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Sample records for calculated harmonic vibrational

  1. Examining the impact of harmonic correlation on vibrational frequencies calculated in localized coordinates

    SciTech Connect

    Hanson-Heine, Magnus W. D.

    2015-10-28

    Carefully choosing a set of optimized coordinates for performing vibrational frequency calculations can significantly reduce the anharmonic correlation energy from the self-consistent field treatment of molecular vibrations. However, moving away from normal coordinates also introduces an additional source of correlation energy arising from mode-coupling at the harmonic level. The impact of this new component of the vibrational energy is examined for a range of molecules, and a method is proposed for correcting the resulting self-consistent field frequencies by adding the full coupling energy from connected pairs of harmonic and pseudoharmonic modes, termed vibrational self-consistent field (harmonic correlation). This approach is found to lift the vibrational degeneracies arising from coordinate optimization and provides better agreement with experimental and benchmark frequencies than uncorrected vibrational self-consistent field theory without relying on traditional correlated methods.

  2. Improving harmonic vibrational frequencies calculations in density functional theory

    NASA Astrophysics Data System (ADS)

    Stratmann, R. Eric; Burant, John C.; Scuseria, Gustavo E.; Frisch, Michael J.

    1997-06-01

    Using a previously introduced weight scheme, microbatching, and grid compression [R. E. Stratmann, G. E. Scuseria and M. J. Frisch, Chem. Phys. Lett. 257, 213 (1996)], we significantly speed up the numerical integration of the exchange-correlation contribution to the Coupled-Perturbed Kohn-Sham equations. In addition, we find that the nature of the integrand is such that it is possible to employ substantially fewer grid points in the quadrature and to use the Gaussian very Fast Multipole Method (GvFMM) with very short multipole expansions for the Coulomb contribution, with negligible loss in accuracy. As a representative example, the computational demand for the exchange-correlation portion of a coronene (C24H12) frequency calculation with a 3-21G basis is reduced by more than one order of magnitude. The overall speed up achieved in this calculation is between a factor of 4 to 6, depending on the specific functional. We also present sample calculations using polarized bases, gradient-corrected functionals, and on even larger systems (C54H18 and C96H24), to illustrate the various effects and improvements that we have accomplished.

  3. Efficient Procedure for the Numerical Calculation of Harmonic Vibrational Frequencies Based on Internal Coordinates

    SciTech Connect

    Miliordos, Evangelos; Xantheas, Sotiris S.

    2013-08-15

    We propose a general procedure for the numerical calculation of the harmonic vibrational frequencies that is based on internal coordinates and Wilson’s GF methodology via double differentiation of the energy. The internal coordinates are defined as the geometrical parameters of a Z-matrix structure, thus avoiding issues related to their redundancy. Linear arrangements of atoms are described using a dummy atom of infinite mass. The procedure has been automated in FORTRAN90 and its main advantage lies in the nontrivial reduction of the number of single-point energy calculations needed for the construction of the Hessian matrix when compared to the corresponding number using double differentiation in Cartesian coordinates. For molecules of C1 symmetry the computational savings in the energy calculations amount to 36N – 30, where N is the number of atoms, with additional savings when symmetry is present. Typical applications for small and medium size molecules in their minimum and transition state geometries as well as hydrogen bonded clusters (water dimer and trimer) are presented. Finally, in all cases the frequencies based on internal coordinates differ on average by <1 cm–1 from those obtained from Cartesian coordinates.

  4. Calculation and analysis of the harmonic vibrational frequencies in molecules at extreme pressure: Methodology and diborane as a test case

    NASA Astrophysics Data System (ADS)

    Cammi, R.; Cappelli, C.; Mennucci, B.; Tomasi, J.

    2012-10-01

    We present a new quantum chemical method for the calculation of the equilibrium geometry and the harmonic vibrational frequencies of molecular systems in dense medium at high pressures (of the order of GPa). The new computational method, named PCM-XP, is based on the polarizable continuum model (PCM), amply used for the study of the solvent effects at standard condition of pressure, and it is accompanied by a new method of analysis for the interpretation of the mechanisms underpinning the effects of pressure on the molecular geometries and the harmonic vibrational frequencies. The PCM-XP has been applied at the density functional theory level to diborane as a molecular system under high pressure. The computed harmonic vibrational frequencies as a function of the pressure have shown a satisfactory agreement with the corresponding experimental results, and the parallel application of the method of analysis has reveled that the effects of the pressure on the equilibrium geometry can be interpreted in terms of direct effects on the electronic charge distribution of the molecular solutes, and that the effects on the harmonic vibrational frequencies can be described in terms of two physically distinct effects of the pressure (curvature and relaxation) on the potential energy for the motion of the nuclei.

  5. Molecular structure, Normal Coordinate Analysis, harmonic vibrational frequencies, Natural Bond Orbital, TD-DFT calculations and biological activity analysis of antioxidant drug 7-hydroxycoumarin

    NASA Astrophysics Data System (ADS)

    Sebastian, S.; Sylvestre, S.; Jayarajan, D.; Amalanathan, M.; Oudayakumar, K.; Gnanapoongothai, T.; Jayavarthanan, T.

    2013-01-01

    In this work, we report harmonic vibrational frequencies, molecular structure, NBO and HOMO, LUMO analysis of Umbelliferone also known as 7-hydroxycoumarin (7HC). The optimized geometric bond lengths and bond angles obtained by computation (monomer and dimmer) shows good agreement with experimental XRD data. Harmonic frequencies of 7HC were determined and analyzed by DFT utilizing 6-311+G(d,p) as basis set. The assignments of the vibrational spectra have been carried out with the help of Normal Coordinate Analysis (NCA) following the Scaled Quantum Mechanical Force Field Methodology (SQMFF). The change in electron density (ED) in the σ* and π* antibonding orbitals and stabilization energies E(2) have been calculated by Natural Bond Orbital (NBO) analysis to give clear evidence of stabilization originating in the hyperconjugation of hydrogen-bonded interaction. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) complements with the experimental findings. The simulated spectra satisfactorily coincides with the experimental spectra. Microbial activity of studied compounds was tested against Staphylococcus aureus, Streptococcus pyogenes, Bacillus subtilis, Escherichia coli, Psuedomonas aeruginosa, Klebsiella pneumoniae, Proteus mirabilis, Shigella flexneri, Salmonella typhi and Enterococcus faecalis.

  6. Application of higher harmonic blade feathering for helicopter vibration reduction

    NASA Technical Reports Server (NTRS)

    Powers, R. W.

    1978-01-01

    Higher harmonic blade feathering for helicopter vibration reduction is considered. Recent wind tunnel tests confirmed the effectiveness of higher harmonic control in reducing articulated rotor vibratory hub loads. Several predictive analyses developed in support of the NASA program were shown to be capable of calculating single harmonic control inputs required to minimize a single 4P hub response. In addition, a multiple-input, multiple-output harmonic control predictive analysis was developed. All techniques developed thus far obtain a solution by extracting empirical transfer functions from sampled data. Algorithm data sampling and processing requirements are minimal to encourage adaptive control system application of such techniques in a flight environment.

  7. An investigation into the vibration of harmonic drive systems

    NASA Astrophysics Data System (ADS)

    Masoumi, M.; Alimohammadi, H.

    2013-12-01

    Harmonic drive systems are precise and specific transmission gear systems which are beneficial in terms of the high transmission ratio and almost zero backlash. These inherent and spectacular properties result in using this mechanism in robotic and space sciences where the precision and lightwieght play an important role. This paper presents a vibration analysis of harmonic drive systems using the shell theory. Equations of vibration for the flexspline and the circular spline of the system are derived and used to find the natural frequencies for both parts and, moreover, vibration response of the system under the operating condition is calculated. Also, obtained vibration equations are utilized to study the effects of different involved parameters such as the geometry of the flexspline and its gear tooth, eccentricity, and unbalancing on the vibrational behavior of the system.

  8. A numerical model for calculating vibration due to a harmonic moving load on a floating-slab track with discontinuous slabs in an underground railway tunnel

    NASA Astrophysics Data System (ADS)

    Hussein, M. F. M.; Hunt, H. E. M.

    2009-03-01

    This paper presents a new method for modelling floating-slab tracks with discontinuous slabs in underground railway tunnels. The track is subjected to a harmonic load moving with a constant velocity. The model consists of two sub-models. The first is an infinite track with periodic double-beam unit formulated as a periodic infinite structure. The second is modelled with a new version of the Pipe-in-Pipe (PiP) model that accounts for a tunnel wall embedded in a half-space. The two sub-models are coupled by writing the force transmitted from the track to the tunnel as a continuous function using Fourier series representation and satisfying the compatibility condition. The displacements at the free surface are calculated for a track with discontinuous slab and compared with those of a track with continuous slab. The results show that the far-field vibration can be significantly increased due to resonance frequencies of slabs for tracks with discontinuous slabs.

  9. Attosecond Probing of Vibrational Dynamics with High-Harmonic Generation

    NASA Astrophysics Data System (ADS)

    Lein, Manfred

    2005-02-01

    The numerical solution of the time-dependent Schrödinger equation for vibrating hydrogen molecules in few-cycle laser pulses shows that high-harmonic generation is sensitive to the laser-induced vibrational motion. More intense harmonics are generated in heavier isotopes, the difference increasing with the harmonic frequency. Analytical theory reveals a dependence of the harmonics on the vibrational autocorrelation function. With the help of a genetic algorithm, the nuclear motion can be reconstructed from the harmonic spectra with sub-fs time resolution.

  10. Higher Harmonic Control for Tiltrotor Vibration Reduction

    NASA Technical Reports Server (NTRS)

    Nixon, Mark W.; Kvaternik, Raymond G.; Settle, T. Ben

    1997-01-01

    The results of a joint NASA/Army/Bell Helicopter Textron wind-tunnel test to assess the potential of higher harmonic control (HHC) for reducing vibrations in tiltrotor aircraft operating in the airplane mode of flight, and to evaluate the effectiveness of a Bell-developed HHC algorithm called MAVSS (Multipoint Adaptive Vibration Suppression System) are presented. The test was conducted in the Langley Transonic Dynamics Tunnel using an unpowered 1/5- scale semispan aeroelastic model of the V-22 which was modified to incorporate an HHC system employing both the rotor swashplate and the wing flaperon. The effectiveness of the swashplate and the flaperon acting either singly or in combination in reducing 1P and 3P wing vibrations over a wide range of tunnel airspeeds and rotor rotational speeds was demonstrated. The MAVSS algorithm was found to be robust to variations in tunnel airspeed and rotor speed, requiring only occasion-al on-line recalculations of the system transfer matrix.

  11. Tiltrotor Vibration Reduction Through Higher Harmonic Control

    NASA Technical Reports Server (NTRS)

    Nixon, Mark W.; Kvaternik, Raymond G.; Settle, T. Ben

    1997-01-01

    The results of a joint NASA/Army/Bell Helicopter Textron wind-tunnel test to assess the potential of higher harmonic control (HHC) for reducing vibrations in tiltrotor aircraft operating in the airplane mode of flight, and to evaluate the effectiveness of a Bell-developed HHC algorithm called MAVSS (Multipoint Adaptive Vibration Suppression System) are presented. The test was conducted in the Langley Transonic Dynamics Tunnel using an unpowered 1/5-scale semispan aeroelastic model of the V-22 which was modified to incorporate an HHC system employing both the rotor swashplate and the wing flaperon. The effectiveness of the swashplate and the flaperon acting either singly or in combination in reducing IP and 3P wing vibrations over a wide range of tunnel airspeeds and rotor rotational speeds was demonstrated. The MAVSS algorithm was found to be robust to variations in tunnel airspeed and rotor speed, requiring only occasional on-line recalculations of the system transfer matrix. HHC had only a small (usually beneficial) effect on blade loads but increased pitch link loads by 25%. No degradation in aeroelastic stability was noted for any of the conditions tested.

  12. Driving an Active Vibration Balancer to Minimize Vibrations at the Fundamental and Harmonic Frequencies

    NASA Technical Reports Server (NTRS)

    Holliday, Ezekiel S. (Inventor)

    2014-01-01

    Vibrations of a principal machine are reduced at the fundamental and harmonic frequencies by driving the drive motor of an active balancer with balancing signals at the fundamental and selected harmonics. Vibrations are sensed to provide a signal representing the mechanical vibrations. A balancing signal generator for the fundamental and for each selected harmonic processes the sensed vibration signal with adaptive filter algorithms of adaptive filters for each frequency to generate a balancing signal for each frequency. Reference inputs for each frequency are applied to the adaptive filter algorithms of each balancing signal generator at the frequency assigned to the generator. The harmonic balancing signals for all of the frequencies are summed and applied to drive the drive motor. The harmonic balancing signals drive the drive motor with a drive voltage component in opposition to the vibration at each frequency.

  13. Vibrational Quantum Beats and High Harmonic Generation in SF6

    NASA Astrophysics Data System (ADS)

    Walters, Zachary B.; Tonzani, Stefano; Greene, Chris H.

    2007-06-01

    Although HHG is commonly understood as an electronic process, vibrational degrees of freedom in molecules allow for phenomena which have no analogue in atomic systems. This was recently demonstrated in experiments performed with SF6 (Wagner et al, PNAS 103 13279, 2006). If a HHG laser pulse is preceded by a weaker pulse which stimulates Raman-active vibrations, the harmonic intensity oscillates with the interpulse delay time at the frequencies of the stimulated modes. We explain this modulation as quantum interference between adjacent vibrational states of the molecule, which are mixed during the high harmonic process. We present an improved version of the three-step model, which uses nonperturbative electron-ion scattering wavefunctions to find the recombination dipole, and which tracks the vibrational wavefunction of the molecule throughout the high harmonic process.

  14. Harmonic balance calculations by using matrices

    NASA Astrophysics Data System (ADS)

    Fergusson, N. J.; Leung, A. Y. T.

    1995-05-01

    The computation of the total and tangential stiffness matrices associated with the harmonic balance method for non-linear ordinary differential equations requires some complicated calculations involving double sums. Some matrix results are presented here that ease the associated book-keeping and allow the matrices to be programmed easily.

  15. Index calculation by means of harmonic expansion

    NASA Astrophysics Data System (ADS)

    Imamura, Yosuke

    2015-11-01

    We review derivation of superconformal indices by means of supersymmetric localization and spherical harmonic expansion for 3d mathcal {N}=2, 4d mathcal {N}=1, and 6d mathcal {N}=(1,0) supersymmetric gauge theories. We demonstrate calculation of indices for vector multiplets in each dimension by analyzing energy eigenmodes in {boldsymbol S}^p × mathbb {R}. For the 6d index we consider the perturbative contribution only. We focus on the technical details of harmonic expansion rather than physical applications.

  16. Analysis of Vibrational Harmonic Response for Printing Double-Sheet Detecting System via ANSYS

    NASA Astrophysics Data System (ADS)

    Guo, Qiang; Cai, Ji-Fei; Wang, Yan; Zhang, Yang

    In order to explore the influence of the harmonic response of system vibration upon the stability of the double-sheet detector system, the mathematical model of vibrational system is established via the mechanical dynamic theory. Vibrational system of double-sheet detector is studied by theoretical modeling, and the dynamic simulation to obtain the amplitude/phase frequency response curve of the system based on ANSYS is completed to make a comparison with the theoretical results. It is shown that the theoretical value is basically consistent with that calculated through ANSYS. Conclusion vibrational characteristics of double-sheet detection system is obtained quickly and accurately, and propound solving measures by some crucial factors, such as the harmonic load, mass and stiffness, which will affect the vibration of the system, contribute to the finite element method is applied to the complex multiple-degree-of-freedom system.

  17. Higher Harmonic Forces in Purely Crossflow Vortex-Induced Vibrations

    NASA Astrophysics Data System (ADS)

    Modarres-Sadeghi, Yahya; Seyed-Aghazadeh, Banafsheh; Bourguet, Remi; Karniadakis, George; Triantafyllou, Michael

    2013-11-01

    In vortex-induced vibrations (VIV) of flexibly-mounted rigid cylinders free to oscillate both in the inline and crossflow directions, higher (3rd) harmonic forces have already been observed in the crossflow direction. In the present work, we report higher harmonic force components for a flexibly-mounted rigid cylinder with only one degree of freedom in the crossflow direction. We show that the inline displacement is not necessary to observe higher harmonic components in the crossflow force spectrum. Due to the relative velocity of the cylinder with respect to the oncoming flow, the lift and drag forces make an angle with respect to the crossflow and inline directions, and the contribution of the components of each of these forces in the crossflow direction results in a 3rd harmonic force component. These higher harmonic components have been observed in self-excited VIV experiments, performed in a water tunnel for a Reynolds number range of Re = 400-1000, as well as in numerical simulation results at Re = 100. We also find that the maximum ratio of the 3rd harmonic to the 1st harmonic occurs when the phase between the crossflow force and displacement changes from 0 to 180 degrees, resulting in a small first harmonic component.

  18. Modeling Stretching Modes of Common Organic Molecules with the Quantum Mechanical Harmonic Oscillator: An Undergraduate Vibrational Spectroscopy Laboratory Exercise

    ERIC Educational Resources Information Center

    Parnis, J. Mark; Thompson, Matthew G. K.

    2004-01-01

    An introductory undergraduate physical organic chemistry exercise that introduces the harmonic oscillator's use in vibrational spectroscopy is developed. The analysis and modeling exercise begins with the students calculating the stretching modes of common organic molecules with the help of the quantum mechanical harmonic oscillator (QMHO) model.

  19. Harmonic Motion Detection in a Vibrating Scattering Medium

    PubMed Central

    Urban, Matthew W.; Chen, Shigao; Greenleaf, James F.

    2008-01-01

    Elasticity imaging is an emerging medical imaging modality that seeks to map the spatial distribution of tissue stiffness. Ultrasound radiation force excitation and motion tracking using pulse-echo ultrasound have been used in numerous methods. Dynamic radiation force is used in vibrometry to cause an object or tissue to vibrate, and the vibration amplitude and phase can be measured with exceptional accuracy. This paper presents a model that simulates harmonic motion detection in a vibrating scattering medium incorporating 3-D beam shapes for radiation force excitation and motion tracking. A parameterized analysis using this model provides a platform to optimize motion detection for vibrometry applications in tissue. An experimental method that produces a multifrequency radiation force is also presented. Experimental harmonic motion detection of simultaneous multifrequency vibration is demonstrated using a single transducer. This method can accurately detect motion with displacement amplitude as low as 100 to 200 nm in bovine muscle. Vibration phase can be measured within 10° or less. The experimental results validate the conclusions observed from the model and show multifrequency vibration induction and measurements can be performed simultaneously. PMID:18986892

  20. Calculating Buckling And Vibrations Of Lattice Structures

    NASA Technical Reports Server (NTRS)

    Anderson, M. S.; Durling, B. J.; Herstrom, C. L.; Williams, F. W.; Banerjee, J. R.; Kennedy, D.; Warnaar, D. B.

    1989-01-01

    BUNVIS-RG computer program designed to calculate vibration frequencies or buckling loads of prestressed lattice structures used in outer space. For buckling and vibration problems, BUNVIS-RG calculates deadload axial forces caused in members by any combination of externally-applied static point forces and moments at nodes, axial preload or prestrain in members, and such acceleration loads as those due to gravity. BUNVIS-RG is FORTRAN 77 computer program implemented on CDC CYBER and VAX computer.

  1. Balancing Vibrations at Harmonic Frequencies by Injecting Harmonic Balancing Signals into the Armature of a Linear Motor/Alternator Coupled to a Stirling Machine

    NASA Technical Reports Server (NTRS)

    Holliday, Ezekiel S. (Inventor)

    2014-01-01

    Vibrations at harmonic frequencies are reduced by injecting harmonic balancing signals into the armature of a linear motor/alternator coupled to a Stirling machine. The vibrations are sensed to provide a signal representing the mechanical vibrations. A harmonic balancing signal is generated for selected harmonics of the operating frequency by processing the sensed vibration signal with adaptive filter algorithms of adaptive filters for each harmonic. Reference inputs for each harmonic are applied to the adaptive filter algorithms at the frequency of the selected harmonic. The harmonic balancing signals for all of the harmonics are summed with a principal control signal. The harmonic balancing signals modify the principal electrical drive voltage and drive the motor/alternator with a drive voltage component in opposition to the vibration at each harmonic.

  2. Effect of acoustic coupling on random and harmonic plate vibrations

    NASA Technical Reports Server (NTRS)

    Frendi, Abdelkader; Robinson, Jay

    1993-01-01

    The effect of acoustic coupling on random and harmonic plate vibrations is studied using two numerical models. In the coupled model, the plate response is obtained by integration of the nonlinear plate equation coupled with the nonlinear Euler equations for the surrounding acoustic fluid. In the uncoupled model, the nonlinear plate equation with an equivalent linear viscous damping term is integrated to obtain the response of the plate subject to the same excitation field. For a low-level, narrow-band excitation, the two models predict the same plate response spectra. As the excitation level is increased, the response power spectrum predicted by the uncoupled model becomes broader and more shifted towards the high frequencies than that obtained by the coupled model. In addition, the difference in response between the coupled and uncoupled models at high frequencies becomes larger. When a high intensity harmonic excitation is used, causing a nonlinear plate response, both models predict the same frequency content of the response. However, the level of the harmonics and subharmonics are higher for the uncoupled model. Comparisons to earlier experimental and numerical results show that acoustic coupling has a significant effect on the plate response at high excitation levels. Its absence in previous models may explain the discrepancy between predicted and measured responses.

  3. First principles semiclassical calculations of vibrational eigenfunctions.

    PubMed

    Ceotto, Michele; Valleau, Stéphanie; Tantardini, Gian Franco; Aspuru-Guzik, Alán

    2011-06-21

    Vibrational eigenfunctions are calculated on-the-fly using semiclassical methods in conjunction with ab initio density functional theory classical trajectories. Various semiclassical approximations based on the time-dependent representation of the eigenfunctions are tested on an analytical potential describing the chemisorption of CO on Cu(100). Then, first principles semiclassical vibrational eigenfunctions are calculated for the CO(2) molecule and its accuracy evaluated. The multiple coherent states initial value representations semiclassical method recently developed by us has shown with only six ab initio trajectories to evaluate eigenvalues and eigenfunctions at the accuracy level of thousands trajectory semiclassical initial value representation simulations. PMID:21837839

  4. Field Balancing and Harmonic Vibration Suppression in Rigid AMB-Rotor Systems with Rotor Imbalances and Sensor Runout

    PubMed Central

    Xu, Xiangbo; Chen, Shao

    2015-01-01

    Harmonic vibrations of high-speed rotors in momentum exchange devices are primary disturbances for attitude control of spacecraft. Active magnetic bearings (AMBs), offering the ability to control the AMB-rotor dynamic behaviors, are preferred in high-precision and micro-vibration applications, such as high-solution Earth observation satellites. However, undesirable harmonic displacements, currents, and vibrations also occur in the AMB-rotor system owing to the mixed rotor imbalances and sensor runout. To compensate the rotor imbalances and to suppress the harmonic vibrations, two control methods are presented. Firstly, a four degrees-of-freedom AMB-rotor model with the static imbalance, dynamic imbalance, and the sensor runout are described. Next, a synchronous current reduction approach with a variable-phase notch feedback is proposed, so that the rotor imbalances can be identified on-line through the analysis of the synchronous displacement relationships of the geometric, inertial, and rotational axes of the rotor. Then, the identified rotor imbalances, which can be represented at two prescribed balancing planes of the rotor, are compensated by discrete add-on weights whose masses are calculated in the vector form. Finally, a repetitive control algorithm is utilized to suppress the residual harmonic vibrations. The proposed field balancing and harmonic vibration suppression strategies are verified by simulations and experiments performed on a control moment gyro test rig with a rigid AMB-rotor system. Compared with existing methods, the proposed strategies do not require trial weights or an accurate model of the AMB-rotor system. Moreover, the harmonic displacements, currents, and vibrations can be well-attenuated simultaneously. PMID:26334281

  5. Field Balancing and Harmonic Vibration Suppression in Rigid AMB-Rotor Systems with Rotor Imbalances and Sensor Runout.

    PubMed

    Xu, Xiangbo; Chen, Shao

    2015-01-01

    Harmonic vibrations of high-speed rotors in momentum exchange devices are primary disturbances for attitude control of spacecraft. Active magnetic bearings (AMBs), offering the ability to control the AMB-rotor dynamic behaviors, are preferred in high-precision and micro-vibration applications, such as high-solution Earth observation satellites. However, undesirable harmonic displacements, currents, and vibrations also occur in the AMB-rotor system owing to the mixed rotor imbalances and sensor runout. To compensate the rotor imbalances and to suppress the harmonic vibrations, two control methods are presented. Firstly, a four degrees-of-freedom AMB-rotor model with the static imbalance, dynamic imbalance, and the sensor runout are described. Next, a synchronous current reduction approach with a variable-phase notch feedback is proposed, so that the rotor imbalances can be identified on-line through the analysis of the synchronous displacement relationships of the geometric, inertial, and rotational axes of the rotor. Then, the identified rotor imbalances, which can be represented at two prescribed balancing planes of the rotor, are compensated by discrete add-on weights whose masses are calculated in the vector form. Finally, a repetitive control algorithm is utilized to suppress the residual harmonic vibrations. The proposed field balancing and harmonic vibration suppression strategies are verified by simulations and experiments performed on a control moment gyro test rig with a rigid AMB-rotor system. Compared with existing methods, the proposed strategies do not require trial weights or an accurate model of the AMB-rotor system. Moreover, the harmonic displacements, currents, and vibrations can be well-attenuated simultaneously. PMID:26334281

  6. Intermediate vibrational coordinate localization with harmonic coupling constraints

    NASA Astrophysics Data System (ADS)

    Hanson-Heine, Magnus W. D.

    2016-05-01

    Optimized normal coordinates can significantly improve the speed and accuracy of vibrational frequency calculations. However, over-localization can occur when using unconstrained spatial localization techniques. The unintuitive mixtures of stretching and bending coordinates that result can make interpreting spectra more difficult and also cause artificial increases in mode-coupling during anharmonic calculations. Combining spatial localization with a constraint on the coupling between modes can be used to generate coordinates with properties in-between the normal and fully localized schemes. These modes preserve the diagonal nature of the mass-weighted Hessian matrix to within a specified tolerance and are found to prevent contamination between the stretching and bending vibrations of the molecules studied without a priori classification of the different types of vibration present. Relaxing the constraint can also be used to identify which normal modes form specific groups of localized modes. The new coordinates are found to center on more spatially delocalized functional groups than their fully localized counterparts and can be used to tune the degree of vibrational correlation energy during anharmonic calculations.

  7. Intermediate vibrational coordinate localization with harmonic coupling constraints.

    PubMed

    Hanson-Heine, Magnus W D

    2016-05-28

    Optimized normal coordinates can significantly improve the speed and accuracy of vibrational frequency calculations. However, over-localization can occur when using unconstrained spatial localization techniques. The unintuitive mixtures of stretching and bending coordinates that result can make interpreting spectra more difficult and also cause artificial increases in mode-coupling during anharmonic calculations. Combining spatial localization with a constraint on the coupling between modes can be used to generate coordinates with properties in-between the normal and fully localized schemes. These modes preserve the diagonal nature of the mass-weighted Hessian matrix to within a specified tolerance and are found to prevent contamination between the stretching and bending vibrations of the molecules studied without a priori classification of the different types of vibration present. Relaxing the constraint can also be used to identify which normal modes form specific groups of localized modes. The new coordinates are found to center on more spatially delocalized functional groups than their fully localized counterparts and can be used to tune the degree of vibrational correlation energy during anharmonic calculations. PMID:27250288

  8. Vibrational spectroscopic studies and DFT calculations of 4-aminoantipyrine

    NASA Astrophysics Data System (ADS)

    Swaminathan, J.; Ramalingam, M.; Sethuraman, V.; Sundaraganesan, N.; Sebastian, S.

    2009-08-01

    The pyrazole derivative, 4-aminoantipyrine (4AAP), used as an intermediate for the synthesis of pharmaceuticals especially antipyretic and analgesic drugs has been analyzed experimentally and theoretically for its vibrational frequencies. The FTIR and FT Raman spectra of the title compound have been compared with the theoretically computed frequencies invoking the standard 6-311g(d,p) and cc-pVDZ basis sets at DFT level of theory (B3LYP). The harmonic vibrational frequencies at B3LYP/cc-pVDZ after appropriate scaling method seem to coincide satisfactorily with the experimental observations rather than B3LYP/6-311g(d,p) results. The theoretical spectrograms for FT-IR and FT-Raman spectra of 4AAP have been also constructed and compared with the experimental spectra. Additionally, thermodynamic data have also been calculated and discussed.

  9. Ab initio DFT calculations of vibrational properties

    NASA Astrophysics Data System (ADS)

    Story, S. M.; Vila, F. D.; Kas, J. J.; Rehr, J. J.

    2014-03-01

    Vibrational properties such as EXAFS and crystallographic Debye-Waller factors, vibrational free energies, phonon self-energies, and phonon contributions to the electron spectral function, are key to understanding many aspects of materials beyond ground state electronic structure. Thus, their simulation using first principles methods is of particular importance. Many of these vibrational properties can be calculated from the dynamical matrix and electron-phonon coupling coefficients obtained from DFT calculations. Here we present a code DMVP that calculates these properties from the output of electronic structure codes such as ABINIT, Gaussian, Quantum Espresso and VASP. Our modular interfacing tool AI2PS allows us to translate the different outputs into a DMVP compatible format and generate vibrational properties in an automated way. Finally, we present some current applications that take advantage of the modular form of AI2PS to extend its capabilities to the calculation of coefficients of thermal expansion and other properties of interest such as infrared spectra. This work was supported by DOE Grant DE-FG02-97ER45623.

  10. Vibrational spectroscopy and relaxation of an anharmonic oscillator coupled to harmonic bath.

    PubMed

    Joutsuka, Tatsuya; Ando, Koji

    2011-05-28

    The vibrational spectroscopy and relaxation of an anharmonic oscillator coupled to a harmonic bath are examined to assess the applicability of the time correlation function (TCF), the response function, and the semiclassical frequency modulation (SFM) model to the calculation of infrared (IR) spectra. These three approaches are often used in connection with the molecular dynamics simulations but have not been compared in detail. We also analyze the vibrational energy relaxation (VER), which determines the line shape and is itself a pivotal process in energy transport. The IR spectra and VER are calculated using the generalized Langevin equation (GLE), the Gaussian wavepacket (GWP) method, and the quantum master equation (QME). By calculating the vibrational frequency TCF, a detailed analysis of the frequency fluctuation and correlation time of the model is provided. The peak amplitude and width in the IR spectra calculated by the GLE with the harmonic quantum correction are shown to agree well with those by the QME though the vibrational frequency is generally overestimated. The GWP method improves the peak position by considering the zero-point energy and the anharmonicity although the red-shift slightly overshoots the QME reference. The GWP also yields an extra peak in the higher-frequency region than the fundamental transition arising from the difference frequency of the center and width oscillations of a wavepacket. The SFM approach underestimates the peak amplitude of the IR spectra but well reproduces the peak width. Further, the dependence of the VER rate on the strength of an excitation pulse is discussed. PMID:21639460

  11. Optimized coordinates in vibrational coupled cluster calculations

    SciTech Connect

    Thomsen, Bo; Christiansen, Ove; Yagi, Kiyoshi

    2014-04-21

    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 variational 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.

  12. Modeling, calculating, and analyzing multidimensional vibrational spectroscopies.

    PubMed

    Tanimura, Yoshitaka; Ishizaki, Akihito

    2009-09-15

    Spectral line shapes in a condensed phase contain information from various dynamic processes that modulate the transition energy, such as microscopic dynamics, inter- and intramolecular couplings, and solvent dynamics. Because nonlinear response functions are sensitive to the complex dynamics of chemical processes, multidimensional vibrational spectroscopies can separate these processes. In multidimensional vibrational spectroscopy, the nonlinear response functions of a molecular dipole or polarizability are measured using ultrashort pulses to monitor inter- and intramolecular vibrational motions. Because a complex profile of such signals depends on the many dynamic and structural aspects of a molecular system, researchers would like to have a theoretical understanding of these phenomena. In this Account, we explore and describe the roles of different physical phenomena that arise from the peculiarities of the system-bath coupling in multidimensional spectra. We also present simple analytical expressions for a weakly coupled multimode Brownian system, which we use to analyze the results obtained by the experiments and simulations. To calculate the nonlinear optical response, researchers commonly use a particular form of a system Hamiltonian fit to the experimental results. The optical responses of molecular vibrational motions have been studied in either an oscillator model or a vibration energy state model. In principle, both models should give the same results as long as the energy states are chosen to be the eigenstates of the oscillator model. The energy state model can provide a simple description of nonlinear optical processes because the diagrammatic Liouville space theory that developed in the electronically resonant spectroscopies can easily handle three or four energy states involved in high-frequency vibrations. However, the energy state model breaks down if we include the thermal excitation and relaxation processes in the dynamics to put the system in a

  13. Quantum Monte Carlo Algorithms for Diagrammatic Vibrational Structure Calculations

    NASA Astrophysics Data System (ADS)

    Hermes, Matthew; Hirata, So

    2015-06-01

    Convergent hierarchies of theories for calculating many-body vibrational ground and excited-state wave functions, such as Møller-Plesset perturbation theory or coupled cluster theory, tend to rely on matrix-algebraic manipulations of large, high-dimensional arrays of anharmonic force constants, tasks which require large amounts of computer storage space and which are very difficult to implement in a parallel-scalable fashion. On the other hand, existing quantum Monte Carlo (QMC) methods for vibrational wave functions tend to lack robust techniques for obtaining excited-state energies, especially for large systems. By exploiting analytical identities for matrix elements of position operators in a harmonic oscillator basis, we have developed stochastic implementations of the size-extensive vibrational self-consistent field (MC-XVSCF) and size-extensive vibrational Møller-Plesset second-order perturbation (MC-XVMP2) theories which do not require storing the potential energy surface (PES). The programmable equations of MC-XVSCF and MC-XVMP2 take the form of a small number of high-dimensional integrals evaluated using Metropolis Monte Carlo techniques. The associated integrands require independent evaluations of only the value, not the derivatives, of the PES at many points, a task which is trivial to parallelize. However, unlike existing vibrational QMC methods, MC-XVSCF and MC-XVMP2 can calculate anharmonic frequencies directly, rather than as a small difference between two noisy total energies, and do not require user-selected coordinates or nodal surfaces. MC-XVSCF and MC-XVMP2 can also directly sample the PES in a given approximation without analytical or grid-based approximations, enabling us to quantify the errors induced by such approximations.

  14. Definitions of non-stationary vibration power for time-frequency analysis and computational algorithms based upon harmonic wavelet transform

    NASA Astrophysics Data System (ADS)

    Heo, YongHwa; Kim, Kwang-joon

    2015-02-01

    While the vibration power for a set of harmonic force and velocity signals is well defined and known, it is not as popular yet for a set of stationary random force and velocity processes, although it can be found in some literatures. In this paper, the definition of the vibration power for a set of non-stationary random force and velocity signals will be derived for the purpose of a time-frequency analysis based on the definitions of the vibration power for the harmonic and stationary random signals. The non-stationary vibration power, defined as the short-time average of the product of the force and velocity over a given frequency range of interest, can be calculated by three methods: the Wigner-Ville distribution, the short-time Fourier transform, and the harmonic wavelet transform. The latter method is selected in this paper because band-pass filtering can be done without phase distortions, and the frequency ranges can be chosen very flexibly for the time-frequency analysis. Three algorithms for the time-frequency analysis of the non-stationary vibration power using the harmonic wavelet transform are discussed. The first is an algorithm for computation according to the full definition, while the others are approximate. Noting that the force and velocity decomposed into frequency ranges of interest by the harmonic wavelet transform are constructed with coefficients and basis functions, for the second algorithm, it is suggested to prepare a table of time integrals of the product of the basis functions in advance, which are independent of the signals under analysis. How to prepare and utilize the integral table are presented. The third algorithm is based on an evolutionary spectrum. Applications of the algorithms to the time-frequency analysis of the vibration power transmitted from an excitation source to a receiver structure in a simple mechanical system consisting of a cantilever beam and a reaction wheel are presented for illustration.

  15. Influence of vibrational states on high-order-harmonic generation and an isolated attosecond pulse from a N2 molecule

    NASA Astrophysics Data System (ADS)

    Guo, Jing; Ge, Xin-Lei; Zhong, Huiying; Zhao, Xi; Zhang, Meixia; Jiang, Yuanfei; Liu, Xue-Shen

    2014-11-01

    The high-order-harmonic generation (HHG) from the N2 molecule in an intense laser field is investigated by applying the Lewenstein method. The initial state is constructed as a linear combination of the highest occupied molecular orbital (HOMO) and the lower-lying orbital below the HOMO, which is well described by a Gaussian wave packet generated by using the gamess-uk package. The HHG with different vibrational states of N2 are calculated and our results show that the harmonic intensity can be enhanced by higher vibrational states, which can be explained by the ionization probability. We also compared the cases with a different full width at half maximum of laser fields together, which can be well understood by the time-frequency analysis and the three-step model. Finally, the attosecond pulse generation is studied with different vibrational states, where a series of attosecond pulses can be produced with the shortest being 91 as.

  16. Ab initio calculation of harmonic force fields and vibrational spectra for the arsine oxides and sulfides R sub 3 AsY (R = H, F; Y = O, S) and related compounds

    SciTech Connect

    Schneider, W.; Thiel, W. ); Komornicki, A. )

    1990-04-05

    Ab initio self-consistent-field calculations using effective core potentials and polarized double-zeta basis sets are reported for the arsenic compounds H{sub 3}As, H{sub 3}AsO, H{sub 3}AsS, F{sub 3}As, F{sub 3}AsO, F{sub 3}AsS, cis- and trans-H{sub 2}AsOH, and HAsO. The calculated geometries, rotational constants, vibrational frequencies, Coriolis coupling constants, centrifugal distortion constants, infrared band intensities, and force fields are compared with the available experimental data. Good agreement is found in the case of the known molecules, especially H{sub 3}As and F{sub 3}As, so that the predictions for the unknown molecules are expected to be realistic. The theoretical results confirm a recent spectroscopic identification of H{sub 3}AsO, H{sub 2}AsOH, and HAsO and suggest reassignment of several observed frequencies.

  17. Calculation of four-particle harmonic-oscillator transformation brackets

    NASA Astrophysics Data System (ADS)

    Germanas, D.; Kalinauskas, R. K.; Mickevičius, S.

    2010-02-01

    A procedure for precise calculation of the three- and four-particle harmonic-oscillator (HO) transformation brackets is presented. The analytical expressions of the four-particle HO transformation brackets are given. The computer code for the calculations of HO transformation brackets proves to be quick, efficient and produces results with small numerical uncertainties. Program summaryProgram title: HOTB Catalogue identifier: AEFQ_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEFQ_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 1247 No. of bytes in distributed program, including test data, etc.: 6659 Distribution format: tar.gz Programming language: FORTRAN 90 Computer: Any computer with FORTRAN 90 compiler Operating system: Windows, Linux, FreeBSD, True64 Unix RAM: 8 MB Classification: 17.17 Nature of problem: Calculation of the three-particle and four-particle harmonic-oscillator transformation brackets. Solution method: The method is based on compact expressions of the three-particle harmonics oscillator brackets, presented in [1] and expressions of the four-particle harmonics oscillator brackets, presented in this paper. Restrictions: The three- and four-particle harmonic-oscillator transformation brackets up to the e=28. Unusual features: Possibility of calculating the four-particle harmonic-oscillator transformation brackets. Running time: Less than one second for the single harmonic-oscillator transformation bracket. References:G.P. Kamuntavičius, R.K. Kalinauskas, B.R. Barret, S. Mickevičius, D. Germanas, Nuclear Physics A 695 (2001) 191.

  18. HVDC-AC system interaction from AC harmonics. Volume 1. Harmonic impedance calculations. Final report

    SciTech Connect

    Breuer, G D; Chow, J H; Lindh, C B; Miller, N W; Numrich, F H; Price, W W; Turner, A E; Whitney, R R

    1982-09-01

    Improved methods are needed to characterize ac system harmonic behavior for ac filter design for HVDC systems. The purpose of this General Electric Company RP1138 research is to evaluate the present filter design practice and to investigate methods for calculating system harmonic impedances. An overview of ac filter design for HVDC systems and a survey of literature related to filter design have been performed. Two methods for calculating system harmonic impedances have been investigated. In the measurement method, an instrumentation system for measuring system voltage and current has been assembled. Different schemes of using the measurements to calculate system harmonic impedances have been studied. In the analytical method, a procedure to include various operating conditions has been proposed. Computer programs for both methods have been prepared, and the results of the measurement and analytical methods analyzed. A conclusion of the project is that the measurement and analytical methods both provided reasonable results. There are correlations between the measured and analytical results for most harmonics, although there are discrepancies between the assumptions used in the two methods. A sensitivity approach has been proposed to further correlate the results. From the results of the analysis, it is recommended that both methods should be tested further. For the measurement method, more testing should be done to cover different system operating conditions. In the analytical method, more detailed models for representing system components should be studied. In addition, alternative statistical and sensitivity approaches should be attempted.

  19. Coupled rotor-flexible fuselage vibration reduction using open loop higher harmonic control

    NASA Technical Reports Server (NTRS)

    Papavassiliou, I.; Friedmann, P. P.; Venkatesan, C.

    1991-01-01

    A fundamental study of vibration prediction and vibration reduction in helicopters using active controls was performed. The nonlinear equations of motion for a coupled rotor/flexible fuselage system have been derived using computer algebra on a special purpose symbolic computer facility. The trim state and vibratory response of the helicopter are obtained in a single pass by applying the harmonic balance technique and simultaneously satisfying the trim and the vibratory response of the helicopter for all rotor and fuselage degrees of freedom. The influence of the fuselage flexibility on the vibratory response is studied. It is shown that the conventional single frequency higher harmonic control is capable of reducing either the hub loads or only the fuselage vibrations but not both simultaneously. It is demonstrated that for simultaneous reduction of hub shears and fuselae vibrations a new scheme called multiple higher harmonic control is required.

  20. Calculation of converged rovibrational energies and partition function for methane using vibrational-rotational configuration interaction.

    PubMed

    Chakraborty, Arindam; Truhlar, Donald G; Bowman, Joel M; Carter, Stuart

    2004-08-01

    The rovibration partition function of CH4 was calculated in the temperature range of 100-1000 K using well-converged energy levels that were calculated by vibrational-rotational configuration interaction using the Watson Hamiltonian for total angular momenta J = 0-50 and the MULTIMODE computer program. The configuration state functions are products of ground-state occupied and virtual modals obtained using the vibrational self-consistent field method. The Gilbert and Jordan potential energy surface was used for the calculations. The resulting partition function was used to test the harmonic oscillator approximation and the separable-rotation approximation. The harmonic oscillator, rigid-rotator approximation is in error by a factor of 2.3 at 300 K, but we also propose a separable-rotation approximation that is accurate within 2% from 100 to 1000 K. PMID:15260761

  1. Application of higher harmonic blade feathering on the OH-6A helicopter for vibration reduction

    NASA Technical Reports Server (NTRS)

    Straub, F. K.; Byrns, E. V., Jr.

    1986-01-01

    The design, implementation, and flight test results of higher harmonic blade feathering for vibration reduction on the OH-6A helicopter are described. The higher harmonic control (HHC) system superimposes fourth harmonic inputs upon the stationary swashplate. These inputs are transformed into 3P, 4P and 5P blade feathering angles. This results in modified blade loads and reduced fuselage vibrations. The primary elements of this adaptive vibration suppression system are: (1) acceleration transducers sensing the vibratory response of the fuselage; (2) a higher harmonic blade pitch actuator system; (3) a flightworthy microcomputer, incorporating the algorithm for reducing vibrations, and (4) a signal conditioning system, interfacing between the sensors, the microcomputer and the HHC actuators. The program consisted of three distinct phases. First, the HHC system was designed and implemented on the MDHC OH-6A helicopter. Then, the open loop, or manual controlled, flight tests were performed, and finally, the closed loop adaptive control system was tested. In 1983, one portion of the closed loop testing was performed, and in 1984, additional closed loop tests were conducted with improved software. With the HHC system engaged, the 4P pilot seat vibration levels were significantly lower than the baseline ON-6A levels. Moreover, the system did not adversely affect blade loads or helicopter performance. In conclusion, this successful proof of concept project demonstrated HHC to be a viable vibration suppression mechanism.

  2. Two-dimensional Raman and infrared vibrational spectroscopy for a harmonic oscillator system nonlinearly coupled with a colored noise bath

    NASA Astrophysics Data System (ADS)

    Kato, Tsuyoshi; Tanimura, Yoshitaka

    2004-01-01

    Multidimensional vibrational response functions of a harmonic oscillator are reconsidered by assuming nonlinear system-bath couplings. In addition to a standard linear-linear (LL) system-bath interaction, we consider a square-linear (SL) interaction. The LL interaction causes the vibrational energy relaxation, while the SL interaction is mainly responsible for the vibrational phase relaxation. The dynamics of the relevant system are investigated by the numerical integration of the Gaussian-Markovian Fokker-Planck equation under the condition of strong couplings with a colored noise bath, where the conventional perturbative approach cannot be applied. The response functions for the fifth-order nonresonant Raman and the third-order infrared (or equivalently the second-order infrared and the seventh-order nonresonant Raman) spectra are calculated under the various combinations of the LL and the SL coupling strengths. Calculated two-dimensional response functions demonstrate that those spectroscopic techniques are very sensitive to the mechanism of the system-bath couplings and the correlation time of the bath fluctuation. We discuss the primary optical transition pathways involved to elucidate the corresponding spectroscopic features and to relate them to the microscopic sources of the vibrational nonlinearity induced by the system-bath interactions. Optical pathways for the fifth-order Raman spectroscopies from an "anisotropic" medium were newly found in this study, which were not predicted by the weak system-bath coupling theory or the standard Brownian harmonic oscillator model.

  3. Two-dimensional Raman and infrared vibrational spectroscopy for a harmonic oscillator system nonlinearly coupled with a colored noise bath.

    PubMed

    Kato, Tsuyoshi; Tanimura, Yoshitaka

    2004-01-01

    Multidimensional vibrational response functions of a harmonic oscillator are reconsidered by assuming nonlinear system-bath couplings. In addition to a standard linear-linear (LL) system-bath interaction, we consider a square-linear (SL) interaction. The LL interaction causes the vibrational energy relaxation, while the SL interaction is mainly responsible for the vibrational phase relaxation. The dynamics of the relevant system are investigated by the numerical integration of the Gaussian-Markovian Fokker-Planck equation under the condition of strong couplings with a colored noise bath, where the conventional perturbative approach cannot be applied. The response functions for the fifth-order nonresonant Raman and the third-order infrared (or equivalently the second-order infrared and the seventh-order nonresonant Raman) spectra are calculated under the various combinations of the LL and the SL coupling strengths. Calculated two-dimensional response functions demonstrate that those spectroscopic techniques are very sensitive to the mechanism of the system-bath couplings and the correlation time of the bath fluctuation. We discuss the primary optical transition pathways involved to elucidate the corresponding spectroscopic features and to relate them to the microscopic sources of the vibrational nonlinearity induced by the system-bath interactions. Optical pathways for the fifth-order Raman spectroscopies from an "anisotropic" medium were newly found in this study, which were not predicted by the weak system-bath coupling theory or the standard Brownian harmonic oscillator model. PMID:15267286

  4. Vibrational analysis of 4-chloro-3-nitrobenzonitrile by quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Sert, Yusuf; Çırak, Çağrı; Ucun, Fatih

    2013-04-01

    In the present study, the experimental and theoretical harmonic and anharmonic vibrational frequencies of 4-chloro-3-nitrobenzonitrile were investigated. The experimental FT-IR (400-4000 cm-1) and μ-Raman spectra (100-4000 cm-1) of the molecule in the solid phase were recorded. Theoretical vibrational frequencies and geometric parameters (bond lengths and bond angles) were calculated using ab initio Hartree Fock (HF), density functional B3LYP and M06-2X methods with 6-311++G(d,p) basis set by Gaussian 09 W program, for the first time. The assignments of the vibrational frequencies were performed by potential energy distribution (PED) analysis by using VEDA 4 program. The theoretical optimized geometric parameters and vibrational frequencies were compared with the corresponding experimental data, and they were seen to be in a good agreement with each other. Also, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies were found.

  5. Non-symmetric and chaotic vibrations of Euler-Bernoulli beams under harmonic and noisy excitations

    NASA Astrophysics Data System (ADS)

    Awrejcewicz, J.; Erofeev, N. P.; Krysko, V. A.

    2016-05-01

    In this paper we study non-linear dynamics of flexible Euler-Bernoulli beams subjected to harmonic load and white noise. We report that in the case of continuous mechanical systems like the studied Euler-Bernoulli beams the action of white noise yieldes novel and unexpected phenomena, i.e. symmetric transversal loads and symmetric boundary conditions imply non-symmetric beam vibration. In addition, regions of non-symmetric beam vibrations for two values of white noise intensity are given and the charts of regular and chaotic vibrations of the studied beams are presented.

  6. Compressive Sensing of Roller Bearing Faults via Harmonic Detection from Under-Sampled Vibration Signals

    PubMed Central

    Tang, Gang; Hou, Wei; Wang, Huaqing; Luo, Ganggang; Ma, Jianwei

    2015-01-01

    The Shannon sampling principle requires substantial amounts of data to ensure the accuracy of on-line monitoring of roller bearing fault signals. Challenges are often encountered as a result of the cumbersome data monitoring, thus a novel method focused on compressed vibration signals for detecting roller bearing faults is developed in this study. Considering that harmonics often represent the fault characteristic frequencies in vibration signals, a compressive sensing frame of characteristic harmonics is proposed to detect bearing faults. A compressed vibration signal is first acquired from a sensing matrix with information preserved through a well-designed sampling strategy. A reconstruction process of the under-sampled vibration signal is then pursued as attempts are conducted to detect the characteristic harmonics from sparse measurements through a compressive matching pursuit strategy. In the proposed method bearing fault features depend on the existence of characteristic harmonics, as typically detected directly from compressed data far before reconstruction completion. The process of sampling and detection may then be performed simultaneously without complete recovery of the under-sampled signals. The effectiveness of the proposed method is validated by simulations and experiments. PMID:26473858

  7. Experimental Analysis of a Piezoelectric Energy Harvesting System for Harmonic, Random, and Sine on Random Vibration

    SciTech Connect

    Cryns, Jackson W.; Hatchell, Brian K.; Santiago-Rojas, Emiliano; Silvers, Kurt L.

    2013-07-01

    Formal journal article Experimental analysis of a piezoelectric energy harvesting system for harmonic, random, and sine on random vibration Abstract: Harvesting power with a piezoelectric vibration powered generator using a full-wave rectifier conditioning circuit is experimentally compared for varying sinusoidal, random and sine on random (SOR) input vibration scenarios. Additionally, the implications of source vibration characteristics on harvester design are discussed. Studies in vibration harvesting have yielded numerous alternatives for harvesting electrical energy from vibrations but piezoceramics arose as the most compact, energy dense means of energy transduction. The rise in popularity of harvesting energy from ambient vibrations has made piezoelectric generators commercially available. Much of the available literature focuses on maximizing harvested power through nonlinear processing circuits that require accurate knowledge of generator internal mechanical and electrical characteristics and idealization of the input vibration source, which cannot be assumed in general application. In this manuscript, variations in source vibration and load resistance are explored for a commercially available piezoelectric generator. We characterize the source vibration by its acceleration response for repeatability and transcription to general application. The results agree with numerical and theoretical predictions for in previous literature that load optimal resistance varies with transducer natural frequency and source type, and the findings demonstrate that significant gains are seen with lower tuned transducer natural frequencies for similar source amplitudes. Going beyond idealized steady state sinusoidal and simplified random vibration input, SOR testing allows for more accurate representation of real world ambient vibration. It is shown that characteristic interactions from more complex vibrational sources significantly alter power generation and power processing

  8. Multi-channel electronic and vibrational dynamics in polyatomic resonant high-order harmonic generation

    PubMed Central

    Ferré, A.; Boguslavskiy, A. E.; Dagan, M.; Blanchet, V.; Bruner, B. D.; Burgy, F.; Camper, A.; Descamps, D.; Fabre, B.; Fedorov, N.; Gaudin, J.; Geoffroy, G.; Mikosch, J.; Patchkovskii, S.; Petit, S.; Ruchon, T.; Soifer, H.; Staedter, D.; Wilkinson, I.; Stolow, A.; Dudovich, N.; Mairesse, Y.

    2015-01-01

    High-order harmonic generation in polyatomic molecules generally involves multiple channels of ionization. Their relative contribution can be strongly influenced by the presence of resonances, whose assignment remains a major challenge for high-harmonic spectroscopy. Here we present a multi-modal approach for the investigation of unaligned polyatomic molecules, using SF6 as an example. We combine methods from extreme-ultraviolet spectroscopy, above-threshold ionization and attosecond metrology. Fragment-resolved above-threshold ionization measurements reveal that strong-field ionization opens at least three channels. A shape resonance in one of them is found to dominate the signal in the 20–26 eV range. This resonance induces a phase jump in the harmonic emission, a switch in the polarization state and different dynamical responses to molecular vibrations. This study demonstrates a method for extending high-harmonic spectroscopy to polyatomic molecules, where complex attosecond dynamics are expected. PMID:25608712

  9. Multi-channel electronic and vibrational dynamics in polyatomic resonant high-order harmonic generation.

    PubMed

    Ferré, A; Boguslavskiy, A E; Dagan, M; Blanchet, V; Bruner, B D; Burgy, F; Camper, A; Descamps, D; Fabre, B; Fedorov, N; Gaudin, J; Geoffroy, G; Mikosch, J; Patchkovskii, S; Petit, S; Ruchon, T; Soifer, H; Staedter, D; Wilkinson, I; Stolow, A; Dudovich, N; Mairesse, Y

    2015-01-01

    High-order harmonic generation in polyatomic molecules generally involves multiple channels of ionization. Their relative contribution can be strongly influenced by the presence of resonances, whose assignment remains a major challenge for high-harmonic spectroscopy. Here we present a multi-modal approach for the investigation of unaligned polyatomic molecules, using SF6 as an example. We combine methods from extreme-ultraviolet spectroscopy, above-threshold ionization and attosecond metrology. Fragment-resolved above-threshold ionization measurements reveal that strong-field ionization opens at least three channels. A shape resonance in one of them is found to dominate the signal in the 20-26 eV range. This resonance induces a phase jump in the harmonic emission, a switch in the polarization state and different dynamical responses to molecular vibrations. This study demonstrates a method for extending high-harmonic spectroscopy to polyatomic molecules, where complex attosecond dynamics are expected. PMID:25608712

  10. Higher harmonic control analysis for vibration reduction of helicopter rotor systems

    NASA Technical Reports Server (NTRS)

    Nguyen, Khanh Q.

    1994-01-01

    An advanced higher harmonic control (HHC) analysis has been developed and applied to investigate its effect on vibration reduction levels, blade and control system fatigue loads, rotor performance, and power requirements of servo-actuators. The analysis is based on a finite element method in space and time. A nonlinear time domain unsteady aerodynamic model, based on the indicial response formulation, is used to calculate the airloads. The rotor induced inflow is computed using a free wake model. The vehicle trim controls and blade steady responses are solved as one coupled solution using a modified Newton method. A linear frequency-domain quasi-steady transfer matrix is used to relate the harmonics of the vibratory hub loads to the harmonics of the HHC inputs. Optimal HHC is calculated from the minimization of the vibratory hub loads expressed in term of a quadratic performance index. Predicted vibratory hub shears are correlated with wind tunnel data. The fixed-gain HHC controller suppresses completely the vibratory hub shears for most of steady or quasi-steady flight conditions. HHC actuator amplitudes and power increase significantly at high forward speeds (above 100 knots). Due to the applied HHC, the blade torsional stresses and control loads are increased substantially. For flight conditions where the blades are stalled considerably, the HHC input-output model is quite nonlinear. For such cases, the adaptive-gain controller is effective in suppressing vibratory hub loads, even though HHC may actually increase stall areas on the rotor disk. The fixed-gain controller performs poorly for such flight conditions. Comparison study of different rotor systems indicates that a soft-inplane hingeless rotor requires less actuator power at high speeds (above 130 knots) than an articulated rotor, and a stiff-inplane hingeless rotor generally requires more actuator power than an articulated or a soft-inplane hingeless rotor. Parametric studies for a hingeless rotor

  11. The effects of molecular vibration on the yield of high-order harmonic generation.

    NASA Astrophysics Data System (ADS)

    Xia, Jiangfan

    2005-05-01

    It is well-accepted that the high-order harmonic spectrum is the results of interference between many attosecond pulses. Each of the attosecond pulse is produced by a three-step process taking place within one laser cycle. For light molecules such as H2, the first step is the ionization of one electron. When the freed electron returns to the H2^+, the internuclear distance is changed. This may cause the electron to miss the ion during its revisit, thus reducing its probability to recombine with the parent ion. As a result, the high harmonic generation yield is lower for H2 than D2, since D2 has a longer vibration period (˜21 fs) than that of H2 (˜15 fs). Here we report, to the best of our knowledge, the first experimental observation of the effects of vibration on the yield of HHG in molecules. We compared the high-order harmonic spectra of H2, HD and D2. The shortest pulses were ˜8 fs, which is almost the same as one half of the vibration period of H2. Using such short pulses assures that the internuclear distances of all three types of molecules are in the increasing phase of a cycle when the harmonics are generated. From the HHG spectra it is evident that the yield of D2 is a factor of two higher than that of H2, while that of HD is in between. This is consistent with the theoretical predictions.

  12. An active control system for helicopter vibration reduction by higher harmonic pitch

    NASA Technical Reports Server (NTRS)

    Taylor, R. B.; Farrar, F. A.; Miao, W.

    1980-01-01

    An analytical study defining the basic configuration of an active control system to reduce helicopter vibrations is presented. Theoretical results for a nonlinear four-bladed single rotor helicopter simulation are discussed, showing that vibration reductions on the order of 80-90% for airspeeds up to 150 kn can be expected when using a higher harmonic pitch in an active feedback control system. The rotor performance penalty associated with this level of vibration reduction is about 1-3% and the increase in rotor blade stresses is considered to be low. The location of sensor accelerometers proved to be significant for vibration reductions, and it is noted that the RTSA controller is tolerant of sensor signal noise.

  13. An ab initio study of the in-plane harmonic force fields and fundamental vibration frequencies of cis- and trans-1,3-butadiene

    NASA Astrophysics Data System (ADS)

    Bock, Charles W.; Trachtman, Mendel; George, Philip

    1980-11-01

    The structure, in-plane force field, and fundamental vibration frequencies of trans- and cis-1,3-butadiene are calculated ab initio using the 4-31G basis set. Using a scaling procedure based on computational results from smaller molecules, the vibration frequencies for the trans-conformer calculated from the ab initio force constant matrix are found on average to be within 2.2% of the experimental values "harmonized" according to Dennison's rule. The values predicted for the cis-conformer, for which experimental spectroscopic data are only now becoming available, should facilitate the complete in-plane assignment of fundamentals in the near future.

  14. Calculation of Vibrational Spectra of p-Ethylbenzenesulfonic Acid Hydrates

    NASA Astrophysics Data System (ADS)

    Zelenkovskii, V. M.; Bezyazychnaya, T. V.; Soldatov, V. S.

    2013-09-01

    Quantum-chemical calculations of vibrational spectra of the sulfonated ion-exchanger model p-ethylbenzenesulfonic acid hydrated by 1-10 water molecules and its dimer were calculated by the non-empirical SCF MO LCAO method with the 6-31G(d) basis set. The calculated results were compared with experimental IR and Raman spectra of sulfonated ion exchangers. The infl uence of hydration on the vibrational frequencies of functional groups in the ion exchangers was analyzed. It was shown that the sulfonic acid was completely dissociated if three and more water molecules per functional group were present. Bands near 1130 cm-1 were due to S-O-H bending vibrations in the absence of water molecules and C-S-O-H3O combination vibrations with 3-6 water molecules per sulfonic acid.

  15. Nonlinear traveling wave vibration of a circular cylindrical shell subjected to a moving concentrated harmonic force

    NASA Astrophysics Data System (ADS)

    Wang, Y. Q.; Guo, X. H.; Li, Y. G.; Li, J.

    2010-03-01

    This is a study of nonlinear traveling wave response of a cantilever circular cylindrical shell subjected to a concentrated harmonic force moving in a concentric circular path at a constant velocity. Donnell's shallow-shell theory is used, so that moderately large vibrations are analyzed. The problem is reduced to a system of ordinary differential equations by means of the Galerkin method. Frequency-responses for six different mode expansions are studied and compared with that for single mode to find the more contracted and accurate mode expansion investigating traveling wave vibration. The method of harmonic balance is applied to study the nonlinear dynamic response in forced oscillations of this system. Results obtained with analytical method are compared with numerical simulation, and the agreement between them bespeaks the validity of the method developed in this paper. The stability of the period solutions is also examined in detail.

  16. Molecular structure, vibrational spectra and DFT molecular orbital calculations (TD-DFT and NMR) of the antiproliferative drug Methotrexate

    NASA Astrophysics Data System (ADS)

    Ayyappan, S.; Sundaraganesan, N.; Aroulmoji, V.; Murano, E.; Sebastian, S.

    2010-09-01

    The FT-IR and FT-Raman spectral studies of the Methotrexate (MTX) were carried out. The equilibrium geometry, various bonding features and harmonic vibrational frequencies of MTX have been investigated with the help of B3LYP density functional theory (DFT) using 6-31G(d) as basis set. Detailed analysis of the vibrational spectra has been made with the aid of theoretically predicted vibrational frequencies. The vibrational analysis confirms the differently acting ring modes, steric repulsion, conjugation and back-donation. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) results complement with the experimental findings. The calculated HOMO and LUMO energies show that charge transfer occur within the molecule. Good correlations between the experimental 1H and 13C NMR chemical shifts in DMSO solution and calculated GIAO shielding tensors were found.

  17. A vibrational spectroscopy study on 3-aminophenylacetic acid by DFT calculations

    NASA Astrophysics Data System (ADS)

    Akkaya, Yasemin; Balci, Kubilay; Goren, Yeliz; Akyuz, Sevim

    2015-08-01

    In this study, in which the group vibrations of 3-aminophenylacetic acid were investigated by electronic structure calculations based on Density Functional Theory (DFT), the possible stable conformers of the molecule were searched through a relaxed "potential energy surface scan" carried out at B3LYP/6-31G(d) level of theory. The corresponding equilibrium geometrical and vibrational spectral data for each of the determined stable conformers and for their possible dimer structures were obtained through "geometry optimisation" and "frequency" calculations carried out at B3LYP/6-31G(d) and B3LYP/6-311G++(d,p) levels of theory. The obtained results confirmed that anharmonic wavenumbers calculated at B3LYP/6-311G++(d,p) level generally quite well agree with the experimental wavenumbers, however, harmonic wavenumbers calculated at both levels of theory need an efficient refinement for a satisfactory agreement with experiment. In particular, the harmonic wavenumbers, IR and Raman intensities refined within Scaled Quantum Mechanical Force Field (SQM FF) methodology constituted the primary data set in the interpretation of the experimental FT-IR, FT-Raman and dispersive Raman spectra of 3-aminophenylacetic acid. By the help of these refined spectral data, the effects of conformation and intermolecular hydrogen bonding on the fundamental bands observed in the experimental spectra could be correctly predicted.

  18. A vibrational spectroscopy study on 3-aminophenylacetic acid by DFT calculations.

    PubMed

    Akkaya, Yasemin; Balci, Kubilay; Goren, Yeliz; Akyuz, Sevim

    2015-08-01

    In this study, in which the group vibrations of 3-aminophenylacetic acid were investigated by electronic structure calculations based on Density Functional Theory (DFT), the possible stable conformers of the molecule were searched through a relaxed "potential energy surface scan" carried out at B3LYP/6-31G(d) level of theory. The corresponding equilibrium geometrical and vibrational spectral data for each of the determined stable conformers and for their possible dimer structures were obtained through "geometry optimisation" and "frequency" calculations carried out at B3LYP/6-31G(d) and B3LYP/6-311G++(d,p) levels of theory. The obtained results confirmed that anharmonic wavenumbers calculated at B3LYP/6-311G++(d,p) level generally quite well agree with the experimental wavenumbers, however, harmonic wavenumbers calculated at both levels of theory need an efficient refinement for a satisfactory agreement with experiment. In particular, the harmonic wavenumbers, IR and Raman intensities refined within Scaled Quantum Mechanical Force Field (SQM FF) methodology constituted the primary data set in the interpretation of the experimental FT-IR, FT-Raman and dispersive Raman spectra of 3-aminophenylacetic acid. By the help of these refined spectral data, the effects of conformation and intermolecular hydrogen bonding on the fundamental bands observed in the experimental spectra could be correctly predicted. PMID:25854610

  19. Vibronic-structure tracking: A shortcut for vibrationally resolved UV/Vis-spectra calculations

    SciTech Connect

    Barton, Dennis; König, Carolin; Neugebauer, Johannes

    2014-10-28

    The vibrational coarse structure and the band shapes of electronic absorption spectra are often dominated by just a few molecular vibrations. By contrast, the simulation of the vibronic structure even in the simplest theoretical models usually requires the calculation of the entire set of normal modes of vibration. Here, we exploit the idea of the mode-tracking protocol [M. Reiher and J. Neugebauer, J. Chem. Phys. 118, 1634 (2003)] in order to directly target and selectively calculate those normal modes which have the largest effect on the vibronic band shape for a certain electronic excitation. This is achieved by defining a criterion for the importance of a normal mode to the vibrational progressions in the absorption band within the so-called “independent mode, displaced harmonic oscillator” (IMDHO) model. We use this approach for a vibronic-structure investigation for several small test molecules as well as for a comparison of the vibronic absorption spectra of a truncated chlorophyll a model and the full chlorophyll a molecule. We show that the method allows to go beyond the often-used strategy to simulate absorption spectra based on broadened vertical excitation peaks with just a minimum of computational effort, which in case of chlorophyll a corresponds to about 10% of the cost for a full simulation within the IMDHO approach.

  20. Calculation of second-harmonic wave pattern generated by focused cylindrical vector beams

    NASA Astrophysics Data System (ADS)

    Ohtsu, A.; Kozawa, Y.; Sato, S.

    2010-03-01

    We calculated the second-harmonic wave pattern induced by focused cylindrically symmetric, polarized vector beams. The second-order nonlinear polarization was expressed for fundamental electric field components passed through a dielectric interface based on vector diffraction theory. Furthermore, the second-harmonic wave pattern was represented on the basis of the far-field approximate expression derived from the formulation of higher-order harmonic generation including a Green's function. For a (110) zinc selenide crystal, the calculated forward emission patterns of the second-harmonic wave were eight-figure shaped as observed in experiment.

  1. Analytic calculations of anharmonic infrared and Raman vibrational spectra.

    PubMed

    Cornaton, Yann; Ringholm, Magnus; Louant, Orian; Ruud, Kenneth

    2016-02-01

    Using a recently developed recursive scheme for the calculation of high-order geometric derivatives of frequency-dependent molecular properties [Ringholm et al., J. Comp. Chem., 2014, 35, 622], we present the first analytic calculations of anharmonic infrared (IR) and Raman spectra including anharmonicity both in the vibrational frequencies and in the IR and Raman intensities. In the case of anharmonic corrections to the Raman intensities, this involves the calculation of fifth-order energy derivatives-that is, the third-order geometric derivatives of the frequency-dependent polarizability. The approach is applicable to both Hartree-Fock and Kohn-Sham density functional theory. Using generalized vibrational perturbation theory to second order, we have calculated the anharmonic infrared and Raman spectra of the non- and partially deuterated isotopomers of nitromethane, where the inclusion of anharmonic effects introduces combination and overtone bands that are observed in the experimental spectra. For the major features of the spectra, the inclusion of anharmonicities in the calculation of the vibrational frequencies is more important than anharmonic effects in the calculated infrared and Raman intensities. Using methanimine as a trial system, we demonstrate that the analytic approach avoids errors in the calculated spectra that may arise if numerical differentiation schemes are used. PMID:26784673

  2. A piezoelectric pulse generator for low frequency non-harmonic vibration

    NASA Astrophysics Data System (ADS)

    Jiang, Hao; Yeatman, Eric M.

    2013-12-01

    This paper reports a new piezoelectric prototype for pulse generation by energy harvesting from low frequency non-harmonic vibration. The pulse generator presented here consists of two parts: the electromechanical part and the load circuit. A metal rolling rod is used as the proof mass, moving along the substrate to achieve both actuating of the piezoelectric cantilever by magnetic coupling and self-synchronous switching of the circuit. By using this new approach, the energy from the piezoelectric transduction mechanism is regulated simultaneously when it is extracted. This allows a series of tuneable pulses to be generated, which can be applied to self-powered RF wireless sensor network (WSN) nodes.

  3. Nonlinear vibrational-state excitation and piezoelectric energy conversion in harmonically driven granular chains

    NASA Astrophysics Data System (ADS)

    Chong, C.; Kim, E.; Charalampidis, E. G.; Kim, H.; Li, F.; Kevrekidis, P. G.; Lydon, J.; Daraio, C.; Yang, J.

    2016-05-01

    This article explores the excitation of different vibrational states in a spatially extended dynamical system through theory and experiment. As a prototypical example, we consider a one-dimensional packing of spherical particles (a so-called granular chain) that is subject to harmonic boundary excitation. The combination of the multimodal nature of the system and the strong coupling between the particles due to the nonlinear Hertzian contact force leads to broad regions in frequency where different vibrational states are possible. In certain parametric regions, we demonstrate that the nonlinear Schrödinger equation predicts the corresponding modes fairly well. The electromechanical model we apply predicts accurately the conversion from the obtained mechanical energy to the electrical energy observed in experiments.

  4. Nonlinear vibrational-state excitation and piezoelectric energy conversion in harmonically driven granular chains.

    PubMed

    Chong, C; Kim, E; Charalampidis, E G; Kim, H; Li, F; Kevrekidis, P G; Lydon, J; Daraio, C; Yang, J

    2016-05-01

    This article explores the excitation of different vibrational states in a spatially extended dynamical system through theory and experiment. As a prototypical example, we consider a one-dimensional packing of spherical particles (a so-called granular chain) that is subject to harmonic boundary excitation. The combination of the multimodal nature of the system and the strong coupling between the particles due to the nonlinear Hertzian contact force leads to broad regions in frequency where different vibrational states are possible. In certain parametric regions, we demonstrate that the nonlinear Schrödinger equation predicts the corresponding modes fairly well. The electromechanical model we apply predicts accurately the conversion from the obtained mechanical energy to the electrical energy observed in experiments. PMID:27300876

  5. Vibrational spectra and quantum mechanical calculations of antiretroviral drugs: Nevirapine

    NASA Astrophysics Data System (ADS)

    Ayala, A. P.; Siesler, H. W.; Wardell, S. M. S. V.; Boechat, N.; Dabbene, V.; Cuffini, S. L.

    2007-02-01

    Nevirapine (11-cyclopropyl-5,11-dihydro-4-methyl-6H-dipyrido[3,2-b:2',3'e][1,4]diazepin-6-one) is an antiretroviral drug belonging to the class of the non-nucleoside inhibitors of the HIV-1 virus reverse transcriptase. As most of this kind of antiretroviral drugs, nevirapine displays a butterfly-like conformation which is preserved in complexes with the HIV-1 reverse transcriptase. In this work, we present a detailed vibrational spectroscopy investigation of nevirapine by using mid-infrared, near-infrared, and Raman spectroscopies. These data are supported by quantum mechanical calculations, which allow us to characterize completely the vibrational spectra of this compound. Based on these results, we discuss the correlation between the vibrational modes and the crystalline structure of the most stable form of nevirapine.

  6. Calculation of mechanical vibration frequencies of stiffened superconducting cavities

    SciTech Connect

    Black, S.J.; Spalek, G.

    1992-09-01

    We calculated the frequencies of transverse and longitudinal mechanical-vibration modes of the HEPL- modified, CERN/DESY four-cell superconducting cavity, using finite-element techniques. We compared the results of these calculations, including the stiffening of the cavity with rods, with mode frequencies measured at HEPL. The correlation between data was significant. The same techniques were also used to design and optimize the stiffening scheme for the seven-cell 805-MHz superconducting cavity being developed at Los Alamos. In this report, we describe the final stiffening scheme and the results of our calculations.

  7. Calculation of mechanical vibration frequencies of stiffened superconducting cavities

    SciTech Connect

    Black, S.J.; Spalek, G.

    1992-01-01

    We calculated the frequencies of transverse and longitudinal mechanical-vibration modes of the HEPL- modified, CERN/DESY four-cell superconducting cavity, using finite-element techniques. We compared the results of these calculations, including the stiffening of the cavity with rods, with mode frequencies measured at HEPL. The correlation between data was significant. The same techniques were also used to design and optimize the stiffening scheme for the seven-cell 805-MHz superconducting cavity being developed at Los Alamos. In this report, we describe the final stiffening scheme and the results of our calculations.

  8. On the effect of acoustic coupling on random and harmonic plate vibrations

    NASA Technical Reports Server (NTRS)

    Frendi, A.; Robinson, J. H.

    1993-01-01

    The effect of acoustic coupling on random and harmonic plate vibrations is studied using two numerical models. In the coupled model, the plate response is obtained by integration of the nonlinear plate equation coupled with the nonlinear Euler equations for the surrounding acoustic fluid. In the uncoupled model, the nonlinear plate equation with an equivalent linear viscous damping term is integrated to obtain the response of the plate subject to the same excitation field. For a low-level, narrow-band excitation, the two models predict the same plate response spectra. As the excitation level is increased, the response power spectrum predicted by the uncoupled model becomes broader and more shifted towards the high frequencies than that obtained by the coupled model. In addition, the difference in response between the coupled and uncoupled models at high frequencies becomes larger. When a high intensity harmonic excitation is used, causing a nonlinear plate response, both models predict the same frequency content of the response. However, the level of the harmonics and subharmonics are higher for the uncoupled model. Comparisons to earlier experimental and numerical results show that acoustic coupling has a significant effect on the plate response at high excitation levels. Its absence in previous models may explain the discrepancy between predicted and measured responses.

  9. Vibrational spectra and DFT calculations of sonderianin diterpene

    NASA Astrophysics Data System (ADS)

    Oliveira, I. M. M.; Santos, H. S.; Sena, D. M.; Cruz, B. G.; Teixeira, A. M. R.; Freire, P. T. C.; Braz-Filho, R.; Sousa, J. W.; Albuquerque, M. R. J. R.; Bandeira, P. N.; Bernardino, A. C. S. S.; Gusmão, G. O. M.; Bento, R. R. F.

    2015-11-01

    In the present study, the natural product sonderianin diterpene (C21H26O4), a diterpenoid isolated from Croton blanchetianus, with potential application in the drug industry, was characterized by nuclear magnetic resonance, infrared and Raman spectroscopy. Vibrational spectra were supported by Density Functional Theory calculations. Infrared and Raman spectra of sonderianin were recorded at ambient temperature in the regions from 400 cm-1 to 3600 cm-1 and from 40 cm-1 to 3500 cm-1, respectively. DFT calculations with the hybrid functional B3LYP and the basis set 6-31 G(d,p) were performed with the purpose of obtaining information on the structural and vibrational properties of this organic compound. A comparison with experimental spectra allowed us to assign all of the normal modes of the crystal. The assignment of the normal modes was carried out by means of potential energy distribution.

  10. Mapping quadrupole collectivity in the Cd isotopes: The breakdown of harmonic vibrational motion

    SciTech Connect

    Garrett, P. E.; Green, K. L.; Bangay, J.; Varela, A. Diaz; Sumithrarachchi, C. S.; Bandyopadhyay, D. S.; Bianco, L.; Demand, G. A.; Finlay, P.; Grinyer, G. F.; Leach, K. G.; Phillips, A. A.; Schumaker, M. A.; Svensson, C. E.; Wong, J.; Austin, R. A. E.; Colosimo, S.; Ball, G. C.; Garnsworthy, A. B.; Hackman, G.

    2011-10-28

    The stable Cd isotopes have long been used as paradigms for spherical vibrational motion. Extensive investigations with in-beam {gamma} spectroscopy have resulted in very-well-established level schemes, including many lifetimes or lifetime limits. A programme has been initiated to complement these studies with very-high-statistics {beta} decay using the 8{pi} spectrometer at the TRIUMF radioactive beam facility. The decays of {sup 112}In and {sup 112}Ag have been studied with an emphasis on the observation of, or the placement of stringent limits on, low-energy branches between potential multi-phonon levels. A lack of suitable 0{sup +} or 2{sup +} three-phonon candidates has been revealed. Further, the sum of the B(E2) strength from spin 0{sup +} and 2{sup +} states up to 3 MeV in excitation energy to the assigned two-phonon levels falls far short of the harmonic-vibrational expectations. This lack of strength points to the failing of collective models based on vibrational phonon structures.

  11. Vibrational and structural study of onopordopicrin based on the FTIR spectrum and DFT calculations.

    PubMed

    Chain, Fernando E; Romano, Elida; Leyton, Patricio; Paipa, Carolina; Catalán, César A N; Fortuna, Mario; Brandán, Silvia Antonia

    2015-11-01

    In the present work, the structural and vibrational properties of the sesquiterpene lactone onopordopicrin (OP) were studied by using infrared spectroscopy and density functional theory (DFT) calculations together with the 6-31G(∗) basis set. The harmonic vibrational wavenumbers for the optimized geometry were calculated at the same level of theory. The complete assignment of the observed bands in the infrared spectrum was performed by combining the DFT calculations with Pulay's scaled quantum mechanical force field (SQMFF) methodology. The comparison between the theoretical and experimental infrared spectrum demonstrated good agreement. Then, the results were used to predict the Raman spectrum. Additionally, the structural properties of OP, such as atomic charges, bond orders, molecular electrostatic potentials, characteristics of electronic delocalization and topological properties of the electronic charge density were evaluated by natural bond orbital (NBO), atoms in molecules (AIM) and frontier orbitals studies. The calculated energy band gap and the chemical potential (μ), electronegativity (χ), global hardness (η), global softness (S) and global electrophilicity index (ω) descriptors predicted for OP low reactivity, higher stability and lower electrophilicity index as compared with the sesquiterpene lactone cnicin containing similar rings. PMID:26057092

  12. Calculation of ground vibration spectra from heavy military vehicles

    NASA Astrophysics Data System (ADS)

    Krylov, V. V.; Pickup, S.; McNuff, J.

    2010-07-01

    The demand for reliable autonomous systems capable to detect and identify heavy military vehicles becomes an important issue for UN peacekeeping forces in the current delicate political climate. A promising method of detection and identification is the one using the information extracted from ground vibration spectra generated by heavy military vehicles, often termed as their seismic signatures. This paper presents the results of the theoretical investigation of ground vibration spectra generated by heavy military vehicles, such as tanks and armed personnel carriers. A simple quarter car model is considered to identify the resulting dynamic forces applied from a vehicle to the ground. Then the obtained analytical expressions for vehicle dynamic forces are used for calculations of generated ground vibrations, predominantly Rayleigh surface waves, using Green's function method. A comparison of the obtained theoretical results with the published experimental data shows that analytical techniques based on the simplified quarter car vehicle model are capable of producing ground vibration spectra of heavy military vehicles that reproduce basic properties of experimental spectra.

  13. An improved filtered spherical harmonic method for transport calculations

    SciTech Connect

    Ahrens, C.; Merton, S.

    2013-07-01

    Motivated by the work of R. G. McClarren, C. D. Hauck, and R. B. Lowrie on a filtered spherical harmonic method, we present a new filter for such numerical approximations to the multi-dimensional transport equation. In several test problems, we demonstrate that the new filter produces results with significantly less Gibbs phenomena than the filter used by McClarren, Hauck and Lowrie. This reduction in Gibbs phenomena translates into propagation speeds that more closely match the correct propagation speed and solutions that have fewer regions where the scalar flux is negative. (authors)

  14. Designs and numerical calculations for echo-enabled harmonic generation at very high harmonics

    NASA Astrophysics Data System (ADS)

    Penn, G.; Reinsch, M.

    2011-09-01

    The echo-enabled harmonic generation (EEHG) scheme for driving an FEL using two seeded energy modulations at much longer wavelengths than the output wavelength is a promising concept for future seeded FELs. There are many competing requirements in the design of an EEHG beamline which need careful optimization. Furthermore, revised simulation tools and methods are necessary because of both the high harmonic numbers simulated and the complicated nature of the phase space manipulations which are intrinsic to the scheme. This paper explores the constraints on performance and the required tolerances for reaching wavelengths well below 1/100th of that of the seed lasers, and describes some of the methodology for designing such a beamline. Numerical tools, developed both for the GENESIS and GINGER FEL codes, are presented and used here for more accurate study of the scheme beyond a time-averaged model. In particular, the impact of the local structure in peak current and bunching, which is an inherent part of the EEHG scheme, is evaluated.

  15. Vibrational spectroscopy of a harmonic oscillator system nonlinearly coupled to a heat bath

    NASA Astrophysics Data System (ADS)

    Kato, Tsuyoshi; Tanimura, Yoshitaka

    2002-10-01

    Vibrational relaxation of a harmonic oscillator nonlinearly coupled to a heat bath is investigated by the Gaussian-Markovian quantum Fokker-Planck equation approach. The system-bath interaction is assumed to be linear in the bath coordinate, but linear plus square in the system coordinate modeling the elastic and inelastic relaxation mechanisms. Interplay of the two relaxation processes induced by the linear-linear and square-linear interactions in Raman or infrared spectra is discussed for various system-bath couplings, temperatures, and correlation times for the bath fluctuations. The one-quantum coherence state created through the interaction with the pump laser pulse relaxes through different pathways in accordance with the mechanisms of the system-bath interactions. Relations between the present theory, Redfield theory, and stochastic theory are also discussed.

  16. On the calculation of classical vibrational energy exchange

    NASA Astrophysics Data System (ADS)

    Gibbons, John P.; Stettler, John D.

    1982-07-01

    A three-dimensional, Monte Carlo classical model for the calculation of vibrational energy relaxation and transfer rates for both diatomic—monatomic and diatomic—diatomic systems was developed, analyzed and implemented. Mediation by internal angular momentum changes was demonstrated to be important in these energy transfer processes. This mechanism was incorporated into the model in order to achieve statistically significant results within reasonable computer running times. This made possible the extension of the model calculations to much lower temperatures than had been previously investigated. This calculational procedure was applied to Ar—O 2, to He—O 2 and to the near resonant CO—N 2 process at several temperatures between room temperature and 4000 K with the use of exponential repulsive intermolecular potential. Three different sets of potential parameters obtained from three independent sources were used. The results were compared to experiment.

  17. A study of coupled rotor-fuselage vibration with higher harmonic control using a symbolic computing facility

    NASA Technical Reports Server (NTRS)

    Papavassiliou, I.; Venkatesan, C.; Friedmann, P. P.

    1990-01-01

    A fundamental study of vibration prediction and vibration reduction in helicopters using active controls was performed. The nonlinear equations of motion for a coupled rotor/flexible fuselage system have been derived using computer algebra on a special purpose symbolic computing facility. The details of the derivation using the MACSYMA program are described. The trim state and vibratory response of the helicopter are obtained in a single pass by applying the harmonic balance technique and simultaneously satisfying the trim and the vibratory response of the helicopter for all rotor and fuselage degrees of freedom. The influence of the fuselage flexibility on the vibratory response is studied. It is shown that the conventional single frequency higher harmonic control (HHC) capable of reducing either the hub loads or only the fuselage vibrations but not both simultaneously. It is demonstrated that for simultaneous reduction of hub shears and fuselage vibrations a new scheme called multiple higher harmonic control (MHHC) is required. The fundamental aspects of this scheme and its uniqueness are described in detail, providing new insight on vibration reduction in helicopters using HHC.

  18. HOTB: High precision parallel code for calculation of four-particle harmonic oscillator transformation brackets

    NASA Astrophysics Data System (ADS)

    Stepšys, A.; Mickevicius, S.; Germanas, D.; Kalinauskas, R. K.

    2014-11-01

    This new version of the HOTB program for calculation of the three and four particle harmonic oscillator transformation brackets provides some enhancements and corrections to the earlier version (Germanas et al., 2010) [1]. In particular, new version allows calculations of harmonic oscillator transformation brackets be performed in parallel using MPI parallel communication standard. Moreover, higher precision of intermediate calculations using GNU Quadruple Precision and arbitrary precision library FMLib [2] is done. A package of Fortran code is presented. Calculation time of large matrices can be significantly reduced using effective parallel code. Use of Higher Precision methods in intermediate calculations increases the stability of algorithms and extends the validity of used algorithms for larger input values. Catalogue identifier: AEFQ_v4_0 Program summary URL: http://cpc.cs.qub.ac.uk/summaries/AEFQ_v4_0.html Program obtainable from: CPC Program Library, Queen’s University of Belfast, N. Ireland Licensing provisions: GNU General Public License, version 3 Number of lines in programs, including test data, etc.: 1711 Number of bytes in distributed programs, including test data, etc.: 11667 Distribution format: tar.gz Program language used: FORTRAN 90 with MPI extensions for parallelism Computer: Any computer with FORTRAN 90 compiler Operating system: Windows, Linux, FreeBSD, True64 Unix Has the code been vectorized of parallelized?: Yes, parallelism using MPI extensions. Number of CPUs used: up to 999 RAM(per CPU core): Depending on allocated binomial and trinomial matrices and use of precision; at least 500 MB Catalogue identifier of previous version: AEFQ_v1_0 Journal reference of previous version: Comput. Phys. Comm. 181, Issue 2, (2010) 420-425 Does the new version supersede the previous version? Yes Nature of problem: Calculation of matrices of three-particle harmonic oscillator brackets (3HOB) and four-particle harmonic oscillator brackets (4HOB) in a more

  19. Super harmonic nonlinear lateral vibrations of a segmented driveline incorporating a tuned damper excited by non-constant velocity joints

    NASA Astrophysics Data System (ADS)

    Browne, Michael; Palazzolo, Alan

    2009-06-01

    Typical industrial vibration problem solving includes utilization of linear vibration measurement and analysis techniques. These techniques have appeared to be sufficient with most vibration problem solving requirements. This is partially due to the lack of proper identification of the nonlinear dynamic response in measured data of actual engineering systems. Therefore, as an example, a vehicle driveshaft exhibits a nonlinear super harmonic jump due to universal joint excitations. This phenomenon is partially responsible for objectionable audible noise in the vehicle. Previously documented measurements or analytical predictions of vehicle driveshaft systems do not indicate nonlinear jump as a typical vibration mode. Physical measurements of the phenomena will be provided with subsequent analysis. Second, the secondary moment exciting the driveshaft system is derived with subsequent analysis showing the harmonic and super harmonic excitations. Third, a derivation of a model incorporating the linear and nonlinear modeling of a large degree of freedom system is introduced. Finally, simulations with the derived model with the universal joint excitations will be presented showing the correlation to physical test results. Therefore, a typical automotive driveshaft system is capable of producing nonlinear response, and thus the assumption of linearity is not sufficient for design validation or problem resolution in this case.

  20. A simplified approach for the calculation of acoustic emission in the case of friction-induced noise and vibration

    NASA Astrophysics Data System (ADS)

    Soobbarayen, K.; Besset, S.; Sinou, J.-. J.

    2015-01-01

    The acoustic response associated with squeal noise radiations is a hard issue due to the need to consider non-linearities of contact and friction, to solve the associated nonlinear dynamic problem and to calculate the noise emissions due to self-excited vibrations. In this work, the focus is on the calculation of the sound pressure in free space generated during squeal events. The calculation of the sound pressure can be performed by the Boundary Element Method (BEM). The inputs of this method are a boundary element model, a field of normal velocity characterized by a unique frequency. However, the field of velocity associated with friction-induced vibrations is composed of several harmonic components. So, the BEM equation has to be solved for each frequency and in most cases, the number of harmonic components is significant. Therefore, the computation time can be prohibitive. The reduction of the number of harmonic component is a key point for the quick estimation of the squeal noise. The proposed approach is based on the detection and the selection of the predominant harmonic components in the mean square velocity. It is applied on two cases of squeal and allows us to consider only few frequencies. In this study, a new method will be proposed in order to quickly well estimate the noise emission in free space. This approach will be based on an approximated acoustic power of brake system which is assumed to be a punctual source, an interpolated directivity and the decrease of the acoustic power levels. This method is applied on two classical cases of squeal with one and two unstable modes. It allows us to well reconstruct the acoustic power levels map. Several error estimators are introduced and show that the reconstructed field is close to the reference calculated with a complete BEM.

  1. Automated calculation of anharmonic vibrational contributions to first hyperpolarizabilities: Quadratic response functions from vibrational configuration interaction wave functions

    NASA Astrophysics Data System (ADS)

    Hansen, Mikkel Bo; Christiansen, Ove; Hättig, Christof

    2009-10-01

    Quadratic response functions are derived and implemented for a vibrational configuration interaction state. Combined electronic and vibrational quadratic response functions are derived using Born-Oppenheimer vibronic product wave functions. Computational tractable expressions are derived for determining the total quadratic response contribution as a sum of contributions involving both electronic and vibrational linear and quadratic response functions. In the general frequency-dependent case this includes a new and more troublesome type of electronic linear response function. Pilot calculations for the FH, H2O, CH2O, and pyrrole molecules demonstrate the importance of vibrational contributions for accurate comparison to experiment and that the vibrational contributions in some cases can be very large. The calculation of transition properties between vibrational states is combined with sum-over-states expressions for analysis purposes. On the basis of this some simple analysis methods are suggested. Also, a preliminary study of the effect of finite lifetimes on quadratic response functions is presented.

  2. Vibrational spectra of α-glucose, β-glucose, and sucrose: anharmonic calculations and experiment.

    PubMed

    Brauer, Brina; Pincu, Madeleine; Buch, Victoria; Bar, Ilana; Simons, John P; Gerber, R Benny

    2011-06-16

    The anharmonic vibrational spectra of α-D-glucose, β-D-glucose, and sucrose are computed by the vibrational self-consistent field (VSCF) method, using potential energy surfaces from electronic structure theory, for the lowest energy conformers that correspond to the gas phase and to the crystalline phase, respectively. The results are compared with ultraviolet-infrared (UV-IR) spectra of phenyl β-D-glucopyranoside in a molecular beam, with literature results for sugars in matrices and with new experimental data for the crystalline state. Car-Parrinello dynamics simulations are also used to study temperature effects on the spectra of α-D-glucose and β-D-glucose and to predict their vibrational spectra at 50, 150, and 300 K. The effects of temperature on the spectral features are analyzed and compared with results of the VSCF calculations conducted at 0 K. The main results include: (i) new potential surfaces, constructed from Hartree-Fock, adjusted to fit harmonic frequencies from Møller-Plesset (MP2) calculations, that give very good agreement with gas phase, matrix, and solid state spectra; (ii) computed infrared spectra of the crystalline solid of α-glucose, which are substantially improved by including mimic groups that represent the effect of the solid environment on the sugar; and (iii) identification of a small number of combination-mode transitions, which are predicted to be strong enough for experimental observation. The results are used to assess the role of anharmonic effects in the spectra of the sugars in isolation and in the solid state and to discuss the spectroscopic accuracy of potentials from different electronic structure methods. PMID:21391638

  3. Spectral Analysis of Vibrational Harmonic Motion by use of a Continuous-Wave CO2 Doppler Lidar

    NASA Technical Reports Server (NTRS)

    Jarzembski, Maurice A.; Srivastava, Vandana

    1999-01-01

    Vibrational motion of a harmonic oscillator was investigated using a focused continuous wave CO2 Doppler lidar at 9.1 microns wavelength. A continuum of frequencies along with many discrete, equally spaced, resonant frequency modes was observed. The frequency modes are similar in structure to the oscillatory longitudinal modes of a laser cavity and arise because of interference of the natural resonant frequency of the oscillator with specific frequencies within the continuum. The spectra revealed departures from linear motion for vigorous vibrations of the oscillator. Each consecutive resonant frequency mode occurred for a movement of the oscillator much less than the wavelength of incident lidar radiation.

  4. Measured Vibration Effect of Numerous Sine Swept Harmonics on Random Shaker Applied to Effective Flight Model Representative Dummy

    NASA Astrophysics Data System (ADS)

    Polome, J.

    2012-07-01

    This paper presents the performance methodology and the achieved results of a vibration test campaign. The test performed by shaker simulates an unusual acoustic excitation containing a harmonic serial superimposed on random noise seen by electronic flight equipment. The paper is focused on main experimental aspects resulting of “helicopter simulation” capability applied on (representative) dummy electronic equipment. Wide internal instrumentation shows that the equipment is effectively answering to the stimuli by resonances excitation.

  5. HOTB: High precision parallel code for calculation of four-particle harmonic oscillator transformation brackets

    NASA Astrophysics Data System (ADS)

    Stepšys, A.; Mickevicius, S.; Germanas, D.; Kalinauskas, R. K.

    2014-11-01

    This new version of the HOTB program for calculation of the three and four particle harmonic oscillator transformation brackets provides some enhancements and corrections to the earlier version (Germanas et al., 2010) [1]. In particular, new version allows calculations of harmonic oscillator transformation brackets be performed in parallel using MPI parallel communication standard. Moreover, higher precision of intermediate calculations using GNU Quadruple Precision and arbitrary precision library FMLib [2] is done. A package of Fortran code is presented. Calculation time of large matrices can be significantly reduced using effective parallel code. Use of Higher Precision methods in intermediate calculations increases the stability of algorithms and extends the validity of used algorithms for larger input values. Catalogue identifier: AEFQ_v4_0 Program summary URL: http://cpc.cs.qub.ac.uk/summaries/AEFQ_v4_0.html Program obtainable from: CPC Program Library, Queen’s University of Belfast, N. Ireland Licensing provisions: GNU General Public License, version 3 Number of lines in programs, including test data, etc.: 1711 Number of bytes in distributed programs, including test data, etc.: 11667 Distribution format: tar.gz Program language used: FORTRAN 90 with MPI extensions for parallelism Computer: Any computer with FORTRAN 90 compiler Operating system: Windows, Linux, FreeBSD, True64 Unix Has the code been vectorized of parallelized?: Yes, parallelism using MPI extensions. Number of CPUs used: up to 999 RAM(per CPU core): Depending on allocated binomial and trinomial matrices and use of precision; at least 500 MB Catalogue identifier of previous version: AEFQ_v1_0 Journal reference of previous version: Comput. Phys. Comm. 181, Issue 2, (2010) 420-425 Does the new version supersede the previous version? Yes Nature of problem: Calculation of matrices of three-particle harmonic oscillator brackets (3HOB) and four-particle harmonic oscillator brackets (4HOB) in a more

  6. Molecular structure and vibrational study of diprotonated guanazolium using DFT calculations and FT-IR and FT-Raman spectroscopies

    NASA Astrophysics Data System (ADS)

    Guennoun, L.; Zaydoun, S.; El jastimi, J.; Marakchi, K.; Komiha, N.; Kabbaj, O. K.; El Hajji, A.; Guédira, F.

    2012-11-01

    The purpose of this manuscript is to discuss our investigations of diprotonated guanazolium chloride using vibrational spectroscopy and quantum chemical methods. The solid phase FT-IR and FT-Raman spectra were recorded in the regions 4000-400 cm-1 and 3600-50 cm-1 respectively, and the band assignments were supported by deuteration effects. Different sites of diprotonation have been theoretically examined at the B3LYP/6-31G∗ level. The results of energy calculations show that the diprotonation process occurs with the two pyridine-like nitrogen N2 and N4 of the triazole ring. The molecular structure, harmonic vibrational wave numbers, infrared intensities and Raman activities were calculated for this form by DFT/B3LYP methods, using a 6-31G∗ basis set. Both the optimized geometries and the theoretical and experimental spectra for diprotonated guanazolium under a stable form are compared with theoretical and experimental data of the neutral molecule reported in our previous work. This comparison reveals that the diprotonation occurs on the triazolic nucleus, and provide information about the hydrogen bonding in the crystal. The scaled vibrational wave number values of the diprotonated form are in close agreement with the experimental data. The normal vibrations were characterized in terms of potential energy distribution (PED) using the VEDA 4 program.

  7. Ab initio calculations of vibrational frequencies and infrared intensities for global warning potential of CFC substitutes. CF{sub 3}CH{sub 2}F (HFC-134a)

    SciTech Connect

    Papasavva, S.; Tai, S.; Esslinger, A.; Illinger, K.H.; Kenny, J.E.

    1995-03-16

    We have investigated the feasibility of using ab initio molecular orbital methods for predicting the global warming potential of the proposed chlorofluorocarbon (CFC) substitute CF{sub 3}CH{sub 2}F, HFC-134a. Various levels of theory and basis sets were used to optimize geometry and calculate harmonic vibrational frequencies and infrared intensities for the molecule using the GAUSSIAN 92 software package. In attempting to assess the quality of the computations, we found it necessary to reconsider the vibrational assignments available in the literature. On the basis of the current assignment, we find that for the highest level calculation, MP2/6-31G{sup **}, the calculated harmonic frequencies agree extremely well with the experimentally observed ones at frequencies below 800 cm{sup {minus}1}, with a systematic error toward higher calculated frequencies becoming apparent above 800 cm{sup {minus}1}. At lower levels of theory, the systematic error is apparent at all frequencies. The regularity of the deviation between calculated and observed frequencies makes ab initio calculations of vibrational frequencies much more useful than semiempirical calculations, which tend to show random deviations, as demonstrated with a PM3-UHF calculation in this work. The calculated absolute intensities are in good agreement with the limited experimental measurements previously reported. 23 refs., 3 figs., 5 tabs.

  8. The influence of higher harmonic flow forces on the response of a curved circular cylinder undergoing vortex-induced vibration

    NASA Astrophysics Data System (ADS)

    Seyed-Aghazadeh, Banafsheh; Budz, Collin; Modarres-Sadeghi, Yahya

    2015-09-01

    Vortex-induced vibration (VIV) of a curved circular cylinder (a quarter of a ring, with no extension added to either end) free to oscillate in the crossflow direction was studied experimentally. Both the concave and the convex orientations (with respect to the oncoming flow direction) were considered. As expected, the amplitude of oscillations in both configurations was decreased compared to a vertical cylinder with the same mass ratio. Flow visualizations showed that the vortices were shed in parallel to the curved cylinder, when the cylinder was free to oscillate. The sudden jump in the phase difference between the flow forces and the cylinder displacement observed in the VIV of vertical cylinders was not observed in the curved cylinders. Higher harmonic force components at frequencies twice and three times the frequency of oscillations were observed in flow forces acting on the vertical cylinder, as well as the curved cylinder. Asymmetry in the wake was responsible for the 2nd harmonic force component and the relative velocity of the structure with respect to the oncoming flow was responsible for the 3rd harmonic force component. The lock-in occurred over the same range of reduced velocities for the curved cylinder in the convex orientation as for a vertical cylinder, but it was extended to higher reduced velocities for a curved cylinder in the concave orientation. Higher harmonic force components were found to be responsible for the extended lock-in range in the concave orientation. Within this range, the higher harmonic forces were even larger than the first harmonic force and the structure was being excited mainly by these higher harmonic forces.

  9. Accurate calculation and assignment of highly excited vibrational levels of floppy triatomic molecules in a basis of adiabatic vibrational eigenstates

    NASA Astrophysics Data System (ADS)

    Bačić, Z.

    1991-09-01

    We show that the triatomic adiabatic vibrational eigenstates (AVES) provide a convenient basis for accurate discrete variable representation (DVR) calculation and automatic assignment of highly excited, large amplitude motion vibrational states of floppy triatomic molecules. The DVR-AVES states are eigenvectors of the diagonal (in the stretch states) blocks of the adiabatically rearranged triatomic DVR-ray eigenvector (DVR-REV) Hamiltonian [J. C. Light and Z. Bačić, J. Chem. Phys. 87, 4008 (1987)]. The transformation of the full triatomic vibrational Hamiltonian from the DVR-REV basis to the new DVR-AVES basis is simple, and does not involve calculation of any new matrix elements. No dynamical approximation is made in the energy level calculation by the DVR-AVES approach; its accuracy and efficiency are identical to those of the DVR-REV method. The DVR-AVES states, as the adiabatic approximation to the vibrational states of a triatomic molecule, are labeled by three vibrational quantum numbers. Consequently, accurate large amplitude motion vibrational levels obtained by diagonalizing the full vibrational Hamiltonian transformed to the DVR-AVES basis, can be assigned automatically by the code, with the three quantum numbers of the dominant DVR-AVES state associated with the largest (by modulus) eigenvector element in the DVR-AVES basis. The DVR-AVES approach is used to calculate accurate highly excited localized and delocalized vibrational levels of HCN/HNC and LiCN/LiNC. A significant fraction of localized states of both systems, below and above the isomerization barrier, is assigned automatically, without inspection of wave function plots or separate approximate calculations.

  10. Calculation of vibration mode and its experimental study in solid rocket motors

    NASA Astrophysics Data System (ADS)

    Zou, Junwei; Sun, Weishen; Xing, Chunjing

    1992-05-01

    A method for the calculation of vibration mode in rocket motors is presented, and a corresponding program is worked out. Values calculated with this program are consistent with theoretical and experimental results, indicating that the program is soundly based. A new type of vibration excitation apparatus-turbo vibration exciter is also introduced and used for determination of natural frequency of acoustic cavities and of acoustic damping coefficients of motor.

  11. Rapid calculations of time-harmonic nearfield pressures produced by rectangular pistons

    PubMed Central

    McGough, Robert J.

    2007-01-01

    A rapid method for calculating the nearfield pressure distribution generated by a rectangular piston is derived for time-harmonic excitations. This rapid approach improves the numerical performance relative to the impulse response with an equivalent integral expression that removes the numerical singularities caused by inverse trigonometric functions. The resulting errors are demonstrated in pressure field calculations using the time-harmonic impulse response solution for a rectangular source 5 wavelengths wide by 7.5 wavelengths high. Simulations using this source geometry show that the rapid method eliminates the singularities introduced by the impulse response. The results of pressure field computations are then evaluated in terms of relative errors and computational speeds. The results show that, when the same number of Gauss abscissas are applied to both approaches for time-harmonic pressure field calculations, the rapid method is consistently faster than the impulse response, and the rapid method consistently produces smaller maximum errors than the impulse response. For specified maximum error values of 10% and 1%, the rapid method is 2.6 times faster than the impulse response for pressure field calculations performed on a 61 by 101 point grid. The rapid approach achieves even greater reductions in the computation time for smaller errors and larger grids. PMID:15139602

  12. Rapid calculations of time-harmonic nearfield pressures produced by rectangular pistons.

    PubMed

    McGough, Robert J

    2004-05-01

    A rapid method for calculating the nearfield pressure distribution generated by a rectangular piston is derived for time-harmonic excitations. This rapid approach improves the numerical performance relative to the impulse response with an equivalent integral expression that removes the numerical singularities caused by inverse trigonometric functions. The resulting errors are demonstrated in pressure field calculations using the time-harmonic impulse response solution for a rectangular source 5 wavelengths wide by 7.5 wavelengths high. Simulations using this source geometry show that the rapid method eliminates the singularities introduced by the impulse response. The results of pressure field computations are then evaluated in terms of relative errors and computational speeds. The results show that, when the same number of Gauss abscissas are applied to both approaches for time-harmonic pressure field calculations, the rapid method is consistently faster than the impulse response, and the rapid method consistently produces smaller maximum errors than the impulse response. For specified maximum error values of 10% and 1%, the rapid method is 2.6 times faster than the impulse response for pressure field calculations performed on a 61 by 101 point grid. The rapid approach achieves even greater reductions in the computation time for smaller errors and larger grids. PMID:15139602

  13. Time-independent eigenstate-free calculation of vibronic spectra beyond the harmonic approximation

    NASA Astrophysics Data System (ADS)

    Petrenko, Taras; Rauhut, Guntram

    2015-12-01

    The calculation of vibronic spectra and resonance Raman intensities can be performed on the basis of the Raman wavefunction (RWF) formalism. In general, the well-known sum-over-states (SOS) and time-dependent methods can be applied for calculating the RWF. We present an alternative route in which the RWF is determined pointwise in a spectral range on the basis of the inhomogeneous Schrödinger equation using an iterative subspace method, in which explicit state-by-state calculations of vibrational eigenstates are bypassed. We study this approach within the framework of vibrational configuration interaction theory in conjunction with high-level electronic structure calculations for the multidimensional Born-Oppenheimer potential energy surface. The method benefits from an implicit account of interference effects between vibrational states, so that its computational cost correlates with the required resolution in the spectra. The accuracy and efficiency of the method with respect to comparable SOS calculations are tested for the simulation of the photoelectron spectra of ClO2, HS2 - , ZnOH-, and Zn(H2O)+.

  14. Calculation of optical second-harmonic susceptibilities and optical activity for crystals

    SciTech Connect

    Levine, Z.H.

    1994-12-31

    A new generation of nearly first-principles calculations predicts both the linear and second-harmonic susceptibilities for a variety of insulating crystals, including GaAs, GaP, AlAs, AlP, Se, {alpha}-quartz, and c-urea. The results are typically in agreement with experimental measurements. The calculations have been extended to optical activity, with somewhat less success to date. The theory, based on a simple self-energy correction to the local density approximation, and results are reviewed herein.

  15. Analysis of Harmonic Vibration of Cable-Stayed Footbridge under the Influence of Changes of the Cables Tension

    NASA Astrophysics Data System (ADS)

    Pakos, Wojciech

    2015-09-01

    The paper presents numerical analysis of harmonically excited vibration of a cable-stayed footbridge caused by a load function simulating crouching (squats) while changing the static tension in chosen cables. The intentional synchronized motion (e.g., squats) of a single person or group of persons on the footbridge with a frequency close to the natural frequency of the structure may lead to the resonant vibrations with large amplitudes. The appropriate tension changes in some cables cause detuning of resonance on account of stiffness changes of structures and hence detuning in the natural frequency that is close to the excitation frequency. The research was carried out on a 3D computer model of a real structure - a cable-stayed steel footbridge in Leśnica, a quarter of Wrocław, Poland, with the help of standard computer software based on FEM COSMOS/M System.

  16. Rotational and vibrational spectra of ethynol from quantum-mechanical calculations

    NASA Technical Reports Server (NTRS)

    Defrees, D. J.; Mclean, A. D.

    1982-01-01

    It is noted that ethynol (HCCOH), despite the theoretical prediction of its stability to tautomerization to ketene, has thus far not been observed. It is shown here that the identification of this unknown molecule, both in space and in the laboratory, can be aided by an ab initio calculation of spectroscopic parameters. At the HF/3-21G level, harmonic vibrational frequencies are computed by way of analytic second differentiation of the Hartee-Fock (HF) energy with respect to the nuclear coordinates. After applying an empirical scale factor, the resultant frequencies are (per cm) 473, 517, 773, 841, 1003, 1217, 2206, 3285, and 3418. The computed dipole moment at the CISD/DZ+P level is 1.79 D. At the CISD+Q/DZ+P level, the molecule's rotational constants are determined. After scaling by empirical correction factors, they are used in deriving the 4(04) - 3(03) frequency of 76.81 + or - 0.3 GHz with a triplet splitting of 0.30 + or - 0.01 GHz. The triplet splitting involves 4(14) - 3(13) and 4(13) - 3(12) relative to the 4(04) - 3(03) transition as the central line.

  17. Revised calculation of four-particle harmonic-oscillator transformation brackets matrix

    NASA Astrophysics Data System (ADS)

    Mickevičius, S.; Germanas, D.; Kalinauskas, R. K.

    2013-02-01

    In this article we present a new, considerably enhanced and more rapid method for calculation of the matrix of four-particle harmonic-oscillator transformation brackets (4HOB). The new method is an improved version of 4HOB matrix calculations which facilitates the matrix calculation by finding the eigenvectors of the 4HOB matrix explicitly. Using this idea the new Fortran code for fast and 4HOB matrix calculation is presented. The calculation time decreases more than a few hundred times for large matrices. As many problems of nuclear and hadron physics structure are modeled on the harmonic oscillator (HO) basis our presented method can be useful for large-scale nuclear structure and many-particle identical fermion systems calculations. Program summaryTitle of program: HOTB_M Catalogue identifier: AEFQ_v3_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEFQ_v3_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GNU General Public License version 3 No. of lines in distributed program, including test data, etc.: 2149 No. of bytes in distributed program, including test data, etc.: 17576 Distribution format: tar.gz Programming language: Fortran 90. Computer: Any computer with Fortran 90 compiler. Operating system: Windows, Linux, FreeBSD, True64 Unix. RAM: Up to a few Gigabytes (see Tables 1 and 2 included in the distribution package) Classification: 17.16, 17.17. Catalogue identifier of previous version: AEFQ_v2_0 Journal reference of previous version: Comput. Phys. Comm. 182(2011)1377 Does the new version supersede the previous version?: Yes Nature of problem: Calculation of the matrix of the 4HOB in a more effective way, which allows us to calculate the matrix of the brackets up to a few hundred times more rapidly than in a previous version. Solution method: The method is based on compact expressions of 4HOB, presented in [1] and its simplifications presented in this paper. Reasons for new version

  18. A structural and vibrational study on the first condensed borosulfate K5[B(SO4)4] by using the FTIR-Raman spectra and DFT calculations

    NASA Astrophysics Data System (ADS)

    Höppe, Henning Alfred; Kazmierczak, Karolina; Romano, Elida; Brandán, Silvia Antonia

    2013-04-01

    The first borosulfate, K5[B(SO4)4] (recently synthesized by Henning A. Höppe, Karolina Kazmierczak, Michael Daub, Katharina Förg, Franziska Fuchs, Harald Hillebrecht, 2012) was characterized by infrared and Raman spectroscopies. Density functional theory (DFT) calculations were used to study the structure and vibrational properties of the compound. Employing the B3P86 and B3LYP levels of theory, the molecular structures of the compound were theoretically determined in gas phase and the harmonic vibrational frequencies were evaluated at the same levels. The calculated harmonic vibrational frequencies for the borosulfate compound are consistent with the experimental IR and Raman spectra. These calculations gave us a precise knowledge of the normal modes of vibration taking into account the type of coordination adopted by sulfate groups of this compound as ligands with C3v and C2v symmetries. A complete assignment of all the observed bands in the IR and Raman spectra for K5[B(SO4)4] was performed. Here, the infrared and Raman spectra of K5[B(SO4)4] were interpreted, discussed and completely assigned. The nature of the Ksbnd O, Ksbnd S, Bsbnd O, and Ssbnd O bonds and the topological properties of the compound were investigated and analyzed by means of Natural Bond Order (NBO) and Bader's Atoms in Molecules theory (AIM), respectively.

  19. Theoretical Characterization of Visual Signatures and Calculation of Approximate Global Harmonic Frequency Scaling Factors

    NASA Astrophysics Data System (ADS)

    Kashinski, D. O.; Nelson, R. G.; Chase, G. M.; di Nallo, O. E.; Byrd, E. F. C.

    2016-05-01

    We are investigating the accuracy of theoretical models used to predict the visible, ultraviolet, and infrared spectra, as well as other properties, of product materials ejected from the muzzle of currently fielded systems. Recent advances in solid propellants has made the management of muzzle signature (flash) a principle issue in weapons development across the calibers. A priori prediction of the electromagnetic spectra of formulations will allow researchers to tailor blends that yield desired signatures and determine spectrographic detection ranges. Quantum chemistry methods at various levels of sophistication have been employed to optimize molecular geometries, compute unscaled harmonic frequencies, and determine the optical spectra of specific gas-phase species. Electronic excitations are being computed using Time Dependent Density Functional Theory (TD-DFT). Calculation of approximate global harmonic frequency scaling factors for specific DFT functionals is also in progress. A full statistical analysis and reliability assessment of computational results is currently underway. Work supported by the ARL, DoD-HPCMP, and USMA.

  20. On methods for application of harmonic control. [helicopter vibration reduction by blade pitch variation

    NASA Technical Reports Server (NTRS)

    Wood, E. R.; Powers, R. W.; Hammond, C. E.

    1978-01-01

    The paper presents data which confirm the effectiveness of higher harmonic blade pitch control in substantially reducing helicopter rotor vibratory hub loads. The data are the result of recent tests on a 2.7-m model conducted in the Langley Research Center's transonic dynamics wind tunnel. Several predictive analyses developed in support of the NASA program are shown capable of accurately predicting both amplitude and phase of the higher harmonic control input required to nullify a single 4/rev force or moment input. The use of multiple blade feathering inputs in the design of a flightworthy higher harmonic control system is discussed.

  1. Vanillin and isovanillin: Comparative vibrational spectroscopic studies, conformational stability and NLO properties by density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Balachandran, V.; Parimala, K.

    This study is a comparative analysis of FT-IR and FT-Raman spectra of vanillin (3-methoxy-4-hydroxybenzaldehyde) and isovanillin (3-hydroxy-4-methoxybenzaldehyde). The molecular structure, vibrational wavenumbers, infrared intensities, Raman scattering activities were calculated for both molecules using the B3LYP density functional theory (DFT) with the standard 6-311++G∗∗ basis set. The computed values of frequencies are scaled using multiple scaling factors to yield good coherence with the observed values. The calculated harmonic vibrational frequencies are compared with experimental FT-IR and FT-Raman spectra. The geometrical parameters and total energies of vanillin and isovanillin were obtained for all the eight conformers (a-h) from DFT/B3LYP method with 6-311++G∗∗ basis set. The computational results identified the most stable conformer of vanillin and isovanillin as in the "a" form. Non-linear properties such as electric dipole moment (μ), polarizability (α), and hyperpolarizability (β) values of the investigated molecules have been computed using B3LYP quantum chemical calculation. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecules.

  2. Efficient calculation of potential energy surfaces for the generation of vibrational wave functions

    NASA Astrophysics Data System (ADS)

    Rauhut, Guntram

    2004-11-01

    An automatic procedure for the generation of potential energy surfaces based on high level ab initio calculations is described. It allows us to determine the vibrational wave functions for molecules of up to ten atoms. Speedups in computer time of about four orders of magnitude in comparison to standard implementations were achieved. Effects due to introduced approximations—within the computation of the potential—on fundamental modes obtained from vibrational self-consistent field and vibrational configuration interaction calculations are discussed. Benchmark calculations are provided for formaldehyde and 1,2,5-oxadiazole (furazan).

  3. Efficient calculation of potential energy surfaces for the generation of vibrational wave functions.

    PubMed

    Rauhut, Guntram

    2004-11-15

    An automatic procedure for the generation of potential energy surfaces based on high level ab initio calculations is described. It allows us to determine the vibrational wave functions for molecules of up to ten atoms. Speedups in computer time of about four orders of magnitude in comparison to standard implementations were achieved. Effects due to introduced approximations--within the computation of the potential--on fundamental modes obtained from vibrational self-consistent field and vibrational configuration interaction calculations are discussed. Benchmark calculations are provided for formaldehyde and 1,2,5-oxadiazole (furazan). PMID:15538851

  4. Analytical Harmonic Vibrational Frequencies for the Green Fluorescent Protein Computed with ONIOM: Chromophore Mode Character and Its Response to Environment.

    PubMed

    Thompson, Lee M; Lasoroski, Aurélie; Champion, Paul M; Sage, J Timothy; Frisch, Michael J; van Thor, Jasper J; Bearpark, Michael J

    2014-02-11

    A systematic comparison of different environmental effects on the vibrational modes of the 4-hydroxybenzylidene-2,3-dimethylimidazolinone (HBDI) chromophore using the ONIOM method allows us to model how the molecule's spectroscopic transitions are modified in the Green Fluorescent Protein (GFP). ONIOM(QM:MM) reduces the expense of normal mode calculations when computing the majority of second derivatives only at the MM level. New developments described here for the efficient solution of the CPHF equations, including contributions from electrostatic interactions with environment charges, mean that QM model systems of ∼100 atoms can be embedded within a much larger MM environment of ∼5000 atoms. The resulting vibrational normal modes, their associated frequencies, and dipole derivative vectors have been used to interpret experimental difference spectra (GFPI2-GFPA), chromophore vibrational Stark shifts, and changes in the difference between electronic and vibrational transition dipoles (mode angles) in the protein environment. PMID:26580050

  5. A comparison of calculations and measurements of the field harmonics as a function of current in the SSC dipole magnets

    SciTech Connect

    Gupta, R.C.; Cottingham, J.G.; Kahn, S.A.; Morgan, G.H.; Wanderer, P.

    1991-01-01

    A large number of short and long superconducting dipole magnets for the Superconducting Super Collider (SSC) have been constructed and measured for their magnetic field properties at Brookhaven National Laboratory (BNL). In this paper we compare the calculations and measurements for the variation of field harmonics as a function of current in 40 mm aperture and 50 mm aperture dipole magnets. The primary purpose of this paper is to examine the iron saturation effects on the field harmonics. The field harmonics also change due to the persistent current in the superconducting wires and due to the deformation of the coil shape because of Lorentz forces. We discuss the variation in the sextupole harmonics (b{sub 2}) with current and explain the differences between the calculations and measurements. We also discuss the skew quadrupole harmonic at high field in the long dipole magnets. 3 refs., 3 figs., 1 tab.

  6. Accurate calculation of vibrational frequencies using explicitly correlated coupled-cluster theory.

    PubMed

    Rauhut, Guntram; Knizia, Gerald; Werner, Hans-Joachim

    2009-02-01

    The recently proposed explicitly correlated CCSD(T)-F12x (x = a,b) approximations [T. B. Adler, G. Knizia, and H.-J. Werner, J. Chem. Phys. 127, 221106 (2007)] are applied to compute equilibrium structures and harmonic as well as anharmonic vibrational frequencies for H(2)O, HCN, CO(2), CH(2)O, H(2)O(2), C(2)H(2), CH(2)NH, C(2)H(2)O, and the trans-isomer of 1,2-C(2)H(2)F(2). Using aug-cc-pVTZ basis sets, the CCSD(T)-F12a equilibrium geometries and harmonic vibrational frequencies are in very close agreement with CCSD(T)/aug-cc-pV5Z values. The anharmonic frequencies are evaluated using vibrational self-consistent field and vibrational configuration interaction methods based on automatically generated potential energy surfaces. The mean absolute deviation of the CCSD(T)-F12a/aug-cc-pVTZ anharmonic frequencies from experimental values amounts to only 4.0 cm(-1). PMID:19206956

  7. Application of a spherical harmonics expansion approach for calculating ligand density distributions around proteins.

    PubMed

    Parimal, Siddharth; Cramer, Steven M; Garde, Shekhar

    2014-11-20

    Protein-ligand interactions are central to many biological applications, including molecular recognition, protein formulations, and bioseparations. Complex, multisite ligands can have affinities for different locations on a protein's surface, depending on the chemical and topographical complementarity. We employ an approach based on the spherical harmonic expansion to calculate spatially resolved three-dimensional atomic density profiles of water and ligands in the vicinity of macromolecules. To illustrate the approach, we first study the hydration of model C180 buckyball solutes, with nonspherical patterns of hydrophobicity/-philicity on their surface. We extend the approach to calculate density profiles of increasingly complex ligands and their constituent groups around a protein (ubiquitin) in aqueous solution. Analysis of density profiles provides information about the binding face of the protein and the preferred orientations of ligands on the binding surface. Our results highlight that the spherical harmonic expansion based approach is easy to implement and efficient for calculation and visualization of three-dimensional density profiles around spherically nonsymmetric and topographically and chemically complex solutes. PMID:25198149

  8. Loss Calculation of Induction Motors Considering Harmonic Electromagnetic Fields in Stator and Rotor

    NASA Astrophysics Data System (ADS)

    Yamazaki, Katsumi

    A method of loss calculation for induction motors is proposed. The combined 3D-2D time stepping finite element analysis is carried out to obtain the copper loss and the time-variation of the magnetic field in the motor. The iron loss is calculated approximately considering the time-variation of the magnetic field direction and the minor hysteresis loops caused by the time-harmonic fields using practical computer resources. The proposed method is applied to 4 types of induction motors, which are the solid rotor induction motors with/without slot and the cage induction motors with/without skew. The measured and the calculated total losses and the iron losses agree well in all cases. The differences of the loss distributions of each motor are also compared and investigated.

  9. Harmonic phonon theory for calculating thermal conductivity spectrum from first-principles dispersion relations

    NASA Astrophysics Data System (ADS)

    Shiga, Takuma; Aketo, Daisuke; Feng, Lei; Shiomi, Junichiro

    2016-05-01

    In recent years, nanostructuring of dielectric and semiconducting crystals has enhanced controllability of their thermal conductivity. To carry out computational materials search for nanostructured materials with desirable thermal conductivity, a key property is the thermal conductivity spectrum of the original single crystal, which determines the appropriate length scale of nanostructures and mutual adaptability of different kinds of nanostructures. Although the first-principles phonon transport calculations have become accessible, the anharmonic lattice dynamics calculations are still expensive to scan many materials. To this end, we have developed an empirical model that describes the thermal conductivity spectrum in terms only of harmonic phonon properties and bulk thermal conductivity. The model was tested for several crystals with different structures and thermal conductivities, and was confirmed to reproduce the overall profiles of thermal conductivity spectra and their accumulation functions obtained by the first-principles anharmonic calculations.

  10. Infrared and Raman spectra, conformational analysis, ab initio calculations and vibrational assignment of 2-chloroethylsilyl chloride

    NASA Astrophysics Data System (ADS)

    Pan, Chunhua; Guirgis, Gamil A.; Durig, James R.

    2005-05-01

    The infrared (3100-40 cm -1) spectra of gaseous and solid and Raman (3200-20 cm -1) spectra of liquid 2-chloroethylsilyl chloride, ClCH 2CH 2SiH 2Cl, have been recorded. There are five possible stable conformers, Gg, Tg, Gt, Tt and Gg' for this molecule where the capital letter G ( gauche) or T ( trans) refer to rotation around the C-C bond and the lower case letters to rotation around the Si-C bond. Most ab initio calculations at the MP2(full) level predicted the order of the stability as Tg>Gg>Gt>Tt>Gg' whereas all density function theory calculations with the B3LYP method predicted the stability as Tg>Tt>Gg>Gt>Gg'. The four more stable conformers have been identified in the fluid phases with the Tg rotamer the only form remaining in the solid. Variable temperature (-105 to -150 °C) studies of the infrared spectra of the samples dissolved in liquid krypton have been recorded and the enthalpy differences determined to be: 50±20 (0.59±0.24 kJ/mol), 172±17 (2.06±0.20 kJ/mol) and 290±40 cm -1 (3.45±0.48 kJ/mol) for the Tg/Gg, Tg/Gt and Tg/Tt conformer pairs with the Tg conformer the most stable form. It is estimated that there is 42±2% of the Tg form, 33±1% of the Gg form, 20±2% of the Gt form, and 5±1% of the Tt form present at ambient temperature. A relatively complete vibrational assignment is proposed for the Tg conformer and many of the fundamentals have been identified for the other three (Gg, Gt and Tt) conformers based on the ab initio MP2(full)/6-31G(d) predicted frequencies, the relative infrared and Raman spectral intensities, and infrared band contours which are supported by normal coordinate calculations. Since the predicted energies between Tg and Gg' conformers from all calculations are very large, it is not surprising that no evidence in either the infrared or Raman spectra could be found for the Gg' conformer. The geometrical parameters, harmonic force constants, vibrational frequencies, infrared intensities, Raman activities

  11. Elucidating low-frequency vibrational dynamics in calcite and water with time-resolved third-harmonic generation spectroscopy.

    PubMed

    Wang, Liang; Liu, Weimin; Fang, Chong

    2015-07-14

    Low-frequency vibrations are foundational for material properties including thermal conductivity and chemical reactivity. To resolve the intrinsic molecular conformational dynamics in condensed phase, we implement time-resolved third-harmonic generation (TRTHG) spectroscopy to unravel collective skeletal motions in calcite, water, and aqueous salt solution in situ. The lifetime of three Raman-active modes in polycrystalline calcite at 155, 282 and 703 cm(-1) is found to be ca. 1.6 ps, 1.3 ps and 250 fs, respectively. The lifetime difference is due to crystallographic defects and anharmonic effects. By incorporating a home-built wire-guided liquid jet, we apply TRTHG to investigate pure water and ZnCl2 aqueous solution, revealing ultrafast dynamics of water intermolecular stretching and librational bands below 500 cm(-1) and a characteristic 280 cm(-1) vibrational mode in the ZnCl4(H2O)2(2-) complex. TRTHG proves to be a compact and versatile technique that directly uses the 800 nm fundamental laser pulse output to capture ultrafast low-frequency vibrational motion snapshots in condensed-phase materials including the omnipresent water, which provides the important time dimension to spectral characterization of molecular structure-function relationships. PMID:26062639

  12. Revised vibrational band assignments for the experimental IR and Raman spectra of 2,3,4-trifluorobenzonitrile based on ab initio, DFT and normal coordinate calculations

    NASA Astrophysics Data System (ADS)

    Hiremath, C. S.; Kalkoti, G. B.; Aralakkanavar, M. K.

    2009-09-01

    In the present study, a systematic vibrational spectroscopic investigation for the experimental IR and Raman spectra of 2,3,4-trifluorobenzonitrile (TFB), aided by electronic structure calculations has been carried out. The electronic structure calculations - ab initio (RHF) and hybrid density functional methods (B3LYP) - have been performed with 6-31G* basis set. Molecular equilibrium geometries, electronic energies, IR intensities, harmonic vibrational frequencies, depolarization ratios and Raman activities have been computed. The results of the calculations have been used to simulate IR and Raman spectra for TFB that showed excellent agreement with the observed spectra. Potential energy distribution (PED) and normal mode analysis have also been performed. The assignments proposed based on the experimental IR and Raman spectra have been reviewed. A complete assignment of the observed spectra has been proposed.

  13. DFT calculation and vibrational spectroscopic studies of 2-(tert-butoxycarbonyl (Boc) -amino)-5-bromopyridine

    NASA Astrophysics Data System (ADS)

    Premkumar, S.; Jawahar, A.; Mathavan, T.; Kumara Dhas, M.; Sathe, V. G.; Milton Franklin Benial, A.

    2014-08-01

    The molecular structure of 2-(tert-butoxycarbonyl (Boc) -amino)-5-bromopyridine (BABP) was optimized by the DFT/B3LYP method with 6-311G (d,p), 6-311++G (d,p) and cc-pVTZ basis sets using the Gaussian 09 program. The most stable optimized structure of the molecule was predicted by the DFT/B3LYP method with cc-pVTZ basis set. The vibrational frequencies, Mulliken atomic charge distribution, frontier molecular orbitals and thermodynamical parameters were calculated. These calculations were done at the ground state energy level of BABP without applying any constraint on the potential energy surface. The vibrational spectra were experimentally recorded using Fourier Transform-Infrared (FT-IR) and micro-Raman spectrometer. The computed vibrational frequencies were scaled by scale factors to yield a good agreement with observed experimental vibrational frequencies. The complete theoretically calculated and experimentally observed vibrational frequencies were assigned on the basis of Potential Energy Distribution (PED) calculation using the VEDA 4.0 program. The vibrational modes assignments were performed by using the animation option of GaussView 05 graphical interface for Gaussian program. The Mulliken atomic charge distribution was calculated for BABP molecule. The molecular reactivity and stability of BABP were also studied by frontier molecular orbitals (FMOs) analysis.

  14. Calculation of flight vibration levels of the AH-1G helicopter and correlation with existing flight vibration measurements

    NASA Technical Reports Server (NTRS)

    Sopher, R.; Twomey, W. J.

    1990-01-01

    NASA-Langley is sponsoring a rotorcraft structural dynamics program with the objective to establish in the U.S. a superior capability to utilize finite element analysis models for calculations to support industrial design of helicopter airframe structures. In the initial phase of the program, teams from the major U.S. manufacturers of helicopter airframes will apply extant finite element analysis methods to calculate loads and vibrations of helicopter airframes, and perform correlations between analysis and measurements. The aforementioned rotorcraft structural dynamics program was given the acronym DAMVIBS (Design Analysis Method for Vibrations). Sikorsky's RDYNE Rotorcraft Dynamics Analysis used for the correlation study, the specifics of the application of RDYNE to the AH-1G, and comparisons of the predictions of the method with flight data for loads and vibrations on the AH-1G are described. RDYNE was able to predict trends of variations of loads and vibrations with airspeed, but in some instances magnitudes differed from measured results by factors of two or three to one. Sensitivities were studied of predictions to rotor inflow modeling, effects of torsional modes, number of blade bending modes, fuselage structural damping, and hub modal content.

  15. Conformational studies of 3-aminomethylene-2,4-pentanedione using vibrational and NMR spectra, and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Gróf, M.; Gatial, A.; Milata, V.; Prónayová, N.; Sümmchen, L.; Salzer, R.

    2007-10-01

    The IR, Raman and NMR spectra of 3-aminomethylene-2,4-pentanedione (AMP) H 2N sbnd CH dbnd C(COCH 3) 2 were measured. According to the NMR spectra in chloroform and more polar DMSO at room temperature, the sample exists as single entity. On the other hand vibrational spectra revealed that in less polar solutions AMP exists as two conformers with EZ or ZZ orientation of acetyl groups whereas in more polar solvent only one EZ conformer is observed. Such interpretation was confirmed also by the temperature-dependent measurements of IR spectra in chloroform. The observed IR and Raman bands were compared with harmonic vibrational frequencies, calculated using ab initio MP2 and B3LYP density functional methods in 6-31G ∗∗ basis set, and assigned on the basis of potential energy distribution. In addition, the geometries and relative energies of possible conformers of AMP were also evaluated at the same levels of theory and compared with the data from X-ray analysis which revealed that AMP exists in solid state as EZ conformer. The influence of environment polarity on this conformational equilibrium is discussed with respect to the SCRF solvent effect calculations using PCM, IPCM and ONSAGER models.

  16. An ab initio study of the harmonic and anharmonic force field and fundamental vibrational frequencies of performic acid

    NASA Astrophysics Data System (ADS)

    Bock, Charles W.; Trachtman, Mendel; George, Philip

    1980-11-01

    The harmonic and anharmonic force fields and fundamental vibrational frequencies of cis-cis and cis-trans performic acid are studied ab initio in the 4-31G basis set using geometries fully optimized at this level. The frequencies predicted for the cis-cis conformer are compared with those derived from spectroscopic observations on the most stable form. An extensive comparison is made between the changes in diagonal and off-diagonal quadratic and cubic force constants, and diagonal stretching quartic constants, in going from the chain to the ring structure in performic and formic acid, and features which these changes have in common are seen to support the view that there is a hydrogen bonding type of interaction in trans-formic acid despite its unfavorable geometry.

  17. Vibration-rotation variational calculations - Precise results on HCN up to 25,000/cm

    NASA Astrophysics Data System (ADS)

    Carter, Stuart; Mills, Ian M.; Handy, Nicholas C.

    1993-09-01

    Variation calculations of the vibration-rotation energy levels of many isotopomers of HCN are reported, for J = 0, 1, and 2, extending up to approximately 8 quanta of each of the stretching vibrations and 14 quanta of the bending mode. The force field, which is represented as a polynomial expansion in Morse coordinates for the bond stretches and even powers of the angle bend, has been refined by least squares to fit simultaneously all observed data on the Sigma and Pi state vibrational energies, and the Sigma state rotational constants, for both HCN and DCN. The observed vibrational energies are fitted to roughly +/- 0.5/cm, and the rotational constants to roughly +/- 0.0001/cm. The force field has been used to predict the vibration rotation spectra of many isotopomers of HCN up to 25,000/cm.

  18. 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.

  19. Hybrid variational-perturbation method for calculating ro-vibrational energy levels of polyatomic molecules

    NASA Astrophysics Data System (ADS)

    Pavlyuchko, A. I.; Yurchenko, S. N.; Tennyson, Jonathan

    2015-07-01

    A procedure for calculation of rotational-vibrational states of medium-sized molecules is presented. It combines the advantages of variational calculations and perturbation theory. The vibrational problem is solved by diagonalising a Hamiltonian matrix, which is partitioned into two sub-blocks. The first, smaller sub-block includes matrix elements with the largest contribution to the energy levels targeted in the calculations. The second, larger sub-block comprises those basis states which have little effect on these energy levels. Numerical perturbation theory, implemented as a Jacobi rotation, is used to compute the contributions from the matrix elements of the second sub-block. Only the first sub-block needs to be stored in memory and diagonalised. Calculations of the vibrational-rotational energy levels also employ a partitioning of the Hamiltonian matrix into sub-blocks, each of which corresponds either to a single vibrational state or a set of resonating vibrational states, with all associated rotational levels. Physically, this partitioning is efficient when the Coriolis coupling between different vibrational states is small. Numerical perturbation theory is used to include the cross-contributions from different vibrational states. Separate individual sub-blocks are then diagonalised, replacing the diagonalisation of a large Hamiltonian matrix with a number of small matrix diagonalisations. Numerical examples show that the proposed hybrid variational-perturbation method greatly speeds up the variational procedure without significant loss of precision for both vibrational-rotational energy levels and transition intensities. The hybrid scheme can be used for accurate nuclear motion calculations on molecules with up to 15 atoms on currently available computers.

  20. Tuning natural modes of vibration by prestress in the design of a harmonic gong.

    PubMed

    McLachlan, Neil; Adams, Ryan; Burvill, Colin

    2012-01-01

    Prestresses are purposefully added to an object to improve its performance, such as tuning a guitar string by adding tension. This paper reports how the normal modes of a sheet metal component can be tuned through the prestresses generated by cold-forging small dimples. Finite element analysis showed that the frequencies of specific mode shapes were differentially affected by the location of residual stress fields due to dimple formation in relation to modal stress fields. The frequencies of overtones were most sensitive to the depth of the dimples located near the maxima of modal stresses. Using this approach a series of musical gongs were designed with up to the first five overtones tuned to within 5% of the harmonic series. The balance of harmonic and inharmonic overtones in these gongs that are well resolved by the human cochlea may constitute a set of recognizable musical timbres with sufficient harmonicity to produce an unambiguous pitch for most listeners. Since many other mechanical properties of sheet metal components are affected by residual stresses this manufacturing technique may have broader application in design engineering. PMID:22280715

  1. Development and applications of algorithms for calculating the transonic flow about harmonically oscillating wings

    NASA Technical Reports Server (NTRS)

    Ehlers, F. E.; Weatherill, W. H.; Yip, E. L.

    1984-01-01

    A finite difference method to solve the unsteady transonic flow about harmonically oscillating wings was investigated. The procedure is based on separating the velocity potential into steady and unsteady parts and linearizing the resulting unsteady differential equation for small disturbances. The differential equation for the unsteady velocity potential is linear with spatially varying coefficients and with the time variable eliminated by assuming harmonic motion. An alternating direction implicit procedure was investigated, and a pilot program was developed for both two and three dimensional wings. This program provides a relatively efficient relaxation solution without previously encountered solution instability problems. Pressure distributions for two rectangular wings are calculated. Conjugate gradient techniques were developed for the asymmetric, indefinite problem. The conjugate gradient procedure is evaluated for applications to the unsteady transonic problem. Different equations for the alternating direction procedure are derived using a coordinate transformation for swept and tapered wing planforms. Pressure distributions for swept, untaped wings of vanishing thickness are correlated with linear results for sweep angles up to 45 degrees.

  2. Vibrationally averaged post Born-Oppenheimer isotopic dipole moment calculations approaching spectroscopic accuracy

    NASA Astrophysics Data System (ADS)

    Arapiraca, A. F. C.; Jonsson, Dan; Mohallem, J. R.

    2011-12-01

    We report an upgrade of the Dalton code to include post Born-Oppenheimer nuclear mass corrections in the calculations of (ro-)vibrational averages of molecular properties. These corrections are necessary to achieve an accuracy of 10-4 debye in the calculations of isotopic dipole moments. Calculations on the self-consistent field level present this accuracy, while numerical instabilities compromise correlated calculations. Applications to HD, ethane, and ethylene isotopologues are implemented, all of them approaching the experimental values.

  3. Vibrationally averaged post Born-Oppenheimer isotopic dipole moment calculations approaching spectroscopic accuracy.

    PubMed

    Arapiraca, A F C; Jonsson, Dan; Mohallem, J R

    2011-12-28

    We report an upgrade of the Dalton code to include post Born-Oppenheimer nuclear mass corrections in the calculations of (ro-)vibrational averages of molecular properties. These corrections are necessary to achieve an accuracy of 10(-4) debye in the calculations of isotopic dipole moments. Calculations on the self-consistent field level present this accuracy, while numerical instabilities compromise correlated calculations. Applications to HD, ethane, and ethylene isotopologues are implemented, all of them approaching the experimental values. PMID:22225162

  4. Towards inclusion of excited vibrational states in ultracold molecule-molecule quantum scattering calculations

    NASA Astrophysics Data System (ADS)

    Ticknor, Christopher; Kendrick, Brian

    2016-05-01

    We report progress towards including excited vibrational states in quantum scattering calculations of NaK-NaK at ultracold temperatures. We systematically use all pair potentials to build a complete 4 body potential energy surface. We study this 4-body potential and the asymptotic ro-vibrational 2-body basis. This allows for a more complete interaction as two molecules approach each other. We study where and how vibrationally excited states influence the asymptotic 2-body ro-vibrational scattering potentials. This work is an intermediate step in performing the complete scattering calculations as we develop tools to bring together the long range, ultracold 2-body scattering problem and the short range 4-body quantum chemistry problem.

  5. Reactive scattering calculations for D + H2 in vibrationally excited states at ultralow temperature

    NASA Astrophysics Data System (ADS)

    Simbotin, Ion; Coté, Robin

    2006-05-01

    We calculate total cross sections for the D + H2(v,j ) collision, and investigate their dependence on the vibrational quantum number v of the initial state of H2. The cross sections increase quasi-exponentially with the excitation energy of the initial vibrational state. This is similar to the exponential dependence observed in the vibrational predissociation of van der Waals complexes. We attempt to explain this simple relationship in terms of the short range details of the single channel atom--molecule wavefunctions and the couplings between the initial and final channels.

  6. Calculation of vibrational spectra for dioxouranium monochloride monomer and dimers

    NASA Astrophysics Data System (ADS)

    Umreiko, D. S.; Shundalau, M. B.; Zazhogin, A. P.; Komyak, A. I.

    2010-09-01

    Structural models were built and spectral characteristics were calculated based on ab initio calculations for the monomer and dimers of dioxouranium monochoride UO2Cl. The calculations were carried out in the effective core potential LANL2DZ approximation for the uranium atom and all-electron basis sets using DFT methods for oxygen and chlorine atoms (B3LYP/cc-pVDZ). The monomer UO2Cl was found to possess an equilibrium planar (close to T-shaped) configuration with C2v symmetry. The obtained spectral characteristics were analyzed and compared with experimental data. The adequacy of the proposed models and the qualitative agreement between calculation and experiment were demonstrated.

  7. Improved calculations of the lowest vibrational transitions in HeH{sup +}

    SciTech Connect

    Bubin, Sergiy; Stanke, Monika; Kedziera, Dariusz; Adamowicz, Ludwik

    2007-08-15

    More accurate variational calculations of the lowest three pure vibrational states (v=0,1,2) of the {sup 4}HeH{sup +} molecular ion have been carried out without assuming the Born-Oppenheimer approximation. In the calculations we included the complete set of {alpha}{sup 2} relativistic corrections, i.e., mass-velocity, Darwin, spin-spin, and orbit-orbit. This allowed us to improve the agreement between the theory and the experiment for the vibrational frequencies of the 1{yields}0 and 2{yields}1 transitions as compared to our previous calculations [Stanke et al., Phys. Rev. Lett. 96, 233002 (2006)].

  8. A computationally efficient software application for calculating vibration from underground railways

    NASA Astrophysics Data System (ADS)

    Hussein, M. F. M.; Hunt, H. E. M.

    2009-08-01

    The PiP model is a software application with a user-friendly interface for calculating vibration from underground railways. This paper reports about the software with a focus on its latest version and the plans for future developments. The software calculates the Power Spectral Density of vibration due to a moving train on floating-slab track with track irregularity described by typical values of spectra for tracks with good, average and bad conditions. The latest version accounts for a tunnel embedded in a half space by employing a toolbox developed at K.U. Leuven which calculates Green's functions for a multi-layered half-space.

  9. PERTURB: A program for calculating vibrational energies by generalized algebraic quantization

    NASA Astrophysics Data System (ADS)

    Fried, Laurence E.; Ezra, Gregory S.

    1988-09-01

    We describe PERTURB, a special purpose algebraic manipulation program which calculates vibrational eigenvalues in coupled oscillator systems. PERTURB implements the method of generalized algebraic quantization (AQ), in which Van Vleck perturbation theory is formulated in a mock phase space. The phase space formulation enables quantum and classical perturbation theory to be treated on the same footing, and allows the systematic calculation of corrections to classical perturbation results in powers of h̷. Generalized AQ is a powerful and efficient technique for calculating semiclassical vibrational energy levels. In many cases, including just the first correction to classical perturbation theory yields highly accurate energies.

  10. Molecular structure and vibrational spectra of three substituted 4-thioflavones by density functional theory and ab initio Hartree-Fock calculations

    NASA Astrophysics Data System (ADS)

    Li, Xiao-Hong; Liu, Xiang-Ru; Zhang, Xian-Zhou

    2011-01-01

    The vibrational frequencies of three substituted 4-thioflavones in the ground state have been calculated using the Hartree-Fock and density functional method (B3LYP) with 6-31G* and 6-31+G** basis sets. The structural analysis shows that there exists H-bonding in the selected compounds and the hydrogen bond lengths increase with the augment of the conjugate parameters of the substituent group on the benzene ring. A complete vibrational assignment aided by the theoretical harmonic wavenumber analysis was proposed. The theoretical spectrograms for FT-IR spectra of the title compounds have been constructed. In addition, it is noted that the selected compounds show significant activity against Shigella flexniri. Several electronic properties and thermodynamic parameters were also calculated.

  11. Calculation of the surface effect in the ferromagnetic conductor with the harmonic electromagnetic field

    NASA Astrophysics Data System (ADS)

    Nosov, G. V.; Kuleshova, E. O.; Vassilyeva, Yu Z.; Elizarov, A. I.

    2016-04-01

    The authors of the paper have obtained formulas for analytical calculation of the constants with the harmonic electromagnetic field, which characterize the surface layer (a skin layer) of the ferromagnetic conductors in case of heating and nonlinear magnetic properties, which can be used for practical calculation of the electromagnetic screens, rotors of the electrical machines and inductive heating installations. A nonlinear dependence of the magnetic induction on the magnetic tension of the ferromagnetic conductor is replaced by one or two linear sections. It is considered that the skin layer of the conductor has constant quantities of the specific conductivity and averaged temperature. Linear electrodynamics equations are solved for the conductive half-space. Parameters of the ferromagnetic conductor's surface layer are calculated: magnetic permeability, the thickness of the skin layer and its averaged temperature, exposure time of the electromagnetic field on the conductor with the established maximum temperature on the conductor's surface, pressure of the field on the conductor and its resistance, inductivity of the internal magnetic field in the conductor, the thermal energy capacity. The methods credibility is confirmed with the concurrence of the resistance and inductiviry of the ferromagnetic conductor with analogous quantities from other methods.

  12. Molecular geometry and vibrational studies of 3,5-diamino-1,2,4-triazole using quantum chemical calculations and FT-IR and FT-Raman spectroscopies

    NASA Astrophysics Data System (ADS)

    Guennoun, L.; El jastimi, J.; Guédira, F.; Marakchi, K.; Kabbaj, O. K.; El Hajji, A.; Zaydoun, S.

    2011-01-01

    The 3,5-diamino-1,2,4-triazole (guanazole) was investigated by vibrational spectroscopy and quantum methods. The solid phase FT-IR and FT-Raman spectra were recorded in the region 4000-400 cm -1 and 3600-50 cm -1 respectively, and the band assignments were supported by deuteration effects. The results of energy calculations have shown that the most stable form is 1H-3,5-diamino-1,2,4-triazole under C 1 symmetry. For this form, the molecular structure, harmonic vibrational wave numbers, infrared intensities and Raman activities were calculated by the ab initio/HF and DFT/B3LYP methods using 6-31G* basis set. The calculated geometrical parameters of the guanazole molecule using B3LYP methodology are in good agreement with the previously reported X-ray data, and the scaled vibrational wave number values are in good agreement with the experimental data. The normal vibrations were characterized in terms of potential energy distribution (PEDs) using VEDA 4 program.

  13. Structure, stability, depolarized light scattering, and vibrational spectra of fullerenols from all-electron density-functional-theory calculations

    NASA Astrophysics Data System (ADS)

    Rivelino, Roberto; Malaspina, Thaciana; Fileti, Eudes E.

    2009-01-01

    We have investigated the stability, electronic properties, Rayleigh (elastic), and Raman (inelastic) depolarization ratios, infrared and Raman absorption vibrational spectra of fullerenols [C60(OH)n] with different degrees of hydroxylation by using all-electron density-functional-theory (DFT) methods. Stable arrangements of these molecules were found by means of full geometry optimizations using Becke’s three-parameter exchange functional with the Lee, Yang, and Parr correlation functional. This DFT level has been combined with the 6-31G(d,p) Gaussian-type basis set, as a compromise between accuracy and capability to treat highly hydroxylated fullerenes, e.g., C60(OH)36 . Thus, the molecular properties of fullerenols were systematically analyzed for structures with n=1 , 2, 3, 4, 8, 10, 16, 18, 24, 32, and 36. From the electronic structure analysis of these molecules, we have evidenced an important effect related to the weak chemical reactivity of a possible C60(OH)24 isomer. To investigate Raman scattering and the vibrational spectra of the different fullerenols, frequency calculations are carried out within the harmonic approximation. In this case a systematic study is only performed for n=1-4 , 8, 10, 16, 18, and 24. Our results give good agreements with the expected changes in the spectral absorptions due to the hydroxylation of fullerenes.

  14. Vibrational, NMR and UV-Visible spectroscopic investigation, VCD and NLO studies on Benzophenone thiosemicarbazone using computational calculations

    NASA Astrophysics Data System (ADS)

    Moorthy, N.; Jobe Prabakar, P. C.; Ramalingam, S.; Periandy, S.; Parasuraman, K.

    2016-04-01

    In order to explore the unbelievable NLO property of prepared Benzophenone thiosemicarbazone (BPTSC), the experimental and theoretical investigation has been made. The theoretical calculations were made using RHF and CAM-B3LYP methods at 6-311++G(d,p) basis set. The title compound contains Cdbnd S ligand which helps to improve the second harmonic generation (SHG) efficiency. The molecule has been examined in terms of the vibrational, electronic and optical properties. The entire molecular behavior was studied by their fundamental IR and Raman wavenumbers and was compared with the theoretical aspect. The molecular chirality has been studied by performing vibrational circular dichroism (circularly polarized infrared radiation). The Mulliken charge levels of the compound ensure the perturbation of atomic charges according to the ligand. The molecular interaction of frontier orbitals emphasizes the modification of chemical properties of the compound through the reaction path. The enormous amount of NLO activity was induced by the Benzophenone in thiosemicarbazone. The Gibbs free energy was evaluated at different temperature and from which the enhancement of chemical stability was stressed. The VCD spectrum was simulated and the optical dichroism of the compound has been analyzed.

  15. Mode vibrations of a matrix transducer for three-dimensional second harmonic transesophageal echocardiography.

    PubMed

    van Neer, Paul L M J; Blaak, Sandra; Bosch, Johan G; Lancée, Charles T; Prins, Christian; van der Steen, Anton F W; de Jong, Nico

    2012-10-01

    Transesophageal echocardiography (TEE) uses the esophagus as an imaging window to the heart. This enables cardiac imaging without interference from the ribs or lungs and allows for higher frequency ultrasound to be used compared with transthoracic echocardiography (TTE). TEE facilitates the successful imaging of obese or elderly patients, where TTE may be unable to produce images of satisfactory quality. Recently, three-dimensional (3-D) TEE has been introduced, which greatly improves the image quality and diagnostic value of TEE by adding an extra dimension. Further improvement could be achieved by optimizing 3-D TEE for harmonic imaging. This article describes the optimal geometry and element configuration for a matrix probe for 3-D second harmonic TEE. The array concept features separated transmit and receive subarrays. The element geometry was studied using finite element modeling and a transmit subarray prototype was examined both acoustically and with laser interferometry. The transmit subarray is suitable for its role, with a 3 MHz resonance frequency, a 40%-50% -3 dB bandwidth and crosstalk levels <-27 dB. The proposed concept for the receive subarray has a 5.6 MHz center frequency and a 50% -3 dB bandwidth. PMID:22958515

  16. Calculation of bulkhead vibrations in a supported shell simulating a plane fuselage

    NASA Astrophysics Data System (ADS)

    Efimtsov, B. M.; Lazarev, L. A.

    2014-09-01

    Noise from external sources penetrates a plane cabin through the board construction in several ways. They include direct penetration through loose-fiber layers and indirect penetration through the attachment points of interior panels to transverse ribs (bulkheads). The analytical method of calculating vibrations of an orthogonally supported shell (developed by us earlier) makes it possible to correctly calculate bulkhead vibrations. As a result, noise penetration into the cabin through the attachment points of interior panels can be determined analytically. The first part of the solution to this problem is presented (i.e., the relations and examples of calculating bulkhead vibrations upon point excitation of the shell and excitation by pressure fluctuations of the turbulent boundary layer are given).

  17. A numerical model for calculating vibration from a railway tunnel embedded in a full-space

    NASA Astrophysics Data System (ADS)

    Hussein, M. F. M.; Hunt, H. E. M.

    2007-08-01

    Vibration generated by underground railways transmits to nearby buildings causing annoyance to inhabitants and malfunctioning to sensitive equipment. Vibration can be isolated through countermeasures by reducing the stiffness of railpads, using floating-slab tracks and/or supporting buildings on springs. Modelling of vibration from underground railways has recently gained more importance on account of the need to evaluate accurately the performance of vibration countermeasures before these are implemented. This paper develops an existing model, reported by Forrest and Hunt, for calculating vibration from underground railways. The model, known as the Pipe-in-Pipe model, has been developed in this paper to account for anti-symmetrical inputs and therefore to model tangential forces at the tunnel wall. Moreover, three different arrangements of supports are considered for floating-slab tracks, one which can be used to model directly-fixed slabs. The paper also investigates the wave-guided solution of the track, the tunnel, the surrounding soil and the coupled system. It is shown that the dynamics of the track have significant effect on the results calculated in the wavenumber-frequency domain and therefore an important role on controlling vibration from underground railways.

  18. Vibrational Spectrum of (CO)2 on Cu(100): Quantum Calculations with 18 Coupled Mode

    NASA Technical Reports Server (NTRS)

    Dzegilenko, Fedor; Bowman, Joel M.; Carter, Stuart; Saini, Subhash (Technical Monitor)

    1998-01-01

    We report calculations of the vibrational frequencies of CO dimer on Cu(100) using recently developed vibrational self-consistent field code. Eighteen modes are treated explicitly within three modes coupling representation. Nine symmetry distinct doublets are observed and the corresponding frequencies are computed. The thermally broadened spectrum of the CO-stretch fundamental is calculated at various temperatures. Both the temperature and coverage dependence of both the average CO-stretch frequency and the corresponding line-width are consistent with experimentally observed trends. The document contains no classified information International clearance is needed.

  19. A simplified spherical harmonic method for coupled electron-photon transport calculations

    SciTech Connect

    Josef, J.A.

    1997-12-01

    In this thesis the author has developed a simplified spherical harmonic method (SP{sub N} method) and associated efficient solution techniques for 2-D multigroup electron-photon transport calculations. The SP{sub N} method has never before been applied to charged-particle transport. He has performed a first time Fourier analysis of the source iteration scheme and the P{sub 1} diffusion synthetic acceleration (DSA) scheme applied to the 2-D SP{sub N} equations. The theoretical analyses indicate that the source iteration and P{sub 1} DSA schemes are as effective for the 2-D SP{sub N} equations as for the 1-D S{sub N} equations. In addition, he has applied an angular multigrid acceleration scheme, and computationally demonstrated that it performs as well as for the 2-D SP{sub N} equations as for the 1-D S{sub N} equations. It has previously been shown for 1-D S{sub N} calculations that this scheme is much more effective than the DSA scheme when scattering is highly forward-peaked. The author has investigated the applicability of the SP{sub N} approximation to two different physical classes of problems: satellite electronics shielding from geomagnetically trapped electrons, and electron beam problems.

  20. First-principles calculation of the second-harmonic-generation coefficients of borate crystals

    NASA Astrophysics Data System (ADS)

    Duan, Chun-Gang; Li, Jun; Gu, Zong-Quan; Wang, Ding-Sheng

    1999-10-01

    We report the calculation of the second-harmonic-generation (SHG) coefficients of LiB3O5 (LBO), CsB3O5 (CBO), and BaB2O4 (BBO) using the linearized augmented plane-wave band method in the local-density approximation with a scissors operator that includes the renormalization of the momentum operator. The analysis that is based on the spectral and spatial decomposition of the calculated results reveals that, for the large component of SHG coefficients, the dominant source of the optical nonlinearities for these borate crystals is the nonlinear response of the high-lying 2p electrons of oxygen atoms, while the cations play a minor role even in the heavier Cs and Ba cases, though they dominate the conduction-band minimum. But for the small SHG component, the role of the cation became important, particularly when the isolated anionic group has little contribution due to the restriction of the symmetry. In the case of LBO and CBO, due to the linkage of anionic groups, the contributions of off-ring O atoms are almost the same as those of in-ring O atoms. Yet for BBO where there is no such linkage, the off-ring O atom plays a much more important role than the in-ring O atom does. We also find that the contribution of the virtual-hole process cannot be ignored as is usually done in the semiconductors case.

  1. Examination of super-harmonics in a multi-degree of freedom nonlinear vibration isolation system: Refined models and comparison with measurements

    NASA Astrophysics Data System (ADS)

    Yoon, Jong-Yun; Singh, Rajendra

    2014-10-01

    A multi-degree of freedom vibration isolation experiment consisting of a powertrain, three powertrain mounts including a dynamic load sensing hydraulic mount, a sub-frame, and 4 bushings is examined in both time and frequency domains. Since the hydraulic mount exhibits nonlinear phenomena, super-harmonics are observed in motion, pressure and interfacial force measurements when the system is sinusoidally excited. Refined indirect force estimation methods are proposed with a focus on the super-harmonics. This includes the development of a quasi-linear fluid system model with embedded spectrally varying and amplitude-sensitive parameters. The reverse path spectral method is employed using the measured relative motion and upper chamber pressure in the nonlinear hydraulic mount. The relevant transfer functions (with effective parameters for both rubber and hydraulic paths) are used to estimate the interfacial forces. Up to six harmonics of the fundamental excitation frequency are examined, and the contribution of each path is clarified. The proposed quasi-linear fluid system model including super-harmonics extends prior work on indirect force estimation methods and successfully predicts the interfacial forces in the multi-degree of freedom vibration isolation system. The quasi-linear fluid system model, however, seems to be inadequate in estimating the sub-harmonic responses.

  2. Calculation of flight vibration levels of the AH-1G helicopter and correlation with existing flight vibration measurements

    NASA Technical Reports Server (NTRS)

    Ditaranto, R. A.; Sankewitsch, V.

    1989-01-01

    Boeing Helicopters, together with other U.S. Helicopter manufacturers, participated in a finite element applications program to give the United States a superior capability to utilize finite element analysis models in support of helicopter airframe design. The program was sponsored by the NASA Langley Research Center. Under this program, an activity was sponsored to evaluate existing analysis methods applicable to calculate coupled rotor-airframe vibrations. The helicopter used in this evaluation was the AH-1G helicopter. The results of the Boeing Helicopters efforts are summarized. The planned analytical procedure is reviewed. Changes to the planned procedure are discussed, and results of the correlation study are presented.

  3. Harmonic generation in the free-electron laser. II. cw calculation for the linearly polarized wiggler

    SciTech Connect

    Al-Abawi, H.; Moore, G.T.; Scully, M.O.

    1982-01-01

    Harmonic generation in the free-electron laser offers a possible means to extend the wavelength range of the device towards high frequency. Numerical solutions to the basic equations describing this process are shown for cw operation using a linearly polarized wiggler. Higher harmonic emission becomes enhanced as the magnetic field is increased and as the energy spread in the electron beam is reduced.

  4. Programmable Calculator Use in Undergraduate Dynamics, Vibrations, and Elementary Structures Courses.

    ERIC Educational Resources Information Center

    Cutchins, M. A.

    1982-01-01

    Presents programmable calculator solutions to selected problems, including area moments of inertia and principal values, the 2-D principal stress problem, C.G. and pitch inertia computations, 3-D eigenvalue problems, 3 DOF vibrations, and a complex flutter determinant. (SK)

  5. Vibrational spectroscopy investigation and density functional theory calculations on (E)-N‧-(4-methoxybenzylidene) benzohydrazide

    NASA Astrophysics Data System (ADS)

    Saleem, H.; Subashchandrabose, S.; Ramesh Babu, N.; Syed Ali Padusha, M.

    2015-05-01

    The FT-IR, FT-Raman and UV-Vis spectra of the Schiff base compound (E)-N‧-(4-methoxybenzylidene) benzohydrazide (MBBH) have been recorded and analyzed. The optimized geometrical parameters were calculated. The complete vibrational assignments were performed on the basis of TED of the vibrational modes, calculated with the help of SQM method. NBO analysis has been carried out to explore the hyperconjugative interactions and their second order stabilization energy within the molecule. The molecular orbitals (MO's) and its energy gap were studied. The first order hyperpolarizability (β0) and related properties (β, α0, Δα) of MBBH are also calculated. All theoretical calculations were performed on the basis of B3LYP/6-311++G(d,p) level of theory.

  6. Calculations of lattice vibrational mode lifetimes using Jazz: a Python wrapper for LAMMPS

    NASA Astrophysics Data System (ADS)

    Gao, Y.; Wang, H.; Daw, M. S.

    2015-06-01

    Jazz is a new python wrapper for LAMMPS [1], implemented to calculate the lifetimes of vibrational normal modes based on forces as calculated for any interatomic potential available in that package. The anharmonic character of the normal modes is analyzed via the Monte Carlo-based moments approximation as is described in Gao and Daw [2]. It is distributed as open-source software and can be downloaded from the website http://jazz.sourceforge.net/.

  7. Low frequency internal vibrations of norbornane and its derivatives studied by IINS and quantum chemistry calculations

    SciTech Connect

    Holderna-Natkaniec, K.; Natkaniec, I.; Khavryutchenko, V. D.

    1999-06-15

    The observed and calculated INS vibrational densities of states for globular molecules of norbornane, norborneole and borneole are compared in the frequency range up to 600 cm{sup -1}. Inelastic incoherent neutron scattering (IINS) spectra were measured at ca. 20 K on the high resolution NERA spectrometer at the IBR-2 pulsed reactor. The IINS intensities were calculated by semi-empirical quantum chemistry method and the assignments of the low-frequency internal modes were proposed.

  8. Nonlinear forced vibration response of smart two-phase nano-composite beams to external harmonic excitations

    NASA Astrophysics Data System (ADS)

    Mareishi, Soraya; Kalhori, Hamed; Rafiee, Mohammad; Hosseini, Seyedeh Marzieh

    2015-01-01

    This paper presents an analytical solution for nonlinear free and forced vibration response of smart laminated nano-composite beams resting on nonlinear elastic foundation and under external harmonic excitation. The structure is under a temperature change and an electric excitation through the piezoelectric layers. Different distribution patterns of the single walled aligned and straight carbon nanotubes (SWCNTs) through the thickness of the beam are considered. The beam complies with Euler-Bernoulli beam theory and von Kármán geometric nonlinearity. The nonlinearity is due to the mid-plane stretching of the beam and the nonlinear stiffness of the elastic foundation. The Multiple Time Scales perturbation scheme is used to perform the nonlinear dynamical analysis of functionally graded carbon nanotube-reinforced beams. Analytical expressions of the nonlinear natural frequencies, nonlinear dynamic response and frequency response of the system in the case of primary resonance have been presented. The effects of different parameters including applied voltage, temperature change, beam geometry, the volume fraction and distribution pattern of the carbon nanotubes on the nonlinear natural frequencies and frequency-response curves are presented. It is found that the volume fractions of SWCNTs as well as their distribution pattern significantly change the behavior of the system.

  9. Convexity considerations and spatial behavior for the harmonic vibrations in thermoelastic plates

    NASA Astrophysics Data System (ADS)

    D'Apice, Ciro

    2005-12-01

    In this paper we study the spatial behavior of the steady-state solutions for the approach of thin thermoelastic plates developed by Lagnese and Lions [J.E. Lagnese, J.-L. Lions, Modelling, Analysis and Control of Thin Plates, Collection RMA, vol. 6, Masson, Paris, 1988]. The model leads to a coupled complex system of partial differential equations, one of fourth order in terms of the amplitude of the vertical deflection and the other of second-order in terms of the amplitude of temperature field. Coupling in an appropriate way the two equations in an integral identity we are able to identify some cross-sectional line integral measures associated with the amplitudes of the vertical deflection and temperature vibrations, provided that the exciting frequency is less than a certain critical frequency. Furthermore, we are able to establish a second-order differential inequality whose integration furnishes a Saint-Venant type decay estimate for a bounded strip and an alternative of Phragmén-Lindelöf type for a semi-infinite strip. The critical frequency is individuated by means of the use of some Wirtinger and Knowles inequalities.

  10. On the benefits of localized modes in anharmonic vibrational calculations for small molecules.

    PubMed

    Panek, Paweł T; Jacob, Christoph R

    2016-04-28

    Anharmonic vibrational calculations can already be computationally demanding for relatively small molecules. The main bottlenecks lie in the construction of the potential energy surface and in the size of the excitation space in the vibrational configuration interaction (VCI) calculations. To address these challenges, we use localized-mode coordinates to construct potential energy surfaces and perform vibrational self-consistent field and L-VCI calculations [P. T. Panek and C. R. Jacob, ChemPhysChem 15, 3365 (2014)] for all vibrational modes of two prototypical test cases, the ethene and furan molecules. We find that the mutual coupling between modes is reduced when switching from normal-mode coordinates to localized-mode coordinates. When using such localized-mode coordinates, we observe a faster convergence of the n-mode expansion of the potential energy surface. This makes it possible to neglect higher-order contributions in the n-mode expansion of the potential energy surface or to approximate higher-order contributions in hybrid potential energy surfaces, which reduced the computational effort for the construction of the anharmonic potential energy surface significantly. Moreover, we find that when using localized-mode coordinates, the convergence with respect to the VCI excitation space proceeds more smoothly and that the error at low orders is reduced significantly. This makes it possible to devise low-cost models for obtaining a first approximation of anharmonic corrections. This demonstrates that the use of localized-mode coordinates can be beneficial already in anharmonic vibrational calculations of small molecules and provides a possible avenue for enabling such accurate calculations also for larger molecules. PMID:27131535

  11. On the benefits of localized modes in anharmonic vibrational calculations for small molecules

    NASA Astrophysics Data System (ADS)

    Panek, Paweł T.; Jacob, Christoph R.

    2016-04-01

    Anharmonic vibrational calculations can already be computationally demanding for relatively small molecules. The main bottlenecks lie in the construction of the potential energy surface and in the size of the excitation space in the vibrational configuration interaction (VCI) calculations. To address these challenges, we use localized-mode coordinates to construct potential energy surfaces and perform vibrational self-consistent field and L-VCI calculations [P. T. Panek and C. R. Jacob, ChemPhysChem 15, 3365 (2014)] for all vibrational modes of two prototypical test cases, the ethene and furan molecules. We find that the mutual coupling between modes is reduced when switching from normal-mode coordinates to localized-mode coordinates. When using such localized-mode coordinates, we observe a faster convergence of the n-mode expansion of the potential energy surface. This makes it possible to neglect higher-order contributions in the n-mode expansion of the potential energy surface or to approximate higher-order contributions in hybrid potential energy surfaces, which reduced the computational effort for the construction of the anharmonic potential energy surface significantly. Moreover, we find that when using localized-mode coordinates, the convergence with respect to the VCI excitation space proceeds more smoothly and that the error at low orders is reduced significantly. This makes it possible to devise low-cost models for obtaining a first approximation of anharmonic corrections. This demonstrates that the use of localized-mode coordinates can be beneficial already in anharmonic vibrational calculations of small molecules and provides a possible avenue for enabling such accurate calculations also for larger molecules.

  12. Quantum Calculation of Inelastic CO Collisions with H. III. Rate Coefficients for Ro-vibrational Transitions

    NASA Astrophysics Data System (ADS)

    Song, L.; Balakrishnan, N.; Walker, K. M.; Stancil, P. C.; Thi, W. F.; Kamp, I.; van der Avoird, A.; Groenenboom, G. C.

    2015-11-01

    We present calculated rate coefficients for ro-vibrational transitions of CO in collisions with H atoms for a gas temperature range of 10 K ≤ T ≤ 3000 K, based on the recent three-dimensional ab initio H-CO interaction potential of Song et al. Rate coefficients for ro-vibrational v=1,j=0-30\\to v\\prime =0,j\\prime transitions were obtained from scattering cross sections previously computed with the close-coupling (CC) method by Song et al. Combining these with the rate coefficients for vibrational v=1-5\\to v\\prime \\lt v quenching obtained with the infinite-order sudden approximation, we propose a new extrapolation scheme that yields the rate coefficients for ro-vibrational v=2-5,j=0-30\\to v\\prime ,j\\prime de-excitation. Cross sections and rate coefficients for ro-vibrational v=2,j=0-30\\to v\\prime =1,j\\prime transitions calculated with the CC method confirm the effectiveness of this extrapolation scheme. Our calculated and extrapolated rates are very different from those that have been adopted in the modeling of many astrophysical environments. The current work provides the most comprehensive and accurate set of ro-vibrational de-excitation rate coefficients for the astrophysical modeling of the H-CO collision system. The application of the previously available and new data sets in astrophysical slab models shows that the line fluxes typically change by 20%-70% in high temperature environments (800 K) with an H/H2 ratio of 1; larger changes occur for lower temperatures.

  13. Molecular structure and vibrational spectra of dithionite ion by ab initio calculations

    NASA Astrophysics Data System (ADS)

    Leszczynski, Jerzy; Zerner, Michael C.

    1989-07-01

    The structure of the dithionite ion, S 2O 42-, is examined using quantum chemical calculations. These studies strongly suggest that only the C 2h (trans) isomer is stable in solution. The C 2v (cis) form reported in Na 2S 2O 4·2H 2O is stabilized by crystal forces. The calculated vibrational spectrum of the C 2h form is in excellent agreement with that observed in aqueous solution. Taking into account the negative frequency calculated for the C 2v structure yields a calculated spectrum in good agreement with that observed for the crystal.

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

    SciTech Connect

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

    2015-12-28

    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.

  15. Rigorous and rapid calculation of the electron repulsion integral over the uncontracted solid harmonic Gaussian-type orbitals

    NASA Astrophysics Data System (ADS)

    Ishida, Kazuhiro

    1999-09-01

    A rigorous general formula for calculating the electron repulsion integral (ERI) over the uncontracted solid harmonic (SH) Gaussian-type orbitals (GTOs) can be derived by the use of the "reducing mixed solid harmonics" defined in this paper. A general algorithm can be obtained inductively from this formula with the use of the "mixed solid harmonics" also defined in this paper. This algorithm is named as accompanying coordinate expansion (ACE) b1k1. This ACE-b1k1 is capable of computing very fast SH-ERIs. The floating-point operation (FLOP) count assessment is shown for the (LL|LL) class of SH-ERIs (L=2-5). It is found that the present ACE-b1k1 algorithm is the fastest among all algorithms in the literature for the ERI over the uncontracted SH-GTOs.

  16. Quantum scattering calculations for ro-vibrational de-excitation of CO by hydrogen atoms

    SciTech Connect

    Song, Lei; Avoird, Ad van der; Karman, Tijs; Groenenboom, Gerrit C.; Balakrishnan, N.

    2015-05-28

    We present quantum-mechanical scattering calculations for ro-vibrational relaxation of carbon monoxide (CO) in collision with hydrogen atoms. Collisional cross sections of CO ro-vibrational transitions from v = 1, j = 0 − 30 to v′ = 0, j′ are calculated using the close coupling method for collision energies between 0.1 and 15 000 cm{sup −1} based on the three-dimensional potential energy surface of Song et al. [J. Phys. Chem. A 117, 7571 (2013)]. Cross sections of transitions from v = 1, j ≥ 3 to v′ = 0, j′ are reported for the first time at this level of theory. Also calculations by the more approximate coupled states and infinite order sudden (IOS) methods are performed in order to test the applicability of these methods to H–CO ro-vibrational inelastic scattering. Vibrational de-excitation rate coefficients of CO (v = 1) are presented for the temperature range from 100 K to 3000 K and are compared with the available experimental and theoretical data. All of these results and additional rate coefficients reported in a forthcoming paper are important for including the effects of H–CO collisions in astrophysical models.

  17. Quantum scattering calculations for ro-vibrational de-excitation of CO by hydrogen atoms

    NASA Astrophysics Data System (ADS)

    Song, Lei; Balakrishnan, N.; van der Avoird, Ad; Karman, Tijs; Groenenboom, Gerrit C.

    2015-05-01

    We present quantum-mechanical scattering calculations for ro-vibrational relaxation of carbon monoxide (CO) in collision with hydrogen atoms. Collisional cross sections of CO ro-vibrational transitions from v = 1, j = 0 - 30 to v' = 0, j' are calculated using the close coupling method for collision energies between 0.1 and 15 000 cm-1 based on the three-dimensional potential energy surface of Song et al. [J. Phys. Chem. A 117, 7571 (2013)]. Cross sections of transitions from v = 1, j ≥ 3 to v' = 0, j' are reported for the first time at this level of theory. Also calculations by the more approximate coupled states and infinite order sudden (IOS) methods are performed in order to test the applicability of these methods to H-CO ro-vibrational inelastic scattering. Vibrational de-excitation rate coefficients of CO (v = 1) are presented for the temperature range from 100 K to 3000 K and are compared with the available experimental and theoretical data. All of these results and additional rate coefficients reported in a forthcoming paper are important for including the effects of H-CO collisions in astrophysical models.

  18. Studies of the molecular geometry, vibrational spectra, Frontier molecular orbital, nonlinear optical and thermodynamics properties of Aceclofenac by quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Suresh, S.; Gunasekaran, S.; Srinivasan, S.

    The solid phase FT-IR and FT-Raman spectra of 2-[2-[2-[(2,6-dichlorophenyl)amino]phenyl]acetyl] oxyacetic acid (Aceclofenac) have been recorded in the region 4000-400 and 4000-100 cm-1 respectively. The optimized molecular geometry and fundamental vibrational frequencies are interpreted with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) method and a comparative study between Hartree Fork (HF) method 6-311++G(d,p) level basis set. The calculated harmonic vibrational frequencies were scaled and have been compared with experimental by obtained FT-IR and FT-Raman spectra. A detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated potential energy distribution (PED). The time dependent DFT method employed to study its absorption energy and oscillator strength. The linear polarizability (α) and the first order hyper polarizability (β) values of the investigated molecule have been computed. The electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MESP) were also performed. Stability of the molecule arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis.

  19. DFT Calculation of Vibrational Frequencies of FeCoB m-RAM

    NASA Astrophysics Data System (ADS)

    Ling, Lee Li; Jesudason, Christopher; Shrivastava, Keshav N.

    2010-07-01

    The present available random access memory materials are semiconductors. It is proposed to develop magnetoresistance based random access memory (m-RAM) materials. Hence, we consider an alloy of Fe, Co and B which will be strongly magnetic and work well as a memory device. We calculate the vibrational frequencies of clusters of atoms of Fe, Co and B. The larger vibrational frequencies indicate larger force constants. The result show that CoB3Fe to have the largest vibrational frequency of 1293.03 cm-1 whereas BFeCo2 has 509.59 cm-1. We identify the ratio of constituents and the structures which have large force constant. Hence, CoB3Fe is better than BFeCo2. The cluster formation depends on the method of quenching. Hence, method of preparation can be modified to achieve large force constants.

  20. The calculation of the vibrational frequencies of crystalline compounds and its implementation in the CRYSTAL code.

    PubMed

    Pascale, F; Zicovich-Wilson, C M; López Gejo, F; Civalleri, B; Orlando, R; Dovesi, R

    2004-04-30

    The problem of numerical accuracy in the calculation of vibrational frequencies of crystalline compounds from the hessian matrix is discussed with reference to alpha-quartz (SiO(2)) as a case study and to the specific implementation in the CRYSTAL code. The Hessian matrix is obtained by numerical differentiation of the analytical gradient of the energy with respect to the atomic positions. The process of calculating vibrational frequencies involves two steps: the determination of the equilibrium geometry, and the calculation of the frequencies themselves. The parameters controlling the truncation of the Coulomb and exchange series in Hartree-Fock, the quality of the grid used for the numerical integration of the Exchange-correlation potential in Density Functional Theory, the SCF convergence criteria, the parameters controlling the convergence of the optimization process as well as those controlling the accuracy of the numerical calculation of the Hessian matrix can influence the obtained vibrational frequencies to some extent. The effect of all these parameters is discussed and documented. It is concluded that with relatively economical computational conditions the uncertainty related to these parameters is smaller than 2-4 cm(-1). In the case of the Local Density Approximation scheme, comparison is possible with recent calculations performed with a Density Functional Perturbation Theory method and a plane-wave basis set. PMID:15011261

  1. Vibrational spectra and DFT calculations of the vibrational modes of Schiff base C18H17N3O2

    NASA Astrophysics Data System (ADS)

    Antunes, J. A.; Silva, L. E.; Bento, R. R. F.; Teixeira, A. M. R.; Freire, P. T. C.; Faria, J. L. B.; Ramos, R. J.; Silva, C. B.; Lima, J. A.

    2012-04-01

    The Schiff base 4-{[(1E)-(2-Hydroxyphenyl)methylidene]amino}-1,5-dimethyl-2-phenyl-1,2-dihydro-3H-pyrazol-3-one (C18H17N3O2) is a synthetic compound with a variety of scientific and technological applications, such as clinic, analytic and pharmacologic. In this work FT-Raman spectrum and FT-infrared spectrum of C18H17N3O2 were investigated at 300 K. Vibrational wavenumber and wave vector have been predicted using Density Functional Theory (B3LYP) calculations with the 6-31 G(d,p) basis set. The description of the normal modes was performed by means of the potential energy distribution. A comparison with experiment allowed us to assign most of the normal modes of the crystal.

  2. Vibrational spectra and ab initio molecular orbital calculations of the novel anti-cancer drug combretastatin A-4 prodrug

    NASA Astrophysics Data System (ADS)

    James, C.; Pettit, G. R.; Nielsen, O. F.; Jayakumar, V. S.; Joe, I. Hubert

    2008-10-01

    The NIR-FT Raman and FT-IR spectral studies of the novel antineoplastic and antiangiogenesis substance comprestatin A-4 prodrug (CA4P) were carried out. The equilibrium geometry, various bonding features and harmonic vibrational frequencies of CA4P have been investigated with the help of B3LYP density functional theory (DFT) method. The most preferred cis-configuration for its bioactivity has been demonstrated on the basis of torsional potential energy surface (PES) scan studies. Stability of the molecule arising from hyperconjugative interactions leading to its bioactivity, charge delocalization and mesomeric effects have been analyzed using natural bond orbital (NBO) analysis. Detailed assignments of the vibrational spectra have been made with the aid of theoretically predicted vibrational frequencies. The optimized geometry shows near-planarity of phenyl rings and perpendicular conformation of meta substituted methoxy group. The vibrational analysis confirms the differently acting ring modes, steric repulsion, π conjugation and back-donation.

  3. A simplified spherical harmonic method for coupled electron-photon transport calculations

    SciTech Connect

    Josef, J.A.

    1996-12-01

    In this thesis we have developed a simplified spherical harmonic method (SP{sub N} method) and associated efficient solution techniques for 2-D multigroup electron-photon transport calculations. The SP{sub N} method has never before been applied to charged-particle transport. We have performed a first time Fourier analysis of the source iteration scheme and the P{sub 1} diffusion synthetic acceleration (DSA) scheme applied to the 2-D SP{sub N} equations. Our theoretical analyses indicate that the source iteration and P{sub 1} DSA schemes are as effective for the 2-D SP{sub N} equations as for the 1-D S{sub N} equations. Previous analyses have indicated that the P{sub 1} DSA scheme is unstable (with sufficiently forward-peaked scattering and sufficiently small absorption) for the 2-D S{sub N} equations, yet is very effective for the 1-D S{sub N} equations. In addition, we have applied an angular multigrid acceleration scheme, and computationally demonstrated that it performs as well for the 2-D SP{sub N} equations as for the 1-D S{sub N} equations. It has previously been shown for 1-D S{sub N} calculations that this scheme is much more effective than the DSA scheme when scattering is highly forward-peaked. We have investigated the applicability of the SP{sub N} approximation to two different physical classes of problems: satellite electronics shielding from geomagnetically trapped electrons, and electron beam problems. In the space shielding study, the SP{sub N} method produced solutions that are accurate within 10% of the benchmark Monte Carlo solutions, and often orders of magnitude faster than Monte Carlo. We have successfully modeled quasi-void problems and have obtained excellent agreement with Monte Carlo. We have observed that the SP{sub N} method appears to be too diffusive an approximation for beam problems. This result, however, is in agreement with theoretical expectations.

  4. An Efficient Computational Approach for the Calculation of the Vibrational Density of States.

    PubMed

    Aieta, Chiara; Gabas, Fabio; Ceotto, Michele

    2016-07-14

    We present an optimized approach for the calculation of the density of fully coupled vibrational states in high-dimensional systems. This task is of paramount importance, because partition functions and several thermodynamic properties can be accurately estimated once the density of states is known. A new code, called paradensum, based on the implementation of the Wang-Landau Monte Carlo algorithm for parallel architectures is described and applied to real complex systems. We test the accuracy of paradensum on several molecular systems, including some benchmarks for which an exact evaluation of the vibrational density of states is doable by direct counting. In addition, we find a significant computational speedup with respect to standard approaches when applying our code to molecules up to 66 degrees of freedom. The new code can easily handle 150 degrees of freedom. These features make paradensum a very promising tool for future calculations of thermodynamic properties and thermal rate constants of complex systems. PMID:26840098

  5. Fluorescence excitation and ultraviolet absorption spectra and theoretical calculations for benzocyclobutane: Vibrations and structure of its excited S{sub 1}(π,π{sup *}) electronic state

    SciTech Connect

    Shin, Hee Won; Ocola, Esther J.; Laane, Jaan; Kim, Sunghwan

    2014-01-21

    The fluorescence excitation spectra of jet-cooled benzocyclobutane have been recorded and together with its ultraviolet absorption spectra have been used to assign the vibrational frequencies for this molecule in its S{sub 1}(π,π{sup *}) electronic excited state. Theoretical calculations at the CASSCF(6,6)/aug-cc-pVTZ level of theory were carried out to compute the structure of the molecule in its excited state. The calculated structure was compared to that of the molecule in its electronic ground state as well as to the structures of related molecules in their S{sub 0} and S{sub 1}(π,π{sup *}) electronic states. In each case the decreased π bonding in the electronic excited states results in longer carbon-carbon bonds in the benzene ring. The skeletal vibrational frequencies in the electronic excited state were readily assigned and these were compared to the ground state and to the frequencies of five similar molecules. The vibrational levels in both S{sub 0} and S{sub 1}(π,π{sup *}) states were remarkably harmonic in contrast to the other bicyclic molecules. The decreases in the frequencies of the out-of-plane skeletal modes reflect the increased floppiness of these bicyclic molecules in their S{sub 1}(π,π{sup *}) excited state.

  6. Molecular structure, vibrational, electronic and thermal properties of 4-vinylcyclohexene by quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Nagabalasubramanian, P. B.; Periandy, S.; Karabacak, Mehmet; Govindarajan, M.

    2015-06-01

    The solid phase FT-IR and FT-Raman spectra of 4-vinylcyclohexene (abbreviated as 4-VCH) have been recorded in the region 4000-100 cm-1. The optimized molecular geometry and vibrational frequencies of the fundamental modes of 4-VCH have been precisely assigned and analyzed with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) method at 6-311++G(d,p) level basis set. The theoretical frequencies were properly scaled and compared with experimentally obtained FT-IR and FT-Raman spectra. Also, the effect due the substitution of vinyl group on the ring vibrational frequencies was analyzed and a detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated total energy distribution (TED). The time dependent DFT (TD-DFT) method was employed to predict its electronic properties, such as electronic transitions by UV-Visible analysis, HOMO and LUMO energies, molecular electrostatic potential (MEP) and various global reactivity and selectivity descriptors (chemical hardness, chemical potential, softness, electrophilicity index). Stability of the molecule arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Atomic charges obtained by Mulliken population analysis and NBO analysis are compared. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures are also calculated.

  7. Molecular structure, vibrational, electronic and thermal properties of 4-vinylcyclohexene by quantum chemical calculations.

    PubMed

    Nagabalasubramanian, P B; Periandy, S; Karabacak, Mehmet; Govindarajan, M

    2015-06-15

    The solid phase FT-IR and FT-Raman spectra of 4-vinylcyclohexene (abbreviated as 4-VCH) have been recorded in the region 4000-100cm(-1). The optimized molecular geometry and vibrational frequencies of the fundamental modes of 4-VCH have been precisely assigned and analyzed with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) method at 6-311++G(d,p) level basis set. The theoretical frequencies were properly scaled and compared with experimentally obtained FT-IR and FT-Raman spectra. Also, the effect due the substitution of vinyl group on the ring vibrational frequencies was analyzed and a detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated total energy distribution (TED). The time dependent DFT (TD-DFT) method was employed to predict its electronic properties, such as electronic transitions by UV-Visible analysis, HOMO and LUMO energies, molecular electrostatic potential (MEP) and various global reactivity and selectivity descriptors (chemical hardness, chemical potential, softness, electrophilicity index). Stability of the molecule arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Atomic charges obtained by Mulliken population analysis and NBO analysis are compared. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures are also calculated. PMID:25795608

  8. Comparative vibrational spectroscopic studies, HOMO-LUMO, NBO analyses and thermodynamic functions of p-cresol and 2-methyl-p-cresol based on DFT calculations

    NASA Astrophysics Data System (ADS)

    Balachandran, V.; Murugan, M.; Nataraj, A.; Karnan, M.; Ilango, G.

    2014-11-01

    In the present study structural properties of p-cresol, and 2-methoxy-p-cresol have been studied by using B3LYP/cc-pvdz and B3PW91/cc-pvdz of Density Functional Theory (DFT) utilizing Becke three exchange functional and Lee Yang Paar correlation functional. The Fourier transform infrared and Fourier transform Raman spectra of title molecules were recorded (solid phase). Optimized geometry, harmonic vibrational frequencies and various thermodynamic parameters of the title compounds were calculated with B3LYP/cc-pvdz, and B3PW91/cc-pvdz basis sets. Non-linear optical (NLO) behavior of the p-cresol and 2-methoxy-p-cresol were investigated by determining of electric dipole moment, polarizability α, and hyperpolarizability β using the above mentioned basis sets. The molecular properties such as ionization potential, electronegativity, chemical potential, electrophilicity have been deduced from HOMO-LUMO analysis employing the same basis sets. A detailed interpretation of the infrared and Raman spectra of title molecules were reported. UV spectrum was measured in different solvent. The energy and oscillator strength are calculated by Time Dependant Density Functional Theory (TD-DFT) results. The calculated HOMO and LUMO energies also confirm that charge transfer occurs within the molecule. The complete assignments were performed on the basis of the potential energy distribution (PED) of vibrational modes, calculated with scaled quantum mechanics (SQM) method. Finally the theoretical FT-IR, FT-Raman, and UV spectra of the title molecules have also been constructed.

  9. Parallel calculations of vibrational properties in complex materials: negative thermal expansion and elastic inhomogeneity

    NASA Astrophysics Data System (ADS)

    Vila, F. D.; Rehr, J. J.

    Effects of thermal vibrations are essential to obtain a more complete understanding of the properties of complex materials. For example, they are important in the analysis and simulation of x-ray absorption spectra (XAS). In previous work we introduced an ab initio approach for a variety of vibrational effects, such as crystallographic and XAS Debye-Waller factors, Debye and Einstein temperatures, and thermal expansion coefficients. This approach uses theoretical dynamical matrices from which the locally-projected vibrational densities of states are obtained using a Lanczos recursion algorithm. In this talk I present recent improvements to our implementation, which permit simulations of more complex materials with up to two orders of magnitude larger simulation cells. The method takes advantage of parallelization in calculations of the dynamical matrix with VASP. To illustrate these capabilities we discuss two problems of considerable interest: negative thermal expansion in ZrW2O8; and local inhomogeneities in the elastic properties of supported metal nanoparticles. Both cases highlight the importance of a local treatment of vibrational properties. Supported by DOE Grant DE-FG02-03ER15476, with computer support from DOE-NERSC.

  10. Vibrational spectra, structure, and theoretical calculations of 2-fluoro- and 3-fluoropyridine.

    PubMed

    Boopalachandran, Praveenkumar; Laane, Jaan

    2011-09-01

    The infrared and Raman spectra of liquid and vapor-phase 2-fluoropyridine and 3-fluoropyridine have been recorded and assigned. Ab initio and DFT calculations were carried out to compute the molecular structures and to verify the vibrational assignments. The observed and calculated spectra agree extremely well. The ring bond distances of the fluoropyridines are very similar to those of pyridine except for a shortening of the C-N(F) bond in 2-fluoropyridine. The C-F bond stretching frequencies are similar to that in fluorobenzene reflecting the influence of the ring π bonding. PMID:21570895

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

    PubMed

    Rashev, Svetoslav; Moule, David C

    2015-04-01

    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. PMID:25615683

  12. Improved ab initio calculation of surface second-harmonic generation from Si(111)(1 ×1 ):H

    NASA Astrophysics Data System (ADS)

    Anderson, Sean M.; Tancogne-Dejean, Nicolas; Mendoza, Bernardo S.; Véniard, Valérie

    2016-06-01

    We carry out an improved ab initio calculation of surface second-harmonic generation (SSHG) from the Si(111)(1 ×1 ):H surface. This calculation includes three new features in one formulation: (i) the scissors correction, (ii) the contribution of the nonlocal part of the pseudopotentials, and (iii) the inclusion of a cut function to extract the surface response, all within the independent particle approximation. We apply these improvements on the Si(111)(1 ×1 ):H surface and compare with various experimental spectra from several different sources. We also revisit the three-layer model for the SSHG yield and demonstrate that it provides more accurate results over several, more common, two-layer models. We demonstrate the importance of using properly relaxed coordinates for the theoretical calculations. We conclude that this approach to the calculation of the second-harmonic spectra is versatile and accurate within this level of approximation. This well-characterized surface offers an excellent platform for comparison with theory and allows us to offer this study as an efficient benchmark for this type of calculation.

  13. Comparison of DFT methods for molecular structure and vibration spectra of ofloxacin calculations

    NASA Astrophysics Data System (ADS)

    Yang, Yue; Gao, Hongwei

    2012-01-01

    Comparison of the performance of different density functional theory (DFT) methods at various basis sets in predicting molecular and vibration spectra of ofloxacin was reported. The methods employed in this study comprise six functionals, namely, mPW1PW91, HCTH, LSDA, PBEPBE, B3PW91 and B3LYP. Different basis sets including LANL2DZ, SDD, LANL2MB, 6-31g, 6-311g and 3-21g were also examined. Comparison between the calculated and experimental data indicates that the mPW1PW91/6-311g level afford the best quality to predict the structure of ofloxacin. The results also indicate that B3LYP/LANL2DZ level show better performance in the vibration spectra prediction of ofloxacin than other DFT methods.

  14. Calculated and Experimental Vibrational Properties of P700 and the Iron Sulfur Cluster in Photosystem I

    NASA Astrophysics Data System (ADS)

    Lamichhane, Hari; Hastings, Gary

    2009-11-01

    Density functional theory (DFT) based vibrational frequency calculations of Fe4S4(SR)4^n- clusters show that the intense iron-sulfur stretching modes lie in the frequency region between 300-400 cm-1. Among them the iron-sulfur ligand (Fe-S^t) stretching modes are more intense and ˜ 30 cm-1 lower in frequency than the iron-sulfur body (Fe-S^b) stretching modes. Calculations in tetrahydrofuran (THF) show that all these iron-sulfur stretching modes of vibration downshift by ˜ 20 cm-1 upon reduction of the molecule. On the other hand, we have not observed any intense bands from chlorophyll a in the frequency region 400 to 320 cm-1 from the calculations. In an attempt to detect modes associated with iron sulfur clusters in PS I we have obtained light induced (P700^+ - P700) FTIR difference spectra for PSI particles from S. 6803 in the far infrared region. We observe difference bands at many frequencies in the 600-300 cm-1 region. Based on our calculations and literature values we claim that the negative bands at 388 cm-1 and 353 cm-1 in the (P700^+ - P700) FTIR difference spectra be assigned to Fe-S^b and Fe-S^t stretching modes of the ground state of the iron-sulfur cluster FB.

  15. Using Electronic Energy Derivative Information in Automated Potential Energy Surface Construction for Vibrational Calculations.

    PubMed

    Sparta, Manuel; Hansen, Mikkel B; Matito, Eduard; Toffoli, Daniele; Christiansen, Ove

    2010-10-12

    The availability of an accurate representation of the potential energy surface (PES) is an essential prerequisite in an anharmonic vibrational calculation. At the same time, the high dimensionality of the fully coupled PES and the adverse scaling properties with respect to the molecular size make the construction of an accurate PES a computationally demanding task. In the past few years, our group tested and developed a series of tools and techniques aimed at defining computationally efficient, black-box protocols for the construction of PESs for use in vibrational calculations. This includes the definition of an adaptive density-guided approach (ADGA) for the construction of PESs from an automatically generated set of evaluation points. Another separate aspect has been the exploration of the use of derivative information through modified Shepard (MS) interpolation/extrapolation procedures. With this article, we present an assembled machinery where these methods are embedded in an efficient way to provide both a general machinery as well as concrete computational protocols. In this framework we introduce and discuss the accuracy and computational efficiency of two methods, called ADGA[2gx3M] and ADGA[2hx3M], where the ADGA recipe is used (with MS interpolation) to automatically define modest sized grids for up to two-mode couplings, while MS extrapolation based on, respectively, gradients only and gradients and Hessians from the ADGA determined points provides access to sufficiently accurate three-mode couplings. The performance of the resulting potentials is investigated in vibrational coupled cluster (VCC) calculations. Three molecular systems serve as benchmarks: a trisubstituted methane (CHFClBr), methanimine (CH2NH), and oxazole (C3H3NO). Furthermore, methanimine and oxazole are addressed in accurate calculations aiming to reproduce experimental results. PMID:26616778

  16. Synthesis, spectroscopy (vibrational, NMR and UV-vis) studies, HOMO-LUMO and NBO analysis of 8-formyl-7-hydroxy-4-methylcoumarin by ab initio calculations

    NASA Astrophysics Data System (ADS)

    Moghanian, Hassan; Mobinikhaledi, Akbar; Monjezi, Roya

    2013-11-01

    In this work, 8-formyl-7-hydroxy-4-methylcoumarin has been synthesized and characterized by elemental analysis, FT-IR, FT Raman, 1H NMR, 13C NMR and UV-vis spectra. The molecular geometry, harmonic vibrational frequencies and gauge including atomic orbital (GIAO) 1H and 13C chemical shift values of the title compound in the ground state have been calculated by using Hartree-Fock (HF) and density functional methods (B3LYP) with 6-311++G(d,p) as basis set. The vibrational assignments of wave numbers were interpreted in terms of potential energy distribution (PED) analysis and the scaled B3LYP/6-311++G(d,p) results show the good agreement with the experimental values. The UV spectra of investigated compound were recorded in the region of 230-500 nm in chloroform solution. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) in gas and CHCl3 theoretically and results were compared with experimental observations. The molecular stability arising from hyperconjugative interactions and charge delocalization have been analyzed using natural bond orbital (NBO) analysis. In addition, Frontier Molecular Orbitals (FMO), Molecular Electrostatic Potential (MEP) and thermodynamic properties of the studied compound such as heat capacity (C), entropy (S) and enthalpy changes (H) at different temperatures have been calculated.

  17. Ab Initio Calculations of Anharmonic Vibrational Spectroscopy for Hydrogen Fluoride (HF)n (n=3,4) and Mixed Hydrogen Fluoride/Water (HF)n(H20)n (n=1,2,4) Clusters

    NASA Technical Reports Server (NTRS)

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

    2001-01-01

    Anharmonic vibrational frequencies and intensities are computed for hydrogen fluoride clusters (HF)n with n=3,4 and mixed clusters of hydrogen fluoride with water (HF)n(H2O)n where n=1,2. For the (HF)4(H2O)4 complex, the vibrational spectra are calculated at the harmonic level, and anharmonic effects are estimated. Potential energy surfaces for these systems are obtained at the MP2/TZP level of electronic structure theory. Vibrational states are calculated from the potential surface points using the correlation-corrected vibrational self-consistent field (CC-VSCF) method. The method accounts for the anharmonicities and couplings between all vibrational modes and provides fairly accurate anharmonic vibrational spectra that can be directly compared with experimental results without a need for empirical scaling. For (HF)n, good agreement is found with experimental data. This agreement shows that the MP2 potential surfaces for these systems are reasonably reliable. The accuracy is best for the stiff intramolecular modes, which indicates the validity of MP2 in describing coupling between intramolecular and intermolecular degrees of freedom. For (HF)n(H2O)n experimental results are unavailable. The computed intramolecular frequencies show a strong dependence on cluster size. Intensity features are predicted for future experiments.

  18. Ab initio calculations of anharmonic vibrational spectroscopy for hydrogen fluoride (HF)n (n = 3, 4) and mixed hydrogen fluoride/water (HF)n(H2O)n (n = 1, 2, 4) clusters

    NASA Technical Reports Server (NTRS)

    Chaban, Galina M.; Gerber, R. Benny

    2002-01-01

    Anharmonic vibrational frequencies and intensities are computed for hydrogen fluoride clusters (HF)n, with n = 3, 4 and mixed clusters of hydrogen fluoride with water (HF)n(H2O)n where n = 1, 2. For the (HF)4(H2O)4 complex, the vibrational spectra are calculated at the harmonic level, and anharmonic effects are estimated. Potential energy surfaces for these systems are obtained at the MP2/TZP level of electronic structure theory. Vibrational states are calculated from the potential surface points using the correlation-corrected vibrational self-consistent field method. The method accounts for the anharmonicities and couplings between all vibrational modes and provides fairly accurate anharmonic vibrational spectra that can be directly compared with experimental results without a need for empirical scaling. For (HF)n, good agreement is found with experimental data. This agreement shows that the Moller-Plesset (MP2) potential surfaces for these systems are reasonably reliable. The accuracy is best for the stiff intramolecular modes, which indicates the validity of MP2 in describing coupling between intramolecular and intermolecular degrees of freedom. For (HF)n(H2O)n experimental results are unavailable. The computed intramolecular frequencies show a strong dependence on cluster size. Intensity features are predicted for future experiments.

  19. 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

  20. Structural, electronic, thermodynamical and charge transfer properties of Chloramphenicol Palmitate using vibrational spectroscopy and DFT calculations

    NASA Astrophysics Data System (ADS)

    Mishra, Rashmi; Srivastava, Anubha; Sharma, Anamika; Tandon, Poonam; Baraldi, Cecilia; Gamberini, Maria Christina

    2013-01-01

    The global problem of advancing bacterial resistance to newer drugs has led to renewed interest in the use of Chloramphenicol Palmitate (C27H42Cl2N2O6) [Palmitic acid alpha ester with D-threo-(-),2-dichloro-N-(beta-hydroxy-alpha-(hydroxymethyl)-p-nitrophenethyl)acetamide also known as Detereopal]. The characterization of the three polymorphic forms of Chloramphenicol Palmitate (CPP) was done spectroscopically by employing FT-IR and FT-Raman techniques. The equilibrium geometry, various bonding features, and harmonic wavenumbers have been investigated for most stable form A with the help of DFT calculations and a good correlation was found between experimental data and theoretical values. Electronic properties have been analyzed employing TD-DFT for both gaseous and solvent phase. The theoretical calculation of thermodynamical properties along with NBO analysis has also been performed to have a deep insight into the molecule for further applications.

  1. Infrared spectra, vibrational assignment, and ab initio calculations for N-bromo-hexafluoro-2-propanimine.

    PubMed

    Panikar, Savitha S; Guirgis, Gamil A; Sheehan, Tracie G; Durig, Douglas T; Durig, James R

    2012-05-01

    The infrared spectra of gaseous and solid N-bromo-hexafluoro-2-propanimine, (CF(3))(2)CNBr, have been obtained from 2000 to 50 cm(-1). The vibrational assignment for the normal modes is proposed based on infrared band contours, group frequencies and normal coordinate calculations utilizing C(s) symmetry. The structural parameters have been obtained from ab initio MP2(full)/6-311+G(d,p) calculations employing the Gaussian-03 program. Additionally, the frequencies and potential energy distributions for the normal modes have been calculated with the MP2(full)/6-31G(d). All of these results are compared to the corresponding data for some similar molecules. PMID:22336042

  2. Non-Born-Oppenheimer calculations of the pure vibrational spectrum of T2 including relativistic corrections

    NASA Astrophysics Data System (ADS)

    Stanke, Monika; Adamowicz, Ludwik

    2014-10-01

    We report very accurate calculations of the complete pure vibrational spectrum of the T2 molecule with an approach where the Born-Oppenheimer (BO) approximation is not assumed. As the considered states correspond to the zero total angular momentum, their non-BO wave functions are spherically symmetric and are expanded in terms of all-particle, one-center, spherically symmetric explicitly correlated Gaussian functions multiplied by even nonnegative powers of the internuclear distance. The nonrelativistic energies of the states obtained in the non-BO calculations are corrected for the relativistic effects of the order of α2 (where α is the fine structure constant) calculated as expectation values of the operators representing these effects.

  3. Non-Born-Oppenheimer calculations of the pure vibrational spectrum of T₂ including relativistic corrections.

    PubMed

    Stanke, Monika; Adamowicz, Ludwik

    2014-10-21

    We report very accurate calculations of the complete pure vibrational spectrum of the T2 molecule with an approach where the Born-Oppenheimer (BO) approximation is not assumed. As the considered states correspond to the zero total angular momentum, their non-BO wave functions are spherically symmetric and are expanded in terms of all-particle, one-center, spherically symmetric explicitly correlated Gaussian functions multiplied by even nonnegative powers of the internuclear distance. The nonrelativistic energies of the states obtained in the non-BO calculations are corrected for the relativistic effects of the order of α(2) (where α is the fine structure constant) calculated as expectation values of the operators representing these effects. PMID:25338891

  4. Infrared spectra, vibrational assignment, and ab initio calculations for N-bromo-hexafluoro-2-propanimine

    NASA Astrophysics Data System (ADS)

    Panikar, Savitha S.; Guirgis, Gamil A.; Sheehan, Tracie G.; Durig, Douglas T.; Durig, James R.

    2012-05-01

    The infrared spectra of gaseous and solid N-bromo-hexafluoro-2-propanimine, (CF3)2Cdbnd NBr, have been obtained from 2000 to 50 cm-1. The vibrational assignment for the normal modes is proposed based on infrared band contours, group frequencies and normal coordinate calculations utilizing Cs symmetry. The structural parameters have been obtained from ab initio MP2(full)/6-311 + G(d,p) calculations employing the Gaussian-03 program. Additionally, the frequencies and potential energy distributions for the normal modes have been calculated with the MP2(full)/6-31G(d). All of these results are compared to the corresponding data for some similar molecules.

  5. Fast vibrational calculation of anharmonic OH-stretch frequencies for two low-energy noradrenaline conformers

    NASA Astrophysics Data System (ADS)

    Benoit, David M.

    2008-12-01

    We introduce a new reduced-coupling technique to accelerate direct calculations of a selected number of vibrational frequencies in large molecular systems. Our method combines the advantages of the single-to-all correlation-corrected vibrational self-consistent field (STA-CC-VSCF) approach [D. M. Benoit, J. Chem. Phys. 125, 244110 (2006)] with those of the fast-CC-VSCF technique [D. M. Benoit, J. Chem. Phys. 120, 562 (2004)] and allows the ab initio calculation of only the relevant parts of the required potential energy surface (PES). We demonstrate, using a set of five aliphatic alcohol molecules, that the new fast-STA-CC-VSCF method is accurate and leads to very substantial time gains for the computations of the PES. We then use the fast-STA-CC-VSCF method to accelerate the computation of the OH-stretch and NH-stretch frequencies of the two lowest-energy conformers of noradrenaline, namely, AG1a and GG1a. Our new approach enables us to run the calculation 89 times faster than the standard CC-VSCF technique and makes it possible to use a high-level MP2/TZP description of the PES. We demonstrate that the influence of the strong mode-mode couplings is crucial for a realistic description of the particular OH-stretch vibrational signature of each conformer. Finally, of the two possible low-energy conformers, we identify AG1a as the one most likely to have been observed in the experiments of Snoek et al. [Mol. Phys. 101, 1239 (2003)].

  6. The calculation of vibrational populations of O2 Herzberg states in the atmospheres of terrestrial planets

    NASA Astrophysics Data System (ADS)

    Kirillov, Andrey S.

    The calculated quenching rate constants of the c1, A'3, A3 states of O2 by molecules in [Kirillov, 2014, Chem. Phys. Lett., v.592, p.103] are applied in the simulation of vibrational populations of the Herzberg states in the nightglow of upper atmosphere of Venus and Mars where carbon dioxide is the main gas and in the mixture of molecular oxygen with CO2, CO, N2 gases for laboratory conditions. The results of the simulation show very important role of electronic-vibrational (EV) energy transfer processes in the redistribution of electronic excitation energy on vibrational levels of the states. The main aim of the simulation is an attempt to explain the high intensities of the Herzberg II band system observed in laboratory experiments with high CO2 concentrations [Lawrence et al., 1977, Science, v.195, p.573; Slanger, 1978, J. Chem. Phys., v.69, p.4779] and registered with spacecraft spectrometers in the nightglow of the Venus atmosphere [Krasnopolsky et al., 1977, Cosmic Res., v.14, p.687; Gerard et al., 2013, Icarus, v.223, p.602].

  7. A comparison of force fields and calculation methods for vibration intervals of isotopic H3(+) molecules

    NASA Astrophysics Data System (ADS)

    Carney, G. D.; Adler-Golden, S. M.; Lesseski, D. C.

    1986-04-01

    This paper reports (1) improved values for low-lying vibration intervals of H3(+), H2D(+), D2H(+), and D3(+) calculated using the variational method and Simons-Parr-Finlan (1973) representations of the Carney-Porter (1976) and Dykstra-Swope (1979) ab initio H3(+) potential energy surfaces, (2) quartic normal coordinate force fields for isotopic H3(+) molecules, (3) comparisons of variational and second-order perturbation theory, and (4) convergence properties of the Lai-Hagstrom internal coordinate vibrational Hamiltonian. Standard deviations between experimental and ab initio fundamental vibration intervals of H3(+), H2D(+), D2H(+), and D3(+) for these potential surfaces are 6.9 (Carney-Porter) and 1.2/cm (Dykstra-Swope). The standard deviations between perturbation theory and exact variational fundamentals are 5 and 10/cm for the respective surfaces. The internal coordinate Hamiltonian is found to be less efficient than the previously employed 't' coordinate Hamiltonian for these molecules, except in the case of H2D(+).

  8. A three-dimensional tunnel model for calculation of train-induced ground vibration

    NASA Astrophysics Data System (ADS)

    Forrest, J. A.; Hunt, H. E. M.

    2006-07-01

    The frequency range of interest for ground vibration from underground urban railways is approximately 20 to 100 Hz. For typical soils, the wavelengths of ground vibration in this frequency range are of the order of the spacing of train axles, the tunnel diameter and the distance from the tunnel to nearby building foundations. For accurate modelling, the interactions between these entities therefore have to be taken into account. This paper describes an analytical three-dimensional model for the dynamics of a deep underground railway tunnel of circular cross-section. The tunnel is conceptualised as an infinitely long, thin cylindrical shell surrounded by soil of infinite radial extent. The soil is modelled by means of the wave equations for an elastic continuum. The coupled problem is solved in the frequency domain by Fourier decomposition into ring modes circumferentially and a Fourier transform into the wavenumber domain longitudinally. Numerical results for the tunnel and soil responses due to a normal point load applied to the tunnel invert are presented. The tunnel model is suitable for use in combination with track models to calculate the ground vibration due to excitation by running trains and to evaluate different track configurations.

  9. Accurate variational calculations and analysis of the HOCl vibrational energy spectrum

    SciTech Connect

    Skokov, S.; Qi, J.; Bowman, J.M.; Yang, C.; Gray, S.K.; Peterson, K.A. |; Mandelshtam, V.A.

    1998-12-01

    Large scale variational calculations for the vibrational states of HOCl are performed using a recently developed, accurate {ital ab initio} potential energy surface. Three different approaches for obtaining vibrational states are employed and contrasted; a truncation/recoupling scheme with direct diagonalization, the Lanczos method, and Chebyshev iteration with filter diagonalization. The complete spectrum of bound states for nonrotating HOCl is computed and analyzed within a random matrix theory framework. This analysis indicates almost entirely regular dynamics with only a small degree of chaos. The nearly regular spectral structure allows us to make assignments for the most significant part of the spectrum, based on analysis of coordinate expectation values and eigenfunctions. Ground state dipole moments and dipole transition probabilities are also calculated using accurate {ital ab initio} data. Computed values are in good agreement with available experimental data. Some exact rovibrational calculations for J=1, including Coriolis coupling, are performed. The exact results are nearly identical with those obtained from the adiabatic rotation approximation and very close to those from the centrifugal sudden approximation, thus indicating a very small degree of asymmetry and Coriolis coupling for the HOCl molecule. {copyright} {ital 1998 American Institute of Physics.}

  10. Calculation of low-frequency vibrational modes of biologically important isomers

    NASA Astrophysics Data System (ADS)

    Jones, Inke; Rainsford, Tamath J.; Fischer, Bernd M.; Abbott, Derek

    2007-12-01

    In this paper we compare the value of different molecular modeling techniques for the prediction of vibrational modes, especially in the mid- and far-infrared region. There is a wide range of different levels of theory available for molecular modelling - the choice depending on the kind of system to be investigated. For our calculations we use different theoretical approaches such as Hartree-Fock and Density functional theory. We also compare the performances of two available electronic structure programs-Gamess-US and Gaussian03. As examples, we use two different retinoids - all-trans retinal and all-trans retinoic acid - derivatives of Vitamin A.

  11. Using symmetry-adapted optimized sum-of-products basis functions to calculate vibrational spectra

    NASA Astrophysics Data System (ADS)

    Leclerc, Arnaud; Carrington, Tucker

    2016-01-01

    Vibrational spectra can be computed without storing full-dimensional vectors by using low-rank sum-of-products (SOP) basis functions. We introduce symmetry constraints in the SOP basis functions to make it possible to separately calculate states in different symmetry subgroups. This is done using a power method to compute eigenvalues and an alternating least squares method to optimize basis functions. Owing to the fact that the power method favours the convergence of the lowest states, one must be careful not to exclude basis functions of some symmetries. Exploiting symmetry facilitates making assignments and improves the accuracy. The method is applied to the acetonitrile molecule.

  12. Lowest vibrational states of {sup 4}He{sup 3}He{sup +}: Non-Born-Oppenheimer calculations

    SciTech Connect

    Stanke, Monika; Bubin, Sergiy; Kedziera, Dariusz; Molski, Marcin; Adamowicz, Ludwik

    2007-11-15

    Very accurate quantum mechanical calculations of the first five vibrational states of the {sup 4}He{sup 3}He{sup +} molecular ion are reported. The calculations have been performed explicitly including the coupling of the electronic and nuclear motions [i.e., without assuming the Born-Oppenheimer (BO) approximation]. The nonrelativistic non-BO wave functions were used to calculate the {alpha}{sup 2} relativistic mass velocity, Darwin, and spin-spin interaction corrections. For the lowest vibrational transition, whose experimental energy is established with high precision, the calculated and the experimental results differ by only 0.16 cm{sup -1}.

  13. Vibrational spectroscopic (FTIR and FT-Raman), first-order hyperpolarizablity, HOMO, LUMO, NBO, Mulliken charge analyses of 2-ethylimidazole based on Hartree-Fock and DFT calculations.

    PubMed

    Arivazhagan, M; Manivel, S; Jeyavijayan, S; Meenakshi, R

    2015-01-01

    The FTIR and FT-Raman spectra of 2-ethylimidazole (2EIDZ) have been recorded in the region 4000-400 cm(-1) and 3500-50 cm(-1), respectively. Utilizing the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. The optimized molecular geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities, were calculated by ab initio Hartree-Fock (HF) and density functional theory (DFT/B3LYP) methods with 6-311++G(d,p) basis set. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. A detailed interpretation of the infrared and Raman spectra of 2EIDZ is also reported based on total energy distribution (TED). The values of the total dipole moment (μ) and the first-order hyperpolarizability (β) of the compound were computed. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. Besides, HOMO and LUMO analysis, Mulliken's charge analysis and several thermodynamic properties have been calculated. PMID:25048284

  14. Conformational and isomerizational studies of 3- N, N-dimethylhydrazino-2-acetyl propenenitrile using X-ray analysis, NMR and vibrational spectra, and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Gróf, M.; Gatial, A.; Milata, V.; Prónayová, N.; Kožíšek, J.; Breza, M.; Matějka, P.

    2009-12-01

    The IR, Raman and NMR spectra of 3- N, N-dimethylhydrazino-2-acetyl propenenitrile (DMHAP) [(H 3C) 2N sbnd NH sbnd CH dbnd C(CN)(COCH 3)] were measured. X-ray analysis revealed that DMHAP exists in solid state as ZZa conformer. Vibrational and NMR spectra confirmed the existence of only one ZZa conformer with an intramolecular hydrogen bond in less polar solvents and next two EZa and EZs conformers of E-isomer with Z-orientation of acetyl group and anti and syn orientation of dimethylhydrazino group in more polar environments. The observed IR and Raman bands were compared with harmonic vibrational frequencies, calculated using ab initio MP2 and DFT/B3LYP methods in 6-31G∗∗ basis set, and assigned on the basis of potential energy distribution. In addition, the geometries and relative energies of the possible isomers and conformers of DMHAP were also evaluated on the same levels and compared with the X-ray data. The influence of environment polarity on this conformational equilibrium is discussed with respect to the SCRF solvent effect calculations using IEFPCM model.

  15. Corrections to vibrational transition probabilities calculated from a three-dimensional model.

    NASA Technical Reports Server (NTRS)

    Stallcop, J. R.

    1972-01-01

    Corrections to the collision-induced vibration transition probability calculated by Hansen and Pearson from a three-dimensional semiclassical model are examined. These corrections come from the retention of higher order terms in the expansion of the interaction potential and the use of the actual value of the deflection angle in the calculation of the transition probability. It is found that the contribution to the transition cross section from previously neglected potential terms can be significant for short range potentials and for the large relative collision velocities encountered at high temperatures. The correction to the transition cross section obtained from the use of actual deflection angles will not be appreciable unless the change in the rotational quantum number is large.

  16. Vibrational spectra of light and heavy water with application to neutron cross section calculations

    SciTech Connect

    Damian, J. I. Marquez; Granada, J. R.; Malaspina, D. C.

    2013-07-14

    The design of nuclear reactors and neutron moderators require a good representation of the interaction of low energy (E < 1 eV) neutrons with hydrogen and deuterium containing materials. These models are based on the dynamics of the material, represented by its vibrational spectrum. In this paper, we show calculations of the frequency spectrum for light and heavy water at room temperature using two flexible point charge potentials: SPC-MPG and TIP4P/2005f. The results are compared with experimental measurements, with emphasis on inelastic neutron scattering data. Finally, the resulting spectra are applied to calculation of neutron scattering cross sections for these materials, which were found to be a significant improvement over library data.

  17. A complete vibrational study on a potential environmental toxicant agent, the 3,3',4,4'-tetrachloroazobenzene combining the FTIR, FTRaman, UV-Visible and NMR spectroscopies with DFT calculations.

    PubMed

    Castillo, María V; Pergomet, Jorgelina L; Carnavale, Gustavo A; Davies, Lilian; Zinczuk, Juan; Brandán, Silvia A

    2015-01-01

    In this study 3,3',4,4'-tetrachloroazobenzene (TCAB) was prepared and then characterized by infrared, Raman, multidimensional nuclear magnetic resonance (NMR) and ultraviolet-visible spectroscopies. The density functional theory (DFT) together with the 6-31G(*) and 6-311++G(**) basis sets were used to study the structures and vibrational properties of the two cis and trans isomers of TCAB. The harmonic vibrational wavenumbers for the optimized geometries were calculated at the same theory levels. A complete assignment of all the observed bands in the vibrational spectra of TCAB was performed combining the DFT calculations with the scaled quantum mechanical force field (SQMFF) methodology. The molecular electrostatic potentials, atomic charges, bond orders and frontier orbitals for the two isomers of TCAB were compared and analyzed. The comparison of the theoretical ultraviolet-visible spectrum with the corresponding experimental demonstrates a good concordance while the calculated (1)H and (13)C chemicals shifts are in good conformity with the corresponding experimental NMR spectra of TCAB in solution. The npp(*) transitions for both forms were studied by natural bond orbital (NBO) while the topological properties were calculated by employing Bader's Atoms in the Molecules (AIM) theory. This study shows that the cis and trans isomers exhibit different structural and vibrational properties and absorption bands. PMID:25106816

  18. Detailed structural study of β-artemether: Density functional theory (DFT) calculations of Infrared, Raman spectroscopy, and vibrational circular dichroism

    NASA Astrophysics Data System (ADS)

    Wang, Zhiqiang; Chen, Jianchao; Li, Linwei; Zhou, Zhixu; Geng, Yiding; Sun, Tiemin

    2015-10-01

    In this study, the experimental and theoretical studies on the structure of β-artemether are presented. The optimized molecular structure, Mulliken atomic charges, vibrational spectra (IR, Raman and vibrational circular dichroism), and molecular electrostatic potential have been calculated by density functional theory (DFT) using B3LYP method with the 6-311++G (2d, p) basis set. Reliable vibrational assignments for Artemether have been made on the basis of potential energy distribution (PED). The vibrational circular dichroism (VCD) has been explored by ab initio calculations, and then was used to compare with the experimental VCD. The consistence between them confirmed the absolute configuration of Artemether. In addition, HOMO-LUMO of the title compound as well as thermo-dynamical parameters has illustrated the stability of β-artemether.

  19. Communication: Towards the binding energy and vibrational red shift of the simplest organic hydrogen bond: Harmonic constraints for methanol dimer

    SciTech Connect

    Heger, Matthias; Suhm, Martin A.; Mata, Ricardo A.

    2014-09-14

    The discrepancy between experimental and harmonically predicted shifts of the OH stretching fundamental of methanol upon hydrogen bonding to a second methanol unit is too large to be blamed mostly on diagonal and off-diagonal anharmonicity corrections. It is shown that a decisive contribution comes from post-MP2 electron correlation effects, which appear not to be captured by any of the popular density functionals. We also identify that the major deficiency is in the description of the donor OH bond. Together with estimates for the electronic and harmonically zero-point corrected dimer binding energies, this work provides essential constraints for a quantitative description of this simple hydrogen bond. The spectroscopic dissociation energy is predicted to be larger than 18 kJ/mol and the harmonic OH-stretching fundamental shifts by about −121 cm{sup −1} upon dimerization, somewhat more than in the anharmonic experiment (−111 cm{sup −1})

  20. Calculations of N 2 triplet states vibrational populations and band emissions in venusian dayglow

    NASA Astrophysics Data System (ADS)

    Bhardwaj, Anil; Jain, Sonal Kumar

    2012-02-01

    A model for N 2 triplet states band emissions in the venusian dayglow has been developed for low and high solar activity conditions. Steady state photoelectron fluxes and volume excitation rates for N 2 triplet states have been calculated using the Analytical Yield Spectra (AYS) technique. Model calculated photoelectron flux is in good agreement with Pioneer Venus Orbiter-observed electron flux. Since inter-state cascading is important for the triplet states of N 2, populations of different levels of N 2 triplet states are calculated under statistical equilibrium considering direct electron impact excitation, and cascading and quenching effects. Densities of all vibrational levels of each triplet state are calculated in the model. Height-integrated overhead intensities of N 2 triplet band emissions are calculated, the values for Vegard-Kaplan (A3Σu+-X1Σg+), First Positive (B3Πg-A3Σu+), Second Positive ( C3Π u - B3Π g), and Wu-Benesch ( W3Δ u - B3Π g) bands of N 2, are 1.9 (3.2), 3 (6), 0.4 (0.8), and 0.5 (1.1) kR, respectively, for solar minimum (maximum) conditions. The intensities of the three strong Vegard-Kaplan bands (0, 5), (0, 6), and (0, 7) are 94 (160), 120 (204), and 114 (194) R, respectively, for solar minimum (maximum) conditions. Limb profiles are calculated for VK (0, 4), (0, 5), (0, 6) and (0, 7) bands. The calculated intensities on Venus are about a factor 10 higher than those on Mars. The present study provides a motivation for a search of N 2 triplet band emissions in the dayglow of Venus.

  1. Vibrations of a floating beam on marine waves

    SciTech Connect

    Sabaneev, Valentin S.; Tovstik, Petr E.; Tovstik, Tatiana M.; Shekhovtsov, Alexei S.

    2015-03-10

    Vertical vibrations of a floating pipe-concrete beam caused by a harmonic waves excitation are studied. The apparent additional mass of water, resisting force and the velocity of towing are considered. The vibration amplitude and the maximum deformations of concrete, caused by these fluctuations, are calculated.

  2. The vibrational behavior of silica clusters at the glass transition: Ab initio calculations and thermodynamic implications.

    PubMed

    Ottonello, G; Zuccolini, M Vetuschi; Belmonte, D

    2010-09-14

    We present the results of a computational investigation with ab initio procedures of the structure-energy and vibrational properties of silica clusters in a dielectric continuum with dielectric constant ε=3.8, through density functional theory/B3LYP gas phase calculations coupled with a polarized continuum model approach [integral equation formalism applied to a polarized continuum (IEFPCM)] and those of the periodical structure D(6h) which leads to the α-cristobalite polymorph of silica when subjected to symmetry operations with the same functional within the linear combination of atomic orbitals (LCAO) approximation and in the framework of Bloch's theorem. Based on the computed energies and vibrational features, an aggregate of the D(6h) network and the monomer locally ordered in the short-medium range and both present in the glass in a mutual arrangement lacking of spatial continuity reproduces satisfactorily the experimentally observed low T heat capacity and the deviation from the Debye T(3) law. Above T(g), the experimental heat capacity of the liquid is perfectly reproduced summing to the internal modes the translational and rotational contributions to the bulk heat capacity and subtracting the (acoustic) terms arising from coherent motion (no longer existent). PMID:20849179

  3. DFT calculations of 2,6-dimethylpyrazine (26DMP) and its complex with chloranilic acid (CLA): Comparison to INS, IR and Raman vibration spectra

    NASA Astrophysics Data System (ADS)

    Pawlukojć, A.; Sobczyk, L.; Prager, M.; Bator, G.; Grech, E.; Nowicka-Scheibe, J.

    2008-12-01

    The inelastic neutron scattering (INS), infrared and Raman spectra of crystalline 2,6-dimethylpyrazine (26DMP) and its complex with chloranilic acid (26DMP·CLA) were measured. Simultaneously the DFT calculations of the molecular structures and frequencies of the normal vibrations were performed by using various functionals. The INS spectra were simulated in the energy range up to 1200 cm -1, on the basis of the calculated frequencies. A very good conformity was obtained between experimental and calculated data with respect to the structure as well as to frequencies, with exception, however, of the CH 3 torsional modes. The structural analysis based on the deviation from the sum of the van der Waals radii showed that the packing of the methyl groups in the 26DMP·CLA complex was markedly stronger than that in the neat 26DMP. However, the DFT calculations overestimated the role of this effect that may be due to a limitation of the applied methods. In addition the anharmonicity of the rotational potential led to the librational energies different from those obtained using a harmonic potential.

  4. H{sub 2}-He vibrational line-shape parameters: Measurement and semiclassical calculation

    SciTech Connect

    Forsman, J.W.; Bonamy, J.; Robert, D.; Berger, J.P.; Saint-Loup, R.; Berger, H.

    1995-10-01

    High-resolution inverse Raman spectroscopy has been used to obtain the line shifting and line broadening coefficients of H{sub 2} perturbed by He. Measurements have been made for the {ital Q}-branch transitions ({ital J}=0{r_arrow}5) in a density range of 10 to 20 amagat and from 296 to 995 K. Up to 795 K we have directly deduced from the experimental broadening coefficients the inelastic rotational state-to-state and vibrational dephasing rates. At higher temperatures, owing to the larger number of channels of relaxation which occur, the results have been analyzed using a scaling law. The line shift and broadening coefficients exhibit a square root and a linear dependence on temperature, respectively, and a significant {ital J} dependence. Semiclassical calculations based on an accurate {ital ab} {ital initio} potential lead to line-shape parameters consistent with experiment. They allow a clear understanding of their observed temperature dependence.

  5. An extended hindered-rotor model with incorporation of Coriolis and vibrational-rotational coupling for calculating partition functions and derived quantities

    NASA Astrophysics Data System (ADS)

    Vansteenkiste, P.; Van Neck, D.; Van Speybroeck, V.; Waroquier, M.

    2006-01-01

    Large-amplitude motions, particularly internal rotations, are known to affect substantially thermodynamic functions and rate constants of reactions in which flexible molecules are involved. Up to now all methods for computing the partition functions of these motions rely on the Pitzer approximation of more than 50 years ago, in which the large-amplitude motion is treated in complete independence of the other (vibrational) degrees of freedom. In this paper an extended hindered-rotor model (EHR) is developed in which the vibrational modes, treated harmonically, are correctly separated from the large-amplitude motion and in which relaxation effects (the changes in the kinetic-energy matrix and potential curvature) are taken into account as one moves along the large-amplitude path. The model also relies on a specific coordinate system in which the Coriolis terms vanish at all times in the Hamiltonian. In this way an increased level of consistency between the various internal modes is achieved, as compared with the more usual hindered-rotor (HR) description. The method is illustrated by calculating the entropies and heat capacities on 1,3-butadiene and 1-butene (with, respectively, one and two internal rotors) and the rate constant for the addition reaction of a vinyl radical to ethene. We also discuss various variants of the one-dimensional hindered-rotor scheme existing in the literature and its relation with the EHR model. It is argued why in most cases the HR approach is already quite successful.

  6. DFT Ab initio Calculation of Vibrational Frequencies in AsSe glass

    NASA Astrophysics Data System (ADS)

    Shrivastava, Keshav; Kassim, Hasan; Nazrul Rosli, Ahmad

    2008-03-01

    By using DFT double zeta wave functions, we calculated the structure, bond length (picometer, pm), frequencies(intensities)[degeneracy] for various clusters of arsenic selenide. Our results are as follows. (i) AsSe(diatomic) bond length 216pm, 244.0(1/cm). (ii) As2Se(linear) bond length 228.5 pm, frequencies 27.6(1.9) and 387.6(4.3). (iii) As2Se(triangular) As-Se 243.4 pm, As-As 223.3 pm, frequencies 237.3(2.4) and 332.4(0.05)(1/cm). (iv) As3Se (triangular) bond length 238.4 pm, frequencies 107.5 and 296(weak)(1/cm). (v) As4Se (square) bond length 250.2 pm, 58.5(0.04), 241.3(5.9)(1/cm). (vi) AsSe3 (triangular), bond length 231.2 pm, 75.9(0.003), 103.5(1.26)[2], 350.9(33.2)[2]. From this study we identify that linear As-Se-As for which the calculated frequency is 27.6(1/cm) is in agreement with the data of Nemanich, Phys. Rev. B 16, 1655(1977), J. C. Phillips et al Phys. Rev B 21, 5724(1980). We have successfully calculated several vibrational frequencies accurately which agree with the Raman data. *V. R. Devi et al J. Non-Cryst. Solids 351, 489(2005);353,111(2007)

  7. Calculation of the Vibrational Stark Effect Using a First-Principles QM/MM Approach

    PubMed Central

    Ringer, Ashley L.; MacKerell, Alexander D.

    2011-01-01

    The proper description of the electric environment of condensed phases is a critical challenge for force field methods. To test and validate the ability of the CHARMM additive force field to describe the electric environment in aqueous solution combined QM/MM calculations have been used to calculate the vibrational Stark effect (VSE). We utilized a first principles methodology using correlated electronic structure techniques to compute the Stark shift between the gas phase and solvent environments and between two different solvent environments of three VSE probes containing acetonitrile or fluorine functionalities which have been well-characterized experimentally. Reasonable agreement with the experimentally determined Stark shifts is obtained when the MM atoms are described by the CHARMM additive force field, though it is essential to employ an anharmonic correction in the frequency calculation. In addition, the electric field created by the solvent is computed along the CN bond and a theoretical Stark tuning rate is determined for acetonitrile and shown to be in satisfactory agreement with experiment. PMID:21423871

  8. The Calculation of Accurate Harmonic Frequencies of Large Molecules: The Polycyclic Aromatic Hydrocarbons, a Case Study

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Arnold, James O. (Technical Monitor)

    1996-01-01

    The vibrational frequencies and infrared intensities of naphthalene neutral and cation are studied at the self-consistent-field (SCF), second-order Moller-Plesset (MP2), and density functional theory (DFT) levels using a variety of one-particle basis sets. Very accurate frequencies can be obtained at the DFT level in conjunction with large basis sets if they are scaled with two factors, one for the C-H stretches and a second for all other modes. We also find remarkably good agreement at the B3LYP/4-31G level using only one scale factor. Unlike the neutral PAHs where all methods do reasonably well for the intensities, only the DFT results are accurate for the PAH cations. The failure of the SCF and MP2 methods is caused by symmetry breaking and an inability to describe charge delocalization. We present several interesting cases of symmetry breaking in this study. An assessment is made as to whether an ensemble of PAH neutrals or cations could account for the unidentified infrared bands observed in many astronomical sources.

  9. Rigorous formula for the fast calculation of the electron repulsion integral over the solid harmonic Gaussian-type orbitals

    NASA Astrophysics Data System (ADS)

    Ishida, Kazuhiro

    1998-07-01

    A rigorous general formula for calculating the electron repulsion integral (ERI) over the solid harmonic (SH) Gaussian-type orbitals (GTOs) can be derived. A general algorithm can be obtained from this formula named as accompanying coordinate expansion (ACE) b3k3. This algorithm is capable of computing very fast SH-ERIs, especially for SH contracted GTOs. Numerical assessment is shown for the (LL|LL) class of SH-ERIs (L=2-5). It is found that the present ACE-b3k3 algorithm is the fastest among all algorithms in the literature in the floating-point-opration (FLOP) count assessment when the degree of contraction is large.

  10. Ab initio calculation of the cross sections for electron impact vibrational excitation of CO via the 2Π shape resonance

    NASA Astrophysics Data System (ADS)

    Falcetta, Michael F.; Fair, Mark C.; Tharnish, Emily M.; Williams, Lorna M.; Hayes, Nathan J.; Jordan, Kenneth D.

    2016-03-01

    The stabilization method is used to calculate the complex potential energy curve of the 2Π state of CO- as a function of bond length, with the refinement that separate potentials are determined for p-wave and d-wave attachment and detachment of the excess electron. Using the resulting complex potentials, absolute vibrational excitation cross sections are calculated as a function of electron energy and scattering angle. The calculated cross sections agree well with experiment.

  11. Full dimensional Franck-Condon factors for the acetylene A{sup ~} {sup 1}A{sub u}—X{sup ~1}Σ{sup +}{sub g}  transition. I. Method for calculating polyatomic linear—bent vibrational intensity factors and evaluation of calculated intensities for the gerade vibrational modes in acetylene

    SciTech Connect

    Park, G. Barratt

    2014-10-07

    Franck-Condon vibrational overlap integrals for the A{sup ~1}A{sub u}—X{sup ~1}Σ{sup +}{sub g} transition in acetylene have been calculated in full dimension in the harmonic normal mode basis. The calculation uses the method of generating functions first developed for polyatomic Franck-Condon factors by Sharp and Rosenstock [J. Chem. Phys. 41(11), 3453–3463 (1964)], and previously applied to acetylene by Watson [J. Mol. Spectrosc. 207(2), 276–284 (2001)] in a reduced-dimension calculation. Because the transition involves a large change in the equilibrium geometry of the electronic states, two different types of corrections to the coordinate transformation are considered to first order: corrections for axis-switching between the Cartesian molecular frames and corrections for the curvilinear nature of the normal modes at large amplitude. The angular factor in the wave function for the out-of-plane component of the trans bending mode, ν{sub 4}{sup ″}, is treated as a rotation, which results in an Eckart constraint on the polar coordinates of the bending modes. To simplify the calculation, the other degenerate bending mode, ν{sub 5}{sup ″}, is integrated in the Cartesian basis and later transformed to the constrained polar coordinate basis, restoring the conventional v and l quantum numbers. An updated A{sup ~}-state harmonic force field obtained recently in the R. W. Field research group is evaluated. The results for transitions involving the gerade vibrational modes are in qualitative agreement with experiment. Calculated results for transitions involving ungerade modes are presented in Paper II of this series [G. B. Park, J. H. Baraban, and R. W. Field, “Full dimensional Franck–Condon factors for the acetylene A{sup ~1}A{sub u}—X{sup ~1}Σ{sup +}{sub g} transition. II. Vibrational overlap factors for levels involving excitation in ungerade modes,” J. Chem. Phys. 141, 134305 (2014)].

  12. Two-Dimensional Spectroscopy for Harmonic Vibrational Modes with Nonlinear System-Bath Interactions. II. Gaussian-Markovian Case

    NASA Astrophysics Data System (ADS)

    Tanimura, Yoshitaka; Steffen, Thomas

    2000-12-01

    The relaxation processes in a quantum system nonlinearly coupled to a harmonic Gaussian-Markovian heat bath are investigated by the quantum Fokker-Planck equation in the hierarchy form. This model describes frequency fluctuations in the quantum system with an arbitrary correlation time and thus bridges the gap between the Brownian oscillator model and the stochastic model by Anderson and Kubo. The effects of the finite correlation time and the system-bath coupling strength are studied for a harmonic model system by numerically integrating the equation of motion. The one-time correlation function of the system coordinate, which is measured in conventional Raman and infrared absorption experiments, already reflects the inhomogeneous character of the relaxation process. The finite correlation time of the frequency fluctuations, however, is directly evident only in the two- and three-time correlation function as probed by multidimensional spectroscopic techniques such as the Raman echo and the fifth-order 2D Raman experiment.

  13. Dispersion-corrected first-principles calculation of terahertz vibration, and evidence for weak hydrogen bond formation

    NASA Astrophysics Data System (ADS)

    Takahashi, Masae; Ishikawa, Yoichi; Ito, Hiromasa

    2013-03-01

    A weak hydrogen bond (WHB) such as CH-O is very important for the structure, function, and dynamics in a chemical and biological system WHB stretching vibration is in a terahertz (THz) frequency region Very recently, the reasonable performance of dispersion-corrected first-principles to WHB has been proven. In this lecture, we report dispersion-corrected first-principles calculation of the vibrational absorption of some organic crystals, and low-temperature THz spectral measurement, in order to clarify WHB stretching vibration. The THz frequency calculation of a WHB crystal has extremely improved by dispersion correction. Moreover, the discrepancy in frequency between an experiment and calculation and is 10 1/cm or less. Dispersion correction is especially effective for intermolecular mode. The very sharp peak appearing at 4 K is assigned to the intermolecular translational mode that corresponds to WHB stretching vibration. It is difficult to detect and control the WHB formation in a crystal because the binding energy is very small. With the help of the latest intense development of experimental and theoretical technique and its careful use, we reveal solid-state WHB stretching vibration as evidence for the WHB formation that differs in respective WHB networks The research was supported by the Ministry of Education, Culture, Sports, Science and Technology of Japan (Grant No. 22550003).

  14. M-shaped asymmetric nonlinear oscillator for broadband vibration energy harvesting: Harmonic balance analysis and experimental validation

    NASA Astrophysics Data System (ADS)

    Leadenham, S.; Erturk, A.

    2014-11-01

    Over the past few years, nonlinear oscillators have been given growing attention due to their ability to enhance the performance of energy harvesting devices by increasing the frequency bandwidth. Duffing oscillators are a type of nonlinear oscillator characterized by a symmetric hardening or softening cubic restoring force. In order to realize the cubic nonlinearity in a cantilever at reasonable excitation levels, often an external magnetic field or mechanical load is imposed, since the inherent geometric nonlinearity would otherwise require impractically high excitation levels to be pronounced. As an alternative to magnetoelastic structures and other complex forms of symmetric Duffing oscillators, an M-shaped nonlinear bent beam with clamped end conditions is presented and investigated for bandwidth enhancement under base excitation. The proposed M-shaped oscillator made of spring steel is very easy to fabricate as it does not require extra discrete components to assemble, and furthermore, its asymmetric nonlinear behavior can be pronounced yielding broadband behavior under low excitation levels. For a prototype configuration, linear and nonlinear system parameters extracted from experiments are used to develop a lumped-parameter mathematical model. Quadratic damping is included in the model to account for nonlinear dissipative effects. A multi-term harmonic balance solution is obtained to study the effects of higher harmonics and a constant term. A single-term closed-form frequency response equation is also extracted and compared with the multi-term harmonic balance solution. It is observed that the single-term solution overestimates the frequency of upper saddle-node bifurcation point and underestimates the response magnitude in the large response branch. Multi-term solutions can be as accurate as time-domain solutions, with the advantage of significantly reduced computation time. Overall, substantial bandwidth enhancement with increasing base excitation is

  15. Calculation of specific, highly excited vibrational states based on a Davidson scheme: application to HFCO.

    PubMed

    Iung, Christophe; Ribeiro, Fabienne

    2005-11-01

    We present the efficiency of a new modified Davidson scheme which yields selectively one high-energy vibrationally excited eigenstate or a series of eigenstates. The calculation of a highly vibrationally excited state psi located in a dense part of the spectrum requires a specific prediagonalization step before the Davidson scheme. It consists in building a small active space P containing the zero-order states which are coupled with the zero-order description of the eigenstate of interest. We propose a general way to define this active space P which plays a crucial role in the method. The efficiency of the method is illustrated by computing and analyzing the high-energy excited overtones of the out-of-plane mode [formula: see text] in HFCO. These overtone energies correspond to the 234th, 713th, and 1774th energy levels in our reference basis set which contains roughly 140,000 states. One of the main advantages of this Davidson scheme comes from the fact that the eigenstate and eigenvalue convergence can be assessed during the iterations by looking at the residual [formula: see text]. The maximum value epsilon allowed for this residual constitutes a very sensitive and efficient parameter which sets the accuracy of the eigenvalues and eigenstates, even when the studied states are highly excited and are localized in a dense part of the spectrum. The physical analysis of the eigenstates associated with the 5th, 7th, and 9th out-of-plane overtones in HFCO provides some interesting information on the energy localization in this mode and on the role played by the in-plane modes. Also, it provides some ideas on the numerical methods which should be developed in the future to tackle higher-energy excited states in polyatomics. PMID:16375515

  16. Calculation of the structures, stabilities, and vibrational spectra of arsenites, thioarsenites and thioarsenates in aqueous solution

    NASA Astrophysics Data System (ADS)

    Tossell, J. A.; Zimmermann, M. D.

    2008-11-01

    Structures, stabilities and vibrational spectra have been calculated using molecular quantum mechanical methods for As(OH) 3, AsO(OH) 3, As(SH) 3, AsS(SH) 3 and their conjugate bases and for several species with partial substitution of S for O. Properties for the neutral gas-phase molecules are calculated with state-of-the-art methods which yield As sbnd L distances within 0. 01 Å and As sbnd L stretching frequencies within 10 cm -1 of experiment. Similar accuracy is obtained for neutral molecules in solution using a polarizable continuum model (PCM). For monoanions such as AsO(OH)2- and AsS(SH)2-1 frequencies can be calculated to within 20 cm -1 of experiment using the polarizable continuum model. Multiply charged anions remain a challenge for accurate frequency calculations, but we have obtained results within the PCM model which at least semiquantitatively reproduce the available data. This allows us to assign the controversial features D, E and F in the Raman data of (Wood S. A., Tait C. D. and Janecky D. R. (2002) A Raman spectroscopic study of arsenite and thioarsenite species in aqueous solution at 25 °C. Geochem. Trans. 3, 31-39). To help in the assignment of the arsenic sulfide spectra we have also calculated energetics for the oxidation of As(III) to As(V) compounds by polysulfides, disproportionation of As(III) compounds and for the dissociation of the oxo- and thio-acids. We have determined that As(III) oxyacids can be transformed to thioacids which can in turn be oxidized to As(V) sulfides by polysulfides and that the p Ka1s of the acids involved can be ordered as follows: AsS(SH) 3 < As(SH) 3 < AsO(OH) 3 < As(OH) 3 in order of increasing p Ka1. We have also established from the calculated energies that the most stable form of the As(III) oxyacid in acidic aqueous solution is indeed As(OH) 3, consistent with previous assignments.

  17. XP-PCM Calculations of High Pressure Structural and Vibrational Properties of P4S3.

    PubMed

    Pagliai, Marco; Cammi, Roberto; Cardini, Gianni; Schettino, Vincenzo

    2016-07-14

    The structure and the vibrational properties of the P4S3 crystal at high pressures are discussed by application of the XP-PCM method. The vibrational assignment has been clarified. The structure and the electron distribution changes as a function of pressure are analyzed. The pressure effect on the vibrational frequencies is satisfactorily reproduced and discussed in terms of confinement and structure relaxation contributions. PMID:26943701

  18. Conformational analysis from low-frequency vibrational data and ab initio calculations for 3-chloropropene

    NASA Astrophysics Data System (ADS)

    Durig, J. R.; Durig, D. T.; Jalilian, M. R.; Zhen, Mengzhang; Little, T. S.

    1989-03-01

    The asymmetric torsion of 3-chloropropene, CH 2CHCH 2Cl, has been investigated by far-infrared and Raman spectra of the gas and the low-frequency Raman spectrum of the liquid at various temperatures. Both the gauche and cis (halogen to double bond) conformers are present in the fluid phases at ambient temperature and the gauche isomer is the predominant form in the liquid. The asymmetric torsion of the cis rotamer is observed in the far-infrared spectrum of the gas at 147.28 cm -1 with four accompanying "hot bands" and the corresponding fundamental of the gauche conformer is observed at 101.97 cm -1 also with four "hot bands". From these data, a potential function governing the internal rotation of the asymmetric top has been determined with potential constants of: V1 = -47±19, V2 = 145±17, V3 = 862±8, V4 = 14±6, V6 = -50±4 cm -1. This potential function is consistent with the cis form being thermodynamically preferred by 81 cm -1 (0.23 kcal mol -1), and a torsional dihedral angle of 122° for the gauche conformer away from the cis form. The calculated cis to gauche, gauche to gauche, and gauche to cis barriers are 969 cm -1 (2.77 kcal mol -1), 734 cm -1 (2.10 kcal mol -1) and 888 cm -1 (2.54 kcal mol -1), respectively. From relative intensities of the Raman lines of the liquid at 245 ( cis) and 289 ( gauche) cm -1 as a function of temperature, the enthalpy difference was found to be 178±11 cm -1 (509±31 cal mol -1) with the gauche form being more stable. The normal vibrations for both the cis and gauche rotamers have been calculated by ab initio Hartree-Fock gradient calculations employing the 3-21G* basis set. The calculated frequencies and force constants are compared to those previously reported. Potential surface calculations and structural determinations have been carried out employing both the 3-21G* and 6-31G* basis sets and compared to those obtained experimentally. These results are compared to similar quantities in some related molecules.

  19. Ab initio calculations of the vibrational and dielectric properties of PbSnTe alloys

    NASA Astrophysics Data System (ADS)

    Scolfaro, Luisa; Rezende Neto, A. R.; Leite Alves, H. W.; Petersen, J. E.; Myers, T. H.; Borges, P. D.

    Thermoelectric devices have promise in dealing with the challenges of the growing demand for alternative clean energy and Te-based materials well-known candidates for them. Recently, we have shown that the high values for the dielectric constant, together with anharmonic LA-TO coupling, reduces the lattice thermal conductivity and enhances the electronic conductivity in PbTe. Also, it was shown that by alloying this material with Se, the electronic conductivity of the alloys is also enhanced. But, it is not clear if the same occurs when alloying with Sn. We show, in this work, our ab initio results for the vibrational and dielectric properties of Pb1-xSnxTe alloys. The calculations were carried out by using the Density Functional Theory, and the alloys were described by both the Virtual Crystal Approximation and Cluster Expansion Method. Our results show that the anharmonic LA-TO coupling enhances and reach its maximum for Sn concentration values of 0.75, corresponding to the maximum value for the dielectric constant, which is higher than that obtained for PbTe

  20. Benchmark Structures and Harmonic Vibrational Frequencies Near the CCSD(T) Complete Basis Set Limit for Small Water Clusters: (H2O)n = 2, 3, 4, 5, 6.

    PubMed

    Howard, J Coleman; Tschumper, Gregory S

    2015-05-12

    A series of (H2O)n clusters ranging from the dimer to the hexamer have been characterized with the CCSD(T) and the 2-body:Many-body CCSD(T):MP2 methods near the complete basis set (CBS) limit to generate benchmark-quality optimized structures and harmonic vibrational frequencies for these important systems. Quadruple-ζ correlation-consistent basis sets that augment the O atoms with diffuse functions have been employed in the analytic computation of harmonic vibrational frequencies for the global minima of the dimer, trimer, tetramer, and pentamer as well as the ring, book, cage, and prism isomers of the hexamer. Prior calibration [J. Chem. Phys. 2013, 139, 184113 and J. Chem. Theory Comput. 2014, 10, 5426] suggests that harmonic frequencies computed with this approach will lie within a few cm(-1) of the canonical CCSD(T) CBS limit. These data are used as reference values to gauge the performance of harmonic frequencies obtained with other ab initio methods (e.g., LCCSD(T) and MP2) and water potentials (e.g., TTM3-F and WHBB). This comparison reveals that it is far more challenging to converge harmonic vibrational frequencies for the bound OH stretching modes in these (H2O)n clusters to the CCSD(T) CBS limit than the free OH stretches, the n intramonomer HOH bending modes and even the 6n - 6 intermonomer modes. Deviations associated with the bound OH stretching harmonic frequencies increase rapidly with the size of the cluster for all methods and potentials examined, as do the corresponding frequency shifts relative to the monomer OH stretches. PMID:26574415

  1. Calculated vibrational populations of O2 Herzberg states in the mixture of CO2, CO, N2, O2 gases

    NASA Astrophysics Data System (ADS)

    Kirillov, A. S.

    2014-05-01

    Calculated in (Kirillov, 2014) constants are applied for simulations of vibrational populations of Herzberg states in mixtures of O2 with CO2, CO, N2 gases for laboratory conditions. Results show very important role of electronic-vibrational processes in redistribution of electronic excitation energy among vibrational levels. It is shown that the interaction between O2(A‧3Δu) and O2 causes effective production O2(c1Σu-,v = 0) observed in laboratory conditions. The inclusion of the interaction between O2(A‧3Δu) and CO2 molecules may explain high intensities of Herzberg II system observed in laboratory experiments with high CO2 concentrations and registered in the nightglow of Venusian atmosphere.

  2. DFT and ab initio calculations of the vibrational frequencies and visible spectra of triazenes derived from cyclic amines

    NASA Astrophysics Data System (ADS)

    Dabbagh, Hossein A.; Teimouri, Abbas; Chermahini, Alireza Najafi; Shiasi, Rezvan

    2007-06-01

    We present a detailed analysis of the structural, infrared spectra and visible spectra of the 4-substituted aminoazo-benzenesulfonyl azides. The preparation of 4-sulfonyl azide benzenediazonium chloride with cyclic amines of various ring sizes (pyrrolidine, piperidine, 4-methylpiperidine, N-methylpiperazine, morpholine and hexamethyleneimine) have been investigated theoretically by performing HF and DFT levels of theory using the standard 6-31G* basis set. The optimized geometries and calculated vibrational frequencies are evaluated via comparison with experimental values. The vibrational spectral data obtained from solid phase FT-IR spectra are assigned modes based on the results of the theoretical calculations. The observed spectra are found to be in good agreement with the calculations.

  3. A unified scheme for the calculation of differentiated and undifferentiated molecular integrals over solid-harmonic Gaussians.

    PubMed

    Reine, Simen; Tellgren, Erik; Helgaker, Trygve

    2007-09-14

    Utilizing the fact that solid-harmonic combinations of Cartesian and Hermite Gaussian atomic orbitals are identical, a new scheme for the evaluation of molecular integrals over solid-harmonic atomic orbitals is presented, where the integration is carried out over Hermite rather than Cartesian atomic orbitals. Since Hermite Gaussians are defined as derivatives of spherical Gaussians, the corresponding molecular integrals become the derivatives of integrals over spherical Gaussians, whose transformation to the solid-harmonic basis is performed in the same manner as for integrals over Cartesian Gaussians, using the same expansion coefficients. The presented solid-harmonic Hermite scheme simplifies the evaluation of derivative molecular integrals, since differentiation by nuclear coordinates merely increments the Hermite quantum numbers, thereby providing a unified scheme for undifferentiated and differentiated four-center molecular integrals. For two- and three-center two-electron integrals, the solid-harmonic Hermite scheme is particularly efficient, significantly reducing the cost relative to the Cartesian scheme. PMID:17712455

  4. A calculation method for torsional vibration of a crankshafting system with a conventional rubber damper by considering rubber form

    SciTech Connect

    Kodama, Tomoaki; Honda, Yasuhiro; Wakabayashi, Katsuhiko; Iwamoto, Shoichi

    1996-09-01

    The cheap and compact rubber dampers of shear-type have been widely employed as the torsional vibration control of the crankshaft system of high-speed, automobile diesel engines. The conventional rubber dampers have various rubber forms owing to the thorough investigation of optimum dampers in the design stage. Their rubber forms can be generally grouped into three classes such as the disk type, the bush type and the composite type. The disk type and the bush type rubber dampers are called the basic-pattern rubber dampers hereafter. The composite type rubber part is supposed to consist of the disk type and the bush type parts, regarded respectively as the basic patterns of the rubber part, at large. The dynamic characteristics of the vibration isolator rubber depend generally on temperature, frequency, strain amplitude, shape and size effect,s so it is difficult to estimate accurately their characteristics. With the present technical level, it is also difficult to determine the suitable rubber geometry which optimizes the vibration control effect. The study refers to the calculation method of the torsional vibration of a crankshaft system with a shear-type rubber damper having various rubber forms in order to offer the useful method for optimum design. In this method, the rheological formula of the three-element Maxwell model, from which the torsional stiffness and the damping coefficient of the damper rubber part in the equivalent vibration system are obtained, are adopted in order to decide the dynamic characteristics of the damper rubber part.

  5. Nuclear magnetic resonance, vibrational spectroscopic studies, physico-chemical properties and computational calculations on (nitrophenyl) octahydroquinolindiones by DFT method.

    PubMed

    Pasha, M A; Siddekha, Aisha; Mishra, Soni; Azzam, Sadeq Hamood Saleh; Umapathy, S

    2015-02-01

    In the present study, 2'-nitrophenyloctahydroquinolinedione and its 3'-nitrophenyl isomer were synthesized and characterized by FT-IR, FT-Raman, (1)H NMR and (13)C NMR spectroscopy. The molecular geometry, vibrational frequencies, (1)H and (13)C NMR chemical shift values of the synthesized compounds in the ground state have been calculated by using the density functional theory (DFT) method with the 6-311++G (d,p) basis set and compared with the experimental data. The complete vibrational assignments of wave numbers were made on the basis of potential energy distribution using GAR2PED programme. Isotropic chemical shifts for (1)H and (13)C NMR were calculated using gauge-invariant atomic orbital (GIAO) method. The experimental vibrational frequencies, (1)H and (13)C NMR chemical shift values were found to be in good agreement with the theoretical values. On the basis of vibrational analysis, molecular electrostatic potential and the standard thermodynamic functions have been investigated. PMID:25440584

  6. Full Dimensional Vibrational Calculations for Methane Using AN Accurate New AB Initio Based Potential Energy Surface

    NASA Astrophysics Data System (ADS)

    Majumder, Moumita; Dawes, Richard; Wang, Xiao-Gang; Carrington, Tucker; Li, Jun; Guo, Hua; Manzhos, Sergei

    2014-06-01

    New potential energy surfaces for methane were constructed, represented as analytic fits to about 100,000 individual high-level ab initio data. Explicitly-correlated multireference data (MRCI-F12(AE)/CVQZ-F12) were computed using Molpro [1] and fit using multiple strategies. Fits with small to negligible errors were obtained using adaptations of the permutation-invariant-polynomials (PIP) approach [2,3] based on neural-networks (PIP-NN) [4,5] and the interpolative moving least squares (IMLS) fitting method [6] (PIP-IMLS). The PESs were used in full-dimensional vibrational calculations with an exact kinetic energy operator by representing the Hamiltonian in a basis of products of contracted bend and stretch functions and using a symmetry adapted Lanczos method to obtain eigenvalues and eigenvectors. Very close agreement with experiment was produced from the purely ab initio PESs. References 1- H.-J. Werner, P. J. Knowles, G. Knizia, 2012.1 ed. 2012, MOLPRO, a package of ab initio programs. see http://www.molpro.net. 2- Z. Xie and J. M. Bowman, J. Chem. Theory Comput 6, 26, 2010. 3- B. J. Braams and J. M. Bowman, Int. Rev. Phys. Chem. 28, 577, 2009. 4- J. Li, B. Jiang and Hua Guo, J. Chem. Phys. 139, 204103 (2013). 5- S Manzhos, X Wang, R Dawes and T Carrington, JPC A 110, 5295 (2006). 6- R. Dawes, X-G Wang, A.W. Jasper and T. Carrington Jr., J. Chem. Phys. 133, 134304 (2010).

  7. On quadrupole vibrations in nearly spherical nuclei

    NASA Astrophysics Data System (ADS)

    Yates, S. W.

    2012-09-01

    A new understanding of low-lying quadrupole vibrations in nuclei is emerging through lifetime measurements performed with fast neutrons at the accelerator laboratory of the University of Kentucky in combination with high-sensitivity measurements with other probes. In the stable cadmium nuclei, which have long been considered to be the best examples of vibrational behavior, we find that many E2 transition probabilities are well below harmonic vibrator expectations, and the B(E2)s cannot be explained with calculations incorporating configuration mixing between vibrational phonon states and intruder excitations. These data place severe limits on the collective models, and it is suggested that the low-lying levels of the Cd isotopes may not be of vibrational origin. An additional example of an apparent quadrupole vibrational nucleus, 62Ni, is considered.

  8. Vibrational spectrum of p-fluoroanisole in the first excited state (S 1) and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Xiao, Daoqing; Yu, Dan; Xu, Xiling; Yu, Zijun; Du, Yikui; Gao, Zhen; Zhu, Qihe; Zhang, Cunhao

    2008-06-01

    The vibronic structure of p-fluoroanisole in the first excited state (S 1) has been investigated with mass selected resonance-enhanced two photon ionization spectroscopy. The band origin of S 1 ← S 0 transition of p-fluoroanisole is measured to be 35149 cm -1, which is red-shifted by 1234 cm -1 with respect to that of anisole. Combining with the ab initio calculations, the measured frequencies 397, 487, 559, 840 and 1150 cm -1 in the S 1 state are assigned as the in-plane ring vibrational mode 9 b, 6 a, 6 b, 1 and 9 a, respectively. The optimized molecular geometries and vibrational frequencies of p-fluoroanisole in the ground state (S 0) and cation ground state (D 0) are also achieved from DFT calculations.

  9. Structural and vibrational properties of α-MoO3 from van der Waals corrected density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Ding, Hong; Ray, Keith G.; Ozolins, Vidvuds; Asta, Mark

    2012-01-01

    Structural and vibrational properties of α-MoO3 are studied employing two recently proposed methodologies for incorporating van der Waals (vdW) contributions in density functional theory (DFT) based calculations. The DFT-D2 [S. Grimme, J. Comput. Chem.JCCHDD0192-865110.1002/jcc.20495 27, 1787 (2006)] and optB88 vdW-DFT [J. Klimeš , J. Phys.: Condens. MatterPRBMDO0953-898410.1088/0953-8984/22/2/022201 22, 022201 (2010)] methods are shown to give rise to increased accuracy in predicted lattice parameters, relative to conventional DFT methods. Calculated vibrational frequencies agree with measurements to within 5% and 10% for modes involving bonded and nonbonded interactions in this compound, respectively.

  10. DFT studies on the vibrational and electronic spectra of acetylsalicylic acid

    NASA Astrophysics Data System (ADS)

    Ye, Yunfeng; Tang, Guodong; Han, Yonghong; Culnane, Lance F.; Zhao, Jianyin; Zhang, Yu

    2016-05-01

    The following is a theoretical and experimental study on the vibrational and electronic properties of acetylsalicylic acid (ASA). Vibrational information was obtained by FT-IR and Raman spectroscopy which agree well with harmonic vibrational frequency calculations. The calculations were carried out using density functional theory B3LYP methods with 6-311G** and LANL2DZ basis sets. The vibrational assignments were calculated by Gaussview. Absorption UV-Vis experiments of ASA reveal three maximum peaks at 203, 224 and 277 nm, which are in agreement with calculated electronic transitions using TD-B3LYP/6-311G**.

  11. Thermal properties of molecular crystals through dispersion-corrected quasi-harmonic ab initio calculations: the case of urea.

    PubMed

    Erba, Alessandro; Maul, Jefferson; Civalleri, Bartolomeo

    2016-01-31

    An ab initio quantum-mechanical theoretical framework is presented to compute the thermal properties of molecular crystals. The present strategy combines dispersion-corrected density-functional-theory (DFT-D), harmonic phonon dispersion, quasi-harmonic approximation to the lattice dynamics for thermal expansion and thermodynamic functions, and quasi-static approximation for anisotropic thermo-elasticity. The proposed scheme is shown to reliably describe thermal properties of the urea molecular crystal by a thorough comparison with experimental data. PMID:26670006

  12. Phase separation of full-Heusler nanostructures in half-Heusler thermoelectrics and vibrational properties from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Page, Alexander; Uher, Ctirad; Poudeu, Pierre Ferdinand; Van der Ven, Anton

    2015-11-01

    Previous studies have indicated that the figure of merit (ZT ) of half-Heusler (HH) alloys with composition M NiSn (M =Ti , Zr, or Hf) is greatly enhanced when the alloys contain a nano-scale full-Heusler (FH) MN i2Sn second phase. However, the formation mechanism of the FHnanostructures in the HH matrix and their vibrational properties are still not well understood. We report on first-principles studies of thermodynamic phase equilibria in the MNiSn-MN i2Sn pseudobinary system as well as HH and FH vibrational properties. Thermodynamic phase diagrams as functions of temperature and Ni concentration were developed using density functional theory (DFT) combined with a cluster expansion and Monte Carlo simulations. The phase diagrams show very low excess Ni solubility in HH alloys even at high temperatures, which indicates that any Ni excess will decompose into a two-phase mixture of HH and FH compounds. Vibrational properties of HH and FH alloys are compared. Imaginary vibrational modes in the calculated phonon dispersion diagram of TiN i2Sn indicate a dynamical instability with respect to cubic [001] transverse acoustic modulations. Displacing atoms along unstable vibrational modes in cubic TiN i2Sn reveals lower-energy structures with monoclinic symmetry. The energy of the monoclinic structures is found to depend strongly on the lattice parameter. The origin of the instability in cubic TiN i2Sn and its absence in cubic ZrN i2Sn and HfN i2Sn is attributed to the small size of the Ti 3 d shells compared to those of Zr and Hf atoms. Lattice constants and heat capacities calculated by DFT agree well with experiment.

  13. Studies on vibrational, NMR spectra and quantum chemical calculations of N-Succinopyridine: An organic nonlinear optical material

    NASA Astrophysics Data System (ADS)

    Kannan, V.; Thirupugalmani, K.; Brahadeeswaran, S.

    2013-10-01

    Single crystals of N-Succinopyridine (NSP) have been grown from water using solution growth method by isothermal solvent evaporation technique. The solid state Fourier Transform Infrared (FTIR) spectrum of the grown crystal shows a broad absorption extending from 3450 down to 400 cm-1, due to H-bond vibrations and other characteristic vibrations. Fourier Transform Raman (FT-Raman) spectrum of NSP single crystal shows Raman intensities ranging from 3100 to 100 cm-1 due the characteristics vibrations of functional groups present in NSP. The proton and carbon positions of NSP have been described by 1H and 13C NMR spectrum respectively. Ab initio quantum chemical calculations on NSP have been performed by density functional theory (DFT) calculations using B3LYP method with 6-311++G(d,p) basis set. The predicted first hyperpolarizability is found to be 1.29 times greater than that of urea and suggests that the title compound could be an attractive material for nonlinear optical applications. The calculated HOMO-LUMO energies show that charge transfers occur within the molecule and other related molecular properties. Molecular properties such as Mulliken population analysis, thermodynamic functions and perturbation theory energy analysis have also been reported. Electrostatic potential map (ESP) of NSP obtained by electron density isosurface provided the information about the size, shape, charge density distribution and site of chemical reactivity of the title molecule. The molecular stability and bond strength have been investigated through the Natural Bond Orbital (NBO) analysis.

  14. Structural, vibrational, and quasiparticle band structure of 1,1-diamino-2,2-dinitroethelene from ab initio calculations

    SciTech Connect

    Appalakondaiah, S.; Vaitheeswaran, G.; Lebègue, S.

    2014-01-07

    The effects of pressure on the structural and vibrational properties of the layered molecular crystal 1,1-diamino-2,2-dinitroethelene (FOX-7) are explored by first principles calculations. We observe significant changes in the calculated structural properties with different corrections for treating van der Waals interactions to Density Functional Theory (DFT), as compared with standard DFT functionals. In particular, the calculated ground state lattice parameters, volume and bulk modulus obtained with Grimme's scheme, are found to agree well with experiments. The calculated vibrational frequencies demonstrate the dependence of the intra and inter-molecular interactions on FOX-7 under pressure. In addition, we also found a significant increment in the N–H...O hydrogen bond strength under compression. This is explained by the change in bond lengths between nitrogen, hydrogen, and oxygen atoms, as well as calculated IR spectra under pressure. Finally, the computed band gap is about 2.3 eV with generalized gradient approximation, and is enhanced to 5.1 eV with the GW approximation, which reveals the importance of performing quasiparticle calculations in high energy density materials.

  15. An ab initio calculation of the rotational-vibrational energies in the electronic ground state of NH2

    NASA Astrophysics Data System (ADS)

    Jensen, Per; Buenker, Robert J.; Hirsch, Gerhard; Rai, Sachchida N.

    We have calculated ab initio the three-dimensional potential-energy surface of the NH2 molecule at 145 nuclear geometries spanning energy ranges of about 18 000 cm-1 for the NH stretch and 12 000 cm-1 for the bend. The ab initio configuration-interaction calculations were done using the multireference MRD-CI method. The calculated equilibrium configuration has NH bond length re = 1·0207 Å and bond angle α = 103·1°. The rotational-vibrational energies for 14NH2, 14NHD and 14ND2 were calculated variationally using the Morse-oscillator rigid-bender internal-dynamics Hamiltonian. For 14NH2 we calculate that υ1 = 3267 (3219) cm-1, υ2 = 1462 (1497) cm-1 and υ3 = 3283 (3301) cm-1, where experimental values are given in parentheses.

  16. Conformational and isomerizational studies of 3- N, N-dimethylhydrazino-2-methylsulfonyl propenenitrile using NMR and vibrational spectra, X-ray analysis and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Gróf, M.; Gatial, A.; Milata, V.; Prónayová, N.; Kožíšek, J.; Breza, M.; Matějka, P.

    2008-11-01

    The IR, Raman and NMR spectra of 3- N, N-dimethylhydrazino-2-methylsulfonyl propenenitrile (DMHSP) [(H 3C) 2N sbnd NH sbnd CH dbnd C(CN) (SO 2CH 3)] as a solid and in different solvents were measured. The spectra and X-ray analysis revealed that DMHSP was prepared as a pure E-isomer and E- syn conformer with the syn orientation of N, N-dimethylhydrazino group towards the C dbnd C double bond in the solid state. Due to the low barrier practically free isomerization process occurred in solutions at room temperature. DMHSP exists in more polar solvents as pure E-isomer in conformational equilibrium between E- syn and E- anti but in a less polar solvent the presence of Z-isomer was observed as well. From the IR and NMR temperature dependence spectra in polar solvents the energy difference between E- anti and E- syn of Δ H = 2.3 ± 0.9 kJ/mol and Δ H = 3.2 ± 0.4 kJ/mol, respectively, was estimated with the syn one being more stable. The geometries and relative energies of possible conformers of DMHSP were evaluated using ab initio MP2 and B3LYP density functional methods in 6-31G ∗∗ basis set and compared with the X-ray data. The interpretation of NMR spectra was supported by ab initio MP2 calculations. The influence of solvent polarity on the conformational equilibrium is discussed with respect to the SCRF solvent effect calculations using PCM model. In addition, the observed IR and Raman bands were compared also with harmonic vibrational frequencies, calculated on the same levels of theory, and assigned on the base of potential energy distribution.

  17. Scaled Quantum Mechanical scale factors for vibrational calculations using alternate polarized and augmented basis sets with the B3LYP density functional calculation model

    NASA Astrophysics Data System (ADS)

    Legler, C. R.; Brown, N. R.; Dunbar, R. A.; Harness, M. D.; Nguyen, K.; Oyewole, O.; Collier, W. B.

    2015-06-01

    The Scaled Quantum Mechanical (SQM) method of scaling calculated force constants to predict theoretically calculated vibrational frequencies is expanded to include a broad array of polarized and augmented basis sets based on the split valence 6-31G and 6-311G basis sets with the B3LYP density functional. Pulay's original choice of a single polarized 6-31G(d) basis coupled with a B3LYP functional remains the most computationally economical choice for scaled frequency calculations. But it can be improved upon with additional polarization functions and added diffuse functions for complex molecular systems. The new scale factors for the B3LYP density functional and the 6-31G, 6-31G(d), 6-31G(d,p), 6-31G+(d,p), 6-31G++(d,p), 6-311G, 6-311G(d), 6-311G(d,p), 6-311G+(d,p), 6-311G++(d,p), 6-311G(2d,p), 6-311G++(2d,p), 6-311G++(df,p) basis sets are shown. The double d polarized models did not perform as well and the source of the decreased accuracy was investigated. An alternate system of generating internal coordinates that uses the out-of plane wagging coordinate whenever it is possible; makes vibrational assignments via potential energy distributions more meaningful. Automated software to produce SQM scaled vibrational calculations from different molecular orbital packages is presented.

  18. Terahertz spectroscopy and solid-state density functional theory calculation of anthracene: Effect of dispersion force on the vibrational modes

    SciTech Connect

    Zhang, Feng; Tominaga, Keisuke E-mail: tominaga@kobe-u.ca.jp; Hayashi, Michitoshi E-mail: tominaga@kobe-u.ca.jp Wang, Houng-Wei; Kambara, Ohki; Sasaki, Tetsuo; Nishizawa, Jun-ichi E-mail: tominaga@kobe-u.ca.jp

    2014-05-07

    The phonon modes of molecular crystals in the terahertz frequency region often feature delicately coupled inter- and intra-molecular vibrations. Recent advances in density functional theory such as DFT-D{sup *} have enabled accurate frequency calculation. However, the nature of normal modes has not been quantitatively discussed against experimental criteria such as isotope shift (IS) and correlation field splitting (CFS). Here, we report an analytical mode-decoupling method that allows for the decomposition of a normal mode of interest into intermolecular translation, libration, and intramolecular vibrational motions. We show an application of this method using the crystalline anthracene system as an example. The relationship between the experimentally obtained IS and the IS obtained by PBE-D{sup *} simulation indicates that two distinctive regions exist. Region I is associated with a pure intermolecular translation, whereas region II features coupled intramolecular vibrations that are further coupled by a weak intermolecular translation. We find that the PBE-D{sup *} data show excellent agreement with the experimental data in terms of IS and CFS in region II; however, PBE-D{sup *} produces significant deviations in IS in region I where strong coupling between inter- and intra-molecular vibrations contributes to normal modes. The result of this analysis is expected to facilitate future improvement of DFT-D{sup *}.

  19. Conformational stability, barriers to internal rotation, vibrational assignment, and ab initio calculations of chloroacetyl fluoride

    NASA Astrophysics Data System (ADS)

    Durig, J. R.; Zhao, Wenyun; Lewis, Durig; Little, T. S.

    1988-08-01

    The far infrared spectrum of gaseous chloroacetyl fluoride, CH2ClC(O)F, has been recorded at a resolution of 0.10 cm-1 in the 350 to 35 cm-1 region. The fundamental asymmetric torsional frequencies of the more stable trans (two halogen atoms oriented trans to one another) and high energy gauche (Cl-C-C=O torsional dihedral angle of 122°) have been observed at 86.5 and 48.8 cm-1, respectively, each with excited states falling to lower frequency. From these data the asymmetric torsional potential function governing internal rotation about the C-C bond has been determined. This potential function is consistent with torsional potential coefficients of: V1=350±12, V2=306±6, V3=420±1, V4=44±1, and V6=2±1 cm-1. The trans to gauche, gauche to gauche, and gauche to trans barriers have been determined to be 796, 245, and 271 cm-1, respectively, with an energy difference between the conformations of 525±24 cm-1 (1.50±0.07 kcal/mol). From studies of the Raman spectrum at variable temperatures the conformational energy difference has been determined to be 445±80 (1.27±0.2 kcal/mol) and 534±68 cm-1 (1.53±0.2 kcal/mol) for the gaseous and liquid phases, respectively. A complete assignment of the vibrational fundamentals observed from the infrared (3500 to 50 cm-1) spectra of the gaseous and solid states and Raman (3200 to 10 cm-1) spectra of the gaseous, liquid, and solid states is proposed. All of these data are compared to the corresponding quantities obtained from ab initio Hartree-Fock gradient calculations employing both the 3-21G* and 6-31G* basis sets. Additionally, complete equilibrium geometries have been determined for both rotamers. The results are discussed and compared with the corresponding quantities obtained for some similar molecules.

  20. Quantum mechanical calculation of electric fields and vibrational Stark shifts at active site of human aldose reductase

    SciTech Connect

    Wang, Xianwei; Zhang, John Z. H.; He, Xiao

    2015-11-14

    Recent advance in biophysics has made it possible to directly measure site-specific electric field at internal sites of proteins using molecular probes with C = O or C≡N groups in the context of vibrational Stark effect. These measurements directly probe changes of electric field at specific protein sites due to, e.g., mutation and are very useful in protein design. Computational simulation of the Stark effect based on force fields such as AMBER and OPLS, while providing good insight, shows large errors in comparison to experimental measurement due to inherent difficulties associated with point charge based representation of force fields. In this study, quantum mechanical calculation of protein’s internal electrostatic properties and vibrational Stark shifts was carried out by using electrostatically embedded generalized molecular fractionation with conjugate caps method. Quantum calculated change of mutation-induced electric field and vibrational Stark shift is reported at the internal probing site of enzyme human aldose reductase. The quantum result is in much better agreement with experimental data than those predicted by force fields, underscoring the deficiency of traditional point charge models describing intra-protein electrostatic properties.

  1. First-principles calculations of the electronic, vibrational, and elastic properties of the magnetic laminate Mn₂GaC

    SciTech Connect

    Thore, A. Dahlqvist, M. E-mail: bjoal@ifm.liu.se Alling, B. E-mail: bjoal@ifm.liu.se Rosén, J. E-mail: bjoal@ifm.liu.se

    2014-09-14

    In this paper, we report the by first-principles predicted properties of the recently discovered magnetic MAX phase Mn₂GaC. The electronic band structure and vibrational dispersion relation, as well as the electronic and vibrational density of states, have been calculated. The band structure close to the Fermi level indicates anisotropy with respect to electrical conductivity, while the distribution of the electronic and vibrational states for both Mn and Ga depend on the chosen relative orientation of the Mn spins across the Ga sheets in the Mn–Ga–Mn trilayers. In addition, the elastic properties have been calculated, and from the five elastic constants, the Voigt bulk modulus is determined to be 157 GPa, the Voigt shear modulus 93 GPa, and the Young's modulus 233 GPa. Furthermore, Mn₂GaC is found relatively elastically isotropic, with a compression anisotropy factor of 0.97, and shear anisotropy factors of 0.9 and 1, respectively. The Poisson's ratio is 0.25. Evaluated elastic properties are compared to theoretical and experimental results for M₂AC phases where M = Ti, V, Cr, Zr, Nb, Ta, and A = Al, S, Ge, In, Sn.

  2. Quantum mechanical calculation of electric fields and vibrational Stark shifts at active site of human aldose reductase.

    PubMed

    Wang, Xianwei; Zhang, John Z H; He, Xiao

    2015-11-14

    Recent advance in biophysics has made it possible to directly measure site-specific electric field at internal sites of proteins using molecular probes with C = O or C≡N groups in the context of vibrational Stark effect. These measurements directly probe changes of electric field at specific protein sites due to, e.g., mutation and are very useful in protein design. Computational simulation of the Stark effect based on force fields such as AMBER and OPLS, while providing good insight, shows large errors in comparison to experimental measurement due to inherent difficulties associated with point charge based representation of force fields. In this study, quantum mechanical calculation of protein's internal electrostatic properties and vibrational Stark shifts was carried out by using electrostatically embedded generalized molecular fractionation with conjugate caps method. Quantum calculated change of mutation-induced electric field and vibrational Stark shift is reported at the internal probing site of enzyme human aldose reductase. The quantum result is in much better agreement with experimental data than those predicted by force fields, underscoring the deficiency of traditional point charge models describing intra-protein electrostatic properties. PMID:26567650

  3. Quantum mechanical calculation of electric fields and vibrational Stark shifts at active site of human aldose reductase

    NASA Astrophysics Data System (ADS)

    Wang, Xianwei; Zhang, John Z. H.; He, Xiao

    2015-11-01

    Recent advance in biophysics has made it possible to directly measure site-specific electric field at internal sites of proteins using molecular probes with C = O or C≡N groups in the context of vibrational Stark effect. These measurements directly probe changes of electric field at specific protein sites due to, e.g., mutation and are very useful in protein design. Computational simulation of the Stark effect based on force fields such as AMBER and OPLS, while providing good insight, shows large errors in comparison to experimental measurement due to inherent difficulties associated with point charge based representation of force fields. In this study, quantum mechanical calculation of protein's internal electrostatic properties and vibrational Stark shifts was carried out by using electrostatically embedded generalized molecular fractionation with conjugate caps method. Quantum calculated change of mutation-induced electric field and vibrational Stark shift is reported at the internal probing site of enzyme human aldose reductase. The quantum result is in much better agreement with experimental data than those predicted by force fields, underscoring the deficiency of traditional point charge models describing intra-protein electrostatic properties.

  4. Full-dimensional vibrational calculations for H5O2+ using an ab initio potential energy surface

    NASA Astrophysics Data System (ADS)

    McCoy, Anne B.; Huang, Xinchuan; Carter, Stuart; Landeweer, Marc Y.; Bowman, Joel M.

    2005-02-01

    We report quantum diffusion Monte Carlo (DMC) and variational calculations in full dimensionality for selected vibrational states of H5O2+ using a new ab initio potential energy surface [X. Huang, B. Braams, and J. M. Bowman, J. Chem. Phys. 122, 044308 (2005)]. The energy and properties of the zero-point state are focused on in the rigorous DMC calculations. OH-stretch fundamentals are also calculated using "fixed-node" DMC calculations and variationally using two versions of the code MULTIMODE. These results are compared with infrared multiphoton dissociation measurements of Yeh et al. [L. I. Yeh, M. Okumura, J. D. Myers, J. M. Price, and Y. T. Lee, J. Chem. Phys. 91, 7319 (1989)]. Some preliminary results for the energies of several modes of the shared hydrogen are also reported.

  5. Improved methods for Feynman path integral calculations and their application to calculate converged vibrational-rotational partition functions, free energies, enthalpies, entropies, and heat capacities for methane

    NASA Astrophysics Data System (ADS)

    Mielke, Steven L.; Truhlar, Donald G.

    2015-01-01

    We present an improved version of our "path-by-path" enhanced same path extrapolation scheme for Feynman path integral (FPI) calculations that permits rapid convergence with discretization errors ranging from O(P-6) to O(P-12), where P is the number of path discretization points. We also present two extensions of our importance sampling and stratified sampling schemes for calculating vibrational-rotational partition functions by the FPI method. The first is the use of importance functions for dihedral angles between sets of generalized Jacobi coordinate vectors. The second is an extension of our stratification scheme to allow some strata to be defined based only on coordinate information while other strata are defined based on both the geometry and the energy of the centroid of the Feynman path. These enhanced methods are applied to calculate converged partition functions by FPI methods, and these results are compared to ones obtained earlier by vibrational configuration interaction (VCI) calculations, both calculations being for the Jordan-Gilbert potential energy surface. The earlier VCI calculations are found to agree well (within ˜1.5%) with the new benchmarks. The FPI partition functions presented here are estimated to be converged to within a 2σ statistical uncertainty of between 0.04% and 0.07% for the given potential energy surface for temperatures in the range 300-3000 K and are the most accurately converged partition functions for a given potential energy surface for any molecule with five or more atoms. We also tabulate free energies, enthalpies, entropies, and heat capacities.

  6. Molecular structure and vibrational and chemical shift assignments of 3'-chloro-4-dimethylamino azobenzene by DFT calculations.

    PubMed

    Toy, Mehmet; Tanak, Hasan

    2016-01-01

    In the present work, a combined experimental and theoretical study on ground state molecular structure, spectroscopic and nonlinear optical properties of azo compound 3'-chloro-4-dimethlamino azobenzene are reported. The molecular geometry, vibrational wavenumbers and the first order hyperpolarizability of the title compound were calculated with the help of density functional theory computations. The optimized geometric parameters obtained by using DFT (B3LYP/6-311++G(d,p)) show good agreement with the experimental data. The vibrational transitions were identified based on the recorded FT-IR spectra in the range of 4000-400cm(-1) for solid state. The (1)H isotropic chemical shifts with respect to TMS were also calculated using the gauge independent atomic orbital (GIAO) method and compared with the experimental data. Using the TD-DFT method, electronic absorption spectra of the title compound have been predicted, and good agreement is determined with the experimental ones. To investigate the NLO properties of the title compound, the polarizability and the first hyperpolarizability were calculated using the density functional B3LYP method with the 6-311++G(d,p) basis set. According to results, the title compound exhibits non-zero first hyperpolarizability value revealing second order NLO behavior. In addition, DFT calculations of the title compound, molecular electrostatic potential and frontier molecular orbitals were also performed at 6-311++G(d,p) level of theory. PMID:25468435

  7. Molecular structure and vibrational and chemical shift assignments of 3‧-chloro-4-dimethylamino azobenzene by DFT calculations

    NASA Astrophysics Data System (ADS)

    Toy, Mehmet; Tanak, Hasan

    2016-01-01

    In the present work, a combined experimental and theoretical study on ground state molecular structure, spectroscopic and nonlinear optical properties of azo compound 3‧-chloro-4-dimethlamino azobenzene are reported. The molecular geometry, vibrational wavenumbers and the first order hyperpolarizability of the title compound were calculated with the help of density functional theory computations. The optimized geometric parameters obtained by using DFT (B3LYP/6-311++G(d,p)) show good agreement with the experimental data. The vibrational transitions were identified based on the recorded FT-IR spectra in the range of 4000-400 cm-1 for solid state. The 1H isotropic chemical shifts with respect to TMS were also calculated using the gauge independent atomic orbital (GIAO) method and compared with the experimental data. Using the TD-DFT method, electronic absorption spectra of the title compound have been predicted, and good agreement is determined with the experimental ones. To investigate the NLO properties of the title compound, the polarizability and the first hyperpolarizability were calculated using the density functional B3LYP method with the 6-311++G(d,p) basis set. According to results, the title compound exhibits non-zero first hyperpolarizability value revealing second order NLO behavior. In addition, DFT calculations of the title compound, molecular electrostatic potential and frontier molecular orbitals were also performed at 6-311++G(d,p) level of theory.

  8. FT-IR and Raman spectra and vibrational investigation of bis (4-acetylanilinium) hexachlorostannate using DFT (B3LYP) calculation

    NASA Astrophysics Data System (ADS)

    Tarchouna, S.; Chaabane, I.; Rahaiem, A. Ben

    2016-09-01

    4-acetylanilinium was used as a ligand for the synthesis of the organic/inorganic compound bis (4-acetylanilinium) hexachlorostannate. Vibrational study in the solid state was performed by FT-Raman of the free 4-acetylanilinium ligand C8H9ON+ and by FT-IR and FT-Raman spectroscopies of the [C8H10NO]2 SnCl6 compound. The comparative analysis of the Raman spectra of the title compound with that of the free ligand was discussed. The structure of the [C8H10NO]2SnCl6 was optimized by density functional theory (DFT) using B3LYP method and shows that the calculated values obtained by B3LYP/LanL2DZ basis are in a better agreement with the experimental data reported by Song et al. (2011) [1] than those obtained by B3LYP/LanL2MB basis. The vibrational frequencies are calculated using density functional theory (DFT) with the B3LYP/LanL2DZ basis, and scaled by various factors. Root mean square (RMS) value was calculated and the small difference between experimental and calculated modes has been interpreted by intermolecular interactions in the crystal.

  9. Tabulation of hybrid theory calculated e-N2 vibrational and rotational cross sections

    NASA Technical Reports Server (NTRS)

    Chandra, N.; Temkin, A.

    1976-01-01

    Vibrational excitation cross sections of N2 by electron impact are tabulated. Integrated cross sections are given for transitions v yields v prime where o=or v=or 8 in the energy range 0.1 eV=or E=or 10 eV. The energy grid is chosen to be most dense in the resonance region (2 to 4 eV) so that the substructure is present in the numerical results. Coefficients in the angular distribution formula (differential scattering cross section) for transitions v=0 yields v prime = or 8 are also numerically given over the same grid of energies. Simultaneous rotation-vibration coefficients are also given for transitions v=o,j=o; 1 yields v prime=o, j=o,2,4; 1,3,5. All results are obtained from the hybrid theory.

  10. Ab initio calculation of the ro-vibrational spectrum of H2F+

    NASA Astrophysics Data System (ADS)

    Kyuberis, Aleksandra A.; Lodi, Lorenzo; Zobov, Nikolai F.; Polyansky, Oleg L.

    2015-10-01

    An ab initio study of the rotation-vibrational spectrum of the electronic ground state of the (gas-phase) fluoronium ion H2F+ is presented. A new potential energy surface (PES) and a new dipole moment surface (DMS) were produced and used to compute rotation-vibrational energy levels, line positions and line intensities. Our computations achieve an accuracy of 0.15 cm-1 for the fundamental vibrational frequencies, which is about 50 times more accurate than previous ab initio results. The computed room-temperature line list should facilitate the experimental observations of new H2F+ lines, in particular of yet unobserved overtone transitions. The H2F+ molecular ion, which is isoelectronic to water, has a non-linear equilibrium geometry but a low-energy barrier to linearity at about 6000 cm-1. As a result the effects of so-called quantum monodromy become apparent already at low bending excitations. An analysis of excited bends in terms of quantum monodromy is presented.