tends to phase separate. The influence of lattice vibrations on the phase diagram is investigated by calculating the phonon density of states. Lattice vibration effects can reduce the critical temperature Tc and increase alloy solid solubilities. This influence is especially significant in the ZB structure. When only chemical interactions are present, the Tc values for WZ- and ZB-CdS1-xSex are 260 K and 249 K, respectively. The lattice vibration enthalpy and entropy lower the Tc to 255 K and 233 K, respectively.

Implementation of a robust hybrid rotary-translational vibration energy harvester for autonomous self-powered acceleration measurement

NASA Astrophysics Data System (ADS)

Payne, Owen R.; Vandewater, Luke A.; Ung, Chandarin; Moss, Scott D.

2015-04-01

In this paper, a self-powered wireless sensor node utilising ambient vibrations for power is described. The device consists of a vibration energy harvester, power management system, microcontroller, accelerometer, RF transmitter/receiver and external LED indicators. The vibration energy harvester is adapted from a previously reported hybrid rotary-translational device and uses a pair of copper coil transducers to convert the mechanical energy of a magnetic sphere into usable electricity. The device requires less than 0.8 mW of power to operate continuously in its present setup (with LED indicators off) while measuring acceleration at a sample rate of 200 Hz, with the power source providing 39.7 mW of power from 500 mg excitations at 5.5 Hz. When usable input energy is removed, the device will continue to transmit data for more than 5 minutes.

Characterization of the X~ 2A1, A~ 2B1, and X~ 2Π electronic states of the Ga2H molecule and the X~ 2A' and A~ 2A'' isomerization transition states connecting the three minima

NASA Astrophysics Data System (ADS)

Wang, Hongyan; Wang, Suyun; Yan, Ge; Yamaguchi, Yukio; Schaefer, Henry F.

2006-01-01

A wide range of highly correlated ab initio methods has been used to predict the geometrical parameters of the linear (X˜Π2) and H-bridged (X˜A12 and ÃB12) Ga2H isomers and two isomerization transition states (X˜A'2 and ÃA″2) connecting the three minima. Dipole moments and vibrational frequencies are also obtained. The global minimum X˜A12 ground state of the H-bridged GaHGa isomer is predicted to lie only 1.6 [1.9 with the zero-point vibrational energy (ZPVE) corrections] kcalmol-1 below the ÃB12 state. The X˜A12 state lies 5.4kcalmol-1 below the X˜Π2 ground state of the linear GaGaH isomer at the coupled-cluster with single, double, and perturbative triple excitations [CCSD(T)] level of theory with the augmented correlation-consistent polarized valence quadruple-zeta (aug-cc-pVQZ) basis set. The full triples coupled-cluster method is found to alter these CCSD(T) predictions by as much as 0.3kcalmol-1. The forward isomerization barriers from the linear ground state to the X˜A'2 and ÃA″2 transition states are determined to be 3.3 and 5.3kcalmol-1, respectively. The reverse isomerization barrier between the X˜A12 GaHGa structure and the X˜Π2 GaGaH structure is predicted to be 8.6 (8.2 with the ZPVE corrections) kcalmol-1 at the aug-cc-pVQZ CCSD(T) level of theory.

The self-consistency model of subjective confidence.

PubMed

Koriat, Asher

2012-01-01

How do people monitor the correctness of their answers? A self-consistency model is proposed for the process underlying confidence judgments and their accuracy. In answering a 2-alternative question, participants are assumed to retrieve a sample of representations of the question and base their confidence on the consistency with which the chosen answer is supported across representations. Confidence is modeled by analogy to the calculation of statistical level of confidence (SLC) in testing hypotheses about a population and represents the participant's assessment of the likelihood that a new sample will yield the same choice. Assuming that participants draw representations from a commonly shared item-specific population of representations, predictions were derived regarding the function relating confidence to inter-participant consensus and intra-participant consistency for the more preferred (majority) and the less preferred (minority) choices. The predicted pattern was confirmed for several different tasks. The confidence-accuracy relationship was shown to be a by-product of the consistency-correctness relationship: It is positive because the answers that are consistently chosen are generally correct, but negative when the wrong answers tend to be favored. The overconfidence bias stems from the reliability-validity discrepancy: Confidence monitors reliability (or self-consistency), but its accuracy is evaluated in calibration studies against correctness. Simulation and empirical results suggest that response speed is a frugal cue for self-consistency, and its validity depends on the validity of self-consistency in predicting performance. Another mnemonic cue-accessibility, which is the overall amount of information that comes to mind-makes an added, independent contribution. Self-consistency and accessibility may correspond to the 2 parameters that affect SLC: sample variance and sample size.

Correlation analysis of motor current and chatter vibration in grinding using complex continuous wavelet coherence

NASA Astrophysics Data System (ADS)

Liu, Yao; Wang, Xiufeng; Lin, Jing; Zhao, Wei

2016-11-01

Motor current is an emerging and popular signal which can be used to detect machining chatter with its multiple advantages. To achieve accurate and reliable chatter detection using motor current, it is important to make clear the quantitative relationship between motor current and chatter vibration, which has not yet been studied clearly. In this study, complex continuous wavelet coherence, including cross wavelet transform and wavelet coherence, is applied to the correlation analysis of motor current and chatter vibration in grinding. Experimental results show that complex continuous wavelet coherence performs very well in demonstrating and quantifying the intense correlation between these two signals in frequency, amplitude and phase. When chatter occurs, clear correlations in frequency and amplitude in the chatter frequency band appear and the phase difference of current signal to vibration signal turns from random to stable. The phase lead of the most correlated chatter frequency is the largest. With the further development of chatter, the correlation grows up in intensity and expands to higher order chatter frequency band. The analyzing results confirm that there is a consistent correlation between motor current and vibration signals in the grinding chatter process. However, to achieve accurate and reliable chatter detection using motor current, the frequency response bandwidth of current loop of the feed drive system must be wide enough to response chatter effectively.

Aerodynamic instability: A case history

NASA Technical Reports Server (NTRS)

Eisenmann, R. C.

1985-01-01

The identification, diagnosis, and final correction of complex machinery malfunctions typically require the correlation of many parameters such as mechanical construction, process influence, maintenance history, and vibration response characteristics. The progression is reviewed of field testing, diagnosis, and final correction of a specific machinery instability problem. The case history presented addresses a unique low frequency instability problem on a high pressure barrel compressor. The malfunction was eventually diagnosed as a fluidic mechanism that manifested as an aerodynamic disturbance to the rotor assembly.

On the bonding mechanism of CO to Pt(111) and its effect on the vibrational frequency of chemisorbed CO

NASA Astrophysics Data System (ADS)

Illas, F.; Zurita, S.; Márquez, A. M.; Rubio, J.

1997-04-01

The chemisorption of CO on the atop site of Pt(111) has been simulated by a Pt4 cluster model. Ab initio self consistent field (SCF) and complete active space self consistent field (CASSCF) cluster model wave functions have been obtained for the electronic ground state. Likewise, ab initio SCF wavefunctions have been obtained for two other electronic states. The optimum geometry and vibrational frequencies of chemisorbed CO are reported for the three states. The interaction energy and vibrational shift of chemisorbed CO, with respect to free gas phase CO, have been analyzed for the three electronic states. This analysis is carried out by means of the constrained space orbital variation (CSOV) method. In all cases the bond is found to be dominated by σ donation and π back-donation, known as Blyholder's mechanism. This mechanism is further supported by SCF calculations on a larger, Pt13, cluster model. For both clusters, the CSOV analysis of the vibrational frequency definitely shows that, contrary to previous recent studies, a major contribution to the experimentally observed vibrational shift comes from the π back-donation mechanism. However, we found that, contrary to common belief, σ donation also acts to lower the CO frequency and not to increase it. Physical reasons for such unexpected behaviour are given.

Relationship between hand-arm vibration exposure and onset time for symptoms in a heavy engineering production workshop.

PubMed

Burström, Lage; Hagberg, Mats; Lundström, Ronnie; Nilsson, Tohr

2006-06-01

This study examined onset time for reported vascular and neurological symptoms in relation to the vibration load in a group of workers exposed to vibration. Information on the self-stated year for the first occurrence of symptoms was collected by means of questionnaires. During interviews data were obtained on self-stated estimations of daily exposure time, type of tool, and number of months or years with different exposures. The estimations of the vibration magnitudes of exposure were based on conducted measurements. From these data, the individual vibration exposure at the time of onset of symptoms was calculated. The incidence was 25.6 and 32.9 per 1000 exposure years for vascular and neurological symptoms, respectively, in the group of workers. The first onset of symptoms appeared after an average of 12 years of exposure. For the workers, the symptoms of vascular or neurological disorders started after about the same number of exposure years. The calculated accumulated acceleration correlated best with the onset time of symptoms. It was concluded that, since the workers' exposure to vibration was below the action level established in the European vibration directive, the results suggest that the action level is not a safe level for avoiding vascular and neurological symptoms.

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.

Calculation of 125Te NMR Chemical Shifts at the Full Four-Component Relativistic Level with Taking into Account Solvent and Vibrational Corrections: A Gateway to Better Agreement with Experiment.

PubMed

Rusakova, Irina L; Rusakov, Yuriy Yu; Krivdin, Leonid B

2017-06-29

Four-component relativistic calculations of 125 Te NMR chemical shifts were performed in the series of 13 organotellurium compounds, potential precursors of the biologically active species, at the density functional theory level under the nonrelativistic and four-component fully relativistic conditions using locally dense basis set scheme derived from relativistic Dyall's basis sets. The relativistic effects in tellurium chemical shifts were found to be of as much as 20-25% of the total calculated values. The vibrational and solvent corrections to 125 Te NMR chemical shifts are about, accordingly, 6 and 8% of their total values. The PBE0 exchange-correlation functional turned out to give the best agreement of calculated tellurium shifts with their experimental values giving the mean absolute percentage error of 4% in the range of ∼1000 ppm, provided all corrections are taken into account.

Vibrational and thermodynamic properties of β-HMX: a first-principles investigation.

PubMed

Wu, Zhongqing; Kalia, Rajiv K; Nakano, Aiichiro; Vashishta, Priya

2011-05-28

Thermodynamic properties of β-HMX crystal are investigated using the quasi-harmonic approximation and density functional theory within the local density approximation (LDA), generalized gradient approximation (GGA), and GGA + empirical van der Waals (vdW) correction. It is found that GGA well describes the thermal expansion coefficient and heat capacity but fails to produce correct bulk modulus and equilibrium volume. The vdW correction improves the bulk modulus and volume, but worsens the thermal expansion coefficient and heat capacity. In contrast, LDA describes all thermodynamic properties with reasonable accuracy, and overall is a good exchange-correlation functional for β-HMX molecular crystal. The results also demonstrate significant contributions of phonons to the equation of state. The static calculation of equilibrium volume for β-HMX differs from the room-temperature value incorporating lattice vibrations by over 5%. Therefore, for molecular crystals, it is essential to include phonon contributions when calculated equation of state is compared with experimental data at ambient condition. © 2011 American Institute of Physics

Hydration and vibrational dynamics of betaine (N,N,N-trimethylglycine)

NASA Astrophysics Data System (ADS)

Li, Tanping; Cui, Yaowen; Mathaga, John; Kumar, Revati; Kuroda, Daniel G.

2015-06-01

Zwitterions are naturally occurring molecules that have a positive and a negative charge group in its structure and are of great importance in many areas of science. Here, the vibrational and hydration dynamics of the zwitterionic system betaine (N,N,N-trimethylglycine) is reported. The linear infrared spectrum of aqueous betaine exhibits an asymmetric band in the 1550-1700 cm-1 region of the spectrum. This band is attributed to the carboxylate asymmetric stretch of betaine. The potential of mean force computed from ab initio molecular dynamic simulations confirms that the two observed transitions of the linear spectrum are related to two different betaine conformers present in solution. A model of the experimental data using non-linear response theory agrees very well with a vibrational model comprising of two vibrational transitions. In addition, our modeling shows that spectral parameters such as the slope of the zeroth contour plot and central line slope are both sensitive to the presence of overlapping transitions. The vibrational dynamics of the system reveals an ultrafast decay of the vibrational population relaxation as well as the correlation of frequency-frequency correlation function (FFCF). A decay of ˜0.5 ps is observed for the FFCF correlation time and is attributed to the frequency fluctuations caused by the motions of water molecules in the solvation shell. The comparison of the experimental observations with simulations of the FFCF from ab initio molecular dynamics and a density functional theory frequency map shows a very good agreement corroborating the correct characterization and assignment of the derived parameters.

Hydration and vibrational dynamics of betaine (N,N,N-trimethylglycine)

PubMed Central

Li, Tanping; Cui, Yaowen; Mathaga, John; Kumar, Revati; Kuroda, Daniel G.

2015-01-01

Zwitterions are naturally occurring molecules that have a positive and a negative charge group in its structure and are of great importance in many areas of science. Here, the vibrational and hydration dynamics of the zwitterionic system betaine (N,N,N-trimethylglycine) is reported. The linear infrared spectrum of aqueous betaine exhibits an asymmetric band in the 1550-1700 cm−1 region of the spectrum. This band is attributed to the carboxylate asymmetric stretch of betaine. The potential of mean force computed from ab initio molecular dynamic simulations confirms that the two observed transitions of the linear spectrum are related to two different betaine conformers present in solution. A model of the experimental data using non-linear response theory agrees very well with a vibrational model comprising of two vibrational transitions. In addition, our modeling shows that spectral parameters such as the slope of the zeroth contour plot and central line slope are both sensitive to the presence of overlapping transitions. The vibrational dynamics of the system reveals an ultrafast decay of the vibrational population relaxation as well as the correlation of frequency-frequency correlation function (FFCF). A decay of ∼0.5 ps is observed for the FFCF correlation time and is attributed to the frequency fluctuations caused by the motions of water molecules in the solvation shell. The comparison of the experimental observations with simulations of the FFCF from ab initio molecular dynamics and a density functional theory frequency map shows a very good agreement corroborating the correct characterization and assignment of the derived parameters. PMID:26049458

A vibration correction method for free-fall absolute gravimeters

NASA Astrophysics Data System (ADS)

Qian, J.; Wang, G.; Wu, K.; Wang, L. J.

2018-02-01

An accurate determination of gravitational acceleration, usually approximated as 9.8 m s-2, has been playing an important role in the areas of metrology, geophysics, and geodetics. Absolute gravimetry has been experiencing rapid developments in recent years. Most absolute gravimeters today employ a free-fall method to measure gravitational acceleration. Noise from ground vibration has become one of the most serious factors limiting measurement precision. Compared to vibration isolators, the vibration correction method is a simple and feasible way to reduce the influence of ground vibrations. A modified vibration correction method is proposed and demonstrated. A two-dimensional golden section search algorithm is used to search for the best parameters of the hypothetical transfer function. Experiments using a T-1 absolute gravimeter are performed. It is verified that for an identical group of drop data, the modified method proposed in this paper can achieve better correction effects with much less computation than previous methods. Compared to vibration isolators, the correction method applies to more hostile environments and even dynamic platforms, and is expected to be used in a wider range of applications.

Effect of self-absorption correction on surface hardness estimation of Fe-Cr-Ni alloys via LIBS.

PubMed

Ramezanian, Zahra; Darbani, Seyyed Mohammad Reza; Majd, Abdollah Eslami

2017-08-20

The effect of self-absorption was investigated on the estimation of surface hardness of Fe-Cr-Ni metallic alloys by the laser-induced breakdown spectroscopy (LIBS) technique. For this purpose, the linear relationship between the ratio of chromium ionic to atomic line intensities (CrII/CrI) and surface hardness was studied, both before and after correcting the self-absorption effect. The correlation coefficient significantly increased from 47% to 90% after self-absorption correction. The results showed the measurements of surface hardness using LIBS can be more accurate and valid by correcting the self-absorption effect.

Comparison of sEMG processing methods during whole-body vibration exercise.

PubMed

Lienhard, Karin; Cabasson, Aline; Meste, Olivier; Colson, Serge S

2015-12-01

The objective was to investigate the influence of surface electromyography (sEMG) processing methods on the quantification of muscle activity during whole-body vibration (WBV) exercises. sEMG activity was recorded while the participants performed squats on the platform with and without WBV. The spikes observed in the sEMG spectrum at the vibration frequency and its harmonics were deleted using state-of-the-art methods, i.e. (1) a band-stop filter, (2) a band-pass filter, and (3) spectral linear interpolation. The same filtering methods were applied on the sEMG during the no-vibration trial. The linear interpolation method showed the highest intraclass correlation coefficients (no vibration: 0.999, WBV: 0.757-0.979) with the comparison measure (unfiltered sEMG during the no-vibration trial), followed by the band-stop filter (no vibration: 0.929-0.975, WBV: 0.661-0.938). While both methods introduced a systematic bias (P < 0.001), the error increased with increasing mean values to a higher degree for the band-stop filter. After adjusting the sEMG(RMS) during WBV for the bias, the performance of the interpolation method and the band-stop filter was comparable. The band-pass filter was in poor agreement with the other methods (ICC: 0.207-0.697), unless the sEMG(RMS) was corrected for the bias (ICC ⩾ 0.931, %LOA ⩽ 32.3). In conclusion, spectral linear interpolation or a band-stop filter centered at the vibration frequency and its multiple harmonics should be applied to delete the artifacts in the sEMG signals during WBV. With the use of a band-stop filter it is recommended to correct the sEMG(RMS) for the bias as this procedure improved its performance. Copyright © 2015 Elsevier Ltd. All rights reserved.

Criteria for acceptable levels of the Shinkansen Super Express train noise and vibration in residential areas

NASA Astrophysics Data System (ADS)

Yamanaka, K.; Nakagawa, T.; Kobayashi, F.; Kanada, S.; Tanahashi, M.; Muramatsu, T.; Yamada, S.

1982-10-01

A survey of 1187 housewives living in 18 areas along the Shinkansen Super Express (bullet train) railway was conducted by means of a self-administered health questionnaire (modified Cornell Medical Index). In addition, geographically corresponding measurements of noise level and vibration intensity were taken. The relationship of noise and vibration to positive responses (health complaints) related to bodily symptoms, illness and emotional disturbances was analyzed. The factors which correlated with an increase in the average number of positive responses included noise, vibration, age and health status. Such factors as marital status, educational level, part time work, duration of inhabitancy and occupation of the head of the houshold correlated poorly with the number of positive responses. Unhealthy respondents compared to healthy respondents are more frequently affected by noise and vibration. The rate of positive responses in the visual, respiratory, cardiovascular, digestive and nervous systems, sleep disturbances and emotional disturbances increased accordingly as noise and vibration increased. Combined effects of noise and vibration stimuli on the total number of positive responses (an indicator of general health) were found. This study has produced results indicating that the maximum permissible noise level should not exceed 70 dB(A) in the residential areas along the Shinkansen railway.

Vibration control of building structures using self-organizing and self-learning neural networks

NASA Astrophysics Data System (ADS)

Madan, Alok

2005-11-01

Past research in artificial intelligence establishes that artificial neural networks (ANN) are effective and efficient computational processors for performing a variety of tasks including pattern recognition, classification, associative recall, combinatorial problem solving, adaptive control, multi-sensor data fusion, noise filtering and data compression, modelling and forecasting. The paper presents a potentially feasible approach for training ANN in active control of earthquake-induced vibrations in building structures without the aid of teacher signals (i.e. target control forces). A counter-propagation neural network is trained to output the control forces that are required to reduce the structural vibrations in the absence of any feedback on the correctness of the output control forces (i.e. without any information on the errors in output activations of the network). The present study shows that, in principle, the counter-propagation network (CPN) can learn from the control environment to compute the required control forces without the supervision of a teacher (unsupervised learning). Simulated case studies are presented to demonstrate the feasibility of implementing the unsupervised learning approach in ANN for effective vibration control of structures under the influence of earthquake ground motions. The proposed learning methodology obviates the need for developing a mathematical model of structural dynamics or training a separate neural network to emulate the structural response for implementation in practice.

Method and apparatus for reconstructing in-cylinder pressure and correcting for signal decay

DOEpatents

Huang, Jian

2013-03-12

A method comprises steps for reconstructing in-cylinder pressure data from a vibration signal collected from a vibration sensor mounted on an engine component where it can generate a signal with a high signal-to-noise ratio, and correcting the vibration signal for errors introduced by vibration signal charge decay and sensor sensitivity. The correction factors are determined as a function of estimated motoring pressure and the measured vibration signal itself with each of these being associated with the same engine cycle. Accordingly, the method corrects for charge decay and changes in sensor sensitivity responsive to different engine conditions to allow greater accuracy in the reconstructed in-cylinder pressure data. An apparatus is also disclosed for practicing the disclosed method, comprising a vibration sensor, a data acquisition unit for receiving the vibration signal, a computer processing unit for processing the acquired signal and a controller for controlling the engine operation based on the reconstructed in-cylinder pressure.

Distributed optical fiber vibration sensing using phase-generated carrier demodulation algorithm

NASA Astrophysics Data System (ADS)

Yu, Zhihua; Zhang, Qi; Zhang, Mingyu; Dai, Haolong; Zhang, Jingjing; Liu, Li; Zhang, Lijun; Jin, Xing; Wang, Gaifang; Qi, Guang

2018-05-01

A novel optical fiber-distributed vibration-sensing system is proposed, which is based on self-interference of Rayleigh backscattering with phase-generated carrier (PGC) demodulation algorithm. Pulsed lights are sent into the sensing fiber and the Rayleigh backscattering light from a certain position along the sensing fiber would interfere through an unbalanced Michelson interferometry to generate the interference light. An improved PGC demodulation algorithm is carried out to recover the phase information of the interference signal, which carries the sensing information. Three vibration events were applied simultaneously to different positions over 2000 m sensing fiber and demodulated correctly. The spatial resolution is 10 m, and the noise level of the Φ-OTDR system we proposed is about 10-3 rad/\\surd {Hz}, and the signal-to-noise ratio is about 30.34 dB.

Auxiliary-fermion approach to critical fluctuations in the two-dimensional quantum antiferromagnetic Heisenberg model

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

Brinckmann, Jan; Woelfle, Peter

2004-11-01

The nearest-neighbor quantum antiferromagnetic (AF) Heisenberg model for spin-1/2 on a two-dimensional square lattice is studied in the auxiliary-fermion representation. Expressing spin operators by canonical fermionic particles requires a constraint on the fermion charge Q{sub i}=1 on each lattice site i, which is imposed approximately through the thermal average. The resulting interacting fermion system is first treated in mean-field theory (MFT), which yields an AF ordered ground state and spin waves in quantitative agreement with conventional spin-wave theory. At finite temperature a self-consistent approximation beyond mean field is required in order to fulfill the Mermin-Wagner theorem. We first discuss amore » fully self-consistent approximation, where fermions are renormalized due to fluctuations of their spin density, in close analogy to FLEX. While static properties like the correlation length, {xi}(T){proportional_to}exp(aJ/T), come out correctly, the dynamical response lacks the magnon-like peaks which would reflect the appearance of short-range order at low T. This drawback, which is caused by overdamping, is overcome in a 'minimal self-consistent approximation' (MSCA), which we derive from the equations of motion. The MSCA features dynamical scaling at small energy and temperature and is qualitatively correct both in the regime of order-parameter relaxation at long wavelengths {lambda}>{xi} and in the short-range-order regime at {lambda}<{xi}. We also discuss the impact of vertex corrections and the problem of pseudo-gap formation in the single-particle density of states due to long-range fluctuations. Finally we show that the (short-range) magnetic order in MFT and MSCA helps to fulfill the constraint on the local fermion occupancy.« less

The Swedish Exercise Self-Efficacy Scale (ESES-S): reliability and validity in a rheumatoid arthritis population.

PubMed

Nessen, Thomas; Demmelmaier, Ingrid; Nordgren, Birgitta; Opava, Christina H

2015-01-01

The aim of the present study was to investigate aspects of reliability and validity of the Exercise Self-Efficacy Scale (ESES-S) in a rheumatoid arthritis (RA) population. A total of 244 people with RA participating in a physical activity study were included. The six-item ESES-S, exploring confidence in performing exercise, was assessed for test-retest reliability over 4-6 months, and for internal consistency. Construct validity investigated correlation with similar and other constructs. An intraclass correlation coefficient (ICC) of 0.59 (95% CI 0.37-0.73) was found for 84 participants with stable health perceptions between measurement occasions. Cronbach's alpha coefficients of 0.87 and 0.89 were found at the first and second measurements. Corrected item-total correlation single ESES-S items ranged between 0.53 and 0.73. Construct convergent validity for the ESES-S was partly confirmed by correlations with health-enhancing physical activity and outcome expectations respectively (Pearson's r = 0.18, p < 0.01). Construct divergent validity was confirmed by the absence of correlations with age or gender. No floor or ceiling effects were found for ESES-S. The results indicate that the ESES-S has moderate test-retest reliability and respectable internal consistency in people with RA. Construct validity was partially supported in the present sample. Further research on construct validity of the ESES-S is recommended. Physical exercise is crucial for management of symptoms and co-morbidity in rheumatoid arthritis. Self-efficacy for exercise is important to address in rehabilitation as it regulates exercise motivation and behavior. Measurement properties of self-efficacy scales need to be assessed in specific populations and different languages.

Dynamical electron-phonon coupling, G W self-consistency, and vertex effect on the electronic band gap of ice and liquid water

NASA Astrophysics Data System (ADS)

Ziaei, Vafa; Bredow, Thomas

2017-06-01

We study the impact of dynamical electron-phonon (el-ph) effects on the electronic band gap of ice and liquid water by accounting for frequency-dependent Fan contributions in the el-ph mediated self-energy within the many-body perturbation theory (MBPT). We find that the dynamical el-ph coupling effects greatly reduce the static el-ph band-gap correction of the hydrogen-rich molecular ice crystal from-2.46 to -0.23 eV in great contrast to the result of Monserrat et al. [Phys. Rev. B 92, 140302 (2015), 10.1103/PhysRevB.92.140302]. This is of particular importance as otherwise the static el-ph gap correction would considerably reduce the electronic band gap, leading to considerable underestimation of the intense peaks of optical absorption spectra of ice which would be in great disagreement to experimental references. By contrast, the static el-ph gap correction of liquid water is very moderate (-0.32 eV), and inclusion of dynamical effects slightly reduces the gap correction to -0.19 eV. Further, we determine the diverse sensitivity of ice and liquid water to the G W self-consistency and show that the energy-only self-consistent approach (GnWn ) exhibits large implicit vertex character in comparison to the quasiparticle self-consistent approach, for which an explicit calculation of vertex corrections is necessary for good agreement with experiment.

First example of a high-level correlated calculation of the indirect spin-spin coupling constants involving tellurium: tellurophene and divinyl telluride.

PubMed

Rusakov, Yury Yu; Krivdin, Leonid B; Østerstrøm, Freja F; Sauer, Stephan P A; Potapov, Vladimir A; Amosova, Svetlana V

2013-08-21

This paper documents the very first example of a high-level correlated calculation of spin-spin coupling constants involving tellurium taking into account relativistic effects, vibrational corrections and solvent effects for medium sized organotellurium molecules. The (125)Te-(1)H spin-spin coupling constants of tellurophene and divinyl telluride were calculated at the SOPPA and DFT levels, in good agreement with experimental data. A new full-electron basis set, av3z-J, for tellurium derived from the "relativistic" Dyall's basis set, dyall.av3z, and specifically optimized for the correlated calculations of spin-spin coupling constants involving tellurium was developed. The SOPPA method shows a much better performance compared to DFT, if relativistic effects calculated within the ZORA scheme are taken into account. Vibrational and solvent corrections are next to negligible, while conformational averaging is of prime importance in the calculation of (125)Te-(1)H spin-spin couplings. Based on the performed calculations at the SOPPA(CCSD) level, a marked stereospecificity of geminal and vicinal (125)Te-(1)H spin-spin coupling constants originating in the orientational lone pair effect of tellurium has been established, which opens a new guideline in organotellurium stereochemistry.

Theoretical formulation of optical conductivity of La0.7Ca0.3MnO3 exhibiting paramagnetic insulator - ferromagnetic metal transition

NASA Astrophysics Data System (ADS)

Satiawati, L.; Majidi, M. A.

2017-07-01

A theory of high-energy optical conductivity of La0.7Ca0.3MnO3 has been proposed previously. The proposed theory works to explain the temperature-dependence of the optical conductivity for the photon energy region above ˜0.5 eV for up to ˜22 eV, but fails to capture the correct physics close to the dc limit in which metal-insulator transition occurs. The missing physics at the low energy has been acknowledged as mainly due to not incorporating phonon degree of freedom and electron-phonon interactions. In this study, we aim to complete the above theory by proposing a more complete Hamiltonian incorporating additional terms such as crystal field, two modes of Jahn-Teller vibrations, and coupling between electrons and the two Jahn-Teller vibrational modes. We solve the model by means of dynamical mean-field theory. At this stage, we aim to derive the analytical formulae involved in the calculation, and formulate the algorithmic implementation for the self-consistent calculation process. Our final goal is to compute the density of states and the optical conductivity for the complete photon energy range from 0 to 22 eV at various temperatures, and compare them with the experimental data. We expect that the improved model preserves the correct temperature-dependent physics at high photon energies, as already captured by the previous model, while it would also reveal ferromagnetic metal - paramagnetic insulator transition at the dc limit.

Fission properties of superheavy nuclei for r -process calculations

NASA Astrophysics Data System (ADS)

Giuliani, Samuel A.; Martínez-Pinedo, Gabriel; Robledo, Luis M.

2018-03-01

We computed a new set of static fission properties suited for r -process calculations. The potential energy surfaces and collective inertias of 3640 nuclei in the superheavy region are obtained from self-consistent mean-field calculations using the Barcelona-Catania-Paris-Madrid energy density functional. The fission path is computed as a function of the quadrupole moment by minimizing the potential energy and exploring octupole and hexadecapole deformations. The spontaneous fission lifetimes are evaluated employing different schemes for the collective inertias and vibrational energy corrections. This allows us to explore the sensitivity of the lifetimes to those quantities together with the collective ground-state energy along the superheavy landscape. We computed neutron-induced stellar reaction rates relevant for r -process nucleosynthesis using the Hauser-Feshbach statistical approach and study the impact of collective inertias. The competition between different reaction channels including neutron-induced rates, spontaneous fission, and α decay is discussed for typical r -process conditions.

Measurement of vibration using phase only correlation technique

NASA Astrophysics Data System (ADS)

Balachandar, S.; Vipin, K.

2017-08-01

A novel method for the measurement of vibration is proposed and demonstrated. The proposed experiment is based on laser triangulation: consists of line laser, object under test and a high speed camera remotely controlled by a software. Experiment involves launching a line-laser probe beam perpendicular to the axis of the vibrating object. The reflected probe beam is recorded by a high speed camera. The dynamic position of the line laser in camera plane is governed by the magnitude and frequency of the vibrating test-object. Using phase correlation technique the maximum distance travelled by the probe beam in CCD plane is measured in terms of pixels using MATLAB. An actual displacement of the object in mm is measured by calibration. Using displacement data with time, other vibration associated quantities such as acceleration, velocity and frequency are evaluated. The preliminary result of the proposed method is reported for acceleration from 1g to 3g, and from frequency 6Hz to 26Hz. The results are closely matching with its theoretical values. The advantage of the proposed method is that it is a non-destructive method and using phase correlation algorithm subpixel displacement in CCD plane can be measured with high accuracy.

A DYNAMIC DENSITY FUNCTIONAL THEORY APPROACH TO DIFFUSION IN WHITE DWARFS AND NEUTRON STAR ENVELOPES

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

Diaw, A.; Murillo, M. S.

2016-09-20

We develop a multicomponent hydrodynamic model based on moments of the Born–Bogolyubov–Green–Kirkwood–Yvon hierarchy equations for physical conditions relevant to astrophysical plasmas. These equations incorporate strong correlations through a density functional theory closure, while transport enters through a relaxation approximation. This approach enables the introduction of Coulomb coupling correction terms into the standard Burgers equations. The diffusive currents for these strongly coupled plasmas is self-consistently derived. The settling of impurities and its impact on cooling can be greatly affected by strong Coulomb coupling, which we show can be quantified using the direct correlation function.

Strong anharmonicity in the phonon spectra of PbTe and SnTe from first principles

NASA Astrophysics Data System (ADS)

Ribeiro, Guilherme A. S.; Paulatto, Lorenzo; Bianco, Raffaello; Errea, Ion; Mauri, Francesco; Calandra, Matteo

2018-01-01

At room temperature, PbTe and SnTe are efficient thermoelectrics with a cubic structure. At low temperature, SnTe undergoes a ferroelectric transition with a critical temperature strongly dependent on the hole concentration, while PbTe is an incipient ferroelectric. By using the stochastic self-consistent harmonic approximation, we investigate the anharmonic phonon spectra and the occurrence of a ferroelectric transition in both systems. We find that vibrational spectra strongly depend on the approximation used for the exchange-correlation kernel in density-functional theory. If gradient corrections and the theoretical volume are employed, then the calculation of the phonon frequencies as obtained from the diagonalization of the free-energy Hessian leads to phonon spectra in good agreement with experimental data for both systems. In PbTe we evaluate the linear thermal expansion coefficient γ =2.3 ×10-5K-1 , finding it to be in good agreement with experimental value of γ =2.04 ×10-5K-1 . Furthermore, we study the phonon spectrum and we do reproduce the transverse optical mode phonon satellite detected in inelastic neutron scattering and the crossing between the transverse optical and the longitudinal acoustic modes along the Γ X direction. The phonon satellite becomes broader at high temperatures but its energy is essentially temperature independent, in agreement with experiments. We decompose the self-consistent harmonic free energy in second-, third-, and fourth-order anharmonic terms. We find that the third- and fourth-order terms are small. However, treating the third-order term perturbatively on top of the second-order self-consistent harmonic free energy overestimates the energy of the satellite associated with the transverse optical mode. On the contrary, a perturbative treatment on top of the harmonic Hamiltonian breaks down and leads to imaginary phonon frequencies already at 300 K. In the case of SnTe, we describe the occurrence of a ferroelectric transition from the high-temperature F m 3 ¯m structure to the low-temperature R 3 m one. The transition temperature is, however, underestimated with respect to the experimental one. No satellites are present in the SnTe phonon spectra despite a not negligible anharmonic broadening of the zone-center TO mode.

Relative importance of first and second derivatives of nuclear magnetic resonance chemical shifts and spin-spin coupling constants for vibrational averaging.

PubMed

Dracínský, Martin; Kaminský, Jakub; Bour, Petr

2009-03-07

Relative importance of anharmonic corrections to molecular vibrational energies, nuclear magnetic resonance (NMR) chemical shifts, and J-coupling constants was assessed for a model set of methane derivatives, differently charged alanine forms, and sugar models. Molecular quartic force fields and NMR parameter derivatives were obtained quantum mechanically by a numerical differentiation. In most cases the harmonic vibrational function combined with the property second derivatives provided the largest correction of the equilibrium values, while anharmonic corrections (third and fourth energy derivatives) were found less important. The most computationally expensive off-diagonal quartic energy derivatives involving four different coordinates provided a negligible contribution. The vibrational corrections of NMR shifts were small and yielded a convincing improvement only for very accurate wave function calculations. For the indirect spin-spin coupling constants the averaging significantly improved already the equilibrium values obtained at the density functional theory level. Both first and complete second shielding derivatives were found important for the shift corrections, while for the J-coupling constants the vibrational parts were dominated by the diagonal second derivatives. The vibrational corrections were also applied to some isotopic effects, where the corrected values reasonably well reproduced the experiment, but only if a full second-order expansion of the NMR parameters was included. Contributions of individual vibrational modes for the averaging are discussed. Similar behavior was found for the methane derivatives, and for the larger and polar molecules. The vibrational averaging thus facilitates interpretation of previous experimental results and suggests that it can make future molecular structural studies more reliable. Because of the lengthy numerical differentiation required to compute the NMR parameter derivatives their analytical implementation in future quantum chemistry packages is desirable.

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

Nishimura, Yoshifumi; Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, 1001 Ta-Hsueh Road, Hsinchu 30010, Taiwan; Lee, Yuan-Pern

Vibrational infrared (IR) spectra of gas-phase O–H⋅⋅⋅O methanol clusters up to pentamer are simulated using self-consistent-charge density functional tight-binding method using two distinct methodologies: standard normal mode analysis and Fourier transform of the dipole time-correlation function. The twofold simulations aim at the direct critical assignment of the C–H stretching region of the recently recorded experimental spectra [H.-L. Han, C. Camacho, H. A. Witek, and Y.-P. Lee, J. Chem. Phys. 134, 144309 (2011)]. Both approaches confirm the previous assignment (ibid.) of the C–H stretching bands based on the B3LYP/ANO1 harmonic frequencies, showing that ν{sub 3}, ν{sub 9}, and ν{sub 2} C–Hmore » stretching modes of the proton-accepting (PA) and proton-donating (PD) methanol monomers experience only small splittings upon the cluster formation. This finding is in sharp discord with the assignment based on anharmonic B3LYP/VPT2/ANO1 vibrational frequencies (ibid.), suggesting that some procedural faults, likely related to the breakdown of the perturbational vibrational treatment, led the anharmonic calculations astray. The IR spectra based on the Fourier transform of the dipole time-correlation function include new, previously unaccounted for physical factors such as non-zero temperature of the system and large amplitude motions of the clusters. The elevation of temperature results in a considerable non-homogeneous broadening of the observed IR signals, while the presence of large-amplitude motions (methyl group rotations and PA-PD flipping), somewhat surprisingly, does not introduce any new features in the spectrum.« less

Impact self-excited vibrations of linear motor

NASA Astrophysics Data System (ADS)

Zhuravlev, V. Ph.

2010-08-01

Impact self-exciting vibration modes in a linear motor of a monorail car are studied. Existence and stability conditions of self-exciting vibrations are found. Ways of avoiding the vibrations are discussed.

Piezoelectric self-sensing actuator for active vibration control of motorized spindle based on adaptive signal separation

NASA Astrophysics Data System (ADS)

He, Ye; Chen, Xiaoan; Liu, Zhi; Qin, Yi

2018-06-01

The motorized spindle is the core component of CNC machine tools, and the vibration of it reduces the machining precision and service life of the machine tools. Owing to the fast response, large output force, and displacement of the piezoelectric stack, it is often used as the actuator in the active vibration control of the spindle. A piezoelectric self-sensing actuator (SSA) can reduce the cost of the active vibration control system and simplify the structure by eliminating the use of a sensor, because a SSA can have both actuating and sensing functions at the same time. The signal separation method of a SSA based on a bridge circuit is widely applied because of its simple principle and easy implementation. However, it is difficult to maintain dynamic balance of the circuit. Prior research has used adaptive algorithm to balance of the bridge circuit on the flexible beam dynamically, but those algorithms need no correlation between sensing and control voltage, which limit the applications of SSA in the vibration control of the rotor-bearing system. Here, the electromechanical coupling model of the piezoelectric stack is established, followed by establishment of the dynamic model of the spindle system. Next, a new adaptive signal separation method based on the bridge circuit is proposed, which can separate relative small sensing voltage from related mixed voltage adaptively. The experimental results show that when the self-sensing signal obtained from the proposed method is used as a displacement signal, the vibration of the motorized spindle can be suppressed effectively through a linear quadratic Gaussian (LQG) algorithm.

Vibrational corrections to the second hyperpolarizabilities of Al{sub n}P{sub n} clusters

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

Feitoza, Luan; Instituto Federal de Brasília–IFB, Campus Planaltina, 73380-900 Brasília, DF; Silveira, Orlando

2015-12-14

In this work, we report results of vibrational corrections to the second hyperpolarizabilities of Al{sub 2}P{sub 2}, Al{sub 3}P{sub 3}, Al{sub 4}P{sub 4}, Al{sub 6}P{sub 6}, and Al{sub 9}P{sub 9} clusters. The vibrational corrections were calculated through the perturbation theoretic method of Bishop and Kirtman and also using a variational methodology at the second order Møller-Plesset perturbation theory level with the aug-cc-pVDZ basis set. Results show that the vibrational corrections are important, accounting for more than half of the corresponding electronic second hyperpolarizabilities at the static limit. Comparisons between results obtained through both methods show very good agreements for themore » terms [α{sup 2}] and [μβ] but significant differences for the term [μ{sup 2}α]. Dynamic vibrational corrections to the second hyperpolarizabilities related to the dc-second harmonic generation, intensity dependent refractive index, and dc-Kerr nonlinear optical processes are also reported.« less

Study on spherical stator for multidegree-of-freedom ultrasonic motor

NASA Astrophysics Data System (ADS)

Nakajima, Shuta; Kajiwara, Hidekazu; Aoyagi, Manabu; Tamura, Hideki; Takano, Takehiro

2016-07-01

A multidegree-of-freedom ultrasonic motor (MDOF-USM) has excellent features such as high torque at a low speed and a self-holding force, compared with other types of MDOF motor. Therefore, the MDOF-USM has been considered for applications in robot joints, multidimensional systems, and spacecraft. In previous research, the MDOF-USM consisting of a spherical rotor and a stator vibrator of various shapes has been mainly studied. In contrast, the MDOF-USM consisting of a spherical stator and a rotor of various shapes is proposed in this paper. The excitation methods for vibration modes and mode rotation using piezoelectric plates and multilayered piezoelectric actuators were examined. Furthermore, a stator support method that does not significantly affect the vibration of the sphere was devised. From the results of experiments using the fabricated prototype stator, the generation of vibration mode and mode rotation were confirmed. Therefore, the possibility of the realization of the MDOF-USM using a spherical stator was indicated.

The free and forced vibrations of structures using the finite dynamic element method. Ph.D. Thesis, Aug. 1991 Final Report

NASA Technical Reports Server (NTRS)

Fergusson, Neil J.

1992-01-01

In addition to an extensive review of the literature on exact and corrective displacement based methods of vibration analysis, a few theorems are proven concerning the various structural matrices involved in such analyses. In particular, the consistent mass matrix and the quasi-static mass matrix are shown to be equivalent, in the sense that the terms in their respective Taylor expansions are proportional to one another, and that they both lead to the same dynamic stiffness matrix when used with the appropriate stiffness matrix.

Vibrational and rotational sequences in 101Mo and 103,4Ru studied via multinucleon transfer reactions

DOE PAGES

Regan, P. H.; Wheldon, C.; Yamamoto, A. D.; ...

2005-04-01

The near-yrast states of 42 101Mo 59 and 44 103,4Ru 59,60 have been studied following their population via heavy-ion multinucleon transfer reactions between a 136 Xe beam and a thin, self-supporting 100Mo target. The ground state sequence in 104Ru can be understood as demonstrating a simple evolution from a quasi-vibrational structure at lower spins to statically deformed, quasi-rotational excitation involving the population of a pair of low-Ω h 11/2 neutron orbitals. The effect of the decoupled h 11/2 orbital on this vibration-to-rotational evolution is demonstrated by an extension of the "E-GOS" prescription to include odd-A nuclei. The experimental results aremore » also compared with self-consistent Total Routhian Surface calculations which also highlight the polarising role of the highly aligned neutron h 11/2 orbital in these nuclei.« less

Structural, electronic and vibrational properties of lanthanide monophosphide at high pressure

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

Panchal, J. M., E-mail: amitjignesh@yahoo.co.in; Department of Physics, University School of Sciences, Gujarat University, Ahmedabad 380009, Gujarat; Joshi, Mitesh

2016-05-06

A first-principles plane wave self-consistent method with the ultra-soft-pseudopotential scheme in the framework of the density functional theory (DFT) is performed to study structural, electronic and vibrational properties of LaP for Rock-salt (NaCl/Bl) and Cesium-chloride (CsCl/B2) phases. The instability of Rock-salt (NaCl/Bl) phases around the transition is discussed. Conclusions based on electronic energy band structure, density of state, phonon dispersion and phonon density of states in both phases are outlined. The calculated results are consistence and confirm the successful applicability of quasi-harmonic phonon theory for structural instability studies for the alloys.

Correlation study between vibrational environmental and failure rates of civil helicopter components

NASA Technical Reports Server (NTRS)

Alaniz, O.

1979-01-01

An investigation of two selected helicopter types, namely, the Models 206A/B and 212, is reported. An analysis of the available vibration and reliability data for these two helicopter types resulted in the selection of ten components located in five different areas of the helicopter and consisting primarily of instruments, electrical components, and other noncritical flight hardware. The potential for advanced technology in suppressing vibration in helicopters was assessed. The are still several unknowns concerning both the vibration environment and the reliability of helicopter noncritical flight components. Vibration data for the selected components were either insufficient or inappropriate. The maintenance data examined for the selected components were inappropriate due to variations in failure mode identification, inconsistent reporting, or inaccurate informaton.

Simulation study on nitrogen vibrational and translational temperature in air breakdown plasma generated by 110 GHz focused microwave pulse

NASA Astrophysics Data System (ADS)

Yang, Wei; Zhou, Qianhong; Dong, Zhiwei

2017-01-01

We report a simulation study on nitrogen vibrational and translational temperature in 3 μs pulse 110 GHz microwave air breakdown at pressure from 1 Torr to 100 Torr. The one-dimensional model is based on a self-consistent solution to Helmholtz equation for microwave field, electron density equation, and the average energy equation for electrons, nitrogen vibrational, and translational degrees. The breakdown threshold is calculated from the transmitted microwave profile, and it agrees well with that from experiment. The spatio-temporal characteristics of vibrational and translational temperature are shown, and the peak values at the end of pulse are compared to the results fitted from optical emission spectroscopy. The dependences of vibrational and translational temperature on normalized microwave fields and gas pressure are investigated, and the underlying mechanisms are unveiled.

The performance of hafnium and gadolinium self powered neutron detectors in the TREAT reactor

NASA Astrophysics Data System (ADS)

Imel, G. R.; Hart, P. R.

1996-05-01

The use of gadolinium and hafnium self powered neutron detectors in a transient reactor is described in this paper. The detectors were calibrated to the fission rate of U-235 using calibrated fission chambers; the calibration factors were tested in two reactors in steady state and found to be consistent. Calibration of the detectors in transient reactor conditions was done by using uranium wires that were analyzed by radiochemistry techniques to determine total fissions during the transient. This was correlated to the time-integrated current of the detectors during the transient. A temperature correction factor was derived to account for self-shielding effects in the hafnium and gadolinium detectors. The dynamic response of the detectors under transient conditions was studied, and found to be excellent.

Theoretical study of LiK and LiK+ in adiabatic representation

NASA Astrophysics Data System (ADS)

Al-dossary, Omar M.; Khelifi, Neji

2014-01-01

The potential energy curves have been calculated for the electronic states of the molecule LiK within the range 3 to 300 a.u., of the internuclear distance R. Using an ab initio method, through a semiempirical spin-orbit pseudo-potential for the Li (1 s 2) and K (1 s 22 s 22 p 63 s 23 p 6) cores and core valence correlation correction added to the electrostatic Hamiltonian with Gaussian basis sets for both atoms. The core valence effects including core-polarization and core-valence correlation are taken into account by using an l-dependent core-polarization potential. The molecular orbitals have been derived from self-consistent field (SCF) calculation. The spectroscopic constants, dipole moments and vibrational levels of the lowest electronic states of the LiK molecule dissociating into K (4 s, 4 p, 5 s, 3 d, and 5 p) + Li (2 s, 2 p, 3 s, and 3 p) in 1, 3Σ, 1, 3Π, and 1, 3Δ symmetries. Adiabatic results are also reported for 2Σ, 2Π, and 2Δ electronic states of the molecular ion LiK+ dissociating into Li (2 s, 2 p, 3 s, and 3 p) + K+ and Li+ + K (4 s, 4 p, 5 s, 3 d, and 5 p). The comparison of the present results with those available in the literature shows a very good agreement in spectroscopic constants of some lowest states of the LiK and LiK+ molecules, especially with the available theoretical works. The existence of numerous avoided crossing between electronic states of 2Σ and 2Π symmetries is related to the charge transfer process between the two ionic systems Li+K and LiK+.

A study on the contribution of body vibrations to the vibratory sensation induced by high-level, complex low-frequency noise.

PubMed

Takahashi, Yukio

2011-01-01

To investigate the contribution of body vibrations to the vibratory sensation induced by high-level, complex low-frequency noise, we conducted two experiments. In Experiment 1, eight male subjects were exposed to seven types of low-frequency noise stimuli: two pure tones [a 31.5-Hz, 100-dB(SPL) tone and a 50-Hz, 100-dB(SPL) tone] and five complex noises composed of the pure tones. For the complex noise stimuli, the sound pressure level of one tonal component was 100 dB(SPL) and that of another one was either 90, 95, or 100 dB(SPL). Vibration induced on the body surface was measured at five locations, and the correlation with the subjective rating of the vibratory sensation at each site of measurement was examined. In Experiment 2, the correlation between the body surface vibration and the vibratory sensation was similarly examined using seven types of noise stimuli composed of a 25-Hz tone and a 50-Hz tone. In both the experiments, we found that at the chest and the abdomen, the rating of the vibratory sensation was in close correlation with the vibration acceleration level (VAL) of the body surface vibration measured at each corresponding location. This was consistent with our previous results and suggested that at the trunk of the body (the chest and the abdomen), the mechanoreception of body vibrations plays an important role in the experience of the vibratory sensation in persons exposed to high-level low-frequency noise. At the head, however, no close correlation was found between the rating of the vibratory sensation and the VAL of body surface vibration. This suggested that at the head, the perceptual mechanisms of vibration induced by high-level low-frequency noise were different from those in the trunk of the body.

The integrated model of sport confidence: a canonical correlation and mediational analysis.

PubMed

Koehn, Stefan; Pearce, Alan J; Morris, Tony

2013-12-01

The main purpose of the study was to examine crucial parts of Vealey's (2001) integrated framework hypothesizing that sport confidence is a mediating variable between sources of sport confidence (including achievement, self-regulation, and social climate) and athletes' affect in competition. The sample consisted of 386 athletes, who completed the Sources of Sport Confidence Questionnaire, Trait Sport Confidence Inventory, and Dispositional Flow Scale-2. Canonical correlation analysis revealed a confidence-achievement dimension underlying flow. Bias-corrected bootstrap confidence intervals in AMOS 20.0 were used in examining mediation effects between source domains and dispositional flow. Results showed that sport confidence partially mediated the relationship between achievement and self-regulation domains and flow, whereas no significant mediation was found for social climate. On a subscale level, full mediation models emerged for achievement and flow dimensions of challenge-skills balance, clear goals, and concentration on the task at hand.

A converged calculation of the energy barrier to internal rotation in the ethylene-sulfur dioxide dimer

NASA Astrophysics Data System (ADS)

Resende, Stella M.; De Almeida, Wagner B.; van Duijneveldt-van de Rijdt, Jeanne G. C. M.; van Duijneveldt, Frans B.

2001-08-01

Geometrical parameters for the equilibrium (MIN) and lowest saddle-point (TS) geometries of the C2H4⋯SO2 dimer, and the corresponding binding energies, were calculated using the Hartree-Fock and correlated levels of ab initio theory, in basis sets ranging from the D95(d,p) double-zeta basis set to the aug-cc-pVQZ correlation consistent basis set. An assessment of the effect of the basis set superposition error (BSSE) on these results was made. The dissociation energy from the lowest vibrational state was estimated to be 705±100 cm-1 at the basis set limit, which is well within the range expected from experiment. The barrier to internal rotation was found to be 53±5 cm-1, slightly higher than the (revised) experimental result of 43 cm-1, probably due to zero-point vibrational effects. Our results clearly show that, in direct contrast with recent ideas, the BSSE correction affects differentially the MIN and TS binding energies and so has to be included in the calculation of small energy barriers such as that in the C2H4⋯SO2 dimer. Previous reports of positive MP2 frozen-core binding energies for this complex in basis D95(d,p) are confirmed. The anomalies are shown to be an artifact arising from an incorrect removal of virtual orbitals by the default frozen-core option in the GAUSSIAN program.

MRCI study on transition dipole moments and transition probabilities of 18 low-lying states of CP+ cation

NASA Astrophysics Data System (ADS)

Zhou, Dan; Wang, Kedong; Li, Xue

2018-07-01

This study calculates the potential energy curves of 18 Λ-S and 50 Ω states, which arise from the C(3Pg) + P+(3Pg) dissociation channel of the CP+ cation. The calculations are made using the CASSCF method, followed by the icMRCI approach with the Davidson correction. Core-valence correlation and scalar relativistic corrections, as well as extrapolation to the complete basis set limit are included. The transition dipole moments are computed for 25 pairs of Λ-S states. The spin-orbit coupling effect on the spectroscopic and vibrational properties is evaluated. The Franck-Condon factors and Einstein coefficients of emissions are calculated. Radiative lifetimes are obtained for several vibrational levels of some states. The transitions are evaluated and spectroscopic measurement schemes for observing these Λ-S states are proposed. The potential energy curves, spectroscopic constants, vibrational levels, transition dipole moments, and transition probabilities reported in this paper can be considered to be very accurate and reliable. Because no experimental observations are currently available, the results obtained here can be used as guidelines for the detection of these states in appropriate spectroscopy experiments, in particular for observations in stellar atmospheres and in interstellar space.

Spinal cord normalization in multiple sclerosis.

PubMed

Oh, Jiwon; Seigo, Michaela; Saidha, Shiv; Sotirchos, Elias; Zackowski, Kathy; Chen, Min; Prince, Jerry; Diener-West, Marie; Calabresi, Peter A; Reich, Daniel S

2014-01-01

Spinal cord (SC) pathology is common in multiple sclerosis (MS), and measures of SC-atrophy are increasingly utilized. Normalization reduces biological variation of structural measurements unrelated to disease, but optimal parameters for SC volume (SCV)-normalization remain unclear. Using a variety of normalization factors and clinical measures, we assessed the effect of SCV normalization on detecting group differences and clarifying clinical-radiological correlations in MS. 3T cervical SC-MRI was performed in 133 MS cases and 11 healthy controls (HC). Clinical assessment included expanded disability status scale (EDSS), MS functional composite (MSFC), quantitative hip-flexion strength ("strength"), and vibration sensation threshold ("vibration"). SCV between C3 and C4 was measured and normalized individually by subject height, SC-length, and intracranial volume (ICV). There were group differences in raw-SCV and after normalization by height and length (MS vs. HC; progressive vs. relapsing MS-subtypes, P < .05). There were correlations between clinical measures and raw-SCV (EDSS:r = -.20; MSFC:r = .16; strength:r = .35; vibration:r = -.19). Correlations consistently strengthened with normalization by length (EDSS:r = -.43; MSFC:r = .33; strength:r = .38; vibration:r = -.40), and height (EDSS:r = -.26; MSFC:r = .28; strength:r = .22; vibration:r = -.29), but diminished with normalization by ICV (EDSS:r = -.23; MSFC:r = -.10; strength:r = .23; vibration:r = -.35). In relapsing MS, normalization by length allowed statistical detection of correlations that were not apparent with raw-SCV. SCV-normalization by length improves the ability to detect group differences, strengthens clinical-radiological correlations, and is particularly relevant in settings of subtle disease-related SC-atrophy in MS. SCV-normalization by length may enhance the clinical utility of measures of SC-atrophy. Copyright © 2014 by the American Society of Neuroimaging.

Gate-controlled current and inelastic electron tunneling spectrum of benzene: a self-consistent study.

PubMed

Liang, Y Y; Chen, H; Mizuseki, H; Kawazoe, Y

2011-04-14

We use density functional theory based nonequilibrium Green's function to self-consistently study the current through the 1,4-benzenedithiol (BDT). The elastic and inelastic tunneling properties through this Au-BDT-Au molecular junction are simulated, respectively. For the elastic tunneling case, it is found that the current through the tilted molecule can be modulated effectively by the external gate field, which is perpendicular to the phenyl ring. The gate voltage amplification comes from the modulation of the interaction between the electrodes and the molecules in the junctions. For the inelastic case, the electron tunneling scattered by the molecular vibrational modes is considered within the self-consistent Born approximation scheme, and the inelastic electron tunneling spectrum is calculated.

Development of rotorcraft interior noise control concepts. Phase 2: Full scale testing, revision 1

NASA Technical Reports Server (NTRS)

Yoerkie, C. A.; Gintoli, P. J.; Moore, J. A.

1986-01-01

The phase 2 effort consisted of a series of ground and flight test measurements to obtain data for validation of the Statistical Energy Analysis (SEA) model. Included in the gound tests were various transfer function measurements between vibratory and acoustic subsystems, vibration and acoustic decay rate measurements, and coherent source measurements. The bulk of these, the vibration transfer functions, were used for SEA model validation, while the others provided information for characterization of damping and reverberation time of the subsystems. The flight test program included measurements of cabin and cockpit sound pressure level, frame and panel vibration level, and vibration levels at the main transmission attachment locations. Comparisons between measured and predicted subsystem excitation levels from both ground and flight testing were evaluated. The ground test data show good correlation with predictions of vibration levels throughout the cabin overhead for all excitations. The flight test results also indicate excellent correlation of inflight sound pressure measurements to sound pressure levels predicted by the SEA model, where the average aircraft speech interference level is predicted within 0.2 dB.

Structural design and analysis for an ultra low CTE optical bench for the Hubble Space Telescope corrective optics

NASA Technical Reports Server (NTRS)

Neam, Douglas C.; Gerber, John D.

1992-01-01

The stringent stability requirements of the Corrective Optics Space Telescope Axial Replacement (COSTAR) necessitates a Deployable Optical Bench (DOB) with both a low CTE and high resonant frequency. The DOB design consists of a monocoque thin shell structure which marries metallic machined parts with graphite epoxy formed structure. Structural analysis of the DOB has been integrated into the laminate design and optimization process. Also, the structural analytical results are compared with vibration and thermal test data to assess the reliability of the analysis.

Vibrationally resolved photoelectron spectra of lower diamondoids: A time-dependent approach

NASA Astrophysics Data System (ADS)

Xiong, Tao; Włodarczyk, Radosław; Gallandi, Lukas; Körzdörfer, Thomas; Saalfrank, Peter

2018-01-01

Vibrationally resolved lowest-energy bands of the photoelectron spectra (PES) of adamantane, diamantane, and urotropine were simulated by a time-dependent correlation function approach within the harmonic approximation. Geometries and normal modes for neutral and cationic molecules were obtained from B3LYP hybrid density functional theory (DFT). It is shown that the simulated spectra reproduce the experimentally observed vibrational finestructure (or its absence) quite well. Origins of the finestructure are discussed and related to recurrences of autocorrelation functions and dominant vibrations. Remaining quantitative and qualitative errors of the DFT-derived PES spectra refer to (i) an overall redshift by ˜0.5 eV and (ii) the absence of satellites in the high-energy region of the spectra. The former error is shown to be due to the neglect of many-body corrections to ordinary Kohn-Sham methods, while the latter has been argued to be due to electron-nuclear couplings beyond the Born-Oppenheimer approximation [Gali et al., Nat. Commun. 7, 11327 (2016)].

Anharmonic phonons and second-order phase-transitions by the stochastic self-consistent harmonic approximation

NASA Astrophysics Data System (ADS)

Mauri, Francesco

Anharmonic effects can generally be treated within perturbation theory. Such an approach breaks down when the harmonic solution is dynamically unstable or when the anharmonic corrections of the phonon energies are larger than the harmonic frequencies themselves. This situation occurs near lattice-related second-order phase-transitions such as charge-density-wave (CDW) or ferroelectric instabilities or in H-containing materials, where the large zero-point motion of the protons results in a violation of the harmonic approximation. Interestingly, even in these cases, phonons can be observed, measured, and used to model transport properties. In order to treat such cases, we developed a stochastic implementation of the self-consistent harmonic approximation valid to treat anharmonicity in the nonperturbative regime and to obtain, from first-principles, the structural, thermodynamic and vibrational properties of strongly anharmonic systems. I will present applications to the ferroelectric transitions in SnTe, to the CWD transitions in NbS2 and NbSe2 (in bulk and monolayer) and to the hydrogen-bond symmetrization transition in the superconducting hydrogen sulfide system, that exhibits the highest Tc reported for any superconductor so far. In all cases we are able to predict the transition temperature (pressure) and the evolution of phonons with temperature (pressure). This project has received funding from the European Union's Horizon 2020 research and innovation programme under Grant agreement No. 696656 GrapheneCore1.

Vibration signal correction of unbalanced rotor due to angular speed fluctuation

NASA Astrophysics Data System (ADS)

Cao, Hongrui; He, Dong; Xi, Songtao; Chen, Xuefeng

2018-07-01

The rotating speed of a rotor is hardly constant in practice due to angular speed fluctuation, which affects the balancing accuracy of the rotor. In this paper, the effect of angular speed fluctuation on vibration responses of the unbalanced rotor is analyzed quantitatively. Then, a vibration signal correction method based on zoom synchrosqueezing transform (ZST) and tacholess order tracking is proposed. The instantaneous angular speed (IAS) of the rotor is extracted by the ZST firstly and then used to calculate the instantaneous phase. The vibration signal is further resampled in angular domain to reduce the effect of angular speed fluctuation. The signal obtained in angular domain is transformed into order domain using discrete Fourier transform (DFT) to estimate the amplitude and phase of the vibration signal. Simulated and experimental results show that the proposed method can successfully correct the amplitude and phase of the vibration signal due to angular speed fluctuation.

Nonlinear optical response of a gold surface in the visible range: A study by two-color sum-frequency generation spectroscopy. I. Experimental determination

NASA Astrophysics Data System (ADS)

Dalstein, L.; Revel, A.; Humbert, C.; Busson, B.

2018-04-01

We experimentally determine the effective nonlinear second-order susceptibility of gold over the visible spectral range. To reach that goal, we probe by vibrational two-color sum-frequency generation spectroscopy the methyl stretching region of a dodecanethiol self-assembled monolayer adsorbed on a gold film. The sum-frequency generation spectra show a remarkable shape reversal when the visible probe wavelength is tuned from 435 to 705 nm. After correcting from Fresnel effects, the methyl stretching vibrations serve as an internal reference, allowing to extract the dispersion of the absolute phase and relative amplitude of the effective nonlinear optical response of gold in the visible range.

Nonlinear vibrational excitations in molecular crystals molecular mechanics calculations

NASA Astrophysics Data System (ADS)

Pumilia, P.; Abbate, S.; Baldini, G.; Ferro, D. R.; Tubino, R.

1992-03-01

The coupling constant for vibrational solitons χ has been examined in a molecular mechanics model for acetanilide (ACN) molecular crystal. According to A.C. Scott, solitons can form and propagate in solid acetanilide over a threshold energy value. This can be regarded as a structural model for the spines of hydrogen bond chains stabilizing the α helical structure of proteins. A one dimensional hydrogen bond chain of ACN has been built, for which we have found that, even though experimental parameters are correctly predicted, the excessive rigidity of the isolated chain prevents the formation of a localized distortion around the excitation. Yet, C=O coupling value with softer lattice modes could be rather high, allowing self-trapping to take place.

Thermodynamic properties of arsenic compounds and the heat of formation of the As atom from high level electronic structure calculations.

PubMed

Feller, David; Vasiliu, Monica; Grant, Daniel J; Dixon, David A

2011-12-29

Structures, vibrational frequencies, atomization energies at 0 K, and heats of formation at 0 and 298 K are predicted for the compounds As(2), AsH, AsH(2), AsH(3), AsF, AsF(2), and AsF(3) from frozen core coupled cluster theory calculations performed with large correlation consistent basis sets, up through augmented sextuple zeta quality. The coupled cluster calculations involved up through quadruple excitations. For As(2) and the hydrides, it was also possible to examine the impact of full configuration interaction on some of the properties. In addition, adjustments were incorporated to account for extrapolation to the frozen core complete basis set limit, core/valence correlation, scalar relativistic effects, the diagonal Born-Oppenheimer correction, and atomic spin orbit corrections. Based on our best theoretical D(0)(As(2)) and the experimental heat of formation of As(2), we propose a revised 0 K arsenic atomic heat of formation of 68.86 ± 0.8 kcal/mol. While generally good agreement was found between theory and experiment, the heat of formation of AsF(3) was an exception. Our best estimate is more than 7 kcal/mol more negative than the single available experimental value, which argues for a re-examination of that measurement. © 2011 American Chemical Society

Zero-point corrections and temperature dependence of HD spin-spin coupling constants of heavy metal hydride and dihydrogen complexes calculated by vibrational averaging.

PubMed

Mort, Brendan C; Autschbach, Jochen

2006-08-09

Vibrational corrections (zero-point and temperature dependent) of the H-D spin-spin coupling constant J(HD) for six transition metal hydride and dihydrogen complexes have been computed from a vibrational average of J(HD) as a function of temperature. Effective (vibrationally averaged) H-D distances have also been determined. The very strong temperature dependence of J(HD) for one of the complexes, [Ir(dmpm)Cp*H2]2 + (dmpm = bis(dimethylphosphino)methane) can be modeled simply by the Boltzmann average of the zero-point vibrationally averaged JHD of two isomers. For this complex and four others, the vibrational corrections to JHD are shown to be highly significant and lead to improved agreement between theory and experiment in most cases. The zero-point vibrational correction is important for all complexes. Depending on the shape of the potential energy and J-coupling surfaces, for some of the complexes higher vibrationally excited states can also contribute to the vibrational corrections at temperatures above 0 K and lead to a temperature dependence. We identify different classes of complexes where a significant temperature dependence of J(HD) may or may not occur for different reasons. A method is outlined by which the temperature dependence of the HD spin-spin coupling constant can be determined with standard quantum chemistry software. Comparisons are made with experimental data and previously calculated values where applicable. We also discuss an example where a low-order expansion around the minimum of a complicated potential energy surface appears not to be sufficient for reproducing the experimentally observed temperature dependence.

Study on hydraulic exciting vibration due to flexible valve in pump system with method of characteristics in the time domain

NASA Astrophysics Data System (ADS)

Yu, Y. H.; Liu, D.; Yang, X. F.; Si, J.

2017-08-01

To analyse the flow characteristics of leakage as well as the mechanism of selfexcited vibration in valves, the method of characteristics was used to assess the effect of flexible valve leakage on the self-excited vibration in water-supply pump system. Piezometric head in upstream of the valve as a function of time was obtained. Two comparative schemes were proposed to simulate the process of self-excited vibration by changing the length, the material of the pipeline and the leakage of valves in the above pump system. It is shown that the length and material of the pipe significantly affect the amplitude and cycle of self-excited vibration as well as the increasing rate of the vibration amplitude. In addition, the leakage of the valve has little influence on the amplitude and cycle of self-excited vibration, but has a significant effect on the increasing rate of vibration amplitude. A pipe explosion accident may occur without the inhibiting of self-excited vibration.

Generalizing the correlated chromophore domain model of reversible photodegradation to include the effects of an applied electric field

NASA Astrophysics Data System (ADS)

Anderson, Benjamin; Kuzyk, Mark G.

2014-03-01

All observations of photodegradation and self-healing follow the predictions of the correlated chromophore domain model [Ramini et al., Polym. Chem. 4, 4948 (2013), 10.1039/c3py00263b]. In the present work, we generalize the domain model to describe the effects of an electric field by including induced dipole interactions between molecules in a domain by means of a self-consistent field approach. This electric field correction is added to the statistical mechanical model to calculate the distribution of domains that are central to healing. Also included in the model are the dynamics due to the formation of an irreversibly damaged species, which we propose involves damage to the polymer mediated through energy transfer from a dopant molecule after absorbing a photon. As in previous studies, the model with one-dimensional domains best explains all experimental data of the population as a function of time, temperature, intensity, concentration, and now applied electric field. Though the precise nature of a domain is yet to be determined, the fact that only one-dimensional domain models are consistent with observations suggests that they might be made of correlated dye molecules along polymer chains. Furthermore, the voltage-dependent measurements suggest that the largest polarizability axis of the molecules are oriented perpendicular to the chain.

Magnetoelectric coupling of a magnetoelectric flux gate sensor in vibration noise circumstance

NASA Astrophysics Data System (ADS)

Chu, Zhaoqiang; Shi, Huaduo; Gao, Xiangyu; Wu, Jingen; Dong, Shuxiang

2018-01-01

A magnetoelectric (ME) flux gate sensor (MEFGS) consisting of piezoelectric PMN-PT single crystals and ferromagnetic amorphous alloy ribbon in a self-differential configuration is featured with the ability of weak magnetic anomaly detection. Here, we further investigated its ME coupling and magnetic field detection performance in vibration noise circumstance, including constant frequency, impact, and random vibration noise. Experimental results show that the ME coupling coefficient of MEFGS is as high as 5700 V/cm*Oe at resonant frequency, which is several orders magnitude higher than previously reported differential ME sensors. It was also found that under constant and impact vibration noise circumstance, the noise reduction and attenuation factor of MEFGS are over 17 and 85.7%, respectively. This work is important for practical application of MEFGS in real environment.

Accurate density functional prediction of molecular electron affinity with the scaling corrected Kohn–Sham frontier orbital energies

NASA Astrophysics Data System (ADS)

Zhang, DaDi; Yang, Xiaolong; Zheng, Xiao; Yang, Weitao

2018-04-01

Electron affinity (EA) is the energy released when an additional electron is attached to an atom or a molecule. EA is a fundamental thermochemical property, and it is closely pertinent to other important properties such as electronegativity and hardness. However, accurate prediction of EA is difficult with density functional theory methods. The somewhat large error of the calculated EAs originates mainly from the intrinsic delocalisation error associated with the approximate exchange-correlation functional. In this work, we employ a previously developed non-empirical global scaling correction approach, which explicitly imposes the Perdew-Parr-Levy-Balduz condition to the approximate functional, and achieve a substantially improved accuracy for the calculated EAs. In our approach, the EA is given by the scaling corrected Kohn-Sham lowest unoccupied molecular orbital energy of the neutral molecule, without the need to carry out the self-consistent-field calculation for the anion.

The Effects of Local Vibration on Balance, Power, and Self-Reported Pain After Exercise.

PubMed

Custer, Lisa; Peer, Kimberly S; Miller, Lauren

2017-05-01

Muscle fatigue and acute muscle soreness occur after exercise. Application of a local vibration intervention may reduce the consequences of fatigue and soreness. To examine the effects of a local vibration intervention after a bout of exercise on balance, power, and self-reported pain. Single-blind crossover study. Laboratory. 19 healthy, moderately active subjects. After a 30-min bout of full-body exercise, subjects received either an active or a sham vibration intervention. The active vibration intervention was performed bilaterally over the muscle bellies of the triceps surae, quadriceps, hamstrings, and gluteals. At least 1 wk later, subjects repeated the bout, receiving the other vibration intervention. Static balance, dynamic balance, power, and self-reported pain were measured at baseline, after the vibration intervention, and 24 h postexercise. After the bout of exercise, subjects had reduced static and dynamic balance and increased self-reported pain regardless of vibration intervention. There were no differences between outcome measures between the active and sham vibration conditions. The local vibration intervention did not affect balance, power, or self-reported pain.

Performance and Self-Consistency of the Generalized Dielectric Dependent Hybrid Functional

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

Brawand, Nicholas P.; Govoni, Marco; Vörös, Márton

Here, we analyze the performance of the recently proposed screened exchange constant functional (SX) on the GW100 test set, and we discuss results obtained at different levels of self-consistency. The SX functional is a generalization of dielectric dependent hybrid functionals to finite systems; it is nonempirical and depends on the average screening of the exchange interaction. We compare results for ionization potentials obtained with SX to those of CCSD(T) calculations and experiments, and we find excellent agreement, on par with recent state of the art methods based on many body perturbation theory. Applying SX perturbatively to correct PBE eigenvalues yieldsmore » improved results in most cases, except for ionic molecules, for which wave function self-consistency is instead crucial. Calculations where wave functions and the screened exchange constant (α SX) are determined self-consistently, and those where α SX is fixed to the value determined within PBE, yield results of comparable accuracy. Perturbative G 0W 0 corrections of eigenvalues obtained with self-consistent αSX are small on average, for all molecules in the GW100 test set.« less

Performance and Self-Consistency of the Generalized Dielectric Dependent Hybrid Functional

DOE PAGES

Brawand, Nicholas P.; Govoni, Marco; Vörös, Márton; ...

2017-05-24

Here, we analyze the performance of the recently proposed screened exchange constant functional (SX) on the GW100 test set, and we discuss results obtained at different levels of self-consistency. The SX functional is a generalization of dielectric dependent hybrid functionals to finite systems; it is nonempirical and depends on the average screening of the exchange interaction. We compare results for ionization potentials obtained with SX to those of CCSD(T) calculations and experiments, and we find excellent agreement, on par with recent state of the art methods based on many body perturbation theory. Applying SX perturbatively to correct PBE eigenvalues yieldsmore » improved results in most cases, except for ionic molecules, for which wave function self-consistency is instead crucial. Calculations where wave functions and the screened exchange constant (α SX) are determined self-consistently, and those where α SX is fixed to the value determined within PBE, yield results of comparable accuracy. Perturbative G 0W 0 corrections of eigenvalues obtained with self-consistent αSX are small on average, for all molecules in the GW100 test set.« less

A self-running standing wave-type bidirectional slider for the ultrasonically levitated thin linear stage.

PubMed

Koyama, Daisuke; Takei, Hiroyuki; Nakamura, Kentaro; Ueha, Sadayuki

2008-08-01

A slider for a self-running standing wave-type, ultrasonically levitated, thin linear stage is discussed. The slider can be levitated and moved using acoustic radiation force and acoustic streaming. The slider has a simple configuration and consists of an aluminum vibrating plate and a piezoelectric zirconate titanate (PZT) element. The large asymmetric vibration distribution for the high thrust and levitation performance was obtained by adjusting the configuration determined by finite elemental analysis (FEA). As a preliminary step, the computed results of the sound pressure distribution in the 1-mm air gap by FEA was com pared with experimental results obtained using a fiber optic probe. The direction of the total driving force for the acoustic streaming in the small air gap was estimated by the sound pressure distribution calculated by FEA, and it was found that the direction of the acoustic streaming could be altered by controlling the vibration mode of the slider. The flexural standing wave could be generated along the vibrating plate near the frequencies predicted based on the FEA results. The slider could be levitated by the acoustic radiation force radiated from its own vibrating plate at several frequencies. The slider could be moved in the negative and positive directions at 68 kHz and 69 kHz, which correspond to the results computed by FEA, with the asymmetric vibration distribution of the slider's vibrating plate. Larger thrust could be obtained with the smaller levitation distance, and the maximum thrust was 19 mN.

Combined effect of noise and vibration produced by high-speed trains on annoyance in buildings.

PubMed

Lee, Pyoung Jik; Griffin, Michael J

2013-04-01

The effects of noise and vibration on annoyance in buildings during the passage of a nearby high-speed train have been investigated in a laboratory experiment with recorded train noise and 20 Hz vibration. The noises included the effects of two types of façade: windows-open and windows-closed. Subjects were exposed to six levels of noise and six magnitudes of vibration, and asked to rate annoyance using an 11-point numerical scale. The experiment consisted of four sessions: (1) evaluation of noise annoyance in the absence of vibration, (2) evaluation of total annoyance from simultaneous noise and vibration, (3) evaluation of noise annoyance in the presence of vibration, and (4) evaluation of vibration annoyance in the absence of noise. The results show that vibration did not influence ratings of noise annoyance, but that total annoyance caused by combined noise and vibration was considerably greater than the annoyance caused by noise alone. The noise annoyance and the total annoyance caused by combined noise and vibration were associated with subject self-ratings of noise sensitivity. Two classical models of total annoyance due to combined noise sources (maximum of the single source annoyance or the integration of individual annoyance ratings) provided useful predictions of the total annoyance caused by simultaneous noise and vibration.

Efficient anharmonic vibrational spectroscopy for large molecules using local-mode coordinates

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

Cheng, Xiaolu; Steele, Ryan P., E-mail: ryan.steele@utah.edu

This article presents a general computational approach for efficient simulations of anharmonic vibrational spectra in chemical systems. An automated local-mode vibrational approach is presented, which borrows techniques from localized molecular orbitals in electronic structure theory. This approach generates spatially localized vibrational modes, in contrast to the delocalization exhibited by canonical normal modes. The method is rigorously tested across a series of chemical systems, ranging from small molecules to large water clusters and a protonated dipeptide. It is interfaced with exact, grid-based approaches, as well as vibrational self-consistent field methods. Most significantly, this new set of reference coordinates exhibits a well-behavedmore » spatial decay of mode couplings, which allows for a systematic, a priori truncation of mode couplings and increased computational efficiency. Convergence can typically be reached by including modes within only about 4 Å. The local nature of this truncation suggests particular promise for the ab initio simulation of anharmonic vibrational motion in large systems, where connection to experimental spectra is currently most challenging.« less

Comfort Contours: Inter-Axis Equivalence

NASA Astrophysics Data System (ADS)

Griefahn, B.; Bröde, P.

1997-07-01

Inter-axis equivalence for sinusoidal vibrations as stipulated by ISO/DIS 2631 for seated persons was studied by adjusting the acceleration of a horizontal sinusoidal test vibration (x∨y) until it caused equal sensation as a vertical sinusoidal reference motion of the same frequency. The reference vibrations consisted of sine waves ranging from 1·6 to 12·5Hz and were presented with three weighted accelerations ofazw=0·3, 0·6 and 1·2ms-2r.m.s. (reference contours). 26 subjects (15 men, 11 women, 20-55yrs, 153-187cm) participated in the respective experiments. Based on the three reference contours, predicted values for horizontal motions were calculated by using the weighting factors provided in ISO/DIS 2631. The International standard was confirmed insofar as the shape of the contours determined for horizontal motions was independent from vibration magnitudes as sensitivity to fore-and-aft and to lateral motions was similar. However, the accelerations adjusted for horizontal vibrations were considerably lower than predicted, suggesting that the weighing factors provided in ISO/DIS 2631 need to be corrected.

Dual origin of pairing in nuclei

NASA Astrophysics Data System (ADS)

Idini, A.; Potel, G.; Barranco, F.; Vigezzi, E.; Broglia, R. A.

2016-11-01

The pairing correlations of the nucleus 120Sn are calculated by solving the Nambu-Gor'kov equations, including medium polarization effects resulting from the interweaving of quasiparticles, spin and density vibrations, taking into account, within the framework of nuclear field theory (NFT), processes leading to self-energy and vertex corrections and to the induced pairing interaction. From these results one can not only demonstrate the inevitability of the dual origin of pairing in nuclei, but also extract information which can be used at profit to quantitatively disentangle the contributions to the pairing gap Δ arising from the bare and from the induced pairing interaction. The first is the strong 1 S 0 short-range NN potential resulting from meson exchange between nucleons moving in time reversal states within an energy range of hundreds of MeV from the Fermi energy. The second results from the exchange of vibrational modes between nucleons moving within few MeV from the Fermi energy. Short- ( v p bare) and long-range ( v p ind) pairing interactions contribute essentially equally to nuclear Cooper pair stability. That is to the breaking of gauge invariance in open-shell superfluid nuclei and thus to the order parameter, namely to the ground state expectation value of the pair creation operator. In other words, to the emergent property of generalized rigidity in gauge space, and associated rotational bands and Cooper pair tunneling between members of these bands.

SQUARE WAVE AMPLIFIER

DOEpatents

Leavitt, M.A.; Lutz, I.C.

1958-08-01

An amplifier circuit is described for amplifying sigmals having an alternating current component superimposed upon a direct current component, without loss of any segnnent of the alternating current component. The general circuit arrangement includes a vibrator, two square wave amplifiers, and recombination means. The amplifier input is connected to the vibrating element of the vibrator and is thereby alternately applied to the input of each square wave amplifier. The detailed circuitry of the recombination means constitutes the novelty of the annplifier and consists of a separate, dual triode amplifier coupled to the output of each square wave amplifier with a recombination connection from the plate of one amplifier section to a grid of one section of the other amplifier. The recombination circuit has provisions for correcting distortion caused by overlapping of the two square wave voltages from the square wave amplifiers.

Simple vertex correction improves G W band energies of bulk and two-dimensional crystals

NASA Astrophysics Data System (ADS)

Schmidt, Per S.; Patrick, Christopher E.; Thygesen, Kristian S.

2017-11-01

The G W self-energy method has long been recognized as the gold standard for quasiparticle (QP) calculations of solids in spite of the fact that the neglect of vertex corrections and the use of a density-functional theory starting point lack rigorous justification. In this work we remedy this situation by including a simple vertex correction that is consistent with a local-density approximation starting point. We analyze the effect of the self-energy by splitting it into short-range and long-range terms which are shown to govern, respectively, the center and size of the band gap. The vertex mainly improves the short-range correlations and therefore has a small effect on the band gap, while it shifts the band gap center up in energy by around 0.5 eV, in good agreement with experiments. Our analysis also explains how the relative importance of short- and long-range interactions in structures of different dimensionality is reflected in their QP energies. Inclusion of the vertex comes at practically no extra computational cost and even improves the basis set convergence compared to G W . Taken together, the method provides an efficient and rigorous improvement over the G W approximation.

Prevalence and characteristics of vibrator use by women in the United States: results from a nationally representative study.

PubMed

Herbenick, Debra; Reece, Michael; Sanders, Stephanie; Dodge, Brian; Ghassemi, Annahita; Fortenberry, J Dennis

2009-07-01

Although vibrators are commonly recommended by clinicians as adjunct to treatment for female sexual dysfunction, and for sexual enhancement, little is known about their prevalence or correlates of use. The aim of this study was to determine the lifetime and recent prevalence of women's vibrator use during masturbation and partnered sex, and the correlates of use related to sociodemographic variables, health behaviors, and sexual function. A nationally representative sample of 3,800 women aged 18-60 years were invited to participate in a cross-sectional Internet-based survey; 2,056 (54.1%) participated. The prevalence of vibrator use, the relationship between vibrator use and physical and psychological well-being (as assessed by the Centers for Disease Control and Prevention [CDC] Healthy Days measure) and health-promoting behaviors, the relationship between vibrator use and women's scores on the Female Sexual Function Index, and an assessment of the frequency and severity of side effects potentially associated with vibrator use. The prevalence of women's vibrator use was found to be 52.5% (95% CI 50.3-54.7%). Vibrator users were significantly more likely to have had a gynecologic exam during the past year (P < 0.001) and to have performed genital self-examination during the previous month (P < 0.001). Vibrator use was significantly related to several aspects of sexual function (i.e., desire, arousal, lubrication, orgasm, pain, overall function) with recent vibrator users scoring higher on most sexual function domains, indicating more positive sexual function. Most women (71.5%) reported having never experienced genital symptoms associated with vibrator use. There were no significant associations between vibrator use and participants' scores on the CDC Healthy Days Measures. Vibrator use among women is common, associated with health-promoting behaviors and positive sexual function, and rarely associated with side effects. Clinicians may find these data useful in responding to patients' sexual issues and recommending vibrator use to improve sexual function. Further research on the relationships between vibrator use and sexual health is warranted.

The usefulness of "corrected" body mass index vs. self-reported body mass index: comparing the population distributions, sensitivity, specificity, and predictive utility of three correction equations using Canadian population-based data.

PubMed

Dutton, Daniel J; McLaren, Lindsay

2014-05-06

National data on body mass index (BMI), computed from self-reported height and weight, is readily available for many populations including the Canadian population. Because self-reported weight is found to be systematically under-reported, it has been proposed that the bias in self-reported BMI can be corrected using equations derived from data sets which include both self-reported and measured height and weight. Such correction equations have been developed and adopted. We aim to evaluate the usefulness (i.e., distributional similarity; sensitivity and specificity; and predictive utility vis-à-vis disease outcomes) of existing and new correction equations in population-based research. The Canadian Community Health Surveys from 2005 and 2008 include both measured and self-reported values of height and weight, which allows for construction and evaluation of correction equations. We focused on adults age 18-65, and compared three correction equations (two correcting weight only, and one correcting BMI) against self-reported and measured BMI. We first compared population distributions of BMI. Second, we compared the sensitivity and specificity of self-reported BMI and corrected BMI against measured BMI. Third, we compared the self-reported and corrected BMI in terms of association with health outcomes using logistic regression. All corrections outperformed self-report when estimating the full BMI distribution; the weight-only correction outperformed the BMI-only correction for females in the 23-28 kg/m2 BMI range. In terms of sensitivity/specificity, when estimating obesity prevalence, corrected values of BMI (from any equation) were superior to self-report. In terms of modelling BMI-disease outcome associations, findings were mixed, with no correction proving consistently superior to self-report. If researchers are interested in modelling the full population distribution of BMI, or estimating the prevalence of obesity in a population, then a correction of any kind included in this study is recommended. If the researcher is interested in using BMI as a predictor variable for modelling disease, then both self-reported and corrected BMI result in biased estimates of association.

Nonlinear Vibrational Spectroscopy: a Method to Study Vibrational Self-Trapping

NASA Astrophysics Data System (ADS)

Hamm, Peter; Edler, Julian

We review the capability of nonlinear vibrational spectroscopy to study vibrational self-trapping in hydrogen-bonded molecular crystals. For that purpose, the two relevant coupling mechanisms, excitonic coupling and nonlinear exciton-phonon coupling, are first introduced separately using appropriately chosen molecular systems as examples. Both coupling mechanisms are subsequently combined, yielding vibrational selftrapping. The experiments unambiguously prove that both the N-H and the C=O band of crystalline acetanilide (ACN), a model system for proteins, show vibrational self-trapping. The C=O band is self-trapped only at low enough temperature, while thermally induced disorder destroys the mechanism at room temperature. The binding energy of the N-H band, on the other hand, is considerably larger and self-trapping survives thermal fluctuations even at room temperature.

Self-consistent conversion of a viscous fluid to particles

NASA Astrophysics Data System (ADS)

Molnar, Denes; Wolff, Zack

2017-02-01

Comparison of hydrodynamic and "hybrid" hydrodynamics+transport calculations with heavy-ion data inevitably requires the conversion of the fluid to particles. For dissipative fluids the conversion is ambiguous without additional theory input complementing hydrodynamics. We obtain self-consistent shear viscous phase-space corrections from linearized Boltzmann transport theory for a gas of hadrons. These corrections depend on the particle species, and incorporating them in Cooper-Frye freeze-out affects identified particle observables. For example, with additive quark model cross sections, proton elliptic flow is larger than pion elliptic flow at moderately high pT in Au+Au collisions at the BNL Relativistic Heavy Ion Collider. This is in contrast to Cooper-Frye freeze-out with the commonly used "democratic Grad" ansatz that assumes no species dependence. Various analytic and numerical results are also presented for massless and massive two-component mixtures to better elucidate how species dependence arises. For convenient inclusion in pure hydrodynamic and hybrid calculations, Appendix G contains self-consistent viscous corrections for each species both in tabulated and parametrized form.

Theoretical spectroscopic characterization at low temperatures of detectable sulfur-organic compounds: Ethyl mercaptan and dimethyl sulfide

NASA Astrophysics Data System (ADS)

Senent, M. L.; Puzzarini, C.; Domínguez-Gómez, R.; Carvajal, M.; Hochlaf, M.

2014-03-01

Highly correlated ab initio methods are used for the spectroscopic characterization of ethyl mercaptan (CH3CH232SH, ETSH) and dimethyl sulfide (CH332SCH3, DMS), considering them on the vibrational ground and excited torsional states. Since both molecules show non-rigid properties, torsional energy barriers and splittings are provided. Equilibrium geometries and the corresponding rotational constants are calculated by means of a composite scheme based on CCSD(T) calculations that accounts for the extrapolation to the complete basis set limit and core-correlation effects. The ground and excited states rotational constants are then determined using vibrational corrections obtained from CCSD/cc-pVTZ force-field calculations, which are also employed to determine anharmonic frequencies for all vibrational modes. CCSD(T) and CCSD force fields are employed to predict quartic and sextic centrifugal-distortion constants, respectively. Equilibrium rotational constants are also calculated using CCSD(T)-F12. The full-dimensional anharmonic analysis does not predict displacements of the lowest torsional excited states due to Fermi resonances with the remaining vibrational modes. Thus, very accurate torsional transitions are calculated by solving variationally two-dimensional Hamiltonians depending on the CH3 and SH torsional coordinates of ethyl mercaptan or on the two methyl groups torsions of dimethyl-sulfide. For this purpose, vibrationally corrected potential energy surfaces are computed at the CCSD(T)/aug-cc-pVTZ level of theory. For ethyl mercaptan, calculations show large differences between the gauche (g) and trans (t) conformer spectral features. Interactions between rotating groups are responsible for the displacements of the g-bands with respect to the t-bands that cannot therefore be described with one-dimensional models. For DMS, the CCSD(T) potential energy surface has been semi-empirically adjusted to reproduce experimental data. New assignments are suggested for the methyl torsion bands of ETSH and a reassignment is proposed for the infrared bands of DMS (0 3 → 0 4 and 1 0 → 1 1). Our accurate spectroscopic data should be useful for the analysis of the microwave and far infrared spectra of ETSH and DMS recorded, at low temperatures, either in laboratory or in the interstellar medium.

Self-vibration cancellation of a novel bi-directional magnetized NdFeB/magnetostrictive/piezoelectric laminate

NASA Astrophysics Data System (ADS)

Leung, Chung Ming; Wang, Feifei; Wang, Ya

2016-06-01

A novel magnetoelectric (ME) laminated composite structure is proposed in this work, aiming to provide a good self-vibration cancellation performance under the magnetic field detection environment. The proposed structure consists of two Terfenol-D magnetostrictive alloy plates which are revised and length-magnetized by two NdFeB magnets bonded on the top surface of a thickness-polarized Pb(Zr, Ti)O3 (PZT) ceramic plate with separate electrodes. Experiments have shown that great vibration suppression up to 44 dB under harmonic disturbance was observed. The ME coefficient of the proposed structure also reaches up to ˜29 mV/Oe at non-resonance frequency and 758 mV/Oe at resonance frequency of 79 kHz which is ˜2 times larger than the traditional L-T Terfenol-D/PZT bilayer configuration of the same scale. Such performance improvement is achieved based on the bi-directional magnetic field bias (HBias) of two NdFeB magnets in magnetostrictive layer, internal in-series electrical wire connection in piezoelectric layer. The proposed design has great potential to be used for industrial applications associated with heavy environmental vibration noise.

Simulation analysis of space remote sensing image quality degradation induced by satellite platform vibration

NASA Astrophysics Data System (ADS)

Yang, Feng; Zhang, Xiaofang; Huang, Yu; Hao, Weiwei; Guo, Baiwei

2012-11-01

Satellite platform vibration causes the image quality to be degraded, it is necessary to study its influence on image quality. The forms of Satellite platform vibration consist of linear vibration, sinusoidal vibration and random vibration. Based on Matlab & Zemax, the simulation system has been developed for simulating impact caused by satellite platform vibration on image quality. Dynamic Data Exchange is used for the communication between Matlab and Zemax. The data of sinusoidal vibration are produced by sinusoidal curve with specific amplitude and frequency. The data of random vibration are obtained by combining sinusoidal signals with 10Hz, 100Hz and 200Hz's frequency, 100, 12, 1.9's amplitude and white noise with zero mean value. Satellite platform vibration data which produced by Matlab are added to the optical system, and its point spread function can be obtained by Zemax. Blurred image can be gained by making the convolution of PSF and the original image. The definition of the original image and the blurred image are evaluated by using average gradient values of image gray. The impact caused by the sine and random vibration of six DOFs on the image quality are respectively simulated. The simulation result reveal that the decenter of X-, Y-, Z- direction and the tilt of Z-direction have a little effect on image quality, while the tilt of X-, Y- direction make image quality seriously degraded. Thus, it can be concluded that correcting the error of satellite platform vibration by FSM is a viable and effective way.

Long-lasting effects of neck muscle vibration and contraction on self-motion perception of vestibular origin.

PubMed

Pettorossi, Vito Enrico; Panichi, Roberto; Botti, Fabio Massimo; Biscarini, Andrea; Filippi, Guido Maria; Schieppati, Marco

2015-10-01

To show that neck proprioceptive input can induce long-term effects on vestibular-dependent self-motion perception. Motion perception was assessed by measuring the subject's error in tracking in the dark the remembered position of a fixed target during whole-body yaw asymmetric rotation of a supporting platform, consisting in a fast rightward half-cycle and a slow leftward half-cycle returning the subject to the initial position. Neck muscles were relaxed or voluntarily contracted, and/or vibrated. Whole-body rotation was administered during or at various intervals after the vibration train. The tracking position error (TPE) at the end of the platform rotation was measured during and after the muscle conditioning maneuvers. Neck input produced immediate and sustained changes in the vestibular perceptual response to whole-body rotation. Vibration of the left sterno-cleido-mastoideus (SCM) or right splenius capitis (SC) or isometric neck muscle effort to rotate the head to the right enhanced the TPE by decreasing the perception of the slow rotation. The reverse effect was observed by activating the contralateral muscle. The effects persisted after the end of SCM conditioning, and slowly vanished within several hours, as tested by late asymmetric rotations. The aftereffect increased in amplitude and persistence by extending the duration of the vibration train (from 1 to 10min), augmenting the vibration frequency (from 5 to 100Hz) or contracting the vibrated muscle. Symmetric yaw rotation elicited a negligible TPE, upon which neck muscle vibrations were ineffective. Neck proprioceptive input induces enduring changes in vestibular-dependent self-motion perception, conditional on the vestibular stimulus feature, and on the side and the characteristics of vibration and status of vibrated muscles. This shows that our perception of whole-body yaw-rotation is not only dependent on accurate vestibular information, but is modulated by proprioceptive information related to previously experienced position of head with respect to trunk. Tonic proprioceptive inflow, as might occur as a consequence of enduring or permanent head postures, can induce adaptive plastic changes in vestibular-dependent motion sensitiveness. These changes might be counteracted by vibration of selected neck muscles. Copyright © 2015 International Federation of Clinical Neurophysiology. Published by Elsevier Ireland Ltd. All rights reserved.

Bold-line Monte Carlo and the nonequilibrium physics of strongly correlated many-body systems

NASA Astrophysics Data System (ADS)

Cohen, Guy

2015-03-01

This talk summarizes real time bold-line diagrammatic Monte-Carlo approaches to quantum impurity models, which make significant headway against the sign problem by summing over corrections to self-consistent diagrammatic expansions rather than a bare diagrammatic series. When the bold-line method is combined with reduced dynamics techniques both local single-time properties and two time correlators such as Green functions can be computed at very long timescales, enabling studies of nonequilibrium steady state behavior of quantum impurity models and creating new solvers for nonequilibrium dynamical mean field theory. This work is supported by NSF DMR 1006282, NSF CHE-1213247, DOE ER 46932, TG-DMR120085 and TG-DMR130036, and the Yad Hanadiv-Rothschild Foundation.

Approximate first-principles anharmonic calculations of polyatomic spectra using MP2 and B3LYP potentials: comparisons with experiment.

PubMed

Roy, Tapta Kanchan; Carrington, Tucker; Gerber, R Benny

2014-08-21

Anharmonic vibrational spectroscopy calculations using MP2 and B3LYP computed potential surfaces are carried out for a series of molecules, and frequencies and intensities are compared with those from experiment. The vibrational self-consistent field with second-order perturbation correction (VSCF-PT2) is used in computing the spectra. The test calculations have been performed for the molecules HNO3, C2H4, C2H4O, H2SO4, CH3COOH, glycine, and alanine. Both MP2 and B3LYP give results in good accord with experimental frequencies, though, on the whole, MP2 gives very slightly better agreement. A statistical analysis of deviations in frequencies from experiment is carried out that gives interesting insights. The most probable percentage deviation from experimental frequencies is about -2% (to the red of the experiment) for B3LYP and +2% (to the blue of the experiment) for MP2. There is a higher probability for relatively large percentage deviations when B3LYP is used. The calculated intensities are also found to be in good accord with experiment, but the percentage deviations are much larger than those for frequencies. The results show that both MP2 and B3LYP potentials, used in VSCF-PT2 calculations, account well for anharmonic effects in the spectroscopy of molecules of the types considered.

An analytical derivation of MC-SCF vibrational wave functions for the quantum dynamical simulation of multiple proton transfer reactions: Initial application to protonated water chains

NASA Astrophysics Data System (ADS)

Drukker, Karen; Hammes-Schiffer, Sharon

1997-07-01

This paper presents an analytical derivation of a multiconfigurational self-consistent-field (MC-SCF) solution of the time-independent Schrödinger equation for nuclear motion (i.e. vibrational modes). This variational MC-SCF method is designed for the mixed quantum/classical molecular dynamics simulation of multiple proton transfer reactions, where the transferring protons are treated quantum mechanically while the remaining degrees of freedom are treated classically. This paper presents a proof that the Hellmann-Feynman forces on the classical degrees of freedom are identical to the exact forces (i.e. the Pulay corrections vanish) when this MC-SCF method is used with an appropriate choice of basis functions. This new MC-SCF method is applied to multiple proton transfer in a protonated chain of three hydrogen-bonded water molecules. The ground state and the first three excited state energies and the ground state forces agree well with full configuration interaction calculations. Sample trajectories are obtained using adiabatic molecular dynamics methods, and nonadiabatic effects are found to be insignificant for these sample trajectories. The accuracy of the excited states will enable this MC-SCF method to be used in conjunction with nonadiabatic molecular dynamics methods. This application differs from previous work in that it is a real-time quantum dynamical nonequilibrium simulation of multiple proton transfer in a chain of water molecules.

Optimized coordinates in vibrational coupled cluster calculations

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

Thomsen, Bo; Christiansen, Ove; Yagi, Kiyoshi

The use of variationally optimized coordinates, which minimize the vibrational self-consistent field (VSCF) ground state energy with respect to orthogonal transformations of the coordinates, has recently been shown to improve the convergence of vibrational configuration interaction (VCI) towards the exact full VCI [K. Yagi, M. Keçeli, and S. Hirata, J. Chem. Phys. 137, 204118 (2012)]. The present paper proposes an incorporation of optimized coordinates into the vibrational coupled cluster (VCC), which has in the past been shown to outperform VCI in approximate calculations where similar restricted state spaces are employed in VCI and VCC. An embarrassingly parallel algorithm for variationalmore » optimization of coordinates for VSCF is implemented and the resulting coordinates and potentials are introduced into a VCC program. The performance of VCC in optimized coordinates (denoted oc-VCC) is examined through pilot applications to water, formaldehyde, and a series of water clusters (dimer, trimer, and hexamer) by comparing the calculated vibrational energy levels with those of the conventional VCC in normal coordinates and VCI in optimized coordinates. For water clusters, in particular, oc-VCC is found to gain orders of magnitude improvement in the accuracy, exemplifying that the combination of optimized coordinates localized to each monomer with the size-extensive VCC wave function provides a supreme description of systems consisting of weakly interacting sub-systems.« less

Composite vibrational spectroscopy of the group 12 difluorides: ZnF2, CdF2, and HgF2.

PubMed

Solomonik, Victor G; Smirnov, Alexander N; Navarkin, Ilya S

2016-04-14

The vibrational spectra of group 12 difluorides, MF2 (M = Zn, Cd, Hg), were investigated via coupled cluster singles, doubles, and perturbative triples, CCSD(T), including core correlation, with a series of correlation consistent basis sets ranging in size from triple-zeta through quintuple-zeta quality, which were then extrapolated to the complete basis set (CBS) limit using a variety of extrapolation procedures. The explicitly correlated coupled cluster method, CCSD(T)-F12b, was employed as well. Although exhibiting quite different convergence behavior, the F12b method yielded the CBS limit estimates closely matching more computationally expensive conventional CBS extrapolations. The convergence with respect to basis set size was examined for the contributions entering into composite vibrational spectroscopy, including those from higher-order correlation accounted for through the CCSDT(Q) level of theory, second-order spin-orbit coupling effects assessed within four-component and two-component relativistic formalisms, and vibrational anharmonicity evaluated via a perturbative treatment. Overall, the composite results are in excellent agreement with available experimental values, except for the CdF2 bond-stretching frequencies compared to spectral assignments proposed in a matrix isolation infrared and Raman study of cadmium difluoride vapor species [Loewenschuss et al., J. Chem. Phys. 50, 2502 (1969); Givan and Loewenschuss, J. Chem. Phys. 72, 3809 (1980)]. These assignments are called into question in the light of the composite results.

Composite vibrational spectroscopy of the group 12 difluorides: ZnF2, CdF2, and HgF2

NASA Astrophysics Data System (ADS)

Solomonik, Victor G.; Smirnov, Alexander N.; Navarkin, Ilya S.

2016-04-01

The vibrational spectra of group 12 difluorides, MF2 (M = Zn, Cd, Hg), were investigated via coupled cluster singles, doubles, and perturbative triples, CCSD(T), including core correlation, with a series of correlation consistent basis sets ranging in size from triple-zeta through quintuple-zeta quality, which were then extrapolated to the complete basis set (CBS) limit using a variety of extrapolation procedures. The explicitly correlated coupled cluster method, CCSD(T)-F12b, was employed as well. Although exhibiting quite different convergence behavior, the F12b method yielded the CBS limit estimates closely matching more computationally expensive conventional CBS extrapolations. The convergence with respect to basis set size was examined for the contributions entering into composite vibrational spectroscopy, including those from higher-order correlation accounted for through the CCSDT(Q) level of theory, second-order spin-orbit coupling effects assessed within four-component and two-component relativistic formalisms, and vibrational anharmonicity evaluated via a perturbative treatment. Overall, the composite results are in excellent agreement with available experimental values, except for the CdF2 bond-stretching frequencies compared to spectral assignments proposed in a matrix isolation infrared and Raman study of cadmium difluoride vapor species [Loewenschuss et al., J. Chem. Phys. 50, 2502 (1969); Givan and Loewenschuss, J. Chem. Phys. 72, 3809 (1980)]. These assignments are called into question in the light of the composite results.

Accurate ab initio Quartic Force Fields of Cyclic and Bent HC2N Isomers

NASA Technical Reports Server (NTRS)

Inostroza, Natalia; Huang, Xinchuan; Lee, Timothy J.

2012-01-01

Highly correlated ab initio quartic force field (QFFs) are used to calculate the equilibrium structures and predict the spectroscopic parameters of three HC2N isomers. Specifically, the ground state quasilinear triplet and the lowest cyclic and bent singlet isomers are included in the present study. Extensive treatment of correlation effects were included using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted CCSD(T). Dunning s correlation-consistent basis sets cc-pVXZ, X=3,4,5, were used, and a three-point formula for extrapolation to the one-particle basis set limit was used. Core-correlation and scalar relativistic corrections were also included to yield highly accurate QFFs. The QFFs were used together with second-order perturbation theory (with proper treatment of Fermi resonances) and variational methods to solve the nuclear Schr dinger equation. The quasilinear nature of the triplet isomer is problematic, and it is concluded that a QFF is not adequate to describe properly all of the fundamental vibrational frequencies and spectroscopic constants (though some constants not dependent on the bending motion are well reproduced by perturbation theory). On the other hand, this procedure (a QFF together with either perturbation theory or variational methods) leads to highly accurate fundamental vibrational frequencies and spectroscopic constants for the cyclic and bent singlet isomers of HC2N. All three isomers possess significant dipole moments, 3.05D, 3.06D, and 1.71D, for the quasilinear triplet, the cyclic singlet, and the bent singlet isomers, respectively. It is concluded that the spectroscopic constants determined for the cyclic and bent singlet isomers are the most accurate available, and it is hoped that these will be useful in the interpretation of high-resolution astronomical observations or laboratory experiments.

Second-order electron self-energy loop-after-loop correction for low- Z hydrogen-like ions

NASA Astrophysics Data System (ADS)

Goidenko, Igor; Labzowsky, Leonti; Plunien, Günter; Soff, Gerhard

2005-07-01

The second-order electron self-energy loop-after-loop correction is investigated for hydrogen-like ions in the region of low nuclear charge numbers Z. Both irreducible and reducible parts of this correction are evaluated for the 1s1/2-state within the Fried-Yennie gauge. We confirm the result obtained first by Mallampalli and Sapirstein. The reducible part of this correction is evaluated numerically for the first time and it is consistent with the corresponding analytical αZ-expansion.

Multiconfiguration Pair-Density Functional Theory: A New Way To Treat Strongly Correlated Systems.

PubMed

Gagliardi, Laura; Truhlar, Donald G; Li Manni, Giovanni; Carlson, Rebecca K; Hoyer, Chad E; Bao, Junwei Lucas

2017-01-17

The electronic energy of a system provides the Born-Oppenheimer potential energy for internuclear motion and thus determines molecular structure and spectra, bond energies, conformational energies, reaction barrier heights, and vibrational frequencies. The development of more efficient and more accurate ways to calculate the electronic energy of systems with inherently multiconfigurational electronic structure is essential for many applications, including transition metal and actinide chemistry, systems with partially broken bonds, many transition states, and most electronically excited states. Inherently multiconfigurational systems are called strongly correlated systems or multireference systems, where the latter name refers to the need for using more than one ("multiple") configuration state function to provide a good zero-order reference wave function. This Account describes multiconfiguration pair-density functional theory (MC-PDFT), which was developed as a way to combine the advantages of wave function theory (WFT) and density functional theory (DFT) to provide a better treatment of strongly correlated systems. First we review background material: the widely used Kohn-Sham DFT (which uses only a single Slater determinant as reference wave function), multiconfiguration WFT methods that treat inherently multiconfigurational systems based on an active space, and previous attempts to combine multiconfiguration WFT with DFT. Then we review the formulation of MC-PDFT. It is a generalization of Kohn-Sham DFT in that the electron kinetic energy and classical electrostatic energy are calculated from a reference wave function, while the rest of the energy is obtained from a density functional. However, there are two main differences with respent to Kohn-Sham DFT: (i) The reference wave function is multiconfigurational rather than being a single Slater determinant. (ii) The density functional is a function of the total density and the on-top pair density rather than being a function of the spin-up and spin-down densities. In work carried out so far, the multiconfigurational wave function is a multiconfiguration self-consistent-field wave function. The new formulation has the advantage that the reference wave function has the correct spatial and spin symmetry and can describe bond dissociation (of both single and multiple bonds) and electronic excitations in a formally and physically correct way. We then review the formulation of density functionals in terms of the on-top pair density. Finally we review successful applications of the theory to bond energies and bond dissociation potential energy curves of main-group and transition metal bonds, to barrier heights (including pericyclic reactions), to proton affinities, to the hydrogen bond energy of water dimer, to ground- and excited-state charge transfer, to valence and Rydberg excitations of molecules, and to singlet-triplet splittings of radicals. We find that that MC-PDFT can give accurate results not only with complete-active-space multiconfiguration wave functions but also with generalized-active-space multiconfiguration wave functions, which are practical for larger numbers of active electrons and active orbitals than are complete-active-space wave functions. The separated-pair approximation, which is a special case of generalized active space self-consistent-field theory, is especially promising. MC-PDFT, because it requires much less computer time and storage than pure WFT methods, has the potential to open larger and more complex strongly correlated systems to accurate simulation.

Adhesion of a bimetallic interface. Ph.D. Thesis - Case Western Reserve Univ.; [for Al, Mg, and Zn

NASA Technical Reports Server (NTRS)

Ferrante, J.

1978-01-01

The Hohenberg-Kohn and Kohn-Sham formalisms are used to examine binding (binding energy as a function of separation) for combinations of the simple metals Al(111), Zn(0001), Mg(0001), and Na(110) in contact. Similar metal contacts between Al, Zn, Mg, and Na are examined self-consistently in an ab initio calculation using the Kohn-Sham formalism. Crystallinity is included using the Aschroft pseudopotential via first order perturbation theory for the electron-ion interaction; and the ion-ion interaction is included exactly via a lattice sum. Binding energy was determined both in the local-density approximation and including gradient corrections to the exchange and correlation energy. Binding was found in all cases. In dissimilar metal contacts, interfacial bonding was greater than that in the weaker material predicting the possibility of metallic transfer. The nonzero position of the energy minimum in like metal contacts is explained in terms of consistency between the Ashcroft pseudopotential and the bulk charge density. Good agreement with experimental surface energies is obtained in the self-consistent calculation when nonlocal terms are included.

Some aspects of self-consistent higher-order interactions

NASA Astrophysics Data System (ADS)

Sakamoto, Hideo

2018-05-01

After a brief review of the formalism of the self-consistent higher-order interactions, applications of a ([Q 3 Q 3](2) · Q 2) type of three-body interaction to the quadrupole moment of the 3‑ state in 208Pb and the energy splitting of the septuplet of states (h 9/23‑)I with I = 3/2, 5/2, …, 15/2 in 209Bi are discussed. It is shown that if the contribution of the three-body interaction is included, the theoretical value of the Qel (3‑) moment becomes rather small compared to the experiment, but the observed small energy splitting of the septuplet can essentially be understood within the particle-vibration coupling model. Roles of non-linear field couplings provided by the self-consistent higher-order interactions are also discussed.

Response theory of the ergodic many-body delocalized phase: Keldysh Finkel'stein sigma models and the 10-fold way

NASA Astrophysics Data System (ADS)

Liao, Yunxiang; Levchenko, Alex; Foster, Matthew S.

2017-11-01

We derive the finite temperature Keldysh response theory for interacting fermions in the presence of quenched short-ranged disorder, as applicable to any of the 10 Altland-Zirnbauer classes in an Anderson delocalized phase with at least a U(1) continuous symmetry. In this formulation of the interacting Finkel'stein nonlinear sigma model, the statistics of one-body wave functions are encoded by the constrained matrix field, while physical correlations follow from the hydrodynamic density or spin response field, which decouples the interactions. Integrating out the matrix field first, we obtain weak (anti) localization and Altshuler-Aronov quantum conductance corrections from the hydrodynamic response function. This procedure automatically incorporates the correct infrared cutoff physics, and in particular gives the Altshuler-Aronov-Khmelnitsky (AAK) equations for dephasing of weak (anti)localization due to electron-electron collisions. We explicate the method by deriving known quantumcorrections in two dimensions for the symplectic metal class AII, as well as the spin-SU(2) invariant superconductor classes C and CI. We show that quantum conductance corrections due to the special modes at zero energy in nonstandard classes are automatically cut off by temperature, as previously expected, while the Wigner-Dyson class Cooperon modes that persist to all energies are cut by dephasing. We also show that for short-ranged interactions, the standard self-consistent solution for the dephasing rate is equivalent to a particular summation of diagrams via the self-consistent Born approximation. This should be compared to the corresponding AAK solution for long-ranged Coulomb interactions, which exploits the Markovian noise correlations induced by thermal fluctuations of the electromagnetic field. We discuss prospects for exploring the many-body localization transition as a dephasing catastrophe in short-range interacting models, as encountered by approaching from the ergodic side.

A refined quartic potential energy surface and large scale vibrational calculations for S0 thiophosgene.

PubMed

Rashev, Svetoslav; Moule, David C

2015-04-05

In this work we present a full 6D quartic potential energy surface (PES) for S0 thiophosgene in curvilinear symmetrized bond-angle coordinates. The PES was refined starting from an ab initio field derived from acc-pVTZ basis set with CCSD(T) corrections for electron correlation. In the present calculations we used our variational method that was recently tested on formaldehyde and some of its isotopomers, along with additional improvements. The lower experimentally known vibrational levels for 35Cl2CS were reproduced quite well in the calculations, which can be regarded as a test for the feasibility of the obtained quartic PES. Copyright © 2015 Elsevier B.V. All rights reserved.

The METER: A Brief, Self-Administered Measure of Health Literacy

PubMed Central

Gunstad, John; Hughes, Joel; Spitznagel, Mary Beth; Potter, Vanessa; Waechter, Donna; Rosneck, James

2009-01-01

Background Given rapidly accumulating evidence that health literacy is correlated with important health-related measures, assessing patients’ health literacy level is of increasing concern for researchers and practitioners. Practical limitations for use of existing health literacy measures include length of time and practitioner involvement in administration. Objective To develop and validate a brief, self-administered measure of health literacy, the Medical Term Recognition Test (METER). Participants 155 participants were recruited from an outpatient cardiology program at an urban hospital. Measures Patients completed measures of health literacy (METER and REALM), neuropsychological function, psychosocial health, and self-report questionnaires about health behaviors. Indicators of cardiovascular health were also recorded from patients’ medical charts. Key results The measure took 2 min to complete. The internal consistency of the METER was 0.93, and it correlated highly with REALM (r = 0.74). Regarding sensitivity and specificity for identifying individuals below REALM’s cutoff for functional literacy, METER resulted in 75% correct identifications and 8% false positives. METER and REALM were both associated with various health-related measures (including significant correlations with measures of neuropsychological function and cardiovascular health). Conclusions These initial findings show that the METER is a quick and practical measure of health literacy for use in clinical settings. PMID:19885705

An Attachable Electromagnetic Energy Harvester Driven Wireless Sensing System Demonstrating Milling-Processes and Cutter-Wear/Breakage-Condition Monitoring.

PubMed

Chung, Tien-Kan; Yeh, Po-Chen; Lee, Hao; Lin, Cheng-Mao; Tseng, Chia-Yung; Lo, Wen-Tuan; Wang, Chieh-Min; Wang, Wen-Chin; Tu, Chi-Jen; Tasi, Pei-Yuan; Chang, Jui-Wen

2016-02-23

An attachable electromagnetic-energy-harvester driven wireless vibration-sensing system for monitoring milling-processes and cutter-wear/breakage-conditions is demonstrated. The system includes an electromagnetic energy harvester, three single-axis Micro Electro-Mechanical Systems (MEMS) accelerometers, a wireless chip module, and corresponding circuits. The harvester consisting of magnets with a coil uses electromagnetic induction to harness mechanical energy produced by the rotating spindle in milling processes and consequently convert the harnessed energy to electrical output. The electrical output is rectified by the rectification circuit to power the accelerometers and wireless chip module. The harvester, circuits, accelerometer, and wireless chip are integrated as an energy-harvester driven wireless vibration-sensing system. Therefore, this completes a self-powered wireless vibration sensing system. For system testing, a numerical-controlled machining tool with various milling processes is used. According to the test results, the system is fully self-powered and able to successfully sense vibration in the milling processes. Furthermore, by analyzing the vibration signals (i.e., through analyzing the electrical outputs of the accelerometers), criteria are successfully established for the system for real-time accurate simulations of the milling-processes and cutter-conditions (such as cutter-wear conditions and cutter-breaking occurrence). Due to these results, our approach can be applied to most milling and other machining machines in factories to realize more smart machining technologies.

An Attachable Electromagnetic Energy Harvester Driven Wireless Sensing System Demonstrating Milling-Processes and Cutter-Wear/Breakage-Condition Monitoring

PubMed Central

Chung, Tien-Kan; Yeh, Po-Chen; Lee, Hao; Lin, Cheng-Mao; Tseng, Chia-Yung; Lo, Wen-Tuan; Wang, Chieh-Min; Wang, Wen-Chin; Tu, Chi-Jen; Tasi, Pei-Yuan; Chang, Jui-Wen

2016-01-01

An attachable electromagnetic-energy-harvester driven wireless vibration-sensing system for monitoring milling-processes and cutter-wear/breakage-conditions is demonstrated. The system includes an electromagnetic energy harvester, three single-axis Micro Electro-Mechanical Systems (MEMS) accelerometers, a wireless chip module, and corresponding circuits. The harvester consisting of magnets with a coil uses electromagnetic induction to harness mechanical energy produced by the rotating spindle in milling processes and consequently convert the harnessed energy to electrical output. The electrical output is rectified by the rectification circuit to power the accelerometers and wireless chip module. The harvester, circuits, accelerometer, and wireless chip are integrated as an energy-harvester driven wireless vibration-sensing system. Therefore, this completes a self-powered wireless vibration sensing system. For system testing, a numerical-controlled machining tool with various milling processes is used. According to the test results, the system is fully self-powered and able to successfully sense vibration in the milling processes. Furthermore, by analyzing the vibration signals (i.e., through analyzing the electrical outputs of the accelerometers), criteria are successfully established for the system for real-time accurate simulations of the milling-processes and cutter-conditions (such as cutter-wear conditions and cutter-breaking occurrence). Due to these results, our approach can be applied to most milling and other machining machines in factories to realize more smart machining technologies. PMID:26907297

Drug Use among Residents of Juvenile Correctional Center in Kerman, Iran, and its Relationship with Personality Dimensions and Self-concept

PubMed Central

Gousheh, Amin; Ziaaddini, Hassan; Baneshi, Mohammad Reza; Nakhaee, Nouzar

2014-01-01

Background Identifying the status of substance misuse and its psychosocial correlates among residents of juvenile correctional centers, as a high risk group, could potentially illuminate the roadmap to prevention of drug use in this group. Methods In this cross-sectional study, 93 individuals aged 13 to 18 were enrolled. A self-administered questionnaire was completed and dropped in a sealed box. It consisted of 4 parts of Piers-Harris Children’s Self-Concept Scale, NEO Personality Inventory, drug use questions, and demographic variables. All questionnaires were well adapted in the Persian language. MANOVA was used to compare the subscale scores between the drug users and nonusers. Findings All respondents were male and 40% were illiterate. More than 40% had drug dependent fathers. Use of cigarette, opium, and alcohol in the previous 30 days was reported by 31.9, 52.2, and 15.9% of respondents, respectively. In this population, the score of 3 of the 5 personality factors (i.e., neuroticism, extraversion, and openness) were higher than in the general population (P < 0.001). More than 88% of subjects had negative self-concept. Both the scores of personality and self-concept showed no significant difference based on the status of drug use. Conclusion Prevalence of lifetime and last-month drug use was found to be high. Regarding the profiles of personality and self-concept, more comprehensive evidence-based interventions are needed for improvement of their mental health. PMID:25140214

The influence of material anisotropy on vibration at onset in a three-dimensional vocal fold model

PubMed Central

Zhang, Zhaoyan

2014-01-01

Although vocal folds are known to be anisotropic, the influence of material anisotropy on vocal fold vibration remains largely unknown. Using a linear stability analysis, phonation onset characteristics were investigated in a three-dimensional anisotropic vocal fold model. The results showed that isotropic models had a tendency to vibrate in a swing-like motion, with vibration primarily along the superior-inferior direction. Anterior-posterior (AP) out-of-phase motion was also observed and large vocal fold vibration was confined to the middle third region along the AP length. In contrast, increasing anisotropy or increasing AP-transverse stiffness ratio suppressed this swing-like motion and allowed the vocal fold to vibrate in a more wave-like motion with strong medial-lateral motion over the entire medial surface. Increasing anisotropy also suppressed the AP out-of-phase motion, allowing the vocal fold to vibrate in phase along the entire AP length. Results also showed that such improvement in vibration pattern was the most effective with large anisotropy in the cover layer alone. These numerical predictions were consistent with previous experimental observations using self-oscillating physical models. It was further hypothesized that these differences may facilitate complete glottal closure in finite-amplitude vibration of anisotropic models as observed in recent experiments. PMID:24606284

The usefulness of “corrected” body mass index vs. self-reported body mass index: comparing the population distributions, sensitivity, specificity, and predictive utility of three correction equations using Canadian population-based data

PubMed Central

2014-01-01

Background National data on body mass index (BMI), computed from self-reported height and weight, is readily available for many populations including the Canadian population. Because self-reported weight is found to be systematically under-reported, it has been proposed that the bias in self-reported BMI can be corrected using equations derived from data sets which include both self-reported and measured height and weight. Such correction equations have been developed and adopted. We aim to evaluate the usefulness (i.e., distributional similarity; sensitivity and specificity; and predictive utility vis-à-vis disease outcomes) of existing and new correction equations in population-based research. Methods The Canadian Community Health Surveys from 2005 and 2008 include both measured and self-reported values of height and weight, which allows for construction and evaluation of correction equations. We focused on adults age 18–65, and compared three correction equations (two correcting weight only, and one correcting BMI) against self-reported and measured BMI. We first compared population distributions of BMI. Second, we compared the sensitivity and specificity of self-reported BMI and corrected BMI against measured BMI. Third, we compared the self-reported and corrected BMI in terms of association with health outcomes using logistic regression. Results All corrections outperformed self-report when estimating the full BMI distribution; the weight-only correction outperformed the BMI-only correction for females in the 23–28 kg/m2 BMI range. In terms of sensitivity/specificity, when estimating obesity prevalence, corrected values of BMI (from any equation) were superior to self-report. In terms of modelling BMI-disease outcome associations, findings were mixed, with no correction proving consistently superior to self-report. Conclusions If researchers are interested in modelling the full population distribution of BMI, or estimating the prevalence of obesity in a population, then a correction of any kind included in this study is recommended. If the researcher is interested in using BMI as a predictor variable for modelling disease, then both self-reported and corrected BMI result in biased estimates of association. PMID:24885210

Virtex-5QV Self Scrubber

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

Wojahn, Christopher K.

2015-10-20

This HDL code (hereafter referred to as "software") implements circuitry in Xilinx Virtex-5QV Field Programmable Gate Array (FPGA) hardware. This software allows the device to self-check the consistency of its own configuration memory for radiation-induced errors. The software then provides the capability to correct any single-bit errors detected in the memory using the device's inherent circuitry, or reload corrupted memory frames when larger errors occur that cannot be corrected with the device's built-in error correction and detection scheme.

In Operation Detection and Correction of Rotor Imbalance in Jet Engines Using Active Vibration Control

NASA Technical Reports Server (NTRS)

Manchala, Daniel W.; Palazzolo, Alan B.; Kascak, Albert F.; Montague, Gerald T.; Brown, Gerald V.; Lawrence, Charles; Klusman, Steve

1994-01-01

Jet Engines may experience severe vibration due to the sudden imbalance caused by blade failure. This research investigates employment of on board magnetic bearings or piezoelectric actuators to cancel these forces in flight. This operation requires identification of the source of the vibrations via an expert system, determination of the required phase angles and amplitudes for the correction forces, and application of the desired control signals to the magnetic bearings or piezo electric actuators. This paper will show the architecture of the software system, details of the control algorithm used for the sudden imbalance correction project described above, and the laboratory test results.

Correlated phonons and the Tc-dependent dynamical phonon anomalies

NASA Astrophysics Data System (ADS)

Hakioğlu, T.; Türeci, H.

1997-11-01

Anomalously large low-temperature phonon anharmonicities can lead to static as well as dynamical changes in the low-temperature properties of the electron-phonon system. In this work, we focus our attention on the dynamically generated low-temperature correlations in an interacting electron-phonon system using a self-consistent dynamical approach in the intermediate coupling range. In the context of the model, the polaron correlations are produced by the charge-density fluctuations which are generated dynamically by the electron-phonon coupling. Conversely, the latter is influenced in the presence of the former. The purpose of this work is to examine the dynamics of this dual mechanism between the two using the illustrative Fröhlich model. In particular, the influence of the low-temperature phonon dynamics on the superconducting properties in the intermediate coupling range is investigated. The influence on the Holstein reduction factor as well as the enhancement in the zero-point fluctuations and in the electron-phonon coupling are calculated numerically. We also examine these effects in the presence of superconductivity. Within this model, the contribution of the electron-phonon interaction as one of the important elements in the mechanisms of superconductivity can reach values as high as 15-20% of the characteristic scale of the lattice vibrational energy. The second motivation of this work is to understand the nature of the Tc-dependent temperature anomalies observed in the Debye-Waller factor, dynamical pair correlations, and average atomic vibrational energies for a number of high-temperature superconductors. In our approach we do not claim nor believe that the electron-phonon interaction is the primary mechanism leading to high-temperature superconductivity. Nevertheless, our calculations suggest that the dynamically induced low-temperature phonon correlation model can account for these anomalies and illustrates their possible common origin. Finally, the relevance of incorporating these low-temperature effects into more realistic models of high-temperature superconductivity including both the charge and spin degrees and other similar ideas existing in the literature are discussed.

Amplitude control of the track-induced self-excited vibration for a maglev system.

PubMed

Zhou, Danfeng; Li, Jie; Zhang, Kun

2014-09-01

The Electromagnet Suspension (EMS) maglev train uses controlled electromagnetic forces to achieve suspension, and self-excited vibration may occur due to the flexibility of the track. In this article, the harmonic balance method is applied to investigate the amplitude of the self-excited vibration, and it is found that the amplitude of the vibration depends on the voltage of the power supplier. Based on this observation, a vibration amplitude control method, which controls the amplitude of the vibration by adjusting the voltage of the power supplier, is proposed to attenuate the vibration. A PI controller is designed to control the amplitude of the vibration at a given level. The effectiveness of this method shows a good prospect for its application to commercial maglev systems. Copyright © 2013 ISA. Published by Elsevier Ltd. All rights reserved.

Design of a hybrid power system based on solar cell and vibration energy harvester

NASA Astrophysics Data System (ADS)

Zhang, Bin; Li, Mingxue; Zhong, Shaoxuan; He, Zhichao; Zhang, Yufeng

2018-03-01

Power source has become a serious restriction of wireless sensor network. High efficiency, self-energized and long-life renewable source is the optimum solution for unmanned sensor network applications. However, single renewable power source can be easily affected by ambient environment, which influences stability of the system. In this work, a hybrid power system consists of a solar panel, a vibration energy harvester and a lithium battery is demonstrated. The system is able to harvest multiple types of ambient energy, which extends its applicability and feasibility. Experiments have been conducted to verify performance of the system.

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

Matanovic, Ivana; Atanassov, Plamen; Kiefer, Boris

The structural equilibrium parameters, the adsorption energies, and the vibrational frequencies of the nitrogen molecule and the hydrogen atom adsorbed on the (111) surface of rhodium have been investigated using different generalized-gradient approximation (GGA), nonlocal correlation, meta-GGA, and hybrid functionals, namely, Perdew, Burke, and Ernzerhof (PBE), Revised-RPBE, vdW-DF, Tao, Perdew, Staroverov, and Scuseria functional (TPSS), and Heyd, Scuseria, and Ernzerhof (HSE06) functional in the plane wave formalism. Among the five tested functionals, nonlocal vdW-DF and meta-GGA TPSS functionals are most successful in describing energetics of dinitrogen physisorption to the Rh(111) surface, while the PBE functional provides the correct chemisorption energymore » for the hydrogen atom. It was also found that TPSS functional produces the best vibrational spectra of the nitrogen molecule and the hydrogen atom on rhodium within the harmonic formalism with the error of 22.62 and 21.1% for the NAN stretching and RhAH stretching frequency. Thus, TPSS functional was proposed as a method of choice for obtaining vibrational spectra of low weight adsorbates on metallic surfaces within the harmonic approximation. At the anharmonic level, by decoupling the RhAH and NAN stretching modes from the bulk phonons and by solving one- and two-dimensional Schr€odinger equation associated with the RhAH, RhAN, and NAN potential energy we calculated the anharmonic correction for NAN and RhAH stretching modes as 231 cm21 and 277 cm21 at PBE level. Anharmonic vibrational frequencies calculated with the use of the hybrid HSE06 function are in best agreement with available experiments.« less

Vibrational spectra and ab initio analysis of tert-butyl, trimethylsilyl, and trimethylgermyl derivatives of 3,3-dimethylcyclopropene IV. 3,3-Dimethyl-1,2-bis(trimethylgermyl)cyclopropene

NASA Astrophysics Data System (ADS)

Panchenko, Yu. N.; De Maré, G. R.; Abramenkov, A. V.; Baird, M. S.; Tverezovsky, V. V.; Nizovtsev, A. V.; Bolesov, I. G.

2003-06-01

The infrared (IR) and Raman spectra of 3,3-dimethyl-1,2-bis(trimethylgermyl)cyclopropene (I) were measured in the liquid phase. Total geometry optimisation was performed at the HF/6-31G* level. The HF/6-31G*//HF6-31G* quantum mechanical force field (QMFF) was calculated and used to determine the theoretical fundamental vibrational frequencies, their predicted IR intensities, Raman activities, and Raman depolarisation ratios. Using Pulay's scaling method and the theoretical molecular geometry, the QMFF of I was scaled by a set of scaling factors comprised of elements transferred from the sets used to correct the QMFF's of 3,3-dimethylbutene-1, and 1-methyl-, 1,2-dimethyl-, and 3,3-dimethylcyclopropene (17 scale factors for a 105-dimensional problem). This set of scale factors was used previously to correct the QMFF of 3,3-dimethyl-1,2-bis(tert-butyl)cyclopropene and 3,3-dimethyl-1,2-bis(trimethylsilyl)cyclopropene. The scaled QMFF obtained was used to solve the vibrational problem. Differential Raman cross-sections were calculated using the quantum mechanical values of the Raman activities. The appropriate theoretical spectrograms for the Raman and IR spectra of I were constructed. Assignments of the experimental vibrational spectra of I are given. They take into account the calculated potential energy distributions and the correlation between the estimations of the experimental IR and Raman intensities and Raman depolarisation ratios and the corresponding theoretical values calculated using the unscaled QMFF.

Combined experimental and numerical investigation of energy harness utilizing vortex induced vibration over half cylinder using piezoelectric beams

NASA Astrophysics Data System (ADS)

Ahmed, Md. Tusher; Hossain, Md. Tanver; Rahman, Md. Ashiqur

2017-06-01

Energy harvesting technology has the ability to create self-powered electronic systems that do not rely on battery power for their operation. Wind energy can be converted into electricity via a piezoelectric transducer during the air flow over a cylinder. The vortex-induced vibration over the cylinder causes the piezoelectric beam to vibrate. Thus useful electric energy at the range 0.2-0.3V is found which can be useful for self-powering small electronic devices. In the present study, prototypes of micro-energy harvester with a shape of 65 mm × 37 mm × 0.4 mm are developed and tested for airflow over D-shaped bluff body for diameters of 15, 20 and 28mm in an experimental setup consisting of a long wind tunnel of 57cm × 57cm with variable speeds of the motor for different flow velocities and the experimental setup is connected at the downstream where flow velocity is the maximum. Experimental results show that the velocity and induced voltage follows a regular linear pattern. A maximum electrical potential of 140 mV for velocity of 1.1 ms-1 at a bluff body diameter of 15 mm is observed in the energy harvester that can be applied in many practical cases for self-powering electronic devices. The simulation of this energy harvesting phenomena is then simulated using COMSOLE multi-physics. Diameter of the bluff bodies as well as flow velocity and size of cantilever beam are varied and the experimental findings are found to be in good agreement with the simulated ones. The simulations along with the experimental data show the possibility of generating electricity from vortex induced vibration and can be applied in many practical cases for self-powering electronic devices.

Many-body calculations of molecular electric polarizabilities in asymptotically complete basis sets

NASA Astrophysics Data System (ADS)

Monten, Ruben; Hajgató, Balázs; Deleuze, Michael S.

2011-10-01

The static dipole polarizabilities of Ne, CO, N2, F2, HF, H2O, HCN, and C2H2 (acetylene) have been determined close to the Full-CI limit along with an asymptotically complete basis set (CBS), according to the principles of a Focal Point Analysis. For this purpose the results of Finite Field calculations up to the level of Coupled Cluster theory including Single, Double, Triple, Quadruple and perturbative Pentuple excitations [CCSDTQ(P)] were used, in conjunction with suited extrapolations of energies obtained using augmented and doubly-augmented Dunning's correlation consistent polarized valence basis sets of improving quality. The polarizability characteristics of C2H4 (ethylene) and C2H6 (ethane) have been determined on the same grounds at the CCSDTQ level in the CBS limit. Comparison is made with results obtained using lower levels in electronic correlation, or taking into account the relaxation of the molecular structure due to an adiabatic polarization process. Vibrational corrections to electronic polarizabilities have been empirically estimated according to Born-Oppenheimer Molecular Dynamical simulations employing Density Functional Theory. Confrontation with experiment ultimately indicates relative accuracies of the order of 1 to 2%.

Static and vibrational properties of equiatomic Na-based binary alloys

NASA Astrophysics Data System (ADS)

Vora, Aditya M.

2007-09-01

The computations of the static and vibrational properties of four equiatomic Na-based binary alloys viz. Na0.5Li0.5, Na0.5K0.5, Na0.5Rb0.5 and Na0.5Cs0.5, to second order in local model potential is discussed in terms of real-space sum of Born von Karman central force constants. The local field correlation functions due to Hartree (H), Ichimaru Utsumi (IU) and Sarkar et al. (S) are used to investigate the influence of the screening effects on the aforesaid properties. Results for the lattice constants C11, C12, C44, C12 C44, C12/C44 and bulk modulus B obtained using the H-local field correction function have higher values in comparison with the results obtained for the same properties using IU- and S-local field correction functions. The results for the Shear modulus (C‧), deviation from Cauchy's relation, Poisson's ratio σ, Young modulus Y, propagation velocity of elastic waves, phonon dispersion curves and degree of anisotropy A are highly appreciable for the four equiatomic Na-based binary alloys.

Dual origin of pairing in nuclei

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

Idini, A.; Potel, G.; Barranco, F.

The pairing correlations of the nucleus {sup 120}Sn are calculated by solving the Nambu–Gor’kov equations, including medium polarization effects resulting from the interweaving of quasiparticles, spin and density vibrations, taking into account, within the framework of nuclear field theory (NFT), processes leading to self-energy and vertex corrections and to the induced pairing interaction. From these results one can not only demonstrate the inevitability of the dual origin of pairing in nuclei, but also extract information which can be used at profit to quantitatively disentangle the contributions to the pairing gap Δ arising from the bare and from the induced pairingmore » interaction. The first is the strong {sup 1}S{sub 0} short-range NN potential resulting from meson exchange between nucleons moving in time reversal states within an energy range of hundreds of MeV from the Fermi energy. The second results from the exchange of vibrational modes between nucleons moving within few MeV from the Fermi energy. Short- (v{sub p}{sup bare}) and long-range (v{sub p}{sup ind}) pairing interactions contribute essentially equally to nuclear Cooper pair stability. That is to the breaking of gauge invariance in open-shell superfluid nuclei and thus to the order parameter, namely to the ground state expectation value of the pair creation operator. In other words, to the emergent property of generalized rigidity in gauge space, and associated rotational bands and Cooper pair tunneling between members of these bands.« less

Reliability (internal consistency) of the job content questionnaire on job stress among office workers of a multinational company in Kuala Lumpur.

PubMed

Maizura, Husna; Masilamani, Retneswari; Aris, Tahir

2009-04-01

This small, cross-sectional study assessed the reliability of 3 scales from the Job Content Questionnaire (JCQ)-decision latitude, psychological job demand, and social support-in a group of office workers in a multinational company in Kuala Lumpur. A universal sample of 30 white-collar workers from a department of the company self-administered the English version of the JCQ comprising 21 core items selected from the full recommended version of 49 items on-site. Reliability (internal consistency) was evaluated using Cronbach's alpha coefficients for each scale. Corrected item-total correlation was presented for each and every item. Cronbach's alpha coefficients were acceptable for decision latitude (.76) and social support (.79) but slightly lower for psychological job demand (.64). Values for all item-total correlations for all 3 scales were greater than .3. In conclusion, this study suggests that the JCQ is a reliable scale for assessing job stress in this group of workers.

Do postoperative radiographically verified technical success, improved cosmesis, and trunk shift corroborate with patient-reported outcomes in Lenke 1C adolescent idiopathic scoliosis?

PubMed

Sharma, Shallu; Bünger, Cody Eric; Andersen, Thomas; Sun, Haolin; Wu, Chunsen; Hansen, Ebbe Stender

2015-07-01

To examine correlation between postoperative radiographic and cosmetic improvements in Lenke 1C adolescent idiopathic scoliosis (AIS) with patients' self-rated outcomes of health and disability at follow-up as determined by the Scoliosis Research Society questionnaire (SRS-30), Oswestry Disability Index score (ODI) and measure of overall health quality Euroqol-5d (EQ-5D). 24 Lenke 1C scoliosis patients, mean age 16.5 (12.8-38.1) years, treated with posterior pedicle screw-only construct, were included. The coronal profile indices (radiographic and cosmetic) regarding magnitude of spinal deformity and truncal balance were measured preoperatively, postoperatively and at final follow-up. A comprehensive index of overall back symmetry was also measured by means of the Posterior Trunk Symmetry Index (POTSI). Pearson's correlation analysis determined the association between the radiographic-cosmetic indices and patient-rated outcomes. Mean follow-up for the cohort was 4.4 (±1.86) years. The thoracic apical vertebra-first thoracic vertebra horizontal distance (AV-TI) correction had significant correlation with function, self-image, and mental health SRS-30 scores (0.55, 0.54, 0.66). Similarly, thoracic apical vertebra horizontal translation from central sacral vertical line (AV-CSVL) correction at follow-up had significant correlation with self-image and management domains (0.57, 0.50). Follow-up POTSI correlated well with SRS-30 and EQ-5D scores (r = -0.64, -0.54). Postoperative leftward trunk shift/spinal imbalance did not influence overall cosmesis and outcomes; significant spinal realignment was evident in follow-up resulting in physiological balance and acceptable cosmesis and outcomes. Significant, but less than "perfect" correlations were observed between the radiographic, cosmetic measures and patient-rated outcomes. Thoracic AV-CSVL, AV-T1 correction and POTSI associated significantly with SRS-30 scores. Whereas, thoracic Cobb angle, Cobb correction, and coronal balance did not correlate with any patient-rated outcome measure. It is, therefore, inferred that the patients-rated subjective outcomes are only poorly reflected by the objectively measured radiographic and cosmetic measures of deformity correction.

Self-efficacy for AIDS preventive behaviors among tenth grade students.

PubMed

Kasen, S; Vaughan, R D; Walter, H J

1992-01-01

To guide acquired immunodeficiency syndrome (AIDS) prevention program planning, 181 tenth grade students residing in or near an AIDS epicenter completed a survey measuring past year involvement in sexual intercourse and condom use, beliefs about self-efficacy for AIDS preventive behaviors, and beliefs about susceptibility to and severity of AIDS, and outcome efficacy of AIDS preventive actions. A degree of uncertainty existed for all areas of self-efficacy surveyed: refusing sexual intercourse under a variety of circumstances, questioning sex partners about past risky behaviors, and correct and consistent condom use. Students were most uncertain of their ability to refuse sex with a desirable partner, under pressure, or after drinking alcohol or using marijuana; to purchase condoms, or use them consistently after drinking alcohol or using marijuana; and to question partners about past homosexual history. Those students with lower self-efficacy for refusing sex were twice as likely to have had sexual intercourse. Similarly, those students with lower self-efficacy for correct, consistent condom use were five times less likely to have used condoms consistently. These associations remained even after adjusting for the influence of other AIDS-related beliefs. Implications of these findings focus on exploiting the link between self-efficacy and behavior by building a prevention program that emphasizes skills-building rather than the traditional knowledge-only approach.

The vibrational spectrum of H2O3: An ab initio investigation

NASA Technical Reports Server (NTRS)

Jackels, Charles F.

1991-01-01

Theoretically determined frequencies and absorption intensities are reported for the vibrational spectrum of the covalent HOOOH and hydrogen bonded HO---HOO intermediates that may form in the reaction of the hydroxyl and hydroperoxyl radicals. Basis sets of DZP quality, augmented by diffuse and second sets of polarization functions have been used with CASSCF wave functions. The calculated harmonic vibrational frequencies of HOOOH have been corrected with empirical factors and presented in the form of a 'stick' spectrum. The oxygen backbone vibrations, predicted to occur at 519, 760, and 870 cm(exp -1), are well separated from most interferences, and may be the most useful for the species' identification. In the case of the hydrogen bonded isomer, emphasis has been placed upon prediction of the shifts in the intramolecular vibrational frequencies that take place upon formation of the complex. In particular, the HO stretch and HOO bend of HO2 are predicted to have shifts of -59 and 53 cm(exp -1), respectively, which should facilitate their identification. It is also noted that the antisymmetric stretching frequency of the oxygen backbone in HOOOH exhibits a strong sensitivity to the degree of electron correlation, such as has been previously observed for the same mode in ozone.

Implementation and Initial Testing of Advanced Processing and Analysis Algorithms for Correlated Neutron Counting

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

Santi, Peter Angelo; Cutler, Theresa Elizabeth; Favalli, Andrea

In order to improve the accuracy and capabilities of neutron multiplicity counting, additional quantifiable information is needed in order to address the assumptions that are present in the point model. Extracting and utilizing higher order moments (Quads and Pents) from the neutron pulse train represents the most direct way of extracting additional information from the measurement data to allow for an improved determination of the physical properties of the item of interest. The extraction of higher order moments from a neutron pulse train required the development of advanced dead time correction algorithms which could correct for dead time effects inmore » all of the measurement moments in a self-consistent manner. In addition, advanced analysis algorithms have been developed to address specific assumptions that are made within the current analysis model, namely that all neutrons are created at a single point within the item of interest, and that all neutrons that are produced within an item are created with the same energy distribution. This report will discuss the current status of implementation and initial testing of the advanced dead time correction and analysis algorithms that have been developed in an attempt to utilize higher order moments to improve the capabilities of correlated neutron measurement techniques.« less

Performance of an Optimally Tuned Range-Separated Hybrid Functional for 0-0 Electronic Excitation Energies.

PubMed

Jacquemin, Denis; Moore, Barry; Planchat, Aurélien; Adamo, Carlo; Autschbach, Jochen

2014-04-08

Using a set of 40 conjugated molecules, we assess the performance of an "optimally tuned" range-separated hybrid functional in reproducing the experimental 0-0 energies. The selected protocol accounts for the impact of solvation using a corrected linear-response continuum approach and vibrational corrections through calculations of the zero-point energies of both ground and excited-states and provides basis set converged data thanks to the systematic use of diffuse-containing atomic basis sets at all computational steps. It turns out that an optimally tuned long-range corrected hybrid form of the Perdew-Burke-Ernzerhof functional, LC-PBE*, delivers both the smallest mean absolute error (0.20 eV) and standard deviation (0.15 eV) of all tested approaches, while the obtained correlation (0.93) is large but remains slightly smaller than its M06-2X counterpart (0.95). In addition, the efficiency of two other recently developed exchange-correlation functionals, namely SOGGA11-X and ωB97X-D, has been determined in order to allow more complete comparisons with previously published data.

77 FR 58301 - Technical Amendment; Airworthiness Standards: Aircraft Engines; Correction

Federal Register 2010, 2011, 2012, 2013, 2014

2012-09-20

... technical amendment, the FAA clarified aircraft engine vibration test requirements in the airworthiness... amendment, the FAA intended to clarify vibration test requirements in Sec. 33.83 of 14 Code of Federal... read as follows: Sec. 33.83 Vibration test. (a) Each engine must undergo vibration surveys to establish...

Theoretical study of hydrogen bond interactions of fluvastatin with ι-carrageenan and λ-carrageenan.

PubMed

Papadopoulos, Anastasios G; Sigalas, Michael P

2011-07-01

The binding of the reductase inhibitor drug fluvastatin, hydroxy-3-methylglutaryl coenzyme A, with the hydrophilic ι- or λ-carrageenan polymers, serving as potential controllers of the drug's release rate, have been studied at the density functional level of theory with the B3LYP exchange correlation functional. Three low energy conformers of fluvastatin have been calculated. The vibrational spectroscopic properties calculated for the most stable conformer were in satisfactory agreement with the experimental data. A series of hydrogen bonded complexes of the most stable conformer of fluvastatin anion with low molecular weight models of the polymers have been fully optimized. In almost all, intermolecular H-bonds are formed between the sulfate groups of ι- or λ-carrageenan and fluvastatin's hydroxyls, resulting in a red shift of the fluvastatin's O - H stretching vibrations. Cooperative intramolecular H-bonds within fluvastatin or ι-, λ-carrageenan are also present. The BSSE and ZPE corrected interaction energies were estimated in the range 281-318 kJ mol⁻¹ for ι-carrageenan - fluvastatin and 145-200 kJ mol⁻¹ for λ-carrageenan - fluvastatin complexes. The electron density (ρ (bcp)) and Laplacian (∇²ρ (bcp)) properties at critical points of the intermolecular hydrogen bonds, estimated by AIM (atoms in molecules) calculations, have a low and positive character (∇²ρ(bcp) > 0), consistent with the electrostatic character of the hydrogen bonds. The structural and energetic data observed, as well as the extent of the red shift of the fluvastatin's O - H stretching vibrations upon complex formation and the properties of electron density show a stronger binding of fluvastatin to ι- than to λ-carrageenan.

Correlation of Hope and Self-Efficacy With Job Satisfaction, Job Stress, and Organizational Commitment for Correctional Officers in the Taiwan Prison System.

PubMed

Law, Fang Mei; Guo, Gwo Jen

2016-08-01

The aim of this study was to explore the correlation of hope and self-efficacy with job satisfaction, job stress, and organizational commitment for correctional officers in the Taiwan prison system while controlling for the shared effects of the nature of the institution (i.e., for male or female inmates) and personal characteristics of the officers (i.e., gender, age, and years of work experience). Hope in the context of this study refers to a cognitive set and motivational state that involves reciprocal interaction between goal-directed energy (agency) and planned pathways to meet the goals (pathway). It is a personality trait of hopefulness, rather than having hope for the prisoners restructuring their future. Self-efficacy refers to the belief that individuals have regarding their ability to perform necessary tasks to achieve goals. Although they share similar constructs, hope theory places emphasis on cross-situational goal-directed thought, whereas the concept of self-efficacy focuses on situation-specific goals. The participants were 133 correctional personnel from two correctional institutions, one with male inmates and the other with female inmates, in central Taiwan. The results of ordinary least squares regression analysis indicated that hope had a significant positive association with job satisfaction and a significant negative association with job stress. Self-efficacy had a significant positive association with job satisfaction and organizational commitment. Finally, job satisfaction had a significant positive association with organizational commitment. © The Author(s) 2015.

The Strength of Hydrogen Bonds between Fluoro-Organics and Alcohols, a Theoretical Study.

PubMed

Rosenberg, Robert E

2018-05-10

Fluorinated organic compounds are ubiquitous in the pharmaceutical and agricultural industries. To better discern the mode of action of these compounds, it is critical to understand the strengths of hydrogen bonds involving fluorine. There are only a few published examples of the strengths of these bonds. This study provides a high level ab initio study of inter- and intramolecular hydrogen bonds between RF and R'OH, where R and R' are aryl, vinyl, alkyl, and cycloalkyl. Intermolecular binding energies average near 5 kcal/mol, while intramolecular binding energies average about 3 kcal/mol. Inclusion of zero-point energies and applying a counterpoise correction lessen the difference. In both series, modest increases in binding energies are seen with increased acidity of R'OH and increased electron donation of R in RF. In the intramolecular compounds, binding energy increases with the rigidity of the F-(C) n -OH ring. Inclusion of free energy corrections at 298 K results in exoergic binding energies for the intramolecular compounds and endoergic binding energies for the intermolecular compounds. Parameters such as bond lengths, vibrational frequencies, and atomic populations are consistent with formation of a hydrogen bond and with slightly stronger binding in the intermolecular cases over the intramolecular cases. However, these parameters correlated poorly with binding energies.

How important is self-consistency for the dDsC density dependent dispersion correction?

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

Brémond, Éric; Corminboeuf, Clémence, E-mail: clemence.corminboeuf@epfl.ch; Golubev, Nikolay

2014-05-14

The treatment of dispersion interactions is ubiquitous but computationally demanding for seamless ab initio approaches. A highly popular and simple remedy consists in correcting for the missing interactions a posteriori by adding an attractive energy term summed over all atom pairs to standard density functional approximations. These corrections were originally based on atom pairwise parameters and, hence, had a strong touch of empiricism. To overcome such limitations, we recently proposed a robust system-dependent dispersion correction, dDsC, that is computed from the electron density and that provides a balanced description of both weak inter- and intramolecular interactions. From the theoretical pointmore » of view and for the sake of increasing reliability, we here verify if the self-consistent implementation of dDsC impacts ground-state properties such as interaction energies, electron density, dipole moments, geometries, and harmonic frequencies. In addition, we investigate the suitability of the a posteriori scheme for molecular dynamics simulations, for which the analysis of the energy conservation constitutes a challenging tests. Our study demonstrates that the post-SCF approach in an excellent approximation.« less

Calibration of piezoelectric RL shunts with explicit residual mode correction

NASA Astrophysics Data System (ADS)

Høgsberg, Jan; Krenk, Steen

2017-01-01

Piezoelectric RL (resistive-inductive) shunts are passive resonant devices used for damping of dominant vibration modes of a flexible structure and their efficiency relies on the precise calibration of the shunt components. In the present paper improved calibration accuracy is attained by an extension of the local piezoelectric transducer displacement by two additional terms, representing the flexibility and inertia contributions from the residual vibration modes not directly addressed by the shunt damping. This results in an augmented dynamic model for the targeted resonant vibration mode, in which the residual contributions, represented by two correction factors, modify both the apparent transducer capacitance and the shunt circuit impedance. Explicit expressions for the correction of the shunt circuit inductance and resistance are presented in a form that is generally applicable to calibration formulae derived on the basis of an assumed single-mode structure, where modal interaction has been neglected. A design procedure is devised and subsequently verified by a numerical example, which demonstrates that effective mitigation can be obtained for an arbitrary vibration mode when the residual mode correction is included in the calibration of the RL shunt.

Non-equilibrium STLS approach to transport properties of single impurity Anderson model

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

Rezai, Raheleh, E-mail: R_Rezai@sbu.ac.ir; Ebrahimi, Farshad, E-mail: Ebrahimi@sbu.ac.ir

In this work, using the non-equilibrium Keldysh formalism, we study the effects of the electron–electron interaction and the electron-spin correlation on the non-equilibrium Kondo effect and the transport properties of the symmetric single impurity Anderson model (SIAM) at zero temperature by generalizing the self-consistent method of Singwi, Tosi, Land, and Sjolander (STLS) for a single-band tight-binding model with Hubbard type interaction to out of equilibrium steady-states. We at first determine in a self-consistent manner the non-equilibrium spin correlation function, the effective Hubbard interaction, and the double-occupancy at the impurity site. Then, using the non-equilibrium STLS spin polarization function in themore » non-equilibrium formalism of the iterative perturbation theory (IPT) of Yosida and Yamada, and Horvatic and Zlatic, we compute the spectral density, the current–voltage characteristics and the differential conductance as functions of the applied bias and the strength of on-site Hubbard interaction. We compare our spectral densities at zero bias with the results of numerical renormalization group (NRG) and depict the effects of the electron–electron interaction and electron-spin correlation at the impurity site on the aforementioned properties by comparing our numerical result with the order U{sup 2} IPT. Finally, we show that the obtained numerical results on the differential conductance have a quadratic universal scaling behavior and the resulting Kondo temperature shows an exponential behavior. -- Highlights: •We introduce for the first time the non-equilibrium method of STLS for Hubbard type models. •We determine the transport properties of SIAM using the non-equilibrium STLS method. •We compare our results with order-U2 IPT and NRG. •We show that non-equilibrium STLS, contrary to the GW and self-consistent RPA, produces the two Hubbard peaks in DOS. •We show that the method keeps the universal scaling behavior and correct exponential behavior of Kondo temperature.« less

Random Vibration Analysis of the Tip-tilt System in the GMT Fast Steering Secondary Mirror

NASA Astrophysics Data System (ADS)

Lee, Kyoung-Don; Kim, Young-Soo; Kim, Ho-Sang; Lee, Chan-Hee; Lee, Won Gi

2017-09-01

A random vibration analysis was accomplished on the tip-tilt system of the fast steering secondary mirror (FSM) for the Giant Magellan Telescope (GMT). As the FSM was to be mounted on the top end of the secondary truss and disturbed by the winds, dynamic effects of the FSM disturbances on the tip-tilt correction performance was studied. The coupled dynamic responses of the FSM segments were evaluated with a suggested tip-tilt correction modeling. Dynamic equations for the tip-tilt system were derived from the force and moment equilibrium on the segment mirror and the geometric compatibility conditions with four design parameters. Statically stationary responses for the tip-tilt actuations to correct the wind-induced disturbances were studied with two design parameters based on the spectral density function of the star image errors in the frequency domain. Frequency response functions and root mean square values of the dynamic responses and the residual star image errors were numerically calculated for the off-axis and on-axis segments of the FSM. A prototype of on-axis segment of the FSM was developed for tip-tilt actuation tests to confirm the ratio of tip-tilt force to tip-tilt angle calculated from the suggested dynamic equations of the tip-tilt system. Tip-tilt actuation tests were executed at 4, 8 and 12 Hz by measuring displacements of piezoelectric actuators and reaction forces acting on the axial supports. The derived ratios of rms tip-tilt force to rms tip-tilt angle from tests showed a good correlation with the numerical results. The suggested process of random vibration analysis on the tip-tilt system to correct the wind-induced disturbances of the FSM segments would be useful to advance the FSM design and upgrade the capability to achieve the least residual star image errors by understanding the details of dynamics.

Self-Compassion and Relationship Maintenance: The Moderating Roles of Conscientiousness and Gender

PubMed Central

Baker, Levi; McNulty, James K.

2010-01-01

Should intimates respond to their interpersonal mistakes with self-criticism or with self-compassion? Although it is reasonable to expect self-compassion to benefit relationships by promoting self-esteem, it is also reasonable to expect self-compassion to hurt relationships by removing intimates’ motivation to correct their interpersonal mistakes. Two correlational studies, 1 experiment, and 1 longitudinal study demonstrated that whether self-compassion helps or hurts relationships depends on the presence versus absence of dispositional sources of the motivation to correct interpersonal mistakes. Among men, the implications of self-compassion were moderated by conscientiousness. Among men high in conscientiousness, self-compassion was associated with greater motivation to correct interpersonal mistakes (Studies 1 and 3), observations of more-constructive problem-solving behaviors (Study 2), reports of more accommodation (Study 3), and fewer declines in marital satisfaction that were mediated by decreases in interpersonal problem severity (Study 4); among men low in conscientiousness, self-compassion was associated with these outcomes in the opposite direction. Among women, in contrast, likely because women are inherently more motivated than men to preserve their relationships for cultural and/or biological reasons, self-compassion was never harmful to the relationship. Instead, women’s self-compassion was positively associated with the motivation to correct their interpersonal mistakes (Study 1) and changes in relationship satisfaction (Study 4), regardless of conscientiousness. Accordingly, theoretical descriptions of the implications of self-promoting thoughts for relationships may be most complete to the extent that they consider the presence versus absence of other sources of the motivation to correct interpersonal mistakes. PMID:21280964

Self-compassion and relationship maintenance: the moderating roles of conscientiousness and gender.

PubMed

Baker, Levi R; McNulty, James K

2011-05-01

Should intimates respond to their interpersonal mistakes with self-criticism or with self-compassion? Although it is reasonable to expect self-compassion to benefit relationships by promoting self-esteem, it is also reasonable to expect self-compassion to hurt relationships by removing intimates' motivation to correct their interpersonal mistakes. Two correlational studies, 1 experiment, and 1 longitudinal study demonstrated that whether self-compassion helps or hurts relationships depends on the presence versus absence of dispositional sources of the motivation to correct interpersonal mistakes. Among men, the implications of self-compassion were moderated by conscientiousness. Among men high in conscientiousness, self-compassion was associated with greater motivation to correct interpersonal mistakes (Studies 1 and 3), observations of more constructive problem-solving behaviors (Study 2), reports of more accommodation (Study 3), and fewer declines in marital satisfaction that were mediated by decreases in interpersonal problem severity (Study 4); among men low in conscientiousness, self-compassion was associated with these outcomes in the opposite direction. Among women, in contrast, likely because women are inherently more motivated than men to preserve their relationships for cultural and/or biological reasons, self-compassion was never harmful to the relationship. Instead, women's self-compassion was positively associated with the motivation to correct their interpersonal mistakes (Study 1) and changes in relationship satisfaction (Study 4), regardless of conscientiousness. Accordingly, theoretical descriptions of the implications of self-promoting thoughts for relationships may be most complete to the extent that they consider the presence versus absence of other sources of the motivation to correct interpersonal mistakes. (c) 2011 APA, all rights reserved.

High-level ab initio predictions for the ionization energy, bond dissociation energies, and heats of formations of iron carbide (FeC) and its cation (FeC+).

PubMed

Lau, Kai-Chung; Chang, Yih-Chung; Lam, Chow-Shing; Ng, C Y

2009-12-31

The ionization energy (IE) of FeC and the 0 K bond dissociation energies (D(0)) and the heats of formation at 0 K (DeltaH(o)(f0)) and 298 K (DeltaH(o)(f298)) for FeC and FeC(+) are predicted by the single-reference wave function based CCSDTQ(Full)/CBS approach, which involves the approximation to the complete basis set (CBS) limit at the coupled cluster level up to full quadruple excitations. The zero-point vibrational energy (ZPVE) correction, the core-valence electronic corrections (up to CCSDT level), spin-orbit couplings, and relativistic effects (up to CCSDTQ level) are included in the calculations. The present calculations provide the correct symmetry predictions for the ground states of FeC and FeC(+) to be (3)Delta and (2)Delta, respectively. We have also examined the theoretical harmonic vibrational frequencies of FeC/FeC(+) at the ROHF-UCCSD(T) and UHF-UCCSD(T) levels. While the UHF-UCCSD(T) harmonic frequencies are in good agreement with the experimental measurements, the ROHF-UCCSD(T) yields significantly higher harmonic frequency predictions for FeC/FeC(+). The CCSDTQ(Full)/CBS IE(FeC) = 7.565 eV is found to compare favorably with the experimental IE value of 7.59318 +/- 0.00006 eV, suggesting that the single-reference-based coupled cluster theory is capable of providing reliable IE prediction for FeC, despite its multireference character. The CCSDTQ(Full)/CBS D(0)(Fe(+)-C) and D(0)(Fe-C) give the prediction of D(0)(Fe(+)-C) - D(0)(Fe-C) = 0.334 eV, which is consistent with the experimental determination of 0.3094 +/- 0.0001 eV. The D(0) calculations also support the experimental D(0)(Fe(+)-C) = 4.1 +/- 0.3 eV and D(0)(Fe-C) = 3.8 +/- 0.3 eV determined by the previous ion photodissociation study. The present calculations also provide the DeltaH(o)(f0)(DeltaH(o)(f298)) predictions for FeC/FeC(+). The analysis of the correction terms in these calculations shows that the core-valence and valence-valence electronic correlations beyond CCSD(T) wave function and the relativistic effects make significant contributions to the calculated thermochemical properties of FeC/FeC(+). For the experimental D(0) and DeltaH(o)(f0) values of FeC/FeC(+), which are not known to high precision, we recommend the CCSDTQ(Full)/CBS predictions [D(0)(Fe-C) = 3.778 eV, D(0)(Fe(+)-C) = 4.112 eV, DeltaH(o)(f0)(FeC) = 760.8 kJ/mol and DeltaH(o)(f0)(FeC(+)) = 1490.6 kJ/mol] based on the ZPVE corrections using the experimental vibrational frequencies of FeC and FeC(+).

Communication: Recovering the flat-plane condition in electronic structure theory at semi-local DFT cost

NASA Astrophysics Data System (ADS)

Bajaj, Akash; Janet, Jon Paul; Kulik, Heather J.

2017-11-01

The flat-plane condition is the union of two exact constraints in electronic structure theory: (i) energetic piecewise linearity with fractional electron removal or addition and (ii) invariant energetics with change in electron spin in a half filled orbital. Semi-local density functional theory (DFT) fails to recover the flat plane, exhibiting convex fractional charge errors (FCE) and concave fractional spin errors (FSE) that are related to delocalization and static correlation errors. We previously showed that DFT+U eliminates FCE but now demonstrate that, like other widely employed corrections (i.e., Hartree-Fock exchange), it worsens FSE. To find an alternative strategy, we examine the shape of semi-local DFT deviations from the exact flat plane and we find this shape to be remarkably consistent across ions and molecules. We introduce the judiciously modified DFT (jmDFT) approach, wherein corrections are constructed from few-parameter, low-order functional forms that fit the shape of semi-local DFT errors. We select one such physically intuitive form and incorporate it self-consistently to correct semi-local DFT. We demonstrate on model systems that jmDFT represents the first easy-to-implement, no-overhead approach to recovering the flat plane from semi-local DFT.

Time-dependent vibrational spectral analysis of first principles trajectory of methylamine with wavelet transform.

PubMed

Biswas, Sohag; Mallik, Bhabani S

2017-04-12

The fluctuation dynamics of amine stretching frequencies, hydrogen bonds, dangling N-D bonds, and the orientation profile of the amine group of methylamine (MA) were investigated under ambient conditions by means of dispersion-corrected density functional theory-based first principles molecular dynamics (FPMD) simulations. Along with the dynamical properties, various equilibrium properties such as radial distribution function, spatial distribution function, combined radial and angular distribution functions and hydrogen bonding were also calculated. The instantaneous stretching frequencies of amine groups were obtained by wavelet transform of the trajectory obtained from FPMD simulations. The frequency-structure correlation reveals that the amine stretching frequency is weakly correlated with the nearest nitrogen-deuterium distance. The frequency-frequency correlation function has a short time scale of around 110 fs and a longer time scale of about 1.15 ps. It was found that the short time scale originates from the underdamped motion of intact hydrogen bonds of MA pairs. However, the long time scale of the vibrational spectral diffusion of N-D modes is determined by the overall dynamics of hydrogen bonds as well as the dangling ND groups and the inertial rotation of the amine group of the molecule.

Higher curvature self-interaction corrections to Hawking radiation

NASA Astrophysics Data System (ADS)

Fairoos, C.; Sarkar, Sudipta; Yogendran, K. P.

2017-07-01

The purely thermal nature of Hawking radiation from evaporating black holes leads to the information loss paradox. A possible route to its resolution could be if (enough) correlations are shown to be present in the radiation emitted from evaporating black holes. A reanalysis of Hawking's derivation including the effects of self-interactions in general relativity shows that the emitted radiation does deviate from pure thermality; however no correlations exist between successively emitted Hawking quanta. We extend the calculations to Einstein-Gauss-Bonnet gravity and investigate if higher curvature corrections to the action lead to some new correlations in the Hawking spectra. The effective trajectory of a massless shell is determined by solving the constraint equations and the semiclassical tunneling probability is calculated. As in the case of general relativity, the radiation is no longer thermal and there is no correlation between successive emissions. The absence of any extra correlations in the emitted radiations even in Gauss-Bonnet gravity suggests that the resolution of the paradox is beyond the scope of semiclassical gravity.

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 vibration compensation system for ARGOS

NASA Astrophysics Data System (ADS)

Peter, D.; Gaessler, W.; Borelli, J.; Kulas, M.

2011-09-01

For every adaptive optics system telescope vibrations can strongly reduce the performance. This is true for the receiver part of the system i.e. the telescope and wave front sensor part as well as for the transmitter part in the case of a laser guide star system. Especially observations in deep fields observed with a laser guide star system without any tip-tilt star will be greatly spoiled by telescope vibrations. The ARGOS GLAO system actually being built for the LBT aims to implement this kind of mode where wave front correction will rely purely on signals from the laser beacons. To remove the vibrations from the uplink path a vibration compensation system will be installed. This system uses accelerometers to measure the vibrations and corrects their effect with a small fast tip-tilt mirror. The controller of the system is built based on the assumption that the vibrations take place at a few distinct frequencies. Here I present a lab set-up of this system and show first results of the performance.

Asymmetric vibration in a two-layer vocal fold model with left-right stiffness asymmetry: Experiment and simulation

PubMed Central

Zhang, Zhaoyan; Hieu Luu, Trung

2012-01-01

Vibration characteristics of a self-oscillating two-layer vocal fold model with left-right asymmetry in body-layer stiffness were experimentally and numerically investigated. Two regimes of distinct vibratory pattern were identified as a function of left-right stiffness mismatch. In the first regime with extremely large left-right stiffness mismatch, phonation onset resulted from an eigenmode synchronization process that involved only eigenmodes of the soft fold. Vocal fold vibration in this regime was dominated by a large-amplitude vibration of the soft fold, and phonation frequency was determined by the properties of the soft fold alone. The stiff fold was only enslaved to vibrate at a much reduced amplitude. In the second regime with small left-right stiffness mismatch, eigenmodes of both folds actively participated in the eigenmode synchronization process. The two folds vibrated with comparable amplitude, but the stiff fold consistently led the soft fold in phase for all conditions. A qualitatively good agreement was obtained between experiment and simulation, although the simulations generally underestimated phonation threshold pressure and onset frequency. The clinical implications of the results of this study are also discussed. PMID:22978891

Asymmetric vibration in a two-layer vocal fold model with left-right stiffness asymmetry: experiment and simulation.

PubMed

Zhang, Zhaoyan; Luu, Trung Hieu

2012-09-01

Vibration characteristics of a self-oscillating two-layer vocal fold model with left-right asymmetry in body-layer stiffness were experimentally and numerically investigated. Two regimes of distinct vibratory pattern were identified as a function of left-right stiffness mismatch. In the first regime with extremely large left-right stiffness mismatch, phonation onset resulted from an eigenmode synchronization process that involved only eigenmodes of the soft fold. Vocal fold vibration in this regime was dominated by a large-amplitude vibration of the soft fold, and phonation frequency was determined by the properties of the soft fold alone. The stiff fold was only enslaved to vibrate at a much reduced amplitude. In the second regime with small left-right stiffness mismatch, eigenmodes of both folds actively participated in the eigenmode synchronization process. The two folds vibrated with comparable amplitude, but the stiff fold consistently led the soft fold in phase for all conditions. A qualitatively good agreement was obtained between experiment and simulation, although the simulations generally underestimated phonation threshold pressure and onset frequency. The clinical implications of the results of this study are also discussed.

Exposed and embedded corrections in aphasia therapy: issues of voice and identity.

PubMed

Simmons-Mackie, Nina; Damico, Jack S

2008-01-01

Because communication after the onset of aphasia can be fraught with errors, therapist corrections are pervasive in therapy for aphasia. Although corrections are designed to improve the accuracy of communication, some corrections can have social and emotional consequences during interactions. That is, exposure of errors can potentially silence the 'voice' of a speaker by orienting to an utterance as unacceptable. Although corrections can marginalize speakers with aphasia, the practice has not been widely investigated. A qualitative study of corrections during aphasia therapy was undertaken to describe corrections in therapy, identify patterns of occurrence, and develop hypotheses regarding the potential effects of corrections. Videotapes of six individual and five group aphasia therapy sessions were analysed. Sequences consistent with a definition of a therapist 'correction' were identified. Corrections were defined as instances when the therapist offered a 'fix' for a perceived error in the client's talk even though the intent was apparent. Two categories of correction were identified and were consistent with Jefferson's (1987) descriptions of exposed and embedded corrections. Exposed corrections involved explicit correcting by the therapist, while embedded corrections occurred implicitly within the ongoing talk. Patterns of occurrence appeared consistent with philosophical orientations of therapy sessions. Exposed corrections were more prevalent in sessions focusing on repairing deficits, while embedded corrections were prevalent in sessions focusing on natural communication events (e.g. conversation). In addition, exposed corrections were sometimes used when client offerings were plausible or appropriate, but were inconsistent with therapist expectations. The observation that some instances of exposed corrections effectively silenced the voice or self-expression of the person with aphasia has significant implications for outcomes from aphasia therapy. By focusing on accurate productions versus communicative intents, therapy runs the risk of reducing self-esteem and communicative confidence, as well as reinforcing a sense of 'helplessness' and disempowerment among people with aphasia. The results suggest that clinicians should carefully calibrate the use of exposed and embedded corrections to balance linguistic and psychosocial goals.

The optimized effective potential and the self-interaction correction in density functional theory: Application to molecules

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

Garza, Jorge; Nichols, Jeffrey A.; Dixon, David A.

2000-05-08

The Krieger, Li, and Iafrate approximation to the optimized effective potential including the self-interaction correction for density functional theory has been implemented in a molecular code, NWChem, that uses Gaussian functions to represent the Kohn and Sham spin-orbitals. The differences between the implementation of the self-interaction correction in codes where planewaves are used with an optimized effective potential are discussed. The importance of the localization of the spin-orbitals to maximize the exchange-correlation of the self-interaction correction is discussed. We carried out exchange-only calculations to compare the results obtained with these approximations, and those obtained with the local spin density approximation,more » the generalized gradient approximation and Hartree-Fock theory. Interesting results for the energy difference (GAP) between the highest occupied molecular orbital, HOMO, and the lowest unoccupied molecular orbital, LUMO, (spin-orbital energies of closed shell atoms and molecules) using the optimized effective potential and the self-interaction correction have been obtained. The effect of the diffuse character of the basis set on the HOMO and LUMO eigenvalues at the various levels is discussed. Total energies obtained with the optimized effective potential and the self-interaction correction show that the exchange energy with these approximations is overestimated and this will be an important topic for future work. (c) 2000 American Institute of Physics.« less

Correlating the vibrational spectra of structurally related molecules: A spectroscopic measure of similarity.

PubMed

Tao, Yunwen; Zou, Wenli; Cremer, Dieter; Kraka, Elfi

2018-03-05

Using catastrophe theory and the concept of a mutation path, an algorithm is developed that leads to the direct correlation of the normal vibrational modes of two structurally related molecules. The mutation path is defined by weighted incremental changes in mass and geometry of the molecules in question, which are successively applied to mutate a molecule into a structurally related molecule and thus continuously converting their normal vibrational spectra from one into the other. Correlation diagrams are generated that accurately relate the normal vibrational modes to each other by utilizing mode-mode overlap criteria and resolving allowed and avoided crossings of vibrational eigenstates. The limitations of normal mode correlation, however, foster the correlation of local vibrational modes, which offer a novel vibrational measure of similarity. It will be shown how this will open new avenues for chemical studies. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Vibrational excitation in O2and Cl2inductively-coupled plasmas and DC discharges

NASA Astrophysics Data System (ADS)

Booth, Jean-Paul; Marinov, Daniil; Foucher, Mickael; Annusova, Adriana; Guerra, Vasco

2016-09-01

Low-energy electrons can interact with molecules via resonances to cause vibrational excitation with large cross-sections. Such processes can absorb significant energy from the plasma electrons, affecting the electron energy distribution and potentially (via vibration-translation (VT) energy transfer) causing substantial gas heating. The presence of vibrationally excited molecules may significant increase the rates of collisional processes, including electron dissociative attachment and electron impact dissociation into neutral atoms. However, the cross-sections of these processes are often poorly known since they are extremely difficult to measure directly, and reliable theoretical calculations are only now appearing for simple diatomic molecules. We have measured the vibrational distributions in discharges in pure O2 and pure Cl2, using high-sensitivity ultra-broadband ultraviolet absorption spectroscopy. In O2 plasmas significant vibrational excitation is observed, up to v'' =18, with a tail temperature of around 8000K. In Cl2 excitation is only observed up to v'' =3, and the distribution appears to be in local equilibrium with the gas translational temperature (up to 1500K). We are developing a detailed self-consistent 0D global model of these systems including vibrational excitation. Work performed in the LABEX Plas@par project, with financial state aid (ANR-11-IDEX-0004-02 and ANR-13-BS09-0019).

Reliability and Validity of a Turkish version of the Prenatal Breastfeeding Self-Efficacy Scale.

PubMed

Aydin, Ayse; Pasinlioglu, Turkan

2018-05-18

This study aims to conduct reliability and validity study of the Turkish version of the "Prenatal Breastfeeding Self-Efficacy Scale", which determines pregnant women's perception of breastfeeding self-efficacy in the prenatal period. This methodological research was carried out between December 2014 and May 2016 in maternity clinics of the Erzurum Nene Hatun Maternity Hospital and Atatürk University Research Hospital. The study population consisted of pregnant women, admitted to the specified clinics for prenatal controls. The study was carried out with 326 pregnant women, who met the inclusion criteria and agreed to participate in the research without any sample selection. "Personal Information Form" and "Prenatal Breastfeeding Self-Efficacy Scale - Turkish Form" were used for data collection. The data were collected by the face-to-face interview method, and analyzed by SPSS 18 software. In the validity-reliability analysis of the scale, language and content validity, explanatory factor analysis, Cronbach's Alpha coefficient, item-total score correlation, and testretest methods were used. Linguistic validity was verified by the translation-backtranslation of the Prenatal Breastfeeding Self-Efficacy Scale, then the necessary corrections were made according to the recommendations of the expert opinions, to ensure the content validity. As a result of the explanatory factor analysis, performed to determine the construct validity of the scale, a single factor structure was found, having factor loadings in the appropriate range (0.30-0.76). In the internal consistency analysis of the scale, Cronbach's Alpha was 0.86, and the item-total score correlations were between 0.23 and 0.65, and no item was removed from the scale. In order to test the time-invariance of the scale, the test-retest correlation value was found to be 0.94. The relationship between the two applications were determined to be statistically significant (p < 0.001). Turkish version of the Prenatal Breastfeeding Self-Efficacy Scale was evaluated in Turkish women and found to be a valid and reliable measurement instrument. Copyright © 2018 Elsevier Ltd. All rights reserved.

Semiconductor laser self-mixing micro-vibration measuring technology based on Hilbert transform

NASA Astrophysics Data System (ADS)

Tao, Yufeng; Wang, Ming; Xia, Wei

2016-06-01

A signal-processing synthesizing Wavelet transform and Hilbert transform is employed to measurement of uniform or non-uniform vibrations in self-mixing interferometer on semiconductor laser diode with quantum well. Background noise and fringe inclination are solved by decomposing effect, fringe counting is adopted to automatic determine decomposing level, a couple of exact quadrature signals are produced by Hilbert transform to extract vibration. The tempting potential of real-time measuring micro vibration with high accuracy and wide dynamic response bandwidth using proposed method is proven by both simulation and experiment. Advantages and error sources are presented as well. Main features of proposed semiconductor laser self-mixing interferometer are constant current supply, high resolution, simplest optical path and much higher tolerance to feedback level than existing self-mixing interferometers, which is competitive for non-contact vibration measurement.

Self-consistent field model for strong electrostatic correlations and inhomogeneous dielectric media.

PubMed

Ma, Manman; Xu, Zhenli

2014-12-28

Electrostatic correlations and variable permittivity of electrolytes are essential for exploring many chemical and physical properties of interfaces in aqueous solutions. We propose a continuum electrostatic model for the treatment of these effects in the framework of the self-consistent field theory. The model incorporates a space- or field-dependent dielectric permittivity and an excluded ion-size effect for the correlation energy. This results in a self-energy modified Poisson-Nernst-Planck or Poisson-Boltzmann equation together with state equations for the self energy and the dielectric function. We show that the ionic size is of significant importance in predicting a finite self energy for an ion in an inhomogeneous medium. Asymptotic approximation is proposed for the solution of a generalized Debye-Hückel equation, which has been shown to capture the ionic correlation and dielectric self energy. Through simulating ionic distribution surrounding a macroion, the modified self-consistent field model is shown to agree with particle-based Monte Carlo simulations. Numerical results for symmetric and asymmetric electrolytes demonstrate that the model is able to predict the charge inversion at high correlation regime in the presence of multivalent interfacial ions which is beyond the mean-field theory and also show strong effect to double layer structure due to the space- or field-dependent dielectric permittivity.

O2 A Band Studies for Cloud Detection and Algorithm Improvement

NASA Technical Reports Server (NTRS)

Chance, K. V.

1996-01-01

Detection of cloud parameters from space-based spectrometers can employ the vibrational bands of O2 in the (sup b1)Sigma(sub +)(sub g) yields X(sub 3) Sigma(sup -)(sub g) spin-forbidden electronic transition manifold, particularly the Delta nu = 0 A band. The GOME instrument uses the A band in the Initial Cloud Fitting Algorithm (ICFA). The work reported here consists of making substantial improvements in the line-by-line spectral database for the A band, testing whether an additional correction to the line shape function is necessary in order to correctly model the atmospheric transmission in this band, and calculating prototype cloud and ground template spectra for comparison with satellite measurements.

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

Engel, Edgar A., E-mail: eae32@cam.ac.uk; Needs, Richard J.; Monserrat, Bartomeu

Surface energies of hexagonal and cubic water ice are calculated using first-principles quantum mechanical methods, including an accurate description of anharmonic nuclear vibrations. We consider two proton-orderings of the hexagonal and cubic ice basal surfaces and three proton-orderings of hexagonal ice prism surfaces, finding that vibrations reduce the surface energies by more than 10%. We compare our vibrational densities of states to recent sum frequency generation absorption measurements and identify surface proton-orderings of experimental ice samples and the origins of characteristic absorption peaks. We also calculate zero point quantum vibrational corrections to the surface electronic band gaps, which range frommore » −1.2 eV for the cubic ice basal surface up to −1.4 eV for the hexagonal ice prism surface. The vibrational corrections to the surface band gaps are up to 12% smaller than for bulk ice.« less

Registered nurses' self-nurturance and life and career satisfaction.

PubMed

Nemcek, Mary Ann

2007-08-01

Knowledge of factors that help nurses thrive, including satisfaction with life and self-nurturance, can be used to enhance retention of a healthy work force. This study determined whether nurses are happy or satisfied with their lives; how self-nurturing or "good to self" they are; and whether a relationship exists among self-nurturance, life satisfaction, and career satisfaction. A descriptive, correlational study of 136 registered nurses involving measures of self-nurturance and life and career satisfaction was conducted. Mean scores for life satisfaction and self-nurturance were consistent with those from studies of well adults. Self-nurturance, life satisfaction, and career satisfaction were positively correlated with each other; thus, improving one is expected to improve the others. Knowledge of the significant positive correlation among life satisfaction, self-nurturance, and career satisfaction may prove useful in improving the mental health and safety of nurses. Strategies consistent with Magnet hospital characteristics are suggested for the occupational health nurse.

Evaluation of postoperative residual spinal deformity and patient outcome in idiopathic scoliosis patients in Japan using the scoliosis research society outcomes instrument.

PubMed

Watanabe, Kei; Hasegawa, Kazuhiro; Hirano, Toru; Uchiyama, Seiji; Endo, Naoto

2007-03-01

This study clarifies the correlation between the components of the Scoliosis Research Society Outcomes Instrument (SRS-24) and the radiographic parameters after surgery in Japanese idiopathic scoliosis patients. To investigate the correlation between the magnitude of back deformity after scoliosis surgery and the components of the SRS-24. Patient outcomes for Japanese scoliosis patients using the SRS-24 have not been fully investigated. Idiopathic scoliosis patients (n = 81) who were treated with surgery and followed up for more than 2 years were evaluated. Radiographic examination included Cobb angle, rotation angle of apical vertebrae, and translation of the C7 vertebra from the center sacral line on the coronal plane. In addition, the score of one new question regarding postoperative scar was investigated and compared with that of the individual SRS-24 domains. A comparison of the SRS-24 and radiographic results revealed a significant inverse correlation between total pain and the postoperative correction of the rotation angle in the thoracic curve (rs = 0.27; P < 0.05). General self-image was inversely correlated with the Cobb angle (rs = -0.23; P < 0.05) and the rotation angle (rs = -0.30; P < 0.01) in the thoracic curve. Self-image after surgery was positively correlated with the correction degree of the thoracic Cobb angle (rs = 0.27; P < 0.05); 60% of patients had some concerns regarding postoperative scar, and the concerned patients demonstrated significantly lower scores in the pain and general self-image domains (P < 0.05) than the unconcerned patients did. Patients with a greater Cobb angle or rotation angle in the thoracic curve had a negative self-image. Self-image improved after surgery by greater correction of the thoracic Cobb angle. Thoracic scoliotic deformity with prominence should be substantially reduced by the surgical treatment to improve satisfaction rates and self-image regarding back appearance. Additionally, physicians should pay more attention to patients' concern regarding their postoperative scars to obtain better outcomes.

Social supports and mental health: a cross-sectional study on the correlation of self-consistency and congruence in China.

PubMed

Gu, YanMei; Hu, Jie; Hu, YaPing; Wang, JianRong

2016-06-28

Psychosocial job characteristics require nursing staff with high self-consistency and good mental health. However, the attention and effort of such study remained very limited in China. A self-administered questionnaire was distributed to the bedside nurses in an affiliated hospital of Hebei Medical University, China. Of 218 registered bedside nurses eligible to participate in the survey anonymously, the data producing sample of 172 subjects resulted in a 79 % of effective response rate.. The Social Support Rating Scale was used to measure social support, and the Self-Consistency and Congruence Scale were used to measure mental health. Compared with the normal referenced group of college students, higher self-flexibility scores, lower self-conflict and self-stethoscope scores from the sample group were obtained with statistical significance in self-conflict scores. The close correlations were observed between participants' social support and Self-Consistency and Congruence Scale score. The difference of Social Support Rating Scale score was significant in demographic features including years of work, marital status, only child family, and levels of cooperation with other health worker. Bedside nurses in this study show a better inner harmony, and their Self-Consistency and Congruence closely correlates with the levels of social support. Thus, it is substantial to improve inner perception of support and external factors, such as the workplace support, and offer beneficial social environment to improve the bedside nurse's sub-health symptoms and decrease the high turnover rate.

A Role of Base Plate Jerk Feedback Scheme for Suppression of the Self Vibration in a Pneumatic Positioning Stage

NASA Astrophysics Data System (ADS)

Wali, Mohebullah; Nakamura, Yukinori; Wakui, Shinji

In this study, a positioning stage is considered, which is actuated by four pneumatic cylinders and vertically supported by four coil-type spring isolators. Previously, we realized the base plate jerk feedback (BPJFB) to be analogues to a Master-Slave system which can synchronize the motion of the stage as a Slave to the motion of the base plate as a Master. However, in the case of real positioning, the stage had slightly self oscillation with higher frequency due to the higher gains set to the outer feedback loop controller besides its oscillation due to the natural vibration of the base plate. The self oscillation of stage was misunderstood to be the natural vibration of base plate due to the reaction force. However, according to the experimental results, the BPJFB scheme was able to control both of the mentioned vibrations. Suppression of the self vibration of stage is an interesting phenomenon, which should be experimentally investigated. Therefore, the current study focuses on the suppression of the self vibration of stage by using the BPJFB scheme. The experimental results show that besides operating as a Master-Slave synchronizing system, the PBJFB scheme is able to increase the damping ratio and stiffness of stage against its self vibration. This newly recognized phenomenon contributes to further increase the proportional gain of the outer feedback loop controller. As a result, the positioning speed and stability can be improved.

How do emotional restrictions affect the use of humor? A behavior genetic analysis of alexithymia and humor styles.

PubMed

Atkinson, Breanna E; Lipton, Debra; Baughman, Holly M; Schermer, Julie A; Harris, Juliette; Vernon, Philip A

2015-04-01

This article reports the first behavioral genetic study of relationships between alexithymia and four styles of humor: affiliative, self-enhancing, self-defeating, and aggressive. A total of 509 MZ pairs and 264 DZ pairs of twins completed the Toronto Alexithymia Scale-20 (TAS-20) and the Humor Styles Questionnaire (HSQ). Consistent with our predictions, alexithymia correlated negatively with affiliative and self-enhancing humor and positively with self-defeating and aggressive humor. All but one of the 16 phenotypic correlations that we report are significant at the 0.01 level. Also consistent with our predictions, the phenotypic correlations between alexithymia and humor styles were primarily attributable to correlated genetic factors and to a lesser extent to correlated non-shared environmental factors. Correlated shared environmental factors had no significant effect. Implications and limitations of this study are discussed.

First and second energy derivative analyses for open-shell self-consistent field wavefunctions

NASA Astrophysics Data System (ADS)

Yamaguchi, Yukio; Schaefer, Henry F., III; Frenking, Gernot

A study of first and second derivatives of the orbital, electronic, nuclear and total energies for the self-consistent field (SCF) wavefunction has been applied to general open-shell SCF systems. The diagonal elements of the Lagrangian matrix for the general open-shell SCF wavefunction are adapted as the 'oŕbital' energies. The first and second derivatives of the orbital energies in terms of the normal coordinates are determined via the finite difference method, while those of the electronic, nuclear and total energies are obtained by analytical techniques. Using three low lying states of the CH2 and H2CO molecules as examples, it is demonstrated that the derivatives of the SCF energetic quantities with respect to the normal coordinates provide useful chemical information concerning the respective molecular structures and reactivities. The conventional concept of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) has been extended to the molecular vibrational motion, and the terminology of vibrationally active MOs (va-MOs), va-HOMO and va-LUMO has been introduced for each normal coordinate. The energy derivative analysis method may be used as a powerful semi-quantitative modelin understanding and interpreting various chemical phenomena.

Fermi orbital derivatives in self-interaction corrected density functional theory: Applications to closed shell atoms

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

Pederson, Mark R., E-mail: mark.pederson@science.doe.gov

2015-02-14

A recent modification of the Perdew-Zunger self-interaction-correction to the density-functional formalism has provided a framework for explicitly restoring unitary invariance to the expression for the total energy. The formalism depends upon construction of Löwdin orthonormalized Fermi-orbitals which parametrically depend on variational quasi-classical electronic positions. Derivatives of these quasi-classical electronic positions, required for efficient minimization of the self-interaction corrected energy, are derived and tested, here, on atoms. Total energies and ionization energies in closed-shell singlet atoms, where correlation is less important, using the Perdew-Wang 1992 Local Density Approximation (PW92) functional, are in good agreement with experiment and non-relativistic quantum-Monte-Carlo results albeitmore » slightly too low.« less

Finite frequency current noise in the Holstein model

NASA Astrophysics Data System (ADS)

Stadler, P.; Rastelli, G.; Belzig, W.

2018-05-01

We investigate the effects of local vibrational excitations in the nonsymmetrized current noise S (ω ) of a nanojunction. For this purpose, we analyze a simple model—the Holstein model—in which the junction is described by a single electronic level that is coupled to two metallic leads and to a single vibrational mode. Using the Keldysh Green's function technique, we calculate the nonsymmetrized current noise to the leading order in the charge-vibration interaction. For the noise associated to the latter, we identify distinct terms corresponding to the mean-field noise and the vertex correction. The mean-field result can be further divided into an elastic correction to the noise and in an inelastic correction, the second one being related to energy exchange with the vibration. To illustrate the general behavior of the noise induced by the charge-vibration interaction, we consider two limit cases. In the first case, we assume a strong coupling of the dot to the leads with an energy-independent transmission, whereas in the second case we assume a weak tunneling coupling between the dot and the leads such that the transport occurs through a sharp resonant level. We find that the noise associated to the vibration-charge interaction shows a complex pattern as a function of the frequency ω and of the transmission function or of the dot's energy level. Several transitions from enhancement to suppression of the noise occurs in different regions, which are determined, in particular, by the vibrational frequency. Remarkably, in the regime of an energy-independent transmission, the zero-order elastic noise vanishes at perfect transmission and at positive frequency, whereas the noise related to the charge-vibration interaction remains finite, enabling the analysis of the pure vibrational-induced current noise.

A method of measuring and correcting tilt of anti - vibration wind turbines based on screening algorithm

NASA Astrophysics Data System (ADS)

Xiao, Zhongxiu

2018-04-01

A Method of Measuring and Correcting Tilt of Anti - vibration Wind Turbines Based on Screening Algorithm is proposed in this paper. First of all, we design a device which the core is the acceleration sensor ADXL203, the inclination is measured by installing it on the tower of the wind turbine as well as the engine room. Next using the Kalman filter algorithm to filter effectively by establishing a state space model for signal and noise. Then we use matlab for simulation. Considering the impact of the tower and nacelle vibration on the collected data, the original data and the filtering data are classified and stored by the Screening algorithm, then filter the filtering data to make the output data more accurate. Finally, we eliminate installation errors by using algorithm to achieve the tilt correction. The device based on this method has high precision, low cost and anti-vibration advantages. It has a wide range of application and promotion value.

All-electron quasiparticle self-consistent GW band structures for SrTiO 3 including lattice polarization corrections in different phases

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

Bhandari, Churna; van Schilfgaarde, Mark; Kotani, Takao

The electronic band structure of SrTiO3 is investigated in the all-electron quasiparticle self-consistent GW (QSGW) approximation. Unlike previous pseudopotential-based QSGW or single-shot G0W0 calculations, the gap is found to be significantly overestimated compared to experiment. After putting in a correction for the underestimate of the screening by the random phase approximation in terms of a 0.8Σ approach, the gap is still overestimated. The 0.8Σ approach is discussed and justified in terms of various recent literature results including electron-hole corrections. Adding a lattice polarization correction (LPC) in the q→0 limit for the screening of W, agreement with experiment is recovered. Themore » LPC is alternatively estimated using a polaron model. Here, we apply our approach to the cubic and tetragonal phases as well as a hypothetical layered postperovskite structure and find that the local density approximation (LDA) to GW gap correction is almost independent of structure.« less

All-electron quasiparticle self-consistent GW band structures for SrTiO 3 including lattice polarization corrections in different phases

DOE PAGES

Bhandari, Churna; van Schilfgaarde, Mark; Kotani, Takao; ...

2018-01-23

The electronic band structure of SrTiO3 is investigated in the all-electron quasiparticle self-consistent GW (QSGW) approximation. Unlike previous pseudopotential-based QSGW or single-shot G0W0 calculations, the gap is found to be significantly overestimated compared to experiment. After putting in a correction for the underestimate of the screening by the random phase approximation in terms of a 0.8Σ approach, the gap is still overestimated. The 0.8Σ approach is discussed and justified in terms of various recent literature results including electron-hole corrections. Adding a lattice polarization correction (LPC) in the q→0 limit for the screening of W, agreement with experiment is recovered. Themore » LPC is alternatively estimated using a polaron model. Here, we apply our approach to the cubic and tetragonal phases as well as a hypothetical layered postperovskite structure and find that the local density approximation (LDA) to GW gap correction is almost independent of structure.« less

Determining the static electronic and vibrational energy correlations via two-dimensional electronic-vibrational spectroscopy

DOE PAGES

Dong, Hui; Lewis, Nicholas H. C.; Oliver, Thomas A. A.; ...

2015-05-07

Changes in the electronic structure of pigments in protein environments and of polar molecules in solution inevitably induce a re-adaption of molecular nuclear structure. Both changes of electronic and vibrational energies can be probed with visible or infrared lasers, such as two-dimensional electronic spectroscopy or vibrational spectroscopy. The extent to which the two changes are correlated remains elusive. The recent demonstration of two-dimensional electronic-vibrational (2DEV) spectroscopy potentially enables a direct measurement of this correlation experimentally. However, it has hitherto been unclear how to characterize the correlation from the spectra. In this report, we present a theoretical formalism to demonstrate themore » slope of the nodal line between the excited state absorption and ground state bleach peaks in the spectra as a characterization of the correlation between electronic and vibrational transition energies. In conclusion, we also show the dynamics of the nodal line slope is correlated to the vibrational spectral dynamics. Additionally, we demonstrate the fundamental 2DEV spectral line-shape of a monomer with newly developed response functions« less

Determining the static electronic and vibrational energy correlations via two-dimensional electronic-vibrational spectroscopy

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

Dong, Hui; Lewis, Nicholas H. C.; Oliver, Thomas A. A.

2015-05-07

Changes in the electronic structure of pigments in protein environments and of polar molecules in solution inevitably induce a re-adaption of molecular nuclear structure. Both changes of electronic and vibrational energies can be probed with visible or infrared lasers, such as two-dimensional electronic spectroscopy or vibrational spectroscopy. The extent to which the two changes are correlated remains elusive. The recent demonstration of two-dimensional electronic-vibrational (2DEV) spectroscopy potentially enables a direct measurement of this correlation experimentally. However, it has hitherto been unclear how to characterize the correlation from the spectra. In this paper, we present a theoretical formalism to demonstrate themore » slope of the nodal line between the excited state absorption and ground state bleach peaks in the spectra as a characterization of the correlation between electronic and vibrational transition energies. We also show the dynamics of the nodal line slope is correlated to the vibrational spectral dynamics. Additionally, we demonstrate the fundamental 2DEV spectral line-shape of a monomer with newly developed response functions.« less

Band-edge positions in G W : Effects of starting point and self-consistency

NASA Astrophysics Data System (ADS)

Chen, Wei; Pasquarello, Alfredo

2014-10-01

We study the effect of starting point and self-consistency within G W on the band-edge positions of semiconductors and insulators. Compared to calculations based on a semilocal starting point, the use of a hybrid-functional starting point shows a larger quasiparticle correction for both band-edge states. When the self-consistent treatment is employed, the band-gap opening is found to result mostly from a shift of the valence-band edge. Within the non-self-consistent methods, we analyse the performance of empirical and nonempirical schemes in which the starting point is optimally tuned. We further assess the accuracy of the band-edge positions through the calculation of ionization potentials of surfaces. The ionization potentials for most systems are reasonably well described by one-shot calculations. However, in the case of TiO2, we find that the use of self-consistency is critical to obtain a good agreement with experiment.

Dispersion Corrected Structural Properties and Quasiparticle Band Gaps of Several Organic Energetic Solids.

PubMed

Appalakondaiah, S; Vaitheeswaran, G; Lebègue, S

2015-06-18

We have performed ab initio calculations for a series of energetic solids to explore their structural and electronic properties. To evaluate the ground state volume of these molecular solids, different dispersion correction methods were accounted in DFT, namely the Tkatchenko-Scheffler method (with and without self-consistent screening), Grimme's methods (D2, D3(BJ)), and the vdW-DF method. Our results reveal that dispersion correction methods are essential in understanding these complex structures with van der Waals interactions and hydrogen bonding. The calculated ground state volumes and bulk moduli show that the performance of each method is not unique, and therefore a careful examination is mandatory for interpreting theoretical predictions. This work also emphasizes the importance of quasiparticle calculations in predicting the band gap, which is obtained here with the GW approximation. We find that the obtained band gaps are ranging from 4 to 7 eV for the different compounds, indicating their insulating nature. In addition, we show the essential role of quasiparticle band structure calculations to correlate the gap with the energetic properties.

Ab initio study of the molecular structure and vibrational spectrum of nitric acid and its protonated forms

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Rice, Julia E.

1992-01-01

The equilibrium structures, harmonic vibrational frequencies, IR intensities, and relative energetics of HNO3 and its protonated form H2NO3+ were investigated using double-zeta plus polarization and triple-zeta plus polarization basis sets in conjunction with high-level ab initio methods. The latter include second-order Moller-Plesset perturbation theory, the single and double excitation coupled cluster (CCSD) methods, a perturbational estimate of the effects of connected triple excitations (CCSD(T)), and the self-consistent field. To determine accurate energy differences CCSD(T) energies were computed using large atomic natural orbital basis sets. Four different isomers of H2NO3+ were considered. The lowest energy form of protonated nitric acid was found to correspond to a complex between H2O and NO2+, which is consistent with earlier theoretical and experimental studies.

Final Scientific/Technical Report: Breakthrough Design and Implementation of Many-Body Theories for Electron Correlation

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

So Hirata

2012-01-03

This report discusses the following highlights of the project: (1) grid-based Hartree-Fock equation solver; (2) explicitly correlated coupled-cluster and perturbation methods; (3) anharmonic vibrational frequencies and vibrationally averaged NMR and structural parameters of FHF; (4) anharmonic vibrational frequencies and vibrationally averaged structures of hydrocarbon combustion species; (5) anharmonic vibrational analysis of the guanine-cytosine base pair; (6) the nature of the Born-Oppenheimer approximation; (7) Polymers and solids Brillouin-zone downsampling - the modulo MP2 method; (8) explicitly correlated MP2 for extended systems; (9) fast correlated method for molecular crystals - solid formic acid; and (10) fast correlated method for molecular crystals -more » solid hydrogen fluoride.« less

Self-attraction effect and correction on the T-1 absolute gravimeter

NASA Astrophysics Data System (ADS)

Li, Z.; Hu, H.; Wu, K.; Li, G.; Wang, G.; Wang, L. J.

2015-12-01

The self-attraction effect (SAE) in an absolute gravimeter is a kind of systematic error due to the gravitation of the instrument to the falling object. This effect depends on the mass distribution of the gravimeter, and is estimated to be a few microgals (1 μGal  =  10-8 m s-2) for the FG5 gravimeter. In this paper, the SAE of a home-made T-1 absolute gravimeter is analyzed and calculated. Most of the stationary components, including the dropping chamber, the laser interferometer, the vibration isolation device and two tripods, are finely modelled, and the related SAEs are computed. In addition, the SAE of the co-falling carriage inside the dropping chamber is carefully calculated because the distance between the falling object and the co-falling carriage varies during the measurement. In order to get the correction of the SAE, two different methods are compared. One is to linearize the SAE curve, the other one is to calculate the perturbed trajectory. The results from these two methods agree with each other within 0.01 μGal. With an uncertainty analysis, the correction of the SAE of the T-1 gravimeter is estimated to be (-1.9  ±  0.1) μGal.

Modeling and experimental characterization of a new piezoelectric sensor for low-amplitude vibration measurement

NASA Astrophysics Data System (ADS)

Hou, X. Y.; Koh, C. G.; Kuang, K. S. C.; Lee, W. H.

2017-07-01

This paper investigates the capability of a novel piezoelectric sensor for low-frequency and low-amplitude vibration measurement. The proposed design effectively amplifies the input acceleration via two amplifying mechanisms and thus eliminates the use of the external charge amplifier or conditioning amplifier typically employed for measurement system. The sensor is also self-powered, i.e. no external power unit is required. Consequently, wiring and electrical insulation for on-site measurement are considerably simpler. In addition, the design also greatly reduces the interference from rotational motion which often accompanies the translational acceleration to be measured. An analytical model is developed based on a set of piezoelectric constitutive equations and beam theory. Closed-form expression is derived to correlate sensor geometry and material properties with its dynamic performance. Experimental calibration is then carried out to validate the analytical model. After calibration, experiments are carried out to check the feasibility of the new sensor in structural vibration detection. From experimental results, it is concluded that the proposed sensor is suitable for measuring low-frequency and low-amplitude vibrations.

The Effects of Writing Anxiety and Motivation on EFL College Students' Self-Evaluative Judgments of Corrective Feedback.

PubMed

Tsao, Jui-Jung; Tseng, Wen-Ta; Wang, Chaochang

2017-04-01

Feedback is regarded as a way to foster students' motivation and to ensure linguistic accuracy. However, mixed findings are reported in the research on written corrective feedback because of its multifaceted nature and its correlations with learners' individual differences. It is necessary, therefore, to conduct further research on corrective feedback from the student's perspective and to examine how individual differences in terms of factors such as writing anxiety and motivation predict learners' self-evaluative judgments of both teacher-corrected and peer-corrected feedback. For this study, 158 Taiwanese college sophomores participated in a survey that comprised three questionnaires. Results demonstrated that intrinsic motivation and different types of writing anxiety predicted English as foreign language learners' evaluative judgments of teacher and peer feedback. The findings have implications for English-writing instruction.

A non-JKL density matrix functional for intergeminal correlation between closed-shell geminals from analysis of natural orbital configuration interaction expansions

NASA Astrophysics Data System (ADS)

van Meer, R.; Gritsenko, O. V.; Baerends, E. J.

2018-03-01

Almost all functionals that are currently used in density matrix functional theory have been created by some a priori ansatz that generates approximations to the second-order reduced density matrix (2RDM). In this paper, a more consistent approach is used: we analyze the 2RDMs (in the natural orbital basis) of rather accurate multi-reference configuration interaction expansions for several small molecules (CH4, NH3, H2O, FH, and N2) and use the knowledge gained to generate new functionals. The analysis shows that a geminal-like structure is present in the 2RDMs, even though no geminal theory has been applied from the onset. It is also shown that the leading non-geminal dynamical correlation contributions are generated by a specific set of double excitations. The corresponding determinants give rise to non-JKL (non Coulomb/Exchange like) multipole-multipole dispersive attractive terms between geminals. Due to the proximity of the geminals, these dispersion terms are large and cannot be omitted, proving pure JKL functionals to be essentially deficient. A second correction emerges from the observation that the "normal" geminal-like exchange between geminals breaks down when one breaks multiple bonds. This problem can be fixed by doubling the exchange between bond broken geminals, effectively restoring the often physically correct high-spin configurations on the bond broken fragments. Both of these corrections have been added to the commonly used antisymmetrized product of strongly orthogonal geminals functional. The resulting non-JKL functional Extended Löwdin-Shull Dynamical-Multibond is capable of reproducing complete active space self-consistent field curves, in which one active orbital is used for each valence electron.

Local-spin-density calculations for iron: Effect of spin interpolation on ground-state properties

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

MacLaren, J.M.; Clougherty, D.P.; Albers, R.C.

1990-08-15

Scalar-relativistic self-consistent linear muffin-tin orbital (LMTO) calculations for bcc and fcc Fe have been performed with several different local approximations to the exchange and correlation energy density and potential. Overall, in contrast to the conclusions of previous studies, we find that the local-spin-density approximation to exchange and correlation can provide an adequate description of bulk Fe {ital provided} that a proper parametrization of the correlation energy density and potential of the homogeneous electron gas over both spin and density is used. Lattice constants, found from the position of the minimum of the total energy as a function of Wigner-Seitz radius,more » agree to within 1% (for {ital s},{ital p},{ital d} LMTO's only) and within 1--2% (for {ital s},{ital p},{ital d},{ital f} LMTO's) of the experimental lattice constants for all forms used for the local correlation. The best agreement, however, was obtained using a local correlation potential derived from the Vosko-Wilk-Nusair form for the spin dependence of the correlation energy density. The calculation performed with this correlation potential was also the only calculation to correctly predict a bcc ferromagnetic ground state.« less

Induced vibrations increase performance of a winged self-righting robot

NASA Astrophysics Data System (ADS)

Othayoth, Ratan; Xuan, Qihan; Li, Chen

When upside down, cockroaches can open their wings to dynamically self-right. In this process, an animal often has to perform multiple unsuccessful maneuvers to eventually right, and often flails its legs. Here, we developed a cockroach-inspired winged self-righting robot capable of controlled body vibrations to test the hypothesis that vibrations assist self-righting transitions. Robot body vibrations were induced by an oscillating mass (10% of body mass) and varied by changing oscillation frequency. We discovered that, as the robot's body vibrations increased, righting probability increased, and righting time decreased (P <0.0001, ANOVA), confirming our hypothesis. To begin to understand the underlying physics, we developed a locomotion energy landscape model. Our model revealed that the kinetic energy fluctuations due to vibrations were comparable to the potential energy barriers required to transition from a metastable overturned orientation to an upright orientation. Our study supports the plausibility of locomotion energy landscapes for understanding locomotor transitions, but highlights the need for further stochastic modeling to capture the uncertain nature of when righting maneuvers result in successful righting.

Fast Electron Correlation Methods for Molecular Clusters without Basis Set Superposition Errors

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

Kamiya, Muneaki; Hirata, So; Valiev, Marat

2008-02-19

Two critical extensions to our fast, accurate, and easy-to-implement binary or ternary interaction method for weakly-interacting molecular clusters [Hirata et al. Mol. Phys. 103, 2255 (2005)] have been proposed, implemented, and applied to water hexamers, hydrogen fluoride chains and rings, and neutral and zwitterionic glycine–water clusters with an excellent result for an initial performance assessment. Our original method included up to two- or three-body Coulomb, exchange, and correlation energies exactly and higher-order Coulomb energies in the dipole–dipole approximation. In this work, the dipole moments are replaced by atom-centered point charges determined so that they reproduce the electrostatic potentials of themore » cluster subunits as closely as possible and also self-consistently with one another in the cluster environment. They have been shown to lead to dramatic improvement in the description of short-range electrostatic potentials not only of large, charge-separated subunits like zwitterionic glycine but also of small subunits. Furthermore, basis set superposition errors (BSSE) known to plague direct evaluation of weak interactions have been eliminated by com-bining the Valiron–Mayer function counterpoise (VMFC) correction with our binary or ternary interaction method in an economical fashion (quadratic scaling n2 with respect to the number of subunits n when n is small and linear scaling when n is large). A new variant of VMFC has also been proposed in which three-body and all higher-order Coulomb effects on BSSE are estimated approximately. The BSSE-corrected ternary interaction method with atom-centered point charges reproduces the VMFC-corrected results of conventional electron correlation calculations within 0.1 kcal/mol. The proposed method is significantly more accurate and also efficient than conventional correlation methods uncorrected of BSSE.« less

A highly accurate ab initio potential energy surface for methane.

PubMed

Owens, Alec; Yurchenko, Sergei N; Yachmenev, Andrey; Tennyson, Jonathan; Thiel, Walter

2016-09-14

A new nine-dimensional potential energy surface (PES) for methane has been generated using state-of-the-art ab initio theory. The PES is based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set limit and incorporates a range of higher-level additive energy corrections. These include core-valence electron correlation, higher-order coupled cluster terms beyond perturbative triples, scalar relativistic effects, and the diagonal Born-Oppenheimer correction. Sub-wavenumber accuracy is achieved for the majority of experimentally known vibrational energy levels with the four fundamentals of (12)CH4 reproduced with a root-mean-square error of 0.70 cm(-1). The computed ab initio equilibrium C-H bond length is in excellent agreement with previous values despite pure rotational energies displaying minor systematic errors as J (rotational excitation) increases. It is shown that these errors can be significantly reduced by adjusting the equilibrium geometry. The PES represents the most accurate ab initio surface to date and will serve as a good starting point for empirical refinement.

A STUDY OF RO-VIBRATIONAL OH EMISSION FROM HERBIG Ae/Be STARS

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

Brittain, Sean D.; Reynolds, Nickalas; Najita, Joan R.

2016-10-20

We present a study of ro-vibrational OH and CO emission from 21 disks around Herbig Ae/Be stars. We find that the OH and CO luminosities are proportional over a wide range of stellar ultraviolet luminosities. The OH and CO line profiles are also similar, indicating that they arise from roughly the same radial region of the disk. The CO and OH emission are both correlated with the far-ultraviolet luminosity of the stars, while the polycyclic aromatic hydrocarbon (PAH) luminosity is correlated with the longer wavelength ultraviolet luminosity of the stars. Although disk flaring affects the PAH luminosity, it is notmore » a factor in the luminosity of the OH and CO emission. These properties are consistent with models of UV-irradiated disk atmospheres. We also find that the transition disks in our sample, which have large optically thin inner regions, have lower OH and CO luminosities than non-transition disk sources with similar ultraviolet luminosities. This result, while tentative given the small sample size, is consistent with the interpretation that transition disks lack a gaseous disk close to the star.« less

Anharmonic force field and vibrational dynamics of CH2F2 up to 5000 cm(-1) studied by Fourier transform infrared spectroscopy and state-of-the-art ab initio calculations.

PubMed

Tasinato, Nicola; Regini, Giorgia; Stoppa, Paolo; Pietropolli Charmet, Andrea; Gambi, Alberto

2012-06-07

Difluoromethane (CH(2)F(2), HFC-32) is a molecule used in refrigerant mixtures as a replacement of the more environmentally hazardous, ozone depleting, chlorofluorocarbons. On the other hand, presenting strong vibration-rotation bands in the 9 μm atmospheric window, it is a greenhouse gas which contributes to global warming. In the present work, the vibrational and ro-vibrational properties of CH(2)F(2), providing basic data for its atmospheric modeling, are studied in detail by coupling medium resolution Fourier transform infrared spectroscopy to high-level electronic structure ab initio calculations. Experimentally a full quantum assignment and accurate integrated absorption cross sections are obtained up to 5000 cm(-1). Ab initio calculations are carried out by using CCSD(T) theory and large basis sets of either the correlation consistent or atomic natural orbital hierarchies. By using vibrational perturbation theory to second order a complete set of vibrational and ro-vibrational parameters is derived from the ab initio quartic anharmonic force fields, which well compares with the spectroscopic constants retrieved experimentally. An excellent agreement between theory and experiment is achieved for vibrational energy levels and integrated absorption cross sections: transition frequencies up to four quanta of vibrational excitation are reproduced with a root mean square deviation (RMSD) of 7 cm(-1) while intensities are predicted within few km mol(-1) from the experiment. Basis set performances and core correlation effects are discussed throughout the paper. Particular attention is focused in the understanding of the anharmonic couplings which rule the vibrational dynamics of the |ν(1)>, |2ν(8)>, |2ν(2)> three levels interacting system. The reliability of the potential energy and dipole moment surfaces in reproducing the vibrational eigenvalues and intensities as well as in modeling the vibrational and ro-vibrational mixings over the whole 400-5000 cm(-1) region is also demonstrated by spectacular spectral simulations carried out by using the ro-vibrational Hamiltonian constants, and the relevant coupling terms, obtained from the perturbation treatment of the ab initio anharmonic force field. The present results suggest CH(2)F(2) as a prototype molecule to test ab initio calculations and theoretical models.

Anharmonic force field and vibrational dynamics of CH2F2 up to 5000 cm-1 studied by Fourier transform infrared spectroscopy and state-of-the-art ab initio calculations

NASA Astrophysics Data System (ADS)

Tasinato, Nicola; Regini, Giorgia; Stoppa, Paolo; Charmet, Andrea Pietropolli; Gambi, Alberto

2012-06-01

Difluoromethane (CH2F2, HFC-32) is a molecule used in refrigerant mixtures as a replacement of the more environmentally hazardous, ozone depleting, chlorofluorocarbons. On the other hand, presenting strong vibration-rotation bands in the 9 μm atmospheric window, it is a greenhouse gas which contributes to global warming. In the present work, the vibrational and ro-vibrational properties of CH2F2, providing basic data for its atmospheric modeling, are studied in detail by coupling medium resolution Fourier transform infrared spectroscopy to high-level electronic structure ab initio calculations. Experimentally a full quantum assignment and accurate integrated absorption cross sections are obtained up to 5000 cm-1. Ab initio calculations are carried out by using CCSD(T) theory and large basis sets of either the correlation consistent or atomic natural orbital hierarchies. By using vibrational perturbation theory to second order a complete set of vibrational and ro-vibrational parameters is derived from the ab initio quartic anharmonic force fields, which well compares with the spectroscopic constants retrieved experimentally. An excellent agreement between theory and experiment is achieved for vibrational energy levels and integrated absorption cross sections: transition frequencies up to four quanta of vibrational excitation are reproduced with a root mean square deviation (RMSD) of 7 cm-1 while intensities are predicted within few km mol-1 from the experiment. Basis set performances and core correlation effects are discussed throughout the paper. Particular attention is focused in the understanding of the anharmonic couplings which rule the vibrational dynamics of the |ν1⟩, |2ν8⟩, |2ν2⟩ three levels interacting system. The reliability of the potential energy and dipole moment surfaces in reproducing the vibrational eigenvalues and intensities as well as in modeling the vibrational and ro-vibrational mixings over the whole 400-5000 cm-1 region is also demonstrated by spectacular spectral simulations carried out by using the ro-vibrational Hamiltonian constants, and the relevant coupling terms, obtained from the perturbation treatment of the ab initio anharmonic force field. The present results suggest CH2F2 as a prototype molecule to test ab initio calculations and theoretical models.

A tape-spring hexapod for deployable telescopes: dynamics

NASA Astrophysics Data System (ADS)

Blanchard, L.; Aridon, G.; Falzon, F.; Rémond, D.; Dufour, R.

2017-11-01

An hexapod based telescope concept whose legs are deployable has been investigated in order to stow the secondary mirror during launch and to self-deploy it in orbit The main advantages of this concept are: a reduced volume for launch with high reduction of passive stability requirements, mass and inertia reduction inducing an agility gain. The positioning errors are corrected thanks to the vertical displacement of the hexapod feet and the final optical performance is reached thanks to adaptive optics. The paper presents the first steps towards the optimal design of a breadboard and the method developed to model the dynamic behaviour of such a structure with highly deformed flexible elements and validated with the results of sine vibration testing of the hexapod. The following part deals with the evaluation of its deployment and correction capabilities.

Simultaneous Measurement of Multiple Mechanical Properties of Single Cells Using AFM by Indentation and Vibration.

PubMed

Zhang, Chuang; Shi, Jialin; Wang, Wenxue; Xi, Ning; Wang, Yuechao; Liu, Lianqing

2017-12-01

The mechanical properties of cells, which are the main characteristics determining their physical performance and physiological functions, have been actively studied in the fields of cytobiology and biomedical engineering and for the development of medicines. In this study, an indentation-vibration-based method is proposed to simultaneously measure the mechanical properties of cells in situ, including cellular mass (m), elasticity (k), and viscosity (c). The proposed measurement method is implemented based on the principle of forced vibration stimulated by simple harmonic force using an atomic force microscope (AFM) system integrated with a piezoelectric transducer as the substrate vibrator. The corresponding theoretical model containing the three mechanical properties is derived and used to perform simulations and calculations. Living and fixed human embryonic kidney 293 (HEK 293) cells were subjected to indentation and vibration to measure and compare their mechanical parameters and verify the proposed approach. The results that the fixed sample cells are more viscous and elastic than the living sample cells and the measured mechanical properties of cell are consistent within, but not outside of the central region of the cell, are in accordance with the previous studies. This work provides an approach to simultaneous measurement of the multiple mechanical properties of single cells using an integrated AFM system based on the principle force vibration and thickness-corrected Hertz model. This study should contribute to progress in biomedical engineering, cytobiology, medicine, early diagnosis, specific therapy and cell-powered robots.

Evidence for maintenance of sex by pathogens in plants.

PubMed

Busch, Jeremiah W; Neiman, Maurine; Koslow, Jennifer M

2004-11-01

The predominance of outcrossing despite the substantial transmission advantage of self-fertilization remains a paradox. Theory suggests that selection can favor outcrossing if it enables the production of offspring that are less susceptible to pathogen attack than offspring produced via self-fertilization. Thus, if pathogen pressure is contributing to the maintenance of outcrossing in plants, there may be a positive correlation between the number of pathogen species attacking plant species and the outcrossing rate of the plant species. We tested this hypothesis by examining the association between outcrossing rate and the number of fungal pathogen species that attack a large, taxonomically diverse set of seed plants. We show that plant species attacked by more fungal pathogen species have higher outcrossing rates than plants with fewer enemies. This relationship persists after correcting for study bias among natural and agricultural species of plants. We also accounted for the nested hierarchy of relationships among plant lineages by conducting phylogenetically independent contrasts (PICs) within genera and families that were adequately represented in our dataset. A meta-analysis of the correlation between pathogen and outcrossing PICs shows that there is a positive correlation between pathogen species number and outcrossing rates. This pattern is consistent with the hypothesis that pathogen-mediated selection may contribute to the maintenance of outcrossing in species of seed plants.

Mating vibrational signal transmission through and between plants of an agricultural pest, the Glassy-Winged Sharpshooter

USDA-ARS?s Scientific Manuscript database

The agricultural pest, glassy-winged sharpshooter (GWSS), Homalodisca vitripennis, relies primarily on successful vibrational communication across its home plant. Males and females engage in a vibrational duet to identify correct species, attractiveness of mate, and location on the plant. The signal...

Laser Spectroscopy and AB Initio Calculations on the TaF Molecule

NASA Astrophysics Data System (ADS)

Ng, Kiu Fung; Zou, Wenli; Liu, Wenjian; Cheung, Allan S. C.

2016-06-01

Electronic transition spectrum of the tantalum monoflouride (TaF) molecule in the spectral region between 448 and 520 nm has been studied using the technique of laser-ablation/reaction free jet expansion and laser induced fluorescence spectroscopy. TaF molecule was produced by reacting laser-ablated tantalum atoms with sulfur hexafluoride gas seeded in argon. Sixteen vibrational bands with resolved rotational structure have been recorded and analyzed, which were organized into six electronic transition systems and the ground state has been identified to be the X3Σ-(0+) state with bond length, ro, and equilibrium vibrational frequency, ωe, determined to be 1.8209 Å and 700.1 wn respectively. In addition, four vibrational bands belong to another transition system involving lower state with Ω = 2 component has also been analyzed. All observed transitions are with ΔΩ = 0. Least-squares fit of the measured line positions yielded molecular constants for the electronic states involved. The Λ-S and Ω states of TaF were calculated at the state-averaged complete active space self-consistent field (SA-CASSCF) and the subsequent internally contracted multi-reference configuration interaction with singles and doubles and Davidson's cluster correction (MRCISD+Q) levels of theory with the active space of 4 electrons in 6 orbitals, that is, the molecular orbitals corresponding to Ta 5d6s are active. The spin-orbit coupling (SOC) is calculated by the state-interaction approach at the SA-CASSCF level via the relativistic effective core potentials (RECPs) spin-orbit operator, where the diagonal elements of the spin-orbit matrix are replaced by the above MRCISD+Q energies. The spectroscopic properties of the ground and many low-lying electronic states of the TaF molecule will be reported. With respect to the observed electronic states in this work, the calculated results are in good agreement with our experimental determinations. This work represents the first experimental investigation of the molecular structure of the TaF molecule.

Accurate thermochemistry and spectroscopy of the oxygen-protonated sulfur dioxide isomers.

PubMed

Puzzarini, Cristina

2011-12-28

Despite the promising relevance of protonated sulfur dioxide in astrophysical and atmospheric fields, its thermochemical and spectroscopic characterization is very limited. High-level quantum-chemical calculations have shown that the most stable isomer is the cis oxygen-protonated sulfur dioxide, HOSO(+), while the trans form is about 2 kcal mol(-1) less stable; even less stable (by about 42 kcal mol(-1)) is the S-protonated isomer [V. Lattanzi et al., J. Chem. Phys., 2010, 133, 194305]. The enthalpy of formation for the cis- and trans-HOSO(+) is presented, based on the well tested HEAT protocol [A. Tajti et al., J. Chem. Phys., 2004, 121, 11599]. Systematically extrapolated ab initio energies, accounting for electron correlation through coupled cluster theory, including up to single, double, triple and quadruple excitations, have been corrected for core-electron correlation, anharmonic zero-point vibrational energy, diagonal Born-Oppenheimer and scalar relativistic effects. As a byproduct, proton affinity of sulfur dioxide and atomization energies have also been obtained at the same levels of theory. Vibrational and rotational spectroscopic properties have been investigated by means of composite schemes that allow us to account for truncation of basis set as well as core correlation. Where available, for both thermochemistry and spectroscopy, very good agreement with experimental data has been observed.

Stability and natural vibration analysis of laminated plates by using a mixed element based on a refined plate theory

NASA Technical Reports Server (NTRS)

Putcha, N. S.; Reddy, J. N.

1986-01-01

A mixed shear flexible finite element, with relaxed continuity, is developed for the geometrically linear and nonlinear analysis of layered anisotropic plates. The element formulation is based on a refined higher order theory which satisfies the zero transverse shear stress boundary conditions on the top and bottom faces of the plate and requires no shear correction coefficients. The mixed finite element developed herein consists of eleven degrees of freedom per node which include three displacements, two rotations and six moment resultants. The element is evaluated for its accuracy in the analysis of the stability and vibration of anisotropic rectangular plates with different lamination schemes and boundary conditions. The mixed finite element described here for the higher order theory gives very accurate results for buckling loads and natural frequencies.

Toward reliable modeling of S-nitrosothiol chemistry: Structure and properties of methyl thionitrite (CH3SNO), an S-nitrosocysteine model

NASA Astrophysics Data System (ADS)

Khomyakov, Dmitry G.; Timerghazin, Qadir K.

2017-07-01

Methyl thionitrite CH3SNO is an important model of S-nitrosated cysteine aminoacid residue (CysNO), a ubiquitous biological S-nitrosothiol (RSNO) involved in numerous physiological processes. As such, CH3SNO can provide insights into the intrinsic properties of the —SNO group in CysNO, in particular, its weak and labile S—N bond. Here, we report an ab initio computational investigation of the structure and properties of CH3SNO using a composite Feller-Peterson-Dixon scheme based on the explicitly correlated coupled cluster with single, double, and perturbative triple excitations calculations extrapolated to the complete basis set limit, CCSD(T)-F12/CBS, with a number of additive corrections for the effects of quadruple excitations, core-valence correlation, scalar-relativistic and spin-orbit effects, as well as harmonic zero-point vibrational energy with an anharmonicity correction. These calculations suggest that the S—N bond in CH3SNO is significantly elongated (1.814 Å) and has low stretching frequency and dissociation energy values, νS—N = 387 cm-1 and D0 = 32.4 kcal/mol. At the same time, the S—N bond has a sizable rotation barrier, △E0≠ = 12.7 kcal/mol, so CH3SNO exists as a cis- or trans-conformer, the latter slightly higher in energy, △E0 = 1.2 kcal/mol. The S—N bond properties are consistent with the antagonistic nature of CH3SNO, whose resonance representation requires two chemically opposite (antagonistic) resonance structures, CH3—S+=N—O- and CH3—S-/NO+, which can be probed using external electric fields and quantified using the natural resonance theory approach (NRT). The calculated S—N bond properties slowly converge with the level of correlation treatment, with the recently developed distinguished cluster with single and double excitations approximation (DCSD-F12) performing significantly better than the coupled cluster with single and double excitations (CCSD-F12), although still inferior to the CCSD(T)-F12 method that includes perturbative triple excitations. Double-hybrid density functional theory (DFT) calculations with mPW2PLYPD/def2-TZVPPD reproduce well the geometry, vibrational frequencies, and the S—N bond rotational barrier in CH3SNO, while hybrid DFT calculations with PBE0/def2-TZVPPD give a better S—N bond dissociation energy.

Molecular structure, vibrational spectroscopic analysis (IR & Raman), HOMO-LUMO and NBO analysis of anti-cancer drug sunitinib using DFT method

NASA Astrophysics Data System (ADS)

Mıhçıokur, Özlem; Özpozan, Talat

2017-12-01

Oxindole and its derivatives have wide applications in different industries such as in synthetic & natural fibers, dyes for hair and plastic materials in addition to their biological importance. In the present study, one of the oxindole derivatives, N-(2-diethylaminoethyl)-5-[(Z)-(5-fluoro-2-oxo-1H-indol-3-ylidene)methyl]-2,4-dimethyl-1H-pyrrole-3-carboxamide (Sunitinib), which is used as an anti-cancer drug, was investigated in terms of structural, vibrational spectroscopic and theoretical analysis. The calculations have been performed for gaseous, aqueous and DMSO phases, respectively. Potential Energy Surface (PES) scan has been carrried out to obtain the most stable structures of all the phases of the title molecule using B3LYP/6-31G(d,p) level and the geometrical variations among them are discussed. The solvent effect for Sunitinib in aqueous and DMSO phases have been performed by means of the self-consistent recognition reaction field (SCRF) method as implemented in the integral equation formalism polarized continuum model (IEFPCM). On the other hand, NBO analysis has been carried out to understand probable hydrogen bonding sites and charge transfers. Additionally, the HOMO and the LUMO energies are calculated using B3LYP/6-31G(d,p) to determine the intra molecular charge transfers (ICT) within the molecule and the kinetic stabilities for each phases. The molecular electrostatic potential surface (MESP) has been plotted over the optimized structure to estimate the reactive sites of electrophilic and nucleophilic attacks regarding Sunitinib molecule. The potential energy distribution (PED) has been calculated using VEDA4 program and vibrational assignments of the experimental spectra (IR & Raman) have been elucidated by means of the calculated vibrational spectra. The observed vibrational spectra of Sunitinib is compared with the calculated spectra obtained by using B3LYP functional both with 6-31G(d,p) and 6-311++G(d,p) basis sets. Theoretical results indicate that the best correlation with experimental data is obtained with B3LYP/6-311++G(d,p) method.

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.

Narcissism and Self-Insight: A Review and Meta-Analysis of Narcissists' Self-Enhancement Tendencies.

PubMed

Grijalva, Emily; Zhang, Luyao

2016-01-01

The current article reviews the narcissism-self-enhancement literature using a multilevel meta-analytic technique. Specifically, we focus on self-insight self-enhancement (i.e., whether narcissists perceive themselves more positively than they are perceived by others); thus, we only include studies that compare narcissists' self-reports to observer reports or objective measures. Results from 171 correlations reported in 36 empirical studies (N = 6,423) revealed that the narcissism-self-enhancement relationship corrected for unreliability in narcissism was .21 (95% confidence interval [CI] = [.17, .25]), and that narcissists tend to self-enhance their agentic characteristics more than their communal characteristics. The average corrected relationship between narcissism and self-enhancement for agentic characteristics was .29 (95% CI = [.25, .33]), whereas for communal characteristics it was .05 (95% CI = [-.01, .10]). In addition, we individually summarized narcissists' self-enhancement for 10 different constructs (i.e., the Big Five, task performance, intelligence, leadership, attractiveness, and likeability). © 2015 by the Society for Personality and Social Psychology, Inc.

0–0 Energies Using Hybrid Schemes: Benchmarks of TD-DFT, CIS(D), ADC(2), CC2, and BSE/GW formalisms for 80 Real-Life Compounds

PubMed Central

2015-01-01

The 0–0 energies of 80 medium and large molecules have been computed with a large panel of theoretical formalisms. We have used an approach computationally tractable for large molecules, that is, the structural and vibrational parameters are obtained with TD-DFT, the solvent effects are accounted for with the PCM model, whereas the total and transition energies have been determined with TD-DFT and with five wave function approaches accounting for contributions from double excitations, namely, CIS(D), ADC(2), CC2, SCS-CC2, and SOS-CC2, as well as Green’s function based BSE/GW approach. Atomic basis sets including diffuse functions have been systematically applied, and several variations of the PCM have been evaluated. Using solvent corrections obtained with corrected linear-response approach, we found that three schemes, namely, ADC(2), CC2, and BSE/GW allow one to reach a mean absolute deviation smaller than 0.15 eV compared to the measurements, the two former yielding slightly better correlation with experiments than the latter. CIS(D), SCS-CC2, and SOS-CC2 provide significantly larger deviations, though the latter approach delivers highly consistent transition energies. In addition, we show that (i) ADC(2) and CC2 values are extremely close to each other but for systems absorbing at low energies; (ii) the linear-response PCM scheme tends to overestimate solvation effects; and that (iii) the average impact of nonequilibrium correction on 0–0 energies is negligible. PMID:26574326

Localization and anharmonicity of the vibrational modes for GC Watson-Crick and Hoogsteen base pairs.

PubMed

Bende, Attila; Bogdan, Diana; Muntean, Cristina M; Morari, Cristian

2011-12-01

We present an ab initio study of the vibrational properties of cytosine and guanine in the Watson-Crick and Hoogsteen base pair configurations. The results are obtained by using two different implementations of the DFT method. We assign the vibrational frequencies to cytosine or to guanine using the vibrational density of states. Next, we investigate the importance of anharmonic corrections for the vibrational modes. In particular, the unusual anharmonic effect of the H(+) vibration in the case of the Hoogsteen base pair configuration is discussed.

On sound transmission through double-walled cylindrical shells lined with poroelastic material: Comparison with Zhou's results and further effect of external mean flow

NASA Astrophysics Data System (ADS)

Liu, Yu; He, Chuanbo

2015-12-01

In this discussion, the corrections to the errors found in the derivations and the numerical code of a recent analytical study (Zhou et al. Journal of Sound and Vibration 333 (7) (2014) 1972-1990) on sound transmission through double-walled cylindrical shells lined with poroelastic material are presented and discussed, as well as the further effect of the external mean flow on the transmission loss. After applying the corrections, the locations of the characteristic frequencies of thin shells remain unchanged, as well as the TL results above the ring frequency where BU and UU remain the best configurations in sound insulation performance. In the low-frequency region below the ring frequency, however, the corrections attenuate the TL amplitude significantly for BU and UU, and hence the BB configuration exhibits the best performance which is consistent with previous observations for flat sandwich panels.

An examination of an adapter method for measuring the vibration transmitted to the human arms.

PubMed

Xu, Xueyan S; Dong, Ren G; Welcome, Daniel E; Warren, Christopher; McDowell, Thomas W

2015-09-01

The objective of this study is to evaluate an adapter method for measuring the vibration on the human arms. Four instrumented adapters with different weights were used to measure the vibration transmitted to the wrist, forearm, and upper arm of each subject. Each adapter was attached at each location on the subjects using an elastic cloth wrap. Two laser vibrometers were also used to measure the transmitted vibration at each location to evaluate the validity of the adapter method. The apparent mass at the palm of the hand along the forearm direction was also measured to enhance the evaluation. This study found that the adapter and laser-measured transmissibility spectra were comparable with some systematic differences. While increasing the adapter mass reduced the resonant frequency at the measurement location, increasing the tightness of the adapter attachment increased the resonant frequency. However, the use of lightweight (≤15 g) adapters under medium attachment tightness did not change the basic trends of the transmissibility spectrum. The resonant features observed in the transmissibility spectra were also correlated with those observed in the apparent mass spectra. Because the local coordinate systems of the adapters may be significantly misaligned relative to the global coordinates of the vibration test systems, large errors were observed for the adapter-measured transmissibility in some individual orthogonal directions. This study, however, also demonstrated that the misalignment issue can be resolved by either using the total vibration transmissibility or by measuring the misalignment angles to correct the errors. Therefore, the adapter method is acceptable for understanding the basic characteristics of the vibration transmission in the human arms, and the adapter-measured data are acceptable for approximately modeling the system.

An examination of an adapter method for measuring the vibration transmitted to the human arms

PubMed Central

Xu, Xueyan S.; Dong, Ren G.; Welcome, Daniel E.; Warren, Christopher; McDowell, Thomas W.

2016-01-01

The objective of this study is to evaluate an adapter method for measuring the vibration on the human arms. Four instrumented adapters with different weights were used to measure the vibration transmitted to the wrist, forearm, and upper arm of each subject. Each adapter was attached at each location on the subjects using an elastic cloth wrap. Two laser vibrometers were also used to measure the transmitted vibration at each location to evaluate the validity of the adapter method. The apparent mass at the palm of the hand along the forearm direction was also measured to enhance the evaluation. This study found that the adapter and laser-measured transmissibility spectra were comparable with some systematic differences. While increasing the adapter mass reduced the resonant frequency at the measurement location, increasing the tightness of the adapter attachment increased the resonant frequency. However, the use of lightweight (≤15 g) adapters under medium attachment tightness did not change the basic trends of the transmissibility spectrum. The resonant features observed in the transmissibility spectra were also correlated with those observed in the apparent mass spectra. Because the local coordinate systems of the adapters may be significantly misaligned relative to the global coordinates of the vibration test systems, large errors were observed for the adapter-measured transmissibility in some individual orthogonal directions. This study, however, also demonstrated that the misalignment issue can be resolved by either using the total vibration transmissibility or by measuring the misalignment angles to correct the errors. Therefore, the adapter method is acceptable for understanding the basic characteristics of the vibration transmission in the human arms, and the adapter-measured data are acceptable for approximately modeling the system. PMID:26834309

Nodeless vibrational amplitudes and quantum nonadiabatic dynamics in the nested funnel for a pseudo Jahn-Teller molecule or homodimer

NASA Astrophysics Data System (ADS)

Peters, William K.; Tiwari, Vivek; Jonas, David M.

2017-11-01

The nonadiabatic states and dynamics are investigated for a linear vibronic coupling Hamiltonian with a static electronic splitting and weak off-diagonal Jahn-Teller coupling through a single vibration with a vibrational-electronic resonance. With a transformation of the electronic basis, this Hamiltonian is also applicable to the anti-correlated vibration in a symmetric homodimer with marginally strong constant off-diagonal coupling, where the non-adiabatic states and dynamics model electronic excitation energy transfer or self-exchange electron transfer. For parameters modeling a free-base naphthalocyanine, the nonadiabatic couplings are deeply quantum mechanical and depend on wavepacket width; scalar couplings are as important as the derivative couplings that are usually interpreted to depend on vibrational velocity in semiclassical curve crossing or surface hopping theories. A colored visualization scheme that fully characterizes the non-adiabatic states using the exact factorization is developed. The nonadiabatic states in this nested funnel have nodeless vibrational factors with strongly avoided zeroes in their vibrational probability densities. Vibronic dynamics are visualized through the vibrational coordinate dependent density of the time-dependent dipole moment in free induction decay. Vibrational motion is amplified by the nonadiabatic couplings, with asymmetric and anisotropic motions that depend upon the excitation polarization in the molecular frame and can be reversed by a change in polarization. This generates a vibrational quantum beat anisotropy in excess of 2/5. The amplitude of vibrational motion can be larger than that on the uncoupled potentials, and the electronic population transfer is maximized within one vibrational period. Most of these dynamics are missed by the adiabatic approximation, and some electronic and vibrational motions are completely suppressed by the Condon approximation of a coordinate-independent transition dipole between adiabatic states. For all initial conditions investigated, the initial nonadiabatic electronic motion is driven towards the lower adiabatic state, and criteria for this directed motion are discussed.

Nodeless vibrational amplitudes and quantum nonadiabatic dynamics in the nested funnel for a pseudo Jahn-Teller molecule or homodimer.

PubMed

Peters, William K; Tiwari, Vivek; Jonas, David M

2017-11-21

The nonadiabatic states and dynamics are investigated for a linear vibronic coupling Hamiltonian with a static electronic splitting and weak off-diagonal Jahn-Teller coupling through a single vibration with a vibrational-electronic resonance. With a transformation of the electronic basis, this Hamiltonian is also applicable to the anti-correlated vibration in a symmetric homodimer with marginally strong constant off-diagonal coupling, where the non-adiabatic states and dynamics model electronic excitation energy transfer or self-exchange electron transfer. For parameters modeling a free-base naphthalocyanine, the nonadiabatic couplings are deeply quantum mechanical and depend on wavepacket width; scalar couplings are as important as the derivative couplings that are usually interpreted to depend on vibrational velocity in semiclassical curve crossing or surface hopping theories. A colored visualization scheme that fully characterizes the non-adiabatic states using the exact factorization is developed. The nonadiabatic states in this nested funnel have nodeless vibrational factors with strongly avoided zeroes in their vibrational probability densities. Vibronic dynamics are visualized through the vibrational coordinate dependent density of the time-dependent dipole moment in free induction decay. Vibrational motion is amplified by the nonadiabatic couplings, with asymmetric and anisotropic motions that depend upon the excitation polarization in the molecular frame and can be reversed by a change in polarization. This generates a vibrational quantum beat anisotropy in excess of 2/5. The amplitude of vibrational motion can be larger than that on the uncoupled potentials, and the electronic population transfer is maximized within one vibrational period. Most of these dynamics are missed by the adiabatic approximation, and some electronic and vibrational motions are completely suppressed by the Condon approximation of a coordinate-independent transition dipole between adiabatic states. For all initial conditions investigated, the initial nonadiabatic electronic motion is driven towards the lower adiabatic state, and criteria for this directed motion are discussed.

An unscaled quantum mechanical harmonic force field for p-benzoquinone

NASA Astrophysics Data System (ADS)

Nonella, Marco; Tavan, Paul

1995-10-01

Structure and harmonic vibrational frequencies of p-benzoquinone have been calculated using quantum chemical ab initio and density functional methods. Our calculations show that a satisfactory description of fundamentals and normal mode compositions is achieved upon consideration of correlation effects by means of Møller-Plesset perturbation expansion (MP2) or by density functional theory (DFT). Furthermore, for correct prediction of CO bondlength and force constant, basis sets augmented by polarization functions are required. Applying such basis sets, MP2 and DFT calculations both give results which are generally in reasonable agreement with experimental data. The quantitatively better agreement, however, is achieved with the computationally less demanding DFT method. This method particularly allows very precise prediction of the experimentally important absorptions in the frequency region between 1500 and 1800 cm -1 and of the isotopic shifts of these vibrations due to 13C or 18O substitution.

Measurement of Vibrated Bulk Density of Coke Particle Blends Using Image Texture Analysis

NASA Astrophysics Data System (ADS)

Azari, Kamran; Bogoya-Forero, Wilinthon; Duchesne, Carl; Tessier, Jayson

2017-09-01

A rapid and nondestructive machine vision sensor was developed for predicting the vibrated bulk density (VBD) of petroleum coke particles based on image texture analysis. It could be used for making corrective adjustments to a paste plant operation to reduce green anode variability (e.g., changes in binder demand). Wavelet texture analysis (WTA) and gray level co-occurrence matrix (GLCM) algorithms were used jointly for extracting the surface textural features of coke aggregates from images. These were correlated with the VBD using partial least-squares (PLS) regression. Coke samples of several sizes and from different sources were used to test the sensor. Variations in the coke surface texture introduced by coke size and source allowed for making good predictions of the VBD of individual coke samples and mixtures of them (blends involving two sources and different sizes). Promising results were also obtained for coke blends collected from an industrial-baked carbon anode manufacturer.

A method for analyzing absorbed power distribution in the hand and arm substructures when operating vibrating tools

NASA Astrophysics Data System (ADS)

Dong, Jennie H.; Dong, Ren G.; Rakheja, Subhash; Welcome, Daniel E.; McDowell, Thomas W.; Wu, John Z.

2008-04-01

In this study it was hypothesized that the vibration-induced injuries or disorders in a substructure of human hand-arm system are primarily associated with the vibration power absorption distributed in that substructure. As the first step to test this hypothesis, the major objective of this study is to develop a method for analyzing the vibration power flow and the distribution of vibration power absorptions in the major substructures (fingers, palm-hand-wrist, forearm and upper arm, and shoulder) of the system exposed to hand-transmitted vibration. A five-degrees-of-freedom model of the system incorporating finger- as well as palm-side driving points was applied for the analysis. The mechanical impedance data measured at the two driving points under four different hand actions involving 50 N grip-only, 15 N grip and 35 N push, 30 N grip and 45 N push, and 50 N grip and 50 N push, were used to identify the model parameters. The vibration power absorption distributed in the substructures were evaluated using vibration spectra measured on many tools. The frequency weightings of the distributed vibration power absorptions were derived and compared with the weighting defined in ISO 5349-1 (2001). This study found that vibration power absorption is primarily distributed in the arm and shoulder when operating low-frequency tools such as rammers, while a high concentration of vibration power absorption in the fingers and hand is observed when operating high-frequency tools, such as grinders. The vibration power absorption distributed in palm-wrist and arm is well correlated with the ISO-weighted acceleration, while the finger vibration power absorption is highly correlated with unweighted acceleration. The finger vibration power absorption-based frequency weighting suggested that exposure to vibration in the frequency range of 16-500 Hz could pose higher risks of developing finger disorders. The results support the use of the frequency weighting specified in the current standard for assessing risks of developing disorders in the palm-wrist-arm substructures. The standardized weighting, however, could overestimate low-frequency effects but greatly underestimate high-frequency effects on the development of finger disorders. The results are further discussed to show that the trends observed in the vibration power absorptions distributed in the substructures are consistent with some major findings of various physiological and epidemiological studies, which provides a support to the hypothesis of this study.

Vibration reduction of a woven composite fan blade by piezoelectric shunted devices

NASA Astrophysics Data System (ADS)

Thierry, Olivier; De Smet, Olivier; Deü, Jean-François

2016-09-01

This study concerns the vibration reduction in the low frequency range of a composite fan blade of a turbojet engine with piezoelectric devices. The interest is to increase lifespan and avoid flutter phenomena by reducing the vibration amplitude. The solution considered in the work consists in using piezoelectric elements connected to a passive electric circuit usually called shunt. The use of woven composite materials for fan blades enables to plan on embedding piezoelectric materials, for instance in the form of patches inserted between the composite and the coating material. The work presented during this conference will illustrate the feasibility of a piezoelectric shunted device integrated in an industrial application that doesn't require electrical supply. For such a structure, it is shown that a purely passive resonant shunt can significantly reduce the level of vibration of the second bending mode and that a good correlation between experiments and simulations validates the best fitting finite element model.

Vibrational self-consistent field theory using optimized curvilinear coordinates.

PubMed

Bulik, Ireneusz W; Frisch, Michael J; Vaccaro, Patrick H

2017-07-28

A vibrational SCF model is presented in which the functions forming the single-mode functions in the product wavefunction are expressed in terms of internal coordinates and the coordinates used for each mode are optimized variationally. This model involves no approximations to the kinetic energy operator and does not require a Taylor-series expansion of the potential. The non-linear optimization of coordinates is found to give much better product wavefunctions than the limited variations considered in most previous applications of SCF methods to vibrational problems. The approach is tested using published potential energy surfaces for water, ammonia, and formaldehyde. Variational flexibility allowed in the current ansätze results in excellent zero-point energies expressed through single-product states and accurate fundamental transition frequencies realized by short configuration-interaction expansions. Fully variational optimization of single-product states for excited vibrational levels also is discussed. The highlighted methodology constitutes an excellent starting point for more sophisticated treatments, as the bulk characteristics of many-mode coupling are accounted for efficiently in terms of compact wavefunctions (as evident from the accurate prediction of transition frequencies).

Accurate potential energy, dipole moment curves, and lifetimes of vibrational states of heteronuclear alkali dimers

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

Fedorov, Dmitry A.; Varganov, Sergey A., E-mail: svarganov@unr.edu; Derevianko, Andrei

2014-05-14

We calculate the potential energy curves, the permanent dipole moment curves, and the lifetimes of the ground and excited vibrational states of the heteronuclear alkali dimers XY (X, Y = Li, Na, K, Rb, Cs) in the X{sup 1}Σ{sup +} electronic state using the coupled cluster with singles doubles and triples method. All-electron quadruple-ζ basis sets with additional core functions are used for Li and Na, and small-core relativistic effective core potentials with quadruple-ζ quality basis sets are used for K, Rb, and Cs. The inclusion of the coupled cluster non-perturbative triple excitations is shown to be crucial for obtainingmore » the accurate potential energy curves. A large one-electron basis set with additional core functions is needed for the accurate prediction of permanent dipole moments. The dissociation energies are overestimated by only 14 cm{sup −1} for LiNa and by no more than 114 cm{sup −1} for the other molecules. The discrepancies between the experimental and calculated harmonic vibrational frequencies are less than 1.7 cm{sup −1}, and the discrepancies for the anharmonic correction are less than 0.1 cm{sup −1}. We show that correlation between atomic electronegativity differences and permanent dipole moment of heteronuclear alkali dimers is not perfect. To obtain the vibrational energies and wave functions the vibrational Schrödinger equation is solved with the B-spline basis set method. The transition dipole moments between all vibrational states, the Einstein coefficients, and the lifetimes of the vibrational states are calculated. We analyze the decay rates of the vibrational states in terms of spontaneous emission, and stimulated emission and absorption induced by black body radiation. In all studied heteronuclear alkali dimers the ground vibrational states have much longer lifetimes than any excited states.« less

Coupled rotor/fuselage dynamic analysis of the AH-1G helicopter and correlation with flight vibrations data

NASA Technical Reports Server (NTRS)

Corrigan, J. C.; Cronkhite, J. D.; Dompka, R. V.; Perry, K. S.; Rogers, J. P.; Sadler, S. G.

1989-01-01

Under a research program designated Design Analysis Methods for VIBrationS (DAMVIBS), existing analytical methods are used for calculating coupled rotor-fuselage vibrations of the AH-1G helicopter for correlation with flight test data from an AH-1G Operational Load Survey (OLS) test program. The analytical representation of the fuselage structure is based on a NASTRAN finite element model (FEM), which has been developed, extensively documented, and correlated with ground vibration test. One procedure that was used for predicting coupled rotor-fuselage vibrations using the advanced Rotorcraft Flight Simulation Program C81 and NASTRAN is summarized. Detailed descriptions of the analytical formulation of rotor dynamics equations, fuselage dynamic equations, coupling between the rotor and fuselage, and solutions to the total system of equations in C81 are included. Analytical predictions of hub shears for main rotor harmonics 2p, 4p, and 6p generated by C81 are used in conjunction with 2p OLS measured control loads and a 2p lateral tail rotor gearbox force, representing downwash impingement on the vertical fin, to excite the NASTRAN model. NASTRAN is then used to correlate with measured OLS flight test vibrations. Blade load comparisons predicted by C81 showed good agreement. In general, the fuselage vibration correlations show good agreement between anslysis and test in vibration response through 15 to 20 Hz.

Effects on auditory-nerve fibers of opening the otic capsule at the apex of the chinchilla cochlea

NASA Astrophysics Data System (ADS)

Recio-Spinoso, Alberto; Temchin, Andrei N.; Ruggero, Mario A.

2015-12-01

Vibration responses to clicks measured at the apex of chinchilla cochleae with open otic capsules have onsets much shorter than those of responses of auditory-nerve fibers (ANFs) corrected for synaptic and neural delays. Apical vibration responses to tones in open cochleae also differ in other respects from the responses to tones of ANFs with low characteristic frequency (CF) in normal chinchilla cochleae. To further specify the origin(s) of these differences, we recorded from chinchilla ANFs after delicately opening a small hole in the otic capsule overlying scala vestibuli in the cochlear apex. In those cochleae, the earliest ANF responses to clicks are often evoked by condensation (rather than rarefaction) clicks and responses to tones often exhibit level-dependent phase changes different from those in normal cochleae. These findings are largely consistent with, and seem to account for, apical vibration responses of cochleae with open otic capsules. An unexpected finding is that the tuning curves of ANFs with moderately high CF and normal CF thresholds often had hypersensitive tails.

Evaluating Attenuation of Vibration Response using Particle Impact Damping for a Range of Equipment Assemblies

NASA Technical Reports Server (NTRS)

Knight, Brent; Parsons, David; Smith, Andrew; Hunt, Ron; LaVerde, Bruce; Towner, Robert; Craigmyle, Ben

2013-01-01

Particle dampers provide a mechanism for diverting energy away from resonant structural vibrations. This experimental study provides data from a series of acoustically excited tests to determine the effectiveness of these dampers for equipment mounted to a curved orthogrid panel for a launch vehicle application. Vibration attenuation trends are examined for variations in particle damper fill level, component mass, and excitation energy. A significant response reduction at the component level was achieved, suggesting that comparatively small, strategically placed, particle damper devices might be advantageously used in launch vehicle design. These test results were compared to baseline acoustic response tests without particle damping devices, over a range of isolation and damping parameters. Instrumentation consisting of accelerometers, microphones, and still photography data will be collected to correlate with the analytical results.

Initial mechanisms for the unimolecular decomposition of electronically excited bisfuroxan based energetic materials.

PubMed

Yuan, Bing; Bernstein, Elliot R

2017-01-07

Unimolecular decomposition of energetic molecules, 3,3'-diamino-4,4'-bisfuroxan (labeled as A) and 4,4'-diamino-3,3'-bisfuroxan (labeled as B), has been explored via 226/236 nm single photon laser excitation/decomposition. These two energetic molecules, subsequent to UV excitation, create NO as an initial decomposition product at the nanosecond excitation energies (5.0-5.5 eV) with warm vibrational temperature (1170 ± 50 K for A, 1400 ± 50 K for B) and cold rotational temperature (<55 K). Initial decomposition mechanisms for these two electronically excited, isolated molecules are explored at the complete active space self-consistent field (CASSCF(12,12)/6-31G(d)) level with and without MP2 correction. Potential energy surface calculations illustrate that conical intersections play an essential role in the calculated decomposition mechanisms. Based on experimental observations and theoretical calculations, NO product is released through opening of the furoxan ring: ring opening can occur either on the S 1 excited or S 0 ground electronic state. The reaction path with the lowest energetic barrier is that for which the furoxan ring opens on the S 1 state via the breaking of the N1-O1 bond. Subsequently, the molecule moves to the ground S 0 state through related ring-opening conical intersections, and an NO product is formed on the ground state surface with little rotational excitation at the last NO dissociation step. For the ground state ring opening decomposition mechanism, the N-O bond and C-N bond break together in order to generate dissociated NO. With the MP2 correction for the CASSCF(12,12) surface, the potential energies of molecules with dissociated NO product are in the range from 2.04 to 3.14 eV, close to the theoretical result for the density functional theory (B3LYP) and MP2 methods. The CASMP2(12,12) corrected approach is essential in order to obtain a reasonable potential energy surface that corresponds to the observed decomposition behavior of these molecules. Apparently, highly excited states are essential for an accurate representation of the kinetics and dynamics of excited state decomposition of both of these bisfuroxan energetic molecules. The experimental vibrational temperatures of NO products of A and B are about 800-1000 K lower than previously studied energetic molecules with NO as a decomposition product.

Survey of Technical Preventative Measures to Reduce Whole-Body Vibration Effects when Designing Mobile Machinery

NASA Astrophysics Data System (ADS)

DONATI, P.

2002-05-01

Engineering solutions to minimize the effects on operators of vibrating mobile machinery can be conveniently grouped into three areas: Reduction of vibration at source by improvement of the quality of terrain, careful selection of vehicle or machine, correct loading, proper maintenance, etc.Reduction of vibration transmission by incorporating suspension systems (tyres, vehicle suspensions, suspension cab and seat) between the operator and the source of vibration.Improvement of cab ergonomics and seat profiles to optimize operator posture. These paper reviews the different techniques and problems linked to categories (2) and (3). According to epidemiological studies, the main health risk with whole-body vibration exposure would appear to be lower back pain. When designing new mobile machinery, all factors which may contribute to back injury should be considered in order to reduce risk. For example, optimized seat suspension is useless if the suspension seat cannot be correctly and easily adjusted to the driver's weight or if the driver is forced to drive in a bent position to avoid his head striking the ceiling due to the spatial requirement of the suspension seat.

Health State Monitoring of Bladed Machinery with Crack Growth Detection in BFG Power Plant Using an Active Frequency Shift Spectral Correction Method.

PubMed

Sun, Weifang; Yao, Bin; He, Yuchao; Chen, Binqiang; Zeng, Nianyin; He, Wangpeng

2017-08-09

Power generation using waste-gas is an effective and green way to reduce the emission of the harmful blast furnace gas (BFG) in pig-iron producing industry. Condition monitoring of mechanical structures in the BFG power plant is of vital importance to guarantee their safety and efficient operations. In this paper, we describe the detection of crack growth of bladed machinery in the BFG power plant via vibration measurement combined with an enhanced spectral correction technique. This technique enables high-precision identification of amplitude, frequency, and phase information (the harmonic information) belonging to deterministic harmonic components within the vibration signals. Rather than deriving all harmonic information using neighboring spectral bins in the fast Fourier transform spectrum, this proposed active frequency shift spectral correction method makes use of some interpolated Fourier spectral bins and has a better noise-resisting capacity. We demonstrate that the identified harmonic information via the proposed method is of suppressed numerical error when the same level of noises is presented in the vibration signal, even in comparison with a Hanning-window-based correction method. With the proposed method, we investigated vibration signals collected from a centrifugal compressor. Spectral information of harmonic tones, related to the fundamental working frequency of the centrifugal compressor, is corrected. The extracted spectral information indicates the ongoing development of an impeller blade crack that occurred in the centrifugal compressor. This method proves to be a promising alternative to identify blade cracks at early stages.

Self-consistent self-interaction corrected density functional theory calculations for atoms using Fermi-Löwdin orbitals: Optimized Fermi-orbital descriptors for Li-Kr

NASA Astrophysics Data System (ADS)

Kao, Der-you; Withanage, Kushantha; Hahn, Torsten; Batool, Javaria; Kortus, Jens; Jackson, Koblar

2017-10-01

In the Fermi-Löwdin orbital method for implementing self-interaction corrections (FLO-SIC) in density functional theory (DFT), the local orbitals used to make the corrections are generated in a unitary-invariant scheme via the choice of the Fermi orbital descriptors (FODs). These are M positions in 3-d space (for an M-electron system) that can be loosely thought of as classical electron positions. The orbitals that minimize the DFT energy including the SIC are obtained by finding optimal positions for the FODs. In this paper, we present optimized FODs for the atoms from Li-Kr obtained using an unbiased search method and self-consistent FLO-SIC calculations. The FOD arrangements display a clear shell structure that reflects the principal quantum numbers of the orbitals. We describe trends in the FOD arrangements as a function of atomic number. FLO-SIC total energies for the atoms are presented and are shown to be in close agreement with the results of previous SIC calculations that imposed explicit constraints to determine the optimal local orbitals, suggesting that FLO-SIC yields the same solutions for atoms as these computationally demanding earlier methods, without invoking the constraints.

Gas-Phase Reaction Pathways and Rate Coefficients for the Dichlorosilane-Hydrogen and Trichlorosilane-Hydrogen Systems

NASA Technical Reports Server (NTRS)

Dateo, Christopher E.; Walch, Stephen P.

2002-01-01

As part of NASA Ames Research Center's Integrated Process Team on Device/Process Modeling and Nanotechnology our goal is to create/contribute to a gas-phase chemical database for use in modeling microelectronics devices. In particular, we use ab initio methods to determine chemical reaction pathways and to evaluate reaction rate coefficients. Our initial studies concern reactions involved in the dichlorosilane-hydrogen (SiCl2H2--H2) and trichlorosilane-hydrogen (SiCl2H-H2) systems. Reactant, saddle point (transition state), and product geometries and their vibrational harmonic frequencies are determined using the complete-active-space self-consistent-field (CASSCF) electronic structure method with the correlation consistent polarized valence double-zeta basis set (cc-pVDZ). Reaction pathways are constructed by following the imaginary frequency mode of the saddle point to both the reactant and product. Accurate energetics are determined using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations (CCSD(T)) extrapolated to the complete basis set limit. Using the data from the electronic structure calculations, reaction rate coefficients are obtained using conventional and variational transition state and RRKM theories.

Relativistic Corrections to the Properties of the Alkali Fluorides

NASA Technical Reports Server (NTRS)

Dyall, Kenneth G.; Partridge, Harry

1993-01-01

Relativistic corrections to the bond lengths, dissociation energies and harmonic frequencies of KF, RbF and CsF have been obtained at the self-consistent field level by dissociating to ions. The relativistic corrections to the bond lengths, harmonic frequencies and dissociation energies to the ions are very small, due to the ionic nature of these molecules and the similarity of the relativistic and nonrelativistic ionic radii.

Kinetics of highly vibrationally excited O2(X) molecules in inductively-coupled oxygen plasmas

NASA Astrophysics Data System (ADS)

Annušová, Adriana; Marinov, Daniil; Booth, Jean-Paul; Sirse, Nishant; Lino da Silva, Mário; Lopez, Bruno; Guerra, Vasco

2018-04-01

The high degree of vibrational excitation of O2 ground state molecules recently observed in inductively coupled plasma discharges is investigated experimentally in more detail and interpreted using a detailed self-consistent 0D global kinetic model for oxygen plasmas. Additional experimental results are presented and used to validate the model. The vibrational kinetics considers vibrational levels up to v = 41 and accounts for electron impact excitation and de-excitation (e-V), vibration-to-translation relaxation (V-T) in collisions with O2 molecules and O atoms, vibration-to-vibration energy exchanges (V-V), excitation of electronically excited states, dissociative electron attachment, and electron impact dissociation. Measurements were performed at pressures of 10–80 mTorr (1.33 and 10.67 Pa) and radio frequency (13.56 MHz) powers up to 500 W. The simulation results are compared with the absolute densities in each O2 vibrational level obtained by high sensitivity absorption spectroscopy measurements of the Schumann–Runge bands for O2(X, v = 4–18), O(3 P) atom density measurements by two-photon absorption laser induced fluorescence (TALIF) calibrated against Xe, and laser photodetachment measurements of the O‑ negative ions. The highly excited O2(X, v) distribution exhibits a shape similar to a Treanor-Gordiets distribution, but its origin lies in electron impact e-V collisions and not in V-V up-pumping, in contrast to what happens in all other molecular gases known to date. The relaxation of vibrational quanta is mainly due to V-T energy-transfer collisions with O atoms and to electron impact dissociation of vibrationally excited molecules, e+O2(X, v)→O(3P)+O(3P).

Towards a fully self-consistent inversion combining historical and paleomagnetic data for geomagnetic field reconstructions

NASA Astrophysics Data System (ADS)

Arneitz, P.; Leonhardt, R.; Fabian, K.; Egli, R.

2017-12-01

Historical and paleomagnetic data are the two main sources of information about the long-term geomagnetic field evolution. Historical observations extend to the late Middle Ages, and prior to the 19th century, they consisted mainly of pure declination measurements from navigation and orientation logs. Field reconstructions going back further in time rely solely on magnetization acquired by rocks, sediments, and archaeological artefacts. The combined dataset is characterized by a strongly inhomogeneous spatio-temporal distribution and highly variable data reliability and quality. Therefore, an adequate weighting of the data that correctly accounts for data density, type, and realistic error estimates represents the major challenge for an inversion approach. Until now, there has not been a fully self-consistent geomagnetic model that correctly recovers the variation of the geomagnetic dipole together with the higher-order spherical harmonics. Here we present a new geomagnetic field model for the last 4 kyrs based on historical, archeomagnetic and volcanic records. The iterative Bayesian inversion approach targets the implementation of reliable error treatment, which allows different record types to be combined in a fully self-consistent way. Modelling results will be presented along with a thorough analysis of model limitations, validity and sensitivity.

An eigenvalue approach to quantum plasmonics based on a self-consistent hydrodynamics method

NASA Astrophysics Data System (ADS)

Ding, Kun; Chan, C. T.

2018-02-01

Plasmonics has attracted much attention not only because it has useful properties such as strong field enhancement, but also because it reveals the quantum nature of matter. To handle quantum plasmonics effects, ab initio packages or empirical Feibelman d-parameters have been used to explore the quantum correction of plasmonic resonances. However, most of these methods are formulated within the quasi-static framework. The self-consistent hydrodynamics model offers a reliable approach to study quantum plasmonics because it can incorporate the quantum effect of the electron gas into classical electrodynamics in a consistent manner. Instead of the standard scattering method, we formulate the self-consistent hydrodynamics method as an eigenvalue problem to study quantum plasmonics with electrons and photons treated on the same footing. We find that the eigenvalue approach must involve a global operator, which originates from the energy functional of the electron gas. This manifests the intrinsic nonlocality of the response of quantum plasmonic resonances. Our model gives the analytical forms of quantum corrections to plasmonic modes, incorporating quantum electron spill-out effects and electrodynamical retardation. We apply our method to study the quantum surface plasmon polariton for a single flat interface.

Highly Accurate Quartic Force Fields, Vibrational Frequencies, and Spectroscopic Constants for Cyclic and Linear C3H3(+)

NASA Technical Reports Server (NTRS)

Huang, Xinchuan; Taylor, Peter R.; Lee, Timothy J.

2011-01-01

High levels of theory have been used to compute quartic force fields (QFFs) for the cyclic and linear forms of the C H + molecular cation, referred to as c-C H + and I-C H +. Specifically the 33 3333 singles and doubles coupled-cluster method that includes a perturbational estimate of connected triple excitations, CCSD(T), has been used in conjunction with extrapolation to the one-particle basis set limit and corrections for scalar relativity and core correlation have been included. The QFFs have been used to compute highly accurate fundamental vibrational frequencies and other spectroscopic constants using both vibrational 2nd-order perturbation theory and variational methods to solve the nuclear Schroedinger equation. Agreement between our best computed fundamental vibrational frequencies and recent infrared photodissociation experiments is reasonable for most bands, but there are a few exceptions. Possible sources for the discrepancies are discussed. We determine the energy difference between the cyclic and linear forms of C H +, 33 obtaining 27.9 kcal/mol at 0 K, which should be the most reliable available. It is expected that the fundamental vibrational frequencies and spectroscopic constants presented here for c-C H + 33 and I-C H + are the most reliable available for the free gas-phase species and it is hoped that 33 these will be useful in the assignment of future high-resolution laboratory experiments or astronomical observations.

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. I. Theory for a dimer

NASA Astrophysics Data System (ADS)

Tiwari, Vivek; Peters, William K.; Jonas, David M.

2017-10-01

Non-adiabatic vibrational-electronic resonance in the excited electronic states of natural photosynthetic antennas drastically alters the adiabatic framework, in which electronic energy transfer has been conventionally studied, and suggests the possibility of exploiting non-adiabatic dynamics for directed energy transfer. Here, a generalized dimer model incorporates asymmetries between pigments, coupling to the environment, and the doubly excited state relevant for nonlinear spectroscopy. For this generalized dimer model, the vibrational tuning vector that drives energy transfer is derived and connected to decoherence between singly excited states. A correlation vector is connected to decoherence between the ground state and the doubly excited state. Optical decoherence between the ground and singly excited states involves linear combinations of the correlation and tuning vectors. Excitonic coupling modifies the tuning vector. The correlation and tuning vectors are not always orthogonal, and both can be asymmetric under pigment exchange, which affects energy transfer. For equal pigment vibrational frequencies, the nonadiabatic tuning vector becomes an anti-correlated delocalized linear combination of intramolecular vibrations of the two pigments, and the nonadiabatic energy transfer dynamics become separable. With exchange symmetry, the correlation and tuning vectors become delocalized intramolecular vibrations that are symmetric and antisymmetric under pigment exchange. Diabatic criteria for vibrational-excitonic resonance demonstrate that anti-correlated vibrations increase the range and speed of vibronically resonant energy transfer (the Golden Rule rate is a factor of 2 faster). A partial trace analysis shows that vibronic decoherence for a vibrational-excitonic resonance between two excitons is slower than their purely excitonic decoherence.

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. I. Theory for a dimer.

PubMed

Tiwari, Vivek; Peters, William K; Jonas, David M

2017-10-21

Non-adiabatic vibrational-electronic resonance in the excited electronic states of natural photosynthetic antennas drastically alters the adiabatic framework, in which electronic energy transfer has been conventionally studied, and suggests the possibility of exploiting non-adiabatic dynamics for directed energy transfer. Here, a generalized dimer model incorporates asymmetries between pigments, coupling to the environment, and the doubly excited state relevant for nonlinear spectroscopy. For this generalized dimer model, the vibrational tuning vector that drives energy transfer is derived and connected to decoherence between singly excited states. A correlation vector is connected to decoherence between the ground state and the doubly excited state. Optical decoherence between the ground and singly excited states involves linear combinations of the correlation and tuning vectors. Excitonic coupling modifies the tuning vector. The correlation and tuning vectors are not always orthogonal, and both can be asymmetric under pigment exchange, which affects energy transfer. For equal pigment vibrational frequencies, the nonadiabatic tuning vector becomes an anti-correlated delocalized linear combination of intramolecular vibrations of the two pigments, and the nonadiabatic energy transfer dynamics become separable. With exchange symmetry, the correlation and tuning vectors become delocalized intramolecular vibrations that are symmetric and antisymmetric under pigment exchange. Diabatic criteria for vibrational-excitonic resonance demonstrate that anti-correlated vibrations increase the range and speed of vibronically resonant energy transfer (the Golden Rule rate is a factor of 2 faster). A partial trace analysis shows that vibronic decoherence for a vibrational-excitonic resonance between two excitons is slower than their purely excitonic decoherence.

Density-Functional Theory with Optimized Effective Potential and Self-Interaction Correction for the Double Ionization of He and Be Atoms

NASA Astrophysics Data System (ADS)

Heslar, John; Telnov, Dmitry; Chu, Shih-I.

2012-06-01

We present a self-interaction-free (SIC) time-dependent density-functional theory (TDDFT) for the treatment of double ionization processes of many-electron systems. The method is based on the Krieger-Li-Iafrate (KLI) treatment of the optimized effective potential (OEP) theory and the incorporation of an explicit self-interaction correction (SIC) term. In the framework of the time-dependent density functional theory, we have performed 3D calculations of double ionization of He and Be atoms by strong near-infrared laser fields. We make use of the exchange-correlation potential with the integer discontinuity which improves the description of the double ionization process. We found that proper description of the double ionization requires the TDDFT exchange-correlation potential with the discontinuity with respect to the variation of the spin particle numbers (SPN) only. The results for the intensity-dependent probabilities of single and double ionization are presented and reproduce the famous ``knee'' structure.

Molecular orientation of organic thin films on dielectric solid substrates: a phase-sensitive vibrational SFG study.

PubMed

Ge, Aimin; Peng, Qiling; Qiao, Lin; Yepuri, Nageshwar R; Darwish, Tamim A; Matsusaki, Michiya; Akashi, Mitsuru; Ye, Shen

2015-07-21

Broadband phase-sensitive vibrational sum frequency generation (SFG) spectroscopy was utilized to study the molecular orientation of molecules adsorbed on dielectric solid substrates. A gold thin film was employed to generate a SFG signal as a local oscillator (LO). To simplify the phase measurement, a self-assembled monolayer (SAM) of octadecyltrichlorosilane (OTS) was used as a standard sample for phase correction of the phase-sensitive SFG measurements on the solid/air interface. It was demonstrated that the absolute orientation of molecules in the LB films on a fused quartz surface can be clearly distinguished by phase-sensitive SFG measurement. In addition, the observation on the SAM of d35-OTS reveals that the two C-H stretching modes for α-CH2 group are in opposite phase. Furthermore, by using the present phase-sensitive SFG setup, the orientation flipping of water molecules on positively and negatively charged solid/liquid interface can be distinguished.

The impact of barriers and self-efficacy on self-care behaviors in type 2 diabetes.

PubMed

Aljasem, L I; Peyrot, M; Wissow, L; Rubin, R R

2001-01-01

This cross-sectional, correlational study examined the relationships of diabetes-specific treatment barriers and self-efficacy with self-care behaviors. A total of 309 people with type 2 diabetes participated in this study. All of the factors were assessed by self-report questionnaires. Self-care behaviors included exercise, diet, skipping medication, testing blood for glucose, adjusting insulin to avoid or correct hyperglycemia, and adjusting diet to avoid or correct hypoglycemia. Perceived barriers to carrying out self-care behaviors were associated with worse diet and exercise behavior. Greater self-efficacy predicted more frequent blood glucose testing, less frequent skipping of medication and binge eating, and closer adherence to an ideal diet. Nontraditional dimensions of self-efficacy were associated with worse self-care. Self-efficacy explained 4% to 10% of the variance in diabetes self-care behaviors beyond that accounted for by patient characteristics and health beliefs about barriers. The findings of this study provided support for Rosenstock's proposal that a person's self-perceived capability to carry out a behavior should be incorporated into an expanded health belief model.

Vibrational spectra and ab initio analysis of tert-butyl, trimethylsilyl, and trimethylgermyl derivatives of 3,3-dimethylcyclopropene III. 3,3-Dimethyl-1-(trimethylsilyl)cyclopropene

NASA Astrophysics Data System (ADS)

De Maré, G. R.; Panchenko, Yu. N.; Abramenkov, A. V.; Baird, M. S.; Tverezovsky, V. V.; Nizovtsev, A. V.; Bolesov, I. G.

2003-07-01

The experimental Raman and IR vibrational spectra of 3,3-dimethyl-1-(trimethylsilyl)cyclopropene in the liquid phase were recorded. Total geometry optimisation was carried out at the HF/6-31G* level and the HF/6-31G*//HF/6-31G* force field was computed. This force field was corrected by scale factors determined previously (using Pulay's method) for correction of the HF/6-31G*//HF/6-31G* force fields of 3,3-dimethylbutene-1, 1-methyl-, 1,2-dimethyl-, and 3,3-dimethylcyclopropene. The theoretical vibrational frequencies calculated from the scaled quantum mechanical force field and the theoretical intensities obtained from the quantum mechanical calculation were used to construct predicted spectra and to perform the vibrational analysis of the experimental spectra.

Terahertz thickness determination with interferometric vibration correction for industrial applications.

PubMed

Pfeiffer, Tobias; Weber, Stefan; Klier, Jens; Bachtler, Sebastian; Molter, Daniel; Jonuscheit, Joachim; Von Freymann, Georg

2018-05-14

In many industrial fields, like automotive and painting industry, the thickness of thin layers is a crucial parameter for quality control. Hence, the demand for thickness measurement techniques continuously grows. In particular, non-destructive and contact-free terahertz techniques access a wide range of thickness determination applications. However, terahertz time-domain spectroscopy based systems perform the measurement in a sampling manner, requiring fixed distances between measurement head and sample. In harsh industrial environments vibrations of sample and measurement head distort the time-base and decrease measurement accuracy. We present an interferometer-based vibration correction for terahertz time-domain measurements, able to reduce thickness distortion by one order of magnitude for vibrations with frequencies up to 100 Hz and amplitudes up to 100 µm. We further verify the experimental results by numerical calculations and find very good agreement.

Probing ionization potential, electron affinity and self-energy effect on the spectral shape and exciton binding energy of quantum liquid water with self-consistent many-body perturbation theory and the Bethe-Salpeter equation.

PubMed

Ziaei, Vafa; Bredow, Thomas

2018-05-31

An accurate theoretical prediction of ionization potential (IP) and electron affinity (EA) is key in understanding complex photochemical processes in aqueous environments. There have been numerous efforts in literature to accurately predict IP and EA of liquid water, however with often conflicting results depending on the level of theory and the underlying water structures. In a recent study based on hybrid-non-self-consistent many-body perturbation theory (MBPT) Gaiduk et al (2018 Nat. Commun. 9 247) predicted an IP of 10.2 eV and EA of 0.2 eV, resulting in an electronic band gap (i.e. electronic gap (IP-EA) as measured by photoelectron spectroscopy) of about 10 eV, redefining the widely cited experimental gap of 8.7 eV in literature. In the present work, we show that GW self-consistency and an implicit vertex correction in MBPT considerably affect recently reported EA values by Gaiduk et al (2018 Nat. Commun. 9 247) by about 1 eV. Furthermore, the choice of pseudo-potential is critical for an accurate determination of the absolute band positions. Consequently, the self-consistent GW approach with an implicit vertex correction based on projector augmented wave (PAW) method on top of quantum water structures predicts an IP of 10.2, an EA of 1.1, a fundamental gap of 9.1 eV and an exciton binding (Eb) energy of 0.9 eV for the first absorption band of liquid water via the Bethe-Salpeter equation (BSE). Only within such a self-consistent approach a simultanously accurate prediction of IP, EA, Eg, Eb is possible.

Probing ionization potential, electron affinity and self-energy effect on the spectral shape and exciton binding energy of quantum liquid water with self-consistent many-body perturbation theory and the Bethe–Salpeter equation

NASA Astrophysics Data System (ADS)

Ziaei, Vafa; Bredow, Thomas

2018-05-01

An accurate theoretical prediction of ionization potential (IP) and electron affinity (EA) is key in understanding complex photochemical processes in aqueous environments. There have been numerous efforts in literature to accurately predict IP and EA of liquid water, however with often conflicting results depending on the level of theory and the underlying water structures. In a recent study based on hybrid-non-self-consistent many-body perturbation theory (MBPT) Gaiduk et al (2018 Nat. Commun. 9 247) predicted an IP of 10.2 eV and EA of 0.2 eV, resulting in an electronic band gap (i.e. electronic gap (IP-EA) as measured by photoelectron spectroscopy) of about 10 eV, redefining the widely cited experimental gap of 8.7 eV in literature. In the present work, we show that GW self-consistency and an implicit vertex correction in MBPT considerably affect recently reported EA values by Gaiduk et al (2018 Nat. Commun. 9 247) by about 1 eV. Furthermore, the choice of pseudo-potential is critical for an accurate determination of the absolute band positions. Consequently, the self-consistent GW approach with an implicit vertex correction based on projector augmented wave (PAW) method on top of quantum water structures predicts an IP of 10.2, an EA of 1.1, a fundamental gap of 9.1 eV and an exciton binding (Eb) energy of 0.9 eV for the first absorption band of liquid water via the Bethe–Salpeter equation (BSE). Only within such a self-consistent approach a simultanously accurate prediction of IP, EA, Eg, Eb is possible.

A study of the chiro-optical properties of Carvone

NASA Astrophysics Data System (ADS)

Lambert, Jason

2011-10-01

The intrinsic optical rotatory dispersion (IORD) and circular dichroism (CD) of the conformationally flexible carvone molecule has been investigated in 17 solvents and compared with results from calculations for the ``free'' (gas phase) molecule. The G3 method was used to determine the relative energies of the six conformers. The ORD of (R)-(-)-carvone at 589 nm was calculated using coupled cluster and density-functional methods, including temperature-dependent vibrational corrections. Vibrational corrections are significant and are primarily associated with normal modes involving the stereogenic carbon atom and the carbonyl group, whose n->&*circ; excitation plays a significant role in the chiroptical response of carvone. However, without the vibrational correction the calculated ORD is of opposite sign to that of the experiment for the CCSD and B3LYP methods. Calculations performed in solution using the PCM model were also opposite in sign to of the experiment when using the B3LYP density functional.

SPIRiT: Iterative Self-consistent Parallel Imaging Reconstruction from Arbitrary k-Space

PubMed Central

Lustig, Michael; Pauly, John M.

2010-01-01

A new approach to autocalibrating, coil-by-coil parallel imaging reconstruction is presented. It is a generalized reconstruction framework based on self consistency. The reconstruction problem is formulated as an optimization that yields the most consistent solution with the calibration and acquisition data. The approach is general and can accurately reconstruct images from arbitrary k-space sampling patterns. The formulation can flexibly incorporate additional image priors such as off-resonance correction and regularization terms that appear in compressed sensing. Several iterative strategies to solve the posed reconstruction problem in both image and k-space domain are presented. These are based on a projection over convex sets (POCS) and a conjugate gradient (CG) algorithms. Phantom and in-vivo studies demonstrate efficient reconstructions from undersampled Cartesian and spiral trajectories. Reconstructions that include off-resonance correction and nonlinear ℓ1-wavelet regularization are also demonstrated. PMID:20665790

Important Variation in Vibrational Properties of LiFePO4 and FePO4 Induced by Magnetism

PubMed Central

Seifitokaldani, Ali; Gheribi, Aïmen E.; Phan, Anh Thu; Chartrand, Patrice; Dollé, Mickaël

2016-01-01

A new thermodynamically self-consistent (TSC) method, based on the quasi-harmonic approximation (QHA), is used to obtain the Debye temperatures of LiFePO4 (LFP) and FePO4 (FP) from available experimental specific heat capacities for a wide temperature range. The calculated Debye temperatures show an interesting critical and peculiar behavior so that a steep increase in the Debye temperatures is observed by increasing the temperature. This critical behavior is fitted by the critical function and the adjusted critical temperatures are very close to the magnetic phase transition temperatures in LFP and FP. Hence, the critical behavior of the Debye temperatures is correlated with the magnetic phase transitions in these compounds. Our first-principle calculations support our conjecture that the change in electronic structures, i.e. electron density of state and electron localization function, and consequently the change in thermophysical properties due to the magnetic transition may be the reason for the observation of this peculiar behavior of the Debye temperatures. PMID:27604551

Important Variation in Vibrational Properties of LiFePO4 and FePO4 Induced by Magnetism

NASA Astrophysics Data System (ADS)

Seifitokaldani, Ali; Gheribi, Aïmen E.; Phan, Anh Thu; Chartrand, Patrice; Dollé, Mickaël

2016-09-01

A new thermodynamically self-consistent (TSC) method, based on the quasi-harmonic approximation (QHA), is used to obtain the Debye temperatures of LiFePO4 (LFP) and FePO4 (FP) from available experimental specific heat capacities for a wide temperature range. The calculated Debye temperatures show an interesting critical and peculiar behavior so that a steep increase in the Debye temperatures is observed by increasing the temperature. This critical behavior is fitted by the critical function and the adjusted critical temperatures are very close to the magnetic phase transition temperatures in LFP and FP. Hence, the critical behavior of the Debye temperatures is correlated with the magnetic phase transitions in these compounds. Our first-principle calculations support our conjecture that the change in electronic structures, i.e. electron density of state and electron localization function, and consequently the change in thermophysical properties due to the magnetic transition may be the reason for the observation of this peculiar behavior of the Debye temperatures.

Important Variation in Vibrational Properties of LiFePO4 and FePO4 Induced by Magnetism.

PubMed

Seifitokaldani, Ali; Gheribi, Aïmen E; Phan, Anh Thu; Chartrand, Patrice; Dollé, Mickaël

2016-09-08

A new thermodynamically self-consistent (TSC) method, based on the quasi-harmonic approximation (QHA), is used to obtain the Debye temperatures of LiFePO4 (LFP) and FePO4 (FP) from available experimental specific heat capacities for a wide temperature range. The calculated Debye temperatures show an interesting critical and peculiar behavior so that a steep increase in the Debye temperatures is observed by increasing the temperature. This critical behavior is fitted by the critical function and the adjusted critical temperatures are very close to the magnetic phase transition temperatures in LFP and FP. Hence, the critical behavior of the Debye temperatures is correlated with the magnetic phase transitions in these compounds. Our first-principle calculations support our conjecture that the change in electronic structures, i.e. electron density of state and electron localization function, and consequently the change in thermophysical properties due to the magnetic transition may be the reason for the observation of this peculiar behavior of the Debye temperatures.

Electronic properties of copper aluminate examined by three theoretical approaches

NASA Astrophysics Data System (ADS)

Christensen, Niels; Svane, Axel

2010-03-01

Electronic properties of 3R.CuAlO2 are derived vs. pressure from ab initio band structure calculations within the local-density approximation (LDA), LDA+U scheme as well as the quasiparticle self-consistent GW approximation (QSGW, van Schilfgaarde, Kotani, and Falaev). The LDA underestimates the gap and places the Cu-3d states at too high energies. An effective U value, 8.2 eV, can be selected so that LDA+U lowers the 3d states to match XPS data and such that the lowest gap agrees rather well with optical absorption experiments. The electrical field gradient (EFG) on Cu is in error when calculated within the LDA. The agreement with experiment can be improved by LDA+U, but a larger U, 13.5 eV, is needed for full adjustment. QSGW yields correct Cu-EFG and, when electron-hole correlations are included, also correct band gaps. The QSGW and LDA band gap deformation potential values differ significantly.

Evidence of Self-correction of Child Sex Ratios in India: A District-Level Analysis of Child Sex Ratios From 1981 to 2011.

PubMed

Diamond-Smith, Nadia; Bishai, David

2015-04-01

Sex ratios in India have become increasingly imbalanced over the past decades. We hypothesize that when sex ratios become very uneven, the shortage of girls will increase girls' future value, leading sex ratios to self-correct. Using data on children under 5 from the last four Indian censuses, we examine the relationship between the sex ratio at one point in time and the change in sex ratio over the next 10 years by district. Fixed-effects models show that when accounting for unobserved district-level characteristics--including total fertility rate, infant mortality rate, percentage literate, percentage rural, percentage scheduled caste, percentage scheduled tribe, and a time trend variable--sex ratios are significantly negatively correlated with the change in sex ratio in the successive 10-year period. This suggests that self-corrective forces are at work on imbalanced sex ratios in India.

Self-interaction-corrected time-dependent density-functional-theory calculations of x-ray-absorption spectra

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

Tu, Guangde; Rinkevicius, Zilvinas; Vahtras, Olav

We outline an approach within time-dependent density functional theory that predicts x-ray spectra on an absolute scale. The approach rests on a recent formulation of the resonant-convergent first-order polarization propagator [P. Norman et al., J. Chem. Phys. 123, 194103 (2005)] and corrects for the self-interaction energy of the core orbital. This polarization propagator approach makes it possible to directly calculate the x-ray absorption cross section at a particular frequency without explicitly addressing the excited-state spectrum. The self-interaction correction for the employed density functional accounts for an energy shift of the spectrum, and fully correlated absolute-scale x-ray spectra are thereby obtainedmore » based solely on optimization of the electronic ground state. The procedure is benchmarked against experimental spectra of a set of small organic molecules at the carbon, nitrogen, and oxygen K edges.« less

Many-body dispersion effects in the binding of adsorbates on metal surfaces

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

Maurer, Reinhard J.; Ruiz, Victor G.; Tkatchenko, Alexandre

2015-09-14

A correct description of electronic exchange and correlation effects for molecules in contact with extended (metal) surfaces is a challenging task for first-principles modeling. In this work, we demonstrate the importance of collective van der Waals dispersion effects beyond the pairwise approximation for organic–inorganic systems on the example of atoms, molecules, and nanostructures adsorbed on metals. We use the recently developed many-body dispersion (MBD) approach in the context of density-functional theory [Tkatchenko et al., Phys. Rev. Lett. 108, 236402 (2012) and Ambrosetti et al., J. Chem. Phys. 140, 18A508 (2014)] and assess its ability to correctly describe the binding ofmore » adsorbates on metal surfaces. We briefly review the MBD method and highlight its similarities to quantum-chemical approaches to electron correlation in a quasiparticle picture. In particular, we study the binding properties of xenon, 3,4,9,10-perylene-tetracarboxylic acid, and a graphene sheet adsorbed on the Ag(111) surface. Accounting for MBD effects, we are able to describe changes in the anisotropic polarizability tensor, improve the description of adsorbate vibrations, and correctly capture the adsorbate–surface interaction screening. Comparison to other methods and experiment reveals that inclusion of MBD effects improves adsorption energies and geometries, by reducing the overbinding typically found in pairwise additive dispersion-correction approaches.« less

Active matter beyond mean-field: ring-kinetic theory for self-propelled particles.

PubMed

Chou, Yen-Liang; Ihle, Thomas

2015-02-01

Recently, Hanke et al. [Phys. Rev. E 88, 052309 (2013)] showed that mean-field kinetic theory fails to describe collective motion in soft active colloids and that correlations must not be neglected. Correlation effects are also expected to be essential in systems of biofilaments driven by molecular motors and in swarms of midges. To obtain correlations in an active matter system from first principles, we derive a ring-kinetic theory for Vicsek-style models of self-propelled agents from the exact N-particle evolution equation in phase space. The theory goes beyond mean-field and does not rely on Boltzmann's approximation of molecular chaos. It can handle precollisional correlations and cluster formation, which are both important to understand the phase transition to collective motion. We propose a diagrammatic technique to perform a small-density expansion of the collision operator and derive the first two equations of the Bogoliubov-Born-Green-Kirkwood-Yvon (BBGKY) hierarchy. An algorithm is presented that numerically solves the evolution equation for the two-particle correlations on a lattice. Agent-based simulations are performed and informative quantities such as orientational and density correlation functions are compared with those obtained by ring-kinetic theory. Excellent quantitative agreement between simulations and theory is found at not-too-small noises and mean free paths. This shows that there are parameter ranges in Vicsek-like models where the correlated closure of the BBGKY hierarchy gives correct and nontrivial results. We calculate the dependence of the orientational correlations on distance in the disordered phase and find that it seems to be consistent with a power law with an exponent around -1.8, followed by an exponential decay. General limitations of the kinetic theory and its numerical solution are discussed.

Influence of resonant collisions on the self-broadening of acetylene

NASA Astrophysics Data System (ADS)

Lehmann, Kevin K.

2017-03-01

Iwakuni et al. [Phys. Rev. Lett. 117, 143902 (2016)] have reported an ortho-para alternation of ˜10% in the self pressure broadening coefficients for ro-vibrational lines of the C2H2 transitions in the ν1+ν3 C-H (local mode) overtone band near 197 THz (1.52 μm). These authors attributed this effect to the contribution of resonant collisions, where the rotational energy change of one molecule is exactly compensated by the rotational energy change of its collision partner. Resonant collisions are known to be important in the case of self pressure broadening of highly polar molecules, such as HCN, but have not previously been invoked in the case of nonpolar molecules, such as acetylene, where the long range potential is dominated by the quadrupole-quadrupole electrostatic interaction. In the present work, the simple semiclassical Anderson-theory approach is used to estimate the rates of C2H2-C2H2 rotationally inelastic collisions and these used to predict pressure broadening rates, ignoring other contributions to the broadening, which should not have resonant enhancements. It is found that exactly resonant collisions do not make a major contribution to the broadening and these calculations predict an ortho-para alternation of the pressure broadening coefficients far below what was inferred by Iwakuni et al. The present results are consistent with a large body of published work that reported self-broadening coefficients of C2H2 ro-vibrational transitions that found negligible dependence on the vibrational transition and no even-odd alternation, even for Q and S branch transitions where any such effect is predicted to be much larger than for the P and R branch transitions studied by Iwakuni et al.

Use of face masks in a primary care outpatient setting in Hong Kong: Knowledge, attitudes and practices.

PubMed

Ho, H S W

2012-12-01

To assess if a knowledge gap exists in the correct use of face masks, and to explore the correlations between knowledge, attitudes and practices regarding the use of face masks among outpatients and their caregivers in an outpatient clinic in Hong Kong. Cross-sectional study. Outpatients and their caregivers who were present at an outpatient setting in Hong Kong were invited to participate in this survey. All participants were asked to complete a self-administered closed-ended questionnaire about their knowledge, attitudes and practices regarding the use of face masks. Data were described using descriptive statistics and correlation coefficients. Among the 399 respondents, 52% knew the correct steps in wearing a face mask, and their attitudes toward face masks were generally positive. Further analyses showed that respondents were more likely to wear a face mask at a clinic than in a public place or at home. Moreover, respondents were more likely to wear a face mask to protect others against influenza-like illness (ILI) than for self-protection. There was low to moderate correlation between attitudes and practices (correlation coefficient 0.26, P < 0.05). This study identified a knowledge gap in the correct use of face masks among outpatients and their caregivers; attitudes and practices regarding the use of face masks were generally positive, but correlation was not high. It is recommended that public health education campaigns should tailor efficient programmes to combat ILI transmission among outpatient clinic populations by improving knowledge about the correct use of face masks. Copyright © 2012 The Royal Society for Public Health. Published by Elsevier Ltd. All rights reserved.

High-pressure phase diagram of hydrogen and deuterium sulfides from first principles: Structural and vibrational properties including quantum and anharmonic effects

NASA Astrophysics Data System (ADS)

Bianco, Raffaello; Errea, Ion; Calandra, Matteo; Mauri, Francesco

2018-06-01

We study the structural and vibrational properties of the high-temperature superconducting sulfur trihydride and trideuteride in the high-pressure I m 3 ¯m and R 3 m phases by first-principles density-functional-theory calculations. On lowering pressure, the rhombohedral transition I m 3 ¯m →R 3 m is expected, with hydrogen-bond desymmetrization and occurrence of trigonal lattice distortion. With both Perdew-Burke-Ernzerhof (PBE) and Becke-Lee-Yang-Parr (BLYP) exchange-correlation functional, in hydrostatic conditions we find that, contrary to what is suggested in some recent experiments, if the rhombohedral distortion exists it affects mainly the hydrogen bonds, whereas the resulting cell distortion is minimal. We estimate that the occurrence of a stress anisotropy of approximately 10 % could explain this discrepancy. Assuming hydrostatic conditions, we calculate the critical pressure at which the rhombohedral transition occurs. Quantum and anharmonic effects, which are relevant in this system, are included at nonperturbative level with the stochastic self-consistent harmonic approximation. Within this approach, we determine the transition pressure by calculating the free-energy Hessian, a method that allows to estimate the critical pressure with much higher precision (and much lower computational cost) compared with the free-energy "finite-difference" approach previously used. Using PBE and BLYP, we find that quantum anharmonic effects are responsible for a strong reduction of the critical pressure with respect to the one obtained with the classical harmonic approach. Interestingly, for the two functionals, even if the transition pressures at classical harmonic level differ by 83 GPa, the transition pressures including quantum anharmonic effects differ only by 23 GPa. Moreover, we observe a prominent isotope effect, as we estimate higher transition pressure for D3S than for H3S . Finally, within the stochastic self-consistent harmonic approximation, with PBE we calculate the anharmonic phonon spectral functions in the I m 3 ¯m phase. The strong anharmonicity of the system is confirmed by the occurrence of very large anharmonic broadenings leading to complex non-Lorentzian line shapes. Generally, for the high-energy hydrogen bond-stretching modes, the anharmonic phonon broadening is of the same magnitude of the electron-phonon one. However, for the vibrational spectra at zone center, accessible, e.g., by infrared spectroscopy, the broadenings are very small (linewidth at most around 2 meV) and anharmonic phonon quasiparticles are well defined.

Ab initio potential energy and dipole moment surfaces of the F(-)(H2O) complex.

PubMed

Kamarchik, Eugene; Toffoli, Daniele; Christiansen, Ove; Bowman, Joel M

2014-02-05

We present full-dimensional, ab initio potential energy and dipole moment surfaces for the F(-)(H2O) complex. The potential surface is a permutationally invariant fit to 16,114 coupled-cluster single double (triple)/aVTZ energies, while the dipole surface is a covariant fit to 11,395 CCSD(T)/aVTZ dipole moments. Vibrational self-consistent field/vibrational configuration interaction (VSCF/VCI) calculations of energies and the IR-spectrum are presented both for F(-)(H2O) and for the deuterated analog, F(-)(D2O). A one-dimensional calculation of the splitting of the ground state, due to equivalent double-well global minima, is also reported. Copyright © 2013 Elsevier B.V. All rights reserved.

Giant number fluctuations in self-propelled particles without alignment

NASA Astrophysics Data System (ADS)

Fily, Yaouen; Henkes, Silke; Marchetti, M. Cristina

2012-02-01

Giant number fluctuations are a ubiquitous property of active systems. They were predicted using a generic continuum description of active nematics, and have been observed in simulations of Vicsek-type models and in experiments on vibrated granular layers and swimming bacteria. In all of these systems, there is an alignment interaction among the self-propelled units, either imposed as a rule, or arising from hydrodynamic or other medium-mediated couplings. Here we report numerical evidence of giant number fluctuations in a minimal model of self-propelled disks in two dimensions in the absence of any alignment mechanism. The direction of self-propulsion evolves via rotational diffusion and the particles interact solely via a finite range repulsive soft potential. It can be shown that in this system self propulsion is equivalent to a non Markovian noise whose correlation time is controlled by the amplitude of the orientational noise.

Wireless Network for Measurement of Whole-Body Vibration

PubMed Central

Koenig, Diogo; Chiaramonte, Marilda S.; Balbinot, Alexandre

2008-01-01

This article presents the development of a system integrated to a ZigBee network to measure whole-body vibration. The developed system allows distinguishing human vibrations of almost 400Hz in three axes with acceleration of almost 50g. The tests conducted in the study ensured the correct functioning of the system for the project's purpose. PMID:27879866

Body-induced vortical flows: a common mechanism for self-corrective trimming control in boxfishes.

PubMed

Bartol, Ian K; Gharib, Morteza; Webb, Paul W; Weihs, Daniel; Gordon, Malcolm S

2005-01-01

Boxfishes (Teleostei: Ostraciidae) are marine fishes having rigid carapaces that vary significantly among taxa in their shapes and structural ornamentation. We showed previously that the keels of the carapace of one species of tropical boxfish, the smooth trunkfish, produce leading edge vortices (LEVs) capable of generating self-correcting trimming forces during swimming. In this paper we show that other tropical boxfishes with different carapace shapes have similar capabilities. We conducted a quantitative study of flows around the carapaces of three morphologically distinct boxfishes (spotted boxfish, scrawled cowfish and buffalo trunkfish) using stereolithographic models and three separate but interrelated analytical approaches: digital particle image velocimetry (DPIV), pressure distribution measurements, and force balance measurements. The ventral keels of all three forms produced LEVs that grew in circulation along the bodies, resembling the LEVs produced around delta-winged aircraft. These spiral vortices formed above the keels and increased in circulation as pitch angle became more positive, and formed below the keels and increased in circulation as pitch angle became more negative. Vortices also formed along the eye ridges of all boxfishes. In the spotted boxfish, which is largely trapezoidal in cross section, consistent dorsal vortex growth posterior to the eye ridge was also present. When all three boxfishes were positioned at various yaw angles, regions of strongest concentrated vorticity formed in far-field locations of the carapace compared with near-field areas, and vortex circulation was greatest posterior to the center of mass. In general, regions of localized low pressure correlated well with regions of attached, concentrated vorticity, especially around the ventral keels. Although other features of the carapace also affect flow patterns and pressure distributions in different ways, the integrated effects of the flows were consistent for all forms: they produce trimming self-correcting forces, which we measured directly using the force balance. These data together with previous work on smooth trunkfish indicate that body-induced vortical flows are a common mechanism that is probably significant for trim control in all species of tropical boxfishes.

Implementation and benchmark of a long-range corrected functional in the density functional based tight-binding method

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

Lutsker, V.; Niehaus, T. A., E-mail: thomas.niehaus@physik.uni-regensburg.de; Aradi, B.

2015-11-14

Bridging the gap between first principles methods and empirical schemes, the density functional based tight-binding method (DFTB) has become a versatile tool in predictive atomistic simulations over the past years. One of the major restrictions of this method is the limitation to local or gradient corrected exchange-correlation functionals. This excludes the important class of hybrid or long-range corrected functionals, which are advantageous in thermochemistry, as well as in the computation of vibrational, photoelectron, and optical spectra. The present work provides a detailed account of the implementation of DFTB for a long-range corrected functional in generalized Kohn-Sham theory. We apply themore » method to a set of organic molecules and compare ionization potentials and electron affinities with the original DFTB method and higher level theory. The new scheme cures the significant overpolarization in electric fields found for local DFTB, which parallels the functional dependence in first principles density functional theory (DFT). At the same time, the computational savings with respect to full DFT calculations are not compromised as evidenced by numerical benchmark data.« less

Magnetic field shift due to mechanical vibration in functional magnetic resonance imaging.

PubMed

Foerster, Bernd U; Tomasi, Dardo; Caparelli, Elisabeth C

2005-11-01

Mechanical vibrations of the gradient coil system during readout in echo-planar imaging (EPI) can increase the temperature of the gradient system and alter the magnetic field distribution during functional magnetic resonance imaging (fMRI). This effect is enhanced by resonant modes of vibrations and results in apparent motion along the phase encoding direction in fMRI studies. The magnetic field drift was quantified during EPI by monitoring the resonance frequency interleaved with the EPI acquisition, and a novel method is proposed to correct the apparent motion. The knowledge on the frequency drift over time was used to correct the phase of the k-space EPI dataset. Since the resonance frequency changes very slowly over time, two measurements of the resonance frequency, immediately before and after the EPI acquisition, are sufficient to remove the field drift effects from fMRI time series. The frequency drift correction method was tested "in vivo" and compared to the standard image realignment method. The proposed method efficiently corrects spurious motion due to magnetic field drifts during fMRI. (c) 2005 Wiley-Liss, Inc.

Phonon dispersions, band structures, and dielectric functions of BeO and BeS polymorphs

NASA Astrophysics Data System (ADS)

Wang, Ke-Long; Gao, Shang-Peng

2018-07-01

Structures, phonon dispersions, electronic structures, and dielectric functions of beryllium oxide (BeO) and beryllium sulfide (BeS) polymorphs are investigated by density functional theory and many-body perturbation theory. Phonon calculations indicate that both wurtzite (w-) and zincblende (zb-) structures are dynamically stable for BeO and BeS, whereas rocksalt (rs-) structures for both BeO and BeS have imaginary phonon frequencies and thus are dynamically unstable at zero pressure. Band structures for the 4 dynamically stable phases show that only w-BeO has a direct band gap. Both the one-shot G0W0 and quasiparticle self-consistent GW methods are used to correct band energies at high symmetry k-points. Bethe-Salpeter equation (BSE), which considers Coulomb correlated electron-hole pairs, is employed to deal with the computation of macroscopic dielectric functions. It is shown that BSE calculation, employing scissors operator derived by self-consistent GW method, can give dielectric functions agreeing very well with experimental measurement of w-BeO. Weak anisotropic characters can be observed for w-BeO and w-BeS. Both zb-BeS and w-BeS show high optical transition probabilities within a narrow ultraviolet energy range.

Similarity-transformed equation-of-motion vibrational coupled-cluster theory.

PubMed

Faucheaux, Jacob A; Nooijen, Marcel; Hirata, So

2018-02-07

A similarity-transformed equation-of-motion vibrational coupled-cluster (STEOM-XVCC) method is introduced as a one-mode theory with an effective vibrational Hamiltonian, which is similarity transformed twice so that its lower-order operators are dressed with higher-order anharmonic effects. The first transformation uses an exponential excitation operator, defining the equation-of-motion vibrational coupled-cluster (EOM-XVCC) method, and the second uses an exponential excitation-deexcitation operator. From diagonalization of this doubly similarity-transformed Hamiltonian in the small one-mode excitation space, the method simultaneously computes accurate anharmonic vibrational frequencies of all fundamentals, which have unique significance in vibrational analyses. We establish a diagrammatic method of deriving the working equations of STEOM-XVCC and prove their connectedness and thus size-consistency as well as the exact equality of its frequencies with the corresponding roots of EOM-XVCC. We furthermore elucidate the similarities and differences between electronic and vibrational STEOM methods and between STEOM-XVCC and vibrational many-body Green's function theory based on the Dyson equation, which is also an anharmonic one-mode theory. The latter comparison inspires three approximate STEOM-XVCC methods utilizing the common approximations made in the Dyson equation: the diagonal approximation, a perturbative expansion of the Dyson self-energy, and the frequency-independent approximation. The STEOM-XVCC method including up to the simultaneous four-mode excitation operator in a quartic force field and its three approximate variants are formulated and implemented in computer codes with the aid of computer algebra, and they are applied to small test cases with varied degrees of anharmonicity.

Similarity-transformed equation-of-motion vibrational coupled-cluster theory

NASA Astrophysics Data System (ADS)

Faucheaux, Jacob A.; Nooijen, Marcel; Hirata, So

2018-02-01

A similarity-transformed equation-of-motion vibrational coupled-cluster (STEOM-XVCC) method is introduced as a one-mode theory with an effective vibrational Hamiltonian, which is similarity transformed twice so that its lower-order operators are dressed with higher-order anharmonic effects. The first transformation uses an exponential excitation operator, defining the equation-of-motion vibrational coupled-cluster (EOM-XVCC) method, and the second uses an exponential excitation-deexcitation operator. From diagonalization of this doubly similarity-transformed Hamiltonian in the small one-mode excitation space, the method simultaneously computes accurate anharmonic vibrational frequencies of all fundamentals, which have unique significance in vibrational analyses. We establish a diagrammatic method of deriving the working equations of STEOM-XVCC and prove their connectedness and thus size-consistency as well as the exact equality of its frequencies with the corresponding roots of EOM-XVCC. We furthermore elucidate the similarities and differences between electronic and vibrational STEOM methods and between STEOM-XVCC and vibrational many-body Green's function theory based on the Dyson equation, which is also an anharmonic one-mode theory. The latter comparison inspires three approximate STEOM-XVCC methods utilizing the common approximations made in the Dyson equation: the diagonal approximation, a perturbative expansion of the Dyson self-energy, and the frequency-independent approximation. The STEOM-XVCC method including up to the simultaneous four-mode excitation operator in a quartic force field and its three approximate variants are formulated and implemented in computer codes with the aid of computer algebra, and they are applied to small test cases with varied degrees of anharmonicity.

Development of hardware system using temperature and vibration maintenance models integration concepts for conventional machines monitoring: a case study

NASA Astrophysics Data System (ADS)

Adeyeri, Michael Kanisuru; Mpofu, Khumbulani; Kareem, Buliaminu

2016-03-01

This article describes the integration of temperature and vibration models for maintenance monitoring of conventional machinery parts in which their optimal and best functionalities are affected by abnormal changes in temperature and vibration values thereby resulting in machine failures, machines breakdown, poor quality of products, inability to meeting customers' demand, poor inventory control and just to mention a few. The work entails the use of temperature and vibration sensors as monitoring probes programmed in microcontroller using C language. The developed hardware consists of vibration sensor of ADXL345, temperature sensor of AD594/595 of type K thermocouple, microcontroller, graphic liquid crystal display, real time clock, etc. The hardware is divided into two: one is based at the workstation (majorly meant to monitor machines behaviour) and the other at the base station (meant to receive transmission of machines information sent from the workstation), working cooperatively for effective functionalities. The resulting hardware built was calibrated, tested using model verification and validated through principles pivoted on least square and regression analysis approach using data read from the gear boxes of extruding and cutting machines used for polyethylene bag production. The results got therein confirmed related correlation existing between time, vibration and temperature, which are reflections of effective formulation of the developed concept.

Communication: The description of strong correlation within self-consistent Green's function second-order perturbation theory

NASA Astrophysics Data System (ADS)

Phillips, Jordan J.; Zgid, Dominika

2014-06-01

We report an implementation of self-consistent Green's function many-body theory within a second-order approximation (GF2) for application with molecular systems. This is done by iterative solution of the Dyson equation expressed in matrix form in an atomic orbital basis, where the Green's function and self-energy are built on the imaginary frequency and imaginary time domain, respectively, and fast Fourier transform is used to efficiently transform these quantities as needed. We apply this method to several archetypical examples of strong correlation, such as a H32 finite lattice that displays a highly multireference electronic ground state even at equilibrium lattice spacing. In all cases, GF2 gives a physically meaningful description of the metal to insulator transition in these systems, without resorting to spin-symmetry breaking. Our results show that self-consistent Green's function many-body theory offers a viable route to describing strong correlations while remaining within a computationally tractable single-particle formalism.

The event-related potential effects of cognitive conflict in a Chinese character-generation task.

PubMed

Qiu, Jiang; Zhang, Qinglin; Li, Hong; Luo, Yuejia; Yin, Qinging; Chen, Antao; Yuan, Hong

2007-06-11

High-density event-related potentials were recorded to examine the electrophysiologic correlates of the evaluation of possible answers provided during a Chinese character-generation task. We examined three conditions: the character given was what participants initially generated (Consistent answer), the character given was correct (Unexpected Correct answer), or it was incorrect (Unexpected Incorrect answer). Results showed that Unexpected Correct and Incorrect answers elicited a more negative event-related potential deflection (N320) than did Consistent answers between 300 and 400 ms. Dipole source analysis of difference waves (Unexpected Correct or Incorrect minus Consistent answers) localized the generator of the N320 in the anterior cingulate cortex. The N320 therefore likely reflects the cognitive change or conflict between old and new ways of thinking while identifying and judging characters.

Elders Health Empowerment Scale: Spanish adaptation and psychometric analysis.

PubMed

Serrani Azcurra, Daniel Jorge Luis

2014-01-01

Empowerment refers to patient skills that allow them to become primary decision-makers in control of daily self-management of health problems. As important the concept as it is, particularly for elders with chronic diseases, few available instruments have been validated for use with Spanish speaking people. Translate and adapt the Health Empowerment Scale (HES) for a Spanish-speaking older adults sample and perform its psychometric validation. The HES was adapted based on the Diabetes Empowerment Scale-Short Form. Where "diabetes" was mentioned in the original tool, it was replaced with "health" terms to cover all kinds of conditions that could affect health empowerment. Statistical and Psychometric Analyses were conducted on 648 urban-dwelling seniors. The HES had an acceptable internal consistency with a Cronbach's α of 0.89. The convergent validity was supported by significant Pearson's Coefficient correlations between the HES total and item scores and the General Self Efficacy Scale (r= 0.77), Swedish Rheumatic Disease Empowerment Scale (r= 0.69) and Making Decisions Empowerment Scale (r= 0.70). Construct validity was evaluated using item analysis, half-split test and corrected item to total correlation coefficients; with good internal consistency (α> 0.8). The content validity was supported by Scale and Item Content Validity Index of 0.98 and 1.0, respectively. HES had acceptable face validity and reliability coefficients; which added to its ease administration and users' unbiased comprehension, could set it as a suitable tool in evaluating elder's outpatient empowerment-based medical education programs.

Elders Health Empowerment Scale

PubMed Central

2014-01-01

Introduction: Empowerment refers to patient skills that allow them to become primary decision-makers in control of daily self-management of health problems. As important the concept as it is, particularly for elders with chronic diseases, few available instruments have been validated for use with Spanish speaking people. Objective: Translate and adapt the Health Empowerment Scale (HES) for a Spanish-speaking older adults sample and perform its psychometric validation. Methods: The HES was adapted based on the Diabetes Empowerment Scale-Short Form. Where "diabetes" was mentioned in the original tool, it was replaced with "health" terms to cover all kinds of conditions that could affect health empowerment. Statistical and Psychometric Analyses were conducted on 648 urban-dwelling seniors. Results: The HES had an acceptable internal consistency with a Cronbach's α of 0.89. The convergent validity was supported by significant Pearson's Coefficient correlations between the HES total and item scores and the General Self Efficacy Scale (r= 0.77), Swedish Rheumatic Disease Empowerment Scale (r= 0.69) and Making Decisions Empowerment Scale (r= 0.70). Construct validity was evaluated using item analysis, half-split test and corrected item to total correlation coefficients; with good internal consistency (α> 0.8). The content validity was supported by Scale and Item Content Validity Index of 0.98 and 1.0, respectively. Conclusions: HES had acceptable face validity and reliability coefficients; which added to its ease administration and users' unbiased comprehension, could set it as a suitable tool in evaluating elder's outpatient empowerment-based medical education programs. PMID:25767307

Neurobiology of Insight Deficits in Schizophrenia: An fMRI Study

PubMed Central

Shad, Mujeeb U.; Keshavan, Matcheri S.

2015-01-01

Prior research has shown insight deficits in schizophrenia to be associated with specific neuroimaging changes (primarily structural) especially in the prefrontal sub-regions. However, little is known about the functional correlates of impaired insight. Seventeen patients with schizophrenia (mean age 40.0±10.3; M/F= 14/3) underwent fMRI on a Philips 3.0 T Achieva system while performing on a self-awareness task containing self- vs. other-directed sentence stimuli. SPM5 was used to process the imaging data. Preprocessing consisted of realignment, coregistration, and normalization, and smoothing. A regression analysis was used to examine the relationship between brain activation in response to self-directed versus other-directed sentence stimuli and average scores on behavioral measures of awareness of symptoms and attribution of symptoms to the illness from Scale to Assess Unawareness of Mental Disorders. Family Wise Error correction was employed in the fMRI analysis. Average scores on awareness of symptoms (1 = aware; 5 = unaware) were associated with activation of multiple brain regions, including prefrontal, parietal and limbic areas as well as basal ganglia. However, average scores on correct attribution of symptoms (1 = attribute; 5 = misattribute) were associated with relatively more localized activation of prefrontal cortex and basal ganglia. These findings suggest that unawareness and misattribution of symptoms may have different neurobiological basis in schizophrenia. While symptom unawareness may be a function of a more complex brain network, symptom misattribution may be mediated by specific brain regions. PMID:25957484

DFT simulations and vibrational spectra of 2-amino-2-methyl-1,3-propanediol

NASA Astrophysics Data System (ADS)

Renuga Devi, T. S.; Sharmi kumar, J.; Ramkumaar, G. R.

2014-12-01

The FTIR and FT-Raman spectra of 2-amino-2-methyl-1,3-propanediol were recorded in the regions 4000-400 cm-1 and 4000-50 cm-1 respectively. The structural and spectroscopic data of the molecule in the ground state were calculated using Hartee-Fock and density functional method (B3LYP) with the augmented-correlation consistent-polarized valence double zeta (aug-cc-pVDZ) basis set. The most stable conformer was optimized and the structural and vibrational parameters were determined based on this. The complete assignments were performed on the basis of the Potential Energy Distribution (PED) of the vibrational modes, calculated using Vibrational Energy Distribution Analysis (VEDA) 4 program. With the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. Thermodynamic properties and Mulliken charges were calculated using both Hartee-Fock and density functional method using the aug-cc-pVDZ basis set and compared. The calculated HOMO-LUMO energy gap revealed that charge transfer occurs within the molecule. 1H and 13C NMR chemical shifts of the molecule were calculated using Gauge-Independent Atomic Orbital (GIAO) method and were compared with experimental results.

Atomic motion from the mean square displacement in a monatomic liquid

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

Wallace, Duane C.; De Lorenzi-Venneri, Giulia; Chisolm, Eric D.

V-T theory is constructed in the many-body Hamiltonian formulation, and is being developed as a novel approach to liquid dynamics theory. In this theory the liquid atomic motion consists of two contributions, normal mode vibrations in a single representative potential energy valley, and transits, which carry the system across boundaries between valleys. The mean square displacement time correlation function (the MSD) is a direct measure of the atomic motion, and our goal is to determine if the V-T formalism can produce a physically sensible account of this motion. We employ molecular dynamics (MD) data for a system representing liquid Na,more » and find the motion evolves in three successive time intervals: on the first 'vibrational' interval, the vibrational motion alone gives a highly accurate account of the MD data; on the second 'crossover' interval, the vibrational MSD saturates to a constant while the transit motion builds up from zero; on the third 'random walk' interval, the transit motion produces a purely diffusive random walk of the vibrational equilibrium positions. Furthermore, this motional evolution agrees with, and adds refinement to, the MSD atomic motion as described by current liquid dynamics theories.« less

Atomic motion from the mean square displacement in a monatomic liquid

DOE PAGES

Wallace, Duane C.; De Lorenzi-Venneri, Giulia; Chisolm, Eric D.

2016-04-08

V-T theory is constructed in the many-body Hamiltonian formulation, and is being developed as a novel approach to liquid dynamics theory. In this theory the liquid atomic motion consists of two contributions, normal mode vibrations in a single representative potential energy valley, and transits, which carry the system across boundaries between valleys. The mean square displacement time correlation function (the MSD) is a direct measure of the atomic motion, and our goal is to determine if the V-T formalism can produce a physically sensible account of this motion. We employ molecular dynamics (MD) data for a system representing liquid Na,more » and find the motion evolves in three successive time intervals: on the first 'vibrational' interval, the vibrational motion alone gives a highly accurate account of the MD data; on the second 'crossover' interval, the vibrational MSD saturates to a constant while the transit motion builds up from zero; on the third 'random walk' interval, the transit motion produces a purely diffusive random walk of the vibrational equilibrium positions. Furthermore, this motional evolution agrees with, and adds refinement to, the MSD atomic motion as described by current liquid dynamics theories.« less

The Caregiver Contribution to Heart Failure Self-Care (CACHS): Further Psychometric Testing of a Novel Instrument.

PubMed

Buck, Harleah G; Harkness, Karen; Ali, Muhammad Usman; Carroll, Sandra L; Kryworuchko, Jennifer; McGillion, Michael

2017-04-01

Caregivers (CGs) contribute important assistance with heart failure (HF) self-care, including daily maintenance, symptom monitoring, and management. Until CGs' contributions to self-care can be quantified, it is impossible to characterize it, account for its impact on patient outcomes, or perform meaningful cost analyses. The purpose of this study was to conduct psychometric testing and item reduction on the recently developed 34-item Caregiver Contribution to Heart Failure Self-care (CACHS) instrument using classical and item response theory methods. Fifty CGs (mean age 63 years ±12.84; 70% female) recruited from a HF clinic completed the CACHS in 2014 and results evaluated using classical test theory and item response theory. Items would be deleted for low (<.05) or high (>.95) endorsement, low (<.3) or high (>.7) corrected item-total correlations, significant pairwise correlation coefficients, floor or ceiling effects, relatively low latent trait and item information function levels (<1.5 and p > .5), and differential item functioning. After analysis, 14 items were excluded, resulting in a 20-item instrument (self-care maintenance eight items; monitoring seven items; and management five items). Most items demonstrated moderate to high discrimination (median 2.13, minimum .77, maximum 5.05), and appropriate item difficulty (-2.7 to 1.4). Internal consistency reliability was excellent (Cronbach α = .94, average inter-item correlation = .41) with no ceiling effects. The newly developed 20-item version of the CACHS is supported by rigorous instrument development and represents a novel instrument to measure CGs' contribution to HF self-care. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Brain activation during self- and other-reflection in bipolar disorder with a history of psychosis: Comparison to schizophrenia

PubMed Central

Zhang, Liwen; Opmeer, Esther M.; Ruhé, Henricus G.; Aleman, André; van der Meer, Lisette

2015-01-01

Objectives Reflecting on the self and on others activates specific brain areas and contributes to metacognition and social cognition. The aim of the current study is to investigate brain activation during self- and other-reflection in patients with bipolar disorder (BD). In addition, we examined whether potential abnormal brain activation in BD patients could distinguish BD from patients with schizophrenia (SZ). Methods During functional magnetic resonance imaging (fMRI), 17 BD patients, 17 SZ patients and 21 healthy controls (HCs) performed a self-reflection task. The task consisted of sentences divided into three conditions: self-reflection, other-reflection and semantic control. Results BD patients showed less activation in the posterior cingulate cortex (PCC) extending to the precuneus during other-reflection compared to HCs (p = 0.028 FWE corrected on cluster-level within the regions of interest). In SZ patients, the level of activation in this area was in between BD patients and HCs, with no significant differences between patients with SZ and BD. There were no group differences in brain activation during self-reflection. Moreover, there was a positive correlation between the PCC/precuneus activation during other-reflection and cognitive insight in SZ patients, but not in BD patients. Conclusions BD patients showed less activation in the PCC/precuneus during other-reflection. This may support an account of impaired integration of emotion and memory (evaluation of past and current other-related information) in BD patients. Correlation differences of the PCC/precuneus activation with the cognitive insight in patients with BD and SZ might reflect an important difference between these disorders, which may help to further explore potentially distinguishing markers. PMID:26106544

Brain activation during self- and other-reflection in bipolar disorder with a history of psychosis: Comparison to schizophrenia.

PubMed

Zhang, Liwen; Opmeer, Esther M; Ruhé, Henricus G; Aleman, André; van der Meer, Lisette

2015-01-01

Reflecting on the self and on others activates specific brain areas and contributes to metacognition and social cognition. The aim of the current study is to investigate brain activation during self- and other-reflection in patients with bipolar disorder (BD). In addition, we examined whether potential abnormal brain activation in BD patients could distinguish BD from patients with schizophrenia (SZ). During functional magnetic resonance imaging (fMRI), 17 BD patients, 17 SZ patients and 21 healthy controls (HCs) performed a self-reflection task. The task consisted of sentences divided into three conditions: self-reflection, other-reflection and semantic control. BD patients showed less activation in the posterior cingulate cortex (PCC) extending to the precuneus during other-reflection compared to HCs (p = 0.028 FWE corrected on cluster-level within the regions of interest). In SZ patients, the level of activation in this area was in between BD patients and HCs, with no significant differences between patients with SZ and BD. There were no group differences in brain activation during self-reflection. Moreover, there was a positive correlation between the PCC/precuneus activation during other-reflection and cognitive insight in SZ patients, but not in BD patients. BD patients showed less activation in the PCC/precuneus during other-reflection. This may support an account of impaired integration of emotion and memory (evaluation of past and current other-related information) in BD patients. Correlation differences of the PCC/precuneus activation with the cognitive insight in patients with BD and SZ might reflect an important difference between these disorders, which may help to further explore potentially distinguishing markers.

Health State Monitoring of Bladed Machinery with Crack Growth Detection in BFG Power Plant Using an Active Frequency Shift Spectral Correction Method

PubMed Central

Sun, Weifang; Yao, Bin; He, Yuchao; Zeng, Nianyin; He, Wangpeng

2017-01-01

Power generation using waste-gas is an effective and green way to reduce the emission of the harmful blast furnace gas (BFG) in pig-iron producing industry. Condition monitoring of mechanical structures in the BFG power plant is of vital importance to guarantee their safety and efficient operations. In this paper, we describe the detection of crack growth of bladed machinery in the BFG power plant via vibration measurement combined with an enhanced spectral correction technique. This technique enables high-precision identification of amplitude, frequency, and phase information (the harmonic information) belonging to deterministic harmonic components within the vibration signals. Rather than deriving all harmonic information using neighboring spectral bins in the fast Fourier transform spectrum, this proposed active frequency shift spectral correction method makes use of some interpolated Fourier spectral bins and has a better noise-resisting capacity. We demonstrate that the identified harmonic information via the proposed method is of suppressed numerical error when the same level of noises is presented in the vibration signal, even in comparison with a Hanning-window-based correction method. With the proposed method, we investigated vibration signals collected from a centrifugal compressor. Spectral information of harmonic tones, related to the fundamental working frequency of the centrifugal compressor, is corrected. The extracted spectral information indicates the ongoing development of an impeller blade crack that occurred in the centrifugal compressor. This method proves to be a promising alternative to identify blade cracks at early stages. PMID:28792453

Indirect (source-free) integration method. II. Self-force consistent radial fall

NASA Astrophysics Data System (ADS)

Ritter, Patxi; Aoudia, Sofiane; Spallicci, Alessandro D. A. M.; Cordier, Stéphane

2016-12-01

We apply our method of indirect integration, described in Part I, at fourth order, to the radial fall affected by the self-force (SF). The Mode-Sum regularization is performed in the Regge-Wheeler gauge using the equivalence with the harmonic gauge for this orbit. We consider also the motion subjected to a self-consistent and iterative correction determined by the SF through osculating stretches of geodesics. The convergence of the results confirms the validity of the integration method. This work complements and justifies the analysis and the results appeared in [Int. J. Geom. Meth. Mod. Phys. 11 (2014) 1450090].

Interfacing the Ab initio multiple spawning method with electronic structure methods in GAMESS: Photodecay of trans-Azomethane

DOE PAGES

Gaenko, Alexander; DeFusco, Albert; Varganov, Sergey A.; ...

2014-10-20

This work presents a nonadiabatic molecular dynamics study of the nonradiative decay of photoexcited trans-azomethane, using the ab initio multiple spawning (AIMS) program that has been interfaced with the General Atomic and Molecular Electronic Structure System (GAMESS) quantum chemistry package for on-the-fly electronic structure evaluation. The interface strategy is discussed, and the capabilities of the combined programs are demonstrated with a nonadiabatic molecular dynamics study of the nonradiative decay of photoexcited trans-azomethane. Energies, gradients, and nonadiabatic coupling matrix elements were obtained with the state-averaged complete active space self-consistent field method, as implemented in GAMESS. The influence of initial vibrational excitationmore » on the outcome of the photoinduced isomerization is explored. Increased vibrational excitation in the CNNC torsional mode shortens the excited state lifetime. Depending on the degree of vibrational excitation, the excited state lifetime varies from ~60–200 fs. As a result, these short lifetimes are in agreement with time-resolved photoionization mass spectroscopy experiments.« less

Structural and vibrational properties of oxcarbazepine, an anticonvulsant substance by using DFT and SCRF calculations

NASA Astrophysics Data System (ADS)

Ladetto, María F.; Márquez, María B.; Brandán, Silvia A.

2014-10-01

In this work, we have presented a structural and vibrational study on the properties in gas and aqueous solution phases of oxcarbazepine, a polymorphic anticonvulsant substance, combining the available IR and Raman spectra with Density Functional Theory (DFT) calculations. Two stable C1 and C2 forms for the title molecule were theoretically determined by using the hybrid B3LYP/6-31G* method. The integral equation formalism variant polarised continuum model (IEFPCM) was employed to study the solvent effects by means of the self-consistent reaction field (SCRF) method. The vibrational spectra for the two forms of oxcarbazepine were completely assigned together with two dimeric species also observed in the solid phase. The presences of the two C1 and C2 forms together with the two dimeric species are supported by the IR and Raman bands between 1424 and 125 cm-1. Here, the properties for both forms of oxcarbazepine are compared and discussed.

Diagrammatic expansion for positive spectral functions beyond GW: Application to vertex corrections in the electron gas

NASA Astrophysics Data System (ADS)

Stefanucci, G.; Pavlyukh, Y.; Uimonen, A.-M.; van Leeuwen, R.

2014-09-01

We present a diagrammatic approach to construct self-energy approximations within many-body perturbation theory with positive spectral properties. The method cures the problem of negative spectral functions which arises from a straightforward inclusion of vertex diagrams beyond the GW approximation. Our approach consists of a two-step procedure: We first express the approximate many-body self-energy as a product of half-diagrams and then identify the minimal number of half-diagrams to add in order to form a perfect square. The resulting self-energy is an unconventional sum of self-energy diagrams in which the internal lines of half a diagram are time-ordered Green's functions, whereas those of the other half are anti-time-ordered Green's functions, and the lines joining the two halves are either lesser or greater Green's functions. The theory is developed using noninteracting Green's functions and subsequently extended to self-consistent Green's functions. Issues related to the conserving properties of diagrammatic approximations with positive spectral functions are also addressed. As a major application of the formalism we derive the minimal set of additional diagrams to make positive the spectral function of the GW approximation with lowest-order vertex corrections and screened interactions. The method is then applied to vertex corrections in the three-dimensional homogeneous electron gas by using a combination of analytical frequency integrations and numerical Monte Carlo momentum integrations to evaluate the diagrams.

Computing Wigner distributions and time correlation functions using the quantum thermal bath method: application to proton transfer spectroscopy.

PubMed

Basire, Marie; Borgis, Daniel; Vuilleumier, Rodolphe

2013-08-14

Langevin dynamics coupled to a quantum thermal bath (QTB) allows for the inclusion of vibrational quantum effects in molecular dynamics simulations at virtually no additional computer cost. We investigate here the ability of the QTB method to reproduce the quantum Wigner distribution of a variety of model potentials, designed to assess the performances and limits of the method. We further compute the infrared spectrum of a multidimensional model of proton transfer in the gas phase and in solution, using classical trajectories sampled initially from the Wigner distribution. It is shown that for this type of system involving large anharmonicities and strong nonlinear coupling to the environment, the quantum thermal bath is able to sample the Wigner distribution satisfactorily and to account for both zero point energy and tunneling effects. It leads to quantum time correlation functions having the correct short-time behavior, and the correct associated spectral frequencies, but that are slightly too overdamped. This is attributed to the classical propagation approximation rather than the generation of the quantized initial conditions themselves.

Interaction of monovalent cations with acetonitrile

NASA Astrophysics Data System (ADS)

Černušák, Ivan; Aranyosiová, Monika; Vollárová, Ol'ga; Velič, Dušan; Kirdajová, Ol'ga; Benko, Ján

Solvation of monovalent cations (Me+) of alkali metals=Na+, K+, Rb+, and Cs+, coinage metals=Cu+, Ag+, Au+, and p-block elements Ga+, In+, and Tl+ with acetonitrile was studied by means of ab initio calculations and time-of-flight secondary ion mass spectrometry (TOF-SIMS). The intermolecular interactions in the complexes Me+···CH3CN were investigated using the coupled clusters theory including single, double, and noniterative triple substitutions (CCSD(T)) in conjunction with the Pol and Pol-dk basis sets. The binding energies of these donor-acceptor complexes were estimated; taking into account the basis set superposition error, zero-point vibrations, correlation contribution, and scalar relativistic corrections. The theoretical ΔG0298 K values based on CCSD(T)/Pol and/or CCSD(T)/Pol-dk binding energies correlated well with experimental transfer Gibbs energies (from water to acetonitrile) for the series of cations. In the case of Au monocation, relativistic correction turned out to be extremely important. Composition of the complex of Ag+ and Na+ with acetonitrile was determined by using SIMS supporting both theoretical and experimental transfer Gibbs energies.

E2/M1 mixing ratios in transitions from the gamma vibrational bands to the ground state rotational bands of 102, 104, 106, 108Mo, 108, 110, 112Ru, and 112, 114, 116Pd

NASA Astrophysics Data System (ADS)

Eldridge, J. M.; Fenker, B.; Hamilton, J. H.; Goodin, C.; Zachary, C. J.; Wang, E.; Ramayya, A. V.; Daniel, A. V.; Ter-Akopian, G. M.; Oganessian, Yu. Ts.; Luo, Y. X.; Rasmussen, J. O.; Zhu, S. J.

2018-02-01

E2/ M1 mixing ratios have been measured for transitions from states in the γ vibrational bands ( I+_{γ}) to states in the ground state bands (I+ or [I-1]+) of the neutron rich, even-even, deformed isotopes, 102, 104, 106, 108Mo, 108, 110, 112Ru, and 112, 114, 116Pd, including from states as high as 9+_{γ}. These measurements were done using the GAMMASPHERE detector array, which, at the time of the experiment, had 101 working HPGe detectors, arranged at 64 different angles. A 62 μCi source of 252Cf was placed inside GAMMASPHERE yielding 5.7× 10^{11} γ-γ-γ and higher coincidence events. The angular correlations between the transitions from the γ-bands to the ground bands, and the pure E2 transitions within the ground band were then measured. These angular correlations yielded the mixing ratios, demonstrating that these transitions are pure or nearly pure E2, in agreement with theory. In order to correct for possible attenuation due to the lifetime of the intermediate state in these correlations, the g-factors of the intermediate states needed to be known. Therefore, the g-factors of the 2+ states in the ground state band have been measured.

Research of rotating machinery vibration parameters - Shaft speed relationship

NASA Astrophysics Data System (ADS)

Kostyukov, V. N.; Kostyukov, A. V.; Zaytsev, A. V.; Teterin, A. O.

2017-08-01

The paper considers the relationship between the parameters of the vibration arising in rotating machinery during operation and the shaft speed. The goal of this paper is to determine the dependence of the vibration parameters on the shaft speed for solving applied engineering problems. To properly evaluate the technical condition of bearing assemblies, we should take into account the pattern of the rotating machinery vibration parameters-shaft speed relationship, which will allow creating new diagnostic features, the totality of which will ensure an increased reliability of diagnosis. We took the check for a correlation between the factor and resultative feature parameters as the correlation analysis method. A high pair linear correlation between the diagnostic features (acceleration, velocity, displacement) and the shaft speed was determined on the basis of the check for correlation between the vibration parameters and the shaft speed, and also the linear correlation coefficients can be used to solve the applied engineering problems of diagnosing the bearing assemblies of the rotating machinery.

Consistency of Pilot Trainee Cognitive Ability, Personality, and Training Performance in Undergraduate Pilot Training

DTIC Science & Technology

2013-09-09

multivariate correction method (Lawley, 1943) was used for all scores except the MAB FSIQ which used the univariate ( Thorndike , 1949) method. FSIQ... Thorndike , R. L. (1949). Personnel selection. NY: Wiley. Tupes, E. C., & Christal, R. C. (1961). Recurrent personality factors based on trait ratings... Thorndike , 1949). aThe correlations for 1995 were not corrected due to the small sample size (N = 17). *p< .05 Consistency of Pilot Attributes

High speed thin plate fatigue crack monitor

NASA Technical Reports Server (NTRS)

Wincheski, Buzz A. (Inventor); Heyman, Joseph S. (Inventor); Namkung, Min (Inventor); Fulton, James P. (Inventor)

1996-01-01

A device and method are provided which non-destructively detect crack length and crack geometry in thin metallic plates. A non-contacting vibration apparatus produces resonant vibrations without introducing extraneous noise. Resulting resonant vibration shifts in cracked plates are correlated to known crack length in plates with similar resonant vibration shifts. In addition, acoustic emissions of cracks at resonance frequencies are correlated to acoustic emissions from known crack geometries.

Reliability of adapted version of Italian Label tobacco Impact Index for the adolescent: ALII.

PubMed

Guerra, F; Mannocci, A; Colamesta, V; De Luca, G; Fiore, M; Firenze, A; Ferrara, M; Langiano, E; De Vito, E; Bonaccorsi, G; La Torre, G

2017-01-01

The aim of this study is to assess the reliability of the Adolescent Label Impact Index (ALII) , it is an adolescent adapted version of Italian LII of the tobacco products warnings. A sample including students aged 13-15 years was considered. The ALII is constructed by 4 items: salience, harm, quitting and forgo. The questionnaire was self-administered to study participants twice with 3 days between each administration (T1 and T2) to measure reliability. The internal consistency using Cronbach's alpha and Corrected Item-Total Correlations (CITC) and the test-retest reliability applying Pearson's correlation were computed. Cronbach's alpha ranges from 0.625 at T1 to 0.715 at T2. The "salience" resulted the item with the lowest CITC value (=0.281). The Pearson's coefficient was r=0.909 (p<0.001). The instruments is low in cost and easy to administer and analyses in a setting people aged 13-15 years. The ALII shown an acceptable consistency and excellent stability over time. However, attention has to be paid when the ALII is administered to the no smoking teens and who has never seen the tobacco product labels to allow an appropriate interpretation of the data collected.

Self-consistent mean-field approach to the statistical level density in spherical nuclei

NASA Astrophysics Data System (ADS)

Kolomietz, V. M.; Sanzhur, A. I.; Shlomo, S.

2018-06-01

A self-consistent mean-field approach within the extended Thomas-Fermi approximation with Skyrme forces is applied to the calculations of the statistical level density in spherical nuclei. Landau's concept of quasiparticles with the nucleon effective mass and the correct description of the continuum states for the finite-depth potentials are taken into consideration. The A dependence and the temperature dependence of the statistical inverse level-density parameter K is obtained in a good agreement with experimental data.

Extension of the KLI approximation toward the exact optimized effective potential.

PubMed

Iafrate, G J; Krieger, J B

2013-03-07

The integral equation for the optimized effective potential (OEP) is utilized in a compact form from which an accurate OEP solution for the spin-unrestricted exchange-correlation potential, Vxcσ, is obtained for any assumed orbital-dependent exchange-correlation energy functional. The method extends beyond the Krieger-Li-Iafrate (KLI) approximation toward the exact OEP result. The compact nature of the OEP equation arises by replacing the integrals involving the Green's function terms in the traditional OEP equation by an equivalent first-order perturbation theory wavefunction often referred to as the "orbital shift" function. Significant progress is then obtained by solving the equation for the first order perturbation theory wavefunction by use of Dalgarno functions which are determined from well known methods of partial differential equations. The use of Dalgarno functions circumvents the need to explicitly address the Green's functions and the associated problems with "sum over states" numerics; as well, the Dalgarno functions provide ease in dealing with inherent singularities arising from the origin and the zeros of the occupied orbital wavefunctions. The Dalgarno approach for finding a solution to the OEP equation is described herein, and a detailed illustrative example is presented for the special case of a spherically symmetric exchange-correlation potential. For the case of spherical symmetry, the relevant Dalgarno function is derived by direct integration of the appropriate radial equation while utilizing a user friendly method which explicitly treats the singular behavior at the origin and at the nodal singularities arising from the zeros of the occupied states. The derived Dalgarno function is shown to be an explicit integral functional of the exact OEP Vxcσ, thus allowing for the reduction of the OEP equation to a self-consistent integral equation for the exact exchange-correlation potential; the exact solution to this integral equation can be determined by iteration with the natural zeroth order correction given by the KLI exchange-correlation potential. Explicit analytic results are provided to illustrate the first order iterative correction beyond the KLI approximation. The derived correction term to the KLI potential explicitly involves spatially weighted products of occupied orbital densities in any assumed orbital-dependent exchange-correlation energy functional; as well, the correction term is obtained with no adjustable parameters. Moreover, if the equation for the exact optimized effective potential is further iterated, one can obtain the OEP as accurately as desired.

Extension of the KLI approximation toward the exact optimized effective potential

NASA Astrophysics Data System (ADS)

Iafrate, G. J.; Krieger, J. B.

2013-03-01

The integral equation for the optimized effective potential (OEP) is utilized in a compact form from which an accurate OEP solution for the spin-unrestricted exchange-correlation potential, Vxcσ, is obtained for any assumed orbital-dependent exchange-correlation energy functional. The method extends beyond the Krieger-Li-Iafrate (KLI) approximation toward the exact OEP result. The compact nature of the OEP equation arises by replacing the integrals involving the Green's function terms in the traditional OEP equation by an equivalent first-order perturbation theory wavefunction often referred to as the "orbital shift" function. Significant progress is then obtained by solving the equation for the first order perturbation theory wavefunction by use of Dalgarno functions which are determined from well known methods of partial differential equations. The use of Dalgarno functions circumvents the need to explicitly address the Green's functions and the associated problems with "sum over states" numerics; as well, the Dalgarno functions provide ease in dealing with inherent singularities arising from the origin and the zeros of the occupied orbital wavefunctions. The Dalgarno approach for finding a solution to the OEP equation is described herein, and a detailed illustrative example is presented for the special case of a spherically symmetric exchange-correlation potential. For the case of spherical symmetry, the relevant Dalgarno function is derived by direct integration of the appropriate radial equation while utilizing a user friendly method which explicitly treats the singular behavior at the origin and at the nodal singularities arising from the zeros of the occupied states. The derived Dalgarno function is shown to be an explicit integral functional of the exact OEP Vxcσ, thus allowing for the reduction of the OEP equation to a self-consistent integral equation for the exact exchange-correlation potential; the exact solution to this integral equation can be determined by iteration with the natural zeroth order correction given by the KLI exchange-correlation potential. Explicit analytic results are provided to illustrate the first order iterative correction beyond the KLI approximation. The derived correction term to the KLI potential explicitly involves spatially weighted products of occupied orbital densities in any assumed orbital-dependent exchange-correlation energy functional; as well, the correction term is obtained with no adjustable parameters. Moreover, if the equation for the exact optimized effective potential is further iterated, one can obtain the OEP as accurately as desired.

An ab initio study of the C3(+) cation using multireference methods

NASA Technical Reports Server (NTRS)

Taylor, Peter R.; Martin, J. M. L.; Francois, J. P.; Gijbels, R.

1991-01-01

The energy difference between the linear 2 sigma(sup +, sub u) and cyclic 2B(sub 2) structures of C3(+) has been investigated using large (5s3p2d1f) basis sets and multireference electron correlation treatments, including complete active space self consistent fields (CASSCF), multireference configuration interaction (MRCI), and averaged coupled-pair functional (ACPF) methods, as well as the single-reference quadratic configuration interaction (QCISD(T)) method. Our best estimate, including a correction for basis set incompleteness, is that the linear form lies above the cyclic from by 5.2(+1.5 to -1.0) kcal/mol. The 2 sigma(sup +, sub u) state is probably not a transition state, but a local minimum. Reliable computation of the cyclic/linear energy difference in C3(+) is extremely demanding of the electron correlation treatment used: of the single-reference methods previously considered, CCSD(T) and QCISD(T) perform best. The MRCI + Q(0.01)/(4s2p1d) energy separation of 1.68 kcal/mol should provide a comparison standard for other electron correlation methods applied to this system.

Summary of the modeling and test correlations of a NASTRAN finite element vibrations model for the AH-1G helicopter, task 1

NASA Technical Reports Server (NTRS)

Cronkhite, J. D.; Berry, V. L.; Dompka, R. V.

1987-01-01

The AH-1G NASTRAN finite element model (FEM) is described and the correlations with measured data that were conducted to verify the model are summarized. Comparisons of the AH-1G NASTRAN FEM calculations with measured data include the following: (1) fuselage and tailboom static load deflection (stiffness) testing, (2) airframe ground vibration testing (0-30 H<), (3) airframe flight vibration testing (main rotor, 2,4, and 6/rev), and (4) tailboom effective skin static testing. A description of the modeling rationale and techniques used to develop the NASTRAN FEM is presented in conjunction with all previous correlation work. In general, the correlations show good agreement between analysis and test in stiffness and vibration response through 15 to 20 Hz. For higher frequencies (equal to or greater than 4/rev (21.6 Hz)), the vibration responses generally did not agree well. Also, the lateral (2/rev (10.8 Hz)) flight vibration responses were much lower in the FEM than test, indicating that there is a significant excitation source other than at the main rotor hub that is affecting the lateral vibrations, such as downwash impingement on the vertical tail.

Nonlinear modal resonances in low-gravity slosh-spacecraft systems

NASA Technical Reports Server (NTRS)

Peterson, Lee D.

1991-01-01

Nonlinear models of low gravity slosh, when coupled to spacecraft vibrations, predict intense nonlinear eigenfrequency shifts at zero gravity. These nonlinear frequency shifts are due to internal quadratic and cubic resonances between fluid slosh modes and spacecraft vibration modes. Their existence has been verified experimentally, and they cannot be correctly modeled by approximate, uncoupled nonlinear models, such as pendulum mechanical analogs. These predictions mean that linear slosh assumptions for spacecraft vibration models can be invalid, and may lead to degraded control system stability and performance. However, a complete nonlinear modal analysis will predict the correct dynamic behavior. This paper presents the analytical basis for these results, and discusses the effect of internal resonances on the nonlinear coupled response at zero gravity.

Vibrational and thermal properties of β-HMX and TATB from dispersion corrected density functional theory

NASA Astrophysics Data System (ADS)

Landerville, Aaron C.; Oleynik, Ivan I.

2017-01-01

Dispersion Corrected Density Functional Theory (DFT+vdW) calculations are performed to predict vibrational and thermal properties of the bulk energetic materials (EMs) β-octahydrocyclotetramethylene-tetranitramine (β-HMX) and triaminotrinitrobenzene (TATB). DFT+vdW calculations of pressure-dependent crystal structure and the hydrostatic equation of state are followed by frozen-phonon calculations of their respective vibration spectra at each pressure. These are then used under the quasi-harmonic approximation to obtain zero-point and thermal free energy contributions to the pressure, resulting in pressure-volume-temperature (PVT) EOS for each material that are in excellent agreement with experiment. Heat capacities, and coefficients of thermal expansion as functions of temperature are also calculated and compared with experiment.

Candidate proof mass actuator control laws for the vibration suppression of a frame

NASA Technical Reports Server (NTRS)

Umland, Jeffrey W.; Inman, Daniel J.

1991-01-01

The vibration of an experimental flexible space truss is controlled with internal control forces produced by several proof mass actuators. Four candidate control law strategies are evaluated in terms of performance and robustness. These control laws are experimentally implemented on a quasi free-free planar truss. Sensor and actuator dynamics are included in the model such that the final closed loop is self-equilibrated. The first two control laws considered are based on direct output feedback and consist of tuning the actuator feedback gains to the lowest mode intended to receive damping. The first method feeds back only the position and velocity of the proof mass relative to the structure; this results in a traditional vibration absorber. The second method includes the same feedback paths as the first plus feedback of the local structural velocity. The third law is designed with robust H infinity control theory. The fourth strategy is an active implementation of a viscous damper, where the actuator is configured to provide a bending moment at two points on the structure. The vibration control system is then evaluated in terms of how it would benefit the space structure's position control system.

Vibration control for the ARGOS laser launch path

NASA Astrophysics Data System (ADS)

Peter, Diethard; Gässler, Wolfgang; Borelli, Jose; Barl, Lothar; Rabien, S.

2012-07-01

Present and future adaptive optics systems aim for the correction of the atmospheric turbulence over a large field of view combined with large sky coverage. To achieve this goal the telescope is equipped with multiple laser beacons. Still, to measure tip-tilt aberrations a natural guide star is used. For some fields such a tilt-star is not available and a correction on the laser beacons alone is applied. For this method to work well the laser beacons must not be affected by telescope vibrations on their up-link path. For the ARGOS system the jitter of the beacons is specified to be below 0.05. To achieve this goal a vibration compensation system is necessary to mitigate the mechanical disturbances. The ARGOS vibration compensation system is an accelerometer based feed forward system. The accelerometer measurements are fed into a real time controller. To achieve high performance the controller of the system is model based. The output is applied to a fast steering mirror. This paper presents the concept of the ARGOS vibration compensation, the hardware, and laboratory results.

Space Shuttle Crawler Transporter Vibration Analysis in Support of Rollout Fatigue Load Spectra Verification Program

NASA Technical Reports Server (NTRS)

Margasahayam, Ravi N.; Meyer, Karl A.; Nerolich, Shaun M.; Burton, Roy C.; Gosselin, Armand M.

2004-01-01

The Crawler Transporter (CT), designed and built for the Apollo Program in the 1960's and surpassing its initial operational life, has become an integral part of the Space Shuttle Program (SSP). The CT transports the Space Shuttle Vehicle (SSV) stack, atop the Mobile Launch Platform (MLP), from the Vehicle Assembly Building (VAB) to the launch pad. This support structure provides hydraulic jacking, leveling and load equalization for the 12 million pound stack on its 3.5-5.0 mile rollout to the launch pad. Major elements of the SSV, consisting of the orbiter, solid rocket boosters (SRB) and external tank (ET) have required fatigue analyses as part of the mission life certification. Compared to rollout vibration, the SSV sees relatively high vibration loads during launch, ascent, descent and landing phases of the mission. Although preliminary measured SRB vibration levels during rollout were of low amplitude and frequency, the duration of the rollout phase is typically high, from 5-6 hours. As part of an expanded mission life assessment, additional certification effort was initiated to define fatigue load spectra for rollout. This study addresses the CT vibration analyses in support of the rollout fatigue study. Structural models developed for modal and vibration analyses were used to identify unique CT, CT/MLP and CT/MLP/SRB vibration characteristics for comparison to instrumented rollout tests. Whereas the main structural and vibration characteristics of the SSV are well defined, minimum analytical and vibration test data on the Crawler Transporter were available. Unique vibration characteristics of the CT are attributable to the drive mechanism, hydraulic jacking system, structural framing and the CT-to-MLP support pad restraints. Initial tests performed on the CT/MLP/SRB configuration showed reasonable correlation with predicted mode shapes and frequencies.

Per-operative vibration analysis: a valuable tool for defining correct stem insertion: preliminary report.

PubMed

Mulier, Michiel; Pastrav, Cesar; Van der Perre, Georges

2008-01-01

Defining the stem insertion end point during total hip replacement still relies on the surgeon's feeling. When a custom-made stem prosthesis with an optimal fit into the femoral canal is used, the risk of per-operative fractures is even greater than with standard prostheses. Vibration analysis is used in other clinical settings and has been tested as a means to detect optimal stem insertion in the laboratory. The first per-operative use of vibration analysis during non-cemented custom-made stem insertion in 30 patients is reported here. Thirty patients eligible for total hip replacement with uncemented stem prosthesis were included. The neck of the stem was connected with a shaker that emitted white noise as excitation signal and an impedance head that measured the frequency response. The response signal was sent to a computer that analyzed the frequency response function after each insertion phase. A technician present in the operating theatre but outside the laminated airflow provided feed-back to the surgeon. The correlation index between the frequency response function measured during the last two insertion hammering sessions was >0.99 in 86.7% of the cases. In four cases the surgeon stopped the insertion procedure because of a perceived risk of fracture. Two special cases illustrating the potential benefit of per-operative vibration analysis are described. The results of intra-operative vibration analysis indicate that this technique may be a useful tool assisting the orthopaedic surgeon in defining the insertion endpoint of the stem. The development of a more user-friendly device is therefore warranted.

Correlates of Condom Use among Male High School Students in Nairobi, Kenya

ERIC Educational Resources Information Center

Kabiru, Caroline W.; Orpinas, Pamela

2009-01-01

Background: Correct and consistent condom use is an effective strategy to reduce the risk of sexually transmitted infections (STIs). This study examines sociodemographic, behavioral, and psychosocial characteristics of 3 groups of adolescent males: consistent, sporadic, and non-condom users. Methods: The sample consisted of 931 sexually…

The Relative Contribution of Interaural Time and Magnitude Cues to Dynamic Sound Localization

NASA Technical Reports Server (NTRS)

Wenzel, Elizabeth M.; Null, Cynthia H. (Technical Monitor)

1995-01-01

This paper presents preliminary data from a study examining the relative contribution of interaural time differences (ITDs) and interaural level differences (ILDs) to the localization of virtual sound sources both with and without head motion. The listeners' task was to estimate the apparent direction and distance of virtual sources (broadband noise) presented over headphones. Stimuli were synthesized from minimum phase representations of nonindividualized directional transfer functions; binaural magnitude spectra were derived from the minimum phase estimates and ITDs were represented as a pure delay. During dynamic conditions, listeners were encouraged to move their heads; the position of the listener's head was tracked and the stimuli were synthesized in real time using a Convolvotron to simulate a stationary external sound source. ILDs and ITDs were either correctly or incorrectly correlated with head motion: (1) both ILDs and ITDs correctly correlated, (2) ILDs correct, ITD fixed at 0 deg azimuth and 0 deg elevation, (3) ITDs correct, ILDs fixed at 0 deg, 0 deg. Similar conditions were run for static conditions except that none of the cues changed with head motion. The data indicated that, compared to static conditions, head movements helped listeners to resolve confusions primarily when ILDs were correctly correlated, although a smaller effect was also seen for correct ITDs. Together with the results for static conditions, the data suggest that localization tends to be dominated by the cue that is most reliable or consistent, when reliability is defined by consistency over time as well as across frequency bands.

Exploring the limits of the self-consistent Born approximation for inelastic electronic transport

NASA Astrophysics Data System (ADS)

Lee, William; Jean, Nicola; Sanvito, Stefano

2009-02-01

The nonequilibrium Green’s function formalism is today the standard computational method for describing elastic transport in molecular devices. This can be extended to include inelastic scattering by the so-called self-consistent Born approximation (SCBA), where the interaction of the electrons with the vibrations of the molecule is assumed to be weak and it is treated perturbatively. The validity of such assumption and therefore of the SCBA is difficult to establish with certainty. In this work we explore the limitations of the SCBA by using a simple tight-binding model with the electron-phonon coupling strength α chosen as a free parameter. As model devices we consider Au monatomic chains and a H2 molecule sandwiched between Pt electrodes. In both cases, our self-consistent calculations demonstrate a breakdown of the SCBA for large α and we identify a weak and a strong-coupling regime. For weak coupling our SCBA results compare closely with those obtained with exact scattering theory. However in the strong-coupling regime large deviations are found. In particular we demonstrate that there is a critical coupling strength, characteristic of the materials system, beyond which multiple self-consistent solutions can be found depending on the initial conditions in the simulation. These are entirely due to the large contribution of the Hartree self-energy and completely disappear when this is neglected. We attribute this feature to the breakdown of the perturbative expansion leading to the SCBA.

The Vibrational Frequencies of CaO2, ScO2, and TiO2: A Comparison of Theoretical Methods

NASA Technical Reports Server (NTRS)

Rosi, Marzio; Bauschlicher, Charles W., Jr.; Chertihin, George V.; Andrews, Lester; Arnold, James O. (Technical Monitor)

1997-01-01

The vibrational frequencies of several states of CaO2, ScO2, and TiO2 are computed at using density functional theory (DFT), the Hatree-Fock approach, second order Moller-Plesset perturbation theory (MP2), and the complete-active-space self-consistent-field theory. Three different functionals are used in the DFT calculations, including two hybrid functionals. The coupled cluster singles and doubles approach including the effect of unlinked triples, determined using perturbation theory, is applied to selected states. The Becke-Perdew 86 functional appears to be the cost effective method of choice, although even this functional does not perform well for one state of CaO2. The MP2 approach is significantly inferior to the DFT approaches.

Self-motion perception and vestibulo-ocular reflex during whole body yaw rotation in standing subjects: the role of head position and neck proprioception.

PubMed

Panichi, Roberto; Botti, Fabio Massimo; Ferraresi, Aldo; Faralli, Mario; Kyriakareli, Artemis; Schieppati, Marco; Pettorossi, Vito Enrico

2011-04-01

Self-motion perception and vestibulo-ocular reflex (VOR) were studied during whole body yaw rotation in the dark at different static head positions. Rotations consisted of four cycles of symmetric sinusoidal and asymmetric oscillations. Self-motion perception was evaluated by measuring the ability of subjects to manually track a static remembered target. VOR was recorded separately and the slow phase eye position (SPEP) was computed. Three different head static yaw deviations (active and passive) relative to the trunk (0°, 45° to right and 45° to left) were examined. Active head deviations had a significant effect during asymmetric oscillation: the movement perception was enhanced when the head was kept turned toward the side of body rotation and decreased in the opposite direction. Conversely, passive head deviations had no effect on movement perception. Further, vibration (100 Hz) of the neck muscles splenius capitis and sternocleidomastoideus remarkably influenced perceived rotation during asymmetric oscillation. On the other hand, SPEP of VOR was modulated by active head deviation, but was not influenced by neck muscle vibration. Through its effects on motion perception and reflex gain, head position improved gaze stability and enhanced self-motion perception in the direction of the head deviation. Copyright © 2010 Elsevier B.V. All rights reserved.

The Shock and Vibration Digest. Volume 12, Number 4.

DTIC Science & Technology

1980-04-01

self -excited oscillations. a great deal of experience has been gained in applying these techniques to practical situations. This Con- INVITED...Outlet Flow Field of Axial Flow Fans Key Words: Pumps, Compressors, Self -excited vibrations, Surges H. Fujita Mechanical Engrg. Res. Lab., Hitachi, Ltd...Tsu- Investigations concerned with the stability of stationary chiura, 300 Japan, NOISE-CON 79, Machinery Noise states and the possibility of self

High-accuracy calculations of the rotation-vibration spectrum of {{\\rm{H}}}_{3}^{+}

NASA Astrophysics Data System (ADS)

Tennyson, Jonathan; Polyansky, Oleg L.; Zobov, Nikolai F.; Alijah, Alexander; Császár, Attila G.

2017-12-01

Calculation of the rotation-vibration spectrum of {{{H}}}3+, as well as of its deuterated isotopologues, with near-spectroscopic accuracy requires the development of sophisticated theoretical models, methods, and codes. The present paper reviews the state-of-the-art in these fields. Computation of rovibrational states on a given potential energy surface (PES) has now become standard for triatomic molecules, at least up to intermediate energies, due to developments achieved by the present authors and others. However, highly accurate Born-Oppenheimer energies leading to highly accurate PESs are not accessible even for this two-electron system using conventional electronic structure procedures (e.g. configuration-interaction or coupled-cluster techniques with extrapolation to the complete (atom-centered Gaussian) basis set limit). For this purpose, highly specialized techniques must be used, e.g. those employing explicitly correlated Gaussians and nonlinear parameter optimizations. It has also become evident that a very dense grid of ab initio points is required to obtain reliable representations of the computed points extending from the minimum to the asymptotic limits. Furthermore, adiabatic, relativistic, and quantum electrodynamic correction terms need to be considered to achieve near-spectroscopic accuracy during calculation of the rotation-vibration spectrum of {{{H}}}3+. The remaining and most intractable problem is then the treatment of the effects of non-adiabatic coupling on the rovibrational energies, which, in the worst cases, may lead to corrections on the order of several cm-1. A promising way of handling this difficulty is the further development of effective, motion- or even coordinate-dependent, masses and mass surfaces. Finally, the unresolved challenge of how to describe and elucidate the experimental pre-dissociation spectra of {{{H}}}3+ and its isotopologues is discussed.

Self-tuning pressure-feedback control by pole placement for vibration reduction of excavator with independent metering fluid power system

NASA Astrophysics Data System (ADS)

Ding, Ruqi; Xu, Bing; Zhang, Junhui; Cheng, Min

2017-08-01

Independent metering control systems are promising fluid power technologies compared with traditional valve controlled systems. By breaking the mechanical coupling between the inlet and outlet, the meter-out valve can open as large as possible to reduce energy consumptions. However, the lack of damping in outlet causes stronger vibrations. To address the problem, the paper designs a hybrid control method combining dynamic pressure-feedback and active damping control. The innovation resides in the optimization of damping by introducing pressure feedback to make trade-offs between high stability and fast response. To achieve this goal, the dynamic response pertaining to the control parameters consisting of feedback gain and cut-off frequency, are analyzed via pole-zero locations. Accordingly, these parameters are tuned online in terms of guaranteed dominant pole placement such that the optimal damping can be accurately captured under a considerable variation of operating conditions. The experiment is deployed in a mini-excavator. The results pertaining to different control parameters confirm the theoretical expectations via pole-zero locations. By using proposed self-tuning controller, the vibrations are almost eliminated after only one overshoot for different operation conditions. The overshoots are also reduced with less decrease of the response time. In addition, the energy-saving capability of independent metering system is still not affected by the improvement of controllability.

Strong-field ionization of Li and Be: a time-dependent density functional theory with self-interaction correction

NASA Astrophysics Data System (ADS)

Telnov, Dmitry A.; Heslar, John T.; Chu, Shih-I.

2011-11-01

In the framework of the time-dependent density functional theory, we have performed 3D calculations of multiphoton ionization of Li and Be atoms by strong near-infrared laser fields. The results for the intensity-dependent probabilities of single and double ionization are presented. We make use of the time-dependent Krieger-Li-Iafrate exchange-correlation potential with self-interaction correction (TD-KLI-SIC). Such a potential possesses an integer discontinuity which improves description of the ionization process. However, we have found that the discontinuity of the TD-KLI-SIC potential is not sufficient to reproduce characteristic feature of double ionization.

Effects of electron doping on the stability of the metal hydride NaH

NASA Astrophysics Data System (ADS)

Olea-Amezcua, M. A.; Rivas-Silva, J. F.; de la Peña-Seaman, O.; Heid, R.; Bohnen, K. P.

2017-04-01

Alkali and alkali-earth metal hydrides have high volumetric and gravimetric hydrogen densities, but due to their high thermodynamic stability, they possess high dehydrogenation temperatures which may be reduced by transforming these compounds into less stable states/configurations. We present a systematic computational study of the electron doping effects on the stability of the alkali metal hydride NaH substituted with Mg, using the self-consistent version of the virtual crystal approximation to model the alloy Na1-x Mg x H. The phonon dispersions were studied paying special attention to the crystal stability and the correlations with the electronic structure taking into account the zero point energy contribution. We found that substitution of Na by Mg in the hydride invokes a reduction of the frequencies, leading to dynamical instabilities for Mg content of 25%. The microscopic origin of these instabilities could be related to the formation of ellipsoidal Fermi surfaces centered at the L point due to the metallization of the hydride by the Mg substitution. Applying the quasiharmonic approximation, thermodynamic properties like heat capacities, vibrational entropies and vibrational free energies as a function of temperature at zero pressure are obtained. These properties determine an upper temperature for the thermodynamic stability of the hydride, which decreases from 600 K for NaH to 300 K at 20% Mg concentration. This significant reduction of the stability range indicates that dehydrogenation could be favoured by electron doping of NaH.

Time-dependent density-functional theory with optimized effective potential and self-interaction correction and derivative discontinuity for the treatment of double ionization of He and Be atoms in intense laser fields

NASA Astrophysics Data System (ADS)

Heslar, John; Telnov, Dmitry A.; Chu, Shih-I.

2013-05-01

We present a self-interaction-free time-dependent density-functional theory (TDDFT) for the treatment of double-ionization processes of many-electron systems. The method is based on the extension of the Krieger-Li-Iafrate (KLI) treatment of the optimized effective potential (OEP) theory and the incorporation of an explicit self-interaction correction (SIC) term. In the framework of the time-dependent density functional theory, we have performed three-dimensional (3D) calculations of double ionization of He and Be atoms by intense near-infrared laser fields. We make use of the exchange-correlation potential with the integer discontinuity which improves the description of the double-ionization process. We found that a proper description of the double ionization requires the TDDFT exchange-correlation potential with the discontinuity with respect to the variation of the total particle number (TPN). The results for the intensity-dependent rates of double ionization of He and Be atoms are presented.

Enhancement to Non-Contacting Stress Measurement of Blade Vibration Frequency

NASA Technical Reports Server (NTRS)

Platt, Michael; Jagodnik, John

2011-01-01

A system for turbo machinery blade vibration has been developed that combines time-of-arrival sensors for blade vibration amplitude measurement and radar sensors for vibration frequency and mode identification. The enabling technology for this continuous blade monitoring system is the radar sensor, which provides a continuous time series of blade displacement over a portion of a revolution. This allows the data reduction algorithms to directly calculate the blade vibration frequency and to correctly identify the active modes of vibration. The work in this project represents a significant enhancement in the mode identification and stress calculation accuracy in non-contacting stress measurement system (NSMS) technology when compared to time-of-arrival measurements alone.

Simulation of the photodetachment spectrum of HHfO- using coupled-cluster calculations

NASA Astrophysics Data System (ADS)

Mok, Daniel K. W.; Dyke, John M.; Lee, Edmond P. F.

2016-12-01

The photodetachment spectrum of HHfO- was simulated using restricted-spin coupled-cluster single-double plus perturbative triple {RCCSD(T)} calculations performed on the ground electronic states of HHfO and HHfO-, employing basis sets of up to quintuple-zeta quality. The computed RCCSD(T) electron affinity of 1.67 ± 0.02 eV at the complete basis set limit, including Hf 5s25p6 core correlation and zero-point energy corrections, agrees well with the experimental value of 1.70 ± 0.05 eV from a recent photodetachment study [X. Li et al., J. Chem. Phys. 136, 154306 (2012)]. For the simulation, Franck-Condon factors were computed which included allowances for anharmonicity and Duschinsky rotation. Comparisons between simulated and experimental spectra confirm the assignments of the molecular carrier and electronic states involved but suggest that the experimental vibrational structure has suffered from poor signal-to-noise ratio. An alternative assignment of the vibrational structure to that suggested in the experimental work is presented.

Influence of support conditions on vertical whole-body vibration of the seated human body.

PubMed

M-Pranesh, Anand; Rakheja, Subhash; Demont, Richard

2010-01-01

The vibration transmission to the lumbar and thoracic segments of seated human subjects exposed to whole body vibration of a vehicular nature have been mostly characterised without the back and hand supports, which is not representative of general driving conditions. This non-invasive experimental study investigated the transmission of vertical seat vibration to selected vertebrae and the head along the vertical and fore-aft axes of twelve male human subjects seated on a rigid seat and exposed to random vertical excitation in the 0.5-20 Hz range. The measurements were performed under four different sitting postures involving combinations of back support conditions and hands positions, and three difference magnitudes of vertical vibration (0.25, 0.5 and 1.0 m/s(2) rms acceleration). The results showed significant errors induced by sensor misalignment and skin effects, which required appropriate correction methodologies. The averaged corrected responses revealed that the back support attenuates vibration in the vertical axis to all the body locations while increasing the fore-aft transmissibility at the C7 and T5. The hands position generally has a relatively smaller effect, showing some influences on the C7 and L5 vibration. Sitting without a back support resulted in very low magnitude fore-aft vibration at T5, which was substantially higher with a back support, suggestive of a probable change in the body's vibration mode. The effect of back support was observed to be very small on the horizontal vibration of the lower thoracic and lumbar regions. The results suggest that distinctly different target body-segment biodynamic functions need to be defined for different support conditions in order to represent the unique contribution of the specific support condition. These datasets may then be useful for the development of biodynamic models.

Attitude toward plagiarism among Iranian medical faculty members.

PubMed

Ghajarzadeh, Mahsa; Norouzi-Javidan, Abbas; Hassanpour, Kiana; Aramesh, Kiarash; Emami-Razavi, Seyed Hassan

2012-01-01

The goal of this study was to assess attitude towards plagiarism in faculty members of Medical School at Tehran University of Medical Sciences. One hundred and twenty medical faculty members of Tehran University of Medical Sciences were enrolled in this cross-sectional study. They were asked to answer to valid and reliable Persian version of attitude towards plagiarism questionnaire. Attitude toward plagiarism, positive attitude toward self-plagiarism and plagiarism acceptance were assessed. Eighty seven filled-up questionnaires were collected. Mean total number of correct answers was 11.6±3.1. Mean number of correct answers to questions evaluating self-plagiarism was 1.7±0.4 and mean number of correct answers to questions evaluating plagiarism acceptance was 1.4±0.2. There was no significant correlation between plagiarism acceptance and self-plagiarism (r=0.17, P=0.1). It is essential to provide materials (such as workshops, leaflets and mandatory courses) to make Iranian medical faculty members familiar with medical research ethics issues such as plagiarism.

Investigation of difficult component effects on finite element model vibration prediction for the Bell AH-1G helicopter. Volume 1: Ground vibration test results

NASA Technical Reports Server (NTRS)

Dompka, R. V.

1989-01-01

Under the NASA-sponsored Design Analysis Methods for VIBrationS (DAMVIBS) program, a series of ground vibration tests and NASTRAN finite element model (FEM) correlations were conducted on the Bell AH-1G helicopter gunship to investigate the effects of difficult components on the vibration response of the airframe. Previous correlations of the AH-1G showed good agreement between NASTRAN and tests through 15 to 20 Hz, but poor agreement in the higher frequency range of 20 to 30 Hz. Thus, this effort emphasized the higher frequency airframe vibration response correlations and identified areas that need further R and T work. To conduct the investigations, selected difficult components (main rotor pylon, secondary structure, nonstructural doors/panels, landing gear, engine, fuel, etc.) were systematically removed to quantify their effects on overall vibratory response of the airframe. The entire effort was planned and documented, and the results reviewed by NASA and industry experts in order to ensure scientific control of the testing, analysis, and correlation exercise. In particular, secondary structure and damping had significant effects on the frequency response of the airframe above 15 Hz. Also, the nonlinear effects of thrust stiffening and elastomer mounts were significant on the low frequency pylon modes below main rotor 1p (5.4 Hz). The results of the ground vibration testing are presented.

Comparisons of measured and self-reported anthropometric variables and blood pressure in a sample of Hong Kong female nurses.

PubMed

Xie, Yao Jie; Ho, Suzanne C; Liu, Zhao Min; Hui, Stanley Sai-Chuen

2014-01-01

To assess the validity of self-reported weight, height, body mass index (BMI), waist circumference and blood pressure compared with standardized clinical measurements and to determine the classification accuracy in overweight/obesity and central adiposity. This pilot study was integrated into a life-course study entitled "Hong Kong Women's Health Study" among 1,253 female nurses in Hong Kong who were aged 35 years to 65 years. Data were collected from self-administered questionnaires that were mailed to the respondents. Of these participants, we obtained the standard body measurements of 144 (11.5%) at our research center. We then compared the self-reported anthropometric variables and blood pressure with the measured data to assess validity based on the level of misreporting, percentage of agreement, consistency, sensitivity and specificity. The self-reported and measured values were highly correlated in terms of anthropometry and blood pressure (correlation coefficients ranged from 0.72 to 0.96). Height was overestimated at an average of 0.42 cm, and waist circumference was underestimated at 2.33 cm (both P<0.05), while no significant differences were observed from weight, blood pressure and BMI (all P>0.05). The proportions of overweight, obesity, and central adiposity by self-reported data did not vary greatly from the measured data (all P>0.05). The self-reporting resulted in correct classifications of BMI, waist circumference, and systolic blood pressure in 85%, 78%, and 87% of women, with corresponding Kappa index values of 0.79, 0.55, and 0.82, respectively. Sensitivity and specificity were 84.6% and 95.7%, respectively, with respect to overweight/obesity detection, whereas those for central adiposity detection were 70.6% and 83.8%, respectively. In a sample of female Hong Kong nurses, the self-reported measures of height, weight, BMI, waist circumference and blood pressure were generally valid. Furthermore, the classification accuracies of overweight/obesity and central adiposity were acceptable.

Statistical quality control through overall vibration analysis

NASA Astrophysics Data System (ADS)

Carnero, M. ^a. Carmen; González-Palma, Rafael; Almorza, David; Mayorga, Pedro; López-Escobar, Carlos

2010-05-01

The present study introduces the concept of statistical quality control in automotive wheel bearings manufacturing processes. Defects on products under analysis can have a direct influence on passengers' safety and comfort. At present, the use of vibration analysis on machine tools for quality control purposes is not very extensive in manufacturing facilities. Noise and vibration are common quality problems in bearings. These failure modes likely occur under certain operating conditions and do not require high vibration amplitudes but relate to certain vibration frequencies. The vibration frequencies are affected by the type of surface problems (chattering) of ball races that are generated through grinding processes. The purpose of this paper is to identify grinding process variables that affect the quality of bearings by using statistical principles in the field of machine tools. In addition, an evaluation of the quality results of the finished parts under different combinations of process variables is assessed. This paper intends to establish the foundations to predict the quality of the products through the analysis of self-induced vibrations during the contact between the grinding wheel and the parts. To achieve this goal, the overall self-induced vibration readings under different combinations of process variables are analysed using statistical tools. The analysis of data and design of experiments follows a classical approach, considering all potential interactions between variables. The analysis of data is conducted through analysis of variance (ANOVA) for data sets that meet normality and homoscedasticity criteria. This paper utilizes different statistical tools to support the conclusions such as chi squared, Shapiro-Wilks, symmetry, Kurtosis, Cochran, Hartlett, and Hartley and Krushal-Wallis. The analysis presented is the starting point to extend the use of predictive techniques (vibration analysis) for quality control. This paper demonstrates the existence of predictive variables (high-frequency vibration displacements) that are sensible to the processes setup and the quality of the products obtained. Based on the result of this overall vibration analysis, a second paper will analyse self-induced vibration spectrums in order to define limit vibration bands, controllable every cycle or connected to permanent vibration-monitoring systems able to adjust sensible process variables identified by ANOVA, once the vibration readings exceed established quality limits.

Development of Methods to Evaluate Safer Flight Characteristics

NASA Technical Reports Server (NTRS)

Basciano, Thomas E., Jr.; Erickson, Jon D.

1997-01-01

The goal of the proposed research is to begin development of a simulation that models the flight characteristics of the Simplified Aid For EVA Rescue (SAFER) pack. Development of such a simulation was initiated to ultimately study the effect an Orbital Replacement Unit (ORU) has on SAFER dynamics. A major function of this program will be to calculate fuel consumption for many ORUs with different masses and locations. This will ultimately determine the maximum ORU mass an astronaut can carry and still perform a self-rescue without jettisoning the unit. A second primary goal is to eventually simulate relative motion (vibration) between the ORU and astronaut. After relative motion is accurately modeled it will be possible to evaluate the robustness of the control system and optimize performance as needed. The first stage in developing the simulation is the ability to model a standardized, total, self-rescue scenario, making it possible to accurately compare different program runs. In orbit an astronaut has only limited data and will not be able to follow the most fuel efficient trajectory; therefore, it is important to correctly model the procedures an astronaut would use in orbit so that good fuel consumption data can be obtained. Once this part of the program is well tested and verified, the vibration (relative motion) of the ORU with respect to the astronaut can be studied.

Investigation of difficult component effects on finite element model vibration prediction for the Bell AG-1G helicopter. Volume 2: Correlation results

NASA Technical Reports Server (NTRS)

Dompka, R. V.

1989-01-01

Under the NASA-sponsored DAMVIBS (Design Analysis Methods for VIBrationS) program, a series of ground vibration tests and NASTRAN finite element model (FEM) correlations were conducted on the Bell AH-1G helicopter gunship to investigate the effects of difficult components on the vibration response of the airframe. Previous correlations of the AG-1G showed good agreement between NASTRAN and tests through 15 to 20 Hz, but poor agreement in the higher frequency range of 20 to 30 Hz. Thus, this effort emphasized the higher frequency airframe vibration response correlations and identified areas that need further R and T work. To conduct the investigations, selected difficult components (main rotor pylon, secondary structure, nonstructural doors/panels, landing gear, engine, furl, etc.) were systematically removed to quantify their effects on overall vibratory response of the airframe. The entire effort was planned and documented, and the results reviewed by NASA and industry experts in order to ensure scientific control of the testing, analysis, and correlation exercise. In particular, secondary structure and damping had significant effects on the frequency response of the airframe above 15 Hz. Also, the nonlinear effects of thrust stiffening and elastomer mounts were significant on the low frequency pylon modes below main rotor 1p (5.4 Hz). The results of the NASTRAN FEM correlations are given.

Explicit hydration of ammonium ion by correlated methods employing molecular tailoring approach

NASA Astrophysics Data System (ADS)

Singh, Gurmeet; Verma, Rahul; Wagle, Swapnil; Gadre, Shridhar R.

2017-11-01

Explicit hydration studies of ions require accurate estimation of interaction energies. This work explores the explicit hydration of the ammonium ion (NH4+) employing Møller-Plesset second order (MP2) perturbation theory, an accurate yet relatively less expensive correlated method. Several initial geometries of NH4+(H2O)n (n = 4 to 13) clusters are subjected to MP2 level geometry optimisation with correlation consistent aug-cc-pVDZ (aVDZ) basis set. For large clusters (viz. n > 8), molecular tailoring approach (MTA) is used for single point energy evaluation at MP2/aVTZ level for the estimation of MP2 level binding energies (BEs) at complete basis set (CBS) limit. The minimal nature of the clusters upto n ≤ 8 is confirmed by performing vibrational frequency calculations at MP2/aVDZ level of theory, whereas for larger clusters (9 ≤ n ≤ 13) such calculations are effected via grafted MTA (GMTA) method. The zero point energy (ZPE) corrections are done for all the isomers lying within 1 kcal/mol of the lowest energy one. The resulting frequencies in N-H region (2900-3500 cm-1) and in O-H stretching region (3300-3900 cm-1) are in found to be in excellent agreement with the available experimental findings for 4 ≤ n ≤ 13. Furthermore, GMTA is also applied for calculating the BEs of these clusters at coupled cluster singles and doubles with perturbative triples (CCSD(T)) level of theory with aVDZ basis set. This work thus represents an art of the possible on contemporary multi-core computers for studying explicit molecular hydration at correlated level theories.

Seminar on Understanding Digital Control and Analysis in Vibration Test Systems, part 2

NASA Technical Reports Server (NTRS)

1975-01-01

A number of techniques for dealing with important technical aspects of the random vibration control problem are described. These include the generation of pseudo-random and true random noise, the control spectrum estimation problem, the accuracy/speed tradeoff, and control correction strategies. System hardware, the operator-system interface, safety features, and operational capabilities of sophisticated digital random vibration control systems are also discussed.

Self-Powered Safety Helmet Based on Hybridized Nanogenerator for Emergency.

PubMed

Jin, Long; Chen, Jun; Zhang, Binbin; Deng, Weili; Zhang, Lei; Zhang, Haitao; Huang, Xi; Zhu, Minhao; Yang, Weiqing; Wang, Zhong Lin

2016-08-23

The rapid development of Internet of Things and the related sensor technology requires sustainable power sources for their continuous operation. Scavenging and utilizing the ambient environmental energy could be a superior solution. Here, we report a self-powered helmet for emergency, which was powered by the energy converted from ambient mechanical vibration via a hybridized nanogenerator that consists of a triboelectric nanogenerator (TENG) and an electromagnetic generator (EMG). Integrating with transformers and rectifiers, the hybridized nanogenerator can deliver a power density up to 167.22 W/m(3), which was demonstrated to light up 1000 commercial light-emitting diodes (LEDs) instantaneously. By wearing the developed safety helmet, equipped with rationally designed hybridized nanogenerator, the harvested vibration energy from natural human motion is also capable of powering a wireless pedometer for real-time transmitting data reporting to a personal cell phone. Without adding much extra weight to a commercial one, the developed wearing helmet can be a superior sustainable power source for explorers, engineers, mine-workers under well, as well as and disaster-relief workers, especially in remote areas. This work not only presents a significant step toward energy harvesting from human biomechanical movement, but also greatly expands the applicability of TENGs as power sources for self-sustained electronics.

Agent-based station for on-line diagnostics by self-adaptive laser Doppler vibrometry

NASA Astrophysics Data System (ADS)

Serafini, S.; Paone, N.; Castellini, P.

2013-12-01

A self-adaptive diagnostic system based on laser vibrometry is proposed for quality control of mechanical defects by vibration testing; it is developed for appliances at the end of an assembly line, but its characteristics are generally suited for testing most types of electromechanical products. It consists of a laser Doppler vibrometer, equipped with scanning mirrors and a camera, which implements self-adaptive bahaviour for optimizing the measurement. The system is conceived as a Quality Control Agent (QCA) and it is part of a Multi Agent System that supervises all the production line. The QCA behaviour is defined so to minimize measurement uncertainty during the on-line tests and to compensate target mis-positioning under guidance of a vision system. Best measurement conditions are reached by maximizing the amplitude of the optical Doppler beat signal (signal quality) and consequently minimize uncertainty. In this paper, the optimization strategy for measurement enhancement achieved by the down-hill algorithm (Nelder-Mead algorithm) and its effect on signal quality improvement is discussed. Tests on a washing machine in controlled operating conditions allow to evaluate the efficacy of the method; significant reduction of noise on vibration velocity spectra is observed. Results from on-line tests are presented, which demonstrate the potential of the system for industrial quality control.

An overview of self-consistent methods for fiber-reinforced composites

NASA Technical Reports Server (NTRS)

Gramoll, Kurt C.; Freed, Alan D.; Walker, Kevin P.

1991-01-01

The Walker et al. (1989) self-consistent method to predict both the elastic and the inelastic effective material properties of composites is examined and compared with the results of other self-consistent and elastically based solutions. The elastic part of their method is shown to be identical to other self-consistent methods for non-dilute reinforced composite materials; they are the Hill (1965), Budiansky (1965), and Nemat-Nasser et al. (1982) derivations. A simplified form of the non-dilute self-consistent method is also derived. The predicted, elastic, effective material properties for fiber reinforced material using the Walker method was found to deviate from the elasticity solution for the v sub 31, K sub 12, and mu sub 31 material properties (fiber is in the 3 direction) especially at the larger volume fractions. Also, the prediction for the transverse shear modulus, mu sub 12, exceeds one of the accepted Hashin bounds. Only the longitudinal elastic modulus E sub 33 agrees with the elasticity solution. The differences between the Walker and the elasticity solutions are primarily due to the assumption used in the derivation of the self-consistent method, i.e., the strain fields in the inclusions and the matrix are assumed to remain constant, which is not a correct assumption for a high concentration of inclusions.

Effects of vibration on inertial wind-tunnel model attitude measurement devices

NASA Technical Reports Server (NTRS)

Young, Clarence P., Jr.; Buehrle, Ralph D.; Balakrishna, S.; Kilgore, W. Allen

1994-01-01

Results of an experimental study of a wind tunnel model inertial angle-of-attack sensor response to a simulated dynamic environment are presented. The inertial device cannot distinguish between the gravity vector and the centrifugal accelerations associated with wind tunnel model vibration, this situation results in a model attitude measurement bias error. Significant bias error in model attitude measurement was found for the model system tested. The model attitude bias error was found to be vibration mode and amplitude dependent. A first order correction model was developed and used for estimating attitude measurement bias error due to dynamic motion. A method for correcting the output of the model attitude inertial sensor in the presence of model dynamics during on-line wind tunnel operation is proposed.

Estimation of Subjective Difficulty and Psychological Stress by Ambient Sensing of Desk Panel Vibrations

NASA Astrophysics Data System (ADS)

Hamaguchi, Nana; Yamamoto, Keiko; Iwai, Daisuke; Sato, Kosuke

We investigate ambient sensing techniques that recognize writer's psychological states by measuring vibrations of handwriting on a desk panel using a piezoelectric contact sensor attached to its underside. In particular, we describe a technique for estimating the subjective difficulty of a question for a student as the ratio of the time duration of thinking to the total amount of time spent on the question. Through experiments, we confirm that our technique correctly recognizes whether or not a person writes something down on paper by measured vibration data at the accuracy of over 80 %, and that the order of computed subjective difficulties of three questions is coincident with that reported by the subject in 60 % of experiments. We also propose a technique to estimate a writer's psychological stress by using the standard deviation of the spectrum of the measured vibration. Results of a proof-of-concept experiment show that the proposed technique correctly estimates whether or not the subject feels stress at least 90 % of the time.

[Validation of the Copenhagen Burnout Inventory to assess professional burnout in Spain].

PubMed

Molinero Ruiz, Emilia; Basart Gómez-Quintero, Helena; Moncada Lluis, Salvador

2013-01-01

The Copenhagen Burnout Inventory (CBI) is a public domain questionnaire measuring the degree of psychological fatigue experienced in three subdimensions of Burnout: personal (PB), work-related (WB), and client-related Burnout (CB). The study aimed to examine the acceptability, reliability and construct validity of the Spanish version of CBI. The study population consisted of 479 workers of educational centers, social work centres, healthcare centres and workers within the industry sector. Data was collected in 2009 through a self-administered questionnaire including the three CBI scales, sixteen scales of psychosocial work environment (COPSOQ ISTAS21) and perceived general and mental health and vitality (SF-36). Response rate was 78.7%. The three scales have an inter-item correlation average between 0.42 and 0.60 and a corrected item-total correlation between 0,49 and 0,83. The internal consistency of the three scales had Cronbach's α values of 0.90 for PB, 0.83 for WB and 0.82 for CB. Burnout was related to both psychosocial work environment and wellbeing measures in the expected direction and intensity. The items of the three scales show good discrimination capacity, good consistency and homogeneity. The three CBI scales have an acceptable internal consistency reliability index, slightly higher in PB. The discrimination capacity of the scales is verified through the discrimination index and the different levels between occupations and activities. These results demonstrate that the Spanish version of the CBI is a reliable and valid instrument for measuring Burnout.

On the correlation between phase-locking modes and Vibrational Resonance in a neuronal model

NASA Astrophysics Data System (ADS)

Morfu, S.; Bordet, M.

2018-02-01

We numerically and experimentally investigate the underlying mechanism leading to multiple resonances in the FitzHugh-Nagumo model driven by a bichromatic excitation. Using a FitzHugh-Nagumo circuit, we first analyze the number of spikes triggered by the system in response to a single sinusoidal wave forcing. We build an encoding diagram where different phase-locking modes are identified according to the amplitude and frequency of the sinusoidal excitation. Next, we consider the bichromatic driving which consists in a low frequency sinusoidal wave perturbed by an additive high frequency signal. Beside the classical Vibrational Resonance phenomenon, we show in real experiments that multiple resonances can be reached by an appropriate setting of the perturbation parameters. We clearly establish a correlation between these resonances and the encoding diagram of the low frequency signal free FitzHugh-Nagumo model. We show with realistic parameters that sharp transitions of the encoding diagram allow to predict the main resonances. Our experiments are confirmed by numerical simulations of the system response.

Semiexperimental equilibrium structures for building blocks of organic and biological molecules: the B2PLYP route.

PubMed

Penocchio, Emanuele; Piccardo, Matteo; Barone, Vincenzo

2015-10-13

The B2PLYP double hybrid functional, coupled with the correlation-consistent triple-ζ cc-pVTZ (VTZ) basis set, has been validated in the framework of the semiexperimental (SE) approach for deriving accurate equilibrium structures of molecules containing up to 15 atoms. A systematic comparison between new B2PLYP/VTZ results and several equilibrium SE structures previously determined at other levels, in particular B3LYP/SNSD and CCSD(T) with various basis sets, has put in evidence the accuracy and the remarkable stability of such model chemistry for both equilibrium structures and vibrational corrections. New SE equilibrium structures for phenylacetylene, pyruvic acid, peroxyformic acid, and phenyl radical are discussed and compared with literature data. Particular attention has been devoted to the discussion of systems for which lack of sufficient experimental data prevents a complete SE determination. In order to obtain an accurate equilibrium SE structure for these situations, the so-called templating molecule approach is discussed and generalized with respect to our previous work. Important applications are those involving biological building blocks, like uracil and thiouracil. In addition, for more general situations the linear regression approach has been proposed and validated.

Optimized Non-Obstructive Particle Damping (NOPD) Treatment for Composite Honeycomb Structures

NASA Technical Reports Server (NTRS)

Panossian, H.

2008-01-01

Non-Obstructive Particle Damping (NOPD) technology is a passive vibration damping approach whereby metallic or non-metallic particles in spherical or irregular shapes, of heavy or light consistency, and even liquid particles are placed inside cavities or attached to structures by an appropriate means at strategic locations, to absorb vibration energy. The objective of the work described herein is the development of a design optimization procedure and discussion of test results for such a NOPD treatment on honeycomb (HC) composite structures, based on finite element modeling (FEM) analyses, optimization and tests. Modeling and predictions were performed and tests were carried out to correlate the test data with the FEM. The optimization procedure consisted of defining a global objective function, using finite difference methods, to determine the optimal values of the design variables through quadratic linear programming. The optimization process was carried out by targeting the highest dynamic displacements of several vibration modes of the structure and finding an optimal treatment configuration that will minimize them. An optimal design was thus derived and laboratory tests were conducted to evaluate its performance under different vibration environments. Three honeycomb composite beams, with Nomex core and aluminum face sheets, empty (untreated), uniformly treated with NOPD, and optimally treated with NOPD, according to the analytically predicted optimal design configuration, were tested in the laboratory. It is shown that the beam with optimal treatment has the lowest response amplitude. Described below are results of modal vibration tests and FEM analyses from predictions of the modal characteristics of honeycomb beams under zero, 50% uniform treatment and an optimal NOPD treatment design configuration and verification with test data.

DFT simulations and vibrational spectra of 2-amino-2-methyl-1,3-propanediol.

PubMed

Renuga Devi, T S; Sharmi kumar, J; Ramkumaar, G R

2014-12-10

The FTIR and FT-Raman spectra of 2-amino-2-methyl-1,3-propanediol were recorded in the regions 4000-400cm(-1) and 4000-50cm(-1) respectively. The structural and spectroscopic data of the molecule in the ground state were calculated using Hartee-Fock and density functional method (B3LYP) with the augmented-correlation consistent-polarized valence double zeta (aug-cc-pVDZ) basis set. The most stable conformer was optimized and the structural and vibrational parameters were determined based on this. The complete assignments were performed on the basis of the Potential Energy Distribution (PED) of the vibrational modes, calculated using Vibrational Energy Distribution Analysis (VEDA) 4 program. With the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. Thermodynamic properties and Mulliken charges were calculated using both Hartee-Fock and density functional method using the aug-cc-pVDZ basis set and compared. The calculated HOMO-LUMO energy gap revealed that charge transfer occurs within the molecule. (1)H and (13)C NMR chemical shifts of the molecule were calculated using Gauge-Independent Atomic Orbital (GIAO) method and were compared with experimental results. Copyright © 2014 Elsevier B.V. All rights reserved.

Hand-arm vibration syndrome: clinical characteristics, conventional electrophysiology and quantitative sensory testing.

PubMed

Rolke, Roman; Rolke, Silke; Vogt, Thomas; Birklein, Frank; Geber, Christian; Treede, Rolf-Detlef; Letzel, Stephan; Voelter-Mahlknecht, Susanne

2013-08-01

Workers exposed to vibrating tools may develop hand-arm vibration syndrome (HAVS). We assessed the somatosensory phenotype using quantitative sensory testing (QST) in comparison to electrophysiology to characterize (1) the most sensitive QST parameter for detecting sensory loss, (2) the correlation of QST and electrophysiology, and (3) the frequency of a carpal tunnel syndrome (CTS) in HAVS. QST, cold provocation tests, fine motor skills, and median nerve neurography were used. QST included thermal and mechanical detection and pain thresholds. Thirty-two patients were examined (54 ± 11 years, 91% men) at the more affected hand compared to 16 matched controls. Vibration detection threshold was the most sensitive parameter to detect sensory loss that was more pronounced in the sensitivity range of Pacinian (150 Hz, x12) than Meissner's corpuscles (20 Hz, x3). QST (84% abnormal) was more sensitive to detect neural dysfunction than conventional electrophysiology (37% abnormal). Motor (34%) and sensory neurography (25%) were abnormal in HAVS. CTS frequency was not increased (9.4%). Findings are consistent with a mechanically-induced, distally pronounced motor and sensory neuropathy independent of CTS. HAVS involves a neuropathy predominantly affecting large fibers with a sensory damage related to resonance frequencies of vibrating tools. Copyright © 2013 International Federation of Clinical Neurophysiology. Published by Elsevier Ireland Ltd. All rights reserved.

Autonomous Modal Identification of the Space Shuttle Tail Rudder

NASA Technical Reports Server (NTRS)

Pappa, Richard S.; James, George H., III; Zimmerman, David C.

1997-01-01

Autonomous modal identification automates the calculation of natural vibration frequencies, damping, and mode shapes of a structure from experimental data. This technology complements damage detection techniques that use continuous or periodic monitoring of vibration characteristics. The approach shown in the paper incorporates the Eigensystem Realization Algorithm (ERA) as a data analysis engine and an autonomous supervisor to condense multiple estimates of modal parameters using ERA's Consistent-Mode Indicator and correlation of mode shapes. The procedure was applied to free-decay responses of a Space Shuttle tail rudder and successfully identified the seven modes of the structure below 250 Hz. The final modal parameters are a condensed set of results for 87 individual ERA cases requiring approximately five minutes of CPU time on a DEC Alpha computer.

Better band gaps for wide-gap semiconductors from a locally corrected exchange-correlation potential that nearly eliminates self-interaction errors

DOE PAGES

Singh, Prashant; Harbola, Manoj K.; Johnson, Duane D.

2017-09-08

Here, this work constitutes a comprehensive and improved account of electronic-structure and mechanical properties of silicon-nitride (more » $${\\rm Si}_{3}$$ $${\\rm N}_{4}$$ ) polymorphs via van Leeuwen and Baerends (LB) exchange-corrected local density approximation (LDA) that enforces the exact exchange potential asymptotic behavior. The calculated lattice constant, bulk modulus, and electronic band structure of $${\\rm Si}_{3}$$ $${\\rm N}_{4}$$ polymorphs are in good agreement with experimental results. We also show that, for a single electron in a hydrogen atom, spherical well, or harmonic oscillator, the LB-corrected LDA reduces the (self-interaction) error to exact total energy to ~10%, a factor of three to four lower than standard LDA, due to a dramatically improved representation of the exchange-potential.« less

F+ and F⁻ affinities of simple N(x)F(y) and O(x)F(y) compounds.

PubMed

Grant, Daniel J; Wang, Tsang-Hsiu; Vasiliu, Monica; Dixon, David A; Christe, Karl O

2011-03-07

Atomization energies at 0 K and heats of formation at 0 and 298 K are predicted for the neutral and ionic N(x)F(y) and O(x)F(y) systems using coupled cluster theory with single and double excitations and including a perturbative triples correction (CCSD(T)) method with correlation consistent basis sets extrapolated to the complete basis set (CBS) limit. To achieve near chemical accuracy (±1 kcal/mol), three corrections to the electronic energy were added to the frozen core CCSD(T)/CBS binding energies: corrections for core-valence, scalar relativistic, and first order atomic spin-orbit effects. Vibrational zero point energies were computed at the CCSD(T) level of theory where possible. The calculated heats of formation are in good agreement with the available experimental values, except for FOOF because of the neglect of higher order correlation corrections. The F(+) affinity in the N(x)F(y) series increases from N(2) to N(2)F(4) by 63 kcal/mol, while that in the O(2)F(y) series decreases by 18 kcal/mol from O(2) to O(2)F(2). Neither N(2) nor N(2)F(4) is predicted to bind F(-), and N(2)F(2) is a very weak Lewis acid with an F(-) affinity of about 10 kcal/mol for either the cis or trans isomer. The low F(-) affinities of the nitrogen fluorides explain why, in spite of the fact that many stable nitrogen fluoride cations are known, no nitrogen fluoride anions have been isolated so far. For example, the F(-) affinity of NF is predicted to be only 12.5 kcal/mol which explains the numerous experimental failures to prepare NF(2)(-) salts from the well-known strong acid HNF(2). The F(-) affinity of O(2) is predicted to have a small positive value and increases for O(2)F(2) by 23 kcal/mol, indicating that the O(2)F(3)(-) anion might be marginally stable at subambient temperatures. The calculated adiabatic ionization potentials and electron affinities are in good agreement with experiment considering that many of the experimental values are for vertical processes. © 2011 American Chemical Society

A correlated ab initio study of the A2 pi <-- X2 sigma+ transition in MgCCH

NASA Technical Reports Server (NTRS)

Woon, D. E.

1997-01-01

The A2 pi <-- X2 sigma+ transition in MgCCH was studied with correlation consistent basis sets and single- and multireference correlation methods. The A2 pi excited state was characterized in detail; the x2 sigma+ ground state has been described elsewhere recently. The estimated complete basis set (CBS) limits for valence correlation, including zero-point energy corrections, are 22668, 23191, and 22795 for the RCCSD(T), MRCI, and MRCI + Q methods, respectively. A core-valence correction of +162 cm-1 shifts the RCCSD(T) value to 22830 cm-1, in good agreement with the experimental result of 22807 cm-1.

Hydration of Sulphobetaine (SB) and Tetra(ethylene glycol) (EG4)-Terminated Self-Assembled Monolayers Studied by Sum Frequency Generation (SFG) Vibrational Spectroscopy

PubMed Central

Stein, M. Jeanette; Weidner, Tobias; McCrea, Keith; Castner, David G.; Ratner, Buddy D.

2010-01-01

Sum frequency generation (SFG) vibrational spectroscopy is used to study the surface and the underlying substrate of both homogeneous and mixed self-assembled monolayers (SAMs) of 11-mercaptoundecyl-1-sulphobetainethiol (HS(CH2)11N+(CH3)2(CH2)3SO3−, SB) and 1-mercapto-11-undecyl tetra(ethylene glycol) (HS(CH2)11O(CH2CH2O)4OH, EG4) with an 11-mercapto-1-undecanol (HS(CH2)11OH, MCU) diluent. SFG results on the C–H region of the dry and hydrated SAMs gave an in situ look into the molecular orientation and suggested an approach to maximize signal-to-noise ratio on these difficult to analyze hydrophilic SAMs. Vibrational fingerprint studies in the 3000–3600 cm−1 spectral range for the SAMs exposed serially to air, water, and deuterated water revealed that a layer of tightly-bound structured water was associated with the surface of a non-fouling monolayer but was not present on a hydrophobic N-undecylmercaptan (HS(CH2)10CH3, UnD) control. The percentage of water retained upon submersion in D2O correlated well with the relative amount of protein that was previously shown to absorb onto the monolayers. These results provide evidence supporting the current theory regarding the role of a tightly-bound vicinal water layer in the protein resistance of a non-fouling group. PMID:19639981

The self-consistent calculation of pseudo-molecule energy levels, construction of energy level correlation diagrams and an automated computation system for SCF-X(Alpha)-SW calculations

NASA Technical Reports Server (NTRS)

Schlosser, H.

1981-01-01

The self consistent calculation of the electronic energy levels of noble gas pseudomolecules formed when a metal surface is bombarded by noble gas ions is discussed along with the construction of energy level correlation diagrams as a function of interatomic spacing. The self consistent field x alpha scattered wave (SCF-Xalpha-SW) method is utilized. Preliminary results on the Ne-Mg system are given. An interactive x alpha programming system, implemented on the LeRC IBM 370 computer, is described in detail. This automated system makes use of special PROCDEFS (procedure definitions) to minimize the data to be entered manually at a remote terminal. Listings of the special PROCDEFS and of typical input data are given.

Middle School Engagement with Mathematics Software and Later Interest and Self-Efficacy for STEM Careers

NASA Astrophysics Data System (ADS)

Ocumpaugh, Jaclyn; San Pedro, Maria Ofelia; Lai, Huei-yi; Baker, Ryan S.; Borgen, Fred

2016-12-01

Research suggests that trajectories toward careers in science, technology, engineering, and mathematics (STEM) emerge early and are influenced by multiple factors. This paper presents a longitudinal study, which uses data from 76 high school students to explore how a student's vocational self-efficacy and interest are related to his or her middle school behavioral and affective engagement. Measures of vocational self-efficacy and interest are drawn from STEM-related scales in CAPAExplore, while measures of middle school performance and engagement in mathematics are drawn from several previously validated automated indicators extracted from logs of student interaction with ASSISTments, an online learning platform. Results indicate that vocational self-efficacy correlates negatively with confusion, but positively with engaged concentration and carelessness. Interest, which also correlates negatively with confusion, correlates positively with correctness and carelessness. Other disengaged behaviors, such as gaming the system, were not correlated with vocational self-efficacy or interest, despite previous studies indicating that they are associated with future college attendance. We discuss implications for these findings, which have the potential to assist educators or counselors in developing strategies to sustain students' interest in STEM-related careers.

Correlations between self-assessed hearing handicap and standard audiometric tests in elderly persons.

PubMed

Pedersen, K; Rosenhall, U

1991-01-01

The relationship between self-assessed hearing handicap and audiometric measures using pure-tone and speech audiometry was studied in a group of elderly persons representative of an urban Swedish population. The study population consisted of two cohorts, one of which was followed longitudinally. Significant correlations between measured and self-assessed hearing were found. Speech discrimination scores showed lower correlations with the self-estimated hearing than pure-tone averages and speech reception threshold. Questions concerning conversation with one person and concerning difficulty in hearing the doorbell showed lower correlations with measured hearing than the other questions. The discrimination score test is an inadequate tool for measuring hearing handicap.

Screening for dietary fat intake of grade six children: self-assessment vs. maternal assessment.

PubMed

Wenhold, Friede; MacIntyre, Una; Rheeder, Paul

2014-10-01

As part of justifiable nutrition promotion, this study aimed to determine internal consistency of a dietary fat screener and to compare self-assessment to maternal assessment of fat intake of grade six (about 12 years old) learners in a South African public primary school. The children completed in school a pictorial, quantitative food frequency-type screener consisting of 10 high-fat food categories; mothers individually completed a text version. Internal consistency was measured with item-total correlations, Cronbach's alpha and the split-half method. Child-mother comparison was based on kappa (κ) statistics, McNemar's tests, Wilcoxon signed-rank test and the Bland-Altman method. In total, 101 (93.5%) children and 78 (72.2%) mothers responded. The screener was internally consistent, regardless of data source and statistical technique. For portion sizes and frequency of intake, children consistently reported higher intake than mothers. This resulted in systematic error, also evidenced by a significant difference from zero for the difference between child's and mother's final test scores for the whole group, and for boys and girls separately (always P < 0.001). In 76% of the pairs, classification into high fat or prudent intake was identical, yet the chance-corrected agreement was poor (κ = 0.16) and non-agreement was non-symmetrical (P = 0.001). Children and mothers reported high fat intakes (93% and 75%, respectively). It was concluded that the dietary fat screener was internally consistent, yet children and mothers did not agree in their assessment. The high fat intakes reported by children and mothers warrant measurement refinement and implementation of primary prevention programmes. © 2012 John Wiley & Sons Ltd.

Altered Neural Correlate of the Self-Agency Experience in First-Episode Schizophrenia-Spectrum Patients: An fMRI Study

PubMed Central

Spaniel, Filip; Tintera, Jaroslav; Rydlo, Jan; Ibrahim, Ibrahim; Kasparek, Tomas; Horacek, Jiri; Zaytseva, Yuliya; Matejka, Martin; Fialova, Marketa; Slovakova, Andrea; Mikolas, Pavol; Melicher, Tomas; Görnerova, Natalie; Höschl, Cyril; Hajek, Tomas

2016-01-01

Background: The phenomenology of the clinical symptoms indicates that disturbance of the sense of self be a core marker of schizophrenia. Aims: To compare neural activity related to the self/other-agency judgment in patients with first-episode schizophrenia-spectrum disorders (FES, n = 35) and healthy controls (HC, n = 35). Method: A functional magnetic resonance imaging (fMRI) using motor task with temporal distortion of the visual feedback was employed. A task-related functional connectivity was analyzed with the use of independent component analysis (ICA). Results: (1) During self-agency experience, FES showed a deficit in cortical activation in medial frontal gyrus (BA 10) and posterior cingulate gyrus, (BA 31; P < .05, Family-Wise Error [FWE] corrected). (2) Pooled-sample task-related ICA revealed that the self/other-agency judgment was dependent upon anti-correlated default mode and central-executive networks (DMN/CEN) dynamic switching. This antagonistic mechanism was substantially impaired in FES during the task. Discussion: During self-agency experience, FES demonstrate deficit in engagement of cortical midline structures along with substantial attenuation of anti-correlated DMN/CEN activity underlying normal self/other-agency discriminative processes. PMID:26685867

Correlation of finite-element structural dynamic analysis with measured free vibration characteristics for a full-scale helicopter fuselage

NASA Technical Reports Server (NTRS)

Kenigsberg, I. J.; Dean, M. W.; Malatino, R.

1974-01-01

The correlation achieved with each program provides the material for a discussion of modeling techniques developed for general application to finite-element dynamic analyses of helicopter airframes. Included are the selection of static and dynamic degrees of freedom, cockpit structural modeling, and the extent of flexible-frame modeling in the transmission support region and in the vicinity of large cut-outs. The sensitivity of predicted results to these modeling assumptions are discussed. Both the Sikorsky Finite-Element Airframe Vibration analysis Program (FRAN/Vibration Analysis) and the NASA Structural Analysis Program (NASTRAN) have been correlated with data taken in full-scale vibration tests of a modified CH-53A helicopter.

Quantum coherence selective 2D Raman–2D electronic spectroscopy

PubMed Central

Spencer, Austin P.; Hutson, William O.; Harel, Elad

2017-01-01

Electronic and vibrational correlations report on the dynamics and structure of molecular species, yet revealing these correlations experimentally has proved extremely challenging. Here, we demonstrate a method that probes correlations between states within the vibrational and electronic manifold with quantum coherence selectivity. Specifically, we measure a fully coherent four-dimensional spectrum which simultaneously encodes vibrational–vibrational, electronic–vibrational and electronic–electronic interactions. By combining near-impulsive resonant and non-resonant excitation, the desired fifth-order signal of a complex organic molecule in solution is measured free of unwanted lower-order contamination. A critical feature of this method is electronic and vibrational frequency resolution, enabling isolation and assignment of individual quantum coherence pathways. The vibronic structure of the system is then revealed within an otherwise broad and featureless 2D electronic spectrum. This method is suited for studying elusive quantum effects in which electronic transitions strongly couple to phonons and vibrations, such as energy transfer in photosynthetic pigment–protein complexes. PMID:28281541

Rate coefficients of exchange reactions accounting for vibrational excitation of reagents and products

NASA Astrophysics Data System (ADS)

Kustova, E. V.; Savelev, A. S.; Kunova, O. V.

2018-05-01

Theoretical models for the vibrational state-resolved Zeldovich reaction are assessed by comparison with the results of quasi-classical trajectory (QCT) calculations. An error in the model of Aliat is corrected; the model is generalized taking into account NO vibrational states. The proposed model is fairly simple and can be easily implemented to the software for non-equilibrium flow modeling. It provides a good agreement with the QCT rate coefficients in the whole range of temperatures and reagent/product vibrational states. The developed models are tested in simulations of vibrational and chemical relaxation of air mixture behind a shock wave. The importance of accounting for excitated NO vibrational states and accurate prediction of Zeldovich reactions rates is shown.

Relationships between Contextual and Task Performance and Interrater Agreement: Are There Any?

PubMed

Díaz-Vilela, Luis F; Delgado Rodríguez, Naira; Isla-Díaz, Rosa; Díaz-Cabrera, Dolores; Hernández-Fernaud, Estefanía; Rosales-Sánchez, Christian

2015-01-01

Work performance is one of the most important dependent variables in Work and Organizational Psychology. The main objective of this paper was to explore the relationships between citizenship performance and task performance measures obtained from different appraisers and their consistency through a seldom-used methodology, intraclass correlation coefficients. Participants were 135 public employees, the total staff in a local government department. Jobs were clustered into job families through a work analysis based on standard questionnaires. A task description technique was used to develop a performance appraisal questionnaire for each job family, with three versions: self-, supervisor-, and peer-evaluation, in addition to a measure of citizenship performance. Only when the self-appraisal bias is controlled, significant correlations appeared between task performance rates. However, intraclass correlations analyses show that only self- (contextual and task) performance measures are consistent, while interrater agreement disappears. These results provide some interesting clues about the procedure of appraisal instrument development, the role of appraisers, and the importance of choosing adequate consistency analysis methods.

Relationships between Contextual and Task Performance and Interrater Agreement: Are There Any?

PubMed Central

Díaz-Cabrera, Dolores; Hernández-Fernaud, Estefanía; Rosales-Sánchez, Christian

2015-01-01

Work performance is one of the most important dependent variables in Work and Organizational Psychology. The main objective of this paper was to explore the relationships between citizenship performance and task performance measures obtained from different appraisers and their consistency through a seldom-used methodology, intraclass correlation coefficients. Participants were 135 public employees, the total staff in a local government department. Jobs were clustered into job families through a work analysis based on standard questionnaires. A task description technique was used to develop a performance appraisal questionnaire for each job family, with three versions: self-, supervisor-, and peer-evaluation, in addition to a measure of citizenship performance. Only when the self-appraisal bias is controlled, significant correlations appeared between task performance rates. However, intraclass correlations analyses show that only self- (contextual and task) performance measures are consistent, while interrater agreement disappears. These results provide some interesting clues about the procedure of appraisal instrument development, the role of appraisers, and the importance of choosing adequate consistency analysis methods. PMID:26473956

Relationship of self-management to personality types and indices.

PubMed

Williams, R L; Verble, J S; Price, D E; Layne, B H

1995-06-01

This study addressed the relationship between self-management (as measured by the Lifestyle Approaches Inventory, Williams, Moore, Pettibone, & Thomas, 1992) and personality types and indexes (as measured by the Myers-Briggs Type Indicator, Myers & McCaulley, 1985) in a sample of 347 university students. Correlational analyses indicated that the self-management factor most consistently linked to the Myers-Briggs indices was Organization of Physical Space. The Myers-Briggs index most consistently correlated with the self-management factors was Judgment-Perception. Overall, male and female subjects showed similar patterns of relationships between the self-management and personality indices. When the self-management scores were compared for the various Myers-Briggs types, the analysis indicated that types having a J (planful and organized) or S (precise and practical) in the typology tended to score higher than those having a P (spontaneous and flexible) or N (imaginative and insightful).

Correction for faking in self-report personality tests.

PubMed

Sjöberg, Lennart

2015-10-01

Faking is a common problem in testing with self-report personality tests, especially in high-stakes situations. A possible way to correct for it is statistical control on the basis of social desirability scales. Two such scales were developed and applied in the present paper. It was stressed that the statistical models of faking need to be adapted to different properties of the personality scales, since such scales correlate with faking to different extents. In four empirical studies of self-report personality tests, correction for faking was investigated. One of the studies was experimental, and asked participants to fake or to be honest. In the other studies, job or school applicants were investigated. It was found that the approach to correct for effects of faking in self-report personality tests advocated in the paper removed a large share of the effects, about 90%. It was found in one study that faking varied as a function of degree of how important the consequences of test results could be expected to be, more high-stakes situations being associated with more faking. The latter finding is incompatible with the claim that social desirability scales measure a general personality trait. It is concluded that faking can be measured and that correction for faking, based on such measures, can be expected to remove about 90% of its effects. © 2015 Psykologisk Metod AB. Scandinavian Journal of Psychology published by Scandinavian Psychological Associations and John Wiley & Sons Ltd.

Parametrization and Benchmark of Long-Range Corrected DFTB2 for Organic Molecules

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

Vuong, Van Quan; Akkarapattiakal Kuriappan, Jissy; Kubillus, Maximilian

In this paper, we present the parametrization and benchmark of long-range corrected second-order density functional tight binding (DFTB), LC-DFTB2, for organic and biological molecules. The LC-DFTB2 model not only improves fundamental orbital energy gaps but also ameliorates the DFT self-interaction error and overpolarization problem, and further improves charge-transfer excited states significantly. Electronic parameters for the construction of the DFTB2 Hamiltonian as well as repulsive potentials were optimized for molecules containing C, H, N, and O chemical elements. We use a semiautomatic parametrization scheme based on a genetic algorithm. With the new parameters, LC-DFTB2 describes geometries and vibrational frequencies of organicmore » molecules similarly well as third-order DFTB3/3OB, the de facto standard parametrization based on a GGA functional. Finally, LC-DFTB2 performs well also for atomization and reaction energies, however, slightly less satisfactorily than DFTB3/3OB.« less

Parametrization and Benchmark of Long-Range Corrected DFTB2 for Organic Molecules

DOE PAGES

Vuong, Van Quan; Akkarapattiakal Kuriappan, Jissy; Kubillus, Maximilian; ...

2017-12-12

In this paper, we present the parametrization and benchmark of long-range corrected second-order density functional tight binding (DFTB), LC-DFTB2, for organic and biological molecules. The LC-DFTB2 model not only improves fundamental orbital energy gaps but also ameliorates the DFT self-interaction error and overpolarization problem, and further improves charge-transfer excited states significantly. Electronic parameters for the construction of the DFTB2 Hamiltonian as well as repulsive potentials were optimized for molecules containing C, H, N, and O chemical elements. We use a semiautomatic parametrization scheme based on a genetic algorithm. With the new parameters, LC-DFTB2 describes geometries and vibrational frequencies of organicmore » molecules similarly well as third-order DFTB3/3OB, the de facto standard parametrization based on a GGA functional. Finally, LC-DFTB2 performs well also for atomization and reaction energies, however, slightly less satisfactorily than DFTB3/3OB.« less

Vibrational Properties of Anhydrous and Partially Hydrated Uranyl Fluoride

DOE PAGES

Anderson, Brian B.; Kirkegaard, Marie C.; Miskowiec, Andrew J.; ...

2017-01-01

Uranyl fluoride (UO 2F 2) is a hygroscopic powder with two main structural phases: an anhydrous crystal and a partially hydrated crystal of the same R¯3m symmetry. The formally closed-shell electron structure of anhydrous UO 2F 2 is amenable to density functional theory calculations. We use density functional perturbation theory (DFPT) to calculate the vibrational frequencies of the anhydrous crystal structure and employ complementary inelastic neutron scattering and temperature-dependent Raman scattering to validate those frequencies. As a model closed-shell actinide, we investigated the effect of LDA, GGA, and non-local vdW functionals as well as the spherically-averaged Hubbard +U correction onmore » vibrational frequencies, electronic structure, and geometry of anhydrous UO 2F 2. A particular choice of U eff = 5.5 eV yields the correct U Oyl bond distance and vibrational frequencies for the characteristic Eg and A1g modes that are within the resolution of experiment. Inelastic neutron scattering and Raman scattering suggest a degree of water coupling to the lattice vibrations in the more experimentally accessible partially hydrated UO 2F 2 system, with the symmetric O-U-O stretching vibration shifted approximately 47 cm -1 lower in energy compared to the anhydrous structure. Evidence of water interaction with the uranyl ion is present from a two-peak decomposition of the uranyl stretching vibration in the Raman spectra and anion hydrogen stretching vibrations in the inelastic neutron scattering spectra. A first-order dehydration phase transition temperature is definitively identified to be 125 °C using temperature-dependent Raman scattering.« less

Vibration-induced particle formation during yogurt fermentation-Effect of frequency and amplitude.

PubMed

Körzendörfer, Adrian; Temme, Philipp; Schlücker, Eberhard; Hinrichs, Jörg; Nöbel, Stefan

2018-05-01

Machinery such as pumps used for the commercial production of fermented milk products cause vibrations that can spread to the fermentation tanks. During fermentation, such vibrations can disturb the gelation of milk proteins by causing texture defects including lumpiness and syneresis. To study the effect of vibrations on yogurt structure systematically, an experimental setup was developed consisting of a vibration exciter to generate defined vibrational states and accelerometers for monitoring. During the fermentation of skim milk, vibrations (frequency sweep: 25 to 1,005 Hz) were introduced at different pH (5.7 to 5.1, step width 0.1 units) for 200 s. Physical properties of set gels (syneresis, firmness) and resultant stirred yogurts (visible particles, rheology, laser diffraction) were analyzed. Vibrational treatments at pH 5.5 to 5.2 increased syneresis, gel firmness, and the number of large particles (d > 0.9 mm); hence, this period was considered critical. The particle number increased from 34 ± 5 to 242 ± 16 particles per 100 g of yogurt due to vibrations at pH 5.4. In further experiments, yogurts were excited with fixed frequencies (30, 300, and 1,000 Hz). All treatments increased syneresis, firmness, and particle formation. As the strongest effect was observed by applying 30 Hz, the amplitude was set to vibration accelerations of a = 5, 10, 15, 20, and 25 m/s 2 in the final experiments. The number of large particles was increased due to each treatment and a positive correlation with the amplitude was found. We concluded that vibrations during gelation increase the collision probability of aggregating milk proteins, resulting in a compressed set gel with syneresis. Resultant stirred yogurts exhibit large particles with a compact structure leading to a reduced water-holding capacity and product viscosity. Copyright © 2018 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Learning How Students Learn: An Exploration of Self-Regulation Strategies in a Two-Year College General Chemistry Class

ERIC Educational Resources Information Center

Miller, Dionne A.

2015-01-01

This study investigated how students in an urban 2-year college used self-regulation strategies in a General Chemistry I course and whether their use was correlated with both performance and the ability to correctly predict performance on a course exam. The 142 students enrolled in all 10 sections of the course were asked to complete the Motivated…

Gyrodampers for large space structures

NASA Technical Reports Server (NTRS)

Aubrun, J. N.; Margulies, G.

1979-01-01

The problem of controlling the vibrations of a large space structures by the use of actively augmented damping devices distributed throughout the structure is addressed. The gyrodamper which consists of a set of single gimbal control moment gyros which are actively controlled to extract the structural vibratory energy through the local rotational deformations of the structure, is described and analyzed. Various linear and nonlinear dynamic simulations of gyrodamped beams are shown, including results on self-induced vibrations due to sensor noise and rotor imbalance. The complete nonlinear dynamic equations are included. The problem of designing and sizing a system of gyrodampers for a given structure, or extrapolating results for one gyrodamped structure to another is solved in terms of scaling laws. Novel scaling laws for gyro systems are derived, based upon fundamental physical principles, and various examples are given.

Analytical and numerical analysis of imaging mechanism of dynamic scanning electron microscopy.

PubMed

Schröter, M-A; Holschneider, M; Sturm, H

2012-11-02

The direct observation of small oscillating structures with the help of a scanning electron beam is a new approach to study the vibrational dynamics of cantilevers and microelectromechanical systems. In the scanning electron microscope, the conventional signal of secondary electrons (SE, dc part) is separated from the signal response of the SE detector, which is correlated to the respective excitation frequency for vibration by means of a lock-in amplifier. The dynamic response is separated either into images of amplitude and phase shift or into real and imaginary parts. Spatial resolution is limited to the diameter of the electron beam. The sensitivity limit to vibrational motion is estimated to be sub-nanometer for high integration times. Due to complex imaging mechanisms, a theoretical model was developed for the interpretation of the obtained measurements, relating cantilever shapes to interaction processes consisting of incident electron beam, electron-lever interaction, emitted electrons and detector response. Conclusions drawn from this new model are compared with numerical results based on the Euler-Bernoulli equation.

Vibration extraction based on fast NCC algorithm and high-speed camera.

PubMed

Lei, Xiujun; Jin, Yi; Guo, Jie; Zhu, Chang'an

2015-09-20

In this study, a high-speed camera system is developed to complete the vibration measurement in real time and to overcome the mass introduced by conventional contact measurements. The proposed system consists of a notebook computer and a high-speed camera which can capture the images as many as 1000 frames per second. In order to process the captured images in the computer, the normalized cross-correlation (NCC) template tracking algorithm with subpixel accuracy is introduced. Additionally, a modified local search algorithm based on the NCC is proposed to reduce the computation time and to increase efficiency significantly. The modified algorithm can rapidly accomplish one displacement extraction 10 times faster than the traditional template matching without installing any target panel onto the structures. Two experiments were carried out under laboratory and outdoor conditions to validate the accuracy and efficiency of the system performance in practice. The results demonstrated the high accuracy and efficiency of the camera system in extracting vibrating signals.

The Shock and Vibration Bulletin. Part 4. Vibration Testing, Instrumentation, Loads and Environments, Tracked Vehicles

DTIC Science & Technology

1978-09-01

self with a nonlinear (thermocouple) function, the limits X os nu 2O being: x Enables Temperature Controller to command heat 0 Code Temnperature ___6...34 Shock and Vi- bration Bulletin 42, 1970. (2) R.T. Fandrich, " Self -Tuning Re- • sonant Fixtures", 47th Shock andVibration Symposium, October 1976. . " (3...is given in Fig. 4. timTit for "ysem From the shape of some of these it is apparent linear respose that in some tests dampino ratios of the order 0 of

The revising of the Tangney Self-Control Scale for Chinese students.

PubMed

Unger, Alexander; Bi, Chongzeng; Xiao, Ying-Ying; Ybarra, Oscar

2016-06-01

Recent studies have characterized self-control as a vital psychological variable that helps explain various problems. Tangney's Self-Control Scale (SCS) is a self-report measurement to assess individual differences in traits of self-control. It has gained popularity in social and psychological science research. In China, there are a few Chinese-version scales measuring general self-control, which can be applied to college students. The purposes of the present study were to evaluate: (a) the psychometric properties of the Chinese version of Tangney's SCS using confirmatory factor analysis, and (b) whether higher scores on the scale correlated with positive outcomes in China. The final sample in this study consisted of 371 Chinese college students aged 17-23 years. The Full SCS and Brief SCS were both found to have a reasonable fitness, which also had satisfactory internal consistencies and a high correlation. Higher scores on the SCS correlated with higher self-esteem, extraversion, better harmony in interpersonal relationships and an appropriate anger expression, less impulsiveness, and state and trait anger. The test-retest reliability was confirmed in two additional samples. Tangney's SCS could be used in China. © 2016 The Institute of Psychology, Chinese Academy of Sciences and John Wiley & Sons Australia, Ltd.

E 2 / M 1 Mixing Ratios in Transitions From the Gamma-Vibrational-Bands to the Ground-State-Rotational-Bands of 102 , 104 , 106 , 108Mo, 108 , 110 , 112Ru, and 112 , 114 , 116Pd

NASA Astrophysics Data System (ADS)

Eldridge, Jonathan M.; Fenker, B.; Goodin, C.; Hamilton, J. H.; Wang, E. H.; Ramayya, A. V.; Daniel, A. V.; Ter-Akopian, G. M.; Luo, Y. X.; Rasmussen, J. O.; Oganesson, Yu. Ts.; Zhu, S. J.

2017-09-01

E 2 / M 1 mixing ratios have been measured for transitions from states in the γ-vibrational-bands (Iγ+) to states in the ground-state-bands (Ig+ or [I- 1 ] g +) of the neutron rich, deformed isotopes, 102 , 104 , 106 , 108Mo, 108 , 110 , 112Ru, and 112 , 114 , 116Pd, including from states as high as 9γ+. These measurements were done using the GAMMASPHERE detector array, which, at the time of the experiment, had 101 working HPGe detectors, arranged at 64 different angles. A 62 μCi source of 252Cf was placed inside GAMMASPHERE yielding 5.7 ×1011 γ - γ - γ and higher coincidence events. The angular correlation between the transitions from the γ-band to the ground band, and the pure E2 transitions within the ground band were then measured. These angular correlations yielded the mixing ratios, demonstrating that these transitions are all pure or nearly pure E2, in agreement with theory. In order to correct for possible attenuation due to the lifetime of the intermediate state in these correlations, the g-factors of the intermediate states needed to be known. Therefore, the g-factors of the 2g+ states in the ground state band have been measured. Supported by the US Department of Energy; Grant No. DE-FG0588ER40407, Contract No. DE-AC03-76SF00098.

Two-loop self-energy in the Lamb shift of the ground and excited states of hydrogenlike ions

NASA Astrophysics Data System (ADS)

Yerokhin, V. A.

2018-05-01

The two-loop self-energy correction to the Lamb shift of hydrogenlike ions is calculated for the 1 s , 2 s , and 2 p1 /2 states and nuclear charge numbers Z =30 -100 . The calculation is performed to all orders in the nuclear binding strength parameter Z α . As compared to previous calculations of this correction, numerical accuracy is improved by an order of magnitude and the region of the nuclear charges is extended. An analysis of the Z dependence of the obtained results demonstrates their consistency with the known Z α -expansion coefficients.

Compact vibration isolation and suspension for Australian International Gravitational Observatory: Local control system

NASA Astrophysics Data System (ADS)

Dumas, Jean-Charles; Barriga, Pablo; Zhao, Chunnong; Ju, Li; Blair, David G.

2009-11-01

High performance vibration isolators are required for ground based gravitational wave detectors. To attain very high performance at low frequencies we have developed multistage isolators for the proposed Australian International Gravitational Observatory detector in Australia. New concepts in vibration isolation including self-damping, Euler springs, LaCoste springs, Roberts linkages, and double preisolation require novel sensors and actuators. Double preisolation enables internal feedback to be used to suppress low frequency seismic noise. Multidegree of freedom control systems are required to attain high performance. Here we describe the control components and control systems used to control all degrees of freedom. Feedback forces are injected at the preisolation stages and at the penultimate suspension stage. There is no direct actuation on test masses. A digital local control system hosted on a digital signal processor maintains alignment and position, corrects drifts, and damps the low frequency linear and torsional modes without exciting the very high Q-factor test mass suspension. The control system maintains an optical cavity locked to a laser with a high duty cycle even in the absence of an autoalignment system. An accompanying paper presents the mechanics of the system, and the optical cavity used to determine isolation performance. A feedback method is presented, which is expected to improve the residual motion at 1 Hz by more than one order of magnitude.

Compact vibration isolation and suspension for Australian International Gravitational Observatory: local control system.

PubMed

Dumas, Jean-Charles; Barriga, Pablo; Zhao, Chunnong; Ju, Li; Blair, David G

2009-11-01

High performance vibration isolators are required for ground based gravitational wave detectors. To attain very high performance at low frequencies we have developed multistage isolators for the proposed Australian International Gravitational Observatory detector in Australia. New concepts in vibration isolation including self-damping, Euler springs, LaCoste springs, Roberts linkages, and double preisolation require novel sensors and actuators. Double preisolation enables internal feedback to be used to suppress low frequency seismic noise. Multidegree of freedom control systems are required to attain high performance. Here we describe the control components and control systems used to control all degrees of freedom. Feedback forces are injected at the preisolation stages and at the penultimate suspension stage. There is no direct actuation on test masses. A digital local control system hosted on a digital signal processor maintains alignment and position, corrects drifts, and damps the low frequency linear and torsional modes without exciting the very high Q-factor test mass suspension. The control system maintains an optical cavity locked to a laser with a high duty cycle even in the absence of an autoalignment system. An accompanying paper presents the mechanics of the system, and the optical cavity used to determine isolation performance. A feedback method is presented, which is expected to improve the residual motion at 1 Hz by more than one order of magnitude.

Psychometric Testing of the Self-Efficacy for Interdisciplinary Plans of Care Scale.

PubMed

Molle, Elizabeth; Froman, Robin

2017-01-01

Computerized interdisciplinary plans of care have revitalized nurse-centric care plans into dynamic and meaningful electronic documents. To maximize the benefits of these documents, it is important to understand healthcare professionals' attitudes, specifically their confidence, for making computerized interdisciplinary care plans useful and meaningful documents. The purpose of the study was to test the psychometric properties of the Self-Efficacy for Interdisciplinary Plans of Care instrument intended to measure healthcare professionals' self-efficacy for using such documents. Content validity was assessed by an expert review panel. Content validity indices ranged from 0.75 to 1.00, with a scale CVI of 0.94. A sample of 389 healthcare providers completed the 14-item instrument. Principal axis factoring was used to assess factor structure. The exploratory factor analysis yielded a single-factor structure accounting for 71.76% of covariance. Cronbach internal consistency coefficient for the single factor solution was .97. The corrected item-total correlations ranged from 0.71 to 0.90. The coefficient of stability, during a 2-week period, with a subset of the sample (n = 38), was estimated at 0.82. The results of this study suggest that the Self-Efficacy for Interdisciplinary Plans of Care has sturdy reliability and validity for measuring the self-efficacy of healthcare providers to make computerized interdisciplinary plans of care meaningful and useful documents.

Self Diagnostic Accelerometer Testing on the C-17 Aircraft

NASA Technical Reports Server (NTRS)

Tokars, Roger P.; Lekki, John D.

2013-01-01

The self diagnostic accelerometer (SDA) developed by the NASA Glenn Research Center was tested for the first time in an aircraft engine environment as part of the Vehicle Integrated Propulsion Research (VIPR) program. The VIPR program includes testing multiple critical flight sensor technologies. One such sensor, the accelerometer, measures vibrations to detect faults in the engine. In order to rely upon the accelerometer, the health of the accelerometer must be ensured. The SDA is a sensor system designed to actively determine the accelerometer structural health and attachment condition, in addition to vibration measurements. The SDA uses a signal conditioning unit that sends an electrical chirp to the accelerometer and recognizes changes in the response due to changes in the accelerometer health and attachment condition. To demonstrate the SDAs flight worthiness and robustness, multiple SDAs were mounted and tested on a C-17 aircraft engine. The engine test conditions varied from engine off, to idle, to maximum power. The SDA attachment conditions were varied from fully tight to loose. The newly developed SDA health algorithm described herein uses cross correlation pattern recognition to discriminate a healthy from a faulty SDA. The VIPR test results demonstrate for the first.

Validity of a figure rating scale assessing body size perception in school-age children.

PubMed

Lombardo, Caterina; Battagliese, Gemma; Pezzuti, Lina; Lucidi, Fabio

2014-01-01

This study aimed to provide data concerning the validity of a short sequence of face valid pictorial stimuli assessing the perception of body size in school-age children. A sequence of gender and age-appropriate silhouettes was administered to 314 boys and girls aged 6-14 years. The self-evaluations provided by the children correlated significantly with their actual BMI corrected for age. Furthermore, the children's self-evaluations always significantly correlated with the evaluations provided by the three external observers; i.e., both parents and the interviewers. The results indicate that this sequence of pictorial stimuli, depicting realistic human forms appropriate for children, is a valid measure of children's body image. Relevant differences across age groups were also found, indicating that before the age of eight, the correlations between the children's self-evaluations and their BMI or the judgments of the three observers are lower than in the other age groups.

Measuring the human psychophysiological conditions without contact

NASA Astrophysics Data System (ADS)

Scalise, L.; Casacanditella, L.; Cosoli, G.

2017-08-01

Heart Rate Variability, HRV, studies the variations of cardiac rhythm caused by the autonomic regulation. HRV analysis can be applied to the study of the effects of mental or physical stressors on the psychophysiological conditions. The present work is a pilot study performed on a 23-year-old healthy subject. The measurement of HRV was performed by means of two sensors, that is an electrocardiograph and a Laser Doppler Vibrometer, which is a non-contact device able to detect the skin vibrations related to the cardiac activity. The present study aims to evaluate the effects of a physical task on HRV parameters (in both time and frequency domain), and consequently on the autonomic regulation, and the capability of Laser Doppler Vibrometry in correctly detecting the effects of stress on the Heart Variability. The results show a significant reduction of HRV parameters caused by the execution of the physical task (i.e. variations of 25-40% for parameters in time domain, also higher in frequency domain); this is consistent with the fact that stress causes a reduced capability of the organism in varying the Heart Rate (and, consequently, a limited HRV). LDV was able to correctly detect this phenomenon in the time domain, while the parameters in the frequency domain show significant deviations with respect to the gold standard technique (i.e. ECG). This may be due to the movement artefacts that have consistently modified the shape of the vibration signal measured by means of LDV, after having performed the physical task. In the future, in order to avoid this drawback, the LDV technique could be used to evaluate the effects of a mental task on HRV signals (i.e. the evaluation of mental stress).

DFT-Assisted Polymorph Identification from Lattice Raman Fingerprinting

PubMed Central

2017-01-01

A combined experimental and theoretical approach, consisting of lattice phonon Raman spectroscopy and density functional theory (DFT) calculations, is proposed as a tool for lattice dynamics characterization and polymorph phase identification. To illustrate the reliability of the method, the lattice phonon Raman spectra of two polymorphs of the molecule 2,7-dioctyloxy[1]benzothieno[3,2-b]benzothiophene are investigated. We show that DFT calculations of the lattice vibrations based on the known crystal structures, including many-body dispersion van der Waals (MBD-vdW) corrections, predict experimental data within an accuracy of ≪5 cm–1 (≪0.6 meV). Due to the high accuracy of the simulations, they can be used to unambiguously identify different polymorphs and to characterize the nature of the lattice vibrations and their relationship to the structural properties. More generally, this work implies that DFT-MBD-vdW is a promising method to describe also other physical properties that depend on lattice dynamics like charge transport. PMID:28731723

Millimeter Wave Spectroscopy and Equilibrium Structure Determination of Pyrimidine (m-C_4H_4N_2)

NASA Astrophysics Data System (ADS)

Heim, Zachary N.; Amberger, Brent K.; Esselman, Brian J.; Woods, R. Claude; McMahon, Robert J.

2015-06-01

Pyrimidine, the meta substituted dinitrogen analog of benzene, has been studied in the mm-wave region from 260 - 360 GHz, expanding on previous studies up to 337 GHz. The spectra of all four of the singly-substituted 13C and 15N isotopologues were observed in natural abundance. Samples of deuterium enriched pyrimidine were synthesized, giving access to several deuterium-substituted isotopologues. The experimental rotational constants have been corrected for vibration-rotation coupling and electron mass. The vibration-rotation corrections were calculated with an anharmonic frequency calculation at the CCSD[T]/ANO1 level using CFOUR. An equilibrium structure determination has been performed using the corrected rotational constants with the xrefit module of CFOUR. Several vibrational satellites of pyrimidine have also been studied. Their rotational constants have been compared to those obtained computationally. Z. Kisiel, L. Pszczolkowski, I. R. Medvedev, M. Winnewisser, F. C. De Lucia, E. Herbst, J. Mol. Spectrosc. 233, 231-243 (2005). G. L. Blackman, R. D. Brown, F. R. Burden, J. Mol. Spectrosc. 35, 444-454 (1970). W. Caminati, D. Damiani, Chem. Phys. Lett. 179, 460-462 (1991).

The density-magnetic field relation in the atomic ISM

NASA Astrophysics Data System (ADS)

Gazol, A.; Villagran, M. A.

2018-07-01

We present numerical experiments aimed to study the correlation between the magnetic field strength, B, and the density, n, in the cold atomic interstellar medium (CNM). We analyse 24 magnetohydrodynamic models with different initial magnetic field intensities (B0 = 0.4, 2.1, 4.2, and 8.3 μG) and/or mean densities (2, 3, and 4 cm-3), in the presence of driven and decaying turbulence, with and without self-gravity, in a cubic computational domain with 100 pc by side. Our main findings are as follows: (i) For forced simulations that reproduce the main observed physical conditions of the CNM in the solar neighbourhood, a positive correlation between B and n develops for all the B0 values. (ii) The density at which this correlation becomes significant (≲30 cm-3) depends on B0 but is not sensitive to the presence of self-gravity. (iii) The effect of self-gravity, when noticeable, consists of producing a shallower correlation at high densities, suggesting that, in the studied regime, self-gravity induces motions along the field lines. (iv) Self-gravitating decaying models where the CNM is subsonic and sub-Alfvénic with β ≲ 1 develop a high-density positive correlation whose slopes are consistent with a constant β(n). (v) Decaying models where the low-density CNM is subsonic and sub-Alfvénic with β > 1 show a negative correlation at intermediate densities, followed by a high-density positive correlation.

The Density-Magnetic Field Relation in the Atomic ISM

NASA Astrophysics Data System (ADS)

Gazol, A.; Villagran, M. A.

2018-04-01

We present numerical experiments aimed to study the correlation between the magnetic field strength, B, and the density, n, in the cold atomic interstellar medium (CNM). We analyze 24 magneto-hydrodynamic models with different initial magnetic field intensities (B0 =0.4, 2.1, 4.2, and 8.3 μG) and/or mean densities (2, 3, and 4 cm-3), in the presence of driven and decaying turbulence, with and without self-gravity, in a cubic computational domain with 100 pc by side. Our main findings are: i) For forced simulations, which reproduce the main observed physical conditions of the CNM in the Solar neighborhood, a positive correlation between B and n develops for all the B0 values. ii) The density at which this correlation becomes significant (≲ 30 cm-3) depends on B0 but is not sensitive to the presence of self-gravity. iii) The effect of self-gravity, when noticeable, consists of producing a shallower correlation at high densities, suggesting that, in the studied regime, self-gravity induces motions along the field lines. iv) Self-gravitating decaying models where the CNM is subsonic and sub-Alfvénic with β ≲ 1 develop a high density positive correlation whose slopes are consistent with a constant β(n). v) Decaying models where the low density CNM is subsonic and sub-Alfvénic with β > 1 show a negative correlation at intermediate densities, followed by a high density positive correlation.

Effect of ladder diagrams on optical absorption spectra in a quasiparticle self-consistent GW framework

NASA Astrophysics Data System (ADS)

Cunningham, Brian; Grüning, Myrta; Azarhoosh, Pooya; Pashov, Dimitar; van Schilfgaarde, Mark

2018-03-01

We present an approach to calculate the optical absorption spectra that combines the quasiparticle self-consistent GW method [Phys. Rev. B 76, 165106 (2007), 10.1103/PhysRevB.76.165106] for the electronic structure with the solution of the ladder approximation to the Bethe-Salpeter equation for the macroscopic dielectric function. The solution of the Bethe-Salpeter equation has been implemented within an all-electron framework, using a linear muffin-tin orbital basis set, with the contribution from the nonlocal self-energy to the transition dipole moments (in the optical limit) evaluated explicitly. This approach addresses those systems whose electronic structure is poorly described within the standard perturbative GW approaches with density-functional theory calculations as a starting point. The merits of this approach have been exemplified by calculating optical absorption spectra of a strongly correlated transition metal oxide, NiO, and a narrow gap semiconductor, Ge. In both cases, the calculated spectrum is in good agreement with the experiment. It is also shown that for systems whose electronic structure is well-described within the standard perturbative GW , such as Si, LiF, and h -BN , the performance of the present approach is in general comparable to the standard GW plus Bethe-Salpeter equation. It is argued that both vertex corrections to the electronic screening and the electron-phonon interaction are responsible for the observed systematic overestimation of the fundamental band gap and spectrum onset.

Force illusions and drifts observed during muscle vibration.

PubMed

Reschechtko, Sasha; Cuadra, Cristian; Latash, Mark L

2018-01-01

We explored predictions of a scheme that views position and force perception as a result of measuring proprioceptive signals within a reference frame set by ongoing efferent process. In particular, this hypothesis predicts force illusions caused by muscle vibration and mediated via changes in both afferent and efferent components of kinesthesia. Healthy subjects performed accurate steady force production tasks by pressing with the four fingers of one hand (the task hand) on individual force sensors with and without visual feedback. At various times during the trials, subjects matched the perceived force using the other hand. High-frequency vibration was applied to one or both of the forearms (over the hand and finger extensors). Without visual feedback, subjects showed a drop in the task hand force, which was significantly smaller under the vibration of that forearm. Force production by the matching hand was consistently higher than that of the task hand. Vibrating one of the forearms affected the matching hand in a manner consistent with the perception of higher magnitude of force produced by the vibrated hand. The findings were consistent between the dominant and nondominant hands. The effects of vibration on both force drift and force mismatching suggest that vibration led to shifts in both signals from proprioceptors and the efferent component of perception, the referent coordinate and/or coactivation command. The observations fit the hypothesis on combined perception of kinematic-kinetic variables with little specificity of different groups of peripheral receptors that all contribute to perception of forces and coordinates. NEW & NOTEWORTHY We show that vibration of hand/finger extensors produces consistent errors in finger force perception. Without visual feedback, finger force drifted to lower values without a drift in the matching force produced by the other hand; hand extensor vibration led to smaller finger force drift. The findings fit the scheme with combined perception of kinematic-kinetic variables and suggest that vibration leads to consistent shifts of the referent coordinate and, possibly, of coactivation command to the effector.

The Analysis and Suppression of the spike noise in vibrator record

NASA Astrophysics Data System (ADS)

Jia, H.; Jiang, T.; Xu, X.; Ge, L.; Lin, J.; Yang, Z.

2013-12-01

During the seismic exploration with vibrator, seismic recording systems have often been affected by random spike noise in the background, which leads to strong data distortions as a result of the cross-correlation processing of the vibrator method. Partial or total loss of the desired seismic information is possible if no automatic spike reduction is available in the field prior to correlation of the field record. Generally speaking, original record of vibrator is uncorrelated data, in which the signal is non-wavelet form. In order to obtain the seismic record similar to explosive source, the signal of uncorrelated data needs to use the correlation algorithm to compress into wavelet form. The correlation process results in that the interference of spike in correlated data is not only being suppressed, but also being expanded. So the spike noise suppression of vibrator is indispensable. According to numerical simulation results, the effect of spike in the vibrator record is mainly affected by the amplitude and proportional points in the uncorrelated record. When the spike noise ratio in uncorrelated record reaches 1.5% and the average amplitude exceeds 200, it will make the SNR(signal-to-noise ratio) of the correlated record lower than 0dB, so that it is difficult to separate the signal. While the amplitude and ratio is determined by the intensity of background noise. Therefore, when the noise level is strong, in order to improve SNR of the seismic data, the uncorrelated record of vibrator need to take necessary steps to suppress spike noise. For the sake of reducing the influence of the spike noise, we need to make the detection and suppression of spike noise process for the uncorrelated record. Because vibrator works by inputting sweep signal into the underground long time, ideally, the peak and valley values of each trace have little change. On the basis of the peak and valley values, we can get a reference amplitude value. Then the spike can be detected and suppressed. After this process, it can reduce the effection of spike noise in the uncorrelated record to improve the SNR. At present, because the memory space of vibrator uncorrelated data is always very large, in order to reduce acquisition costs, we usually record correlated data directly. It's reasonable if there is no strong spike sneaking into uncorrelated record. However, due to the fact that the random spike in the background is not avoidable in the acquisition process, and the instantaneous input energy of the vibrator is probably smaller than spike noise, which makes the uncorrelated data contain a certain amount of spike noise, it severely reduces the acquisition quality of vibrator if there is no noise suppression module beforehand. Of course, the suppressing process of spike noise can be carried out in the field acquisition or data processing stage. In the field of vibrator acquisition system, we can use the spike noise suppression before the correlated module, so that it can directly record correlated data without the spike affection. If in the stage of data processing, it is necessary to record uncorrelated data.

Development of battering ram vibrator system

NASA Astrophysics Data System (ADS)

Sun, F.; Chen, Z.; Lin, J.; Tong, X.

2012-12-01

This paper researched the battering ram vibrator system, by electric machinery we can control oil system of battering ram, we realized exact control of battering ram, after analyzed pseudorandom coding, code "0" and "1" correspond to rest and shake of battering ram, then we can get pseudorandom coding which is the same with battering ram vibrator. After testing , by the reference trace and single shot record, when we using pseudorandom coding mode, the ratio of seismic wavelet to correlation interfere is about 68 dB, while the general mode , the ratio of seismic wavelet to correlation interfere only is 27.9dB, by battering ram vibrator system, we can debase the correlation interfere which come from the single shaking frequency of battering ram, this system advanced the signal-to-noise ratio of seismic data, which can give direction of the application of battering ram vibrator in metal mine exploration and high resolving seismic exploration.

Analysis of Vibration and Noise of Construction Machinery Based on Ensemble Empirical Mode Decomposition and Spectral Correlation Analysis Method

NASA Astrophysics Data System (ADS)

Chen, Yuebiao; Zhou, Yiqi; Yu, Gang; Lu, Dan

In order to analyze the effect of engine vibration on cab noise of construction machinery in multi-frequency bands, a new method based on ensemble empirical mode decomposition (EEMD) and spectral correlation analysis is proposed. Firstly, the intrinsic mode functions (IMFs) of vibration and noise signals were obtained by EEMD method, and then the IMFs which have the same frequency bands were selected. Secondly, we calculated the spectral correlation coefficients between the selected IMFs, getting the main frequency bands in which engine vibration has significant impact on cab noise. Thirdly, the dominated frequencies were picked out and analyzed by spectral analysis method. The study result shows that the main frequency bands and dominated frequencies in which engine vibration have serious impact on cab noise can be identified effectively by the proposed method, which provides effective guidance to noise reduction of construction machinery.

Evaluation of the structural, electronic, topological and vibrational properties of N-(3,4-dimethoxybenzyl)-hexadecanamide isolated from Maca (Lepidium meyenii) using different spectroscopic techniques

NASA Astrophysics Data System (ADS)

Chain, Fernando; Iramain, Maximiliano Alberto; Grau, Alfredo; Catalán, César A. N.; Brandán, Silvia Antonia

2017-01-01

N-(3,4-dimethoxybenzyl)-hexadecanamide (DMH) was characterized by using Fourier Transform infrared (FT-IR) and Raman (FT-Raman), Ultraviolet- Visible (UV-Visible) and Hydrogen and Carbon Nuclear Magnetic Resonance (1H and 13C NMR) spectroscopies. The structural, electronic, topological and vibrational properties were evaluated in gas phase and in n-hexane employing ONIOM and self-consistent force field (SCRF) calculations. The atomic charges, molecular electrostatic potentials, stabilization energies and topological properties of DMH were analyzed and compared with those calculated for N-(3,4-dimethoxybenzyl)-acetamide (DMA) in order to evaluate the effect of the side chain on the properties of DMH. The reactivity and behavior of this alkamide were predicted by using the gap energies and some descriptors. Force fields and the corresponding force constants were reported for DMA only in gas phase and n-hexane due to the high number of vibration normal modes showed by DMH, while the complete vibrational assignments are presented for DMA and both forms of DMH. The comparisons between the experimental FTIR, FT-Raman, UV-Visible and 1H and 13C NMR spectra with the corresponding theoretical ones showed a reasonable concordance.

Effectiveness of external cold and vibration for procedural pain relief during peripheral intravenous cannulation in pediatric patients.

PubMed

Canbulat, Nejla; Ayhan, Fatma; Inal, Sevil

2015-02-01

The aim of this study was to investigate the effect of external cold and vibration stimulation via Buzzy on the pain and anxiety level of children during peripheral intravenous (IV) cannulation. This study was a prospective, randomized controlled trial. The sample consisted of 176 children ages 7 to 12 years who were randomly assigned to two groups: a control group that received no peripheral IV cannulation intervention and an experimental group that received external cold and vibration via Buzzy. The same nurse conducted the peripheral IV cannulation in all the children, and the same researcher applied the external cold and vibration to all the children. The external cold and the vibration were applied 1 minute before the peripheral IV cannulation procedure and continued until the end of the procedure. Preprocedural anxiety was assessed using the Children's Fear Scale, along with reports by the children, their parents, and an observer. Procedural anxiety was assessed with the Children's Fear Scale and the parents' and the observer's reports. Procedural pain was assessed using the Wong Baker Faces Scale and the visual analog scale self-reports of the children. Preprocedural anxiety did not differ significantly. Comparison of the two groups showed significantly lower pain and anxiety levels in the experimental group than in the control group during the peripheral IV cannulation. Buzzy can be considered to provide an effective combination of coldness and vibration. This method can be used during pediatric peripheral IV cannulation by pediatric nurses. Copyright © 2015 American Society for Pain Management Nursing. Published by Elsevier Inc. All rights reserved.

Spin-resolved correlations in the warm-dense homogeneous electron gas

NASA Astrophysics Data System (ADS)

Arora, Priya; Kumar, Krishan; Moudgil, R. K.

2017-04-01

We have studied spin-resolved correlations in the warm-dense homogeneous electron gas by determining the linear density and spin-density response functions, within the dynamical self-consistent mean-field theory of Singwi et al. The calculated spin-resolved pair-correlation function gσσ'(r) is compared with the recent restricted path-integral Monte Carlo (RPIMC) simulations due to Brown et al. [Phys. Rev. Lett. 110, 146405 (2013)], while interaction energy Eint and exchange-correlation free energy Fxc with the RPIMC and very recent ab initio quantum Monte Carlo (QMC) simulations by Dornheim et al. [Phys. Rev. Lett. 117, 156403 (2016)]. g↑↓(r) is found to be in good agreement with the RPIMC data, while a mismatch is seen in g↑↑(r) at small r where it becomes somewhat negative. As an interesting result, it is deduced that a non-monotonic T-dependence of g(0) is driven primarily by g↑↓(0). Our results of Eint and Fxc exhibit an excellent agreement with the QMC study due to Dornheim et al., which deals with the finite-size correction quite accurately. We observe, however, a visible deviation of Eint from the RPIMC data for high densities ( 8% at rs = 1). Further, we have extended our study to the fully spin-polarized phase. Again, with the exception of high density region, we find a good agreement of Eint with the RPIMC data. This points to the need of settling the problem of finite-size correction in the spin-polarized phase also. Interestingly, we also find that the thermal effects tend to oppose spatial localization as well as spin polarization of electrons. Supplementary material in the form of one zip file available from the Journal web page at http://https://doi.org/10.1140/epjb/e2017-70532-y

Electronic structure of the BaO molecule with dipole moments and ro-vibrational calculations

NASA Astrophysics Data System (ADS)

Khatib, Mohamed; Korek, Mahmoud

2018-03-01

The twenty-three low-lying electronic states (singlet and triplet) of the BaO molecule have been studied by using an ab initio method. These electronic states have been investigated by using the Complete Active Apace Self-Consistent Field (CASSCF) followed by multi-reference configuration interaction (MRCI + Q) with Davidson correction. The potential energy curves, the internuclear distance Re, the harmonic frequency ωe, the rotational constant Be, the electronic energy with respect to the ground state Te and the static and transition dipole moment have been investigated. The Einstein spontaneous and induced emission coefficients A21 and B21ω as well as the spontaneous radiative lifetime τspon, emission wavelength λ21 and oscillator strength f21 have been calculated by using the transition dipole moment between some doublet electronic states. The calculation of the eigenvalues Ev, the rotational constant Bv, the centrifugal distortion constant Dv, and the abscissas of the turning points Rmin and Rmax have been done by using the canonical functions approach. A very good agreement is shown by comparing the values of our work to those found in the literature for many electronic states. Eighteen new electronic states have been studied here for the first time.

Explicit calculation of the two-loop corrections to the chiral magnetic effect with the NJL model

NASA Astrophysics Data System (ADS)

Chu, Kit-fai; Huang, Peng-hui; Liu, Hui

2018-05-01

The chiral magnetic effect (CME) is usually believed to not receive higher-order corrections due to the nonrenormalization of the AVV triangle diagram in the framework of quantum field theory. However, the CME-relevant triangle, which is obtained by expanding the current-current correlation, requires zero momentum on the axial vertex and is not equivalent to the general AVV triangle when taking the zero-momentum limit owing to the infrared problem on the axial vertex. Therefore, it is still significant to check if there exists perturbative higher-order corrections to the current-current correlation. In this paper, we explicitly calculate the two-loop corrections of CME within the Nambu-Jona-Lasinio model with a Chern-Simons term, which ensures a consistent μ5 . The result shows the two-loop corrections to the CME conductivity are zero, which confirms the nonrenomalization of CME conductivity.

[Dynamics of vegetative indicators induced by low-frequency magnetotherapy and EHF-puncture in hypertensive workers exposed to vibration].

PubMed

Drobyshev, V A; Efremov, A V; Loseva, M I; Sukharevskaia, T M; Michurin, A I

2002-01-01

Low-frequency magnetic fields and EHF-therapy have been used in correction of autonomic homeostasis in workers exposed to vibration for different periods of time. The workers suffered from early arterial hypertension. Vegetative status and central hemodynamics improved best in workers exposed to vibration for less than 5 years. If the exposure was 6-15 years, a positive trend occurred in the tension of regulatory mechanisms. Workers with long exposure to vibration suffering from vagotonia showed an inadequate response of the autonomic parameters to treatment. This necessitates enhancement of therapeutic measures with medicines.

Cross-Cultural and Psychometric Properties Assessment of the Exercise Self-Efficacy Scale in Individuals with Spinal Cord Injury.

PubMed

Pisconti, Fernando; Mahmoud Smaili Santos, Suhaila; Lopes, Josiane; Rosa Cardoso, Jefferson; Lopes Lavado, Edson

2017-11-29

The Exercise Self-Efficacy scale (ESES) is a reliable measure, in the English language, of exercise self-efficacy in individuals with spinal cord injury. The aim of this study was to culturally adjust and validate the Exercise Self-Efficacy scale in the Portuguese language. The Exercise Self-Efficacy scale was applied to 76 subjects, with three-month intervals (three applications in total). The reliability was appraised using the intra-class correlation coefficient and Bland-Altman methods, and the internal consistency was evaluated using Cronbach´s alpha. The Exercise Self-Efficacy scale was correlated with the domains of the Quality of life Questionnaire SF-36 and Functional Independence Measure and tested using the Spearman rho coefficient. The Exercise Self-Efficacy scale-Brazil presented good internal consistency (alpha 1 = 0.856; alpha 2 = 0.855; alpha 3 = 0.822) and high reliability in the test-retest (intra-class correlation coefficient = 0.97). There was a strong correlation between the Exercise Self-Efficacy scale-Brazil and the SF-36 only in the functional capacity domain (rho = 0.708). There were no changes in Exercise Self-Efficacy scale-Brazil scores between the three applications (p = 0.796). The validation of the Exercise Self-Efficacy scale questionnaire permits the assessor to use it reliably in Portuguese speaking countries, since it is the first instrument measuring self-efficacy specifically during exercises in individuals with spinal cord injury. Furthermore, the questionnaire can be used as an instrument to verify the effectiveness of interventions that use exercise as an outcome. The results of the Brazilian version of the Exercise Self-Efficacy scale support its use as a reliable and valid measurement of exercise self-efficacy for this population.

Methodological study of computational approaches to address the problem of strong correlations

NASA Astrophysics Data System (ADS)

Lee, Juho

The main focus of this thesis is the detailed investigation of computational methods to tackle strongly correlated materials in which a rich variety of exotic phenomena are found. A many-body problem with sizable electronic correlations can no longer be explained by independent-particle approximations such as density functional theory (DFT) or tight-binding approaches. The influence of an electron to the others is too strong for each electron to be treated as an independent quasiparticle and consequently those standard band-structure methods fail even at a qualitative level. One of the most powerful approaches for strong correlations is the dynamical mean-field theory (DMFT), which has enlightened the understanding of the Mott transition based on the Hubbard model. For realistic applications, the dynamical mean-field theory is combined with various independent-particles approaches. The most widely used one is the DMFT combined with the DFT in the local density approximation (LDA), so-called LDA+DMFT. In this approach, the electrons in the weakly correlated orbitals are calculated by LDA while others in the strongly correlated orbitals are treated by DMFT. Recently, the method combining DMFT with Hedin's GW approximation was also developed, in which the momentum-dependent self-energy is also added. In this thesis, we discuss the application of those methodologies based on DMFT. First, we apply the dynamical mean-field theory to solve the 3-dimensional Hubbard model in Chap. 3. In this application, we model the interface between the thermodynamically coexisting metal and Mott insulator. We show how to model the required slab geometry and extract the electronic spectra. We construct an effective Landau free energy and compute the variation of its parameters across the phase diagram. Finally, using a linear mixture of the density and double-occupancy, we identify a natural Ising order parameter which unifies the treatment of the bandwidth and filling controlled Mott transitions. Secondly, we study the double-counting problem, a subtle issue that arises in LDA+DMFT. We propose a highly precise double-counting functional, in which the intersection of LDA and DMFT is calculated exactly, and implement a parameter-free version of the LDA+DMFT that is tested on one of the simplest strongly correlated systems, the H2 molecule. We show that the exact double-counting treatment along with a good DMFT projector leads to very accurate and total energy and excitation spectrum of H2 molecule. Finally, we implement various versions of GW+DMFT, in its fully self-consistent way, one shot GW approximation, and quasiparticle self-consistent scheme, and studied how well these combined methods perform on H2 molecule as compared to more established methods such as LDA+DMFT. We found that most flavors of GW+DMFT break down in strongly correlated regime due to causality violation. Among GW+DMFT methods, only the self-consistent quasiparticle GW+DMFT with static double-counting, and a new method with causal double-counting, correctly recover the atomic limit at large H-atom separation. While some flavors of GW+DMFT improve the single-electron spectra of LDA+DMFT, the total energy is best predicted by LDA+DMFT, for which the exact double-counting is known, and is static.

Modal Correction Method For Dynamically Induced Errors In Wind-Tunnel Model Attitude Measurements

NASA Technical Reports Server (NTRS)

Buehrle, R. D.; Young, C. P., Jr.

1995-01-01

This paper describes a method for correcting the dynamically induced bias errors in wind tunnel model attitude measurements using measured modal properties of the model system. At NASA Langley Research Center, the predominant instrumentation used to measure model attitude is a servo-accelerometer device that senses the model attitude with respect to the local vertical. Under smooth wind tunnel operating conditions, this inertial device can measure the model attitude with an accuracy of 0.01 degree. During wind tunnel tests when the model is responding at high dynamic amplitudes, the inertial device also senses the centrifugal acceleration associated with model vibration. This centrifugal acceleration results in a bias error in the model attitude measurement. A study of the response of a cantilevered model system to a simulated dynamic environment shows significant bias error in the model attitude measurement can occur and is vibration mode and amplitude dependent. For each vibration mode contributing to the bias error, the error is estimated from the measured modal properties and tangential accelerations at the model attitude device. Linear superposition is used to combine the bias estimates for individual modes to determine the overall bias error as a function of time. The modal correction model predicts the bias error to a high degree of accuracy for the vibration modes characterized in the simulated dynamic environment.

Stiffness Corrections for the Vibration Frequency of a Stretched Wire

ERIC Educational Resources Information Center

Hornung, H. G.; Durie, M. J.

1977-01-01

Discusses the need of introducing corrections due to wire stiffness arising from end constraints and wire axis distribution curvature in the measurement of ac electrical frequency by exciting transverse standing waves in a stretched steel wire. (SL)

Analog self-powered harvester achieving switching pause control to increase harvested energy

NASA Astrophysics Data System (ADS)

Makihara, Kanjuro; Asahina, Kei

2017-05-01

In this paper, we propose a self-powered analog controller circuit to increase the efficiency of electrical energy harvesting from vibrational energy using piezoelectric materials. Although the existing synchronized switch harvesting on inductor (SSHI) method is designed to produce efficient harvesting, its switching operation generates a vibration-suppression effect that reduces the harvested levels of electrical energy. To solve this problem, the authors proposed—in a previous paper—a switching method that takes this vibration-suppression effect into account. This method temporarily pauses the switching operation, allowing the recovery of the mechanical displacement and, therefore, of the piezoelectric voltage. In this paper, we propose a self-powered analog circuit to implement this switching control method. Self-powered vibration harvesting is achieved in this study by attaching a newly designed circuit to an existing analog controller for SSHI. This circuit aims to effectively implement the aforementioned new switching control strategy, where switching is paused in some vibration peaks, in order to allow motion recovery and a consequent increase in the harvested energy. Harvesting experiments performed using the proposed circuit reveal that the proposed method can increase the energy stored in the storage capacitor by a factor of 8.5 relative to the conventional SSHI circuit. This proposed technique is useful to increase the harvested energy especially for piezoelectric systems having large coupling factor.

Are Informant Reports of Personality More Internally Consistent Than Self Reports of Personality?

PubMed

Balsis, Steve; Cooper, Luke D; Oltmanns, Thomas F

2015-08-01

The present study examined whether informant-reported personality was more or less internally consistent than self-reported personality in an epidemiological community sample (n = 1,449). Results indicated that across the 5 NEO (Neuroticism-Extraversion-Openness) personality factors and the 10 personality disorder trait dimensions, informant reports tended to be more internally consistent than self reports, as indicated by equal or higher Cronbach's alpha scores and higher average interitem correlations. In addition, the informant reports collectively outperformed the self reports for predicting responses on a global measure of health, indicating that the informant reports are not only more reliable than self reports, but they can also be useful in predicting an external criterion. Collectively these findings indicate that informant reports tend to have greater internal consistency than self reports. © The Author(s) 2014.

Genetic Variance in Homophobia: Evidence from Self- and Peer Reports.

PubMed

Zapko-Willmes, Alexandra; Kandler, Christian

2018-01-01

The present twin study combined self- and peer assessments of twins' general homophobia targeting gay men in order to replicate previous behavior genetic findings across different rater perspectives and to disentangle self-rater-specific variance from common variance in self- and peer-reported homophobia (i.e., rater-consistent variance). We hypothesized rater-consistent variance in homophobia to be attributable to genetic and nonshared environmental effects, and self-rater-specific variance to be partially accounted for by genetic influences. A sample of 869 twins and 1329 peer raters completed a seven item scale containing cognitive, affective, and discriminatory homophobic tendencies. After correction for age and sex differences, we found most of the genetic contributions (62%) and significant nonshared environmental contributions (16%) to individual differences in self-reports on homophobia to be also reflected in peer-reported homophobia. A significant genetic component, however, was self-report-specific (38%), suggesting that self-assessments alone produce inflated heritability estimates to some degree. Different explanations are discussed.

Measuring the bias, precision, accuracy, and validity of self-reported height and weight in assessing overweight and obesity status among adolescents using a surveillance system.

PubMed

Pérez, Adriana; Gabriel, Kelley; Nehme, Eileen K; Mandell, Dorothy J; Hoelscher, Deanna M

2015-07-27

Evidence regarding bias, precision, and accuracy in adolescent self-reported height and weight across demographic subpopulations is lacking. The bias, precision, and accuracy of adolescent self-reported height and weight across subpopulations were examined using a large, diverse and representative sample of adolescents. A second objective was to develop correction equations for self-reported height and weight to provide more accurate estimates of body mass index (BMI) and weight status. A total of 24,221 students from 8th and 11th grade in Texas participated in the School Physical Activity and Nutrition (SPAN) surveillance system in years 2000-2002 and 2004-2005. To assess bias, the differences between the self-reported and objective measures, for height and weight were estimated. To assess precision and accuracy, the Lin's concordance correlation coefficient was used. BMI was estimated for self-reported and objective measures. The prevalence of students' weight status was estimated using self-reported and objective measures; absolute (bias) and relative error (relative bias) were assessed subsequently. Correction equations for sex and race/ethnicity subpopulations were developed to estimate objective measures of height, weight and BMI from self-reported measures using weighted linear regression. Sensitivity, specificity and positive predictive values of weight status classification using self-reported measures and correction equations are assessed by sex and grade. Students in 8th- and 11th-grade overestimated their height from 0.68cm (White girls) to 2.02 cm (African-American boys), and underestimated their weight from 0.4 kg (Hispanic girls) to 0.98 kg (African-American girls). The differences in self-reported versus objectively-measured height and weight resulted in underestimation of BMI ranging from -0.23 kg/m2 (White boys) to -0.7 kg/m2 (African-American girls). The sensitivity of self-reported measures to classify weight status as obese was 70.8% and 81.9% for 8th- and 11th-graders, respectively. These estimates increased when using the correction equations to 77.4% and 84.4% for 8th- and 11th-graders, respectively. When direct measurement is not practical, self-reported measurements provide a reliable proxy measure across grade, sex and race/ethnicity subpopulations of adolescents. Correction equations increase the sensitivity of self-report measures to identify prevalence of overall overweight/obesity status.

3D digital image correlation methods for full-field vibration measurement

NASA Astrophysics Data System (ADS)

Helfrick, Mark N.; Niezrecki, Christopher; Avitabile, Peter; Schmidt, Timothy

2011-04-01

In the area of modal test/analysis/correlation, significant effort has been expended over the past twenty years in order to make reduced models and to expand test data for correlation and eventual updating of the finite element models. This has been restricted by vibration measurements which are traditionally limited to the location of relatively few applied sensors. Advances in computers and digital imaging technology have allowed 3D digital image correlation (DIC) methods to measure the shape and deformation of a vibrating structure. This technique allows for full-field measurement of structural response, thus providing a wealth of simultaneous test data. This paper presents some preliminary results for the test/analysis/correlation of data measured using the DIC approach along with traditional accelerometers and a scanning laser vibrometer for comparison to a finite element model. The results indicate that all three approaches correlated well with the finite element model and provide validation for the DIC approach for full-field vibration measurement. Some of the advantages and limitations of the technique are presented and discussed.

On the accurate theoretical determination of the static hyperpolarizability of trans-butadiene

NASA Astrophysics Data System (ADS)

Maroulis, George

1999-07-01

Finite-field many-body perturbation theory and coupled cluster calculations are reported for the static second dipole hyperpolarizability γαβγδ of trans-butadiene. A very large basis set of [9s6p4d1f/6s3p1d] size (336 contracted Gaussian-type functions) should lead to self-consistent field (SCF) values of near-Hartree-Fock quality. We report γxxxx=6.19, γxxxz=-0.44, γxxyy=3.42, γzzxx=2.07, γxyyz=-0.50, γxzzz=1.73, γyyyy=14.72, γyyzz=8.46, γzzzz=24.10 and γ¯=14.58 for 10-3×γαβγδ/e4a04Eh-3 at the experimental geometry (molecule on the xz plane with z as the main axis). γ¯=(14.6±0.4)×103e4a04Eh-3 should be a very reliable estimate of the Hartree-Fock limit of the mean hyperpolarizability. Keeping all other molecular geometry parameters constant, we find that near the Hartree-Fock limit the mean hyperpolarizability varies with the C=C bond length as 10-3×γ¯(RC=C)/e4a04Eh-3=14.93+31.78ΔR+30.88ΔR2-2.96ΔR3 and with the C-C bond length as 10-3×γ¯(RC-C)/e4a04Eh-3=14.93-7.20ΔR+3.04ΔR2, where ΔR/a0 is the displacement from the respective experimental value. The dependence of the components of γαβγδ on the molecular geometry parameters is not uniform. Electron correlation corrections have been calculated at various molecular geometries at the coupled-cluster single, double and perturbatively linked triple excitations level of theory for all independent components of γαβγδ. In absolute terms, electron correlation affects strongly the γzzzz, less strongly the γxxxx, and even less strongly the out-of-plane component γyyyy. The present analysis suggests a conservative estimate of (3.0±0.6)×103e4a04Eh-3 for the electron correlation correction to γ¯ at the experimental molecular geometry. Most of this value is appropriate to γzzzz. A static limit of γ¯=(17.6±1.0)×103e4a04Eh-3 is advanced (neglecting vibrational averaging). Even if a crude theoretical estimate of the dispersion of γ¯ at 1064 nm is added to this value, the result sets up an unambiguous claim to accord with the experimental value of (20.18±0.11)×103e4a04Eh-3 [D. P. Shelton, Phys. Rev. A 42, 2578 (1990)].

Towards black-box calculations of tunneling splittings obtained from vibrational structure methods based on normal coordinates.

PubMed

Neff, Michael; Rauhut, Guntram

2014-02-05

Multidimensional potential energy surfaces obtained from explicitly correlated coupled-cluster calculations and further corrections for high-order correlation contributions, scalar relativistic effects and core-correlation energy contributions were generated in a fully automated fashion for the double-minimum benchmark systems OH3(+) and NH3. The black-box generation of the potentials is based on normal coordinates, which were used in the underlying multimode expansions of the potentials and the μ-tensor within the Watson operator. Normal coordinates are not the optimal choice for describing double-minimum potentials and the question remains if they can be used for accurate calculations at all. However, their unique definition is an appealing feature, which removes remaining errors in truncated potential expansions arising from different choices of curvilinear coordinate systems. Fully automated calculations are presented, which demonstrate, that the proposed scheme allows for the determination of energy levels and tunneling splittings as a routine application. Copyright © 2013 Elsevier B.V. All rights reserved.

Revisiting Our Reappraisal of the (Surprisingly Few) Benefits of High Self-Esteem.

PubMed

Baumeister, Roy F; Vohs, Kathleen D

2018-03-01

Our 2003 article clashed with conventional wisdom by concluding that high self-esteem has only a couple of benefits, notably high initiative (based on trusting one's own judgment) and feeling good. Its high citation rate reflects not only the novel conclusions but also widespread interest in self-esteem both among researchers and in the broader society. Psychology may have lost some credibility by advocating efforts to raise self-esteem that were based on correlational evidence, which may be a salutary lesson for the field. There is still much to learn about self-esteem, but future work can improve by noting weaknesses in self-report data and correcting for confounds.

Summary of AH-1G flight vibration data for validation of coupled rotor-fuselage analyses

NASA Technical Reports Server (NTRS)

Dompka, R. V.; Cronkhite, J. D.

1986-01-01

Under a NASA research program designated DAMVIBS (Design Analysis Methods for VIBrationS), four U. S. helicopter industry participants (Bell Helicopter, Boeing Vertol, McDonnell Douglas Helicopter, and Sikorsky Aircraft) are to apply existing analytical methods for calculating coupled rotor-fuselage vibrations of the AH-1G helicopter for correlation with flight test data from an AH-1G Operational Load Survey (OLS) test program. Bell Helicopter, as the manufacturer of the AH-1G, was asked to provide pertinent rotor data and to collect the OLS flight vibration data needed to perform the correlations. The analytical representation of the fuselage structure is based on a NASTRAN finite element model (FEM) developed by Bell which has been extensively documented and correlated with ground vibration tests.The AH-1G FEM was provided to each of the participants for use in their coupled rotor-fuselage analyses. This report describes the AH-1G OLS flight test program and provides the flight conditions and measured vibration data to be used by each participant in their correlation effort. In addition, the mechanical, structural, inertial and aerodynamic data for the AH-1G two-bladed teetering main rotor system are presented. Furthermore, modifications to the NASTRAN FEM of the fuselage structure that are necessary to make it compatible with the OLS test article are described. The AH-1G OLS flight test data was found to be well documented and provide a sound basis for evaluating currently existing analysis methods used for calculation of coupled rotor-fuselage vibrations.

Qualitative models of seat discomfort including static and dynamic factors.

PubMed

Ebe, K; Griffin, M J

2000-06-01

Judgements of overall seating comfort in dynamic conditions sometimes correlate better with the static characteristics of a seat than with measures of the dynamic environment. This study developed qualitative models of overall seat discomfort to include both static and dynamic seat characteristics. A dynamic factor that reflected how vibration discomfort increased as vibration magnitude increased was combined with a static seat factor which reflected seating comfort without vibration. The ability of the model to predict the relative and overall importance of dynamic and static seat characteristics on comfort was tested in two experiments. A paired comparison experiment, using four polyurethane foam cushions (50, 70, 100, 120 mm thick), provided different static and dynamic comfort when 12 subjects were exposed to one-third octave band random vertical vibration with centre frequencies of 2.5 and 5.5 Hz, at magnitudes of 0.00, 0.25 and 0.50 m x s(-2) rms measured beneath the foam samples. Subject judgements of the relative discomfort of the different conditions depended on both static and dynamic characteristics in a manner consistent with the model. The effect of static and dynamic seat factors on overall seat discomfort was investigated by magnitude estimation using three foam cushions (of different hardness) and a rigid wooden seat at six vibration magnitudes with 20 subjects. Static seat factors (i.e. cushion stiffness) affected the manner in which vibration influenced the overall discomfort: cushions with lower stiffness were more comfortable and more sensitive to changes in vibration magnitude than those with higher stiffness. The experiments confirm that judgements of overall seat discomfort can be affected by both the static and dynamic characteristics of a seat, with the effect depending on vibration magnitude: when vibration magnitude was low, discomfort was dominated by static seat factors; as the vibration magnitude increased, discomfort became dominated by dynamic factors.

Separation of overlapping vibrational peaks in terahertz spectra using two-dimensional correlation spectroscopy

NASA Astrophysics Data System (ADS)

Hoshina, Hiromichi; Ishii, Shinya; Otani, Chiko

2014-07-01

In this study, the terahertz (THz) absorption spectra of poly(3-hydroxybutyrate) (PHB) were measured during isothermal crystallization at 90-120 °C. The temporal changes in the absorption spectra were analyzed using two-dimensional correlation spectroscopy (2DCOS). In the asynchronous plot, cross peaks were observed around 2.4 THz, suggesting that two vibrational modes overlap in the raw spectrum. By comparing this to the peak at 2.9 THz corresponding to the stretching mode of the helical structure of PHB and the assignment obtained using polarization spectroscopy, we concluded that the high-frequency band could be attributed to the vibration of the helical structure and the low-frequency band to the vibration between the helical structures. The exact frequencies of the overlapping vibrational bands and their assignments provide a new means to inspect the thermal behavior of the intermolecular vibrational modes. The large red-shift of the interhelix vibrational mode suggests a large anharmonicity in the vibrational potential.

Charge and spin diffusion on the metallic side of the metal-insulator transition: A self-consistent approach

NASA Astrophysics Data System (ADS)

Wellens, Thomas; Jalabert, Rodolfo A.

2016-10-01

We develop a self-consistent theory describing the spin and spatial electron diffusion in the impurity band of doped semiconductors under the effect of a weak spin-orbit coupling. The resulting low-temperature spin-relaxation time and diffusion coefficient are calculated within different schemes of the self-consistent framework. The simplest of these schemes qualitatively reproduces previous phenomenological developments, while more elaborate calculations provide corrections that approach the values obtained in numerical simulations. The results are universal for zinc-blende semiconductors with electron conductance in the impurity band, and thus they are able to account for the measured spin-relaxation times of materials with very different physical parameters. From a general point of view, our theory opens a new perspective for describing the hopping dynamics in random quantum networks.

Calculations with the quasirelativistic local-spin-density-functional theory for high-Z atoms

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

Guo, Y.; Whitehead, M.A.

1988-10-01

The generalized-exchange local-spin-density-functional theory (LSD-GX) with relativistic corrections of the mass velocity and Darwin terms has been used to calculate statistical total energies for the neutral atoms, the positive ions, and the negative ions for high-Z elements. The effect of the correlation and relaxation correction on the statistical total energy is discussed. Comparing the calculated results for the ionization potentials and electron affinities for the atoms (atomic number Z from 37 to 56 and 72 to 80) with experiment, shows that for the atoms rubidium to barium both the LSD-GX and the quasirelativistic LSD-GX, with self-interaction correction, Gopinathan, Whitehead, andmore » Bogdanovic's Fermi-hole parameters (Phys. Rev. A 14, 1 (1976)), and Vosko, Wilk, and Nusair's correlation correction (Can. J. Phys. 58, 1200 (1980)), are very good methods for calculating ionization potentials and electron affinities. For the atoms hafnium to mercury the relativistic effect has to be considered.« less

Seismic reflection response from cross-correlations of ambient vibrations on non-conventional hidrocarbon reservoir

NASA Astrophysics Data System (ADS)

Huerta, F. V.; Granados, I.; Aguirre, J.; Carrera, R. Á.

2017-12-01

Nowadays, in hydrocarbon industry, there is a need to optimize and reduce exploration costs in the different types of reservoirs, motivating the community specialized in the search and development of alternative exploration geophysical methods. This study show the reflection response obtained from a shale gas / oil deposit through the method of seismic interferometry of ambient vibrations in combination with Wavelet analysis and conventional seismic reflection techniques (CMP & NMO). The method is to generate seismic responses from virtual sources through the process of cross-correlation of records of Ambient Seismic Vibrations (ASV), collected in different receivers. The seismic response obtained is interpreted as the response that would be measured in one of the receivers considering a virtual source in the other. The acquisition of ASV records was performed in northern of Mexico through semi-rectangular arrays of multi-component geophones with instrumental response of 10 Hz. The in-line distance between geophones was 40 m while in cross-line was 280 m, the sampling used during the data collection was 2 ms and the total duration of the records was 6 hours. The results show the reflection response of two lines in the in-line direction and two in the cross-line direction for which the continuity of coherent events have been identified and interpreted as reflectors. There is certainty that the events identified correspond to reflections because the time-frequency analysis performed with the Wavelet Transform has allowed to identify the frequency band in which there are body waves. On the other hand, the CMP and NMO techniques have allowed to emphasize and correct the reflection response obtained during the correlation processes in the frequency band of interest. The results of the processing and analysis of ASV records through the seismic interferometry method have allowed us to see interesting results in light of the cross-correlation process in combination with the Wavelet analysis and conventional seismic reflection techniques. Therefore it was possible to recover the seismic response on each analyzed source-receiver pair, allowing us to obtain the reflection response of each analyzed seismic line.

Third-order Douglas-Kroll Relativistic Coupled-Cluster Theory through Connected Single, Double, Triple, and Quadruple Substitutions: Applications to Diatomic and Triatomic Hydrides

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

Hirata, So; Yanai, Takeshi; De Jong, Wibe A.

Coupled-cluster methods including through and up to the connected single, double, triple, and quadruple substitutions (CCSD, CCSDT, and CCSDTQ) have been automatically derived and implemented for sequential and parallel executions for use in conjunction with a one-component third-order Douglas-Kroll (DK3) approximation for relativistic corrections. A combination of the converging electron-correlation methods, the accurate relativistic reference wave functions, and the use of systematic basis sets tailored to the relativistic approximation has been shown to predict the experimental singlet-triplet separations within 0.02 eV (0.5 kcal/mol) for five triatomic hydrides (CH2, NH2+, SiH2, PH2+, and AsH2+), the experimental bond lengths within 0.002 angstroms,more » rotational constants within 0.02 cm-1, vibration-rotation constants within 0.01 cm-1, centrifugal distortion constants within 2 %, harmonic vibration frequencies within 9 cm-1 (0.4 %), anharmonic vibrational constants within 2 cm-1, and dissociation energies within 0.03 eV (0.8 kcal/mol) for twenty diatomic hydrides (BH, CH, NH, OH, FH, AlH, SiH, PH, SH, ClH, GaH, GeH, AsH, SeH, BrH, InH, SnH, SbH, TeH, and IH) containing main-group elements across the second through fifth periods of the periodic table. In these calculations, spin-orbit effects on dissociation energies, which were assumed to be additive, were estimated from the measured spin-orbit coupling constants of atoms and diatomic molecules, and an electronic energy in the complete-basis-set, complete-electron-correlation limit has been extrapolated by the formula which was in turn based on the exponential-Gaussian extrapolation formula of the basis set dependence.« less

Selection of active spaces for multiconfigurational wavefunctions

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

Keller, Sebastian; Boguslawski, Katharina; Reiher, Markus, E-mail: markus.reiher@phys.chem.ethz.ch

2015-06-28

The efficient and accurate description of the electronic structure of strongly correlated systems is still a largely unsolved problem. The usual procedures start with a multiconfigurational (usually a Complete Active Space, CAS) wavefunction which accounts for static correlation and add dynamical correlation by perturbation theory, configuration interaction, or coupled cluster expansion. This procedure requires the correct selection of the active space. Intuitive methods are unreliable for complex systems. The inexpensive black-box unrestricted natural orbital (UNO) criterion postulates that the Unrestricted Hartree-Fock (UHF) charge natural orbitals with fractional occupancy (e.g., between 0.02 and 1.98) constitute the active space. UNOs generally approximatemore » the CAS orbitals so well that the orbital optimization in CAS Self-Consistent Field (CASSCF) may be omitted, resulting in the inexpensive UNO-CAS method. A rigorous testing of the UNO criterion requires comparison with approximate full configuration interaction wavefunctions. This became feasible with the advent of Density Matrix Renormalization Group (DMRG) methods which can approximate highly correlated wavefunctions at affordable cost. We have compared active orbital occupancies in UNO-CAS and CASSCF calculations with DMRG in a number of strongly correlated molecules: compounds of electronegative atoms (F{sub 2}, ozone, and NO{sub 2}), polyenes, aromatic molecules (naphthalene, azulene, anthracene, and nitrobenzene), radicals (phenoxy and benzyl), diradicals (o-, m-, and p-benzyne), and transition metal compounds (nickel-acetylene and Cr{sub 2}). The UNO criterion works well in these cases. Other symmetry breaking solutions, with the possible exception of spatial symmetry, do not appear to be essential to generate the correct active space. In the case of multiple UHF solutions, the natural orbitals of the average UHF density should be used. The problems of the UNO criterion and their potential solutions are discussed: finding the UHF solutions, discontinuities on potential energy surfaces, and inclusion of dynamical electron correlation and generalization to excited states.« less

Selection of active spaces for multiconfigurational wavefunctions

NASA Astrophysics Data System (ADS)

Keller, Sebastian; Boguslawski, Katharina; Janowski, Tomasz; Reiher, Markus; Pulay, Peter

2015-06-01

The efficient and accurate description of the electronic structure of strongly correlated systems is still a largely unsolved problem. The usual procedures start with a multiconfigurational (usually a Complete Active Space, CAS) wavefunction which accounts for static correlation and add dynamical correlation by perturbation theory, configuration interaction, or coupled cluster expansion. This procedure requires the correct selection of the active space. Intuitive methods are unreliable for complex systems. The inexpensive black-box unrestricted natural orbital (UNO) criterion postulates that the Unrestricted Hartree-Fock (UHF) charge natural orbitals with fractional occupancy (e.g., between 0.02 and 1.98) constitute the active space. UNOs generally approximate the CAS orbitals so well that the orbital optimization in CAS Self-Consistent Field (CASSCF) may be omitted, resulting in the inexpensive UNO-CAS method. A rigorous testing of the UNO criterion requires comparison with approximate full configuration interaction wavefunctions. This became feasible with the advent of Density Matrix Renormalization Group (DMRG) methods which can approximate highly correlated wavefunctions at affordable cost. We have compared active orbital occupancies in UNO-CAS and CASSCF calculations with DMRG in a number of strongly correlated molecules: compounds of electronegative atoms (F2, ozone, and NO2), polyenes, aromatic molecules (naphthalene, azulene, anthracene, and nitrobenzene), radicals (phenoxy and benzyl), diradicals (o-, m-, and p-benzyne), and transition metal compounds (nickel-acetylene and Cr2). The UNO criterion works well in these cases. Other symmetry breaking solutions, with the possible exception of spatial symmetry, do not appear to be essential to generate the correct active space. In the case of multiple UHF solutions, the natural orbitals of the average UHF density should be used. The problems of the UNO criterion and their potential solutions are discussed: finding the UHF solutions, discontinuities on potential energy surfaces, and inclusion of dynamical electron correlation and generalization to excited states.

Consistency of the Relations of Cognitive Ability and Personality Traits to Pilot Training Performance

DTIC Science & Technology

2014-08-22

MAB-II scores. The univariate Case II correction ( Thorndike , 1949) was used for the NEO-PI-R scores due to a lack of sufficient data to apply the...pilot training, AFRL-RH-WP-TR-2013-0081. Wright-Patterson AFB, OH: Air Force Research Laboratory, Decision Making Division. Thorndike , R. L...NEO domain scores were corrected using the univariate Case 2 ( Thorndike , 1949) method. Correlations in the column labeled rfc were corrected for both

First Principles Study of Chemically Functionalized Graphene

NASA Astrophysics Data System (ADS)

Jha, Sanjiv; Vasiliev, Igor

2015-03-01

The electronic, structural and vibrational properties of carbon nanomaterials can be affected by chemical functionalization. We applied ab initio computational methods based on density functional theory to study the covalent functionalization of graphene with benzyne, carboxyl groups and tetracyanoethylene oxide (TCNEO). Our calculations were carried out using the SIESTA and Quantum-ESPRESSO electronic structure codes combined with the local density and generalized gradient approximations for the exchange correlation functional and norm-conserving Troullier-Martins pseudopotentials. The simulated Raman and infrared spectra of graphene functionalized with carboxyl groups and TCNEO were consistent with the available experimental results. The computed vibrational spectra of graphene functionalized with carboxyl groups showed that the presence of point defects near the functionalization site affects the Raman and infrared spectroscopic signatures of functionalized graphene. Supported by NSF CHE-1112388.

Teacher Candidates' Learning Strategies and Academic Self-Efficacy Levels: Is There a Relation between the Two?

ERIC Educational Resources Information Center

Akçaoglu, Mustafa Öztürk

2016-01-01

The current study aimed to identify teacher candidates' learning strategies and academic self-efficacy levels. Furthermore, the correlations between these variables and gender and departments were looked into. The study was mainly descriptive and correlational. The sample of the study consisted of 256 teacher candidates enrolled at a faculty of…

Career Decision-Making Self-Efficacy and Career Commitment: Gender and Ethnic Differences among College Students.

ERIC Educational Resources Information Center

Chung, Y. Barry

2002-01-01

Analysis of responses from 165 undergraduates on the Career Decision Making Self Efficacy Scale revealed high internal consistency for the instrument and moderate correlation between it and the Career Commitment Scale. No gender or ethnic differences were found in this correlation. Blacks scored significantly higher than whites on both measures.…

Correction of body-mass index using body-shape perception and socioeconomic status in adolescent self-report surveys.

PubMed

Legleye, Stéphane; Beck, François; Spilka, Stanislas; Chau, Nearkasen

2014-01-01

To propose a simple correction of body-mass index (BMI) based on self-reported weight and height (reported BMI) using gender, body shape perception and socioeconomic status in an adolescent population. 341 boys and girls aged 17-18 years were randomly selected from a representative sample of 2165 French adolescents living in Paris surveyed in 2010. After an anonymous self-administered pen-and-paper questionnaire asking for height, weight, body shape perception (feeling too thin, about the right weight or too fat) and socioeconomic status, subjects were measured and weighed. BMI categories were computed according to Cole's cut-offs. Reported BMIs were corrected using linear regressions and ROC analyses and checked with cross-validation and multiple imputations to handle missing values. Agreement between actual and corrected BMI values was estimated with Kappa indexes and Intraclass correlation coefficients (ICC). On average, BMIs were underreported, especially among girls. Kappa indexes between actual and reported BMI were low, especially for girls: 0.56 95%CI = [0.42-0.70] for boys and 0.45 95%CI = [0.30-0.60] for girls. The regression of reported BMI by gender and body shape perception gave the most balanced results for both genders: the Kappa and ICC obtained were 0.63 95%CI = [0.50-0.76] and 0.67, 95%CI = [0.58-0.74] for boys; 0.65 95%CI = [0.52-0.78] and 0.74, 95%CI = [0.66-0.81] for girls. The regression of reported BMI by gender and socioeconomic status led to similar corrections while the ROC analyses were inaccurate. Using body shape perception, or socioeconomic status and gender is a promising way of correcting BMI in self-administered questionnaires, especially for girls.

Transport properties of carbon dioxide and methane from molecular dynamics simulations.

PubMed

Aimoli, C G; Maginn, E J; Abreu, C R A

2014-10-07

Transport properties of carbon dioxide and methane are predicted for temperatures between (273.15 and 573.15) K and pressures up to 800 MPa by molecular dynamics simulations. Viscosities and thermal conductivities were obtained through the Green-Kubo formalism, whereas the Einstein relation was used to provide self-diffusion coefficient estimates. The differences in property predictions due to the force field nature and parametrization were investigated by the comparison of seven different CO2 models (two single-site models, three rigid three-site models, and two fully flexible three-site models) and three different CH4 models (two single-site models and one fully flexible five-site model). The simulation results show good agreement with experimental data, except for thermal conductivities at low densities. The molecular structure and force field parameters play an important role in the accuracy of the simulations, which is within the experimental deviations reported for viscosities and self-diffusion coefficients considering the most accurate CO2 and CH4 models studied. On the other hand, the molecular flexibility does not seem to improve accuracy, since the explicit account of vibrational and bending degrees of freedom in the CO2 flexible models leads to slightly less accurate results. Nonetheless, the use of a correctional term to account for vibrational modes in rigid models generally improves estimations of thermal conductivity values. At extreme densities, the caging effect observed with single-site representations of the molecules restrains mobility and leads to an unphysical overestimation of viscosities and, conversely, to the underestimation of self-diffusion coefficients. This result may help to better understand the limits of applicability of such force fields concerning structural and transport properties of dense systems.

Spectroscopic Studies of Molecular Systems relevant in Astrobiology

NASA Astrophysics Data System (ADS)

Fornaro, Teresa

2016-01-01

In the Astrobiology context, the study of the physico-chemical interactions involving "building blocks of life" in plausible prebiotic and space-like conditions is fundamental to shed light on the processes that led to emergence of life on Earth as well as to molecular chemical evolution in space. In this PhD Thesis, such issues have been addressed both experimentally and computationally by employing vibrational spectroscopy, which has shown to be an effective tool to investigate the variety of intermolecular interactions that play a key role in self-assembling mechanisms of nucleic acid components and their binding to mineral surfaces. In particular, in order to dissect the contributions of the different interactions to the overall spectroscopic signals and shed light on the intricate experimental data, feasible computational protocols have been developed for the characterization of the spectroscopic properties of such complex systems. This study has been carried out through a multi-step strategy, starting the investigation from the spectroscopic properties of the isolated nucleobases, then studying the perturbation induced by the interaction with another molecule (molecular dimers), towards condensed phases like the molecular solid, up to the case of nucleic acid components adsorbed on minerals. A proper modeling of these weakly bound molecular systems has required, firstly, a validation of dispersion-corrected Density Functional Theory methods for simulating anharmonic vibrational properties. The isolated nucleobases and some of their dimers have been used as benchmark set for identifying a general, reliable and effective computational procedure based on fully anharmonic quantum mechanical computations of the vibrational wavenumbers and infrared intensities within the generalized second order vibrational perturbation theory (GVPT2) approach, combined with the cost-effective dispersion-corrected density functional B3LYP-D3, in conjunction with basis sets of double-ζ quality such as N07D and SNSD. Such a protocol has been then applied to the dimers of nucleobases in order to study the perturbation on the vibrational frequencies and infrared intensities induced by the intermolecular hydrogen-bonding interactions. Efforts have been made to challenge the problems of simulating strongly anharmonic vibrations within hydrogen-bonded bridges, focusing on the requirement of a very accurate description of the underlying potential energy surface. Improvements for such vibrations have been achieved by means of hybrid models, where the harmonic part of the force-field is computed at a higher level of theory like B2PLYP, or by application of the less demanding ONIOM B2PLYP:B3LYP scheme, which is a focused model where only the part of the molecular system forming the hydrogen bonds is treated at B2PLYP level of theory. Moreover, for improving the vibrational frequencies of modes like the stretching of C=O and N-H functional groups, which are particularly sensitive to hydrogen-bonding, correction parameters for the B3LYP-D3/N07D frequencies have been determined. Afterwards, the treatment of the vibrational properties of nucleobases in condensed phases has been faced, focusing on uracil in the solid state. In particular, a heptamer cluster of uracil molecules has been considered as model to represent the properties in the solid state. The relative vibrational frequencies have been computed at anharmonic level within the VPT2 framework, combining two cost-effective approaches, namely the hybrid B3LYP-D3/N07D:DFTBA model, where the harmonic frequencies are computed with B3LYP-D3/N07D method and the anharmonic corrections are evaluated with the less expensive DFTBA method, and the reduced dimensionality VPT2 (RD-VPT2) approach, in which only selected vibrational modes are calculated anharmonically (including the couplings with the other modes) while the remaining modes are treated at the harmonic level, using the B3LYP-D3/N07D method only. The reliability of such theoretical results has been validated with respect to experiments, by performing infrared measurements of uracil in the solid state through the Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) technique. The good performance in predicting the experimental shifts of the vibrational frequencies of uracil due to the intermolecular hydrogen bonds in the solid state with respect to uracil isolated in Argon matrix, has allowed also to provide some new assignments of the experimental spectrum of uracil in the solid state. Finally, the study of molecule-mineral interactions has been addressed, investigating experimentally the thermodynamics of the adsorption process of nucleic acid components on brucite, a serpentinite-hosted hydrothermal mineral, through determination of the equilibrium adsorption isotherms. Additionally, surface complexation studies have been carried out to get the stoichiometry of surface reactions and the associated electrical work. Such surface complexation modeling has provided reasonable inferences for the possible surface complexes, determining the number of inner/outer-sphere linkages for the adsorbates and the number of surface sites involved in the reaction stoichiometry. However, to distinguish the specific functional groups which constitute the points of attachment to the surface, further quantum mechanical simulations on the energetics of these complexes and spectroscopic characterizations are in progress.

Simulation study of 2D spectrum of molecular aggregates coupled to correlated vibrations

NASA Astrophysics Data System (ADS)

Abramavicius, Darius; Butkus, Vytautas; Valkunas, Leonas; Mukamel, Shaul

2011-03-01

Oscillatory dynamics of two-dimensional (2D) spectra of photosynthetic pigment-protein complexes raise the questions of how to disentangle various origins of these oscillations, which may include quantum beats, quantum transport, or molecular vibrations. We study the effects of correlated overdamped fluctuations and under-damped vibrations on the 2D spectra of Fenna-Matthews-Olson (FMO) aggregate, which has well-resolved exciton resonances, and a circular porphyrin aggregate (P6), whose absorption shows vibrational progression. We use a generic exciton Hamiltonian coupled to a bath, characterized by a spectral density. Fluctuations have smooth, while vibtations have δ -type spectral densities. We show how various scenarios of correlated molecular fluctuations lead to some highly oscillatory crosspeaks. Molecular vibrations cause progression of diagonal peaks in the 2D spectrum and make their corresponding cross-peaks highly oscillatory. We, thus, demonstrate that bath fluctuations and molecular vibrations of realistic molecular aggregates are highly entangled in 2D spectroscopy. DA acknowledges grant VP1-3.1-SMM-07-V, SM - the grants CHE0745892 (NSF), DRPA BAA-10-40 QUBE.

Raman spectral evidence of methyl rotation in liquid toluene.

PubMed

Kapitán, Josef; Hecht, Lutz; Bour, Petr

2008-02-21

In order to rationalize subtle details in the liquid phase toluene Raman backscattering spectra, an analysis was performed based on a quantum-mechanical Hamiltonian operator comprising rotation of the methyl group and the angular dependence of vibrational frequencies and polarizability derivatives. The separation of the methyl torsion from the other vibrational motions appears to be necessary in order to explain relative intensity ratios of several bands and an anomalous broadening of spectral intensity observed at 1440 cm(-1). These results suggest that the CH3 group in the liquid phase rotates almost freely, similarly as in the gaseous phase, and that the molecule consequently exhibits effectively C(2v) point group symmetry. A classical description and an adiabatic separation of the methyl rotation from other molecular motion previously used in peptide models is not applicable to toluene because of a strong coupling with other vibrational motions. Density functional computations, particularly the BPW91 functional, provide reasonable estimates of harmonic frequencies and spectral intensities, as well as qualitatively correct fourth-order anharmonic corrections to the vibrational potential.

Fully automatic assignment of small molecules' NMR spectra without relying on chemical shift predictions.

PubMed

Castillo, Andrés M; Bernal, Andrés; Patiny, Luc; Wist, Julien

2015-08-01

We present a method for the automatic assignment of small molecules' NMR spectra. The method includes an automatic and novel self-consistent peak-picking routine that validates NMR peaks in each spectrum against peaks in the same or other spectra that are due to the same resonances. The auto-assignment routine used is based on branch-and-bound optimization and relies predominantly on integration and correlation data; chemical shift information may be included when available to fasten the search and shorten the list of viable assignments, but in most cases tested, it is not required in order to find the correct assignment. This automatic assignment method is implemented as a web-based tool that runs without any user input other than the acquired spectra. Copyright © 2015 John Wiley & Sons, Ltd.

Self-consistent assessment of Englert-Schwinger model on atomic properties

NASA Astrophysics Data System (ADS)

Lehtomäki, Jouko; Lopez-Acevedo, Olga

2017-12-01

Our manuscript investigates a self-consistent solution of the statistical atom model proposed by Berthold-Georg Englert and Julian Schwinger (the ES model) and benchmarks it against atomic Kohn-Sham and two orbital-free models of the Thomas-Fermi-Dirac (TFD)-λvW family. Results show that the ES model generally offers the same accuracy as the well-known TFD-1/5 vW model; however, the ES model corrects the failure in the Pauli potential near-nucleus region. We also point to the inability of describing low-Z atoms as the foremost concern in improving the present model.

Self-consistent assessment of Englert-Schwinger model on atomic properties.

PubMed

Lehtomäki, Jouko; Lopez-Acevedo, Olga

2017-12-21

Our manuscript investigates a self-consistent solution of the statistical atom model proposed by Berthold-Georg Englert and Julian Schwinger (the ES model) and benchmarks it against atomic Kohn-Sham and two orbital-free models of the Thomas-Fermi-Dirac (TFD)-λvW family. Results show that the ES model generally offers the same accuracy as the well-known TFD-15vW model; however, the ES model corrects the failure in the Pauli potential near-nucleus region. We also point to the inability of describing low-Z atoms as the foremost concern in improving the present model.

Novel design of a self powered and self sensing magneto-rheological damper

NASA Astrophysics Data System (ADS)

Meftahul Ferdaus, Mohammad; Rashid, M. M.; Bhuiyan, M. M. I.; Muthalif, Asan Gani Bin Abdul; Hasan, M. R.

2013-12-01

Magneto-rheological (MR) dampers are semi-active control devices and use MR fluids. Magneto-rheological dampers have successful applications in mechatronics engineering, civil engineering and numerous areas of engineering. At present, traditional MR damper systems, require a isolated power supply and dynamic sensor. This paper presents the achievability and accuracy of a self- powered and self-sensing magneto-rheological damper using harvested energy from the vibration and shock environment in which it is deployed and another important part of this paper is the increased yield stress of the Magneto rheological Fluids. Magneto rheological fluids using replacement of glass beads for Magnetic Particles to surge yield stress is implemented here. Clearly this shows better result on yield stress, viscosity, and settling rate. Also permanent magnet generator (PMG) is designed and attached to a MR damper. For evaluating the self-powered MR damper's vibration mitigating capacity, an Engine Mount System using the MR damper is simulated. The ideal stiffness of the PMG for the Engine Mount System (EMS) is calculated by numerical study. The vibration mitigating performance of the EMS employing the self-powered & self sensing MR damper is theoretically calculated and evaluated in the frequency domain.

Correlations among self-esteem, aggression, adverse childhood experiences and depression in inmates of a female juvenile correctional facility in Japan.

PubMed

Matsuura, Naomi; Hashimoto, Toshiaki; Toichi, Motomi

2009-08-01

The purpose of this study was to examine the following hypothesis: (i) Self-esteem and aggressiveness, adverse childhood experiences (ACE), and a depressive tendency interact with each other. (ii) The subjects show a strong depressive tendency, and each of the other factors exerts a main effect on, and interacts with, the depressive tendency. The subjects were 91 juveniles (all female) admitted to a female juvenile correctional facility between November 2005 and December 2006. They were aged 15-19 years, with a mean age of 17.0 (SD = 1.18) years. Self-esteem scale, aggression scale, ACE questionnaire, and depression scale were conducted. Significant main effects (R(2) = 0.50, P < 0.001) on the depression score were observed in self-esteem (beta = -0.41, P < 0.001) and aggression (beta = 0.21, P < 0.05). Self-esteem, aggression, ACE, and depression were found to be interrelated. Low self-esteem was also shown to exert marked effects on various factors. About half of the inmates of the facility were depressed, and the main effects of self-esteem, aggression, and the ACE score were shown to influence the depression score.

On the correlation between bond-length change and vibrational frequency shift in halogen-bonded complexes

NASA Astrophysics Data System (ADS)

Wang, Weizhou; Zhang, Yu; Ji, Baoming; Tian, Anmin

2011-06-01

The C-Hal (Hal = Cl, Br, or I) bond-length change and the corresponding vibrational frequency shift of the C-Hal stretch upon the C-Hal ⋯Y (Y is the electron donor) halogen bond formation have been determined by using density functional theory computations. Plots of the C-Hal bond-length change versus the corresponding vibrational frequency shift of the C-Hal stretch all give straight lines. The coefficients of determination range from 0.94366 to 0.99219, showing that the correlation between the C-Hal bond-length change and the corresponding frequency shift is very good in the halogen-bonded complexes. The possible effects of vibrational coupling, computational method, and anharmonicity on the bond-length change-frequency shift correlation are discussed in detail.

Principal component analysis of Raman spectra for TiO2 nanoparticle characterization

NASA Astrophysics Data System (ADS)

Ilie, Alina Georgiana; Scarisoareanu, Monica; Morjan, Ion; Dutu, Elena; Badiceanu, Maria; Mihailescu, Ion

2017-09-01

The Raman spectra of anatase/rutile mixed phases of Sn doped TiO2 nanoparticles and undoped TiO2 nanoparticles, synthesised by laser pyrolysis, with nanocrystallite dimensions varying from 8 to 28 nm, was simultaneously processed with a self-written software that applies Principal Component Analysis (PCA) on the measured spectrum to verify the possibility of objective auto-characterization of nanoparticles from their vibrational modes. The photo-excited process of Raman scattering is very sensible to the material characteristics, especially in the case of nanomaterials, where more properties become relevant for the vibrational behaviour. We used PCA, a statistical procedure that performs eigenvalue decomposition of descriptive data covariance, to automatically analyse the sample's measured Raman spectrum, and to interfere the correlation between nanoparticle dimensions, tin and carbon concentration, and their Principal Component values (PCs). This type of application can allow an approximation of the crystallite size, or tin concentration, only by measuring the Raman spectrum of the sample. The study of loadings of the principal components provides information of the way the vibrational modes are affected by the nanoparticle features and the spectral area relevant for the classification.