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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. A harmonic adiabatic approximation to calculate highly excited vibrational levels of ``floppy molecules''

    NASA Astrophysics Data System (ADS)

    Lauvergnat, David; Nauts, André; Justum, Yves; Chapuisat, Xavier

    2001-04-01

    The harmonic adiabatic approximation (HADA), an efficient and accurate quantum method to calculate highly excited vibrational levels of molecular systems, is presented. It is well-suited to applications to "floppy molecules" with a rather large number of atoms (N>3). A clever choice of internal coordinates naturally suggests their separation into active, slow, or large amplitude coordinates q', and inactive, fast, or small amplitude coordinates q″, which leads to an adiabatic (or Born-Oppenheimer-type) approximation (ADA), i.e., the total wave function is expressed as a product of active and inactive total wave functions. However, within the framework of the ADA, potential energy data concerning the inactive coordinates q″ are required. To reduce this need, a minimum energy domain (MED) is defined by minimizing the potential energy surface (PES) for each value of the active variables q', and a quadratic or harmonic expansion of the PES, based on the MED, is used (MED harmonic potential). In other words, the overall picture is that of a harmonic valley about the MED. In the case of only one active variable, we have a minimum energy path (MEP) and a MEP harmonic potential. The combination of the MED harmonic potential and the adiabatic approximation (harmonic adiabatic approximation: HADA) greatly reduces the size of the numerical computations, so that rather large molecules can be studied. In the present article however, the HADA is applied to our benchmark molecule HCN/CNH, to test the validity of the method. Thus, the HADA vibrational energy levels are compared and are in excellent agreement with the ADA calculations (adiabatic approximation with the full PES) of Light and Bačić [J. Chem. Phys. 87, 4008 (1987)]. Furthermore, the exact harmonic results (exact calculations without the adiabatic approximation but with the MEP harmonic potential) are compared to the exact calculations (without any sort of approximation). In addition, we compare the densities of

  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. Efficient procedure for the numerical calculation of harmonic vibrational frequencies based on internal coordinates.

    PubMed

    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. In all cases the frequencies based on internal coordinates differ on average by <1 cm(-1) from those obtained from Cartesian coordinates.

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

    PubMed

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

    2012-10-21

    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.

  6. 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.

  7. Perturbative treatment of scalar-relativistic effects in coupled-cluster calculations of equilibrium geometries and harmonic vibrational frequencies using analytic second-derivative techniques

    NASA Astrophysics Data System (ADS)

    Michauk, Christine; Gauss, Jürgen

    2007-07-01

    An analytic scheme for the computation of scalar-relativistic corrections to nuclear forces is presented. Relativistic corrections are included via a perturbative treatment involving the mass-velocity and the one-electron and two-electron Darwin terms. Such a scheme requires mixed second derivatives of the nonrelativistic energy with respect to the relativistic perturbation and the nuclear coordinates and can be implemented using available second-derivative techniques. Our implementation for Hartree-Fock self-consistent field, second-order Møller-Plesset perturbation theory, as well as the coupled-cluster level is used to investigate the relativistic effects on the geometrical parameters and harmonic vibrational frequencies for a set of molecules containing light elements (HX, X =F, Cl, Br; H2X, X =O, S; HXY, X =O, S and Y =F, Cl, Br). The focus of our calculations is the basis-set dependence of the corresponding relativistic effects, additivity of electron correlation and relativistic effects, and the importance of core correlation on relativistic effects.

  8. Perturbative treatment of scalar-relativistic effects in coupled-cluster calculations of equilibrium geometries and harmonic vibrational frequencies using analytic second-derivative techniques.

    PubMed

    Michauk, Christine; Gauss, Jürgen

    2007-07-28

    An analytic scheme for the computation of scalar-relativistic corrections to nuclear forces is presented. Relativistic corrections are included via a perturbative treatment involving the mass-velocity and the one-electron and two-electron Darwin terms. Such a scheme requires mixed second derivatives of the nonrelativistic energy with respect to the relativistic perturbation and the nuclear coordinates and can be implemented using available second-derivative techniques. Our implementation for Hartree-Fock self-consistent field, second-order Moller-Plesset perturbation theory, as well as the coupled-cluster level is used to investigate the relativistic effects on the geometrical parameters and harmonic vibrational frequencies for a set of molecules containing light elements (HX, X=F, Cl, Br; H2X, X=O, S; HXY, X=O, S and Y=F, Cl, Br). The focus of our calculations is the basis-set dependence of the corresponding relativistic effects, additivity of electron correlation and relativistic effects, and the importance of core correlation on relativistic effects.

  9. 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.

  10. 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.

  11. 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.

  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. 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.

  14. Vibration response and harmonic wave propagation of ultrasonic arc drivers

    NASA Astrophysics Data System (ADS)

    Smithmaitrie, Pruittikorn; DeHaven, J. G.; Higuchi, K.; Tzou, H. S.

    2007-02-01

    A piezoelectric curvilinear arc driver designed for an ultrasonic curvilinear motor is evaluated in this study. A design of piezoelectric curvilinear arc driver is proposed and its governing equations, vibration behaviour and wave propagation are investigated. Then, analysis of forced vibration response or driving characteristics to harmonic excitations in the modal domain is conducted. Finite element modelling and analysis of the arc driver are also discussed. Analytical results of free vibration characteristics are compared favourably with the finite element results. Harmonic analyses of the three finite element models reveal changes of dynamic behaviours of three models and also imply operating frequencies with a significant travelling wave component. Parametric study of mathematical and finite element simulation results suggests that stable travelling waves can be generated to drive a rotor on the proposed curvilinear arc motor system.

  15. Anharmonic and harmonic intermolecular vibrational modes of the DNA base pairs

    NASA Astrophysics Data System (ADS)

    Špirko, Vladimír; Šponer, Jiří; Hobza, Pavel

    1997-01-01

    Intermolecular vibrational modes of the H-bonded adenine…thymine Watson-Crick (AT) base pair were studied for the first time using multidimensional nonharmonic treatment. Relying on a Born-Oppenheimer-like separation of the fast and slow vibrational motions, the complete multidimensional vibrational problem is reduced to a six-dimensional subproblem in which all rearrangements between the pair fragments (i.e., adenine and thymine) can be described. Following the Hougen-Bunker-Johns approach and using appropriate vibrational coordinates, a nonrigid reference is defined which covers all motions on the low-lying part of the intermolecular potential surface and which facilitates the derivation of a suitable model Hamiltonian. The potential energy surface is determined at the ab initio Hartree-Fock level with minimal basis set (HF/MINI-1) and an analytic potential energy function is obtained by fitting to the ab initio data. This function is used to calculate vibrational energy levels and effective geometries within the framework of the model Hamiltonian, disregarding the role of the kinematic and potential (in-plane)-(out-of-plane) interactions. The calculations are in reasonable agreement with the normal coordinate analysis (harmonic treatment) thus indicating physical correctness of this standard approach for an approximate description of the lowest vibrational states of the AT base pair. In addition, to get a deeper insight, harmonic vibrational frequencies of the AT pair and 28 other base pairs are evaluated at the same and higher levels of theory [ab initio Hartree-Fock level with split-valence basis set (HF/6-31G**)]. The HF/MINI-1 and HF/6-31G** intermolecular harmonic vibrational frequencies differ by less than 30%. For all the base pairs, the buckle and propeller vibrational modes [for definition and nomenclature see R. E. Dickerson et al., EMBO J. 8, 1 (1989)] are the lowest ones, all being in the narrow interval (from 4 to 30 cm-1 in the harmonic

  16. Harmonic motion detection in a vibrating scattering medium.

    PubMed

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

    2008-09-01

    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 degrees or less. The experimental results validate the conclusions observed from the model and show multifrequency vibration induction and measurements can be performed simultaneously.

  17. 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

  18. Intense-field molecular spectroscopy: Vibrational and rotational effects in harmonic generation by H+2

    NASA Astrophysics Data System (ADS)

    Aubanel, E. E.; Zuo, T.; Bandrauk, A. D.

    1994-05-01

    We present results of a complete treatment of electronic, vibrational, and rotational motion in numerical calculation of harmonic generation (HG) of 1064-nm laser radiation by the H+2 molecular ion for intensities 1013<=I<=1014 W/cm2. We show that efficient HG can be enhanced by suppression of photodissociation, a phenomenon which results from vibrational trapping in laser-field-induced potential wells. The HG spectra exhibit peaks clustered around even and odd harmonic orders. All peaks can be assigned to Raman-like transitions between dressed eigenstates of the field-molecule system. Rotational excitation is shown to compete with HG. Thus harmonic generation and photon scattering in molecules holds the promise of a potential diagnostic for molecular stabilization by intense laser fields.

  19. 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.

  20. 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.

  1. Anharmonic Vibrational Frequency Calculations Are Not Worthwhile for Small Basis Sets.

    PubMed

    Jacobsen, Ruth L; Johnson, Russell D; Irikura, Karl K; Kacker, Raghu N

    2013-02-12

    Anharmonic calculations using vibrational perturbation theory are known to provide near-spectroscopic accuracy when combined with high-level ab initio potential energy functions. However, performance with economical, popular electronic structure methods is less well characterized. We compare the accuracy of harmonic and anharmonic predictions from Hartree-Fock, second-order perturbation, and density functional theories combined with 6-31G(d) and 6-31+G(d,p) basis sets. As expected, anharmonic frequencies are closer than harmonic frequencies to experimental fundamentals. However, common practice is to correct harmonic predictions using multiplicative scaling. The surprising conclusion is that scaled anharmonic calculations are no more accurate than scaled harmonic calculations for the basis sets we used. The data used are from the Computational Chemistry Comparison and Benchmark Database (CCCBDB), maintained by the National Institute of Standards and Technology, which includes more than 3939 independent vibrations for 358 molecules.

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

    PubMed

    Xu, Xiangbo; Chen, Shao

    2015-08-31

    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.

  3. 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

  4. 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.

  5. Analysis of vibrational resonance in bi-harmonically driven plasma

    NASA Astrophysics Data System (ADS)

    Roy-Layinde, T. O.; Laoye, J. A.; Popoola, O. O.; Vincent, U. E.

    2016-09-01

    The phenomenon of vibrational resonance (VR) is examined and analyzed in a bi-harmonically driven two-fluid plasma model with nonlinear dissipation. An equation for the slow oscillations of the system is analytically derived in terms of the parameters of the fast signal using the method of direct separation of motion. The presence of a high frequency externally applied electric field is found to significantly modify the system's dynamics, and consequently, induce VR. The origin of the VR in the plasma model has been identified, not only from the effective plasma potential but also from the contributions of the effective nonlinear dissipation. Beside several dynamical changes, including multiple symmetry-breaking bifurcations, attractor escapes, and reversed period-doubling bifurcations, numerical simulations also revealed the occurrence of single and double resonances induced by symmetry breaking bifurcations.

  6. 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.

  7. 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.

  8. Vibration analysis of nonlinear systems with the bilinear hysteretic oscillator by using incremental harmonic balance method

    NASA Astrophysics Data System (ADS)

    Xiong, Huai; Kong, Xianren; Li, Haiqin; Yang, Zhenguo

    2017-01-01

    This paper considers dynamics of bilinear hysteretic systems, which are widely used for vibration control and vibration absorption such as magneto-rheological damper, metal-rubber. The method of incremental harmonic balance (IHB) technique that hysteresis is considered in the corrective term is improved in order to determine periodic solutions of bilinear hysteretic systems. The improved continuation method called two points tracing algorithm which is stable to the turning point makes the calculation more efficient for tracing amplitude-frequency response. Precise Hsu's method for analysing the stability of periodic solutions is introduced. The effects of different parameters of bilinear hysteretic oscillator on the response are discussed numerically. Some numerical simulations of considered bilinear hysteretic systems, including a single DOF and a 2DOF system, are effectively obtained by the modified IHB method and the results compare very well with the 4-oder Runge-Kutta method.

  9. Harmonic Vibrations of Shells with Cutouts Under Kinematic Conditions at Their Periphery

    NASA Astrophysics Data System (ADS)

    Lerman, L. B.

    2001-06-01

    Problems on harmonic vibrations of shells with openings are considered for the case where displacements and angles of turn are specified at their periphery. A technique for determination of the natural frequencies and modes of vibrations is stated. The technique replaces the unknown peripheral forces and moments by a system of local statically equivalent loads. The intensity of these loads is found from the boundary conditions at the opening periphery. The solutions of the equations of shell theory for local loads are constructed by expanding the sought-for quantities into series in terms of the natural modes of the shell without openings. The performance of the approach developed is illustrated by calculating the natural frequencies and modes of shallow shells with a rectangular planform and various Gaussian curvatures

  10. 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.

  11. 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.

  12. 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.

  13. The importance of nonlinearity on the higher harmonic control of helicopter vibration

    NASA Technical Reports Server (NTRS)

    Molusis, J. A.

    1984-01-01

    The effect of nonlinearity on the higher harmonic control (HHC) of helicopter vibration is investigated using a nonlinear aeroelastic simulation. A nonlinear solution is proposed which relates the HHC inputs to vibration outputs on the basis of a Volterra functional series. The Volterra series solution is shown to reduce to a vector polynomial equation relating HHC inputs to vibration outputs at any harmonic frequency. The nonlinear transfer relationship is identified from a nonlinear vibration analysis computer program, and the identification model is examined in detail. Improvements to current HHC algorithms are presented, and several Kalman filter divergence problems are quantified.

  14. On the Use of Active Higher Harmonic Blade Pitch Control for Helicopter Vibration Reduction,

    DTIC Science & Technology

    1980-06-01

    G., and Gabel, R.: Vibration Optimization of the CH-47C Helicopter Using NASTRAN . Symposium on Mathematical Modeling in Structural Engineering... helicopter . DESCRIPTION OF MODEL AND TESTS The basic wind tunnel model used in this investigation was the Structures Laboratory Aeroelastic Rotor...dynamically-scaled helicopter rotor model in which an active control system employing higher harmonic blade pitch was used for helicopter vibration

  15. 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.

  16. 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.

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

    PubMed

    Sert, Yusuf; Çırak, Çağrı; Ucun, Fatih

    2013-04-15

    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.

  18. 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.

  19. High-order harmonic generation of CO2 with different vibrational modes in an intense laser field

    NASA Astrophysics Data System (ADS)

    Du, Hui; Zhang, Hong-Dan; Zhang, Jun; Liu, Hai-Feng; Pan, Xue-Fei; Guo, Jing; Liu, Xue-Shen

    2016-11-01

    We apply the strong-field Lewenstein model to demonstrate the high-order harmonic generation of CO2 with three vibrational modes (balance vibration, bending vibration, and stretching vibration) driven by an intense laser field. The results show that the intensity of harmonic spectra is sensitive to molecular vibrational modes, and the high harmonic efficiency with stretching vibrational mode is the strongest. The underlying physical mechanism of the harmonic emission can be well explained by the corresponding ionization yield and the time-frequency analysis. Finally, we demonstrate the attosecond pulse generation with different vibrational modes and an isolated attosecond pulse with a duration of about 112 as is generated. Project supported by the National Natural Science Foundation of China (Grant Nos. 61575077, 11271158, and 11574117).

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

    PubMed

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

    2015-10-09

    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.

  1. Classical harmonic vibrations with micro amplitudes and low frequencies monitored by quantum entanglement

    NASA Astrophysics Data System (ADS)

    Huang, Yong-Yi

    2016-02-01

    We study the entanglement dynamics of the two two-level atoms coupled with a single-mode polarized cavity field after incorporating the decoupled atomic centers of mass classical harmonic vibrations with micro amplitudes and low frequencies. We discover a new quantum mechanical measurement effect for the entanglement dynamics. We propose a quantitative vibrant factor to modify the concurrence of the two atomic states. When the vibrant frequencies are very low, we obtain that: (1) the factor depends on the relative vibrant displacements and the initial phases rather than the absolute amplitudes, and reduces the concurrence to three orders of magnitude; (2) the concurrence increases with the increase of the initial phases; (3) the frequency of the harmonic vibration can be obtained by measuring the maximal value of the concurrence during a small measurement time. These results indicate that the extremely weak classical harmonic vibrations can be monitored by the entanglement of quantum states. The effect reported in the paper always works well as long as the internal degrees of freedom of the system (regardless of unitary evolution or non-unitary evolution with time) are decoupled with the external classical harmonic vibrations of atomic centers of mass.

  2. 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

  3. 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

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

    NASA Astrophysics Data System (ADS)

    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.

  5. Effective one-electron approaches to calculate high harmonic generation

    NASA Astrophysics Data System (ADS)

    Rohringer, Nina; Santra, Robin

    2006-05-01

    The single-active electron approach (SAE) is frequently applied to calculate high harmonic generation in atoms and consists in solving a one-particle Schr"odinger equation in an appropriate model potential. As an ad hoc approach it is difficult to be systematically improved. Starting with the time-dependent configuration interaction singles (TDCIS) technique we derive a new class of effective one-electron approaches. The resulting one-electron equations are in general non-local and non-unitary. A local approximation to TDCIS can be derived by restricting the total many-body Hamiltonian to a local mean-field Hamiltonian (those usually used in SAE calculations). The resulting equations are similar to traditional SAE approaches but include an additional term which destroys the unitarity of the time-evolution. We show that this correction term is essential and improves on traditional SAE approaches. Numerical tests show that this improved SAE method gives dipole-moments in better agreement with exact results than time-dependent Hartree Fock. The test system is a one-dimensional model of helium which allows for a straightforward numerical solution and therefore provides a benchmark to assess the quality of the different approximations.

  6. Free vibration analysis of beams and shafts by programmable calculators

    NASA Astrophysics Data System (ADS)

    de Almeida, M. T.; Dias, J. C.

    1984-01-01

    The general problem of free vibration analysis of beams and shafts is presented in such a way that the necessary computations can be carried out by using tables, a programmable calculator, or a microcomputer. This approach is of interest to both the vibration specialist and the design engineer. Illustrative examples are given, in which the transfer matrix method is implemented with a programmable calculator or microcomputer.

  7. 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

  8. Ensemble approach to coherence between two scalar harmonic light vibrations and the phase difference

    SciTech Connect

    Luis, Alfredo

    2009-05-15

    We develop an approach to coherence between two scalar harmonic light vibrations derived from the ensemble interpretation of statistical optics. Coherence is presented as a statistical variable itself that turns out to be the phase difference between the two vibrations. This provides a natural and simple extension of second-order coherence to cover more complicated situations. This includes in a single formalism both classic and quantum light states, allowing the most accurate interferometric measurements, even if they are incoherent according to the standard second-order approach.

  9. Nonlinear vibrations of thin arbitrarily laminated composite plates subjected to harmonic excitations using DKT elements

    NASA Technical Reports Server (NTRS)

    Chiang, C. K.; Xue, David Y.; Mei, Chuh

    1993-01-01

    A finite element formulation is presented for determining the large-amplitude free and steady-state forced vibration response of arbitrarily laminated anisotropic composite thin plates using the Discrete Kirchhoff Theory (DKT) triangular elements. The nonlinear stiffness and harmonic force matrices of an arbitrarily laminated composite triangular plate element are developed for nonlinear free and forced vibration analyses. The linearized updated-mode method with nonlinear time function approximation is employed for the solution of the system nonlinear eigenvalue equations. The amplitude-frequency relations for convergence with gridwork refinement, triangular plates, different boundary conditions, lamination angles, number of plies, and uniform versus concentrated loads are presented.

  10. 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.

  11. Generation of higher harmonics in longitudinal vibration of beams with breathing cracks

    NASA Astrophysics Data System (ADS)

    Broda, D.; Pieczonka, L.; Hiwarkar, V.; Staszewski, W. J.; Silberschmidt, V. V.

    2016-10-01

    Classical nonlinear vibration methods used for structural damage detection are often based on higher- and sub-harmonic generation. However, nonlinearities arising from sources other than damage - e.g. boundary conditions or a measurement chain - are a primary concern in these methods. This paper focuses on localisation of damage-related nonlinearities based on higher harmonic generation. Numerical and experimental investigations in longitudinal vibration of beams with breathing cracks are presented. Numerical modelling is performed using a two-dimensional finite element approach. Different crack depths, locations and boundary conditions are investigated. The results demonstrate that nonlinearities in cracked beams are particularly strong in the vicinity of damage, allowing not only for damage localisation but also for separation of crack induced nonlinearity from other sources of nonlinearities.

  12. 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.

  13. Vibrational spectroscopic studies of Isoleucine by quantum chemical calculations.

    PubMed

    Moorthi, P P; Gunasekaran, S; Ramkumaar, G R

    2014-04-24

    In this work, we reported a combined experimental and theoretical study on molecular structure, vibrational spectra and NBO analysis of Isoleucine (2-Amino-3-methylpentanoic acid). The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments, thermodynamics properties, NBO analyses, NMR chemical shifts and ultraviolet-visible spectral interpretation of Isoleucine have been studied by performing MP2 and DFT/cc-pVDZ level of theory. The FTIR, FT-Raman spectra were recorded in the region 4000-400 cm(-1) and 3500-50 cm(-1) respectively. The UV-visible absorption spectra of the compound were recorded in the range of 200-800 nm. Computational calculations at MP2 and B3LYP level with basis set of cc-pVDZ is employed in complete assignments of Isoleucine molecule on the basis of the potential energy distribution (PED) of the vibrational modes, calculated using VEDA-4 program. The calculated wavenumbers are compared with the experimental values. The difference between the observed and calculated wavenumber values of most of the fundamentals is very small. (13)C and (1)H nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method and compared with experimental results. The formation of hydrogen bond was investigated in terms of the charge density by the NBO calculations. Based on the UV spectra and TD-DFT calculations, the electronic structure and the assignments of the absorption bands were carried out. Besides, molecular electrostatic potential (MEP) were investigated using theoretical calculations.

  14. Rejecting harmonic vibrations at Gemini with real-time vibration tracking

    NASA Astrophysics Data System (ADS)

    Rippa, Mathew J.; Bonnet, Henri; Hayward, Thomas L.; Trujillo, Chadwick; Cavedoni, Chas P.; Cumming, Tom; Yamasaki, Chris; Masuda, Neal; Bagano, Cy; Hardash, Steve

    2016-08-01

    Fighting vibrations on large telescopes is an arduous task. At Gemini, vibrations originating from cryogenic coolers have been shown to degrade the optical wavefront, in certain cases by as much as 40%. This paper discusses a general solution to vibration compensation by tracking the real time vibration state of the telescope and using M2 to apply corrections. Two approaches are then presented: an open loop compensation at M2 based on the signal of accelerometers at the M1 glass, and a closed loop compensation at M2 based on optical measurements from the wave front sensor. The paper elaborates on the pros and cons of each approach and the challenges faced during commissioning. A conclusion is presented with the final results of vibration tracking integrated with operations.

  15. Density functional theory calculations on the molecular structures and vibration spectra of platinum(II) antitumor drugs.

    PubMed

    Gao, Hongwei; Xia, FengYi; Huang, ChangJiang; Lin, Kuangfei

    2011-04-01

    A comparison of six density functional theory (DFT) methods and six basis sets for predicting the molecular structures and vibration spectra of cisplatin is reported. The theoretical results are discussed and compared with the experimental data. It is remarkable that LSDA/SDD level is clearly superior to all the remaining density functional methods (including mPW1PW) in predicting the structures of cisplatin. Mean deviation between the calculated harmonic and observed fundamental vibration frequencies for each method is also calculated. The results indicate that PBE1PBE/SDD is the best method to predict all frequencies on average for cisplatin molecule in DFT methods.

  16. Calculation of HVDC converter noncharacteristic harmonics using digital time-domain simulation method

    SciTech Connect

    Sarshar, A.; Iravani, M.R.; Li, J.

    1996-01-01

    In this paper, noncharacteristic harmonics of an HVdc converter station are calculated based on the use of digital time-domain simulation methods. An enhanced version of the Electromagnetic Transients Program (EMTP) is used for the studies. The noncharacteristic harmonics of interest are (1) the dc side triplen harmonics, and (2) the ac side second harmonic. Impacts of loading conditions, neutral filter, and converter firing angle on the dc side triplen harmonics are discussed. Effects of ac side network parameters, static VAR compensator (SVC), transformer half-cycle saturation, and Geomagnetically Induced Current (GIC) on the ac side second harmonic instability are also presented. This paper concludes that the digital time-domain simulation method provides significant flexibility for accurate prediction of (1) generation mechanism, and (2) adverse impacts of HVdc noncharacteristic harmonics.

  17. Molecular structure and vibrational analysis of 5-nitro-6-methyluracil molecule based on monomer, dimer and trimer calculations

    NASA Astrophysics Data System (ADS)

    Alam, M. J.; Bhat, S. A.; Ahmad, S.

    2016-05-01

    Molecular structure and vibrational spectra of 5-nitro-6-methyluracil molecule have been studied by the simulation of its monomer, dimer and trimer forms using DFT and MP2 methods with 6-311G(d,p) basis set. Anharmonic force field calculations have been carried out for the isolated monomer, while the calculations on dimer and trimer have been done in the harmonic approximation. An accurate numerical integration grid has been used for geometry optimization as well as frequency calculation. Anharmonic vibrational frequencies have been computed using VPT2 algorithm (Barone's method) as well as VSCF and VSCF-PT2 approaches. These methods yield results that are in remarkable agreement with the experiment. The coupling strengths between pair of modes have been also calculated using coupling integral based on 2MR-QFF approximation. The vibrational assignments have been made with the help of potential energy distribution values and animated modes.

  18. 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.

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

    PubMed

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

    2016-02-07

    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.

  20. Analytic calculations of anharmonic infrared and Raman vibrational spectra

    PubMed Central

    Louant, Orian; Ruud, Kenneth

    2016-01-01

    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

  1. Comparison of methods for calculating Franck-Condon factors beyond the harmonic approximation: how important are Duschinsky rotations?

    NASA Astrophysics Data System (ADS)

    Meier, Patrick; Rauhut, Guntram

    2015-12-01

    Three different approaches for calculating Franck-Condon factors beyond the harmonic approximation are compared and discussed in detail. Duschinsky effects are accounted for either by a rotation of the initial or final wavefunctions - which are obtained from state-specific configuration-selective vibrational configuration interaction calculations - or by a rotation of the underlying multi-dimensional potential energy surfaces being determined from explicitly correlated coupled-cluster approaches. An analysis of the Duschinsky effects in dependence on the rotational angles and the anisotropy of the wavefunction is provided. Benchmark calculations for the photoelectron spectra of ClO2, HS-2 and ZnOH- are presented. An application of the favoured approach for calculating Franck-Condon factors to the oxidation of Zn(H2O)+ and Zn2(H2O)+ demonstrates its applicability to systems with more than three atoms.

  2. Diabatic Versus Adiabatic Calculation of Torsion-Vibration Interactions

    NASA Astrophysics Data System (ADS)

    Hougen, Jon T.

    2013-06-01

    The introductory part of this talk will deal briefly with two historical topics: (i) use of the words adiabatic, nonadiabatic, and diabatic in thermodynamics and quantum mechanics, and (ii) application of diabatic and adiabatic ideas to vibrational energy level calculations for a pair of diatomic-molecule potential energy curves exhibiting an avoided crossing. The main part of the talk will be devoted to recent work with Li-Hong Xu and Ron Lees on how ab initio projected frequency calculations for small-amplitude vibrations along the large-amplitude internal rotation path in methanol can best be used to help guide experimental assignments and fits in the IR vibrational spectrum. The three CH stretching vibrations for CH_{3}OH can conveniently be represented as coefficients multiplying three different types of basis vibrations, i.e., as coefficients of: (i) the local mode C-H_i bond displacements δr_{i} for hydrogens H_{1}, H_{2} and H_{3} of the methyl top, (ii) symmetrized linear combinations of the three δr_{i} of species A_{1} oplus E in the permutation-inversion group G_{6} = C_{3v} appropriate for methanol, or (iii) symmetrized linear combinations of the three δr_{i} of species 2A_{1} oplus A_{2} in the permutation-inversion group G_{6}. In this talk, we will focus on diabatic and adiabatic computations for the A_{1} oplus E basis vibrations of case (ii) above. We will briefly explain how Jahn-Teller-like and Renner-Teller-like torsion-vibration interaction terms occurring in the potential energy expression in the diabatic calculation become torsion-vibration Coriolis interaction terms occurring in the kinetic energy expression of the adiabatic calculations, and also show how, for algebraically solvable parameter choices, the same energy levels are obtained from either calculation. A final conclusion as to which approach is computationally superior for the numerical data given in a quantum chemistry output file has not yet been arrived at.

  3. Nonlinear coupled rotor-fuselage helicopter vibration studies with higher harmonic control

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

    This paper addresses the problem of vibration prediction and vibration reduction in helicopters by means of active control methodologies. The nonlinear equations of a coupled rotor/flexible-fuselage system have been derived using computer algebra, thus relegating this tedious task to the computer. In the solution procedure the trim state and vibratory response of the helicopter are obtained in a single pass by using a harmonic balance technique and simultaneously satisfying the trim and the vibratory response of the helicopter in all the rotor and fuselage degrees of freedom. Using this solution procedure, the influence of the fuselage flexibility on the vibratory response is studied. In addition, it is shown that the conventional single frequency HHC is capable of reducing either the hub loads or only the fuselage vibrations but not both simultaneously. A new scheme called MHHC, having multiple higher harmonic pitch inputs, was used to accomplish this task of simultaneously reducing both the vibratory hub loads and fuselage vibratory response. In addition, the uniqueness of this MHHC scheme is explained in detail.

  4. Calculating vibrational spectra of molecules using tensor train decomposition

    NASA Astrophysics Data System (ADS)

    Rakhuba, Maxim; Oseledets, Ivan

    2016-09-01

    We propose a new algorithm for calculation of vibrational spectra of molecules using tensor train decomposition. Under the assumption that eigenfunctions lie on a low-parametric manifold of low-rank tensors we suggest using well-known iterative methods that utilize matrix inversion (locally optimal block preconditioned conjugate gradient method, inverse iteration) and solve corresponding linear systems inexactly along this manifold. As an application, we accurately compute vibrational spectra (84 states) of acetonitrile molecule CH3CN on a laptop in one hour using only 100 MB of memory to represent all computed eigenfunctions.

  5. Calculating vibrational spectra using modified Shepard interpolated potential energy surfaces.

    PubMed

    Evenhuis, Christian R; Manthe, Uwe

    2008-07-14

    A potential energy interpolation approach based on modified Shepard interpolation and specifically designed for calculation of vibrational states is presented. The importance of the choice of coordinates for the rate of convergence is demonstrated. Studying the vibrational states of the water molecule as a test case, a coordinate system comprised of inverse bond distances and trigonometric functions of the bond angle is found to be particularly efficient. Different sampling schemes used to locate the reference points in the modified Shepard interpolation are investigated. A final scheme is recommended, which allows the construction of potential energy surfaces to sub-wave-number accuracy.

  6. The calculation of vibrational intensities in forbidden electronic transitions

    NASA Astrophysics Data System (ADS)

    Johnson, Philip M.; Xu, Haifeng; Sears, Trevor J.

    2006-10-01

    A method is described for the use of electronic structure and Franck-Condon factor programs in the calculation of the vibrational intensities in forbidden electronic transitions. Using the B˜B22-X˜B12 electronic transition of benzonitrile cation as a test case, transition moments were calculated using the symmetry adapted cluster/configuration interaction method at various points along the normal mode displacements of the molecule, from which transition moment derivatives were obtained. The transition moments were found to vary almost linearly with respect to the normal mode displacements. Using these, along with Franck-Condon factors, an expansion of the transition moment with respect to the normal coordinates provides a measure of vibrational intensities, including the effects of geometry change and Duschinsky rotation [Acta Physicochim. URSS 7, 551 (1937)]. Second order terms in the moment expansion are calculated, and it is determined that they must be included if the intensity of combination bands is to be properly obtained.

  7. The calculation of vibrational intensities in forbidden electronic transitions.

    PubMed

    Johnson, Philip M; Xu, Haifeng; Sears, Trevor J

    2006-10-28

    A method is described for the use of electronic structure and Franck-Condon factor programs in the calculation of the vibrational intensities in forbidden electronic transitions. Using the B 2B2-X 2B1 electronic transition of benzonitrile cation as a test case, transition moments were calculated using the symmetry adapted cluster/configuration interaction method at various points along the normal mode displacements of the molecule, from which transition moment derivatives were obtained. The transition moments were found to vary almost linearly with respect to the normal mode displacements. Using these, along with Franck-Condon factors, an expansion of the transition moment with respect to the normal coordinates provides a measure of vibrational intensities, including the effects of geometry change and Duschinsky rotation [Acta Physicochim. URSS 7, 551 (1937)]. Second order terms in the moment expansion are calculated, and it is determined that they must be included if the intensity of combination bands is to be properly obtained.

  8. 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.

  9. Magnetostrictive vibrations model of a three-phase transformer core and the contribution of the fifth harmonic in the grid voltage

    NASA Astrophysics Data System (ADS)

    Gorji Ghalamestani, Setareh; Vandevelde, Lieven; Dirckx, Joris J. J.; Melkebeek, Jan A. A.

    2014-05-01

    The effect of the fifth harmonic in the grid voltage (with fundamental frequency of 50 Hz) on the vibrations of a three-phase transformer core is computed, since such harmonic has the largest contribution in the European grid voltage. The computational method is a two-dimensional (2D) finite element technique. The modal vibrations under various magnetisations (viz with different fifth harmonic components) are compared with those obtained under a purely sinusoidal magnetisation and showed that the variations for the 100 Hz harmonic of the vibrations are small. However, the 200 Hz harmonic showed a significant increase when a fifth harmonic was present on the applied voltage. In fact, the presence of a fundamental component with 50 Hz frequency and a fifth harmonic on the magnetisation signal generates a 200 Hz harmonic on the magnetostriction strains (and the magnetic forces), and thus this harmonic increases significantly.

  10. 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.

  11. 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)

  12. 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.

  13. 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.

  14. 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

    2015-01-01

    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.

  15. 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.

  16. Harmonic pulsed excitation and motion detection of a vibrating reflective target.

    PubMed

    Urban, Matthew W; Greenleaf, James F

    2008-01-01

    Elasticity imaging is an emerging medical imaging modality. Methods involving acoustic radiation force excitation and pulse-echo ultrasound motion detection have been investigated to assess the mechanical response of tissue. In this work new methods for dynamic radiation force excitation and motion detection are presented. The theory and model for harmonic motion detection of a vibrating reflective target are presented. The model incorporates processing of radio frequency data acquired using pulse-echo ultrasound to measure harmonic motion with amplitudes ranging from 100 to 10,000 nm. A numerical study was performed to assess the effects of different parameters on the accuracy and precision of displacement amplitude and phase estimation and showed how estimation errors could be minimized. Harmonic pulsed excitation is introduced as a multifrequency radiation force excitation method that utilizes ultrasound tonebursts repeated at a rate f(r). The radiation force, consisting of frequency components at multiples of f(r), is generated using 3.0 MHz ultrasound, and motion detection is performed simultaneously with 9.0 MHz pulse-echo ultrasound. A parameterized experimental analysis showed that displacement can be measured with small errors for motion with amplitudes as low as 100 nm. The parameterized numerical and experimental analyses provide insight into how to optimize acquisition parameters to minimize measurement errors.

  17. Anharmonic zero point vibrational energies: Tipping the scales in accurate thermochemistry calculations?

    NASA Astrophysics Data System (ADS)

    Pfeiffer, Florian; Rauhut, Guntram; Feller, David; Peterson, Kirk A.

    2013-01-01

    Anharmonic zero point vibrational energies (ZPVEs) calculated using both conventional CCSD(T) and MP2 in combination with vibrational second-order perturbation theory (VPT2) are compared to explicitly correlated CCSD(T)-F12 and MP2-F12 results that utilize vibrational configuration interaction (VCI) theory for 26 molecules of varying size. Sequences of correlation consistent basis sets are used throughout. It is found that the explicitly correlated methods yield results close to the basis set limit even with double-zeta quality basis sets. In particular, the anharmonic contributions to the ZPVE are accurately recovered at just the MP2 (or MP2-F12) level of theory. Somewhat surprisingly, the best vibrational CI results agreed with the VPT2 values with a mean unsigned deviation of just 0.09 kJ/mol and a standard deviation of just 0.11 kJ/mol. The largest difference was observed for C4H4O (0.34 kJ/mol). A simplified version of the vibrational CI procedure that limited the modal expansion to at most 2-mode coupling yielded anharmonic corrections generally within about 0.1 kJ/mol of the full 3- or 4-mode results, except in the cases of C3H8 and C4H4O where the contributions were underestimated by 1.3 and 0.8 kJ/mol, respectively (34% and 40%, respectively). For the molecules considered in this work, accurate anharmonic ZPVEs are most economically obtained by combining CCSD(T)-F12a/cc-pVDZ-F12 harmonic frequencies with either MP2/aug-cc-pVTZ/VPT2 or MP2-F12/cc-pVDZ-F12/VCI anharmonic corrections.

  18. Self-Consistent Calculation of Half-Harmonic Emission with an Electromagnetic Zakharov Model

    NASA Astrophysics Data System (ADS)

    Zhang, J.; Myatt, J. F.; Maximov, A. V.; Short, R. W.; Dubois, D. F.; Russell, D. A.; Vu, H. X.

    2015-11-01

    Half-harmonic emission has been regarded as a signal of two-plasmon decay or stimulated Raman scattering (SRS). Experimental observations at the Omega Laser Facility show both blue and red shifts of half-harmonic light. The red shift might be a powerful diagnostic tool to measure electron temperature near quarter-critical density. However, the interpretation of the half-harmonics spectrum is difficult because of its complicated generation mechanism. To resolve this problem, a self-consistent electromagnetic Zakharov code that is able to calculate half harmonics emission has been developed, including all the possible generation mechanisms such as absolute SRS, Thomson down-scattering, linear mode conversion, and nonlinear mode conversion. This material is based upon work supported by the Department of Energy National Nuclear Security Administration under Award Number DE-NA0001944.

  19. An analytical derivative procedure for the calculation of vibrational Raman optical activity spectra

    NASA Astrophysics Data System (ADS)

    Liégeois, Vincent; Ruud, Kenneth; Champagne, Benoît

    2007-11-01

    We present an analytical time-dependent Hartree-Fock algorithm for the calculation of the derivatives of the electric dipole-magnetic dipole polarizability with respect to atomic Cartesian coordinates. Combined with analogous procedures to determine the derivatives of the electric dipole-electric dipole and electric dipole-electric quadrupole polarizabilities, it enables a fully analytical evaluation of the three frequency-dependent vibrational Raman optical activity (VROA) invariants within the harmonic approximation. The procedure employs traditional non-London atomic orbitals, and the gauge-origin dependence of the VROA intensities has, therefore, been assessed for the commonly used aug-cc-pVDZ and rDPS:3-21G basis sets.

  20. 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.

  1. Detecting the classical harmonic vibrations of micro amplitudes and low frequencies with an atomic Mach-Zehnder interferometer

    NASA Astrophysics Data System (ADS)

    Huang, Yong-Yi

    2014-01-01

    We study the effects of atomic beams classical harmonic vibrations of micro amplitudes and low frequencies perpendicular to the wave vectors of atomic branches on the mean numbers of atoms arriving at the detectors in an atomic Mach-Zehnder interferometer, where the two atomic beams are in the same wave surface and have the same phase. We propose a vibrant factor to quantitatively describe the effects of atomic beams vibrations. It shows that: (i) the vibrant factor depends on the relative vibrant displacement and the initial phase rather than the absolute amplitude, (ii) the factor increases with the increase of the initial phase, and (iii) the frequencies can be derived from equal time interval measurements of the mean numbers of atoms arriving at the detectors. These results indicate that it is possible to detect the classical harmonic vibrations of micro amplitudes and low frequencies by measuring the variations in the mean numbers of atoms arriving at the detectors.

  2. Predicting the structure and vibrational frequencies of ethylene using harmonic and anharmonic approaches at the Kohn-Sham complete basis set limit.

    PubMed

    Buczek, Aneta; Kupka, Teobald; Broda, Małgorzata A; Żyła, Adriana

    2016-01-01

    In this work, regular convergence patterns of the structural, harmonic, and VPT2-calculated anharmonic vibrational parameters of ethylene towards the Kohn-Sham complete basis set (KS CBS) limit are demonstrated for the first time. The performance of the VPT2 scheme implemented using density functional theory (DFT-BLYP and DFT-B3LYP) in combination with two Pople basis sets (6-311++G** and 6-311++G(3df,2pd)), the polarization-consistent basis sets pc-n, aug-pc-n, and pcseg-n (n = 0, 1, 2, 3, 4), and the correlation-consistent basis sets cc-pVXZ and aug-cc-pVXZ (X = D, T, Q, 5, 6) was tested.The BLYP-calculated harmonic frequencies were found to be markedly closer than the B3LYP-calculated harmonic frequencies to the experimentally derived values, while the calculated anharmonic frequencies consistently underestimated the observed wavenumbers. The different basis set families gave very similar estimated values for the CBS parameters. The anharmonic frequencies calculated with B3LYP/aug-pc-3 were consistently significantly higher than those obtained with the pc-3 basis set; applying the aug-pcseg-n basis set family alleviated this problem. Utilization of B3LYP/aug-pcseg-n basis sets instead of B3LYP/aug-cc-pVXZ, which is computationally less expensive, is suggested for medium-sized molecules. Harmonic BLYP/pc-2 calculations produced fairly accurate ethylene frequencies. Graphical Abstract In this study, the performance of the VPT2 scheme implemented using density functional theory (DFT-BLYP and DFT-B3LYP) in combination with the polarization-consistent basis sets pc-n, aug-pc-n, and pcseg-n (n = 0, 1, 2, 3, 4), and the correlation-consistent basis sets cc-pVXZ and aug-cc-pVXZ (X = D, T, Q, 5, and 6) was tested. For the first time, we demonstrated regular convergence patterns of the structural, harmonic, and VPT2-calculated anharmonic vibrational parameters of ethylene towards the Kohn-Sham complete basis set (KS CBS) limit.

  3. Optimal semi-active vibration absorber for harmonic excitation based on controlled semi-active damper

    NASA Astrophysics Data System (ADS)

    Weber, F.

    2014-09-01

    The semi-active vibration absorber (SVA) based on controlled semi-active damper is formulated to realize the behaviour of the passive undamped vibration absorber tuned to the actual harmonic disturbing frequency. It is shown that the controlled stiffness force, which is emulated by the semi-active damper to realize the precise real-time frequency tuning of the SVA, is unpreventably combined with the generation of undesirable damping in the semi-active damper whereby the SVA does not behave as targeted. The semi-active stiffness force is therefore optimized for minimum primary structure response. The results point out that the optimal semi-active stiffness force reduces the undesirable energy dissipation in the SVA at the expenses of slight imprecise frequency tuning. Based on these findings, a real-time applicable suboptimal SVA is formulated that also takes the relative motion constraint of real mass dampers into account. The results demonstrate that the performance of the suboptimal SVA is closer to that of the active solution than that of the passive mass damper.

  4. Calculation and manipulation of the chirp rates of high-order harmonics

    SciTech Connect

    Murakami, M.; Mauritsson, J.; Schafer, K.J.; Gaarde, M.B.; L'Huillier, A.

    2005-01-01

    We calculate the linear chirp rates of high-order harmonics in argon, generated by intense, 810 nm laser pulses, and explore the dependence of the chirp rate on harmonic order, driving laser intensity, and pulse duration. By using a time-frequency representation of the harmonic fields we can identify several different linear chirp contributions to the plateau harmonics. Our results, which are based on numerical integration of the time-dependent Schroedinger equation, are in good agreement with the adiabatic predictions of the strong field approximation for the chirp rates. Extending the theoretical analysis in the recent paper by Mauritsson et al. [Phys. Rev. A 70, 021801(R) (2004)], we also manipulate the chirp rates of the harmonics by adding a chirp to the driving pulse. We show that the chirp rate for harmonic q is given by the sum of the intrinsic chirp rate, which is determined by the new duration and peak intensity of the chirped driving pulse, and q times the external chirp rate.

  5. 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.

  6. Large vibrational effects upon calculated phase boundaries in Al-Sc.

    PubMed

    Ozoliņs, V; Asta, M

    2001-01-15

    The fcc portion of the Al-Sc phase diagram is calculated from first principles including contributions to alloy free energies associated with ionic vibrations. It is found that vibrational entropy accounts for a 27-fold increase in the calculated solubility limits for Sc in fcc Al at high temperatures, bringing calculated and measured values into very good agreement. The present work gives a clear example demonstrating a large effect of vibrational entropy upon calculated phase boundaries in substitutional alloys.

  7. Crystal and molecular structure, conformational, vibrational properties and DFT calculations of melaminium bis (hydrogen oxalate)

    NASA Astrophysics Data System (ADS)

    Sangeetha, V.; Govindarajan, M.; Kanagathara, N.; Gunasekaran, S.; Rajakumar, P. R.; Anbalagan, G.

    2014-06-01

    Single crystals of melaminium bis (hydrogen oxalate) (MOX) were grown by slow evaporation method. X-ray powder diffraction analysis indicates that MOX crystallizes in monoclinic system (space group C2/c) and the calculated lattice constants are a = 20.075 ± 0.123 Ǻ, b = 8.477 ± 0.045 Ǻ, c = 6.983 ± 0.015, α = γ 90° and β = 102.6 ± 0.33°. Thermal analysis confirms that MOX is thermally stable up to 250 °C. A detailed interpretation of the FT-IR, FT-Raman and NMR spectra were reported. The equilibrium geometry, bonding features, and harmonic vibrational frequencies have been investigated with the help of PM6, HF and DFT/B3LYP methods. The potential energy curve shows that MOX molecule has two stable structures and the computational results diagnose that Rot I is the most stable conformer. The 1H and 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the Gauge-Invariant Atomic Orbital (GIAO) method. Stability of the molecule, arising from hyperconjugative interactions and charge delocalization, has been analyzed using Natural Bond Orbital (NBO) analysis. The electronic properties, such as HOMO and LUMO energies, were calculated by Time-Dependent DFT (TD-DFT) approach. To estimate chemical reactivity of the molecule, the molecular electrostatic potential (MEP) surface map is calculated for the optimized geometry of the molecule.

  8. 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

  9. 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.

  10. Perspective: Accurate ro-vibrational calculations on small molecules

    NASA Astrophysics Data System (ADS)

    Tennyson, Jonathan

    2016-09-01

    In what has been described as the fourth age of quantum chemistry, variational nuclear motion programs are now routinely being used to obtain the vibration-rotation levels and corresponding wavefunctions of small molecules to the sort of high accuracy demanded by comparison with spectroscopy. In this perspective, I will discuss the current state-of-the-art which, for example, shows that these calculations are increasingly competitive with measurements or, indeed, replacing them and thus becoming the primary source of data on key processes. To achieve this accuracy ab initio requires consideration of small effects, routinely ignored in standard calculations, such as those due to quantum electrodynamics. Variational calculations are being used to generate huge lists of transitions which provide the input for models of radiative transport through hot atmospheres and to fill in or even replace measured transition intensities. Future prospects such as the study of molecular states near dissociation, which can provide a link with low-energy chemical reactions, are discussed.

  11. 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.

  12. Harmonic Vibrational Frequencies: Approximate Global Scaling Factors for TPSS, M06, and M11 Functional Families Using Several Common Basis Sets.

    PubMed

    Kashinski, D O; Chase, G M; Nelson, R G; Di Nallo, O E; Scales, A N; VanderLey, D L; Byrd, E F C

    2017-03-23

    We propose new approximate global multiplicative scaling factors for the DFT calculation of ground state harmonic vibrational frequencies using functionals from the TPSS, M06, and M11 functional families with standard correlation consistent cc-pVxZ and aug-cc-pVxZ (x = D, T, and Q), 6-311G split valence family, Sadlej and Sapporo polarized triple-ζ basis sets. Results for B3LYP, CAM-B3LYP, B3PW91, PBE, and PBE0 functionals with these basis sets are also reported. A total of 99 harmonic frequencies were calculated for 26 gas-phase organic and nonorganic molecules typically found in detonated solid propellant residue. Our proposed approximate multiplicative scaling factors are determined using a least-squares approach comparing the computed harmonic frequencies to experimental counterparts well established in the scientific literature. A comparison of our work to previously published global scaling factors is made to verify method reliability and the applicability of our molecular test set.

  13. Detection Enhancement of Protein Structural Vibrations: Measurements and Calculations

    NASA Astrophysics Data System (ADS)

    Niessen, Katherine; Xu, Mengyang; Snell, Edward; Cody, Vivian; Pace, James; Schmidt, Marius; Markelz, Andrea

    2015-03-01

    Narrow band intramolecular protein vibrations have been successfully measured using crystal anisotropy THz microscopy (CATM), a near-field technique, on protein crystals. To address the question of how these motions are related to protein function we developed a variation of this technique to rapidly measure a variety of protein crystals. The variation anisotropy measurement consists of introducing a wire-grid polarizer in the THz path and rotating the polarizer between measurements, instead of the sample. While the resulting anisotropic spectra confirm reproducibility and protein specific nature of the response the signal is not directly related to the absorption spectra and in fact shows more structure than CATM. This is due to the polarization sensitivity of the electro-optical detection crystal and the changing THz polarization direction and amplitude at the detector. This combination leads to an enhancement of specific resonances and increased sensitivity to rotation of the THz polarization from the sample itself. Preliminary calculations suggest that the technique is sensitive to the birefringence associated with anisotropic absorbance. The results and significance of these measurements on protein and sucrose crystals and the calculated expected response will be discussed.

  14. Vibrational spectroscopy and DFT calculations of flavonoid derriobtusone A

    NASA Astrophysics Data System (ADS)

    Marques, A. N. L.; Mendes Filho, J.; Freire, P. T. C.; Santos, H. S.; Albuquerque, M. R. J. R.; Bandeira, P. N.; Leite, R. V.; Braz-Filho, R.; Gusmão, G. O. M.; Nogueira, C. E. S.; Teixeira, A. M. R.

    2017-02-01

    Flavonoids are secondary metabolites of plants which perform various functions. One subclass of flavonoid is auronol that can present immunostimulating activity. In this work Fourier-Transform Infrared with Attenuated Total Reflectance (FTIR-ATR) and Fourier-Transform Raman (FT-Raman) spectra of an auronol, derriobtusone A (C18H12O4), were obtained at room temperature. Theoretical calculations using Density Functional Theory (DFT) were performed in order to assign the normal modes and to interpret the spectra of the derriobtusone A molecule. The FTIR-ATR and FT-Raman spectra of the crystal, were recorded at room temperature in the regions 600 cm-1 to 4000 cm-1 and 40 cm-1 to 4000 cm-1, respectively. The normal modes of vibrations were obtained using Density Functional Theory with B3LYP functional and 6-31G+ (d,p) basis set. The calculated frequencies are in good agreement with those obtained experimentally. Detailed assignments of the normal modes present in both the Fourier-Transform infrared and the Fourier-Transform Raman spectra of the crystal are given.

  15. Calculated Vibrational States of Ozone up to Dissociation

    NASA Astrophysics Data System (ADS)

    Dawes, Richard; Ndengue, Steve Alexandre; Wang, Xiao-Gang; Carrington, Tucker; Guo, Hua

    2016-06-01

    A new accurate global potential energy surface for the ground electronic state of ozone [J. Chem. Phys. 139, 201103 (2013)] was published fairly recently. The topography near dissociation differs significantly from previous surfaces, without spurious submerged reefs and corresponding van der Waals wells. This has enabled significantly improved descriptions of scattering processes, capturing the negative temperature dependence and large kinetic isotope effects in exchange reaction rates. The exchange reactivity was found to depend on the character of near-threshold resonances and their overlap with reactant and product wavefunctions, which in turn are sensitive to the potential. Here we present global "three-well" calculations of all bound vibrational states of three isotopic combinations of ozone for J = 0 and J = 1 with a focus on the character and density of highly excited states. The calculations were done using a parallel symmetry-adapted Lanczos method with the RTR code, enabling the use of as many as 64.8 million basis functions. Tunneling splittings and the pseudorotation isomerization path will be discussed.

  16. 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.

  17. 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.

  18. 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.

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

    PubMed

    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 4000-400cm(-1) and 3600-50cm(-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.

  20. 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.

  1. Vibrational Energy Levels via Finite-Basis Calculations Using a Quasi-Analytic Form of the Kinetic Energy.

    PubMed

    Vázquez, Juana; Harding, Michael E; Stanton, John F; Gauss, Jürgen

    2011-05-10

    A variational method for the calculation of low-lying vibrational energy levels of molecules with small amplitude vibrations is presented. The approach is based on the Watson Hamiltonian in rectilinear normal coordinates and characterized by a quasi-analytic integration over the kinetic energy operator (KEO). The KEO beyond the harmonic approximation is represented by a Taylor series in terms of the rectilinear normal coordinates around the equilibrium configuration. This formulation of the KEO enables its extension to arbitrary order until numerical convergence is reached for those states describing small amplitude motions and suitably represented with a rectilinear system of coordinates. A Gauss-Hermite quadrature grid representation of the anharmonic potential is used for all the benchmark examples presented. Results for a set of molecules with linear and nonlinear configurations, i.e., CO2, H2O, and formyl fluoride (HFCO), illustrate the performance of the method and the versatility of our implementation.

  2. Automatic generation of force fields and property surfaces for use in variational vibrational calculations of anharmonic vibrational energies and zero-point vibrational averaged properties.

    PubMed

    Kongsted, Jacob; Christiansen, Ove

    2006-09-28

    An automatic and general procedure for the calculation of geometrical derivatives of the energy and general property surfaces for molecular systems is developed and implemented. General expressions for an n-mode representation are derived, where the n-mode representation includes only the couplings between n or less degrees of freedom. The general expressions are specialized to derivative force fields and property surfaces, and a scheme for calculation of the numerical derivatives is implemented. The implementation is interfaced to electronic structure programs and may be used for both ground and excited electronic states. The implementation is done in the context of a vibrational structure program and can be used in combination with vibrational self-consistent field (VSCF), vibrational configuration interaction (VCI), vibrational Moller-Plesset, and vibrational coupled cluster calculations of anharmonic wave functions and calculation of vibrational averaged properties at the VSCF and VCI levels. Sample calculations are presented for fundamental vibrational energies and vibrationally averaged dipole moments and frequency dependent polarizabilities and hyperpolarizabilities of water and formaldehyde.

  3. Combining transition state calculations with quasiclassical trajectory calculations. II. Collinear collisions involving vibrationally excited reagents

    NASA Astrophysics Data System (ADS)

    Frost, Robert J.; Smith, Ian W. M.

    1987-02-01

    Conventional quasiclassical trajectory simulations of collinear reactive collisions, A + BC ( v = 0, 1 and 2) → AB + C, have been compared with trajectories integrated forward and backward in time from points along a dividing line S * in the strong interaction zone. Calculations have been performed on three different potential energy surfaces, ranging from a strongly attractive surface with a 1 kcal mol -1 barrier to a strongly repulsive surface with a 10 kcal mol -1 barrier, and for all combinations of light (1 amu) and heavy (35 amu) atoms. Two methods of selecting S* have been examined. The first, based on defining vibrationally adiabatic states orthogonal to the minimum energy path by an approximate analysis, works well for many combinations of potential energy surface and atomic masses. However, a better method is to use pods (periodic orbiting dividing surfaces) for which the action over one cycle of the pods motion is equal to ( v + 1/2h. In only a few cases, where the pods cross the minimum energy path after substantial curvature in the latter, is the agreement between the two sets of calculations less than very good. The results confirm that reagent vibrational motion is in many cases strongly adiabatic up to S* (i.e. the transition state), and suggest that similar combined calculations on three-dimensional systems should provide a substantial saving in computer effort compared with conventional quasiclassical trajectory methods.

  4. Multiple-source multiple-harmonic active vibration control of variable section cylindrical structures: A numerical study

    NASA Astrophysics Data System (ADS)

    Liu, Jinxin; Chen, Xuefeng; Gao, Jiawei; Zhang, Xingwu

    2016-12-01

    Air vehicles, space vehicles and underwater vehicles, the cabins of which can be viewed as variable section cylindrical structures, have multiple rotational vibration sources (e.g., engines, propellers, compressors and motors), making the spectrum of noise multiple-harmonic. The suppression of such noise has been a focus of interests in the field of active vibration control (AVC). In this paper, a multiple-source multiple-harmonic (MSMH) active vibration suppression algorithm with feed-forward structure is proposed based on reference amplitude rectification and conjugate gradient method (CGM). An AVC simulation scheme called finite element model in-loop simulation (FEMILS) is also proposed for rapid algorithm verification. Numerical studies of AVC are conducted on a variable section cylindrical structure based on the proposed MSMH algorithm and FEMILS scheme. It can be seen from the numerical studies that: (1) the proposed MSMH algorithm can individually suppress each component of the multiple-harmonic noise with an unified and improved convergence rate; (2) the FEMILS scheme is convenient and straightforward for multiple-source simulations with an acceptable loop time. Moreover, the simulations have similar procedure to real-life control and can be easily extended to physical model platform.

  5. Vibrational mode analysis and heat capacity calculation of K2SiSi3O9-wadeite

    NASA Astrophysics Data System (ADS)

    Chang, Linlin; Liu, Xi; Liu, Hong; Kojitani, Hiroshi; Wang, Sicheng

    2013-07-01

    The phonon dispersions and vibrational density of state (VDoS) of the K2SiSi3O9-wadeite (Wd) have been calculated by the first-principles method using density functional perturbation theory. The vibrational frequencies at the Brillouin zone center are in good correspondence with the Raman and infrared experimental data. The calculated VDoS was then used in conjunction with a quasi-harmonic approximation to compute the isobaric heat capacity ( C P ) and vibrational entropy (S_{298}0), yielding C P ( T) = 469.4(6) - 2.90(2) × 103 T -0.5 - 9.5(2) × 106 T -2 + 1.36(3) × 109 T -3 for the T range of 298-1,000 K and S_{298}0 = 250.4 J mol-1 K-1. In comparison, these thermodynamic properties were calculated by a second method, the classic Kieffer's lattice vibrational model. On the basis of the vibrational mode analysis facilitated by the first-principles simulation result, we developed a new Kieffer's model for the Wd phase. This new Kieffer's model yielded C P ( T) = 475.9(6) - 3.15(2) × 103 T -0.5 - 8.8(2) × 106 T -2 + 1.31(3) × 109 T -3 for the T range of 298-1,000 K and S_{298}0 = 249.5(40) J mol-1 K-1, which are in good agreement both with the results from our first method containing the component of the first-principles calculation and with some calorimetric measurements in the literature.

  6. Variational Calculations of IR Ro-Vibrational Spectra for Nitric Acid

    NASA Astrophysics Data System (ADS)

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

    2013-09-01

    To model the atmospheric composition of the potentially habitable planets, it is essential to have comprehensive data on the spectroscopic properties of the main molecular absorbers. This is especially true in the infrared region which is dominated by transitions of polyatomic molecules [1]. Nitric acid (HNO3) is an important constituent of the Earth atmosphere where it is a prominent bio-signature. Here we present simulations of the absorption spectra for HNO3. We have developed a variational method to solve the ro-vibrational Schrödinger equation for a general polyatomic molecule. The ro-vibrational Hamiltonian is given by [2] where the internal curvilinear vibrational coordinates qi are used to represent the displacements of the bond lengths and bond angles, ?ij(q) are elements of the matrix of the kinematic coefficients, t is the determinant of this matrix, 'a are the Euler angles, and μab(q) is the inverse matrix of the tensor of inertia. The potential energy function, V (q), is given by a fourthorder polynomial expansion in terms of Morse variables xi = 1 - e-iqi for the stretching coordinates and xi = qi for the bending coordinates. The dipole moment of the molecule is presented in the form of a Taylor series of the 2nd order in terms of qi. The parameters of the potential energy and the dipole moment functions of HNO3 were calculated by the quantum chemical method at the CCSD(T)/aug-cc-pVQZ level of theory. With this potential energy function, agreement between the calculated and experimental fundamental frequencies of vibrations is within 5 cm -1. The harmonic part of the potential function was then optimized by fitting to the experimental fundamental frequencies and used to simulate the IR spectra of HNO3. The results are in good agreement with the experimental data. The figure shows an example of the simulated spectra of HNO3 in the area of the strong Fermi resonance between the -5 and 2-9 bands along with an experimental counterpart. The resulting

  7. A systematic theoretical study of harmonic vibrational frequencies: The ammonium ion NH4+ and other simple molecules

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Yukio; Schaefer, Henry F.

    1980-09-01

    Analytic gradient techniques have been used to predict the harmonic vibrational frequencies of HCN, H2CO, H2O, CH4 and NH4+ at several levels of molecular electronic structure theory. Basis sets of double zeta, double zeta plus polarization, and extended plus polarization quality have been used in conjunction with self-consistent-field and configuration interaction methods. For the four spectroscopically characterized molecules, comparison with theory is particularly appropriate because experimental harmonic frequencies are available. For the 16 vibrational frequencies thus considered, the DZ SCF level of theory yields average errors of 166 cm-1 or 8.0%. The DZ+P SCF results are of comparable accuracy, differing on the average from experiment by 176 cm-1 or 8.3%. With the extended basis set, the comparable SCF frequency errors are only slightly less. The explicit incorporation of correlation effects qualitatively improves the agreement between theoretical and experimental harmonic vibrational frequencies. The DZ CI frequencies differ on the average by only 44 cm-1 or 2.0%. Perhaps surprisingly, the use of larger basis sets in conjunction with CI including all singly and doubly excited configurations leads to larger average errors in the vibrational frequencies. For example, the DZ+P CI frequencies have average errors of 80 cm-1 or 3.5%. Thus it seems clear that higher excitations (probably unlinked clusters especially) have a significant effect (order of 50 cm-1) on the theoretical prediction of polyatomic vibrational frequencies. The apparent discrepancy between the theoretical and experimental equilibrium geometry of CH4 is resolved here, and shown to have been a simple consequence of basis set incompleteness. Finally, the gas phase NH4+ equilibrium bond distance is predicted to be 1.022 Å, or 0.01-0.02 Å shorter than found by Ibers and Stevenson for NH4+ in crystalline NH4Cl and NH4F.

  8. Calculating vibrational spectra without determining excited eigenstates: Solving the complex linear equations of damped response theory for vibrational configuration interaction and vibrational coupled cluster states.

    PubMed

    Godtliebsen, Ian H; Christiansen, Ove

    2015-10-07

    It is demonstrated how vibrational IR and Raman spectra can be calculated from damped response functions using anharmonic vibrational wave function calculations, without determining the potentially very many eigenstates of the system. We present an implementation for vibrational configuration interaction and vibrational coupled cluster, and describe how the complex equations can be solved using iterative techniques employing only real trial vectors and real matrix-vector transformations. Using this algorithm, arbitrary frequency intervals can be scanned independent of the number of excited states. Sample calculations are presented for the IR-spectrum of water, Raman spectra of pyridine and a pyridine-silver complex, as well as for the infra-red spectrum of oxazole, and vibrational corrections to the polarizability of formaldehyde.

  9. Calculating vibrational spectra without determining excited eigenstates: Solving the complex linear equations of damped response theory for vibrational configuration interaction and vibrational coupled cluster states

    NASA Astrophysics Data System (ADS)

    Godtliebsen, Ian H.; Christiansen, Ove

    2015-10-01

    It is demonstrated how vibrational IR and Raman spectra can be calculated from damped response functions using anharmonic vibrational wave function calculations, without determining the potentially very many eigenstates of the system. We present an implementation for vibrational configuration interaction and vibrational coupled cluster, and describe how the complex equations can be solved using iterative techniques employing only real trial vectors and real matrix-vector transformations. Using this algorithm, arbitrary frequency intervals can be scanned independent of the number of excited states. Sample calculations are presented for the IR-spectrum of water, Raman spectra of pyridine and a pyridine-silver complex, as well as for the infra-red spectrum of oxazole, and vibrational corrections to the polarizability of formaldehyde.

  10. Calculation of Raman optical activity spectra for vibrational analysis.

    PubMed

    Mutter, Shaun T; Zielinski, François; Popelier, Paul L A; Blanch, Ewan W

    2015-05-07

    By looking back on the history of Raman Optical Activity (ROA), the present article shows that the success of this analytical technique was for a long time hindered, paradoxically, by the deep level of detail and wealth of structural information it can provide. Basic principles of the underlying theory are discussed, to illustrate the technique's sensitivity due to its physical origins in the delicate response of molecular vibrations to electromagnetic properties. Following a short review of significant advances in the application of ROA by UK researchers, we dedicate two extensive sections to the technical and theoretical difficulties that were overcome to eventually provide predictive power to computational simulations in terms of ROA spectral calculation. In the last sections, we focus on a new modelling strategy that has been successful in coping with the dramatic impact of solvent effects on ROA analyses. This work emphasises the role of complementarity between experiment and theory for analysing the conformations and dynamics of biomolecules, so providing new perspectives for methodological improvements and molecular modelling development. For the latter, an example of a next-generation force-field for more accurate simulations and analysis of molecular behaviour is presented. By improving the accuracy of computational modelling, the analytical capabilities of ROA spectroscopy will be further developed so generating new insights into the complex behaviour of molecules.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. Molecular structure, normal coordinate analysis, harmonic vibrational frequencies, NBO, HOMO-LUMO analysis and detonation properties of (S)-2-(2-oxopyrrolidin-1-yl) butanamide by density functional methods.

    PubMed

    Renuga, S; Muthu, S

    2014-01-24

    Density functional theory (DFT) computations have become an efficient tool in the prediction of molecular structure, harmonic force fields, vibrational wave numbers as well as the IR and Raman intensities of pharmaceutically important molecule. In this work, we report harmonic vibrational frequencies, molecular structure, NBO and HOMO, LUMO analysis and detonation properties of (S)-2-(2-oxopyrrolidin-1-yl) butanamide. The solid phase FT-IR and FT-Raman spectra of (S)-2-(2-oxopyrrolidin-1-yl) butanamide were recorded in the region 4000-450 cm(-1) and 4000-50 cm(-1) respectively. Harmonic frequencies of this compound were determined and analyzed by DFT utilizing 6-31G(d,p), 6-31+G(d,p) basis sets. 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 calculated infrared and Raman spectra of the title compounds were also stimulated utilizing the scaled force fields and the computed dipole derivatives for IR intensities and polarizability derivatives for Raman intensities. The change in electron density (ED) in the σ(*) and π(*) antibonding orbital's 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. Heat of formation (HOF) and calculated density were estimated to evaluate detonation properties using Kamlet-Jacobs equations. The linear polarizability (α) and the first order hyperpolarizability (β) values of the investigated molecule have been computed using DFT calculations. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. The observed and calculated wave numbers are found to be in good agreement. On the basis of vibrational analyses, the thermodynamic properties of title compound at different temperatures have been calculated.

  16. Molecular structure, normal coordinate analysis, harmonic vibrational frequencies, NBO, HOMO-LUMO analysis and detonation properties of (S)-2-(2-oxopyrrolidin-1-yl) butanamide by density functional methods

    NASA Astrophysics Data System (ADS)

    Renuga, S.; Muthu, S.

    2014-01-01

    Density functional theory (DFT) computations have become an efficient tool in the prediction of molecular structure, harmonic force fields, vibrational wave numbers as well as the IR and Raman intensities of pharmaceutically important molecule. In this work, we report harmonic vibrational frequencies, molecular structure, NBO and HOMO, LUMO analysis and detonation properties of (S)-2-(2-oxopyrrolidin-1-yl) butanamide. The solid phase FT-IR and FT-Raman spectra of (S)-2-(2-oxopyrrolidin-1-yl) butanamide were recorded in the region 4000-450 cm-1 and 4000-50 cm-1 respectively. Harmonic frequencies of this compound were determined and analyzed by DFT utilizing 6-31G(d,p), 6-31+G(d,p) basis sets. 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 calculated infrared and Raman spectra of the title compounds were also stimulated utilizing the scaled force fields and the computed dipole derivatives for IR intensities and polarizability derivatives for Raman intensities. The change in electron density (ED) in the σ* and π* antibonding orbital's 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. Heat of formation (HOF) and calculated density were estimated to evaluate detonation properties using Kamlet-Jacobs equations. The linear polarizability (α) and the first order hyperpolarizability (β) values of the investigated molecule have been computed using DFT calculations. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. The observed and calculated wave numbers are found to be in good agreement. On the basis of vibrational analyses, the thermodynamic properties of title compound at different temperatures have been calculated.

  17. Calculation of three-dimensional unsteady flows in turbomachinery using the linearized harmonic Euler equations

    SciTech Connect

    Hall, K.C.; Lorence, C.B. . Dept. of Mechanical Engineering and Materials Science)

    1993-10-01

    An efficient three-dimensional Euler analysis of unsteady flows in turbomachinery is presented. The unsteady flow is modeled as the sun of a steady or mean flow field plus a harmonically varying small perturbation flow. The linearized Euler equations, which describe the small perturbation unsteady flow, are found to be linear, variable coefficient differential equations whose coefficients depend on the mean flow. A pseudo-time time-marching finite-volume Lax-Wendroff scheme is used to discretize and solve the linearized equations for the unknown perturbation flow quantities. Local time stepping and multiple-grid acceleration techniques are used to speed convergence. For unsteady flow problems involving blade motion, a harmonically deforming computational grid, which conforms to the motion of the vibrating blades, is used to eliminate large error-producing extrapolation terms that would otherwise appear in the airfoil surface boundary conditions and in the evaluation of the unsteady surface pressure. Results are presented for both linear and annular cascade geometries, and for the latter, both rotating and nonrotating blade row.

  18. Calculations for shortening the bunch length in storage rings using a harmonic cavity

    NASA Astrophysics Data System (ADS)

    Fan, Hao; Wu, Cong-Feng; He, Duo-Hui

    2014-08-01

    Using the Hefei Light Source phase II project (HLS- II) as an example, a theoretical analysis of shortening the bunch lengths using a higher harmonic cavity (HHC) is given. The threshold voltage of an active HHC and the threshold tuning angle of a passive HHC are first analysed. The optimum tuning angle for the constant detuning scenario and the optimum harmonic voltage for the constant voltage scenario are presented. The calculated results show that the reduced bunch length is about half that of the nominal bunch. The bunch lengths vary from 11 mm at 0.1 A to 7 mm at 0.4 A for the constant detuning scenario, while the bunch lengths are around 7 mm over the beam current range for the constant voltage scenario. In addition, the synchrotron frequency spread is increased. It indicates that HHC may be used to reduce the bunch length and increase the Landau damping of synchrotron oscillations in a storage ring.

  19. Calculations of operating schemes for a passive harmonic cavity in HLS- II

    NASA Astrophysics Data System (ADS)

    Fan, Hao; Wu, Cong-Feng; Liu, Guang-Chao

    2012-09-01

    A passive higher harmonic cavity (HHC) will be used in the Hefei Light Source II Project (HLS- II) to lengthen the bunch and consequently increase the beam lifetime dominated by Touschek scattering. The effects of constant voltage and constant detuning have been calculated and compared over the operating current from 0.4 to 0.2 A on the bunch lengthening for the passive normal conducting harmonic cavity system in HLS- II. The results show that the bunch shape has less change and the lifetime improvement factors are not less than 2.7 over the beam currents for the constant voltage case. The constant voltage operating scheme may be applied to our machine.

  20. Pressure dependence of harmonic and an harmonic lattice dynamics in MgO: A first-principles calculation and implications for lattice thermal conductivity

    SciTech Connect

    Tang, Xiaoli; Dong, Jianjun

    2009-06-01

    We report a recent first-principles calculation of harmonic and anharmonic lattice dynamics of MgO. The 2nd order harmonic and 3rd order anharmonic interatomic interaction terms are computed explicitly, and their pressure dependences are discussed. The phonon mode Grueneisen parameters derived based on our calculated 3rd order lattice anharmonicity are in good agreement with those estimated using the finite difference method. The implications for lattice thermal conductivity at high pressure are discussed based on a simple kinetic transport theory.

  1. Tight binding calculations of vibrational and thermal properties of amorphous silicon

    NASA Astrophysics Data System (ADS)

    Mehl, Michael; Feldman, Joseph; Papaconstantopoulos, Dimitris; Bernstein, Noam

    2006-03-01

    By displacing atoms by different amounts and computing atomic forces within the NRL tight binding method we obtain all second order (harmonic) and some third order (anharmonic) coupling constants of a 1000 atom TB-relaxed Wooten CRN model of amorphous silicon. The harmonic force constant results allow us to study various properties including vibrational density of states, dynamic structure factors, specific heat and thermal conductivity within Kubo theory. We shall present results of these applications and compare to experiment and previous work based on the Stillinger Weber potential.

  2. 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.

  3. Vibrational spectra, ab initio calculations and vibrational assignments of 3-butyn-1-ol

    NASA Astrophysics Data System (ADS)

    Nielsen, Claus J.; Horn, Anne; Klaeboe, Peter; Guirgis, Gamil A.

    2008-08-01

    The infrared spectra of 3-butyn-1-ol, HC tbnd CCH 2CH 2OH, have been recorded as a vapour in the range 3600-50 cm -1 and as a liquid between 3600 and 400 cm -1. Additional spectra of the alcohol isolated in an argon matrix at ca. 5 K were obtained and spectra were recorded after annealing to various temperatures between 10 and 35 K. Raman spectra of the liquid were recorded at room temperature and at various temperatures between 295 and 143 K. Spectra of an amorphous solid were recorded at 78 K. In spite of several attempts and many different annealing temperatures, the sample crystallized neither in the IR nor in the Raman cryostats. In the variable temperature Raman spectra, some bands of the liquid changed in relative intensity and were interpreted in terms of conformational equilibria between two of the five possible conformers. Complete assignments were made for all the bands of the most stable conformer gg, in which the OH group is approaching the triple bond, forming an intramolecular hydrogen bond. From various bands assigned to a second conformer aa, in which OH is oriented anti to the sbnd C tbnd C sbnd bond, or a third conformer ag, the conformational enthalpy difference was found to be Δ confH( ag-gg) = 0.9 kJ mol -1 in the liquid. The two highest energy conformers g'g and ag were not detected. Quantum-chemical calculations have been carried out at the MP2 and B3LYP levels with a variety of basis sets. The calculations revealed that gg was the low energy conformer and CBS-QB3 calculations suggested the gg conformer was more stable by 5.4 and 4.2 kJ mol -1 relative to ag and aa, respectively, in the vapour. Vibrational wavenumbers and infrared and Raman band intensities for the three low energy conformers are reported from B3LYP/cc-pVTZ calculations.

  4. 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.

  5. [Contemporary hygienic regulation of industrial vibration: harmonizing national and foreign approaches].

    PubMed

    Prokopenko, L V; Kravchenko, O K; Kur'erov, N N

    2009-01-01

    The authors compared approaches to vibration safety regulations, presented by new Russian Federal governmental standards, international standards and rules from one hand, and by Russian Federal Sanitary Regulation documents from the other hand. Main directions to improve hygienic regulation of occupational vibration in new technical regulation system are determined.

  6. 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.

  7. Molecular structure, vibrational analysis (FT-IR, FT-Raman), NMR, UV, NBO and HOMO-LUMO analysis of N,N-Diphenyl Formamide based on DFT calculations.

    PubMed

    Mathammal, R; Monisha, N R; Yasaswini, S; Krishnakumar, V

    2015-03-15

    In this work, the vibrational spectral analysis is carried out by using Raman and infrared spectroscopy in the range 4000-400 cm(-1) and 4000-50 cm(-1) respectively for N,N-Diphenyl Formamide (DPF) molecule. The optimized molecular structures, vibrational frequencies and corresponding vibrational assignments, nuclear magnetic resonance (NMR) and ultraviolet-visible (UV-VIS) spectra of the title molecule are evaluated using density functional theory (DFT) with standard B3LYP/6-31G(d,p) basis set. The harmonic vibrational frequencies are calculated and the scaled values have been compared with experimental FT-IR and FT-Raman spectra. The observed and calculated frequencies are found to be in good agreement. The stability of the molecule arising from hyper conjugative interactions and the charge delocalization has been analyzed using natural bond (NBO) analysis. The possible electronic transitions are determined by HOMO-LUMO orbital shapes and their energies. Thermodynamic properties (heat capacity, entropy and enthalpy) and the first hyperpolarizability of the title compound are calculated. The Mulliken charges and electric dipole moment of the molecule are computed using DFT calculations. The (1)H and (13)C nuclear magnetic resonance (NMR) chemical shift of the molecules are calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results.

  8. On-the-fly ab intito calculations of anharmonic vibrational frequencies: Local-monomer theory and application to HCl clusters

    NASA Astrophysics Data System (ADS)

    Mancini, John S.; Bowman, Joel M.

    2013-10-01

    We present an on-the-fly quantum mechanical method to obtain anharmonic vibrational frequencies for molecular clusters. The basis for the method is the local-monomer model, a "divide and conquer" approach to theoretical spectroscopy, previously applied using full-dimensional surfaces [Y. Wang and J. M. Bowman, J. Chem. Phys. 134, 154510 (2011)]. The model consists of performing a local normal-mode analysis for each monomer in a cluster in the field of the surrounding monomers. Anharmonic vibrational frequencies are then determined for each monomer by numerically solving the Schrödinger equation in terms of the local coordinates using ab initio energies obtained directly. Residual monomer-monomer coupling is accounted for using the Hückel-coupling extension [Y. Wang and J. M. Bowman, J. Chem. Phys. 136, 144113 (2012)]. In addition to the direct local-monomer approach, we propose and demonstrate a composite ab initio technique to reduce computational costs for calculating the anharmonic frequencies of large clusters. This technique utilizes two ab initio methods, a lower level of theory to compute geometries and perform harmonic analyses and a subsequent higher level of theory to compute the energies used in the anharmonic frequency calculations. We demonstrate the on-the-fly approach on hydrogen chloride clusters ranging in size from the dimer to the hexamer. Comparisons of the theoretical frequencies are made to previous experiments. We find the method to be an effective and computationally efficient approach to compute anharmonic frequencies.

  9. RESEARCH NOTE: On the efficient calculation of ordinary and generalized spherical harmonics

    NASA Astrophysics Data System (ADS)

    Masters, Guy; Richards-Dinger, Keith

    1998-10-01

    Algorithms for the stable computation of generalized and ordinary spherical harmonics are presented. The algorithms are fast and have the useful property that they can compute harmonics for isolated harmonic degrees. fortran and C programs implementing these algorithms are available from the authors.

  10. Four-body continuum-discretized coupled-channels calculations using a transformed harmonic oscillator basis

    SciTech Connect

    Rodriguez-Gallardo, M.; Arias, J. M.; Gomez-Camacho, J.; Moro, A. M.; Johnson, R. C.; Tostevin, J. A.; Thompson, I. J.

    2008-06-15

    The scattering of a weakly bound three-body system by a target is discussed. A transformed harmonic oscillator basis is used to provide an appropriate discrete and finite basis for treating the continuum part of the spectrum of the projectile. The continuum-discretized coupled-channels framework is used for the scattering calculations. The formalism is applied to different reactions, {sup 6}He+{sup 12}C at 229.8 MeV, {sup 6}He+{sup 64}Zn at 10 and 13.6 MeV, and {sup 6}He+{sup 208}Pb at 22 MeV, induced by the Borromean nucleus {sup 6}He. Both the Coulomb and nuclear interactions with a target are taken into account.

  11. Analytical transformed harmonic oscillator basis for continuum discretized coupled channels calculations

    SciTech Connect

    Moro, A. M.; Arias, J. M.; Gomez-Camacho, J.; Perez-Bernal, F.

    2009-11-15

    A new method for continuum discretization in continuum-discretized coupled-channels calculations is proposed. The method is based on an analytic local-scale transformation of the harmonic-oscillator wave functions proposed for other purposes in a recent work [Karatagladis et al., Phys. Rev. C 71, 064601 (2005)]. The new approach is compared with the standard method of continuum discretization in terms of energy bins for the reactions d+{sup 58}Ni at 80 MeV, {sup 6}Li+{sup 40}Ca at 156 MeV, and {sup 6}He+{sup 208}Pb at 22 MeV and 240 MeV/nucleon. In all cases very good agreement between both approaches is found.

  12. 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.

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

    PubMed

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

    2014-08-14

    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. 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.

  15. Calculation of HVDC-converter harmonics in frequency domain with regard to asymmetries and comparison with time domain simulations

    SciTech Connect

    Rittiger, J.; Kulicke, B.

    1995-10-01

    In order to study the effects of large HVDC converters to the feeding ac networks, it is of importance to explain and to calculate harmonic phenomena which are a result of converter operation. During commissioning of real HVDC converters it could be seen, that harmonics resulting from unsymmetries in the system voltages or from unsymmetries in converter operation led to significant difficulties concerning the system design. For this reason, not only the effects of characteristic but also the effects of noncharacteristic converter harmonics must be taken into account. The aim is to describe the steady state harmonic behavior of the converter. The harmonic spectra are not determined by time domain analysis but instead the solution is found by frequency domain calculations. This can result in reduced calculation time in comparison to conventional fourier analysis of the time functions. The converter is interpreted as an amplitude modulator with voltage and current converter functions which describe the coupling of the dc circuit and the ac network through the converter. To verify the theory, comparison of frequency domain with time domain calculations were carried out.

  16. 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.

  17. 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.

  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. 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.

  20. 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.

  1. Calculated low-energy electron-impact vibrational excitation cross sections for CO2 molecule

    NASA Astrophysics Data System (ADS)

    Laporta, V.; Tennyson, J.; Celiberto, R.

    2016-12-01

    Vibrational-excitation cross sections of ground electronic states of a carbon dioxide molecule by electron-impact through CO2-≤ft({{}2}{{\\Pi}u}\\right) shape resonance is considered in the separation of the normal modes approximation. Resonance curves and widths are computed for each vibrational mode. The calculations assume a decoupling between normal modes and employ the local complex potential model for the treatment of nuclear dynamics, usually adopted for electron-scattering involving diatomic molecules. Results are presented for excitation up to 10 vibrational levels in each mode and a comparison with data present in the literature is discussed.

  2. Anharmonic vibrational studies of L-aspartic acid using HF and DFT calculations

    NASA Astrophysics Data System (ADS)

    Alam, Mohammad Jane; Ahmad, Shabbir

    2012-10-01

    The experimental and theoretical studies on the structure, molecular properties and vibrational spectra of L-aspartic acid are presented. The molecular structure, harmonic and anharmonic vibrational frequencies, molecular properties, MEP mapping, NBO analysis and electronic spectra of L-aspartic acid have been reported. Computed geometrical parameters and anharmonic frequencies of fundamental, combination and overtone transitions were found in satisfactory agreement with the experimental data. The UV-Vis spectrum of present molecule has been recorded and the electronic properties such as HOMO and LUMO energies and few low lying excited states were carried out by using time dependent density functional theory (TD-DFT) approach. Natural Bond Orbital (NBO) analysis has been performed for analyzing charge delocalization throughout the molecule. Molecular electrostatic potential map has also been used for quantitative measure of the chemical activities of various sites of the molecule.

  3. Geometric phase and topology of elastic oscillations and vibrations in model systems: Harmonic oscillator and superlattice

    NASA Astrophysics Data System (ADS)

    Deymier, P. A.; Runge, K.; Vasseur, J. O.

    2016-12-01

    We illustrate the concept of geometric phase in the case of two prototypical elastic systems, namely the one-dimensional harmonic oscillator and a one-dimensional binary superlattice. We demonstrate formally the relationship between the variation of the geometric phase in the spectral and wave number domains and the parallel transport of a vector field along paths on curved manifolds possessing helicoidal twists which exhibit non-conventional topology.

  4. Coupled vibration of driving sections for an electromechanical integrated harmonic piezodrive system

    NASA Astrophysics Data System (ADS)

    Li, Chong; Xing, Jichun; Xu, Lizhong

    2014-03-01

    An electromechanical integrated harmonic piezodrive system was developed that elicits fast responses with nanoscale accuracy and large torque density. The operating principle of the drive system is discussed and its dynamic equations are deduced. Coupled with boundary conditions and continuity conditions, these equations provide the natural frequencies and modal functions. The effects of the principal factors affecting the natural frequencies are investigated. These results provide a basis for improving the rotational accuracy of such systems.

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

    PubMed

    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 C1 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.

  6. 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.

  7. 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.

  8. Dependence of calculated postshock thermodynamic variables on vibrational equilibrium and input uncertainty

    DOE PAGES

    Campbell, Matthew Frederick; Owen, Kyle G.; Davidson, David F.; ...

    2017-01-30

    The purpose of this article is to explore the dependence of calculated postshock thermodynamic properties in shock tube experiments upon the vibrational state of the test gas and upon the uncertainties inherent to calculation inputs. This paper first offers a comparison between state variables calculated according to a Rankine–Hugoniot–equation-based algorithm, known as FROSH, and those derived from shock tube experiments on vibrationally nonequilibrated gases. It is shown that incorrect vibrational relaxation assumptions could lead to errors in temperature as large as 8% for 25% oxygen/argon mixtures at 3500 K. Following this demonstration, this article employs the algorithm to show themore » importance of correct vibrational equilibration assumptions, noting, for instance, that errors in temperature of up to about 2% at 3500 K may be generated for 10% nitrogen/argon mixtures if vibrational relaxation is not treated properly. Lastly, this article presents an extensive uncertainty analysis, showing that postshock temperatures can be calculated with root-of-sum-of-square errors of better than ±1% given sufficiently accurate experimentally measured input parameters.« less

  9. Testing a simple control law to reduce broadband frequency harmonic vibrations using semi-active tuned mass dampers

    NASA Astrophysics Data System (ADS)

    Moutinho, Carlos

    2015-05-01

    This paper is focused on the control problems related to semi-active tuned mass dampers (TMDs) used to reduce harmonic vibrations, specially involving civil structures. A simplified version of the phase control law is derived and its effectiveness is investigated and evaluated. The objective is to improve the functioning of control systems of this type by simplifying the measurement process and reducing the number of variables involved, making the control system more feasible and reliable. Because the control law is of ON/OFF type, combined with appropriate trigger conditions, the activity of the actuation system may be significantly reduced, which may be of few seconds a day in many practical cases, increasing the durability of the device and reducing its maintenance. Moreover, due to the ability of the control system to command the motion of the inertial mass, the semi-active TMD is relatively insensitive to its initial tuning, resulting in the capability of self-tuning and in the possibility of controlling several vibration modes of a structure over a significant broadband frequency.

  10. Calculation of rotor impedance for use in design analysis of helicopter airframe vibrations

    NASA Technical Reports Server (NTRS)

    Nygren, Kip P.

    1990-01-01

    Excessive vibration is one of the most prevalent technical obstacles encountered in the development of new rotorcraft. The inability to predict these vibrations is primarily due to deficiencies in analysis and simulation tools. The Langley Rotorcraft Structural Dynamics Program was instituted in 1984 to meet long term industry needs in the area of rotorcraft vibration prediction. As a part of the Langley program, this research endeavors to develop an efficient means of coupling the rotor to the airframe for preliminary design analysis of helicopter airframe vibrations. The main effort was to modify the existing computer program for modeling the dynamic and aerodynamic behavior of rotorcraft called DYSCO (DYnamic System COupler) to calculate the rotor impedance. DYSCO was recently developed for the U.S. Army and has proven to be adaptable for the inclusion of new solution methods. The solution procedure developed to use DYSCO for the calculation of rotor impedance is presented. Verification of the procedure by comparison with a known solution for a simple wind turbine model is about 75 percent completed, and initial results are encouraging. After the wind turbine impedance is confirmed, the verification effort will continue by comparison to solutions of a more sophisticated rotorcraft model. Future work includes determination of the sensitivity of the rotorcraft airframe vibrations to helicopter flight conditions and rotor modeling assumptions. When completed, this research will ascertain the feasibility and efficiency of the impedance matching method of rotor-airframe coupling for use in the analysis of airframe vibrations during the preliminary rotorcraft design process.

  11. 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.

  12. 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.

  13. Evaluation of the effect of vibration nonlinearity on convergence behavior of adaptive higher harmonic controllers

    NASA Technical Reports Server (NTRS)

    Molusis, J. A.; Mookerjee, P.; Bar-Shalom, Y.

    1983-01-01

    Effect of nonlinearity on convergence of the local linear and global linear adaptive controllers is evaluated. A nonlinear helicopter vibration model is selected for the evaluation which has sufficient nonlinearity, including multiple minimum, to assess the vibration reduction capability of the adaptive controllers. The adaptive control algorithms are based upon a linear transfer matrix assumption and the presence of nonlinearity has a significant effect on algorithm behavior. Simulation results are presented which demonstrate the importance of the caution property in the global linear controller. Caution is represented by a time varying rate weighting term in the local linear controller and this improves the algorithm convergence. Nonlinearity in some cases causes Kalman filter divergence. Two forms of the Kalman filter covariance equation are investigated.

  14. Decentralized harmonic active vibration control of a flexible plate using piezoelectric actuator-sensor pairs.

    PubMed

    Baudry, Matthieu; Micheau, Philippe; Berry, Alain

    2006-01-01

    We have investigated decentralized active control of periodic panel vibration using multiple pairs combining PZT actuators and PVDF sensors distributed on the panel. By contrast with centralized MIMO controllers used to actively control the vibrations or the sound radiation of extended structures, decentralized control using independent local control loops only requires identification of the diagonal terms in the plant matrix. However, it is difficult to a priori predict the global stability of such decentralized control. In this study, the general situation of noncollocated actuator-sensor pairs was considered. Frequency domain gradient and Newton-Raphson adaptation of decentralized control were analyzed, both in terms of performance and stability conditions. The stability conditions are especially derived in terms of the adaptation coefficient and a control effort weighting coefficient. Simulations and experimental results are presented in the case of a simply supported panel with four PZT-PVDF pairs distributed on it. Decentralized vibration control is shown to be highly dependent on the frequency, but can be as effective as a fully centralized control even when the plant matrix is not diagonal-dominant or is not strictly positive real (not dissipative).

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

    PubMed

    Keçeli, Murat; Hirata, So; Yagi, Kiyoshi

    2010-07-21

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

  16. VSCF calculations for the intra- and intermolecular vibrational modes of the water dimer and its isotopologs

    NASA Astrophysics Data System (ADS)

    Monteiro, João G. S.; Barbosa, André G. H.

    2016-11-01

    In this work we show how the VSCF method may be successfully used to describe all fundamental vibrational transitions of several isotopologs of water dimer. By expressing the normal mode displacements in terms of appropriate delocalized internal coordinates we are able to minimize the mode-mode coupling in the PES and thus yield PT2-VSCF frequencies in good agreement with the experiment. The use of curvilinear normal modes is of paramount importance to describe vibrational transitions of the very soft intermolecular modes. Within our approach the maximum calculated error for the (H2O)2 intermolecular frequencies are reduced from 311 cm-1 (Cartesian normal modes) to just 56 cm-1 (curvilinear normal modes). Plots of the diagonal intermolecular potential and of the vibrational wave function illustrate the remarkable effect of different coordinate systems. In conclusion, our PT2-VSCF calculations provide a fair anharmonic description of the fundamental transitions of water dimers.

  17. Vibrational absorption spectra from vibrational coupled cluster damped linear response functions calculated using an asymmetric Lanczos algorithm

    NASA Astrophysics Data System (ADS)

    Thomsen, Bo; Hansen, Mikkel Bo; Seidler, Peter; Christiansen, Ove

    2012-03-01

    We report the theory and implementation of vibrational coupled cluster (VCC) damped response functions. From the imaginary part of the damped VCC response function the absorption as function of frequency can be obtained, requiring formally the solution of the now complex VCC response equations. The absorption spectrum can in this formulation be seen as a matrix function of the characteristic VCC Jacobian response matrix. The asymmetric matrix version of the Lanczos method is used to generate a tridiagonal representation of the VCC response Jacobian. Solving the complex response equations in the relevant Lanczos space provides a method for calculating the VCC damped response functions and thereby subsequently the absorption spectra. The convergence behaviour of the algorithm is discussed theoretically and tested for different levels of completeness of the VCC expansion. Comparison is made with results from the recently reported [P. Seidler, M. B. Hansen, W. Györffy, D. Toffoli, and O. Christiansen, J. Chem. Phys. 132, 164105 (2010)] vibrational configuration interaction damped response function calculated using a symmetric Lanczos algorithm. Calculations of IR spectra of oxazole, cyclopropene, and uracil illustrate the usefulness of the new VCC based method.

  18. Vibrational absorption spectra from vibrational coupled cluster damped linear response functions calculated using an asymmetric Lanczos algorithm.

    PubMed

    Thomsen, Bo; Hansen, Mikkel Bo; Seidler, Peter; Christiansen, Ove

    2012-03-28

    We report the theory and implementation of vibrational coupled cluster (VCC) damped response functions. From the imaginary part of the damped VCC response function the absorption as function of frequency can be obtained, requiring formally the solution of the now complex VCC response equations. The absorption spectrum can in this formulation be seen as a matrix function of the characteristic VCC Jacobian response matrix. The asymmetric matrix version of the Lanczos method is used to generate a tridiagonal representation of the VCC response Jacobian. Solving the complex response equations in the relevant Lanczos space provides a method for calculating the VCC damped response functions and thereby subsequently the absorption spectra. The convergence behaviour of the algorithm is discussed theoretically and tested for different levels of completeness of the VCC expansion. Comparison is made with results from the recently reported [P. Seidler, M. B. Hansen, W. Györffy, D. Toffoli, and O. Christiansen, J. Chem. Phys. 132, 164105 (2010)] vibrational configuration interaction damped response function calculated using a symmetric Lanczos algorithm. Calculations of IR spectra of oxazole, cyclopropene, and uracil illustrate the usefulness of the new VCC based method.

  19. Vibrational spectroscopy [FTIR and FTRaman] investigation, computed vibrational frequency analysis and IR intensity and Raman activity peak resemblance analysis on 4-chloro 2-methylaniline using HF and DFT [LSDA, B3LYP and B3PW91] calculations.

    PubMed

    Ramalingam, S; Periandy, S

    2011-03-01

    In the present study, the FT-IR and FT-Raman spectra of 4-chloro-2-methylaniline (4CH2MA) have been recorded in the range of 4000-100 cm(-1). The fundamental modes of vibrational frequencies of 4CH2MA are assigned. All the geometrical parameters have been calculated by HF and DFT (LSDA, B3LYP and B3PW91) methods with 6-31G (d, p) and 6-311G (d, p) basis sets. Optimized geometries of the molecule have been interpreted and compared with the reported experimental values for aniline and some substituted aniline. The harmonic and anharmonic vibrational wavenumbers, IR intensities and Raman activities are calculated at the same theory levels used in geometry optimization. The calculated frequencies are scaled and compared with experimental values. The scaled vibrational frequencies at LSDA/B3LYP/6-311G (d, p) seem to coincide with the experimentally observed values with acceptable deviations. The impact of substitutions on the benzene structure is investigated. The molecular interactions between the substitutions (Cl, CH(3) and NH(2)) are also analyzed.

  20. 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.

  1. 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)

  2. 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/.

  3. 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.

  4. 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.

  5. A Lanczos-chain driven approach for calculating damped vibrational configuration interaction response functions

    NASA Astrophysics Data System (ADS)

    Hansen, Mikkel Bo; Seidler, Peter; Győrffy, Werner; Christiansen, Ove

    2010-09-01

    We present an approach based on the Lanczos method for calculating the vibrational configuration interaction response functions necessary for evaluating the pure vibrational contributions to the polarizabilities and first hyperpolarizabilities of molecules. The method iteratively builds a tridiagonal representation of the central response matrix, which is subsequently used for solving the response equations. From the same chain, the response functions can be evaluated approximately for any frequency as well as using any complex damping factor. Applications to formaldehyde, cyclopropene, and uracil illustrate the concepts presented.

  6. Active vibration control of a ring-stiffened cylindrical shell in contact with unbounded external fluid and subjected to harmonic disturbance by piezoelectric sensor and actuator

    NASA Astrophysics Data System (ADS)

    Kwak, Moon K.; Yang, Dong-Ho

    2013-09-01

    This paper is concerned with the suppression of vibrations and radiated sound of a ring-stiffened circular cylindrical shell in contact with unbounded external fluid by means of piezoelectric sensors and actuators. The dynamic model of a circular cylindrical shell based on the Sanders shell theory was considered together with a ring stiffener model. The mass and stiffness matrices for a ring stiffener were newly derived in this study and added to the mass and stiffness matrices of the cylindrical shell, respectively. The fluid-added mass matrix, which was derived by using the baffled shell theory, was also added to the mass matrix. Finally, the equations representing the piezoelectric sensor measurement and piezoelectric actuation complete the theoretical model for the addressed problem. The natural vibration characteristics of the ring-stiffened cylindrical shell both in air and in water were investigated both theoretically and experimentally. The theoretical predictions were in good agreement with the experimental results. An active vibration controller which can cope with a harmonic disturbance was designed by considering the modified higher harmonic control, which is, in fact, a band rejection filter. An active vibration control experiment on the submerged cylindrical shell was carried out in a water tank and the digital control system was used. The experimental results showed that both vibrations and radiation sound of the submerged cylindrical shell were suppressed by a pair of piezoelectric sensor and actuator.

  7. Studies of the molecular geometry, vibrational spectra, frontier molecular orbital, nonlinear optical and thermodynamics properties of aceclofenac by quantum chemical calculations.

    PubMed

    Suresh, S; Gunasekaran, S; Srinivasan, S

    2014-05-05

    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.

  8. Calculation of Dipole Transition Matrix Elements and Expectation Values by Vibrational Coupled Cluster Method.

    PubMed

    Banik, Subrata; Pal, Sourav; Prasad, M Durga

    2010-10-12

    An effective operator approach based on the coupled cluster method is described and applied to calculate vibrational expectation values and absolute transition matrix elements. Coupled cluster linear response theory (CCLRT) is used to calculate excited states. The convergence pattern of these properties with the rank of the excitation operator is studied. The method is applied to a water molecule. Arponen-type double similarity transformation in extended coupled cluster (ECCM) framework is also used to generate an effective operator, and the convergence pattern of these properties is compared to the normal coupled cluster (NCCM) approach. It is found that the coupled cluster method provides an accurate description of these quantities for low lying vibrational excited states. The ECCM provides a significant improvement for the calculation of the transition matrix elements.

  9. Three-dimensional quantum calculations on the ground and excited state vibrations of ethylene

    NASA Astrophysics Data System (ADS)

    Groenenboom, Gerrit Cornelis

    Three dimensional potential energy surfaces of the ground and excited states of ethylene were calculated at the MRCEPA (Multi Reference Coupled Electronic Pair Approximation) level. The modes included are the torsion, the CC stretch, and the symmetric scissors. Full vibrational calculations were performed using the Lanczos/grid method. The avoided crossing between the V and the R state was dealt with in a diabetic model. The ground state results agree within 3 up to the highest vibrational level known experimentally. The origin and the maximum of the V back arrow N band are calculated at 5.68 and 7.82 eV, respectively, approximately 0.2 eV above the somewhat ambiguous experimental values. This work considerably diminishes the existing gap of approximately 0.5 eV between theory and experiment.

  10. 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.

  11. Pressure broadening calculations for OH in collisions with argon: Rotational, vibrational, and electronic transitions

    NASA Astrophysics Data System (ADS)

    Dagdigian, Paul J.

    2017-03-01

    Collisional parameters describing both the pressure-induced broadening and shifting of isolated lines in the spectrum of the hydroxyl radical in collisions with argon have been determined through quantum scattering calculations using accurate potential energy surfaces describing the OH(X2 Π , A2Σ+)-Ar interactions. These calculations have been carried for pure rotational, vibrational, and electronic transitions. The calculated pressure broadening coefficients are in good agreement with the available measurements in the microwave, infrared, and ultraviolet spectral regions. Computed pressure broadening coefficients as a function of temperature are reported for these three types of transitions.

  12. 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.

  13. Ab initio calculation of vibrational properties of a-Si:H with inner voids

    NASA Astrophysics Data System (ADS)

    Nakhmanson, S. M.; Drabold, D. A.

    1998-05-01

    We have performed an ab initio calculation of vibrational properties of hydrogenated amorphous silicon (a-Si:H) using a molecular dynamics method. A Wooten, Winer, Weaire (WWW) 216 atom model for pure amorphous silicon (a-Si) updated by Djordjevic, Thorpe and Wooten has been employed as a ``base'' for our a-Si:H models with voids that were made by removing a cluster of silicon atoms out of the bulk and terminating the resulting dangling bonds with hydrogens. Our calculation shows that the presence of voids leads to localized low energy (30-50 cm-1) states in vibrational spectrum of the system. The nature and localization properies of these states are carefully analysed by various visualization techniques. Web resources: http://www.phy.ohiou.edu/ ĩnakhmans/Professional/Bubbles/bubpr.htm

  14. Comparison of algorithms for the calculation of molecular vibrational level densities

    NASA Astrophysics Data System (ADS)

    Hansen, K.

    2008-05-01

    Level densities of vibrational degrees of freedom are calculated numerically with formulas based on the inversion of the canonical vibrational partition function. The calculated level densities are compared with other approximate equations from literature and with the exact Beyer-Swinehart values, for which a simplified but equivalent version is given. All approximate equations agree at high excitation energies, but our results are vastly superior at low energies for large molecules. The results presented here are therefore of particular relevance for thermal processes of very large molecules, e.g., of biological nature, for which the exact state counting can be prohibitively slow. Furthermore, it is valid for situations where anharmonic motion significantly influences the thermal properties.

  15. Full dimensional Franck-Condon factors for the acetylene tilde{{A}} 1Au—{tilde{X}} {^1Σ _g^+} transition. I. Method for calculating polyatomic linear—bent vibrational intensity factors and evaluation of calculated intensities for the gerade vibrational modes in acetylene

    NASA Astrophysics Data System (ADS)

    Park, G. Barratt

    2014-10-01

    Franck-Condon vibrational overlap integrals for the tilde{A} {^1A_u}—{tilde{X}} {^1Σ _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 wavefunction for the out-of-plane component of the trans bending mode, ν _4^' ' }, 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 _5^' ' }, 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 tilde{A}-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 tilde{A} {^1A_u}—{tilde{X}} {^1Σ _g^+} transition. II. Vibrational overlap factors for levels involving excitation in ungerade modes," J. Chem. Phys. 141, 134305 (2014)].

  16. Full dimensional Franck-Condon factors for the acetylene à (1)A(u)-X̃ (1)Σ(g)(+) transition. I. Method for calculating polyatomic linear-bent vibrational intensity factors and evaluation of calculated intensities for the gerade vibrational modes in acetylene.

    PubMed

    Park, G Barratt

    2014-10-07

    Franck-Condon vibrational overlap integrals for the à Au1-X̃ 1Σg+ 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 wavefunction for the out-of-plane component of the trans bending mode, ν4(″), 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, ν5(″), 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 Ã-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 à Au1-X̃ 1Σg+ transition. II. Vibrational overlap factors for levels involving excitation in ungerade modes," J. Chem. Phys. 141, 134305 (2014)].

  17. Assignment of absolute stereostructures through quantum mechanics electronic and vibrational circular dichroism calculations.

    PubMed

    Dai, Peng; Jiang, Nan; Tan, Ren-Xiang

    2016-01-01

    Elucidation of absolute configuration of chiral molecules including structurally complex natural products remains a challenging problem in organic chemistry. A reliable method for assigning the absolute stereostructure is to combine the experimental circular dichroism (CD) techniques such as electronic and vibrational CD (ECD and VCD), with quantum mechanics (QM) ECD and VCD calculations. The traditional QM methods as well as their continuing developments make them more applicable with accuracy. Taking some chiral natural products with diverse conformations as examples, this review describes the basic concepts and new developments of QM approaches for ECD and VCD calculations in solution and solid states.

  18. Vibrational Spectra, DFT Calculations, and Assignments of the syn and the gauche Forms of Vinylphosphine.

    PubMed

    Benidar, A.; Le Doucen, R.; Guillemin, J. C.; Mó, O.; Yáñez, M.

    2001-02-01

    Infrared spectra (3500-600 cm(-1)) of vinylphosphine and its P-dideuterated derivative in the gas phase were recorded at 1 cm(-1) resolution. Both the infrared absorption bands of the syn and gauche conformers of the vinylphosphine were observed and assigned. The assignment was based on density functional theory calculations performed at the B3LYP/6-311G(d) level. The agreement between calculated and observed frequencies for both CH(2)&dbond;CHPH(2) and CH(2)&dbond;CHPD(2) was fairly good. The integrated intensities of isolated and overlapping vibrational bands were determined experimentally. Copyright 2001 Academic Press.

  19. 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.

  20. Vibrational predissociation spectroscopy of Ar-tagged, trisubstituted silyl cations

    NASA Astrophysics Data System (ADS)

    DeBlase, Andrew F.; Scerba, Michael T.; Lectka, Thomas; Johnson, Mark A.

    2013-05-01

    Vibrational predissociation spectra of the (CH3)2RSi+·Arn, (R = H and CH3, n = 1 and 2) ions are compared with harmonic calculations to structurally characterize these putative reactive intermediates. Although the vibrational photofragmentation behavior indicates that the Ar-Si bond is quite strong relative to that found in closed shell ions, formation of the Ar adducts is calculated to cause only minor perturbations to the intrinsic vibrational band patterns of the isolated ions. In both (R = H and CH3) cases, the vibrational spectra are very simple, consisting entirely of sharp features readily assigned to fundamentals anticipated by their harmonic spectra.

  1. Vibrational Frequencies of Fractionally Charged Molecular Species: Benchmarking DFT Results against ab Initio Calculations.

    PubMed

    Bâldea, Ioan

    2017-03-23

    Recent advances in nano/molecular electronics and electrochemistry made it possible to continuously tune the fractional charge q of single molecules and to use vibrational spectroscopic methods to monitor such changes. Approaches to compute vibrational frequencies ω(q) of fractionally charged species based on the density functional theory (DFT) are faced with an important issue: the basic quantity used in these calculations, the total energy, should exhibit piecewise linearity with respect to the fractional charge, but approximate, commonly utilized exchange correlation functionals do not obey this condition. In this paper, with the aid of a simple and representative example, we benchmark results for ω(q) obtained within the DFT against ab initio methods, namely, coupled cluster singles and doubles and also second- and third-order Møller-Plesset perturbation) expansions. These results indicate that, in spite of missing the aforementioned piecewise linearity, DFT-based values ω(q) can reasonably be trusted.

  2. Calculated strain response of vibrational modes for H-containing point defects in diamond.

    PubMed

    Goss, Jonathan P; Briddon, Patrick R

    2011-06-28

    The low mass of hydrogen leads to highly localised, high-frequency vibrational modes associated with H-containing defects in crystalline materials. In addition to vibrational spectroscopy, the presence of hydrogen in diamond has been identified from several experimental techniques. In particular, paramagnetic resonance shows that H is often associated with lattice vacancies, but in many cases the microscopic structure of the defects remains to be determined. We present the results of first-principles density-functional modelling of selected H-containing point defects, reporting both the calculated frequencies and the change in frequencies with applied strain. We show that more constrained environments lead to significantly larger strain-related shifts in frequency than more open environments, such as where the H is associated with lattice vacancies.

  3. Vibrational dynamics of the bifluoride ion. III. F-F (ν1) eigenstates and vibrational intensity calculations

    NASA Astrophysics Data System (ADS)

    Epa, V. C.; Thorson, W. R.

    1990-09-01

    This paper concludes a theoretical study of vibrational dynamics in the bifluoride ion FHF-, which exhibits strongly anharmonic and coupled motions. Two previous papers have described an extended model potential surface for the system, developed a scheme for analysis based on a zero-order adiabatic separation of the proton bending and stretching motions (ν2,ν3) from the slower F-F symmetric-stretch motion (ν1), and presented results of accurate calculations of the adiabatic protonic eigenstates. Here the ν1 motion has been treated, in adiabatic approximation and also including nonadiabatic couplings in close-coupled calculations with up to three protonic states (channels). States of the system involving more than one quantum of protonic excitation (e.g., 2ν2, 2ν3 σg states; 3ν2, ν2+2ν3 πu states; ν3+2ν2, 3ν3 σu states) exhibit strong mixing at avoided crossings of protonic levels, and these effects are discussed in detail. Dipole matrix elements and relative intensities for vibrational transitions have been computed with an electronic dipole moment function based on ab initio calculations for an extended range of geometries. Frequencies, relative IR intensities and other properties of interest are compared with high resolution spectroscopic data for the gas-phase free ion and with the IR absorption spectra of KHF2(s) and NaHF2(s). Errors in the ab initio potential surface yield fundamental frequencies ν2 and ν3 100-250 cm-1 higher than those observed in either the free ion or the crystalline solids, but these differences are consistent and an unambiguous assignment of essentially all transitions in the IR spectrum of KHF2 is made. Calculated relative intensities for stretching mode (ν3, σu symmetry) transitions agree well with those observed in both KHF2 [e.g., bands (ν3+nν1), (ν3+2ν2), (3ν3), etc.] and the free ion (ν3,ν3+ν1). Calculated intensities for bending mode (ν2, πu symmetry) transitions agree well with experiment for the ν2

  4. 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.

  5. 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.

  6. Systematic vibration thermodynamic properties of bromine

    NASA Astrophysics Data System (ADS)

    Liu, G. Y.; Sun, W. G.; Liao, B. T.

    2015-11-01

    Based on the analysis of the maturity and finiteness of vibrational levels of bromine molecule in ground state and evaluating the effect on statistical computation, according to the elementary principles of quantum statistical theorem, using the full set of bromine molecular vibrational levels determined with algebra method, the statistical contribution for bromine systematical macroscopic thermodynamic properties is discussed. Thermodynamic state functions Helmholtz free energy, entropy and observable vibration heat capacity are calculated. The results show that the determination of full set of vibrational levels and maximum vibrational quantum number is the key in the correct statistical analysis of bromine systematical thermodynamic property. Algebra method results are clearly different from data of simple harmonic oscillator and the related algebra method results are no longer analytical but numerical and are superior to simple harmonic oscillator results. Compared with simple harmonic oscillator's heat capacities, the algebra method's heat capacities are more consistent with the experimental data in the given temperature range of 600-2100 K.

  7. 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.

  8. Molecular structure, vibrational spectral studies of pyrazole and 3,5-dimethyl pyrazole based on density functional calculations.

    PubMed

    Krishnakumar, V; Jayamani, N; Mathammal, R

    2011-09-01

    In this work, the experimental and theoretical vibrational spectra of pyrazole (PZ) and 3,5-dimethyl pyrazole (DMP) have been studied. FTIR and FT-Raman spectra of the title compounds in the solid phase are recorded in the region 4000-400 cm(-1) and 4000-50 cm(-1), respectively. The structural and spectroscopic data of the molecules in the ground state are calculated using density functional methods (B3LYP) with 6-311+G** basis set. The vibrational frequencies are calculated and scaled values are compared with experimental FTIR and FT-Raman spectra. The observed and calculated frequencies are found to be in good agreement. The complete vibrational assignments are performed on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanical (SM) method. 13C and 1H NMR chemical shifts results are compared with the experimental values.

  9. 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

  10. Vibrational infrared spectrum of NH 3 adsorbed on MgO(100). I. Ab initio calculations

    NASA Astrophysics Data System (ADS)

    Allouche, A.; Corà, F.; Girardet, C.

    1995-12-01

    The perturbed cluster approach, previously devoted to the calculation of the stable adsorption site and energy for ammonia adsorbed on MgO(100), is used to determine the frequency and the intensity of the main peaks associated with the normal vibrational modes of the admolecule. The ab initio model based on a cluster embedded in an array of point charges is then compared to the perturbed cluster approach and used to investigate different molecular orientations and associations on the surface in order to give an interpretation to the occurrence of the infrared signals. Six normal modes for each admolecule are calculated due to the removing of internal degeneracy by adsorption. The characteristics of the calculated spectrum are compared to the experimental infrared data and it is shown that the set of selected situations is able to explain almost every band in the spectrum without implication of NH 3 dissociation on the surface.

  11. Rate calculations for the simultaneous vibrational relaxation and dissociation of nitrogen

    NASA Technical Reports Server (NTRS)

    Gonzales, David A.; Varghese, Philip L.

    1992-01-01

    Experimental data on vibrational relaxation and dissociation rates in highly nonequilibrium gases are scarce. Recently there have been several attempts at generating these rates by direct calculation of inelastic collision cross-sections. Some issues that need to be considered if such calculations are to be used as a basis for analysis and design are examined. In particular, the following are examined: (1) collinear vs 3D scattering models, (2) accurate intermolecular potentials, (3) closed channels and acceleration schemes, (4) thermal averaging and thermal rates, and (5) code validation. It has been necessary to confront these issues during the course of N2-N2 and N2-N inelastic cross-section calculations.

  12. Hydrogen vibrational modes on graphene and relaxation of the C-H stretch excitation from first-principles calculations.

    PubMed

    Sakong, Sung; Kratzer, Peter

    2010-08-07

    Density functional theory (DFT) calculations are used to determine the vibrational modes of hydrogen adsorbed on graphene in the low-coverage limit. Both the calculated adsorption energy of a H atom of 0.8 eV and calculated C-H stretch vibrational frequency of 2552 cm(-1) are unusually low for hydrocarbons, but in agreement with data from electron energy loss spectroscopy on hydrogenated graphite. The clustering of two adsorbed H atoms observed in scanning tunneling microscopy images shows its fingerprint also in our calculated spectra. The energetically preferred adsorption on different sublattices correlates with a blueshift of the C-H stretch vibrational modes in H adatom clusters. The C-H bending modes are calculated to be in the 1100 cm(-1) range, resonant with the graphene phonons. Moreover, we use our previously developed methods to calculate the relaxation of the C-H stretch mode via vibration-phonon interaction, using the Born-Oppenheimer surface for all local modes as obtained from the DFT calculations. The total decay rate of the H stretch into other H vibrations, thereby creating or annihilating one graphene phonon, is determined from Fermi's golden rule. Our calculations using the matrix elements derived from DFT calculations show that the lifetime of the H stretch mode on graphene is only several picoseconds, much shorter than on other semiconductor surfaces such as Ge(001) and Si(001).

  13. Structural, elastic, vibrational and electronic properties of amorphous Al2O3 from ab initio calculations.

    PubMed

    Davis, Sergio; Gutiérrez, Gonzalo

    2011-12-14

    First-principles molecular dynamics calculations of the structural, elastic, vibrational and electronic properties of amorphous Al(2)O(3), in a system consisting of a supercell of 80 atoms, are reported. A detailed analysis of the interatomic correlations allows us to conclude that the short-range order is mainly composed of AlO(4) tetrahedra, but, in contrast with previous results, also an important number of AlO(6) octahedra and AlO(5) units are present. The vibrational density of states presents two frequency bands, related to bond-bending and bond-stretching modes. It also shows other recognizable features present in similar amorphous oxides. We also present the calculation of elastic properties (bulk modulus and shear modulus). The calculated electronic structure of the material, including total and partial electronic density of states, charge distribution, electron localization function and the ionicity for each species, gives evidence of correlation between the ionicity and the coordination for each Al atom.

  14. 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].

  15. 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(+).

  16. A conformational study of hydroxyflavones by vibrational spectroscopy coupled to DFT calculations

    NASA Astrophysics Data System (ADS)

    Machado, N. F. L.; Batista de Carvalho, L. A. E.; Otero, J. C.; Marques, M. P. M.

    2013-05-01

    The conformational preferences of a series of hydroxyflavones were studied by Raman and FTIR spectroscopies, coupled to Density Functional Theory calculations. Special attention was paid to the effect of hydroxyl substitution, due to its importance on the biological activity of these compounds. Their conformational preferences were found to be determined mainly by the orientation of the hydroxylic groups at C7 and within the catechol moiety, leading to the occurrence of distinct conformers in the solid state. A complete assignment of the experimental spectra was carried out for these molecules, in the light of their most stable conformers and the corresponding predicted vibrational pattern.

  17. 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.

  18. The Impact of Complex Forcing on the Viscous Torsional Vibration Damper's Work in the Crankshaft of the Rotating Combustion Engine

    NASA Astrophysics Data System (ADS)

    Jagiełowicz-Ryznar, C.

    2016-12-01

    The numerical calculations results of torsional vibration of the multi-cylinder crankshaft in the serial combustion engine (MC), including a viscous damper (VD), at complex forcing, were shown. In fact, in the MC case the crankshaft rotation forcings spectrum is the sum of harmonic forcing whose amplitude can be compared with the amplitude of the 1st harmonic. A significant impact, in the engine operational velocity, on the vibration damping process of MC, may be the amplitude of the 2nd harmonic of a forcing moment. The calculations results of MC vibration, depending on the amplitude of the 2nd harmonic of the forcing moment, for the first form of the torsional vibration, were shown. Higher forms of torsional vibrations have no practical significance. The calculations assume the optimum damping coefficient VD, when the simple harmonic forcing is equal to the base critical velocity of the MC crankshaft.

  19. Concept study of a novel energy harvesting-enabled tuned mass-damper-inerter (EH-TMDI) device for vibration control of harmonically-excited structures

    NASA Astrophysics Data System (ADS)

    Salvi, Jonathan; Giaralis, Agathoklis

    2016-09-01

    A novel dynamic vibration absorber (DVA) configuration is introduced for simultaneous vibration suppression and energy harvesting from oscillations typically exhibited by large-scale low-frequency engineering structures and structural components. The proposed configuration, termed energy harvesting-enabled tuned mass-damper-inerter (EH-TMDI) comprises a mass grounded via an in-series electromagnetic motor (energy harvester)-inerter layout, and attached to the primary structure through linear spring and damper in parallel connection. The governing equations of motion are derived and solved in the frequency domain, for the case of harmonically-excited primary structures, here modelled as damped single-degree- of-freedom (SDOF) systems. Comprehensive parametric analyses proved that by varying the mass amplification property of the grounded inerter, and by adjusting the stiffness and the damping coefficients using simple optimum tuning formulae, enhanced vibration suppression (in terms of primary structure peak displacement) and energy harvesting (in terms of relative velocity at the terminals of the energy harvester) may be achieved concurrently and at nearresonance frequencies, for a fixed attached mass. Hence, the proposed EH-TMDI allows for relaxing the trade-off between vibration control and energy harvesting purposes, and renders a dual-objective optimisation a practically-feasible, reliable task.

  20. An ab initio calculation of the fundamental and overtone HCl stretching vibrations for the HCl dimer

    NASA Astrophysics Data System (ADS)

    Jensen, Per; Bunker, P. R.; Epa, V. C.; Karpfen, A.

    1992-02-01

    We have previously determined an analytical ab initio six-dimensional potential energy surface for the HCl dimer, and have used it to determine the minimum energy path for the trans-tunneling motion. In the present paper we refine this path by fitting to data. We calculate a further 178 ab initio points in order to determine the HCl stretching energies, and HCl stretching dipole moment functions, at eight positions along the minimum energy path. We use these ab initio results to compute the stretching wavenumbers and transition moments from the v1 = v2 = 0 state to all states of (HCl) 2 that have v1 + v2 ≤ 3, where v1 and v2 are the local mode quantum numbers for the HCl stretching vibrations. In doing this calculation we have assumed an adiabatic separation of the HCl stretching motion from the other vibrational motions in the dimer, and have used the semirigid bender Hamiltonian to average over the trans-tunneling motion. We obtain the fundamental "free-H" stretch v1 at 2877 cm -1 and the fundamental "bound-H" stretch v2 at 2861 cm -1; the experimental values are 2880 and 2854 cm -1, respectively.

  1. 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

    2015-01-05

    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.

  2. Improved methods for Feynman path integral calculations of vibrational-rotational free energies and application to isotopic fractionation of hydrated chloride ions.

    PubMed

    Mielke, Steven L; Truhlar, Donald G

    2009-04-23

    We present two enhancements to our methods for calculating vibrational-rotational free energies by Feynman path integrals, namely, a sequential sectioning scheme for efficiently generating random free-particle paths and a stratified sampling scheme that uses the energy of the path centroids. These improved methods are used with three interaction potentials to calculate equilibrium constants for the fractionation behavior of Cl(-) hydration in the presence of a gas-phase mixture of H(2)O, D(2)O, and HDO. Ion cyclotron resonance experiments indicate that the equilibrium constant, K(eq), for the reaction Cl(H(2)O)(-) + D(2)O right harpoon over left harpoon Cl(D(2)O)(-) + H(2)O is 0.76, whereas the three theoretical predictions are 0.946, 0.979, and 1.20. Similarly, the experimental K(eq) for the Cl(H(2)O)(-) + HDO right harpoon over left harpoon Cl(HDO)(-) + H(2)O reaction is 0.64 as compared to theoretical values of 0.972, 0.998, and 1.10. Although Cl(H(2)O)(-) has a large degree of anharmonicity, K(eq) values calculated with the harmonic oscillator rigid rotator (HORR) approximation agree with the accurate treatment to within better than 2% in all cases. Results of a variety of electronic structure calculations, including coupled cluster and multireference configuration interaction calculations, with either the HORR approximation or with anharmonicity estimated via second-order vibrational perturbation theory, all agree well with the equilibrium constants obtained from the analytical surfaces.

  3. 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.

  4. 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

    2015-02-05

    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.

  5. 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.

  6. DFT calculation of vibrational frequencies of clusters in GaAs and the Raman spectra

    NASA Astrophysics Data System (ADS)

    Radhika Devi, V.; Shrivastava, Keshav N.

    2012-09-01

    We have calculated the vibrational frequencies of clusters of Ga and As atoms from the first principles using the density-functional theory (DFT) method and the local-density approximation (LDA). We find that the calculated value of 286.2 cm-1 for a linear cluster of Ga2As2 is very near the experimental value of 292 ± 4 cm-1. The calculated value of 289.4 cm-1 for Ga2As6 (dumb bell) cluster is indeed very near the experimental value. There are strong phonon correlations so that the cluster frequency is within the dispersion relation of the crystal LO value. There is a weak line in the experimental Raman spectrum at 268 cm-1 which is very near the value of 267.3 cm-1 calculated for the Ga2As (triangular) cluster. The weak lines corresponding to the linear bonds provide the strength to the amorphous samples. There are clusters of atoms in the glassy state of GaAs.

  7. 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.

  8. Structural and vibrational study of primidone based on monomer and dimer calculations.

    PubMed

    Celik, Sefa; Kecel-Gunduz, Serda; Ozel, Aysen E; Akyuz, Sevim

    2015-01-01

    Primidone (Mysoline), with the chemical formula 5-ethyl-5-phenyl-hexahydropyrimidine- 4,6-dione (C12H14N2O2), has been a valuable drug in the treatment of epilepsy. In the present work, the experimental IR and Raman spectra of solid phase primidone were recorded, and the results were compared with theoretical wavenumber values of monomer and dimer forms of the title molecule. Vibrational spectral simulations in the dimer form were carried out to improve the assignment of the bands in the solid phase experimental spectra. The possible stable conformers of free molecule were searched by means of torsion potential energy surfaces scan studies through two dihedral angles. The molecular geometries of the monomer and dimer forms of title molecule were optimized using DFT method at B3LYP/6-31++G(d,p) level of theory. Using PEDs determined the contributions of internal (stretching, bending, etc.) coordinates to each normal mode of vibration. Further, HOMO-LUMO energy gap and NBO properties of the investigated molecule in monomer and dimer forms were also calculated.

  9. 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).

  10. A general rigorous quantum dynamics algorithm to calculate vibrational energy levels of pentaatomic molecules

    NASA Astrophysics Data System (ADS)

    Yu, Hua-Gen

    2009-08-01

    An exact variational algorithm is presented for calculating vibrational energy levels of pentaatomic molecules without any dynamical approximation. The quantum mechanical Hamiltonian of the system is expressed in a set of orthogonal coordinates defined by four scattering vectors in the body-fixed frame. The eigenvalue problem is solved using a two-layer Lanczos iterative diagonalization method in a mixed grid/basis set. A direct product potential-optimized discrete variable representation (PO-DVR) basis is used for the radial coordinates while a non-direct product finite basis representation (FBR) is employed for the angular variables. The two-layer Lanczos method requires only the actions of the Hamiltonian operator on the Lanczos vectors, where the potential-vector products are accomplished via a pseudo-spectral transform technique. By using Jacobi, Radau and orthogonal satellite vectors, we have proposed 21 types of orthogonal coordinate systems so that the algorithm is capable of describing most five-atom systems with small and/or large amplitude vibrational motions. Finally, an universal program ( PetroVib) has been developed. Its applications to the molecules CH and HO2-, and the van der Waals cluster HeCl are also discussed.

  11. Vibalizer: a free, web-based tool for rapid, quantitative comparison and analysis of calculated vibrational modes.

    PubMed

    Grafton, Anthony K

    2007-05-01

    This report describes the development and applications of a software package called Vibalizer, the first and only method that provides free, fast, interactive, and quantitative comparison and analysis of calculated vibrational modes. Using simple forms and menus in a web-based interface, Vibalizer permits the comparison of vibrational modes from different, but similar molecules and also performs rapid calculation and comparison of isotopically substituted molecules' normal modes. Comparing and matching complex vibrational modes can be completed in seconds with Vibalizer, whereas matching vibrational modes manually can take hours and gives only qualitative comparisons subject to human error and differing individual judgments. In addition to these core features, Vibalizer also provides several other useful features, including the ability to automatically determine first-approximation mode descriptions, to help users analyze the results of vibrational frequency calculations. Because the software can be dimensioned to handle almost arbitrarily large systems, Vibalizer may be of particular use when analyzing the vibrational modes of complex systems such as proteins and extended materials systems. Additionally, the ease of use of the Vibalizer interface and the straightforward interpretation of results may find favor with educators who incorporate molecular modeling into their classrooms. The Vibalizer interface is available for free use at http://www.compchem.org, and it is also available as a locally-installable package that will run on a Linux-based web server.

  12. Computer-simulation calculations of the electronic stopping of fast heavy charges by a classical harmonic oscillator

    SciTech Connect

    Jakas, M. M.; Perez de la Rosa, F. J.; Custidiano, E. R.

    2003-09-01

    The accuracy of Bohr's and more recent analytical calculations of the electronic stopping of heavy charges by a classical harmonic oscillator is analyzed. According to results in this paper, for |{xi}|{>=}100 ({xi} being the Bohr stopping parameter) the present simulations agree with previous theoretical calculations, whereas for smaller |{xi}| values, discrepancies are evident. In fact, for |{xi}|<100 the stopping cross section seems to be sensitive to the sign of the ion charge. The so-called Barkas effect is unambiguously observed and positively charged projectiles appear to have a larger stopping compared to that of negative ones at the same {xi}. Bohr's calculations, however, seem to reproduce the stopping of negative charges relatively well, but those of positive ions are consequently underestimated. By giving the electron an initial velocity, the so-called inner-shell effect on the stopping can be readily studied. The present simulations show that previous analytical predictions of this effect do not account for the present results.

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

    PubMed

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

    2006-01-28

    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.

  14. Intramolecular hydrogen bonding in myricetin and myricitrin. Quantum chemical calculations and vibrational spectroscopy

    NASA Astrophysics Data System (ADS)

    Vojta, Danijela; Dominković, Katarina; Miljanić, Snežana; Spanget-Larsen, Jens

    2017-03-01

    The molecular structures of myricetin (3,3‧,4‧,5,5‧,7-hexahydroxyflavone; MCE) and myricitrin (myricetin 3-O-rhamnoside; MCI) are investigated by quantum chemical calculations (B3LYP/6-311G**). Two preferred molecular rotamers of MCI are predicted, corresponding to different conformations of the O-rhamnoside subunit. The rotamers are characterized by different hydrogen bonded cross-links between the hydroxy groups of the rhamnoside substituent and the parent MCE moiety. The predicted OH stretching frequencies are compared with vibrational spectra of MCE and MCI recorded for the sake of this investigation (IR and Raman). In addition, a reassignment of the Cdbnd O stretching bands is suggested.

  15. The spectrum of vibration modes in soft opals.

    PubMed

    Cheng, W; Wang, J J; Jonas, U; Steffen, W; Fytas, G; Penciu, R S; Economou, E N

    2005-09-22

    Numerous vibrational modes of spherical submicrometer particles in fabricated soft opals are experimentally detected by Brillouin light scattering and theoretically identified by their spherical harmonics by means of single-phonon scattering-cross-section calculations. The particle size polydispersity is reflected in the line shape of the low-frequency modes, whereas lattice vibrations are probably responsible for the observed overdamped transverse mode.

  16. 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.

  17. 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})

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

    PubMed

    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(-1) upon dimerization, somewhat more than in the anharmonic experiment (-111 cm(-1)).

  19. Vibrational spectrum, ab initio calculations, conformational equilibria and torsional modes of 1,3-dichloropropane

    NASA Astrophysics Data System (ADS)

    Duffy, Daniel J.; Quenneville, Jason; Baumbaugh, T. M.; Kitchener, S. A.; McCormick, R. K.; Dormady, C. N.; Croce, T. A.; Navabi, A.; Stidham, Howard D.; Hsu, Shaw L.; Guirgis, Gamil A.; Deng, Shiping; Durig, James R.

    2004-02-01

    Ab initio calculations are reported for three of four possible conformers of 1,3-dichloropropane. The fourth conformer, with C s symmetry, has a predicted enthalpy difference of more than 1500 cm -1 from the most stable conformer from each calculation regardless of the basis set used, so there is little chance of observing it. Thus, there is no evidence in the infrared or Raman spectrum of the presence of a fourth conformer. The order of stability given by the ab initio calculations is C 2(GG)>C 1(AG)>C 2v(AA)>C s(GG'), where A indicates the anti form for one of the CH 2Cl groups and G indicates the gauche conformation for the other CH 2Cl group relative to the plane of the carbon atoms. Almost every band observed can be confidently assigned to one or another of the conformers. Many observed bands proved to be of a composite nature, with several nearly coincident vibrations of different conformers contributing to the band contour. Nonetheless, a complete assignment of fundamentals is possible for the most stable C 2 conformer, and 5 of the fundamentals of the C 2v conformer and 13 those of the C 1 conformer can be confidently assigned.

  20. Structure-dependent vibrational dynamics of Mg(BH 4 ) 2 polymorphs probed with neutron vibrational spectroscopy and first-principles calculations

    DOE PAGES

    Dimitrievska, Mirjana; White, James L.; Zhou, Wei; ...

    2016-08-19

    We investigated the structure-dependent vibrational properties of different Mg(BH4)2 polymorphs (α, β, γ, and δ phases) with a combination of neutron vibrational spectroscopy (NVS) measurements and density functional theory (DFT) calculations, with emphasis placed on the effects of the local structure and orientation of the BH4- anions. DFT simulations closely match the neutron vibrational spectra. The main bands in the low-energy region (20–80 meV) are associated with the BH4- librational modes. The features in the intermediate energy region (80–120 meV) are attributed to overtones and combination bands arising from the lower-energy modes. The features in the high-energy region (120–200 meV)more » correspond to the BH4- symmetric and asymmetric bending vibrations, of which four peaks located at 140, 142, 160, and 172 meV are especially intense. There are noticeable intensity distribution variations in the vibrational bands for different polymorphs. We can explain these differences using the spatial distribution of BH4- anions within various structures. An example of the possible identification of products after the hydrogenation of MgB2, using NVS measurements, is presented. Our results provide fundamental insights of benefit to researchers currently studying these promising hydrogen-storage materials.« less

  1. Structure-dependent vibrational dynamics of Mg(BH 4 ) 2 polymorphs probed with neutron vibrational spectroscopy and first-principles calculations

    SciTech Connect

    Dimitrievska, Mirjana; White, James L.; Zhou, Wei; Stavila, Vitalie; Klebanoff, Leonard E.; Udovic, Terrence J.

    2016-01-01

    The structure-dependent vibrational properties of different Mg(BH4)2 polymorphs (..alpha.., ..beta.., ..gamma.., and ..delta.. phases) were investigated with a combination of neutron vibrational spectroscopy (NVS) measurements and density functional theory (DFT) calculations, with emphasis placed on the effects of the local structure and orientation of the BH4- anions. DFT simulations closely match the neutron vibrational spectra. The main bands in the low-energy region (20-80 meV) are associated with the BH4- librational modes. The features in the intermediate energy region (80-120 meV) are attributed to overtones and combination bands arising from the lower-energy modes. The features in the high-energy region (120-200 meV) correspond to the BH4- symmetric and asymmetric bending vibrations, of which four peaks located at 140, 142, 160, and 172 meV are especially intense. There are noticeable intensity distribution variations in the vibrational bands for different polymorphs. This is explained by the differences in the spatial distribution of BH4- anions within various structures. An example of the possible identification of products after the hydrogenation of MgB2, using NVS measurements, is presented. These results provide fundamental insights of benefit to researchers currently studying these promising hydrogen-storage materials.

  2. Structure-dependent vibrational dynamics of Mg(BH 4 ) 2 polymorphs probed with neutron vibrational spectroscopy and first-principles calculations

    SciTech Connect

    Dimitrievska, Mirjana; White, James L.; Zhou, Wei; Stavila, Vitalie; Klebanoff, Leonard E.; Udovic, Terrence J.

    2016-08-19

    We investigated the structure-dependent vibrational properties of different Mg(BH4)2 polymorphs (α, β, γ, and δ phases) with a combination of neutron vibrational spectroscopy (NVS) measurements and density functional theory (DFT) calculations, with emphasis placed on the effects of the local structure and orientation of the BH4- anions. DFT simulations closely match the neutron vibrational spectra. The main bands in the low-energy region (20–80 meV) are associated with the BH4- librational modes. The features in the intermediate energy region (80–120 meV) are attributed to overtones and combination bands arising from the lower-energy modes. The features in the high-energy region (120–200 meV) correspond to the BH4- symmetric and asymmetric bending vibrations, of which four peaks located at 140, 142, 160, and 172 meV are especially intense. There are noticeable intensity distribution variations in the vibrational bands for different polymorphs. We can explain these differences using the spatial distribution of BH4- anions within various structures. An example of the possible identification of products after the hydrogenation of MgB2, using NVS measurements, is presented. Our results provide fundamental insights of benefit to researchers currently studying these promising hydrogen-storage materials.

  3. Mutual Co-Assignment of the Calculated Vibrational Frequencies in the Ground and Lowest Excited Electronic States

    NASA Astrophysics Data System (ADS)

    Panchenko, Yurii N.

    2013-06-01

    The shifts of the molecular vibrational frequencies when going from the ground electronic state to the lowest excited electronic states pose some problems for the mutual co-assignment of the calculated vibrational frequencies in the different excited states. The trans-{C_2 O_2 F_2} shift of the frequency of the symmetrical ν(C=O) stretching vibration between the S_0 and T_1 is 373 wn. The feasibility of mutual co-assignments of the vibrational frequencies in these electronic states has been demonstrated for trans-{C_2 O_2 F_2}. Matrices analogous to the Duschinsky matrix were used to juxtapose the a_g vibrational frequencies of this molecule calculated at the CASPT2/cc-pVTZ level in the ground S_0 and excited triplet T_1 and singlet S_1 electronic states. The analog of the Duschinsky matrix D was obtained for this molecule using the equation D = (L_{I})^{-1} L_{II} where L_{I} and L_{II} are the matrices of the vibrational modes (normalized atomic displacements) obtained by solving the vibrational problems for the S_0 and T_1 electronic states, respectively. Choosing the dominant elements in columns of the D matrix and permuting these columns to arrange these elements along the diagonal of the transformed matrix D^* makes it possible to establish the correct mutual co-assignments of the calculated a_g vibrational frequencies of the trans-{C_2 O_2 F_2} molecule in the S_0 and T_1 electronic states. The analogous procedure was performed for the trans-{C_2 O_2 F_2} molecule in the T_1 and S_1 excited electronic states. The recent reassignments of the νb{2} and νb{3} calculated vibrational frequencies in the trans-{C_2 O_2 F_2} molecule in the ground state were also obtained for the triplet T_1 and singlet S_1 excited electronic states. The approach set forth in this text makes it possible to juxtapose the calculated vibrational frequencies of the same molecule in the different electronic states and to refine the assignments of these frequencies. This is essential

  4. 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)].

  5. Absorption Spectra of Fe, Mn, and Mg Water Complexes Calculated Using Density Functional Theory

    DTIC Science & Technology

    2013-08-20

    the calculated absorption spectra of isolated molecules can help to identify intramolecular vibrational modes of various materials. A series of...Transformation A molecule in 3-dimensions has a total of 3N-6 normal mode vibrations . The Schrodinger equation for the harmonic...oscillations of these normal modes has known solutions. The quantum mechanical spectrum of each of these vibrations is given in the harmonic approximation

  6. 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).

  7. Electronic, vibrational, and superconducting properties of CaBeSi : First-principles calculations

    NASA Astrophysics Data System (ADS)

    Bersier, C.; Floris, A.; Sanna, A.; Profeta, G.; Continenza, A.; Gross, E. K. U.; Massidda, S.

    2009-03-01

    We report first-principles calculations on the normal and superconducting state of CaBexSi2-x (x=1) , in the framework of density-functional theory for superconductors. CaBeSi is isostructural and isoelectronic to MgB2 and this makes possible a direct comparison of the electronic and vibrational properties and the electron-phonon interaction of the two materials. Despite many similarities with MgB2 (e.g., σ and π bands at the Fermi level and an even larger density of states), according to our calculations CaBeSi has a very low critical temperature Tc≈0.4K consistent with the experiment. CaBeSi exhibits a complex gap structure, with three gaps at the Fermi level: besides the σ and π gaps (present also in MgB2 ), the appearance of a third gap is related to the anisotropy of the Coulomb repulsion, acting in different ways on the bonding and antibonding electronic π states.

  8. 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.

  9. A new efficient method for the calculation of interior eigenpairs and its application to vibrational structure problems

    NASA Astrophysics Data System (ADS)

    Petrenko, Taras; Rauhut, Guntram

    2017-03-01

    Vibrational configuration interaction theory is a common method for calculating vibrational levels and associated IR and Raman spectra of small and medium-sized molecules. When combined with appropriate configuration selection procedures, the method allows the treatment of configuration spaces with up to 1010 configurations. In general, this approach pursues the construction of the eigenstates with significant contributions of physically relevant configurations. The corresponding eigenfunctions are evaluated in the subspace of selected configurations. However, it can easily reach the dimension which is not tractable for conventional eigenvalue solvers. Although Davidson and Lanczos methods are the methods of choice for calculating exterior eigenvalues, they usually fall into stagnation when applied to interior states. The latter are commonly treated by the Jacobi-Davidson method. This approach in conjunction with matrix factorization for solving the correction equation (CE) is prohibitive for larger problems, and it has limited efficiency if the solution of the CE is based on Krylov's subspace algorithms. We propose an iterative subspace method that targets the eigenvectors with significant contributions to a given reference vector and is based on the optimality condition for the residual norm corresponding to the error in the solution vector. The subspace extraction and expansion are modified according to these principles which allow very efficient calculation of interior vibrational states with a strong multireference character in different vibrational structure problems. The convergence behavior of the method and its performance in comparison with the aforementioned algorithms are investigated in a set of benchmark calculations.

  10. 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.

  11. Coherent acoustic vibrations in silicon submicron spiral arrays

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Masashi; Liu, Jianxun; Ye, Dexian; Lu, Toh-Ming

    2009-08-01

    Mechanical properties of complex silicon submicron structures have been studied both experimentally and theoretically using time resolved ultrafast spectroscopy and finite element analysis. Periodic and random arrays of single-turned silicon submircron spirals were grown using the oblique angle deposition technique. Resonant vibrational modes of the submicron spirals were coherently excited by femtosecond laser pulses. Excitation of multiple harmonics of the resonant vibrations has been observed, and the mode patterns of the excited vibrations in the submicron spirals have been calculated.

  12. Vibrational self-consistent field calculations for spectroscopy of biological molecules: new algorithmic developments and applications.

    PubMed

    Roy, Tapta Kanchan; Gerber, R Benny

    2013-06-28

    This review describes the vibrational self-consistent field (VSCF) method and its other variants for computing anharmonic vibrational spectroscopy of biological molecules. The superiority and limitations of this algorithm are discussed with examples. The spectroscopic accuracy of the VSCF method is compared with experimental results and other available state-of-the-art algorithms for various biologically important systems. For large biological molecules with many vibrational modes, the scaling of computational effort is investigated. The accuracy of the vibrational spectra of biological molecules using the VSCF approach for different electronic structure methods is also assessed. Finally, a few open problems and challenges in this field are discussed.

  13. A band Lanczos approach for calculation of vibrational coupled cluster response functions: simultaneous calculation of IR and Raman anharmonic spectra for the complex of pyridine and a silver cation.

    PubMed

    Godtliebsen, Ian H; Christiansen, Ove

    2013-07-07

    We describe new methods for the calculation of IR and Raman spectra using vibrational response theory. Using damped linear response functions that incorporate a Lorentzian line-shape function from the outset, it is shown how the calculation of Raman spectra can be carried out through the calculation of a set of vibrational response functions in the same manner as described previously for IR spectra. The necessary set of response functions can be calculated for both vibrational coupled cluster (VCC) and vibrational configuration interaction (VCI) anharmonic vibrational wave-functions. For the efficient and simultaneous calculation of the full set of necessary response functions, a non-hermitian band Lanczos algorithm is implemented for VCC, and a hermitian band Lanczos algorithm is implemented for VCI. It is shown that the simultaneous calculation of several response functions is often advantageous. Sample calculations are presented for pyridine and the complex between pyridine and the silver cation.

  14. Crystal structure and vibrational properties of RFe3(BO3)4 (R = Ce - Lu) ferroborate crystal: ab initio calculations

    NASA Astrophysics Data System (ADS)

    Petrov, V. P.; Chernyshev, V. A.; Nikiforov, A. E.

    2016-12-01

    The ab initio calculations of the crystal structure and lattice dynamics of ferroborate crystal family RFe3(BO3)4 (R = Ce, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), S.G. R32, has been carried out within the framework of the MO LCAO approach by using density functional theory and effective 4f-in-core pseudopotential for rare earth element. The fully optimized geometry as well as vibrational frequencies has been calculated.

  15. Nonperturbative quantum and classical calculations of multiphoton vibrational excitation and dissociation of Morse molecules^1

    NASA Astrophysics Data System (ADS)

    Dimitriou, K. I.; Mercouris, Th.; Constantoudis, V.; Komninos, Y.; Nicolaides, C. A.

    2006-05-01

    The multiphoton vibrational excitation and dissociation of Morse molecules have been computed nonperturbatively using Hamilton's and Schrφdinger's time-dependent equations, for a range of laser pulse parameters. The time-dependent Schrφdinger equation is solved by the state-specific expansion approach [e.g.,1]. For its solution, emphasis has been given on the inclusion of the continuous spectrum, whose contribution to the multiphoton probabilities for resonance excitation to a number of excited discrete states as well as to dissociation has been examined as a function of laser intensity, frequency and pulse duration. An analysis of possible quantal-classical correspondences for this system is being carried out. We note that distinct features exist from previous classical calculations [2]. For example, the dependence on the laser frequency gives rise to an asymmetry around the red-shifted frequency corresponding to the maximum probability. [1] Th. Mercouris, I. D. Petsalakis and C. A. Nicolaides, J. Phys. B 27, L519 (1994). [2] V. Constantoudis and C. A. Nicolaides, Phys. Rev. E 64, 562112 (2001). ^1This work was supported by the program 'Pythagoras' which is co - funded by the European Social Fund (75%) and Natl. Resources (25%). ^2Physics Department, National Technical University, Athens, Greece.^3Theoretical and Physical Chemistry Institute, Hellenic Research Foundation, Athens, Greece.

  16. 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

  17. Theoretical calculations of infrared absorption, vibrational circular dichroism, and two-dimensional vibrational spectra of acetylproline in liquids water and chloroform.

    PubMed

    Hahn, Seungsoo; Lee, Hochan; Cho, Minhaeng

    2004-07-22

    Infrared absorption, vibrational circular dichroism, and two-dimensional infrared pump-probe and photon echo spectra of acetylproline solutions are theoretically calculated and directly compared with experiments. In order to quantitatively determine interpeptide interaction-induced amide I mode frequency shifts, high-level quantum chemistry calculations were performed. The solvatochromic amide I mode frequency shift and fluctuation were taken into account by carrying out molecular dynamics simulations of acetylproline dissolved in liquids water and chloroform and by using the extrapolation method developed recently. We first studied correlation time scales of the two amide I vibrational frequency fluctuations, cross correlation between the two fluctuating local mode frequencies, ensemble averaged conformations of the acetylproline molecule in liquids water and chloroform. The corresponding conformations of the acetylproline in liquids water and chloroform are close to the ideal 3(10) helix and the C(7) structure, respectively. A few methods proposed to determine the angle between the two transition dipoles associated with the amide I vibrations were tested and their limitations are discussed.

  18. Vibrational energy levels of the simplest Criegee intermediate (CH2OO) from full-dimensional Lanczos, MCTDH, and MULTIMODE calculations

    NASA Astrophysics Data System (ADS)

    Yu, Hua-Gen; Ndengue, Steve; Li, Jun; Dawes, Richard; Guo, Hua

    2015-08-01

    Accurate vibrational energy levels of the simplest Criegee intermediate (CH2OO) were determined on a recently developed ab initio based nine-dimensional potential energy surface using three quantum mechanical methods. The first is the iterative Lanczos method using a conventional basis expansion with an exact Hamiltonian. The second and more efficient method is the multi-configurational time-dependent Hartree (MCTDH) method in which the potential energy surface is refit to conform to the sums-of-products requirement of MCTDH. Finally, the energy levels were computed with a vibrational self-consistent field/virtual configuration interaction method in MULTIMODE. The low-lying levels obtained from the three methods are found to be within a few wave numbers of each other, although some larger discrepancies exist at higher levels. The calculated vibrational levels are very well represented by an anharmonic effective Hamiltonian.

  19. Vibrational energy levels of the simplest Criegee intermediate (CH2OO) from full-dimensional Lanczos, MCTDH, and MULTIMODE calculations.

    PubMed

    Yu, Hua-Gen; Ndengue, Steve; Li, Jun; Dawes, Richard; Guo, Hua

    2015-08-28

    Accurate vibrational energy levels of the simplest Criegee intermediate (CH2OO) were determined on a recently developed ab initio based nine-dimensional potential energy surface using three quantum mechanical methods. The first is the iterative Lanczos method using a conventional basis expansion with an exact Hamiltonian. The second and more efficient method is the multi-configurational time-dependent Hartree (MCTDH) method in which the potential energy surface is refit to conform to the sums-of-products requirement of MCTDH. Finally, the energy levels were computed with a vibrational self-consistent field/virtual configuration interaction method in MULTIMODE. The low-lying levels obtained from the three methods are found to be within a few wave numbers of each other, although some larger discrepancies exist at higher levels. The calculated vibrational levels are very well represented by an anharmonic effective Hamiltonian.

  20. Key hydride vibrational modes in [NiFe] hydrogenase model compounds studied by resonance Raman spectroscopy and density functional calculations.

    PubMed

    Shafaat, Hannah S; Weber, Katharina; Petrenko, Taras; Neese, Frank; Lubitz, Wolfgang

    2012-11-05

    Hydrogenase proteins catalyze the reversible conversion of molecular hydrogen to protons and electrons. While many enzymatic states of the [NiFe] hydrogenase have been studied extensively, there are multiple catalytically relevant EPR-silent states that remain poorly characterized. Analysis of model compounds using new spectroscopic techniques can provide a framework for the study of these elusive states within the protein. We obtained optical absorption and resonance Raman (RR) spectra of (dppe)Ni(μ-pdt)Fe(CO)(3) and [(dppe)Ni(μ-pdt)(μ-H)Fe(CO)(3)][BF(4)], which are structural and functional model compounds for the EPR-silent Ni-SI and Ni-R states of the [NiFe] hydrogenase active site. The studies presented here use RR spectroscopy to probe vibrational modes of the active site, including metal-hydride stretching vibrations along with bridging ligand-metal and Fe-CO bending vibrations, with isotopic substitution used to identify key metal-hydride modes. The metal-hydride vibrations are essentially uncoupled and represent isolated, localized stretching modes; the iron-hydride vibration occurs at 1530 cm(-1), while the nickel-hydride vibration is observed at 945 cm(-1). The significant discrepancy between the metal-hydride vibrational frequencies reflects the slight asymmetry in the metal-hydride bond lengths. Additionally, time-dependent density functional theory (TD-DFT) calculations were carried out to obtain theoretical RR spectra of these compounds. On the basis of the detailed comparison of theory and experiment, the dominant electronic transitions and significant normal modes probed in the RR experiments were assigned; the primary transitions in the visible wavelengths represent metal-to-metal and metal-to-ligand charge transfer bands. Inherent properties of metal-hydride vibrational modes in resonance Raman spectra and DFT calculations are discussed together with the prospects of observing such vibrational modes in metal-hydride-containing proteins. Such a

  1. Temperature echoes revisited to probe the vibrational behavior of dendrimers

    NASA Astrophysics Data System (ADS)

    Paulo, Pedro M. R.

    2010-03-01

    Temperature quench echoes were induced in molecular dynamics simulations of dendrimers. This phenomenon was used to probe the vibrational behavior of these molecules by comparing simulation results with harmonic model predictions. The echo depth for short time intervals between temperature quenches is well described by the harmonic approximation and the fluctuations observed are related to the vibrational density of states. The echo depth for long time intervals decays progressively revealing dephasing due to anharmonic interactions. The density of states was calculated from the temperature fluctuations after the first quench and high-frequency modes were assigned by comparison with vibrational spectra of similar dendrimers.

  2. Temperature echoes revisited to probe the vibrational behavior of dendrimers.

    PubMed

    Paulo, Pedro M R

    2010-03-21

    Temperature quench echoes were induced in molecular dynamics simulations of dendrimers. This phenomenon was used to probe the vibrational behavior of these molecules by comparing simulation results with harmonic model predictions. The echo depth for short time intervals between temperature quenches is well described by the harmonic approximation and the fluctuations observed are related to the vibrational density of states. The echo depth for long time intervals decays progressively revealing dephasing due to anharmonic interactions. The density of states was calculated from the temperature fluctuations after the first quench and high-frequency modes were assigned by comparison with vibrational spectra of similar dendrimers.

  3. 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.

  4. MR harmonic quad study

    SciTech Connect

    Yang, M.-J.; /Fermilab

    1995-01-01

    To understand the effect of Main Ring harmonic quadruple correctors. Previous data taken with the harmonic quads did not agree well with the SYNCH calculation. The ultimate goal of this study was to be able to change the harmonic quads and verify the changes in lattice function.

  5. Synthesis, molecular structure and vibrational analysis of D-D-A based carbazole decorated phenothiazine-3-carbaldehyde: Experimental (FT-IR, UV and NMR) and density functional theory (DFT) calculations

    NASA Astrophysics Data System (ADS)

    Karuppasamy, Ayyanar; Gokula Krishnan, Kannan; Pillai Velayutham Pillai, Muthiah; Ramalingan, Chennan

    2017-01-01

    A novel molecule, 10-(9-hexyl-9H-carbazol-3yl)-10H-phenothiazine-3-carbaldehyde (CZPTZA) has been synthesized and characterized through FT-IR, UV-Vis, NMR spectroscopic studies and molecular orbital calculations. Optimized geometrical structure, harmonic vibrational frequencies and NMR are computed with B3LYP method using 6-311++G (d,p) basis set. The geometrical parameters of the title compound obtained from Single Crystal XRD studies have been found in accord with the calculated (DFT) values. The experimentally observed vibrational frequencies are compared with the calculated ones, which were found to be in good agreement with each other. UV-Vis spectra of the title compound have also been recorded and the electronic properties, viz. excitation energies, calculated energies, oscillator strengths, frontier orbital energies and band gap energies are computed with TD-DFT/CAM-B3LYP method using 6-311++G (d,p) as the basis set. The 1H and 13C NMR chemical shifts of the molecule have been calculated by the Gauge Independent Atomic Orbital (GIAO) method and compared with the experimental outcome. Also, the values of dipole moment, polarizabilities and first order hyperpolarizabilities have been computed.

  6. 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.

  7. 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).

  8. Vibration eigenmodes of the Au-(5 ×2 ) /Si(111) surface studied by Raman spectroscopy and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Liebhaber, M.; Halbig, B.; Bass, U.; Geurts, J.; Neufeld, S.; Sanna, S.; Schmidt, W. G.; Speiser, E.; Räthel, J.; Chandola, S.; Esser, N.

    2016-12-01

    Ordered submonolayers of adsorbate atoms on semiconductor surfaces constitute a playground for electronic correlation effects, which are tightly connected to the local atomic arrangement and the corresponding vibration eigenmodes. We report on a study of the vibration eigenmodes of Au-covered Si(111) surfaces with (5 ×2 ) reconstruction using polarized Raman spectroscopy and first-principles calculations. Upon Au coverage, the vibration eigenmodes of the clean reconstructed Si(111)-(7 ×7 ) surface are quenched and replaced by new eigenmodes, determined by the Au-(5 ×2 ) reconstruction. Several polarization-dependent surface eigenmodes emerge in the spectral range from 25 to 120 cm-1 , with the strongest ones at 29, 51, and 106 cm-1. In our first-principles calculations we have determined the vibration frequencies, the corresponding elongation patterns, and the Raman intensities for two different structure models currently discussed in the literature. The best agreement with the experimental results is achieved for a model with 0.7 monolayer coverage and seven Au atoms per unit cell, proposed by S. G. Kwon and M. H. Kang [Phys. Rev. Lett. 113, 086101 (2014), 10.1103/PhysRevLett.113.086101].

  9. Matching Rules for Collective Behaviors on Complex Networks: Optimal Configurations for Vibration Frequencies of Networked Harmonic Oscillators

    PubMed Central

    Zhan, Meng; Liu, Shuai; He, Zhiwei

    2013-01-01

    The structure-dynamics-function has become one of central problems in modern sciences, and it is a great challenge to unveil the organization rules for different dynamical processes on networks. In this work, we study the vibration spectra of the classical mass spring model with different masses on complex networks, and pay our attention to how the mass spatial configuration influences the second-smallest vibrational frequency () and the largest one (). For random networks, we find that becomes maximal and becomes minimal if the node degrees are point-to-point-positively correlated with the masses. In these cases, we call it point-to-point matching. Moreover, becomes minimal under the condition that the heaviest mass is placed on the lowest-degree vertex, and is maximal as long as the lightest mass is placed on the highest-degree vertex, and in both cases all other masses can be arbitrarily settled. Correspondingly, we call it single-point matching. These findings indicate that the matchings between the node dynamics (parameter) and the node position rule the global systems dynamics, and sometimes only one node is enough to control the collective behaviors of the whole system. Therefore, the matching rules might be the common organization rules for collective behaviors on networks. PMID:24386088

  10. Matching rules for collective behaviors on complex networks: optimal configurations for vibration frequencies of networked harmonic oscillators.

    PubMed

    Zhan, Meng; Liu, Shuai; He, Zhiwei

    2013-01-01

    The structure-dynamics-function has become one of central problems in modern sciences, and it is a great challenge to unveil the organization rules for different dynamical processes on networks. In this work, we study the vibration spectra of the classical mass spring model with different masses on complex networks, and pay our attention to how the mass spatial configuration influences the second-smallest vibrational frequency (ω2) and the largest one (ωN). For random networks, we find that ω2 becomes maximal and ωN becomes minimal if the node degrees are point-to-point-positively correlated with the masses. In these cases, we call it point-to-point matching. Moreover, ω2 becomes minimal under the condition that the heaviest mass is placed on the lowest-degree vertex, and ωN is maximal as long as the lightest mass is placed on the highest-degree vertex, and in both cases all other masses can be arbitrarily settled. Correspondingly, we call it single-point matching. These findings indicate that the matchings between the node dynamics (parameter) and the node position rule the global systems dynamics, and sometimes only one node is enough to control the collective behaviors of the whole system. Therefore, the matching rules might be the common organization rules for collective behaviors on networks.

  11. Synthesis, X-ray structure analysis, thermodynamic and electronic properties of 4-acetamido benzaldehyde using vibrational spectroscopy and DFT calculations

    NASA Astrophysics Data System (ADS)

    Jeeva Jasmine, N.; Arunagiri, C.; Subashini, A.; Stanley, N.; Thomas Muthiah, P.

    2017-02-01

    Theoretical Spectrograms, namely, FT-Raman (3500-50 cm-1) and FT-Infrared (4000-400 cm-1) spectra have been studied for 4-acetamido benzaldehyde (4ABA) and are assigned to different normal modes of the molecule. Vibrational spectral analysis was compared with the experimental and theoretical, FT-IR and FT-Raman spectra. The effect of polarity on the Harmonic vibrational frequencies, intensities, optimized geometrical parameters and several thermodynamic parameters in the ground state have been computed by the B3LYP method using 6-311 + G(d,p) basis set. The results of the optimized molecular structure is presented and compared with the XRD values. The global chemical reactivity relate to some parameters, such as HOMO, LUMO, gap energy (ΔE) and other parameters, including electronegativity (χ) and global hardness (η). The values of the reactivity descriptors indicated that the interaction between 4ABA molecules reduced its reactivity in comparison with the exhibited in gas phase. In addition, the local reactivity has been analyzed through the Fukui function and condensed softness indices.

  12. An exact variational method to calculate vibrational energies of five atom molecules beyond the normal mode approach

    DOE PAGES

    Yu, Hua-Gen

    2002-01-01

    We present a full dimensional variational algorithm to calculate vibrational energies of penta-atomic molecules. The quantum mechanical Hamiltonian of the system for J=0 is derived in a set of orthogonal polyspherical coordinates in the body-fixed frame without any dynamical approximation. Moreover, the vibrational Hamiltonian has been obtained in an explicitly Hermitian form. Variational calculations are performed in a direct product discrete variable representation basis set. The sine functions are used for the radial coordinates, whereas the Legendre polynomials are employed for the polar angles. For the azimuthal angles, the symmetrically adapted Fourier–Chebyshev basis functions are utilized. The eigenvalue problem ismore » solved by a Lanczos iterative diagonalization algorithm. The preliminary application to methane is given. Ultimately, we made a comparison with previous results.« less

  13. 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.

  14. Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic-Water Complexes Using Density Functional Theory

    DTIC Science & Technology

    2016-06-03

    of Arsenic- Water Complexes Using Density Functional Theory June 3, 2016 Approved for public release; distribution is unlimited. L. Huang S.g...NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic- Water Complexes Using... water molecules should be associated with response features that are intermediate between that of isolated molecules and that of a bulk system. DFT and

  15. 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.

  16. 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**.

  17. The quantum dynamics of interfacial hydrogen: Path integral maximum entropy calculation of adsorbate vibrational line shapes for the H/Ni(111) system

    NASA Astrophysics Data System (ADS)

    Kim, Dongsup; Doll, J. D.; Gubernatis, J. E.

    1997-01-01

    Vibrational line shapes for a hydrogen atom on an embedded atom model (EAM) of the Ni(111) surface are extracted from path integral Monte Carlo data. Maximum entropy methods are utilized to stabilize this inversion. Our results indicate that anharmonic effects are significant, particularly for vibrational motion parallel to the surface. Unlike their normal mode analogs, calculated quantum line shapes for the EAM potential predict the correct ordering of vibrational features corresponding to parallel and perpendicular adsorbate motion.

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

    PubMed

    Zhang, Feng; Hayashi, Michitoshi; Wang, Houng-Wei; Tominaga, Keisuke; Kambara, Ohki; Nishizawa, Jun-ichi; Sasaki, Tetsuo

    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(*) 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(*) 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(*) data show excellent agreement with the experimental data in terms of IS and CFS in region II; however, PBE-D(*) 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(*).

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

    NASA Astrophysics Data System (ADS)

    Zhang, Feng; Hayashi, Michitoshi; Wang, Houng-Wei; Tominaga, Keisuke; Kambara, Ohki; Nishizawa, Jun-ichi; Sasaki, Tetsuo

    2014-05-01

    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* 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* 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* data show excellent agreement with the experimental data in terms of IS and CFS in region II; however, PBE-D* 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*.

  20. Exploring the correlation between network structure and electron binding energy in the (H2O)7- cluster through isomer-photoselected vibrational predissociation spectroscopy and ab initio calculations: Addressing complexity beyond types I-III

    NASA Astrophysics Data System (ADS)

    Roscioli, Joseph R.; Hammer, Nathan I.; Johnson, Mark A.; Diri, Kadir; Jordan, Kenneth D.

    2008-03-01

    We report a combined photoelectron and vibrational spectroscopy study of the (H2O)7- cluster anions in order to correlate structural changes with the observed differences in electron binding energies of the various isomers. Photoelectron spectra of the (H2O)7-ṡArm clusters are obtained over the range of m =0-10. These spectra reveal the formation of a new isomer (I') for m >5, the electron binding energy of which is about 0.15eV higher than that of the type I form previously reported to be the highest binding energy species [Coe et al., J. Chem. Phys. 92, 3980 (1990)]. Isomer-selective vibrational predissociation spectra are obtained using both the Ar dependence of the isomer distribution and photochemical depopulation of the more weakly (electron) binding isomers. The likely structures of the isomers at play are identified with the aid of electronic structure calculations, and the electron binding energies, as well as harmonic vibrational spectra, are calculated for 28 low-lying forms for comparison with the experimental results. The HOH bending spectrum of the low binding type II form is dominated by a band that is moderately redshifted relative to the bending origin of the bare water molecule. Calculations trace this feature primarily to the bending vibration localized on a water molecule in which a dangling H atom points toward the electron cloud. Both higher binding forms (I and I') display the characteristic patterns in the bending and OH stretching regions signaling electron attachment primarily to a water molecule in an AA binding site, a persistent motif found in non-isomer-selective spectra of the clusters up to (H2O)50-.

  1. Ground vibration due to railway traffic—The calculation of the effects of moving static loads and their experimental verification

    NASA Astrophysics Data System (ADS)

    Auersch, L.

    2006-06-01

    The propagation of waves through homogeneous or layered soil is calculated based on half-space theory. The moving dynamic loads of a train are approximated by fixed dynamic loads and the wave field can be calculated if the spectrum of the dynamic train loads is known. In addition to this dynamic wave field, there are three different components at three different frequency ranges which are caused by the passage of the static loads: the regular static component at low frequencies, the irregular static component at medium frequencies, the sleeper-passing component at high frequencies. For each of these components, an approximate solution is presented. The calculated wave field is compared with measurements of different trains at different sites. The measurement of impulse and harmonic point load excitation verifies the soil dynamic base of the method.

  2. 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.

    PubMed

    Mielke, Steven L; Truhlar, Donald G

    2015-01-28

    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.

  3. Calculation of spherical harmonics and Wigner d functions by FFT. Applications to fast rotational matching in molecular replacement and implementation into AMoRe.

    PubMed

    Trapani, Stefano; Navaza, Jorge

    2006-07-01

    The FFT calculation of spherical harmonics, Wigner D matrices and rotation function has been extended to all angular variables in the AMoRe molecular replacement software. The resulting code avoids singularity issues arising from recursive formulas, performs faster and produces results with at least the same accuracy as the original code. The new code aims at permitting accurate and more rapid computations at high angular resolution of the rotation function of large particles. Test calculations on the icosahedral IBDV VP2 subviral particle showed that the new code performs on the average 1.5 times faster than the original code.

  4. Calculations of the electronic levels, spin-Hamiltonian parameters and vibrational spectra for the CrCl3 layered crystals

    NASA Astrophysics Data System (ADS)

    Avram, C. N.; Gruia, A. S.; Brik, M. G.; Barb, A. M.

    2015-12-01

    Calculations of the Cr3+ energy levels, spin-Hamiltonian parameters and vibrational spectra for the layered CrCl3 crystals are reported for the first time. The crystal field parameters and the energy level scheme were calculated in the framework of the Exchange Charge Model of crystal field. The spin-Hamiltonian parameters (zero-field splitting parameter D and g-factors) for Cr3+ ion in CrCl3 crystals were obtained using two independent techniques: i) semi-empirical crystal field theory and ii) density functional theory (DFT)-based model. In the first approach, the spin-Hamiltonian parameters were calculated from the perturbation theory method and the complete diagonalization (of energy matrix) method. The infrared (IR) and Raman frequencies were calculated for both experimental and fully optimized geometry of the crystal structure, using CRYSTAL09 software. The obtained results are discussed and compared with the experimental available data.

  5. Environmental effects on vibrational properties of carotenoids: experiments and calculations on peridinin.

    PubMed

    Bovi, Daniele; Mezzetti, Alberto; Vuilleumier, Rodolphe; Gaigeot, Marie-Pierre; Chazallon, Bertrand; Spezia, Riccardo; Guidoni, Leonardo

    2011-12-21

    Carotenoids are employed in light-harvesting complexes of dinoflagellates with the two-fold aim to extend the spectral range of the antenna and to protect it from radiation damage. We have studied the effect of the environment on the vibrational properties of the carotenoid peridinin in different solvents by means of vibrational spectroscopies and QM/MM molecular dynamics simulations. Three prototypical solvents were considered: cyclohexane (an apolar/aprotic solvent), deuterated acetonitrile (a polar/aprotic solvent) and methanol (a polar/protic solvent). Thanks to effective normal mode analysis, we were able to assign the experimental Raman and IR bands and to clarify the effect of the solvent on band shifts. In the 1500-1650 cm(-1) region, seven vibrational modes of the polyene chain were identified and assigned to specific molecular vibrations. In the 1700-1800 cm(-1) region a strong progressive down-shift of the lactonic carbonyl frequency is observed passing from cyclohexane to methanol solutions. This has been rationalized here in terms of solvent polarity and solute-solvent hydrogen bond interactions. On the basis of our data we propose a classification of non-equivalent peridinins in the Peridinin-Chlorophyll-Proteins, light-harvesting complexes of dinoflagellates.

  6. NIR-VCD, vibrational circular dichroism in the near-infrared: experiments, theory and calculations.

    PubMed

    Abbate, Sergio; Castiglioni, Ettore; Gangemi, Fabrizio; Gangemi, Roberto; Longhi, Giovanna

    2009-01-01

    The first well documented experiments of Near Infrared Vibrational Circular Dichroism (NIR-VCD) were performed around 1975. We review the thirty year history of NIR-VCD, encompassing both instrumental development and theoretical/computational methods that allow interpretation of experimental spectra, harvesting useful structural information therefrom. We hope to stimulate interest in this still scarcely explored spectroscopy of chiral molecules.

  7. 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.

  8. 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.

  9. 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.

  10. Vibrational investigation on FT-IR and FT-Raman spectra, IR intensity, Raman activity, peak resemblance, ideal estimation, standard deviation of computed frequencies analyses and electronic structure on 3-methyl-1,2-butadiene using HF and DFT (LSDA/B3LYP/B3PW91) calculations

    NASA Astrophysics Data System (ADS)

    Ramalingam, S.; Jayaprakash, A.; Mohan, S.; Karabacak, M.

    2011-11-01

    FT-IR and FT-Raman (4000-100 cm -1) spectral measurements of 3-methyl-1,2-butadiene (3M12B) have been attempted in the present work. Ab-initio HF and DFT (LSDA/B3LYP/B3PW91) calculations have been performed giving energies, optimized structures, harmonic vibrational frequencies, IR intensities and Raman activities. Complete vibrational assignments on the observed spectra are made with vibrational frequencies obtained by HF and DFT (LSDA/B3LYP/B3PW91) at 6-31G(d,p) and 6-311G(d,p) basis sets. The results of the calculations have been used to simulate IR and Raman spectra for the molecule that showed good agreement with the observed spectra. The potential energy distribution (PED) corresponding to each of the observed frequencies are calculated which confirms the reliability and precision of the assignment and analysis of the vibrational fundamentals modes. The oscillation of vibrational frequencies of butadiene due to the couple of methyl group is also discussed. A study on the electronic properties such as HOMO and LUMO energies, were performed by time-dependent DFT (TD-DFT) approach. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. The thermodynamic properties of the title compound at different temperatures reveal the correlations between standard heat capacities ( C) standard entropies ( S), and standard enthalpy changes ( H).

  11. A FEM-based method using harmonic overtones to determine the effective elastic, dielectric, and piezoelectric parameters of freely vibrating thick piezoelectric disks.

    PubMed

    Jonsson, Ulf G; Andersson, Britt M; Lindahl, Olof A

    2013-01-01

    To gain an understanding of the electroelastic properties of tactile piezoelectric sensors used in the characterization of soft tissue, the frequency-dependent electric impedance response of thick piezoelectric disks has been calculated using finite element modeling. To fit the calculated to the measured response, a new method was developed using harmonic overtones for tuning of the calculated effective elastic, piezoelectric, and dielectric parameters. To validate the results, the impedance responses of 10 piezoelectric disks with diameter-to-thickness ratios of 20, 6, and 2 have been measured from 10 kHz to 5 MHz. A two-dimensional, general purpose finite element partial differential equation solver with adaptive meshing capability run in the frequency-stepped mode, was used. The equations and boundary conditions used by the solver are presented. Calculated and measured impedance responses are presented, and resonance frequencies have been compared in detail. The comparison shows excellent agreement, with average relative differences in frequency of 0.27%, 0.19%, and 0.54% for the samples with diameter-to-thickness ratios of 20, 6, and 2, respectively. The method of tuning the effective elastic, piezoelectric, and dielectric parameters is an important step toward a finite element model that describes the properties of tactile sensors in detail.

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

    PubMed

    Toy, Mehmet; Tanak, Hasan

    2016-01-05

    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.

  13. Vibrational structure of defect luminescence bands in GaN from electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Alkauskas, Audrius; van de Walle, Chris G.

    2012-02-01

    Optical methods are among the most powerful to characterize defects in materials. The study of optical signatures based on state-of-the-art electronic structure methods is therefore very important. In this work we investigate the vibrational structure of luminescence bands pertaining to deep defect levels in GaN. Since luminescence lineshapes depend sensitively on defect geometries and vibrational frequencies, these should be described accurately. The latter is achieved through the use of hybrid density functionals. Both quasi-localized and bulk phonons are included in our description. In the case of transitions accompanied by very large lattice relaxations, anharmonic effects become sizeable, and these are also accounted for. For the defects studied a very good agreement with available experimental data is achieved. For instance, in the case of wide luminescence bands the resulting line widths are within 0.05 eV of the experimental values. This work was supported by the Swiss NSF and by NSF.

  14. The Vibrational Spectra of Bactericide molecules: Terahertz Spectroscopy and Density Functional Theory Calculations

    NASA Astrophysics Data System (ADS)

    Wang, Xiaowei; Wang, Qiang

    2011-02-01

    In the room temperature and nitrogen conditions, we presented well-resolved absorption spectra and indexes of refraction of bactericide molecules in the far infrared radiation (FIR) spectral region recorded by terahertz time-domain spectroscopy (THz-TDS). As illustrative examples we discussed the absorption spectra of captan and folpet in THz region. The absorption coefficient and index of refraction of them were obtained. Meanwhile, density functional theory (DFT) with software package Gaussian 03 using B3LYP theory was employed for optimization and vibration analysis. With the help of Gaussian View 3.09, the distinct absorption peaks of those molecules were assigned with reliable accuracy. They were caused by intermolecular hydrogen-bonding, molecular torsion or vibration modes, absorption of water molecules, etc. As the absorption spectra are highly sensitive to the overall structure and configuration of the molecules, the THz-TDS procedure can provide a direct fingerprint of the molecular structure or conformational state of a compound.

  15. Use of a nondirect-product basis for treating singularities in triatomic rotational-vibrational calculations.

    PubMed

    Czakó, Gábor; Furtenbacher, Tibor; Barletta, Paolo; Császár, Attila G; Szalay, Viktor; Sutcliffe, Brian T

    2007-07-14

    A technique has been developed which in principle allows the determination of the full rotational-vibrational eigenspectrum of triatomic molecules by treating the important singularities present in the triatomic rotational-vibrational kinetic energy operator given in Jacobi coordinates and the R(1) embedding. The singular term related to the diatom-type coordinate, R(1), deemed to be unimportant for spectroscopic applications, is given no special attention. The work extends a previous [J. Chem. Phys., 2005, 122, 024101] vibration-only approach and employs a generalized finite basis representation (GFBR) resulting in a nonsymmetric Hamiltonian matrix [J. Chem. Phys., 2006, 124, 014110]. The basis set to be used is obtained by taking the direct product of a 1-D DVR basis, related to R(1), with a 5-D nondirect-product basis, the latter formed by coupling Bessel-DVR functions depending on the distance-type coordinate causing the singularity, associated Legendre polynomials depending on the Jacobi angle, and rotational functions depending on the three Euler angles. The robust implicitly restarted Arnoldi method within the ARPACK package is used for the determination of a number of eigenvalues of the nonsymmetric Hamiltonian matrix. The suitability of the proposed approach is shown by the determination of the rotational-vibrational energy levels of the ground electronic state of H(3)(+) somewhat above its barrier to linearity. Convergence of the eigenenergies is checked by an alternative approach, employing a Hamiltonian expressed in Radau coordinates, a standard direct-product basis, and no treatment of the singularities.

  16. Infrared and NMR spectra, tautomerism, vibrational assignment, normal coordinate analysis, and quantum mechanical calculations of 4-amino-5-pyrimidinecarbonitrile

    NASA Astrophysics Data System (ADS)

    Afifi, Mahmoud S.; Farag, Rabei S.; Shaaban, Ibrahim A.; Wilson, Lee D.; Zoghaib, Wajdi M.; Mohamed, Tarek A.

    2013-07-01

    The infrared (4000-200 cm-1) spectrum for 4-amino-5-pyrimidinecarbonitrile (APC, C5H4N4) was acquired in the solid phase. In addition, the 1H and 13C NMR spectra of APC were obtained in DMSO-d6 along with its mass spectrum. Initially, six isomers were hypothesized and then investigated by means of DFT/B3LYP and MP2(full) quantum mechanical calculations using a 6-31G(d) basis set. Moreover, the 1H and 13C NMR chemical shifts were predicted using a GIAO approximation at the 6-311+G(d,p) basis set and the B3LYP method with (and without) solvent effects using PCM method. The correlation coefficients showed good agreement between the experimental/theoretical chemical shift values of amino tautomers (1 and 2) rather than the eliminated imino tautomers (3-6), in agreement with the current quantum mechanical calculations. Structures 3-6 are less stable than the amino tautomers (1 and 2) by about 5206-8673 cm-1 (62.3-103.7 kJ/mol). The MP2(full)/6-31G(d) computational results favor the amino structure 1 with a pyramidal NH2 moiety and calculated real vibrational frequencies, however; structure 2 is considered a transition state owing to the calculated imaginary frequency. It is worth mentioning that, the calculated structural parameters suggest a strong conjugation between the amino nitrogen and pyrimidine ring. Aided by frequency calculations, normal coordinate analysis, force constants and potential energy distributions (PEDs), a complete vibrational assignment for the observed bands is proposed herein. Finally, NH2 internal rotation barriers for the stable non-planar isomer (1) were carried out using MP2(full)/6-31G(d) optimized structural parameters. Our results are discussed herein and compared to structural parameters for similar molecules whenever appropriate.

  17. Study of conformational stability, structural, electronic and charge transfer properties of cladrin using vibrational spectroscopy and DFT calculations.

    PubMed

    Singh, Swapnil; Singh, Harshita; Srivastava, Anubha; Tandon, Poonam; Sinha, Kirti; Bharti, Purnima; Kumar, Sudhir; Kumar, Padam; Maurya, Rakesh

    2014-11-11

    In the present work, a detailed conformational study of cladrin (3-(3,4-dimethoxy phenyl)-7-hydroxychromen-4-one) has been done by using spectroscopic techniques (FT-IR/FT-Raman/UV-Vis/NMR) and quantum chemical calculations. The optimized geometry, wavenumber and intensity of the vibrational bands of the cladrin in ground state were calculated by density functional theory (DFT) employing 6-311++G(d,p) basis sets. The study has been focused on the two most stable conformers that are selected after the full geometry optimization of the molecule. A detailed assignment of the FT-IR and FT-Raman spectra has been done for both the conformers along with potential energy distribution for each vibrational mode. The observed and scaled wavenumber of most of the bands has been found to be in good agreement. The UV-Vis spectrum has been recorded and compared with calculated spectrum. In addition, 1H and 13C nuclear magnetic resonance spectra have been also recorded and compared with the calculated data that shows the inter or intramolecular hydrogen bonding. The electronic properties such as HOMO-LUMO energies were calculated by using time-dependent density functional theory. Molecular electrostatic potential has been plotted to elucidate the reactive part of the molecule. Natural bond orbital analysis was performed to investigate the molecular stability. Non linear optical property of the molecule have been studied by calculating the electric dipole moment (μ) and the first hyperpolarizability (β) that results in the nonlinearity of the molecule.

  18. Multi-layer Lanczos iteration approach to calculations of vibrational energies and dipole transition intensities for polyatomic molecules

    SciTech Connect

    Yu, Hua-Gen

    2015-01-28

    We report a rigorous full dimensional quantum dynamics algorithm, the multi-layer Lanczos method, for computing vibrational energies and dipole transition intensities of polyatomic molecules without any dynamics approximation. The multi-layer Lanczos method is developed by using a few advanced techniques including the guided spectral transform Lanczos method, multi-layer Lanczos iteration approach, recursive residue generation method, and dipole-wavefunction contraction. The quantum molecular Hamiltonian at the total angular momentum J = 0 is represented in a set of orthogonal polyspherical coordinates so that the large amplitude motions of vibrations are naturally described. In particular, the algorithm is general and problem-independent. An application is illustrated by calculating the infrared vibrational dipole transition spectrum of CH{sub 4} based on the ab initio T8 potential energy surface of Schwenke and Partridge [Spectrochimica Acta, Part A 57, 887 (2001)] and the low-order truncated ab initio dipole moment surfaces of Yurchenko et al. [J. Mol. Spectrosc. 291, 69 (2013)]. A comparison with experiments is made. The algorithm is also applicable for Raman polarizability active spectra.

  19. Multi-layer Lanczos iteration approach to calculations of vibrational energies and dipole transition intensities for polyatomic molecules

    DOE PAGES

    Yu, Hua-Gen

    2015-01-28

    We report a rigorous full dimensional quantum dynamics algorithm, the multi-layer Lanczos method, for computing vibrational energies and dipole transition intensities of polyatomic molecules without any dynamics approximation. The multi-layer Lanczos method is developed by using a few advanced techniques including the guided spectral transform Lanczos method, multi-layer Lanczos iteration approach, recursive residue generation method, and dipole-wavefunction contraction. The quantum molecular Hamiltonian at the total angular momentum J = 0 is represented in a set of orthogonal polyspherical coordinates so that the large amplitude motions of vibrations are naturally described. In particular, the algorithm is general and problem-independent. An applicationmore » is illustrated by calculating the infrared vibrational dipole transition spectrum of CH₄ based on the ab initio T8 potential energy surface of Schwenke and Partridge and the low-order truncated ab initio dipole moment surfaces of Yurchenko and co-workers. A comparison with experiments is made. The algorithm is also applicable for Raman polarizability active spectra.« less

  20. Multi-layer Lanczos iteration approach to calculations of vibrational energies and dipole transition intensities for polyatomic molecules

    SciTech Connect

    Yu, Hua-Gen

    2015-01-28

    We report a rigorous full dimensional quantum dynamics algorithm, the multi-layer Lanczos method, for computing vibrational energies and dipole transition intensities of polyatomic molecules without any dynamics approximation. The multi-layer Lanczos method is developed by using a few advanced techniques including the guided spectral transform Lanczos method, multi-layer Lanczos iteration approach, recursive residue generation method, and dipole-wavefunction contraction. The quantum molecular Hamiltonian at the total angular momentum J = 0 is represented in a set of orthogonal polyspherical coordinates so that the large amplitude motions of vibrations are naturally described. In particular, the algorithm is general and problem-independent. An application is illustrated by calculating the infrared vibrational dipole transition spectrum of CH₄ based on the ab initio T8 potential energy surface of Schwenke and Partridge and the low-order truncated ab initio dipole moment surfaces of Yurchenko and co-workers. A comparison with experiments is made. The algorithm is also applicable for Raman polarizability active spectra.

  1. Determination of the absolute configuration of the natural product Klaivanolide via density functional calculations of vibrational circular dichroism (VCD).

    PubMed

    Devlin, Frank J; Stephens, Philip J; Figadère, Bruno

    2009-01-01

    The absolute configuration (AC) of the antiprotozoal lactone, Klaivanolide, 1, from Uvaria klaineana, has been determined using Vibrational Circular Dichroism (VCD) spectroscopy. The experimental VCD spectrum of the (+) enantiomer of 1 was measured. To analyze the AC of (+)-1, the conformationally-averaged VCD spectrum of 7-S-1 was calculated using density functional theory (DFT) and the GAUSSIAN 03 program. The B3PW91/TZ2P conformationally-averaged VCD spectrum of 7-S-1 proves that the AC of 1 is 7-S-(+).

  2. Quantum-Chemical Calculation and Visualization of the Vibrational Modes of Graphene in Different Points of the Brillouin Zone

    NASA Astrophysics Data System (ADS)

    Lebedieva, Tetiana; Gubanov, Victor; Dovbeshko, Galyna; Pidhirnyi, Denys

    2015-07-01

    Different notations of graphene irreducible representations and optical modes could be found in the literature. The goals of this paper are to identify the correspondence between available notations, to calculate the optical modes of graphene in different points of the Brillouin zone, and to compare them with experimental data obtained by Raman and coherent anti-Stokes Raman scattering (CARS) spectroscopy. The mechanism of the resonance enhancement of vibration modes of the molecules adsorbed on graphene in CARS experiments is proposed. The possibility of appearance of the discrete breathing modes is discussed.

  3. Quantum-Chemical Calculation and Visualization of the Vibrational Modes of Graphene in Different Points of the Brillouin Zone.

    PubMed

    Lebedieva, Tetiana; Gubanov, Victor; Dovbeshko, Galyna; Pidhirnyi, Denys

    2015-12-01

    Different notations of graphene irreducible representations and optical modes could be found in the literature. The goals of this paper are to identify the correspondence between available notations, to calculate the optical modes of graphene in different points of the Brillouin zone, and to compare them with experimental data obtained by Raman and coherent anti-Stokes Raman scattering (CARS) spectroscopy. The mechanism of the resonance enhancement of vibration modes of the molecules adsorbed on graphene in CARS experiments is proposed. The possibility of appearance of the discrete breathing modes is discussed.

  4. Vibrational spectra, NBO analysis, first order hyperpolarizabilities, thermodynamic functions and NMR chemical shielding anisotropy (CSA) parameters of 5-nitro-2-furoic acid by ab initio HF and DFT calculations.

    PubMed

    Balachandran, V; Rajeswari, S; Lalitha, S

    2013-09-01

    In this work, FT-IR and FT-Raman spectra are recorded on the solid phase of 5-nitro-2-furoic acid (abbreviated as NFA) in the regions 4000-400 cm(-1) and 3500-100 cm(-1) respectively. The geometrical parameters, vibrational assignments, HOMO-LUMO energies and NBO calculations are obtained for the monomer and dimer of NFA from HF and DFT (B3LYP) with 6-311++G (d, p) basis set calculations. Second order perturbation energies and electron density (ED) transfer from filled lone pairs of Lewis base to unfilled Lewis acid sites of NFA are discussed on the basis of NBO analysis. Intermolecular hydrogen bonds exist through COOH groups; give the evidence for the formation of dimer entities in the title molecule. The theoretically calculated harmonic frequencies are scaled by common scale factor. The observed and the calculated frequencies are found to be in good agreement. The thermodynamic functions were obtained for the range of temperature 100-1000 K. The polarizability, first hyperpolarizability, anisotropy polarizability invariant has been computed using quantum chemical calculations. The chemical parameters were calculated from the HOMO and LUMO values. The NMR chemical shielding anisotropy (CSA) parameters were also computed for the title molecule.

  5. Particle-vibration coupling: Recent advances in microscopic calculations with the Skyrme Hamiltonian

    NASA Astrophysics Data System (ADS)

    Colò, G.; Baldo, M.; Bortignon, P. F.; Rizzo, D.; Bocchi, G.

    2016-11-01

    In this contribution, we report some recent progress in our understanding of particle-vibration coupling (PVC) in nuclei. In particular, we first review the formal development that has allowed some of us to deduce the PVC equations within the Green's functionmethod. Applications are then discussed, both in the case of single-particle states and giant resonances in magic nuclei. We also present a new model that extends the PVC ansatz and is meant to account for the complete low-lying spectra of odd nuclei.

  6. Comparison of DFT with Traditional Methods for the Calculation of Vibrational Frequencies and Bond Energies

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W.; Arnold, James O. (Technical Monitor)

    1997-01-01

    The vibrational frequencies of MO2 are computed at many levels of theory, including HF, B3LYP, BP86, CASSCF, MP2, and CCSD(T). The computed results are compared with the available experimental results. Most of the methods fail for at least one state of the systems considered. The accuracy of the results and the origin of the observed failures are discussed. The B3LYP bond energies are compared with traditional methods for a variety of systems, ranging from FeCOn+ to SiCln and its positive ions. The cases where B3LYP differs from the traditional methods are discussed.

  7. Vibrational Spectra and Density functional calculation of Organic Nonlinear Optic Crystal p-Amino Acetanilide

    NASA Astrophysics Data System (ADS)

    Saja, D.; Joe, I. Hubert; Jayakumar, V. S.

    2006-01-01

    The NIR-FT Raman, FT-IR spectral analysis of potential NLO material P-Amino Acetanilide is carried out by density functional computations. The optimized geometry shows that NH2 and NHCOCH3 groups substituted in para position of phenyl ring are non-planar which predicts maximum conjugation of molecule with donor and acceptor groups. Vibrational analysis reveals that simultaneous IR and Raman activation of the phenyl ring modes also provide evidence for the charge transfer interaction between the donors and the acceptor can make the molecule highly polarized and the intra molecular charge transfer interaction must be responsible for the NLO properties of PAA.

  8. Structure and vibrational modes of AgI-doped AsSe glasses: Raman scattering and ab initio calculations

    SciTech Connect

    Kostadinova, O.; Chrissanthopoulos, A.; Petkova, T.; Petkov, P.; Yannopoulos, S.N.

    2011-02-15

    We report an investigation of the structure and vibrational modes of (AgI){sub x} (AsSe){sub 100-x}, bulk glasses using Raman spectroscopy and first principles calculations. The short- and medium-range structural order of the glasses was elucidated by analyzing the reduced Raman spectra, recorded at off-resonance conditions. Three distinct local environments were revealed for the AsSe glass including stoichiometric-like and As-rich network sub-structures, and cage-like molecules (As{sub 4}Se{sub n}, n=3, 4) decoupled from the network. To facilitate the interpretation of the Raman spectra ab initio calculations are employed to study the geometric and vibrational properties of As{sub 4}Se{sub n} molecular units that are parts of the glass structure. The incorporation of AgI causes appreciable structural changes into the glass structure. AgI is responsible for the population reduction of molecular units and for the degradation of the As-rich network-like sub-structure via the introduction of As-I terminal bonds. Ab initio calculations of mixed chalcohalide pyramids AsSe{sub m}I{sub 3-m} provided useful information augmenting the interpretation of the Raman spectra. -- Graphical abstract: Raman scattering and ab initio calculations are employed to study the structure of AgI-AsSe superionic glasses. The role of mixed chalcohalide pyramidal units as illustrated in the figure is elucidated. Display Omitted Research highlights: {yields} Doping binary As-Se glasses with AgI cause dramatic changes in glass structure. {yields} Raman scattering and ab initio calculations determine changes in short- and medium-range order. {yields} Three local environments exist in AsSe glass including a network sub-structure and cage-like molecules. {yields} Mixed chalcohalide pyramids AsSe{sub m}I{sub 3-m} dominate the AgI-doped glass structure.

  9. Analysis of vibrational spectra of 4-amino-2,6-dichloropyridine and 2-chloro-3,5-dinitropyridine based on density functional theory calculations.

    PubMed

    Krishnakumar, V; Dheivamalar, S; Xavier, R John; Balachandran, V

    2006-09-01

    This work deals with the vibrational spectroscopy of 4-amino-2,6-dichloropyridine (ADCP) and 2-chloro-3,5-dinitropyridine (CDNP) by means of quantum chemical calculations. The mid and far FTIR and FT-Raman spectra were measured in the condensed state. The fundamental vibrational frequencies and intensity of vibrational bands were evaluated using density functional theory (DFT) with the standard B3LYP/6-31G(*) and B3LYP/6-311+G(**) methods and basis set combinations, and was scaled using various scale factors which yields a good agreement between observed and calculated frequencies. The vibrational spectra were interpreted with the aid of normal coordinate analysis based on scaled density functional force field. The results of the calculations were applied to simulated infrared and Raman spectra of the title compounds, which showed excellent agreement with the observed spectra.

  10. Ab Initio Potential Energy Surfaces and the Calculation of Accurate Vibrational Frequencies

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Dateo, Christopher E.; Martin, Jan M. L.; Taylor, Peter R.; Langhoff, Stephen R. (Technical Monitor)

    1995-01-01

    Due to advances in quantum mechanical methods over the last few years, it is now possible to determine ab initio potential energy surfaces in which fundamental vibrational frequencies are accurate to within plus or minus 8 cm(exp -1) on average, and molecular bond distances are accurate to within plus or minus 0.001-0.003 Angstroms, depending on the nature of the bond. That is, the potential energy surfaces have not been scaled or empirically adjusted in any way, showing that theoretical methods have progressed to the point of being useful in analyzing spectra that are not from a tightly controlled laboratory environment, such as vibrational spectra from the interstellar medium. Some recent examples demonstrating this accuracy will be presented and discussed. These include the HNO, CH4, C2H4, and ClCN molecules. The HNO molecule is interesting due to the very large H-N anharmonicity, while ClCN has a very large Fermi resonance. The ab initio studies for the CH4 and C2H4 molecules present the first accurate full quartic force fields of any kind (i.e., whether theoretical or empirical) for a five-atom and six-atom system, respectively.

  11. Voids at the tunnel-soil interface for calculation of ground vibration from underground railways

    NASA Astrophysics Data System (ADS)

    Jones, Simon; Hunt, Hugh

    2011-01-01

    Voids at the tunnel-soil interface are not normally considered when predicting ground vibration from underground railways. The soil is generally assumed to be continuously bonded to the outer surface of the tunnel to simplify the modelling process. Evidence of voids around underground railways motivated the study presented herein to quantify the level of uncertainty in ground vibration predictions associated with neglecting to include such voids at the tunnel-soil interface. A semi-analytical method is developed which derives discrete transfers for the coupled tunnel-soil model based on the continuous Pipe-in-Pipe method. The void is simulated by uncoupling the appropriate nodes at the interface to prevent force transfer between the systems. The results from this investigation show that relatively small voids ( 4 m×90∘) can significantly affect the rms velocity predictions in the near-field and moderately affect predictions in the far-field. Sensitivity of the predictions to void length and void sector angle are both deemed to be significant. The findings from this study suggest that the uncertainty associated with assuming a perfect bond at the tunnel-soil interface in an area with known voidage can reasonably reach ±5 dB and thus should be considered in the design process.

  12. Molecular docking, TG/DTA, molecular structure, harmonic vibrational frequencies, natural bond orbital and TD-DFT analysis of diphenyl carbonate by DFT approach

    NASA Astrophysics Data System (ADS)

    Xavier, S.; Periandy, S.; Carthigayan, K.; Sebastian, S.

    2016-12-01

    Vibrational spectral analysis of Diphenyl Carbonate (DPC) is carried out by using FT-IR and FT-Raman spectroscopic techniques. It is found that all vibrational modes are in the expected region. Gaussian computational calculations were performed using B3LYP method with 6-311++G (d, p) basis set. The computed geometric parameters are in good agreement with XRD data. The observation shows that the structure of the carbonate group is unsymmetrical by ∼5° due to the attachment of the two phenyl rings. The stability of the molecule arising from hyperconjugative interaction and charge delocalization are analyzed by Natural Bond Orbital (NBO) study and the results show the lone pair transition has higher stabilization energy compared to all other. The 1H and 13C NMR chemical shifts are calculated using the Gauge-Including Atomic Orbital (GIAO) method with B3LYP/6-311++G (d, p) method. The chemical shifts computed theoretically go very closer to the experimental results. A study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies and Molecular electrostatic potential (MEP) exhibit the high reactivity nature of the molecule. The non-linear optical property of the DPC molecule predicted theoretically found to be good candidate for NLO material. TG/DTA analysis was made and decomposition of the molecule with respect to the temperature was studied. DPC having the anthelmintic activity is docked in the Hemoglobin of Fasciola hepatica protein. The DPC has been screened to antimicrobial activity and found to exhibit antibacterial effects.

  13. Study of NH stretching vibrations in small ammonia clusters by infrared spectroscopy in He droplets and ab initio calculations

    SciTech Connect

    Slipchenko, Mikhail N; Sartakov, Boris G; Vilesov, Andrey F; Xantheas, Sotiris S

    2007-08-09

    Infrared spectra of the NH stretching vibrations of (NH3)n clusters (n=2-4) have been obtained using the helium droplet isolation technique and first principles electronic structure anharmonic calculations. The measured spectra exhibit well-resolved bands, which have been assigned to the v1, v3, and 2v4 modes of the ammonia fragments in the clusters. The formation of a hydrogen bond in ammonia dimers leads to an increase of the infrared intensity by about a factor of four. In the larger clusters the infrared intensity per hydrogen bond is close to the one for dimers and approaches the value in the NH3 crystal. The intensity of the 2v4 overtone band in the trimer and tetramer increases by a factor of 10 relative to that in the monomer and dimer, and is comparable to the intensity of the v1 and v3 fundamental bands in larger clusters. This indicates the onset of the strong anharmonic coupling of the 2v4 and v1 modes in larger clusters. The experimental assignments are compared to the ones obtained from first principles electronic structure anharmonic calculations for the dimer and trimer clusters. The anharmonic calculations were performed at the Møller-Plesset (MP2) level of electronic structure theory and were based on a second-order perturbative evaluation of rovibrational parameters and their effects on the vibrational spectra and average structures. In general there is excellent (<20 cm-1) agreement between the experimentally measured band origins for the N-H stretching frequencies and the calculated anharmonic vibrational frequencies. However, the calculations were found to overestimate the infrared intensities in clusters by about a factor of four. This work was supported by the Office of Basic Energy Sciences of the Department of Energy, in part by the Chemical Sciences program and in part by the Engineering and Geosciences

  14. Conformational and Vibrational Studies of Triclosan

    NASA Astrophysics Data System (ADS)

    Özişik, Haci; Bayari, S. Haman; Saǧlam, Semran

    2010-01-01

    The conformational equilibrium of triclosan (5-chloro-2-(2, 4-dichlorophenoxy) phenol) have been calculated using density functional theory (DFTe/B3LYP/6-311++G(d, p)) method. Four different geometries were found to correspond to energy minimum conformations. The IR spectrum of triclosan was measured in the 4000-400 cm-1 region. We calculated the harmonic frequencies and intensities of the most stable conformers in order to assist in the assignment of the vibrational bands in the experimental spectrum. The fundamental vibrational modes were characterized depending on their total energy distribution (TED%) using scaled quantum mechanical (SQM) force field method.

  15. First-principle calculation of reduced masses in vibrational analysis using generalized internal coordinates: some crucial aspects and examples.

    PubMed

    Stare, Jernej

    2007-01-01

    In this paper we present and analyze the most essential aspects of reduced masses along generalized internal coordinates. The definition of reduced masses in the internal coordinate formalism is established through the Wilson G-matrix concept and includes sophisticated relations between internal and Cartesian coordinates. Moreover, reduced masses in internal coordinates are, in general, no longer constant but coordinate-dependent. Based on the approach presented earlier [Stare, J.; Balint-Kurti, G. G. J. Phys. Chem. A 2003, 107, 7204-7214] and on our experience with reduced masses discussed in this paper, we have developed a robust program for the calculation of Wilson G-matrix elements and their functional coordinate dependence. The approach is based on the first principles and can be used in virtually any (internal) coordinate set. Since the program allows for projection of any kind of nuclear motion on the selected internal coordinates, the method is particularly suitable for ab initio or DFT potential energy functions calculated by partial geometry optimization. Moreover, reduced masses obtained by this program can be used as a decision tool for selecting the most appropriate internal coordinates for the considered vibrational problem and for the inclusion or omission of the kinetic coupling terms in the vibrational Hamiltonian.

  16. Metal-organic frameworks in cadmium(II) complexes with 5-methoxyindole-2-carboxylic acid: structure, vibrational spectra and DFT calculations

    NASA Astrophysics Data System (ADS)

    Morzyk-Ociepa, Barbara; Szmigiel, Ksenia; Dysz, Karolina; Turowska-Tyrk, Ilona; Michalska, Danuta

    2016-11-01

    Two new complexes of Cd(II) with an O-deprotonated anion of 5-methoxyindole-2-carboxylic acid (5-MeOI2CA), of the formulas [Cd(5-MeOI2CA)2(H2O)2]n (1) and [Cd3(5-MeOI2CA)6(H2O)4(DMSO)4]ṡ2DMSO (2) were synthesized. In the polymeric complex 1, the 5-MeOI2CA anion acts as a bidentate bridging ligand and the coordination environment around the Cd(II) ion can be described as a distorted octahedron. Single crystal X-ray diffraction analysis of 2 has revealed that this complex is a trimer and it crystallizes in the monoclinic system (space group P21/c with a = 20.3403(4), b = 14.3079(2), c = 15.0603(3) Å, β = 92.4341(17)°, V = 4379.00(14) Å3 and Z = 2). In 2, the 5-MeOI2CA anions act as bidentate bridging and bidentate chelating ligands. The asymmetric unit of 2 contains two crystallographically independent Cd(II) cations. One of the cations is coordinated to six oxygen atoms and shows an octahedral geometry with a rhombic deformation. The other Cd(II) cation adopts a distorted seven-coordinate pentagonal-bipyramidal geometry involving seven oxygen atoms. In 2, the DMSO solvent molecules play a key role in the formation of metal-organic frameworks by filling voids, which are created by the bridging and chelating 5-MeOI2CA anions, the cadmium cations and the other DMSO molecules coordinated to cadmium. Comprehensive theoretical calculations (including the optimized structural parameters, harmonic frequencies and vibrational intensities) were performed for 2 using the B3LYP method with the 6-311++G(d,p)/LanL2DZ basis sets. The infrared and Ramana spectra were measured and a detailed assignment of the experimental spectra of 2 was performed. All cadmium-oxygen stretching vibrations occur in the range below 400 cm-1.

  17. Infrared and Raman spectra, conformational stability, vibration assignment, and ab initio calculations for 3-bromo-3,3-difluoropropene

    NASA Astrophysics Data System (ADS)

    Shen, Shiyu; Guirgis, Gamil A.; Gao, Jian; Durig, James R.

    2001-12-01

    The infrared spectra (3200-50 cm -1) of gaseous and solid and Raman spectra (3200-10 cm -1) of the liquid with qualitative depolarization ratios and solid 3-bromo-3,3-difluoropropene CH 2CHCBrF 2 have been recorded. Both the gauche and cis conformers have been identified in the fluid phase, but the gauche conformer is thermodynamically more stable than the cis rotamer and it is the only rotamer present in the spectrum of the annealed solid. Variable temperature (-105 to -150°C) studies of the infrared spectra of the sample dissolved in liquid krypton has been carried out. From these data, the enthalpy difference has been determined to be 281±28 cm -1 (3.36±0.33 kJ mol -1), with the gauche conformer as the more stable rotamer, which is in agreement with the ab initio predictions at all levels of calculations. It is estimated that there is only 11% of the cis conformer present at an ambient temperature. A complete vibration assignment is proposed for the gauche conformer which is based on infrared band contours, depolarization values, and group frequencies which is supported by normal coordinate calculations utilizing the force constants from ab initio MP2/6-31G (d) calculations. The conformational stabilities, barriers to internal rotation, and fundamental vibrational frequencies which have been determined experimentally are compared to those obtained from the ab initio calculations. The results are discussed and compared with the corresponding properties of some similar molecules.

  18. Variational Calculations of Ro-Vibrational Energy Levels and Transition Intensities for Tetratomic Molecules

    NASA Technical Reports Server (NTRS)

    Schwenke, David W.; Langhoff, Stephen R. (Technical Monitor)

    1995-01-01

    A description is given of an algorithm for computing ro-vibrational energy levels for tetratomic molecules. The expressions required for evaluating transition intensities are also given. The variational principle is used to determine the energy levels and the kinetic energy operator is simple and evaluated exactly. The computational procedure is split up into the determination of one dimensional radial basis functions, the computation of a contracted rotational-bending basis, followed by a final variational step coupling all degrees of freedom. An angular basis is proposed whereby the rotational-bending contraction takes place in three steps. Angular matrix elements of the potential are evaluated by expansion in terms of a suitable basis and the angular integrals are given in a factorized form which simplifies their evaluation. The basis functions in the final variational step have the full permutation symmetries of the identical particles. Sample results are given for HCCH and BH3.

  19. Contribution to harmonic balance calculations of self-sustained periodic oscillations with focus on single-reed instruments.

    PubMed

    Farner, Snorre; Vergez, Christophe; Kergomard, Jean; Lizée, Aude

    2006-03-01

    The harmonic balance method (HBM) was originally developed for finding periodic solutions of electronical and mechanical systems under a periodic force, but has been adapted to self-sustained musical instruments. Unlike time-domain methods, this frequency-domain method does not capture transients and so is not adapted for sound synthesis. However, its independence of time makes it very useful for studying any periodic solution, whether stable or unstable, without care of particular initial conditions in time. A computer program for solving general problems involving nonlinearly coupled exciter and resonator, HARMBAL, has been developed based on the HBM. The method as well as convergence improvements and continuation facilities are thoroughly presented and discussed in the present paper. Applications of the method are demonstrated, especially on problems with severe difficulties of convergence: the Helmholtz motion (square signals) of single-reed instruments when no losses are taken into account, the reed being modeled as a simple spring.

  20. Effective representation of amide III, II, I, and A modes on local vibrational modes: Analysis of ab initio quantum calculation results

    NASA Astrophysics Data System (ADS)

    Hahn, Seungsoo

    2016-10-01

    The Hamiltonian matrix for the first excited vibrational states of a protein can be effectively represented by local vibrational modes constituting amide III, II, I, and A modes to simulate various vibrational spectra. Methods for obtaining the Hamiltonian matrix from ab initio quantum calculation results are discussed, where the methods consist of three steps: selection of local vibrational mode coordinates, calculation of a reduced Hessian matrix, and extraction of the Hamiltonian matrix from the Hessian matrix. We introduce several methods for each step. The methods were assessed based on the density functional theory calculation results of 24 oligopeptides with four different peptide lengths and six different secondary structures. The completeness of a Hamiltonian matrix represented in the reduced local mode space is improved by adopting a specific atom group for each amide mode and reducing the effect of ignored local modes. The calculation results are also compared to previous models using C=O stretching vibration and transition dipole couplings. We found that local electric transition dipole moments of the amide modes are mainly bound on the local peptide planes. Their direction and magnitude are well conserved except amide A modes, which show large variation. Contrary to amide I modes, the vibrational coupling constants of amide III, II, and A modes obtained by analysis of a dipeptide are not transferable to oligopeptides with the same secondary conformation because coupling constants are affected by the surrounding atomic environment.

  1. Effective representation of amide III, II, I, and A modes on local vibrational modes: Analysis of ab initio quantum calculation results.

    PubMed

    Hahn, Seungsoo

    2016-10-28

    The Hamiltonian matrix for the first excited vibrational states of a protein can be effectively represented by local vibrational modes constituting amide III, II, I, and A modes to simulate various vibrational spectra. Methods for obtaining the Hamiltonian matrix from ab initio quantum calculation results are discussed, where the methods consist of three steps: selection of local vibrational mode coordinates, calculation of a reduced Hessian matrix, and extraction of the Hamiltonian matrix from the Hessian matrix. We introduce several methods for each step. The methods were assessed based on the density functional theory calculation results of 24 oligopeptides with four different peptide lengths and six different secondary structures. The completeness of a Hamiltonian matrix represented in the reduced local mode space is improved by adopting a specific atom group for each amide mode and reducing the effect of ignored local modes. The calculation results are also compared to previous models using C=O stretching vibration and transition dipole couplings. We found that local electric transition dipole moments of the amide modes are mainly bound on the local peptide planes. Their direction and magnitude are well conserved except amide A modes, which show large variation. Contrary to amide I modes, the vibrational coupling constants of amide III, II, and A modes obtained by analysis of a dipeptide are not transferable to oligopeptides with the same secondary conformation because coupling constants are affected by the surrounding atomic environment.

  2. Microhydrated dihydrogen phosphate clusters probed by gas phase vibrational spectroscopy and first principles calculations

    DOE PAGES

    Sun, Shou -Tian; Jiang, Ling; Liu, J. W.; ...

    2015-06-05

    We report infrared multiple photon dissociation (IRMPD) spectra of cryogenically-cooled H2PO4-(H2O)n anions (n = 2–12) in the spectral range of the stretching and bending modes of the solute anion (600–1800 cm-1). The spectra cannot be fully understood using the standard technique of comparison to harmonic spectra of minimum-energy structures; a satisfactory assignment requires considering anharmonic effects as well as entropy-driven hydrogen bond network fluctuations. Aided by finite temperature ab initio molecular dynamics simulations, the observed changes in the position, width and intensity of the IRMPD bands with cluster size are related to the sequence of microsolvation. Due to stronger hydrogenmore » bonding to the two terminal P=O groups, these are hydrated before the two P–OH groups. By n = 6, all four end groups are involved in the hydrogen bond network and by n = 12, the cluster spectra show similarities to the condensed phase spectrum of H2PO4-(aq). Our results reveal some of the microscopic details concerning the formation of the aqueous solvation environment around H2PO4-, provide ample testing grounds for the design of model solvation potentials for this biologically relevant anion, and support a new paradigm for the interpretation of IRMPD spectra of microhydrated ions.« less

  3. Coupled flexural-torsional vibrations of anisotropic bars from polymer composite materials. II - Comparisons of calculated and experimental data for carbon-fiber composite bars

    NASA Astrophysics Data System (ADS)

    Ekel'Chik, V. S.; Perren, A. A.; Riabov, V. M.; Iartsev, B. A.

    1992-04-01

    A number of primary natural frequencies of flexural and torsional vibrations are determined experimentally for specimens cut from a unidirectional CFRP plate at the angles phi = 0, 90 deg to the reinforcement direction. The flexural and torsional vibration values yielded primary values of elasticity and shear moduli, which were then corrected on the basis of a comparison of the experimental data and theoretical calculations of the frequencies of coupled flexural-torsional vibrations of specimens cut at angles of 15, 30, 45, 60 and 75 deg. Good agreement between the calculated and experimental data is obtained, and it is shown that the flexural-torsional interaction must be considered in studying the natural vibrations for specimens whose longitudinal axes do not coincide with the elasticity symmetry axis.

  4. An efficient method for calculating RMS von Mises stress in a random vibration environment

    SciTech Connect

    Segalman, D.J.; Fulcher, C.W.G.; Reese, G.M.; Field, R.V. Jr.

    1998-02-01

    An efficient method is presented for calculation of RMS von Mises stresses from stress component transfer functions and the Fourier representation of random input forces. An efficient implementation of the method calculates the RMS stresses directly from the linear stress and displacement modes. The key relation presented is one suggested in past literature, but does not appear to have been previously exploited in this manner.

  5. Molecular structure and vibrational analysis of Trifluoperazine by FT-IR, FT-Raman and UV-Vis spectroscopies combined with DFT calculations.

    PubMed

    Rajesh, P; Gunasekaran, S; Gnanasambandan, T; Seshadri, S

    2015-02-25

    The complete vibrational assignment and analysis of the fundamental vibrational modes of Trifluoperazine (TFZ) was carried out using the experimental FT-IR, FT-Raman and UV-Vis data and quantum chemical studies. The observed vibrational data were compared with the wavenumbers derived theoretically for the optimized geometry of the compound from the DFT-B3LYP gradient calculations employing 6-31G (d,p) basis set. Thermodynamic properties like entropy, heat capacity and enthalpy have been calculated for the molecule. The HOMO-LUMO energy gap has been calculated. The intramolecular contacts have been interpreted using natural bond orbital (NBO) and natural localized molecular orbital (NLMO) analysis. Important non-linear properties such as first hyperpolarizability of TFZ have been computed using B3LYP quantum chemical calculation.

  6. Carbonyl-functionalized quaterthiophenes: a study of the vibrational Raman and electronic absorption/emission properties guided by theoretical calculations.

    PubMed

    Aragó, Juan; Ponce Ortiz, Rocío; Nieto-Ortega, Belén; Hernández, Víctor; Casado, Juan; Facchetti, Antonio; Marks, Tobin J; Viruela, Pedro M; Ortí, Enrique; López Navarrete, Juan T

    2012-01-16

    This work investigates the evolution of the molecular, vibrational, and optical properties within a family of carbonyl-functionalized quaterthiophenes: 5,5'''-diheptanoyl-2,2':5',2'':5'',2'''-quaterthiophene (1), 5,5'''-diperfluorohexylcarbonyl-2,2':5',2'':5'',2'''-quaterthiophene (2), and 2,7-[bis(5-perfluorohexylcarbonylthien-2-yl)]-4H-cyclopenta[2,1-b:3,4-b']-dithiophene-4-one (3). The analysis is performed by Raman and UV/Vis absorption/excitation/fluorescence spectroscopy in combination with density functional calculations. Theoretical calculations show that substitution with carbonyl groups and perfluorohexyl chains induces progressive quinoidization of the π-conjugated backbone in comparison to the carbonyl-free compound 5,5'''-dimethyl-2,2':5',2'':5'',2'''-quaterthiophene (DM-4T) used as reference. Raman spectra are dominated by a strong Raman line which mainly corresponds to a combination of C-C/C=C stretching vibrations spreading over the whole thiophene core. This band undergoes a remarkable downshift as a consequence of the structural changes induced by the electron-withdrawing groups on the π-conjugated backbone. The band splitting on incorporation of a central carbonyl bridge evidences the formation of two structural domains in the molecule. The excitation and fluorescence spectra recorded at low temperature show well-resolved vibronic structures associated with the most intense collective C-C/C=C stretching mode. Optical absorption and fluorescence bands exhibit remarkable bathochromic dispersion on carbonyl functionalization, indicative of extension of π conjugation. TDDFT calculations enable a detailed description of the trends observed in the absorption spectra. Resonance Raman spectra reflect the structural changes predicted for the S(0)→S(1) electronic transition and evidence the cross-conjugated character that the central carbonyl group confers on 3.

  7. A time-dependent approach to flux calculation in molecular photofragmentation: Vibrational predissociation of HF-DF

    NASA Astrophysics Data System (ADS)

    Zhang, Dong H.; Wu, Qian; Zhang, John Z. H.

    1995-01-01

    We present in this paper a time-dependent approach to the calculation of photofragmentation dynamics using the flux formulation. The method is essentially a time-dependent version of the flux formulation for photodissociation calculation recently pursued by Manolopoulos and Alexander. In the present approach, the partial decay width of photofragmentation is obtained by calculating the flux at a given surface using a time-dependent method. This particular time-dependent approach for photofragmentation has two principal advantages. First, it is superior in computational scaling: CPU time ∝Nα(α<2) vs N3 in standard time-independent propagation method. Second, it is quite straightforward to handle the photofragmentation process involving rearrangement with the application of optical potentials. In addition, no bound state projection is necessary using the time-dependent flux method, which is required using the time-dependent golden rule method. This time-dependent method is applied to the calculation of decay width for vibrational predissociation of hydrogen-bonded HFDF, and the computed lifetime are compared with the recent experimental measurement of Farrell and Nesbitt. We also present the results of the full dimensional (6D) calculation of bound state energies for the HFDF complex. The exact dissociation energies are calculated to be 1057.33 cm-1 for (HF)2, 1166.6 cm-1 for (DF)2, 1142.7 cm-1 for HF-DF, and 1078.4 cm-1 for DF-HF. All theoretical calculations have used the SQSBDE potential energy surface due to Quack and Suhm.

  8. High-Level, First-Principles, Full-Dimensional Quantum Calculation of the Ro-vibrational Spectrum of the Simplest Criegee Intermediate (CH2OO).

    PubMed

    Li, Jun; Carter, Stuart; Bowman, Joel M; Dawes, Richard; Xie, Daiqian; Guo, Hua

    2014-07-03

    The ro-vibrational spectrum of the simplest Criegee intermediate (CH2OO) has been determined quantum mechanically based on nine-dimensional potential energy and dipole surfaces for its ground electronic state. The potential energy surface is fitted to more than 50 000 high-level ab initio points with a root-mean-square error of 25 cm(-1), using a recently proposed permutation invariant polynomial neural network method. The calculated rotational constants, vibrational frequencies, and spectral intensities of CH2OO are in excellent agreement with experiment. The potential energy surface provides a valuable platform for studying highly excited vibrational and unimolecular reaction dynamics of this important molecule.

  9. Full-dimensional quantum calculations of vibrational levels of NH4+ and isotopomers on an accurate ab initio potential energy surface

    DOE PAGES

    Hua -Gen Yu; Han, Huixian; Guo, Hua

    2016-03-29

    Vibrational energy levels of the ammonium cation (NH4+) and its deuterated isotopomers are calculated using a numerically exact kinetic energy operator on a recently developed nine-dimensional permutation invariant semiglobal potential energy surface fitted to a large number of high-level ab initio points. Like CH4, the vibrational levels of NH4+ and ND4+ exhibit a polyad structure, characterized by a collective quantum number P = 2(v1 + v3) + v2 + v4. As a result, the low-lying vibrational levels of all isotopomers are assigned and the agreement with available experimental data is better than 1 cm–1.

  10. Strength, hardness, and lattice vibrations of Z-carbon and W-carbon: First-principles calculations

    NASA Astrophysics Data System (ADS)

    Li, Zhiping; Gao, Faming; Xu, Ziming

    2012-04-01

    The strength, hardness, and lattice vibrations of two superhard carbon allotropies, Z-carbon and W-carbon are investigated by first-principles calculations. Phonon dispersion calculations indicate that Z-carbon and W-carbon are dynamically stable at least up to 300 GPa. The strength calculations reveal that the failure mode in Z-carbon is dominated by the tensile type, and the [010] direction is the weakest one. In W-carbon, the failure mode is dominated by the shear type, and the (101)[111¯] direction is the weakest one. Although the ideal strength of diamond is distinctly greater than that of Z-carbon and W-carbon, the tensile strength and shear strength for Z-carbon and W-carbon show much lower anisotropies than that of diamond. The hardness calculations indicate that the average hardness of Z-carbon is less than that of diamond but greater than that of the W-carbon, M-carbon, and body-centered-tetragonal-C4 carbon. The simulated Raman spectra show that the Ag modes at 1094 cm-1 for Z-carbon and 1109.7 cm-1 for W-carbon are in agreement with that of 1082 cm-1 observed in the experiment of cold-compressed graphite at 9.8 GPa.

  11. Microhydrated dihydrogen phosphate clusters probed by gas phase vibrational spectroscopy and first principles calculations

    SciTech Connect

    Sun, Shou -Tian; Jiang, Ling; Liu, J. W.; Heine, Nadja; Yacovitch, Tara I.; Wende, Torsten; Asmis, Knut R.; Neumark, Daniel M.; Liu, Zhi -Feng

    2015-06-05

    We report infrared multiple photon dissociation (IRMPD) spectra of cryogenically-cooled H2PO4-(H2O)n anions (n = 2–12) in the spectral range of the stretching and bending modes of the solute anion (600–1800 cm-1). The spectra cannot be fully understood using the standard technique of comparison to harmonic spectra of minimum-energy structures; a satisfactory assignment requires considering anharmonic effects as well as entropy-driven hydrogen bond network fluctuations. Aided by finite temperature ab initio molecular dynamics simulations, the observed changes in the position, width and intensity of the IRMPD bands with cluster size are related to the sequence of microsolvation. Due to stronger hydrogen bonding to the two terminal P=O groups, these are hydrated before the two P–OH groups. By n = 6, all four end groups are involved in the hydrogen bond network and by n = 12, the cluster spectra show similarities to the condensed phase spectrum of H2PO4-(aq). Our results reveal some of the microscopic details concerning the formation of the aqueous solvation environment around H2PO4-, provide ample testing grounds for the design of model solvation potentials for this biologically relevant anion, and support a new paradigm for the interpretation of IRMPD spectra of microhydrated ions.

  12. Infinitesimal cranking for triaxial angular-momentum-projected configuration-mixing calculations and its application to the γ vibrational band

    NASA Astrophysics Data System (ADS)

    Tagami, Shingo; Shimizu, Yoshifumi R.

    2016-02-01

    Inclusion of time-odd components into the wave function is important for a reliable description of rotational motion by the angular-momentum-projection method; the cranking procedure with infinitesimal rotational frequency is an efficient way to realize it. In the present work we investigate the effect of this infinitesimal cranking for a triaxially deformed nucleus, where there are three independent cranking axes. It is found that the effects of cranking about three axes on the triaxial energy spectrum are quite different and inclusion of all of them considerably modifies the resultant spectrum from the one obtained without cranking. Employing the Gogny D1S force as an effective interaction, we apply the method to the calculation of the multiple γ vibrational bands in 164Er as a typical example, where the angular-momentum-projected configuration mixing with respect to the triaxial shape degree of freedom is performed. With this method, both the K =0 and the K =4 two-phonon γ vibrational bands are obtained with considerable anharmonicity. Reasonably good agreement, though not perfect, is obtained for both the spectrum and transition probabilities with rather small average triaxial deformation γ ≈9∘ for the ground-state rotational band. The relation to the wobbling motion at high-spin states is also briefly discussed.

  13. Density functional theory calculations of the molecular structure and the vibrational spectra of bis-tetrapropyl-ammonium hexachloro-dizincate

    NASA Astrophysics Data System (ADS)

    Ben Gzaiel, M.; Oueslati, A.; Chaabane, I.; Gargouri, M.

    2016-10-01

    The molecular structure and vibrational spectra of bis-tetrapropyl-ammonium hexachloro-dizincate in the ground state have been investigated by density functional method (DFT) using the B3LYP method with the LanL2DZ and LanL2MB basis set. Infrared and Raman spectroscopes of the [N(C3H7)4]2Zn2Cl6 compound have been measured at room temperature in the frequencies range (3500-400 cm-1) and (3500-100 cm-1), respectively. The optimized geometric shows that the calculated values obtained by B3LYP/LanL2DZ basis are in much better agreement with the experimental data than those obtained by B3LYP/LanL2MB. Actually the theoretical vibrational spectra (B3LYP/LanL2DZ) of the title compound have been interpreted by means of potential energy distribution (PED) which is in good agreement with the experimental data. The comparison of the infrared spectrum of the tetrapropyl-ammonium chloride ligand with those of the bis-tetrapropyl-ammonium hexachloro-dizincate compound confirms an increase of the wavenumber in the [N(C3H7)4]2Zn2Cl6 compound. This can be explained by an increase of the electrostatic interactions of the [N(C3H7)4]Cl ligand.

  14. Calculation of exact vibration modes for plane grillages by the dynamic stiffness method

    NASA Technical Reports Server (NTRS)

    Hallauer, W. L., Jr.; Liu, R. Y. L.

    1982-01-01

    A dynamic stiffness method is developed for the calculation of the exact modal parameters for plane grillages which consist of straight and uniform beams with coincident elastic and inertial axes. Elementary bending-torsion beam theory is utilized, and bending translation is restricted to one direction. The exact bending-torsion dynamic stiffness matrix is obtained for a straight and uniform beam element with coincident elastic and inertial axes. The element stiffness matrices are assembled using the standard procedure of the static stiffness method to form the dynamic stiffness matrix of the complete grillage. The exact natural frequencies, mode shapes, and generalized masses of the grillage are then calculated by solving a nonlinear eigenvalue problem based on the dynamic stiffness matrix. The exact modal solutions for an example grillage are calculated and compared with the approximate solutions obtained by using the finite element method.

  15. Analysis of methods for calculating the transition frequencies of the torsional vibration of acrolein isomers in the ground ( S 0) electronic state

    NASA Astrophysics Data System (ADS)

    Koroleva, L. A.; Tyulin, V. I.; Matveev, V. K.; Pentin, Yu. A.

    2013-05-01

    B3LYP, MP2, CCSD(T), and MP4/MP2 in the 6-311G( d, p), 6-311++G( d, p), cc-pVTZ, aug-cc-pVTZ bases used to calculate the transition frequencies of torsional vibration of trans- and cis-isomers of acrolein in the ground electronic state ( S 0) are analyzed. It is found that for trans-isomers, all methods of calculation except for B3LYP in the cc-pVTZ basis yield good agreement between the calculated and experimental values. It is noted that for the cis-isomer of acrolein, no method of calculation confirms the experimental value of the frequency of torsional vibration (138 cm-1). It is shown that the calculated and experimental values for obertones at 273.0 cm-1 and other transitions of torsional vibration are different for this isomer in particular. However, it is established that in some calculation methods (B3LYP, MP2), the frequency of the torsional vibration of the cis-isomer coincides with another experimental value of this frequency (166.5 cm-1). It is concluded that in analyzing the vibrational structure of the UV spectrum, the calculated and experimental values of its obertone (331.3 cm-1) coincide, along with its frequency. It is also noted that the frequency of torsional vibration for the cis-isomer (166.5 cm-1) can also be found in other experimental works if we change the allocation of torsional transition 18{1/1}.

  16. Calculation of cross sections for vibrational excitation and dissociative attachment in electron collisions with HBr and DBr

    SciTech Connect

    Horacek, J. |||; Domcke, W. ||

    1996-04-01

    The nonlocal resonance model developed earlier for the description of low-energy inelastic and reactive electron-HCl collisions has been adapted to the electron-HBr collision system. The parameters of the model have been determined by fitting the eigenphase sum in the fixed-nuclei approximation to the data of an {ital ab} {ital initio} {ital R}-matrix calculation of Morgan, Burke, and collaborators. The Schwinger-Lanczos method has been employed to solve the nuclear scattering problem with a nonlocal, complex, and energy-dependent effective potential. Fully converged cross sections have been obtained on a dense grid of energies for many vibrational excitation, deexcitation, and dissociative channels in both HBr and DBr. The computed cross sections are generally in good agreement with experiment as far as data are available. {copyright} {ital 1996 The American Physical Society.}

  17. IOS and ECS line coupling calculation for the CO-He system - Influence on the vibration-rotation band shapes

    NASA Technical Reports Server (NTRS)

    Boissoles, J.; Boulet, C.; Robert, D.; Green, S.

    1987-01-01

    Line coupling coefficients resulting from rotational excitation of CO perturbed by He are computed within the infinite order sudden approximation (IOSA) and within the energy corrected sudden approximation (ECSA). The influence of this line coupling on the 1-0 CO-He vibration-rotation band shape is then computed for the case of weakly overlapping lines in the 292-78 K temperature range. The IOS and ECS results differ only at 78 K by a weak amount at high frequencies. Comparison with an additive superposition of Lorentzian lines shows strong modifications in the troughs between the lines. These calculated modifications are in excellent quantitative agreement with recent experimental data for all the temperatures considered. The applicability of previous approaches to CO-He system, based on either the strong collision model or exponential energy gap law, is also discussed.

  18. Experimental study on the structure and vibrational, thermal and dielectric properties of bis(2-methylanilinium) selenate accomplished with DFT calculation

    NASA Astrophysics Data System (ADS)

    Ben hassen, C.; Boujelbene, M.; Bahri, M.; Zouari, N.; Mhiri, T.

    2014-09-01

    The present paper undertakes the study of a new hybrid compound [2-CH3C6H4NH3]2SeO4 characterized by the X-ray diffraction, IR, DFT calculation, TG-DTA, DSC and electrical conductivity. This new organic-inorganic hybrid compound crystallizes in the monoclinic system with P21/c space group and the following parameters a = 14.821 (5) Å; b = 16.245 (5) Å; c = 6.713 (5) Å; ß = 102.844 (5)°, Z = 4 and V = 1575.8 (14) Å3. The atomic arrangement can be described as isolated tetrahedral SeO42- connected with the organic groups by means of Nsbnd H⋯O hydrogen bonds to form infinite sinusoidal chains in the c-direction. BHHLYP/6-311g** method was used to determine the harmonic frequencies for two optimized cluster structures. The calculated modes were animated using the Molden graphical package to give tentative assignments of the observed IR spectra. Thermal analysis of the title compound does not indicate the occurrence of a phase transition in the temperature range of 300-650 K. Dielectric study of this compound has been measured, in order to determine the conductivity. The conductivity relaxation parameters associated with some H+ conduction have been determined from an analysis of the M″/M″max spectrum measured in a wide temperature range.

  19. Identification of hydrogen defects in SrTiO3 by first principles local vibrational mode calculations

    SciTech Connect

    T-Thienprasert, J; Fongkaew, Ittipon; Singh, David J; Du, Mao-Hua; Limpijumnong, Sukit

    2012-01-01

    For over three decades, the infrared spectroscopy peaks of around 3500 cm{sup -1} observed in hydrogen-doped SrTiO{sub 3} samples have been assigned to an interstitial hydrogen (H{sub i}) attached to a lattice oxygen with two possible configuration models: the octahedral edge (OE) and the cubic face (CF) models. Based on our first-principles calculations of H{sub i} around O, both OE and CF configurations are not energetically stable. Starting from either configuration, the H{sub i} would spontaneously relax into an off axis (OA) site; lowering the energy by 0.25 eV or more. The calculated vibrational frequency of 2745 cm{sup -1} for OA invalidates the assignment of H{sub i} to the observed 3500 cm{sup -1} peak. In addition, the calculated diffusion barrier is low, suggesting that H{sub i} can be easily annealed out. We propose that the observed peaks around 3500 cm{sup -1} are associated with defect complexes. A Sr vacancy (V{sub Sr}) can trap H{sub i} and form a H-V{sub Sr} complex which is both stable and has the frequency in agreement with the observed main peak. The complex can also trap another H{sub i} and form 2H-V{sub Sr}; consistent with the observed additional peaks at slightly higher frequencies (3510-3530 cm{sup -1}).

  20. Calculation of Dynamic Loads Due to Random Vibration Environments in Rocket Engine Systems

    NASA Technical Reports Server (NTRS)

    Christensen, Eric R.; Brown, Andrew M.; Frady, Greg P.

    2007-01-01

    An important part of rocket engine design is the calculation of random dynamic loads resulting from internal engine "self-induced" sources. These loads are random in nature and can greatly influence the weight of many engine components. Several methodologies for calculating random loads are discussed and then compared to test results using a dynamic testbed consisting of a 60K thrust engine. The engine was tested in a free-free condition with known random force inputs from shakers attached to three locations near the main noise sources on the engine. Accelerations and strains were measured at several critical locations on the engines and then compared to the analytical results using two different random response methodologies.

  1. Theoretical calculations and vibrational potential energy surface of 4-silaspiro(3,3)heptane

    SciTech Connect

    Ocola, Esther J.; Medders, Cross; Laane, Jaan; Meinander, Niklas

    2014-04-28

    Theoretical computations have been carried out on 4-silaspiro(3,3)heptane (SSH) in order to calculate its molecular structure and conformational energies. The molecule has two puckered four-membered rings with dihedral angles of 34.2° and a tilt angle of 9.4° between the two rings. Energy calculations were carried out for different conformations of SSH. These results allowed the generation of a two-dimensional ring-puckering potential energy surface (PES) of the form V = a(x{sub 1}{sup 4} + x{sub 2}{sup 4}) – b(x{sub 1}{sup 2} + x{sub 2}{sup 2}) + cx{sub 1}{sup 2}x{sub 2}{sup 2}, where x{sub 1} and x{sub 2} are the ring-puckering coordinates for the two rings. The presence of sufficiently high potential energy barriers prevents the molecule from undergoing pseudorotation. The quantum states, wave functions, and predicted spectra resulting from the PESs were calculated.

  2. Harmonic and Anharmonic Properties of Diamond Structure Crystals with Application to the Calculation of the Thermal Expansion of Silicon. Ph.D. Thesis. Final Report

    NASA Technical Reports Server (NTRS)

    Wanser, K. H.

    1981-01-01

    Silicon has interesting harmonic and anharmonic properties such as the low lying transverse acoustic modes at the X and L points of the Brillouin zone, negative Gruneisen parameters, negative thermal expansion and anomalous acoustic attenuation. In an attempt to understand these properties, a lattice dynamical model employing long range, nonlocal, dipole-dipole interactions was developed. Analytic expression for the Gruneisen parameters of several modes are presented. These expressions explain how the negative Gruneisen parameters arise. This model is applied to the calculation of the thermal expansion of silicon from 5K to 1700K. The thermoelastic contribution to the acoustic attenuation of silicon is computed from 1 to 300 K. Strong attenuation anomalies associated with negative thermal expansion are found in the vicinity of 17K and 125K.

  3. Method for the calculation of the vibrational frequency shift of physisorbed molecules. Application to H2 adsorbed in NaA zeolite

    NASA Astrophysics Data System (ADS)

    Larin, A. V.; Cohen De Lara, E.

    1994-11-01

    The vibrational frequency shift of physisorbed diatomic molecules is related to the interaction with the adsorbent expressed in terms of the internuclear distance ρ. It is calculated by the Schrödinger equation, the perturbation theory, and a simplified method. We show that it is sufficient to calculate the interaction potential for the values of ρ in the ground and first vibrational states in order to get a precision of 10% on the frequency shift. The comparison between the theoretical and experimental frequency shift of H2 adsorbed in NaA zeolite is used to adjust the interaction potential, especially in terms of the ionicity of the crystal.

  4. Time-synchronous-averaging of gear-meshing-vibration transducer responses for elimination of harmonic contributions from the mating gear and the gear pair

    NASA Astrophysics Data System (ADS)

    Mark, William D.

    2015-10-01

    The transmission-error frequency spectrum of meshing gear pairs, operating at constant speed and constant loading, is decomposed into harmonics arising from the fundamental period of the gear pair, rotational harmonics of the individual gears of the pair, and tooth-meshing harmonics. In the case of hunting-tooth gear pairs, no rotational harmonics from the individual gears, other than the tooth-meshing harmonics, are shown to occur at the same frequencies. Time-synchronous averages utilizing a number of contiguous revolutions of the gear of interest equal to an integer multiple of the number of teeth on the mating gear is shown to eliminate non-tooth-meshing transmission-error rotational-harmonic contributions from the mating gear, and those from the gear pair, in the case of hunting-tooth gear pairs, and to minimize these contributions in the case of non-hunting-tooth gear pairs. An example computation is shown to illustrate the effectiveness of the suggested time-synchronous-averaging procedure.

  5. Synthesis, crystal structure, thermal analysis and vibrational spectroscopy accomplished with DFT calculation of new hybrid compound [2-CH3C6H4NH3]HSO4.H2O

    NASA Astrophysics Data System (ADS)

    Ben Hassen, C.; Boujelbene, M.; Marweni, S.; Bahri, M.; Mhiri, T.

    2015-10-01

    The present paper undertakes the study of a new organic/inorganic hybrid compound [2-CH3C6H4NH3]HSO4.H2O characterized by the X-ray diffraction, TG-DTA, IR and Raman spectroscopy accomplished with DFT calculation. It is crystallized in the monoclinic system with the centrosymmetric space group P 21/c, with a = 9.445 (5) Å, b = 10.499 Å, c = 10.073 Å, β = 90.627 (5)° and Z = 4. The atomic arrangement can be described as inorganic layers built by infinite chains, parallel to the (a c) planes between which the organic cations are inserted. In this atomic arrangement, hydrogen bonds and π-π interactions between the different species have an important role in the tri-dimensional network cohesion. Besides, the X-ray powder diffraction of the title compound confirms the existence of only one phase at room temperature. The thermal decomposition of precursors studied by thermo gravimetric analysis (TGA), the differential thermal analysis (DTA) and the temperature-dependent X-ray diffraction, show crystalline anhydrous compounds upon dehydration. DFT/BHHLYP calculations were performed, using the DZV (d,p) basis set, to determine the harmonic frequencies of the vibrational modes of an optimized cluster structure. The calculated modes were animated using the Molden graphical package to give tentative assignments of the observed IR and Raman spectra.

  6. Vibrational, structural and electronic study of a pyridinium salt assisted by SXRD studies and DFT calculations

    NASA Astrophysics Data System (ADS)

    Labra-Vázquez, Pablo; Palma-Contreras, Miguel; Santillan, Rosa; Farfán, Norberto

    2017-03-01

    The molecular structure of 1-[2-oxo-2-(2-pyridinyl)ethyl]pyridinium iodide (C12H11IN2O) is discussed using an experimental (FT-IR/ATR, NMR, SXRD) and theoretical (DFT, B3LYP/6-311G**) approach. Compound 2 crystallized in the monoclinic P21/c space group with 4 molecules per unit cell and unit cell dimensions a = 7.5629 Å (3), b = 21.5694 Å (7), c = 7.8166 Å (3). The crystal packing is governed by ion-dipole contacts and π-π stacking. High electrostatic potential at the ethanone hydrogens was derived from DFT calculations, further explaining the acidity and reactivity of the molecule as a Michael donor.

  7. Vibrational spectrum of the spin crossover complex [Fe(phen)(2)(NCS)(2)] studied by IR and Raman spectroscopy, nuclear inelastic scattering and DFT calculations.

    PubMed

    Ronayne, Kate L; Paulsen, Hauke; Höfer, Andreas; Dennis, Andrew C; Wolny, Juliusz A; Chumakov, Aleksandr I; Schünemann, Volker; Winkler, Heiner; Spiering, Hartmut; Bousseksou, Azzedine; Gütlich, Philipp; Trautwein, Alfred X; McGarvey, John J

    2006-10-28

    The vibrational modes of the low-spin and high-spin isomers of the spin crossover complex [Fe(phen)(2)(NCS)(2)] (phen = 1,10-phenanthroline) have been measured by IR and Raman spectroscopy and by nuclear inelastic scattering. The vibrational frequencies and normal modes and the IR and Raman intensities have been calculated by density functional methods. The vibrational entropy difference between the two isomers, DeltaS(vib), which is--together with the electronic entropy difference DeltaS(el)--the driving force for the spin-transition, has been determined from the measured and from the calculated frequencies. The calculated difference (DeltaS(vib) = 57-70 J mol(-1) K(-1), depending on the method) is in qualitative agreement with experimental values (20-36 J mol(-1) K(-1)). Only the low energy vibrational modes (20% of the 147 modes of the free molecule) contribute to the entropy difference and about three quarters of the vibrational entropy difference are due to the 15 modes of the central FeN(6) octahedron.

  8. Study of molecular structure, vibrational, electronic and NMR spectra of oncocalyxone A using DFT and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Joshi, Bhawani Datt; Srivastava, Anubha; Honorato, Sara Braga; Tandon, Poonam; Pessoa, Otília Deusdênia Loiola; Fechine, Pierre Basílio Almeida; Ayala, Alejandro Pedro

    2013-09-01

    Oncocalyxone A (C17H18O5) is the major secondary metabolite isolated from ethanol extract from the heartwood of Auxemma oncocalyx Taub popularly known as “pau branco”. Oncocalyxone A (Onco A) has many pharmaceutical uses such as: antitumor, analgesic, antioxidant and causative of inhibition of platelet activation. We have performed the optimized geometry, total energy, conformational study, molecular electrostatic potential mapping, frontier orbital energy gap and vibrational frequencies of Onco A employing ab initio Hartree-Fock (HF) and density functional theory (DFT/B3LYP) method with 6-311++G(d, p) basis set. Stability of the molecule arising from hyperconjugative interactions and/or charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV-vis spectrum of the compound was recorded in DMSO and MeOH solvent. The TD-DFT calculations have been performed to explore the influence of electronic absorption spectra in the gas phase, as well as in solution environment using IEF-PCM and 6-31G basis set. The 13C NMR chemical shifts have been calculated with the B3LYP/6-311++G(d, p) basis set and compared with the experimental values. These methods have been used as tools for structural characterization of Onco A.

  9. Ab initio calculations, potential representation and vibrational dynamics of He2Br2 van der Waals complex.

    PubMed

    Valdés, Alvaro; Prosmiti, Rita; Villarreal, Pablo; Delgado-Barrio, Gerardo

    2005-01-22

    An intermolecular potential energy surface for He(2)Br(2) complex in the ground state is calculated at the levels of fourth-order (MP4) Moller-Plesset and coupled-cluster [CCSD(T)] approximations, using large-core pseudopotential for Br atoms and the aug-cc-pV5Z basis set for He. The surface is characterized by three minima and the minimum energy pathways through them. The global minimum corresponds to a linear He-Br(2)-He configuration, while the two other ones to "police-nightstick" and tetrahedral structures. The corresponding well depths are -90.39/-89.18, -81.23/-80.78 and -74.40/-74.02 cm(-1), respectively, at MP4/CCSD(T) levels of theory. It is found that results obtained by summing three-body parametrized HeBr(2) interactions and the He-He interaction are in very good accord with the corresponding MP4/CSSD(T) configuration energies of the He(2)Br(2). Variational calculations using a sum of three-body interactions are presented to study the bound states of the vdW He(2)Br(2) complex. The binding energy D(0) and the corresponding vibrationally averaged structure are determined for different isomers of the cluster and their comparison with the available experimental data is discussed.

  10. Calculating vibrational spectra with sum of product basis functions without storing full-dimensional vectors or matrices

    NASA Astrophysics Data System (ADS)

    Leclerc, Arnaud; Carrington, Tucker

    2014-05-01

    We propose an iterative method for computing vibrational spectra that significantly reduces the memory cost of calculations. It uses a direct product primitive basis, but does not require storing vectors with as many components as there are product basis functions. Wavefunctions are represented in a basis each of whose functions is a sum of products (SOP) and the factorizable structure of the Hamiltonian is exploited. If the factors of the SOP basis functions are properly chosen, wavefunctions are linear combinations of a small number of SOP basis functions. The SOP basis functions are generated using a shifted block power method. The factors are refined with a rank reduction algorithm to cap the number of terms in a SOP basis function. The ideas are tested on a 20-D model Hamiltonian and a realistic CH3CN (12 dimensional) potential. For the 20-D problem, to use a standard direct product iterative approach one would need to store vectors with about 1020 components and would hence require about 8 × 1011 GB. With the approach of this paper only 1 GB of memory is necessary. Results for CH3CN agree well with those of a previous calculation on the same potential.

  11. Study of molecular structure, vibrational, electronic and NMR spectra of oncocalyxone A using DFT and quantum chemical calculations.

    PubMed

    Joshi, Bhawani Datt; Srivastava, Anubha; Honorato, Sara Braga; Tandon, Poonam; Pessoa, Otília Deusdênia Loiola; Fechine, Pierre Basílio Almeida; Ayala, Alejandro Pedro

    2013-09-01

    Oncocalyxone A (C17H18O5) is the major secondary metabolite isolated from ethanol extract from the heartwood of Auxemma oncocalyx Taub popularly known as "pau branco". Oncocalyxone A (Onco A) has many pharmaceutical uses such as: antitumor, analgesic, antioxidant and causative of inhibition of platelet activation. We have performed the optimized geometry, total energy, conformational study, molecular electrostatic potential mapping, frontier orbital energy gap and vibrational frequencies of Onco A employing ab initio Hartree-Fock (HF) and density functional theory (DFT/B3LYP) method with 6-311++G(d,p) basis set. Stability of the molecule arising from hyperconjugative interactions and/or charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV-vis spectrum of the compound was recorded in DMSO and MeOH solvent. The TD-DFT calculations have been performed to explore the influence of electronic absorption spectra in the gas phase, as well as in solution environment using IEF-PCM and 6-31G basis set. The (13)C NMR chemical shifts have been calculated with the B3LYP/6-311++G(d,p) basis set and compared with the experimental values. These methods have been used as tools for structural characterization of Onco A.

  12. Modelling the matrix shift on the vibrational frequency of ThO by DFT-D3 calculations

    NASA Astrophysics Data System (ADS)

    Kovács, Attila; Rode, Joanna E.

    2017-03-01

    Benchmark calculations with a goal to find dispersion-corrected DFT-D3 methods suitable for a reliable estimation of matrix shifts on the vibrational frequency were carried out on the ThO molecule in three rare gas (Rg = Ne, Ar, and Kr) matrices. The matrices were modelled by the explicit approach, in which a single and a double shell of Rg atoms around ThO was considered. The selection of exchange-correlation functionals was based on test calculations on triatomic ThO⋯ Rg models. The B3LYP, PBE0, CAM-B3LYP, and LC-ω PBE functionals were found to be the best suited for the estimation of matrix shifts. The single shell of Rg's around ThO accounted for a major part of the shifts; the addition of a second Rg shell resulted only in a minor improvement. Continuum solvation models considerably overestimated the effect of Rg matrices both when the whole matrix was treated by the model and when the first shell was treated explicitly and the rest with a continuum solvation model.

  13. Intermolecular vibrations of (CH2)2O-HF and -DF hydrogen bonded complexes investigated by Fourier transform infrared spectroscopy and ab initio calculations.

    PubMed

    Cirtog, M; Asselin, P; Soulard, P; Madebène, B; Alikhani, M E

    2010-10-14

    A series of Fourier transform infrared spectra (FTIR) of the hydrogen bonded complexes (CH(2))(2)O-HF and -DF have been recorded in the 50-750 cm(-1) range up to 0.1 cm(-1) resolution in a static cell maintained at near room temperature. The direct observation of three intermolecular transitions enabled us to perform band contour analysis of congested cell spectra and to determine reliable rovibrational parameters such as intermolecular frequencies, rovibrational and anharmonic coupling constants involving two l(1) and l(2) librations and one σ stretching intermolecular motion. Inter-inter anharmonic couplings could be identified between ν(l(1)), ν(l(2)), ν(σ) and the two lowest frequency bending modes. The positive sign of coupling constants (opposite with respect to acid stretching intra-inter ones) reveals a weakening of the hydrogen bond upon intermolecular excitation. The four rovibrational parameters ν(σ) and x(σj) (j = σ, δ(1), δ(2)) derived in the present far-infrared study and also in a previous mid-infrared one [Phys. Chem. Chem. Phys. 2005, 1, 592] make deviations appear smaller than 1% for frequencies and 12% for coupling constants which gives confidence to the reliability of the data obtained. Anharmonic frequencies obtained at the MP2 level with Aug-cc-pvTZ basis set agree well with experimental values over a large set of frequencies and coupling constants. An estimated anharmonic corrected value of the dissociation energy D for both oxirane-HF (2424 cm(-1)) and -DF (2566 cm(-1)) has been derived using a level of theory as high as CCSD(T)/Aug-cc-pvQZ, refining the harmonic value previously calculated for oxirane-HF with the MP2 method and a smaller basis set. Finally, contrary to short predissociation lifetimes evidenced for acid stretching excited states, any homogeneous broadening related to vibrational dynamics of (CH(2))(2)O-HF and -DF has been observed within the three highest frequency intermolecular states, as expected with low

  14. Ab Initio Calculation Of Vibrational Frequencies In AsxS1-x Glass And The Raman Spectra

    NASA Astrophysics Data System (ADS)

    Rosli, Ahmad Nazrul; Kassim, Hasan Abu; Shrivastava, Keshav N.

    2009-06-01

    We have made many different models for the understanding of the structure of AsS glass. In particular, we made the models of AsS3 (triangular), AsS3 (pyramid), AsS4 (3S on one side, one on the other side of As, S3-As-S), AsS4 (pyramid), AsS4 (tetrahedral), AsS7, As2S6 (dumb bell), As2S3 (bipyramid), As2S3 (zig-zag), As3S2 (bipyramid), As3S2 (linear), As4S4 (cubic), As4S4 (ring), As4S (tetrahedral), As4S (pyramid), As4S3 (linear) and As6S2 (dumb bell) by using the density functional theory which solves the Schrödinger equation for the given number of atoms in a cluster in the local density approximation. The models are optimized for the minimum energy which determines the structures, bond lengths and angles. For the optimized clusters, we calculated the vibrational frequencies in each case by calculating the gradients of the first principles potential. We compare the experimentally observed Raman frequencies with those calculated so that we can identify whether the cluster is present in the glass. In this way we find that AsS4 (S3-As-S), As4S4 (ring), As2S3 (bipyramid), As4S4 (cubic), As4S3 (linear), As2S3 (zig-zag), AsS4 (Td), As2S6 (dumb bell), AsS3 (triangle) and AsS3 (pyramid) structures are present in the actual glass.

  15. DVR3D: a program suite for the calculation of rotation-vibration spectra of triatomic molecules

    NASA Astrophysics Data System (ADS)

    Tennyson, Jonathan; Kostin, Maxim A.; Barletta, Paolo; Harris, Gregory J.; Polyansky, Oleg L.; Ramanlal, Jayesh; Zobov, Nikolai F.

    2004-11-01

    The DVR3D program suite calculates energy levels, wavefunctions, and where appropriate dipole transition moments, for rotating and vibrating triatomic molecules. Potential energy and, where necessary, dipole surfaces must be provided. Expectation values of geometrically defined functions can be calculated, a feature which is particularly useful for fitting potential energy surfaces. The programs use an exact (within the Born-Oppenheimer approximation) Hamiltonian and offer a choice of Jacobi or Radau internal coordinates and several body-fixed axes. Rotationally excited states are treated using an efficient two-step algorithm. The programs uses a Discrete Variable Representation (DVR) based on Gauss-Jacobi and Gauss-Laguerre quadrature for all 3 internal coordinates and thus yields a fully point-wise representation of the wavefunctions. The vibrational step uses successive diagonalisation and truncation which is implemented for a number of possible coordinate orderings. The rotational, expectation value and transition dipole programs exploit the savings offered by performing integrals on a DVR grid. The new version has been rewritten in FORTRAN 90 to exploit the dynamic array allocations and the algorithm for dipole and spectra calculations have been substantially improved. New modules allow the z-axis to be embedded perpendicular to the plane of the molecule and for the calculation of expectation values. Program summaryTitle of the program: DVR3D suite Catalogue number: ADTI Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADTI Program obtainable from: CPC Program Library, Queen's University of Belfast, N. Ireland Programming language: Fortran 90 No. of lines in distributed program, including test data, etc.: 61 574 No. of bytes in distributed program, including test data, etc.: 972 404 Distribution format: tar.gz New version summaryTitle of program: DVR3DRJZ Catalogue number: ADTB Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADTB Program obtainable

  16. Scaling properties of the harmonic oscillator basis calculations for N = Z nuclei in the infrared limit with the JISP16 potential

    NASA Astrophysics Data System (ADS)

    Constantinou, Chrysovalantis; Caprio, Mark A.; Vary, James P.; Maris, Pieter

    2014-03-01

    It has recently been found that when no-core configuration interaction (NCCI) calculations of low-mass nuclei are plotted against an infrared momentum cutoff λsc (scaling cutoff), a universal curve is obtained for the energy and the RMS radius. The plotted results must have an ultraviolet (UV) cutoff ΛUV greater than or equal to the intrinsic cutoff ΛNN of the interaction. This assures that UV convergence is reached. The scaling property then allows for the performance of extrapolations in the IR limit. Here we conduct NCCI calculations in the harmonic oscillator basis with the JISP16 potential. In the IR limit we obtain universal curves for N = Z nuclei up to and including 8Be . An extrapolation in the IR limit for the ground state energy and the RMS radius is performed, and extrapolated results are obtained. Supported by US DOE (DE-FG02-95ER-40934, DESC0008485 SciDAC/NUCLEI, DE-FG02-87ER40371), US NSF (0904782), and Research Corporation for Science Advancement (Cottrell Scholar Award). Computational resources provided by NERSC (US DOE DE-AC02-05CH11231).

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

    PubMed

    Mort, Brendan C; Autschbach, Jochen

    2006-08-09

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

  18. Vibrational spectroscopic studies and DFT calculations on NaCH3CO2(aq) and CH3COOH(aq).

    PubMed

    Rudolph, Wolfram W; Fischer, Dieter; Irmer, Gert

    2014-02-28

    Aqueous solutions of sodium acetate, NaCH3CO2, and acetic acid, CH3COOH, were studied using Raman and infrared spectroscopy. The spectra were recorded over a large concentration range, in the terahertz region and up to 4000 cm(-1). In the isotropic Raman spectrum in R-format, a polarized band at 189 cm(-1) was assigned to the ν1Na-O stretch of the hydrated Na(+)-ion and a shoulder at 245 cm(-1) to the restricted translation band, νsO-H···O* of the hydrated acetate ion, CH3CO2(-)(aq). The CH3CO2(-)(aq) and the hydrated acetic acid, CH3COOH(aq), possess pseudo Cs symmetry. Geometrical parameters for the species in the gas phase and for CH3CO2(-)(aq) and CH3COOH(aq) are reported. Characteristic bands for CH3CO2(-)(aq) and CH3COOH(aq) were assigned under the guidance of the DFT vibrational frequency calculations and discussed in detail. In aqueous NaCH3CO2 solutions, at high concentrations, no contact ion pairs could be detected, but instead solvent separated ion pairs were found. In LiCH3CO2(aq), however, contact ion pairs are formed which is indicated by the appearance of a shoulder at 939 cm(-1) and the shift of the symmetric stretching mode of the -CO2(-) group to higher wavenumbers.

  19. Crystal and molecular structure of N-(4-nitrophenyl)-β-alanine—Its vibrational spectra and theoretical calculations

    NASA Astrophysics Data System (ADS)

    Marchewka, M. K.; Drozd, M.; Janczak, J.

    2011-08-01

    The N-(4-nitrophenyl)-β-alanine in crystalline form directly by the addition of 4-nitroaniline to the acrylic acid in aqueous solution has been obtained. The title β-alanine derivative crystallizes in the P2 1/ c space group of monoclinic system with four molecules per unit cell. The X-ray geometry of β-alanine derivative molecule has been compared with those obtained by molecular orbital calculations corresponding to the gas phase. In the crystal the molecules related by an inversion center interact via symmetrically equivalent O-H⋯O hydrogen bonds with O⋯O distance of 2.656(2) Å forming a dimeric structure. The dimers of β-alanine derivative weakly interact via N-H⋯O hydrogen bonds between the H atom of β-amine groups and one of O atom of nitro groups. The room temperature powder vibrational (infrared and Raman) measurements are in accordance with the X-ray analysis. In aqueous solution of 4-nitroaniline and acrylic acid, the double C dbnd C bond of vinyl group of acrylic acid breaks as result of 4-nitroaniline addition.

  20. Crystal and molecular structure of N-(4-nitrophenyl)-β-alanine--its vibrational spectra and theoretical calculations.

    PubMed

    Marchewka, M K; Drozd, M; Janczak, J

    2011-08-15

    The N-(4-nitrophenyl)-β-alanine in crystalline form directly by the addition of 4-nitroaniline to the acrylic acid in aqueous solution has been obtained. The title β-alanine derivative crystallizes in the P2(1)/c space group of monoclinic system with four molecules per unit cell. The X-ray geometry of β-alanine derivative molecule has been compared with those obtained by molecular orbital calculations corresponding to the gas phase. In the crystal the molecules related by an inversion center interact via symmetrically equivalent O-H···O hydrogen bonds with O···O distance of 2.656(2) Å forming a dimeric structure. The dimers of β-alanine derivative weakly interact via N-H···O hydrogen bonds between the H atom of β-amine groups and one of O atom of nitro groups. The room temperature powder vibrational (infrared and Raman) measurements are in accordance with the X-ray analysis. In aqueous solution of 4-nitroaniline and acrylic acid, the double CC bond of vinyl group of acrylic acid breaks as result of 4-nitroaniline addition.

  1. Full-dimensional vibrational calculations of five-atom molecules using a combination of Radau and Jacobi coordinates: Applications to methane and fluoromethane

    NASA Astrophysics Data System (ADS)

    Zhao, Zhiqiang; Chen, Jun; Zhang, Zhaojun; Zhang, Dong H.; Lauvergnat, David; Gatti, Fabien

    2016-05-01

    Full quantum mechanical calculations of vibrational energies of methane and fluoromethane are carried out using a polyspherical description combining Radau and Jacobi coordinates. The Hamiltonian is built in a potential-optimized discrete variable representation, and vibrational energies are solved using an iterative eigensolver. This new approach can be applied to a large variety of molecules. In particular, we show that it is able to accurately and efficiently compute eigenstates for four different molecules : CH4, CHD3, CH2D2, and CH3F. Very good agreement is obtained with the results reported previously in the literature with different approaches and with experimental data.

  2. Vibrational energy levels of the simplest Criegee intermediate (CH{sub 2}OO) from full-dimensional Lanczos, MCTDH, and MULTIMODE calculations

    SciTech Connect

    Yu, Hua-Gen E-mail: dawesr@mst.edu; Ndengue, Steve; Dawes, Richard E-mail: dawesr@mst.edu; Li, Jun; Guo, Hua E-mail: dawesr@mst.edu

    2015-08-28

    Accurate vibrational energy levels of the simplest Criegee intermediate (CH{sub 2}OO) were determined on a recently developed ab initio based nine-dimensional potential energy surface using three quantum mechanical methods. The first is the iterative Lanczos method using a conventional basis expansion with an exact Hamiltonian. The second and more efficient method is the multi-configurational time-dependent Hartree (MCTDH) method in which the potential energy surface is refit to conform to the sums-of-products requirement of MCTDH. Finally, the energy levels were computed with a vibrational self-consistent field/virtual configuration interaction method in MULTIMODE. The low-lying levels obtained from the three methods are found to be within a few wave numbers of each other, although some larger discrepancies exist at higher levels. The calculated vibrational levels are very well represented by an anharmonic effective Hamiltonian.

  3. Ab initio structures and vibrational analysis of the isoprene conformers

    NASA Astrophysics Data System (ADS)

    Bock, Ch. W.; Panchenko, Yu. N.; Krasnoshchiokov, S. V.; Aroca, R.

    1987-09-01

    Complete gradient optimizations of the structures and the calculation of the harmonic force fields of the s- trans( anti) and gauche conformers of isoprene (2-methylbuta-1,3-diene) are reported at the RHF/6-31G level. The dihedral angle of the gauche conformer is found to be 41.0° from the planar s- cis( syn) form. The force fields obtained are refined using scale factors transferred from analogous calculations for trans-butadiene-1,3 and ethane. The direct vibrational problems are solved for both conformers of isoprene. A complete assignment of the experimental vibrational frequencies is given.

  4. Hybrid MP2/MP4 potential surfaces in VSCF calculations of IR spectra: applications for organic molecules.

    PubMed

    Knaanie, Roie; Šebek, Jiří; Kalinowski, Jaroslaw; Benny Gerber, R

    2014-02-05

    This study introduces an improved hybrid MP2/MP4 ab initio potential for vibrational spectroscopy calculations which is very accurate, yet without high computational demands. The method uses harmonic vibrational calculations with the MP4(SDQ) potential to construct an improved MP2 potential by coordinate scaling. This improved MP2 potential is used for the anharmonic VSCF calculation. The method was tested spectroscopically for four molecules: butane, acetone, ethylene and glycine. Very good agreement with experiment was found. For most of the systems, the more accurate harmonic treatment considerably improved the MP2 anharmonic results.

  5. Quantum mechanical calculations of vibrational population inversion in chemical reactions - Numerically exact L-squared-amplitude-density study of the H2Br reactive system

    NASA Technical Reports Server (NTRS)

    Zhang, Y. C.; Zhang, J. Z. H.; Kouri, D. J.; Haug, K.; Schwenke, D. W.

    1988-01-01

    Numerically exact, fully three-dimensional quantum mechanicl reactive scattering calculations are reported for the H2Br system. Both the exchange (H + H-prime Br to H-prime + HBr) and abstraction (H + HBR to H2 + Br) reaction channels are included in the calculations. The present results are the first completely converged three-dimensional quantum calculations for a system involving a highly exoergic reaction channel (the abstraction process). It is found that the production of vibrationally hot H2 in the abstraction reaction, and hence the extent of population inversion in the products, is a sensitive function of initial HBr rotational state and collision energy.

  6. A general discrete variable method to calculate vibrational energy levels of three- and four-atom molecules

    NASA Astrophysics Data System (ADS)

    Bramley, Matthew J.; Carrington, Tucker, Jr.

    1993-12-01

    We present a general variational method to calculate vibrational energy levels of polyatomic molecules without dynamical approximation. The method is based on a Lanczos algorithm, which does not require storage of the Hamiltonian matrix. The rate-determining step of each Lanczos iteration is the evaluation of the product of the matrix and a trial vector. We use simple product basis functions and write the Hamiltonian as a sum of factorizable terms. With n one-dimensional functions in each of f dimensions, the matrix-vector product requires no more than cnf+1 multiplications for a single term involving c coordinates. Choosing a (potential optimized) discrete variable representation (DVR) in each dimension, the potential energy matrix is diagonal. The rate-determining step is now the multiplication of a vector by the kinetic energy matrix and c is effectively (with rare exceptions) at most two. The nf+1 scaling holds for both diagonal and mixed second derivative operators. The method is directly applicable to any three-atom and any nonlinear four-atom molecule. We use a variety of coordinate systems (Jacobi, Radau, a hybrid of the two, and bond), for which the total number of factorizable terms in the exact kinetic energy operator is never large, to calculate very well-converged band origins of H2O up to 22 000 cm-1, of H+3 up to 18 000 cm-1, and of CH2O up to 5700 cm-1; and low-lying levels of H2O2. The results for CH2O are new, and those for H+3 clarify the causes of discrepancies in published work. The product basis results in very large matrices (up to 500 000×500 000 for four atoms), but the cost is within an order of magnitude of that of contracted-basis approaches using explicit diagonalization. While contracted basis approaches are molecule and Hamiltonian specific, it was possible to apply the DVR-Lanczos method to all the examples presented here with a single computer program. The principal advantage of our method is thus its generality, and in this

  7. Molecular structure, vibrational spectra and HOMO, LUMO analysis of yohimbine hydrochloride by density functional theory and ab initio Hartree-Fock calculations

    NASA Astrophysics Data System (ADS)

    Joshi, Bhawani Datt; Srivastava, Anubha; Tandon, Poonam; Jain, Sudha

    2011-11-01

    Yohimbine hydrochloride (YHCl) is an aphrodisiac and promoted for erectile dysfunction, weight loss and depression. The optimized geometry, total energy, potential energy surface and vibrational wavenumbers of yohimbine hydrochloride have been determined using ab initio, Hartree-Fock (HF) and density functional theory (DFT/B3LYP) method with 6-311++G(d,p) basis set. A complete vibrational assignment is provided for the observed Raman and IR spectra of YHCl. The UV absorption spectrum was examined in ethanol solvent and compared with the calculated one in gas phase as well as in solvent environment (polarizable continuum model, PCM) using TD-DFT/6-31G basis set. These methods are proposed as a tool to be applied in the structural characterization of YHCl. The calculated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) with frontier orbital gap are presented.

  8. Vibrational properties of Ti3C2 and Ti3C2T2 (T = O, F, OH) monosheets by first-principles calculations: a comparative study.

    PubMed

    Hu, Tao; Wang, Jiemin; Zhang, Hui; Li, Zhaojin; Hu, Minmin; Wang, Xiaohui

    2015-04-21

    We present a comparative study on the static and dynamical properties of bare Ti3C2 and T-terminated Ti3C2T2 (T = O, F, OH) monosheets using density functional theory calculations. First, the crystal structures are optimized to be of trigonal configurations (P3[combining macron]m1), which are thermodynamically and dynamically stable. It is demonstrated that the terminations modulate the crystal structures through valence electron density redistribution of the atoms, particularly surface Ti (Ti2) in the monosheets. Second, lattice dynamical properties including phonon dispersion and partial density of states (PDOS) are investigated. Phonon PDOS analysis shows a clear collaborative feature in the vibrations, reflecting the covalent nature of corresponding bonds in the monosheets. In the bare Ti3C2 monosheet, there is a phonon band gap between 400 and 500 cm(-1), while it disappears in Ti3C2O2 and Ti3C2(OH)2 as the vibrations associated with the terminal atoms (O and OH) bridge the gap. Third, both Raman (Eg and A1g) and infrared-active (Eu and A2u) vibrational modes are predicted and conclusively assigned. A comparative study indicates that the terminal atoms remarkably influence the vibrational frequencies. Generally, the terminal atoms weaken the vibrations in which surface Ti atoms are involved while strengthening the out-of-plane vibration of C atoms. Temperature-dependent micro Raman measurements agree with the theoretical prediction if the complexity in the experimentally obtained lamellae for the Raman study is taken into account.

  9. Investigating pure vibrational dephasing of I3- in solution: Temperature dependence of T2* for the fundamental and first harmonic of ν1

    NASA Astrophysics Data System (ADS)

    Gershgoren, Erez; Wang, Zhaohui; Ruhman, Sanford; Vala, Jiri; Kosloff, Ronnie

    2003-02-01

    Pure ν1 vibrational dephasing of triiodide is recorded in ethanol and methyl-tetrahydrofurane solutions from 300 to 100 K, for the vibrational fundamental and its first overtone. Using impulsive Raman spectroscopy, dephasing is demonstrated to be homogeneous throughout the temperature range studied. Independent measures of T1 prove that population relaxation contributes negligibly to the dephasing rates. The reduction in temperature gradually leads to a ˜2-fold decrease in the rate of pure dephasing. With cooling the ratio of T2(n=1)*/T2(n=2)* reduces slightly but remains in the range of 2.7 to 2. These results are discussed in terms of Kubo lineshape and Poisson dephasing theories. Neither of these consistently explains the experimental observations assuming reasonable intensities and rates of intermolecular encounters in the solutions.

  10. Vibrational [FT-IR, FT-Raman] analysis, NMR and mass - Spectroscopic investigation on 3,6-Dimethylphenanthrene using computational calculation

    NASA Astrophysics Data System (ADS)

    Manzoor Ali, M.; George, Gene; Ramalingam, S.; Periandy, S.; Gokulakrishnan, V.

    2015-11-01

    In this research work, in order to the vibrational, physical and chemical properties, a thorough investigation has been made by recording FT-IR, FT-Raman, Mass and 13C and 1H NMR spectra of pharmaceutically important compound; 3,6-Dimethylphenanthrene. The altered geometrical parameters of Phenanthrene due to the addition of methyl groups have been calculated using HF and DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the discussion are made on their corresponding results. The alternation of the vibrational pattern of the molecule due to the injection of the substitutions; CH3 is investigated. The keen observation is made over the excitations between the electronic energy levels of the molecule which lead to the study of electronic properties. The alternation of distribution of Mulliken charges after the formation of present molecule has been correlated with the vibrational pattern of the molecular bonds. The charge transformation over the frontier molecular orbitals between the ligand and rings has been studied. The cause of the linear and non linear optical activity of the molecule is interpreted in detail from the average Polarizability first order diagonal hyperpolarizability calculations. The variation of thermodynamic properties; heat capacity, entropy, and enthalpy of the present compound at different temperatures are calculated using NIST thermodynamical function program and interpreted.

  11. First example of the correlated calculation of the one-bond tellurium-carbon spin-spin coupling constants: Relativistic effects, vibrational corrections, and solvent effects.

    PubMed

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

    2016-06-05

    This work reports on the comprehensive calculation of the NMR one-bond spin-spin coupling constants (SSCCs) involving carbon and tellurium, (1) J((125) Te,(13) C), in four representative compounds: Te(CH3 )2 , Te(CF3 )2 , Te(CCH)2 , and tellurophene. A high-level computational treatment of (1) J((125) Te,(13) C) included calculations at the SOPPA level taking into account relativistic effects evaluated at the 4-component RPA and DFT levels of theory, vibrational corrections, and solvent effects. The consistency of different computational approaches including the level of theory of the geometry optimization of tellurium-containing compounds, basis sets, and methods used for obtainig spin-spin coupling values have also been discussed in view of reproducing the experimental values of the tellurium-carbon SSCCs. Relativistic corrections were found to play a major role in the calculation of (1) J((125) Te,(13) C) reaching as much as almost 50% of the total value of (1) J((125) Te,(13) C) while relativistic geometrical effects are of minor importance. The vibrational and solvent corrections account for accordingly about 3-6% and 0-4% of the total value. It is shown that taking into account relativistic corrections, vibrational corrections and solvent effects at the DFT level essentially improves the agreement of the non-relativistic theoretical SOPPA results with experiment. © 2016 Wiley Periodicals, Inc.

  12. Vibrational spectroscopic and DFT calculation studies of 2-amino-7-bromo-5-oxo-[1]benzopyrano [2,3-b]pyridine-3 carbonitrile

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    The vibrational spectra of 2-amino-7-bromo-5-oxo-[1]benzopyrano [2,3-b]pyridine-3 carbonitrile were recorded using fourier transform-infrared and fourier transform-Raman spectrometer. The optimized structural parameters, vibrational frequencies, Mulliken atomic charge distribution, frontier molecular orbitals, thermodynamic properties, temperature dependence of thermodynamic parameters, first order hyperpolarizability and natural bond orbital calculations of the molecule were performed using the Gaussian 09 program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using the VEDA 4.0 program. The calculated first order hyperpolarizability of ABOBPC molecule was obtained as 6.908 × 10-30 issue, which was 10.5 times greater than urea. The nonlinear optical activity of the molecule was also confirmed by the frontier molecular orbitals and natural bond orbital analysis. The frontier molecular orbitals analysis shows that the lower energy gap of the molecule, which leads to the higher value of first order hyperpolarizability. The natural bond orbital analysis indicates that the nonlinear optical activity of the molecule arises due to the π → π∗ transitions. The Mulliken atomic charge distribution confirms the presence of intramolecular charge transfer within the molecule. The reactive site of the molecule was predicted from the molecular electrostatic potential contour map. The values of thermo dynamic parameters were increasing with increasing temperature.

  13. Vibrational spectroscopic and DFT calculation studies of 2-amino-7-bromo-5-oxo-[1]benzopyrano [2,3-b]pyridine-3 carbonitrile.

    PubMed

    Premkumar, S; Jawahar, A; Mathavan, T; Kumara Dhas, M; Milton Franklin Benial, A

    2015-03-05

    The vibrational spectra of 2-amino-7-bromo-5-oxo-[1]benzopyrano [2,3-b]pyridine-3 carbonitrile were recorded using fourier transform-infrared and fourier transform-Raman spectrometer. The optimized structural parameters, vibrational frequencies, Mulliken atomic charge distribution, frontier molecular orbitals, thermodynamic properties, temperature dependence of thermodynamic parameters, first order hyperpolarizability and natural bond orbital calculations of the molecule were performed using the Gaussian 09 program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using the VEDA 4.0 program. The calculated first order hyperpolarizability of ABOBPC molecule was obtained as 6.908×10(-30) issue, which was 10.5 times greater than urea. The nonlinear optical activity of the molecule was also confirmed by the frontier molecular orbitals and natural bond orbital analysis. The frontier molecular orbitals analysis shows that the lower energy gap of the molecule, which leads to the higher value of first order hyperpolarizability. The natural bond orbital analysis indicates that the nonlinear optical activity of the molecule arises due to the π→π(∗) transitions. The Mulliken atomic charge distribution confirms the presence of intramolecular charge transfer within the molecule. The reactive site of the molecule was predicted from the molecular electrostatic potential contour map. The values of thermo dynamic parameters were increasing with increasing temperature.

  14. Optimal geometries and harmonic vibrational frequencies of the global minima of water clusters (H2O)n, n = 2–6, and several hexamer local minima at the CCSD(T) level of theory

    SciTech Connect

    Miliordos, Evangelos; Aprà, Edoardo; Xantheas, Sotiris S.

    2013-01-01

    We report the first optimum geometries and harmonic vibrational frequencies for the ring pentamer and several water hexamer (prism, cage, cyclic and two book) at the CCSD(T)/aug-cc-pVDZ level of theory. All five hexamer isomer minima previously reported by MP2 are also minima on the CCSD(T) potential energy surface (PES). In addition, all CCSD(T) minimum energy structures for the n=2-6 cluster isomers are quite close to the ones previously obtained by MP2 on the respective PESs, as confirmed by a modified Procrustes analysis that quantifies the difference between any two cluster geometries. The CCSD(T) results confirm the cooperative effect of the homodromic ring networks (systematic contraction of the nearest-neighbor (nn) intermolecular separations with cluster size) previously reported by MP2, albeit with O-O distances shorter by ~0.02 Å, indicating that MP2 overcorrects this effect. The harmonic frequencies at the minimum geometries were obtained by the double differentiation of the CCSD(T) energy using an efficient scheme based on internal coordinates that reduces the number of required single point energy evaluations by ~15% when compared to the corresponding double differentiation using Cartesian coordinates. Negligible differences between MP2 and CCSD(T) are found for the librational modes, while uniform increases of ~15 and ~25 cm-1 are observed for the bending and “free” OH harmonic frequencies. The largest differences between MP2 and CCSD(T) are observed for the harmonic hydrogen bonded frequencies. The CCSD(T) red shifts from the monomer frequencies (Δω) are smaller than the MP2 ones, due to the fact that the former produces shorter elongations (ΔR) of the respective hydrogen bonded OH lengths from the monomer value with respect to the latter. Both the MP2 and CCSD(T) results for the hydrogen bonded frequencies were found to closely follow the relation - Δω = s · ΔR, with a rate of s = 20.3 cm-1 / 0.001 Å. The CCSD

  15. Applications of higher harmonic control to hingeless rotor systems

    NASA Technical Reports Server (NTRS)

    Nguyen, Khanh; Chopra, Inderjit

    1991-01-01

    A comprehensive analytical formulation was developed to predict the vibratory hub loads of a helicopter rotor system in forward flight. This analysis is used to calculate the optimal higher harmonic control inputs and associated actuator power required to minimize these hub loads. The present formulation is based on a finite element method in space and time. A nonlinear time domain, unsteady aerodynamic model is used to obtain the airloads, and the rotor induced inflow is calculated using a nonuniform inflow model. Predicted vibratory hub loads are correlated with experimental data from a scale model rotor. Results of a parametric study on a hindgeless rotor show that blade flap, lag and torsion vibration characteristics, offset of blade center of mass from elastic axis, offset of elastic axis from quarter-chord axis, and blade thrust greatly affect the higher harmonic control actuator power requirement.

  16. Anharmonic Vibrational Spectroscopy on Metal Transition Complexes

    NASA Astrophysics Data System (ADS)

    Latouche, Camille; Bloino, Julien; Barone, Vincenzo

    2014-06-01

    Advances in hardware performance and the availability of efficient and reliable computational models have made possible the application of computational spectroscopy to ever larger molecular systems. The systematic interpretation of experimental data and the full characterization of complex molecules can then be facilitated. Focusing on vibrational spectroscopy, several approaches have been proposed to simulate spectra beyond the double harmonic approximation, so that more details become available. However, a routine use of such tools requires the preliminary definition of a valid protocol with the most appropriate combination of electronic structure and nuclear calculation models. Several benchmark of anharmonic calculations frequency have been realized on organic molecules. Nevertheless, benchmarks of organometallics or inorganic metal complexes at this level are strongly lacking despite the interest of these systems due to their strong emission and vibrational properties. Herein we report the benchmark study realized with anharmonic calculations on simple metal complexes, along with some pilot applications on systems of direct technological or biological interest.

  17. Harmonicity in slow protein dynamics

    NASA Astrophysics Data System (ADS)

    Hinsen, Konrad; Petrescu, Andrei-Jose; Dellerue, Serge; Bellissent-Funel, Marie-Claire; Kneller, Gerald R.

    2000-11-01

    The slow dynamics of proteins around its native folded state is usually described by diffusion in a strongly anharmonic potential. In this paper, we try to understand the form and origin of the anharmonicities, with the principal aim of gaining a better understanding of the principal motion types, but also in order to develop more efficient numerical methods for simulating neutron scattering spectra of large proteins. First, we decompose a molecular dynamics (MD) trajectory of 1.5 ns for a C-phycocyanin dimer surrounded by a layer of water into three contributions that we expect to be independent: the global motion of the residues, the rigid-body motion of the sidechains relative to the backbone, and the internal deformations of the sidechains. We show that they are indeed almost independent by verifying the factorization of the incoherent intermediate scattering function. Then, we show that the global residue motions, which include all large-scale backbone motions, can be reproduced by a simple harmonic model which contains two contributions: a short-time vibrational term, described by a standard normal mode calculation in a local minimum, and a long-time diffusive term, described by Brownian motion in an effective harmonic potential. The potential and the friction constants were fitted to the MD data. The major anharmonic contribution to the incoherent intermediate scattering function comes from the rigid-body diffusion of the sidechains. This model can be used to calculate scattering functions for large proteins and for long-time scales very efficiently, and thus provides a useful complement to MD simulations, which are best suited for detailed studies on smaller systems or for shorter time scales.

  18. Study of the thymine molecule: equilibrium structure from joint analysis of gas-phase electron diffraction and microwave data and assignment of vibrational spectra using results of ab initio calculations.

    PubMed

    Vogt, Natalja; Khaikin, Leonid S; Grikina, Olga E; Rykov, Anatolii N; Vogt, Jürgen

    2008-08-21

    Thymine is one of the nucleobases which forms the nucleic acid (NA) base pair with adenine in DNA. The study of molecular structure and dynamics of nucleobases can help to understand and explain some processes in biological systems and therefore it is of interest. Because the scattered intensities on the C, N, and O atoms as well as some bond lengths in thymine are close to each other the structural problem cannot been solved by the gas phase electron diffraction (GED) method alone. Therefore the rotational constants from microvawe (MW) studies and differences in the groups of N-C, C=O, N-H, and C-H bond lengths from MP2 (full)/cc-pVQZ calculations were used as supplementary data. The analysis of GED data was based on the C(s) molecular symmetry according to results of the structure optimizations at the MP2 (full) level using 6-311G (d,p), cc-pVTZ, and cc-pVQZ basis sets confirmed by vibrational frequency calculations with 6-311G (d,p) and cc-pVTZ basis sets. Mean-square amplitudes as well as harmonic and anharmonic vibrational corrections to the internuclear distances (r(e)-r(a)) and to the rotational constants (B(e)(k)-B(0)(k), where k = A, B, C) were calculated from the quadratic (MP2 (full)/cc-pVTZ) and cubic (MP2 (full)/6-311G (d,p)) force constants (the latter were used only for anharmonic corrections). The harmonic force field was scaled using published IR and Raman spectra of the parent and N1,N3-dideuterated species, which were for the first time completely assigned in the present work. The main equilibrium structural parameters of the thymine molecule determined from GED data supplemented by MW rotational constants and results of MP2 calculations are the following (bond lengths in Angstroms and bond angles in degrees with 3sigma in parentheses): r(e) (C5=C6) = 1.344 (16), r(e) (C5-C9) = 1.487 (8), r(e) (N1-C6) = 1.372 (3), r(e) (N1-C2) = 1.377 (3), r(e) (C2-N3) = 1.378 (3), r(e) (N3-C4) = 1.395 (3), r(e) (C2=O7) = 1.210 (1), r(e) (C4=O8) = 1.215 (1

  19. Application of quasi-degenerate perturbation theory to the calculation of rotational energy levels of methane vibrational polyads

    SciTech Connect

    Cassam-Chenaï, P. Rousseau, G.; Ilmane, A.; Bouret, Y.; Rey, M.

    2015-07-21

    In previous works, we have introduced an alternative perturbation scheme to find approximate solutions of the spectral problem for the rotation-vibration molecular Hamiltonian. An important feature of our approach is that the zero order Hamiltonian is the direct product of a purely vibrational Hamiltonian with the identity on the rotational degrees of freedom. The convergence of our method for the methane vibrational ground state was very satisfactory and our predictions were quantitative. In the present article, we provide further details on the implementation of the method in the degenerate and quasi-degenerate cases. The quasi-degenerate version of the method is tested on excited polyads of methane, and the results are assessed with respect to a variational treatment. The optimal choice of the size of quasi-degenerate spaces is determined by a trade-off between speed of convergence of the perturbation series and the computational effort to obtain the effective super-Hamiltonian.

  20. Discriminating harmonicity

    NASA Astrophysics Data System (ADS)

    Kidd, Gerald; Mason, Christine R.; Brughera, Andrew; Chiu, Chung-Yiu Peter

    2003-08-01

    Simultaneous tones that are harmonically related tend to be grouped perceptually to form a unitary auditory image. A partial that is mistuned stands out from the other tones, and harmonic complexes with different fundamental frequencies can readily be perceived as separate auditory objects. These phenomena are evidence for the strong role of harmonicity in perceptual grouping and segregation of sounds. This study measured the discriminability of harmonicity directly. In a two interval, two alternative forced-choice (2I2AFC) paradigm, the listener chose which of two sounds, signal or foil, was composed of tones that more closely matched an exact harmonic relationship. In one experiment, the signal was varied from perfectly harmonic to highly inharmonic by adding frequency perturbation to each component. The foil always had 100% perturbation. Group mean performance decreased from greater than 90% correct for 0% signal perturbation to near chance for 80% signal perturbation. In the second experiment, adding a masker presented simultaneously with the signals and foils disrupted harmonicity. Both monaural and dichotic conditions were tested. Signal level was varied relative to masker level to obtain psychometric functions from which slopes and midpoints were estimated. Dichotic presentation of these audible stimuli improved performance by 3-10 dB, due primarily to a release from ``informational masking'' by the perceptual segregation of the signal from the masker.

  1. MULTIMODE quantum calculations of vibrational energies and IR spectrum of the NO{sup +}(H{sub 2}O) cluster using accurate potential energy and dipole moment surfaces

    SciTech Connect

    Homayoon, Zahra

    2014-09-28

    A new, full (nine)-dimensional potential energy surface and dipole moment surface to describe the NO{sup +}(H{sub 2}O) cluster is reported. The PES is based on fitting of roughly 32 000 CCSD(T)-F12/aug-cc-pVTZ electronic energies. The surface is a linear least-squares fit using a permutationally invariant basis with Morse-type variables. The PES is used in a Diffusion Monte Carlo study of the zero-point energy and wavefunction of the NO{sup +}(H{sub 2}O) and NO{sup +}(D{sub 2}O) complexes. Using the calculated ZPE the dissociation energies of the clusters are reported. Vibrational configuration interaction calculations of NO{sup +}(H{sub 2}O) and NO{sup +}(D{sub 2}O) using the MULTIMODE program are performed. The fundamental, a number of overtone, and combination states of the clusters are reported. The IR spectrum of the NO{sup +}(H{sub 2}O) cluster is calculated using 4, 5, 7, and 8 modes VSCF/CI calculations. The anharmonic, coupled vibrational calculations, and IR spectrum show very good agreement with experiment. Mode coupling of the water “antisymmetric” stretching mode with the low-frequency intermolecular modes results in intensity borrowing.

  2. Ab initio and density functional theory calculations of molecular structure and vibrational spectra of 4-(2-Hydroxyethyl) piperazine-1-ethanesulfonic acid

    NASA Astrophysics Data System (ADS)

    Kumar, J. Sharmi; Devi, T. S. Renuga; Ramkumaar, G. R.; Bright, A.

    2016-01-01

    The FTIR and FT-Raman spectra of 4-(2-Hydroxyethyl) piperazine-1-ethanesulfonic acid were recorded and the structural and spectroscopic data of the molecule in the ground state were calculated using Hartree-Fock and Density Functional Method (B3LYP). The most stable conformer was optimized and the structural and vibrational parameters were determined. With the observed FTIR and FT-Raman data, a complete vibrational band assignment and analysis of the fundamental modes of the compound were carried out. Thermodynamic properties, Mulliken and natural atomic charge distribution were calculated using both Hartree-Fock and Density Functional Method and compared. UV-Visible and HOMO-LUMO analysis were carried out. 1H and 13C NMR chemical shifts of the molecule were calculated using gauge including atomic orbital method and were compared with experimental results. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital analysis. The first order hyperpolarizability (β) and molecular electrostatic potential of the molecule was computed using DFT calculations. The electron density based local reactivity descriptor such as Fukui functions were calculated to explain the chemically reactive site in the molecule.

  3. A formulation of rotor-airframe coupling for design analysis of vibrations of helicopter airframes

    NASA Technical Reports Server (NTRS)

    Kvaternik, R. G.; Walton, W. C., Jr.

    1982-01-01

    A linear formulation of rotor airframe coupling intended for vibration analysis in airframe structural design is presented. The airframe is represented by a finite element analysis model; the rotor is represented by a general set of linear differential equations with periodic coefficients; and the connections between the rotor and airframe are specified through general linear equations of constraint. Coupling equations are applied to the rotor and airframe equations to produce one set of linear differential equations governing vibrations of the combined rotor airframe system. These equations are solved by the harmonic balance method for the system steady state vibrations. A feature of the solution process is the representation of the airframe in terms of forced responses calculated at the rotor harmonics of interest. A method based on matrix partitioning is worked out for quick recalculations of vibrations in design studies when only relatively few airframe members are varied. All relations are presented in forms suitable for direct computer implementation.

  4. Vibrational spectroscopic (FT-IR, FT-Raman) studies, Hirshfeld surfaces analysis, and quantum chemical calculations of m-acetotoluidide and m-thioacetotoluidide

    NASA Astrophysics Data System (ADS)

    Śmiszek-Lindert, Wioleta Edyta; Chełmecka, Elżbieta; Góralczyk, Stefan; Kaczmarek, Marian

    2017-01-01

    Theoretical calculations of the m-acetotoluidide and m-thioacetotoluidide isolated molecules were performed by using density functional theory (DFT) method at B3LYP/6-311++G (d,p) and B3LYP/6-311++G (3df,2pd) basis set levels. The Hirshfeld surfaces analysis and FT-IR and FT-Raman spectroscopy studies have been reported. The geometrical parameters of the title amide and thioamide are in a good agreement with the XRD experiment. The vibrational frequencies were calculated and scaled, and subsequently values have been compared with the experimental Infrared and Raman spectra. The observed and calculated frequencies are found to be in good agreement. The analysis of the Hirshfeld surface has been well correlated to the spectroscopic studies. Additionally, the highest occupied molecular orbital energy (EHOMO), lowest unoccupied molecular orbital energy (ELUMO) and the energy gap between EHOMO and ELUMO (ΔEHOMO-LUMO) have been calculated.

  5. Characterization of 1,5-dimethoxynaphthalene by vibrational spectroscopy (FT-IR and FT-Raman) and density functional theory calculations.

    PubMed

    Kandasamy, M; Velraj, G; Kalaichelvan, S; Mariappan, G

    2015-01-05

    In this work, we reported a combined experimental and theoretical study on molecular structure, vibrational spectra and natural bond orbital (NBO) analysis of 1,5-dimethoxynaphthalene. The optimized molecular structure, atomic charges, vibrational frequencies and natural bond orbital analysis of 1,5-dimethoxynaphthalene have been studied by performing DFT/B3LYP/6-31G(d,p) level of theory. The FTIR, FT-Raman spectra were recorded in the region of 4000-400 cm(-1) and 3500-50 cm(-1) respectively. The scaled wavenumbers are compared with the experimental values. The difference between the observed and scaled wavenumber values of the most fundamentals is very small. The formation of hydrogen bond was investigated in terms of the charge density by the NBO analysis. Natural Population Analysis (NPA) was used for charge determination in the title molecule. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis were investigated using theoretical calculations.

  6. Comparison of the performance of different DFT methods in the calculations of the molecular structure and vibration spectra of serotonin (5-hydroxytryptamine, 5-HT)

    NASA Astrophysics Data System (ADS)

    Yang, Yue; Gao, Hongwei

    2012-04-01

    Serotonin (5-hydroxytryptamine, 5-HT) is a monoamine neurotransmitter which plays an important role in treating acute or clinical stress. The comparative performance of different density functional theory (DFT) methods at various basis sets in predicting the molecular structure and vibration spectra of serotonin was reported. The calculation results of different methods including mPW1PW91, HCTH, SVWN, PBEPBE, B3PW91 and B3LYP with various basis sets including LANL2DZ, SDD, LANL2MB, 6-31G, 6-311++G and 6-311+G* were compared with the experimental data. It is remarkable that the SVWN/6-311++G and SVWN/6-311+G* levels afford the best quality to predict the structure of serotonin. The results also indicate that PBEPBE/LANL2DZ level show better performance in the vibration spectra prediction of serotonin than other DFT methods.

  7. Characterization of 1,5-dimethoxynaphthalene by vibrational spectroscopy (FT-IR and FT-Raman) and density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Kandasamy, M.; Velraj, G.; Kalaichelvan, S.; Mariappan, G.

    2015-01-01

    In this work, we reported a combined experimental and theoretical study on molecular structure, vibrational spectra and natural bond orbital (NBO) analysis of 1,5-dimethoxynaphthalene. The optimized molecular structure, atomic charges, vibrational frequencies and natural bond orbital analysis of 1,5-dimethoxynaphthalene have been studied by performing DFT/B3LYP/6-31G(d,p) level of theory. The FTIR, FT-Raman spectra were recorded in the region of 4000-400 cm-1 and 3500-50 cm-1 respectively. The scaled wavenumbers are compared with the experimental values. The difference between the observed and scaled wavenumber values of the most fundamentals is very small. The formation of hydrogen bond was investigated in terms of the charge density by the NBO analysis. Natural Population Analysis (NPA) was used for charge determination in the title molecule. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis were investigated using theoretical calculations.

  8. Ab initio calculation of a global potential, vibrational energies, and wave functions for HCN/HNC, and a simulation of the (A-tilde)-(X-tilde) emission spectrum

    NASA Technical Reports Server (NTRS)

    Bowman, Joel M.; Gazdy, Bela; Bentley, Joseph A.; Lee, Timothy J.; Dateo, Christopher E.

    1993-01-01

    A potential energy surface for the HCN/HNC system which is a fit to extensive, high-quality ab initio, coupled-cluster calculations is presented. All HCN and HNC states with energies below the energy of the first delocalized state are reported and characterized. Vibrational transition energies are compared with all available experimental data on HCN and HNC, including high CH-overtone states up to 23,063/cm. A simulation of the (A-tilde)-(X-tilde) stimulated emission pumping (SEP) spectrum is also reported, and the results are compared to experiment. Franck-Condon factors are reported for odd bending states of HCN, with one quantum of vibrational angular momentum, in order to compare with the recent assignment by Jonas et al. (1992), on the basis of axis-switching arguments of a number of previously unassigned states in the SEP spectrum.

  9. The Shock and Vibration Digest. Volume 17. Number 3

    DTIC Science & Technology

    1985-03-01

    use of pro- Objective: This course on vibrations of grammable calculators; turbine - generator reciprocating machinery includes piping and balancing...either externally applied loads or obliquely jected to horizontal harmonic excitation is incident waves with a general transient examined. For slender...Aerospace Congress and Exp 1 - 2-7 international Gas Turbine Sysep.- da SELoAnesC (A) sius and Exposition [Gas Turbine Div., 2&-24 ]Power Generation

  10. Femtosecond nonlinear spectroscopy at surfaces: Second-harmonic probing of hole burning at the Si(111)7x7 surface and fourier-transform sum-frequency vibrational spectroscopy

    SciTech Connect

    McGuire, John Andrew

    2004-11-24

    The high temporal resolution and broad bandwidth of a femtosecond laser system are exploited in a pair of nonlinear optical studies of surfaces. The dephasing dynamics of resonances associated with the adatom dangling bonds of the Si(111)7 x 7 surface are explored by transient second-harmonic hole burning, a process that can be described as a fourth-order nonlinear optical process. Spectral holes produced by a 100 fs pump pulse at about 800 nm are probed by the second harmonic signal of a 100 fs pulse tunable around 800 nm. The measured spectral holes yield homogeneous dephasing times of a few tens of femtoseconds. Fits with a Lorentzian spectral hole centered at zero probe detuning show a linear dependence of the hole width on pump fluence, which suggests that charge carrier-carrier scattering dominates the dephasing dynamics at the measured excitation densities. Extrapolation of the deduced homogeneous dephasing times to zero excitation density yields an intrinsic dephasing time of {approx} 70 fs. The presence of a secondary spectral hole indicates that scattering of the surface electrons with surface optical phonons at 570 cm-1 occurs within the first 200 fs after excitation. The broad bandwidth of femtosecond IR pulses is used to perform IR-visible sum frequency vibrational spectroscopy. By implementing a Fourier-transform technique, we demonstrate the ability to obtain sub-laser-bandwidth spectral resolution. FT-SFG yields a greater signal when implemented with a stretched visible pulse than with a femtosecond visible pulse. However, when compared with multichannel spectroscopy using a femtosecond IR pulse but a narrowband visible pulse, Fourier-transform SFG is found to have an inferior signal-to-noise ratio. A mathematical analysis of the signal-to-noise ratio illustrates the constraints on the Fourier-transform approach.

  11. Application of the generalized Euler series transformation for calculation of vibration-rotation energy levels of diatomic molecules

    NASA Astrophysics Data System (ADS)

    Kruglova, T. V.

    2004-01-01

    The detailed spectroscope information about highly excited molecules and radicals such us as H+3, H2, HI, H2O, CH2 is needed for a number of applications in the field of laser physics, astrophysics and chemistry. Studies of highly excited molecular vibration-rotation states face several problems connected with slowly convergence or even divergences of perturbation expansions. The physical reason for a perturbation expansion divergence is the large amplitude motion and strong vibration-rotation coupling. In this case one needs to use the special method of series summation. There were a number of papers devoted to this problem: papers 1-10 in the reference list are only example of studies on this topic. The present report is aimed at the application of GET method (Generalized Euler Transformation) to the diatomic molecule. Energy levels of a diatomic molecule is usually represented as Dunham series on rotational J(J+1) and vibrational (V+1/2) quantum numbers (within the perturbation approach). However, perturbation theory is not applicable for highly excited vibration-rotation states because the perturbation expansion in this case becomes divergent. As a consequence one need to use special method for the series summation. The Generalized Euler Transformation (GET) is known to be efficient method for summing of slowly convergent series, it was already used for solving of several quantum problems Refs.13 and 14. In this report the results of Euler transformation of diatomic molecule Dunham series are presented. It is shown that Dunham power series can be represented of functional series that is equivalent to its partial summation. It is also shown that transformed series has the butter convergent properties, than the initial series.

  12. Fan Flutter Computations Using the Harmonic Balance Method

    NASA Technical Reports Server (NTRS)

    Bakhle, Milind A.; Thomas, Jeffrey P.; Reddy, T.S.R.

    2009-01-01

    An experimental forward-swept fan encountered flutter at part-speed conditions during wind tunnel testing. A new propulsion aeroelasticity code, based on a computational fluid dynamics (CFD) approach, was used to model the aeroelastic behavior of this fan. This threedimensional code models the unsteady flowfield due to blade vibrations using a harmonic balance method to solve the Navier-Stokes equations. This paper describes the flutter calculations and compares the results to experimental measurements and previous results from a time-accurate propulsion aeroelasticity code.

  13. Towards clarifying the N-M vibrational nature of metallo-phthalocyanines. Infrared spectrum of phthalocyanine magnesium complex: density functional calculations.

    PubMed

    Zhang, Xianxi; Zhang, Yuexing; Jiang, Jianzhuang

    2004-08-01

    Infrared frequencies and intensities for the magnesium phthalocyanine complex MgPc have been calculated at density functional B3LYP level using the 6-31G(d) basis set. Detailed assignments of the metal-nitrogen (N-M) vibrational bands in the IR spectrum have been made on the basis of comparison of the calculated data of MgPc with the experimental result and also with that of H(2)Pc. The empirical controversial assignment of the characteristic band at 886-919 cm(-1) for metallo-phthalocyanines is also clearly interpreted. Nevertheless, the previous assignments of N-H stretchings, in-plane bending (IPB) and out-of-plane bending (OPB) modes made based on the comparative calculation of H(2)Pc and D(2)Pc are confirmed again by the present research result.

  14. Vibrational Heat Transport in Molecular Junctions.

    PubMed

    Segal, Dvira; Agarwalla, Bijay Kumar

    2016-05-27

    We review studies of vibrational energy transfer in a molecular junction geometry, consisting of a molecule bridging two heat reservoirs, solids or large chemical compounds. This setup is of interest for applications in molecular electronics, thermoelectrics, and nanophononics, and for addressing basic questions in the theory of classical and quantum transport. Calculations show that system size, disorder, structure, dimensionality, internal anharmonicities, contact interaction, and quantum coherent effects are factors that combine to determine the predominant mechanism (ballistic/diffusive), effectiveness (poor/good), and functionality (linear/nonlinear) of thermal conduction at the nanoscale. We review recent experiments and relevant calculations of quantum heat transfer in molecular junctions. We recount the Landauer approach, appropriate for the study of elastic (harmonic) phononic transport, and outline techniques that incorporate molecular anharmonicities. Theoretical methods are described along with examples illustrating the challenge of reaching control over vibrational heat conduction in molecules.

  15. Structural and vibrational study of maprotiline

    NASA Astrophysics Data System (ADS)

    Yavuz, A. E.; Haman Bayarı, S.; Kazancı, N.

    2009-04-01

    Maprotiline ( N-methyl-9,10-ethanoanthracene-9(10H)-propanamine) is a tetra cyclic antidepressant. It is a highly selective inhibitor of norepinephrine reuptake. The solid and solution in CCl 4 and methanol infrared spectra of maprotiline were recorded. The fully optimized equilibrium structure of maprotiline was obtained from DFT calculations by using the B3LYP functional in combination with 6-31G and 6-311G(d,p) basis sets. The results of harmonic and anharmonic frequency calculations on maprotiline were presented. The vibrational spectra were interpreted, with the aid of normal coordinate analysis based on a scaled quantum mechanical (SQM) force field. Vibrational assignment of all the fundamentals was made using the total energy distribution (TED). The possible interaction between maprotiline and neurotransmitter serotonin (5-HT) were investigated.

  16. Vibrational Heat Transport in Molecular Junctions

    NASA Astrophysics Data System (ADS)

    Segal, Dvira; Agarwalla, Bijay Kumar

    2016-05-01

    We review studies of vibrational energy transfer in a molecular junction geometry, consisting of a molecule bridging two heat reservoirs, solids or large chemical compounds. This setup is of interest for applications in molecular electronics, thermoelectrics, and nanophononics, and for addressing basic questions in the theory of classical and quantum transport. Calculations show that system size, disorder, structure, dimensionality, internal anharmonicities, contact interaction, and quantum coherent effects are factors that combine to determine the predominant mechanism (ballistic/diffusive), effectiveness (poor/good), and functionality (linear/nonlinear) of thermal conduction at the nanoscale. We review recent experiments and relevant calculations of quantum heat transfer in molecular junctions. We recount the Landauer approach, appropriate for the study of elastic (harmonic) phononic transport, and outline techniques that incorporate molecular anharmonicities. Theoretical methods are described along with examples illustrating the challenge of reaching control over vibrational heat conduction in molecules.

  17. Vibrations of the carbon dioxide dimer

    NASA Astrophysics Data System (ADS)

    Chen, Hua; Light, J. C.

    2000-03-01

    Fully coupled four-dimensional quantum-mechanical calculations are presented for intermolecular vibrational states of rigid carbon dioxide dimer for J=0. The Hamiltonian operator is given in collision coordinates. The Hamiltonian matrix elements are evaluated using symmetrized products of spherical harmonics for angles and a potential optimized discrete variable representation (PO-DVR) for the intermolecular distance. The lowest ten or so states of each symmetry are reported for the potential energy surface (PES) given by Bukowski et al. [J. Chem. Phys. 110, 3785 (1999)]. Due to symmetries, there is no interconversion tunneling splitting for the ground state. Our calculations show that there is no tunneling shift of the ground state within our computation precision (0.01 cm-1). Analysis of the wave functions shows that only the ground states of each symmetry are nearly harmonic. The van der Waals frequencies and symmetry adapted force constants are found and compared to available experimental values. Strong coupling between the stretching coordinates and the bending coordinates are found for vibrationally excited states. The interconversion tunneling shifts are discussed for the vibrationally excited states.

  18. Vibration Control of Shallow Shell Structures Using a Shell-Type Dynamic Vibration Absorber

    NASA Astrophysics Data System (ADS)

    Aida, T.; Aso, T.; Nakamoto, K.; Kawazoe, K.

    1998-11-01

    In this study, a new shell-type dynamic vibration absorber is presented for suppressing several modes of vibration of the shallow shell (main shell) under harmonic load. It consists of a shallow shell (the dynamic absorbing shell), under the same boundary condition and with the same shape as those of the main shell, with connecting springs and dampers in the vertical direction between the main and dynamic absorbing shells. Formulae for an approximate tuning method for the shell-type dynamic absorber are also presented using the optimum tuning method for a dynamic absorber in the two-degree-of-freedom system, obtained by the Den Hartog method. Subsequently, numerical calculations are presented which demonstrate the usefulness of the shell-type dynamic vibration absorbers.

  19. The fictitious force method for efficient calculation of vibration from a tunnel embedded in a multi-layered half-space

    NASA Astrophysics Data System (ADS)

    Hussein, M. F. M.; François, S.; Schevenels, M.; Hunt, H. E. M.; Talbot, J. P.; Degrande, G.

    2014-12-01

    This paper presents an extension of the Pipe-in-Pipe (PiP) model for calculating vibrations from underground railways that allows for the incorporation of a multi-layered half-space geometry. The model is based on the assumption that the tunnel displacement is not influenced by the existence of a free surface or ground layers. The displacement at the tunnel-soil interface is calculated using a model of a tunnel embedded in a full space with soil properties corresponding to the soil in contact with the tunnel. Next, a full space model is used to determine the equivalent loads that produce the same displacements at the tunnel-soil interface. The soil displacements are calculated by multiplying these equivalent loads by Green's functions for a layered half-space. The results and the computation time of the proposed model are compared with those of an alternative coupled finite element-boundary element model that accounts for a tunnel embedded in a multi-layered half-space. While the overall response of the multi-layered half-space is well predicted, spatial shifts in the interference patterns are observed that result from the superposition of direct waves and waves reflected on the free surface and layer interfaces. The proposed model is much faster and can be run on a personal computer with much less use of memory. Therefore, it is a promising design tool to predict vibration from underground tunnels and to assess the performance of vibration countermeasures in an early design stage.

  20. Vibrational spectroscopic analysis of cyanopyrazine-2-carboxamide derivatives and investigation of their reactive properties by DFT calculations and molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Beegum, Shargina; Mary, Y. Sheena; Varghese, Hema Tresa; Panicker, C. Yohannan; Armaković, Stevan; Armaković, Sanja J.; Zitko, Jan; Dolezal, Martin; Van Alsenoy, C.

    2017-03-01

    Using density functional theory technique in the B3LYP approximation and cc-pVDZ (5D, 7F) basis set, the molecular structural parameters and vibrational wave numbers of two cyanopyrazine-2-carboxamide derivatives have been investigated. On the basis of potential energy distribution detailed vibrational assignments of observed FT-IR and FT-Raman bands have been proposed. Using molecular electrostatic potential map relative reactivities towards electrophilic and nucleophilic attack are predicted. The first and second hyperpolarizabilities are calculated and the first hyperpolarizability of the title compounds are greater than that of the standard NLO material urea. Molecular studies reveal that the predicted binding affinities of the best poses were -8.7 kcal/mol for BACPC, -9.0 kcal/mol for CBACPC, and -8.8 kcal/mol for the original inhibitor. Efforts were made in order to investigate local reactivity properties of title compounds as well. In order to do so we have calculated average local ionization energy (ALIE) surfaces, Fukui functions, bond dissociation energies (BDE) (within the framework of DFT calculations) and radial distribution functions (RDF) (within the molecular dynamics simulations). ALIE surfaces and Fukui functions gave us initial information on the site reactivity towards electrophilic and nucleophilic attacks. BDE indicated locations that might be prone to autoxidation mechanism, while RDF indicated which atoms of title molecules are having pronounced interactions with water.

  1. Structural, vibrational spectroscopic studies and quantum chemical calculations of n-(2,4-dinitrophenyl)-L-alanine methyl ester by density functional theory

    NASA Astrophysics Data System (ADS)

    Govindarasu, K.; Kavitha, E.

    2015-05-01

    In this paper, the vibrational wavenumbers of N-(2,4-dinitrophenyl)-L-alanine methyl ester (abbreviated as Dnp-ala-ome) were obtained from ab initio studies based on the density functional theory approach with B3LYP and M06-2X/6-31G(d,p) level of theories. The optimized geometry and structural features of the most potential nonlinear optical crystal Dnp-ala-ome and the vibrational spectral investigations have been thoroughly described with the FT-Raman and FT-IR spectra supported by the DFT computations. FT-IR (4000-400 cm-1) and FT-Raman spectra (3500-50 cm-1) in the solid phase and the UV-Vis spectra that dissolved in ethanol were recorded in the range of 200-800 nm. The Natural population analysis and natural bond orbital (NBO) analysis have also been carried out to analyze the effects of intramolecular charge transfer, intramolecular and hyperconjugative interactions on the geometries. The effects of frontier orbitals, HOMO and LUMO, transition of electron density transfer have also been discussed. The first order hyperpolarizability (β0) and related properties (β, α0 and Δα) of Dnp-ala-ome were calculated. In addition, molecular electrostatic potential (MEP) was investigated using theoretical calculations. The chemical reactivity and thermodynamic properties (heat capacity, entropy and enthalpy) of at different temperature are calculated.

  2. Vibrational normal modes calculation in the crystalline state of methylated monosaccharides: Anomers of the methyl-D-glucopyranoside and methyl-D-xylopyranoside molecules.

    PubMed

    Taleb-Mokhtari, Ilham Naoual; Lazreg, Abbassia; Sekkal-Rahal, Majda; Bestaoui, Noreya

    2016-01-15

    A structural investigation of the organic molecules is being carried out using vibrational spectroscopy. In this study, normal co-ordinate calculations of anomers of the methyl-D-glucopyranoside and methyl-β-D-xylopyranoside in the crystalline state have been performed using the modified Urey-Bradley-Shimanouchi force field (mUBSFF) combined with an intermolecular potential energy function. The latter includes Van der Waals interactions, electrostatic terms, and explicit hydrogen bond functions. The vibrational spectra of the compounds recorded in the crystalline state, in the 4000-500 cm(-1) spectral region for the IR spectra, and in the 4000-20 cm(-1) spectral range for the Raman spectra are presented. After their careful examination, several differences in the intensities and frequency shifts have been observed. The theoretical spectra have been obtained after a tedious refinement of the force constants. Thus, on the basis of the obtained potential distribution, each observed band in IR and in Raman has been assigned to a vibrational mode. The obtained results are indeed in agreement with those observed experimentally and thus confirm the previous assignments made for the methyl-α and β-D-glucopyranoside, as well as for the methyl-β-D-xylopyranoside.

  3. Structural, electronic, topological and vibrational properties of a series of N-benzylamides derived from Maca (Lepidium meyenii) combining spectroscopic studies with ONION calculations

    NASA Astrophysics Data System (ADS)

    Chain, Fernando E.; Ladetto, María Florencia; Grau, Alfredo; Catalán, César A. N.; Brandán, Silvia Antonia

    2016-02-01

    In the present work, the structural, topological and vibrational properties of four members of the N-benzylamides series derived from Maca (Lepidium meyenii) whose names are, N-benzylpentadecanamide, N-benzylhexadecanamide, N-benzylheptadecanamide and N-benzyloctadecanamide, were studied combining the FTIR, FT-Raman and 1H and 13C-NMR spectroscopies with density functional theory (DFT) and ONION calculations. Furthermore, the N-benzylacetamide, N-benzylpropilamide and N-benzyl hexanamide derivatives were also studied in order to compare their properties with those computed for the four macamides. These seven N-benzylamides series have a common structure, C8H8NO-R, being R the side chain [-(CH2)n-CH3] with a variable n number of CH2 groups. Here, the atomic charges, molecular electrostatic potentials, stabilization energies, topological properties of those macamides were analyzed as a function of the number of C atoms of the side chain while the frontier orbitals were used to compute the gap energies and some descriptors in order to predict their reactivities and behaviors in function of the longitude of the side chain. Here, the force fields, the complete vibrational assignments and the corresponding force constants were only reported for N-benzylacetamide, N-benzyl hexanamide and N-benzylpentadecanamide due to the high number of vibration normal modes that present the remains macamides.

  4. Vibrational normal modes calculation in the crystalline state of methylated monosaccharides: Anomers of the methyl-D-glucopyranoside and methyl-D-xylopyranoside molecules

    NASA Astrophysics Data System (ADS)

    Taleb-Mokhtari, Ilham Naoual; Lazreg, Abbassia; Sekkal-Rahal, Majda; Bestaoui, Noreya

    2016-01-01

    A structural investigation of the organic molecules is being carried out using vibrational spectroscopy. In this study, normal co-ordinate calculations of anomers of the methyl-D-glucopyranoside and methyl-β-D-xylopyranoside in the crystalline state have been performed using the modified Urey-Bradley-Shimanouchi force field (mUBSFF) combined with an intermolecular potential energy function. The latter includes Van der Waals interactions, electrostatic terms, and explicit hydrogen bond functions. The vibrational spectra of the compounds recorded in the crystalline state, in the 4000-500 cm- 1 spectral region for the IR spectra, and in the 4000-20 cm- 1 spectral range for the Raman spectra are presented. After their careful examination, several differences in the intensities and frequency shifts have been observed. The theoretical spectra have been obtained after a tedious refinement of the force constants. Thus, on the basis of the obtained potential distribution, each observed band in IR and in Raman has been assigned to a vibrational mode. The obtained results are indeed in agreement with those observed experimentally and thus confirm the previous assignments made for the methyl-α and β-D-glucopyranoside, as well as for the methyl-β-D-xylopyranoside.

  5. High-order harmonic generation and above-threshold ionization in H: Calculations using expansions over field-free state-specific wave functions

    NASA Astrophysics Data System (ADS)

    Dionissopoulou, S.; Mercouris, Th.; Lyras, A.; Komninos, Y.; Nicolaides, C. A.

    1995-04-01

    We have computed the above-threshold ionization and the emitted harmonic spectra of H interacting with short laser pulses, with photon energies ranging from 1.16 to 5.44 eV and with peak intensities ranging from 6×1013 to 7×1014 W/cm2, by solving the time-dependent Schrödinger equation (TDSE). The method of solution involves the expansion of the time-dependent wave function Ψ(r-->,t) over the exact wave functions of the discrete and the continuous spectrum, computed numerically, and the subsequent integration of the resulting coupled first-order differential equations by a Taylor series expansion technique. This state-specific approach (SSA) to the solution of the TDSE allows systematic understanding of convergence as a function of the number and type of the field-free states for each value of the laser frequency (ω) and peak intensity (I0). For example, the method allows practical numerical study of the degree of participation of high (n,l) (l=0,1,...,n-1) Rydberg, as well as of high-energy scattering states for each partial wave. For the harmonic spectra, comparisons are made between the results obtained by the SSA and those obtained in recent years by a number of researchers from the application of finite-difference grid methods. As regards economy, a general observation is that in the SSA the necessary number of partial waves is smaller than that required in the grid methods. Predictions are made for the case of ħω=2 eV, I0=2×1014 W/cm2, in the context of a study of the effect of the pulse shape on the harmonic-generation spectrum. It is shown that the number of harmonics and the appearance of the plateau depend on the duration of the peak intensity.

  6. Full-dimensional quantum calculations of vibrational spectra of six-atom molecules. I. Theory and numerical results

    NASA Astrophysics Data System (ADS)

    Yu, Hua-Gen

    2004-02-01

    Two quantum mechanical Hamiltonians have been derived in orthogonal polyspherical coordinates, which can be formed by Jacobi and/or Radau vectors etc., for the study of the vibrational spectra of six-atom molecules. The Hamiltonians are expressed in an explicit Hermitian form in the spatial representation. Their matrix representations are described in both full discrete variable representation (DVR) and mixed DVR/nondirect product finite basis representation (FBR) bases. The two-layer Lanczos iteration algorithm [H.-G. Yu, J. Chem. Phys. 117, 8190 (2002)] is employed to solve the eigenvalue problem of the system. A strategy regarding how to carry out the Hamiltonian-vector products for a high-dimensional problem is discussed. By exploiting the inversion symmetry of molecules, a unitary sequential 1D matrix-vector multiplication algorithm is proposed to perform the action of the Hamiltonian on the wavefunction in a symmetrically adapted DVR or FBR basis in the azimuthal angular variables. An application to the vibrational energy levels of the molecular hydrogen trimer (H2)3 in full dimension (12D) is presented. Results show that the rigid-H2 approximation can underestimate the binding energy of the trimer by 27%. Finally, it is demonstrated that the two-layer Lanczos algorithm is also capable of computing the eigenvectors of the system with minor effort.

  7. Calculation of the structure, potential energy surface, vibrational dynamics, and electric dipole properties for the Xe:HI van der Waals complex.

    PubMed

    Preller, M; Grunenberg, J; Bulychev, V P; Bulanin, M O

    2011-05-07

    We report the structure and spectroscopic characteristics for the Xe:HI van der Waals binary isomers determined from variational solutions of two-dimensional and three-dimensional (3D) vibrational Schrödinger equations. The solutions are based on a potential energy surface computed at the coupled-cluster level of theory including single and double excitations and a non-iterative perturbation treatment of triple excitations [CCSD(T)]. The dipole moment surface was calculated using quadratic configuration interaction (QCISD). The global potential minimum is shown to be located at the anti-hydrogen-bonded Xe-IH isomer, 21 cm(-1) below the secondary local minimum associated with the hydrogen-bonded Xe-HI isomeric form. The dissociation energy from the global minimum is 245.9 cm(-1). 3D Schrödinger equations are solved for the rotational quantum numbers J = k = 0, 1, and 2, without invoking an adiabatic separation of high- and low-frequency degrees of freedom. The vibrational ground state resides in the Xe-HI potential well, while the first excited state, 8.59 cm(-1) above the ground, occupies the Xe-IH well. We find that intra-complex dynamics exhibits a sudden transformation upon increase of the r(HI) bond length, accompanied by abrupt changes in the geometric and dipole parameters. A similar chaotic behavior is predicted to occur for Xe:DI at a shorter r(DI) bond length, which implies stronger coupling between low- and high-frequency motions in the heavier complex. Our calculations confirm a strong enhancement for the r(HI) stretch fundamental and a significant weakening for the first overtone vibrational transitions in Xe:HI, as compared to those in the free HI molecule. A qualitative explanation of this, earlier experimentally detected effect is suggested.

  8. X-ray crystal structure, vibrational spectra and DFT calculations of 3-chloro-7-azaindole: a case of dual N-H⋯N hydrogen bonds in dimers.

    PubMed

    Morzyk-Ociepa, Barbara; Dysz, Karolina; Turowska-Tyrk, Ilona; Michalska, Danuta

    2015-02-05

    3-Chloro-7-azaindole (3Cl7AI) is the carrier ligand in a new anticancer platinum(II) agent cis-[PtCl2(3Cl7AI)2]. In this work 3Cl7AI has been studied by a single crystal X-ray diffraction, infrared and Raman spectroscopy and density functional calculations. The compound crystallizes in the monoclinic system, space group P21/n, with a=12.3438(3), b=3.85964(11), c=14.4698(4)Å, β=100.739(2)°, V=677.31(3)Å(3) and Z=4. In the crystal, a pair of 3Cl7AI molecules forms a centrosymmetric dimer linked by the moderately strong dual N-H⋯N hydrogen bonds. The nitrogen atom in the pyrrole ring acts as the proton donor, while the nitrogen atom in the pyridine ring is the proton acceptor. The FT-IR and FT-Raman spectra (3500-60 cm(-1)) have been recorded. The theoretical studies on the molecular structures and vibrational spectra of the monomeric and dimeric forms of 3Cl7AI and its N-deuterated derivative were performed using the B3LYP method with 6-311++G(d,p) basis set. The theoretically predicted Raman spectrum for the dimer shows very good agreement with experiment. Detailed vibrational assignments for the two isotopomers have been made on the basis of the calculated potential energy distributions (PEDs). The dual N-H⋯N hydrogen bonds in 3Cl7AI dimer are characterized by a very broad and complicated structure of the absorption band between 3300 and 2500 cm(-1), which is caused by multiple Fermi resonances between the N-H stretching vibration and various combinations bands.

  9. Monte Carlo trajectory calculation of state-to-state cross sections for vibrational-rotational-translational energy transfer in Ar-H/sub 2/ collisions

    SciTech Connect

    Blais, N.C.; Truhlar, D.G.

    1982-01-01

    We have carried out quasiclassical trajectory calculations of the energy transfer cross sections for five initial states of H/sub 2/ ((v,j) = (0,6), (0,18), (2,18), (4,6), and (2,18)) in collisions with Ar at a fixed total energy of 1.0 eV (with respect to the energy of Ar + 2H). The first of these states has an internal excitation energy that is 7% of the dissociation energy D/sub 0/, and the other four states have internal excitation energies from 45 to 63% of D/sub 0/. The calculations are based on the most accurate available potential energy surface. The results are presented as tables of state-to-state cross sections and as contour maps of these cross sections as functions of the final quantum numbers. For the four highly excited initial states these maps show large changes of v and j, extensive vibrational-rotational energy transfer, and the population of 57-142 final states. The total vibrational-change cross sections for these states are 3.7 to 7.4 times larger than for the (0,6) state. No simple functional form gives a quantitative fit to all the pure-rotational-translational energy-transfer cross sections, and a quantitative fit to all the cross sections poses an even more severe theoretical challenge.

  10. Reinvestigation of the crystal structure, vibrational spectroscopic studies and DFT calculations of 5-bromo-7-azaindole with dual N-HṡṡṡN hydrogen bonds in dimers

    NASA Astrophysics Data System (ADS)

    Morzyk-Ociepa, Barbara; Dysz, Karolina; Turowska-Tyrk, Ilona; Michalska, Danuta

    2015-12-01

    5-Bromo-7-azaindole (5Br7AI) may act as the carrier ligand for platinum(II), in new anticancer agent, cis-[PtCl2(5Br7AI)2]. The crystal and molecular structure of the title molecule has been reinvestigated by a single crystal X-ray diffraction. The FT-IR and FT-Raman spectra of (5Br7AI) and its N-deuterated derivative have been recorded. The molecular structures of monomer and dimer, natural charges on atoms and theoretical vibrational spectra have been studied by density functional B3LYP method using 6-311++G(d,p) basis set. The results have shown that in the crystal, a pair of 5Br7AI molecules forms a centrosymmetric dimer linked by the moderately strong, dual and nearly linear N-HṡṡṡN hydrogen bonds between the pyrrole and pyridine rings. The optimized geometry of the (5Br7AI)2 dimer and the calculated spectra show very good agreement with the experiment. Detailed vibrational assignments for all the species have been made on the basis of the calculated potential energy distributions (PEDs). It is concluded that a complicated spectral features of the NH (ND) stretching absorption bands are due to multiple Fermi resonances, and they are characteristic for the doubly hydrogen bonded N-HṡṡṡN dimers of 7-azaindole and its halogeno derivatives.

  11. A contracted basis-Lanczos calculation of vibrational levels of methane: Solving the Schrödinger equation in nine dimensions

    NASA Astrophysics Data System (ADS)

    Wang, Xiao-Gang; Carrington, Tucker

    2003-07-01

    We present a contracted basis-iterative method for calculating numerically exact vibrational energy levels of methane (a 9D calculation). The basis functions we use are products of eigenfunctions of bend and stretch Hamiltonians obtained by freezing coordinates at equilibrium. The basis functions represent the desired wavefunctions well, yet are simple enough that matrix-vector products may be evaluated efficiently. We use Radau polyspherical coordinates. The bend functions are computed in a nondirect product finite basis representation [J. Chem. Phys. 118, 6956 (2003)] and the stretch functions are computed in a product potential optimized discrete variable (PODVR) basis. The memory required to store the bend basis is reduced by a factor of ten by storing it on a compacted grid. The stretch basis is optimized by discarding PODVR functions with high potential energies. The size of the primitive basis is 33 billion. The size of the product contracted basis is six orders of magnitude smaller. Parity symmetry and exchange symmetry between two of the H atoms are employed in the final product contracted basis. A large number of vibrational levels are well converged. These include almost all states up to 8000 cm-1 and some higher local mode stretch bands.

  12. Calculation of the fundamental vibrational frequencies and intensities of H2, D2, and N2 in the presence of Li(+) or Na

    NASA Astrophysics Data System (ADS)

    Bishop, David M.; Cybulski, Slawomir M.

    1994-11-01

    Self-consistent-field (SCF) and second-order Moller-Plesset (MP2) calculations, using large basis sets, have been carried out for the system X2...Y(+), with X = H, D, and N and Y = Li and Na. In particular, the fundamental vibrational frequency shifts and intensities induced in the diatomic by the cation have been found. For Y = Na these properties may be compared with the experimental infrared spectra of the same diatomics when trapped in a NaA zeolite. There is good agreement between theory and experiment for the frequency shifts but the calculated intensity for N2...Na(+) is several times larger than that found in the zeolite. This indicates that either the model for the trapped species is too simple or the experimental result needs reassessment.

  13. The vibrational spectrum of the water trimer: Comparison between anharmonic ab initio calculations and neon matrix infrared data between 11,000 and 90 cm -1

    NASA Astrophysics Data System (ADS)

    Tremblay, B.; Madebène, B.; Alikhani, M. E.; Perchard, J. P.

    2010-12-01

    The infrared spectrum of the water trimer trapped in solid neon has been identified. Eighteen groups of absorptions between 1600 and 11,000 cm -1 were assigned to one-, two- and three-quanta transitions of the intramolecular modes. Because of the near equivalence of the three molecules and their weak interactions most of these modes correspond to quasi degenerate vibrations involving the bending δ, free OH stretching (OH f) and bonded OH stretching (OH b) of the three subunits at 1608, 3725 and 3525-3473 cm -1, respectively. In the last case the 52 cm -1 splitting is due to the coupling between the OH b oscillators. Calculated anharmonic frequencies correctly agree with these observations and allow to propose a new assignment of the intermolecular modes. Finally combinations of intra + intermolecular transitions were identified and assigned on the basis of calculated anharmonicity coefficients.

  14. Vibrational spectroscopic investigation of p-, m- and o-nitrobenzonitrile by using Hartree-Fock and density functional theory

    NASA Astrophysics Data System (ADS)

    Sert, Y.; Ucun, F.

    2013-08-01

    In the present work, the theoretical vibrational spectra of p-, m- and o-nitrobenzonitrile molecules have been analyzed. The harmonic vibrational frequencies and geometric parameters (bond lengths and bond angles) of these molecules have been calculated using ab initio Hartree-Fock and density functional theory methods with 6-311++G(d,p) basis set by Gaussian 03 W, for the first time. Assignments of the vibrational frequencies have been performed by potential energy distribution by using VEDA 4 program. The optimized geometric parameters and harmonic vibrational frequencies have been compared with the corresponding experimental data and seen to be in a good agreement with each other. Also, the highest occupied molecular orbital and lowest unoccupied molecular orbital energies have been obtained.

  15. Simulation of Payload Vibration Protection by Shape Memory Alloy Parts

    NASA Astrophysics Data System (ADS)

    Volkov, Aleksandr E.; Evard, Margarita E.; Red'kina, Kristina V.; Vikulenkov, Andrey V.; Makarov, Vyacheslav P.; Moisheev, Aleksandr A.; Markachev, Nikolay A.; Uspenskiy, Evgeniy S.

    2014-07-01

    A system of vibroisolation under consideration consists of a payload connected to a vibrating housing by plane shape memory alloy (SMA) slotted elements. The calculation of the mechanical behavior of the SMA is based on a microstructural theory. Simulations of harmonic and of impact excitations are carried out. The results have shown that protective properties of this system depend on the SMA state. The maximum reduction of the acceleration amplitude for harmonic excitation is reached when the SMA is in the martensitic (pseudo-plastic) state or in the two-phase state. A variation of temperature allows changing the resonance frequency and thus escaping from the resonance and controlling a mode of vibration.

  16. DENSITY FUNCTIONAL CALCULATION OF ENERGIES AND VIBRATIONAL FREQUENCIES OF GLUCOSE AND GLUCOSE-WATER COMPLEXES: WATER PLACEMENT AND GLUCOSE CONFORMATIONAL EFFECTS ON THE CALCULATED INFRARED SPECTRUM

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The structures and energies of glucose and glucose monohydrates have been calculated at the B3LYP/6-311++G** level of theory. Both the alpha and beta anomers were studied, with all possible combinations of hydroxymethyl rotamer (gg, gt, or tg) and hydroxyl orientation (clockwise or counter-clockwis...

  17. Relating normal vibrational modes to local vibrational modes: benzene and naphthalene.

    PubMed

    Zou, Wenli; Kalescky, Robert; Kraka, Elfi; Cremer, Dieter

    2013-07-01

    Local vibrational modes can be directly derived from normal vibrational modes using the method of Konkoli and Cremer (Int J Quant Chem 67:29, 1998). This implies the calculation of the harmonic force constant matrix F (q) (expressed in internal coordinates q) from the corresponding Cartesian force constant matrix f (x) with the help of the transformation matrix U = WB (†)(BWB (†))(-1) (B: Wilson's B-matrix). It is proven that the local vibrational modes are independent of the choice of the matrix W. However, the choice W = M (-1) (M: mass matrix) has numerical advantages with regard to the choice W = I (I: identity matrix), where the latter is frequently used in spectroscopy. The local vibrational modes can be related to the normal vibrational modes in the form of an adiabatic connection scheme (ACS) after rewriting the Wilson equation with the help of the compliance matrix. The ACSs of benzene and naphthalene based on experimental vibrational frequencies are discussed as nontrivial examples. It is demonstrated that the local-mode stretching force constants provide a quantitative measure for the C-H and C-C bond strength.

  18. Molecular structure of the trans and cis isomers of metal-free phthalocyanine studied by gas-phase electron diffraction and high-level quantum chemical calculations: NH tautomerization and calculated vibrational frequencies.

    PubMed

    Strenalyuk, Tatyana; Samdal, Svein; Volden, Hans Vidar

    2008-05-29

    The molecular structure of the trans isomer of metal-free phthalocyanine (H2Pc) is determined using the gas electron diffraction (GED) method and high-level quantum chemical calculations. B3LYP calculations employing the basis sets 6-31G**, 6-311++G**, and cc-pVTZ give two tautomeric isomers for the inner H atoms, a trans isomer having D2h symmetry and a cis isomer having C2v symmetry. The trans isomer is calculated to be 41.6 (B3LYP/6-311++G**, zero-point corrected) and 37.3 kJ/mol (B3LYP/cc-pVTZ, not zero-point corrected) more stable than the cis isomer. However, Hartree-Fock (HF) calculations using different basis sets predict that cis is preferred and that trans does not exist as a stable form of the molecule. The equilibrium composition in the gas phase at 471 degrees C (the temperature of the GED experiment) calculated at the B3LYP/6-311++G** level is 99.8% trans and 0.2% cis. This is in very good agreement with the GED data, which indicate that the mole fraction of the cis isomer is close to zero. The transition states for two mechanisms of the NH tautomerization have been characterized. A concerted mechanism where the two H atoms move simultaneously yields a transition state of D2h symmetry and an energy barrier of 95.8 kJ/mol. A two-step mechanism where a trans isomer is converted to a cis isomer, which is converted into another trans isomer, proceeds via two transition states of C(s) symmetry and an energy barrier of 64.2 kJ/mol according to the B3LYP/6-311++G** calculation. The molecular geometry determined from GED is in very good agreement with the geometry obtained from the quantum chemical calculations. Vibrational frequencies, IR, and Raman intensities have been calculated using B3LYP/6-311++G**. These calculations indicate that the molecule is rather flexible with six vibrational frequencies in the range of 20-84 cm(-1) for the trans isomer. The cis isomer might be detected by infrared matrix spectroscopy since the N-H stretching frequencies are

  19. Analysis on Non-Resonance Standing Waves and Vibration Tracks of Strings

    ERIC Educational Resources Information Center

    Fang, Tian-Shen

    2007-01-01

    This paper presents an experimental technique to observe the vibration tracks of string standing waves. From the vibration tracks, we can analyse the vibration directions of harmonic waves. For the harmonic wave vibrations of strings, when the driving frequency f[subscript s] = Nf[subscript n] (N = 1, 2, 3, 4,...), both resonance and non-resonance…

  20. Extended aeroelastic analysis for helicopter rotors with prescribed hub motion and blade appended penduluum vibration absorbers

    NASA Technical Reports Server (NTRS)

    Bielawa, R. L.

    1984-01-01

    The mathematical development for the expanded capabilities of the G400 rotor aeroelastic analysis was examined. The G400PA expanded analysis simulates the dynamics of all conventional rotors, blade pendulum vibration absorbers, and the higher harmonic excitations resulting from prescribed vibratory hub motions and higher harmonic blade pitch control. The methodology for modeling the unsteady stalled airloads of two dimensional airfoils is discussed. Formulations for calculating the rotor impedance matrix appropriate to the higher harmonic blade excitations are outlined. This impedance matrix, and the associated vibratory hub loads, are the rotor dynamic characteristic elements for use in the simplified coupled rotor/fuselage vibration analysis (SIMVIB). Updates to the development of the original G400 theory, program documentation, user instructions and information are presented.

  1. Adaptive local basis set for Kohn-Sham density functional theory in a discontinuous Galerkin framework II: Force, vibration, and molecular dynamics calculations

    NASA Astrophysics Data System (ADS)

    Zhang, Gaigong; Lin, Lin; Hu, Wei; Yang, Chao; Pask, John E.

    2017-04-01

    Recently, we have proposed the adaptive local basis set for electronic structure calculations based on Kohn-Sham density functional theory in a pseudopotential framework. The adaptive local basis set is efficient and systematically improvable for total energy calculations. In this paper, we present the calculation of atomic forces, which can be used for a range of applications such as geometry optimization and molecular dynamics simulation. We demonstrate that, under mild assumptions, the computation of atomic forces can scale nearly linearly with the number of atoms in the system using the adaptive local basis set. We quantify the accuracy of the Hellmann-Feynman forces for a range of physical systems, benchmarked against converged planewave calculations, and find that the adaptive local basis set is efficient for both force and energy calculations, requiring at most a few tens of basis functions per atom to attain accuracies required in practice. Since the adaptive local basis set has implicit dependence on atomic positions, Pulay forces are in general nonzero. However, we find that the Pulay force is numerically small and systematically decreasing with increasing basis completeness, so that the Hellmann-Feynman force is sufficient for basis sizes of a few tens of basis functions per atom. We verify the accuracy of the computed forces in static calculations of quasi-1D and 3D disordered Si systems, vibration calculation of a quasi-1D Si system, and molecular dynamics calculations of H2 and liquid Al-Si alloy systems, where we show systematic convergence to benchmark planewave results and results from the literature.

  2. Vibrational Spectral Studies and Ab initio Computations of a Nonlinear Food Dye Carmoisine

    NASA Astrophysics Data System (ADS)

    Snehalatha, M.; Ravikumar, C.; Sekar, N.; Jayakumar, V. S.; Joe, I. Hubert

    2008-11-01

    FT-IR and Raman techniques were employed for the vibrational characterization of the food dye Carmoisine (E122). The equilibrium geometry, various bonding features, and harmonic vibrational wavenumbers have been investigated with the help of density functional theory (DFT) calculations. The first hyperpolarizability of the molecule is calculated. A good correlation was found between the computed and experimental wavenumbers. Azo stretching wavenumbers have been lowered due to conjugation and π-electron delocalization. The optimized structure indicates intramolecular C-H …O=S hydrogen bonding in the molecule. Intramolecular charge transfer (ICT) responsible for the optical nonlinearity of the dye molecule has been discussed theoretically and experimentally.

  3. The use of harmonic analysis of the strain response in Pb(Mg(1/3)Nb(2/3)) O3-based ceramics to calculate electrostrictive coefficients.

    PubMed

    DiAntonio, C B; Williams, F A; Pilgrim, S M

    2001-11-01

    The electromechanical response of ceramics has long been described with Landau Devonshire phenomenology, wherein the strain response is linked to a polynomial expansion in electric field or dielectric displacement. Consequently, the electromechanical response has been modeled with a variety of basis functions. However, these models have failed to accommodate hysteresis and the harmonic response that arises with saturation phenomena. In addition, no quantitative criterion has been used to truncate the expansion. By implementing a discrete Fourier transform in conjunction with Devonshire phenomenology, these three problems can be overcome as demonstrated with a dielectrically aged, lead magnesium niobate relaxor ferroelectric well above its Tmax, i.e., operating in the electrostrictive regime.

  4. Dynamic Analysis of Wind Turbine Planetary Gears Using an Extended Harmonic Balance Approach: Preprint

    SciTech Connect

    Guo, Y.; Keller, J.; Parker, R. G.

    2012-06-01

    The dynamics of wind turbine planetary gears with gravity effects are investigated using an extended harmonic balance method that extends established harmonic balance formulations to include simultaneous internal and external excitations. The extended harmonic balance method with arc-length continuation and Floquet theory is applied to a lumped-parameter planetary gear model including gravity, fluctuating mesh stiffness, bearing clearance, and nonlinear tooth contact to obtain the planetary gear dynamic response. The calculated responses compare well with time domain integrated mathematical models and experimental results. Gravity is a fundamental vibration source in wind turbine planetary gears and plays an important role in system dynamics, causing hardening effects induced by tooth wedging and bearing-raceway contacts. Bearing clearance significantly reduces the lowest resonant frequencies of translational modes. Gravity and bearing clearance together lowers the speed at which tooth wedging occurs lower than the resonant frequency.

  5. Harmonic generation at high intensities

    SciTech Connect

    Schafer, K.J.; Krause, J.L.; Kulander, K.C.

    1993-06-01

    Atomic electrons subject to intense laser fields can absorb many photons, leading either to multiphoton ionization or the emission of a single, energetic photon which can be a high multiple of the laser frequency. The latter process, high-order harmonic generation, has been observed experimentally using a range of laser wavelengths and intensities over the past several years. Harmonic generation spectra have a generic form: a steep decline for the low order harmonics, followed by a plateau extending to high harmonic order, and finally an abrupt cutoff beyond which no harmonics are discernible. During the plateau the harmonic production is a very weak function of the process order. Harmonic generation is a promising source of coherent, tunable radiation in the XUV to soft X-ray range which could have a variety of scientific and possibly technological applications. Its conversion from an interesting multiphoton phenomenon to a useful laboratory radiation source requires a complete understanding of both its microscopic and macroscopic aspects. We present some recent results on the response of single atoms at intensities relevant to the short pulse experiments. The calculations employ time-dependent methods, which we briefly review in the next section. Following that we discuss the behavior of the harmonics as a function of laser intensity. Two features are notable: the slow scaling of the harmonic intensities with laser intensity, and the rapid variation in the phase of the individual harmonics with respect to harmonic order. We then give a simple empirical formula that predicts the extent of the plateau for a given ionization potential, wavelength and intensity.

  6. Ethylenediammonium dication: H-bonded complexes with terephthalate, chloroacetate, phosphite, selenite and sulfamate anions. Detailed vibrational spectroscopic and theoretical studies of ethylenediammonium terephthalate.

    PubMed

    Marchewka, M K; Drozd, M

    2012-12-01

    Crystalline complexes between ethylenediammonium dication and terephthalate, chloroacetate, phosphite, selenite and sulfamate anions were obtained by slow evaporation from water solution method. Room temperature powder infrared and Raman measurements were carried out. For ethylenediammonium terephthalate theoretical calculations of structure were performed by two ways: ab-initio HF and semiempirical PM3. In this case the PM3 method gave more accurate structure (closer to X-ray results). The additional PM3 calculations of vibrational spectra were performed. On the basis theoretical approach and earlier vibrational studies of similar compounds the vibrational assignments for observed bands have been proposed. All compounds were checked for second harmonic generation (SHG).

  7. Quasibound continuum states in SiF4 (D~ 2A1) photoionization: Photoelectron-vibrational coupling

    NASA Astrophysics Data System (ADS)

    Montuoro, Raffaele; Lucchese, Robert R.; Bozek, John D.; Das, Aloke; Poliakoff, E. D.

    2007-06-01

    The authors report a fully vibrationally resolved photoelectron spectroscopy investigation of a nonplanar molecule studied over a range of excitation energies. Experimental results for all four fundamental vibrational modes are presented. In each case significant non-Franck-Condon effects are seen. The vibrational branching ratio for the totally symmetric mode ν1+ is found to be strongly affected by resonant excitation in the SiF4+ (D˜A12) photoionization channel. This is shown to be the result of two distinct shape resonances, which for the first time have been both confirmed by theoretical calculations. Vibrationally resolved Schwinger photoionization calculations are used to understand the vibronic coupling for the photoelectrons, both using ab initio and harmonic vibrational wave functions.

  8. Determination of the vibrational contribution to the entropy change at the martensitic transformation in Ni-Mn-Sn metamagnetic shape memory alloys: a combined approach of time-of-flight neutron spectroscopy and ab initio calculations.

    PubMed

    Recarte, V; Zbiri, M; Jiménez-Ruiz, M; Sánchez-Alarcos, V; Pérez-Landazábal, J I

    2016-05-25

    The different contributions to the entropy change linked to the austenite-martensitic transition in a Ni-Mn-Sn metamagnetic shape memory alloy have been determined by combining different experimental techniques. The vibrational contribution has been inferred from the vibrational density of states of both the martensitic and austenite phases. This has been accomplished by combining time-of-flight neutron scattering measurements and ab initio calculations. Further, the electronic part of the entropy change has also been calculated. Since the martensitic transformation takes place between two paramagnetic phases, the magnetic contribution can be neglected and the entropy change can be reduced to the sum of two terms: vibrational and electronic. The obtained value of the vibrational contribution ([Formula: see text]) nearly provides the total entropy change measured by calorimetry ([Formula: see text]), the difference being the electronic contribution within the experimental error.

  9. Vibrational frequency shifts of diatomic molecules in interaction with a Na + cation by ab initio calculations. Comparison with experiment on H 2 and N 2 adsorbed in NaA zeolite

    NASA Astrophysics Data System (ADS)

    Koubi, Laure; Blain, Monique; de Lara, Evelyne Cohen; Leclerq, Jean-Marie

    1994-01-01

    Ab initio calculations on H 2 and N 2 and on the same molecules in the presence of a Na + cation are presented. The equilibrium configuration and the vibrational frequency shift due to the interaction are calculated. The potential energy surfaces are obtained by local osculatory interpolations and extrapolations. The vibrational frequencies are calculated by the Numerov—Cooley method. The direction of the frequency shift is found to be related to the orientation of the diatomic molecule with respect to the cation. The results are compared with experimental data on induced infrared bands of H 2 and N 2 adsorbed in NaA zeolite.

  10. Harmonic engine

    DOEpatents

    Bennett, Charles L.

    2009-10-20

    A high efficiency harmonic engine based on a resonantly reciprocating piston expander that extracts work from heat and pressurizes working fluid in a reciprocating piston compressor. The engine preferably includes harmonic oscillator valves capable of oscillating at a resonant frequency for controlling the flow of working fluid into and out of the expander, and also preferably includes a shunt line connecting an expansion chamber of the expander to a buffer chamber of the expander for minimizing pressure variations in the fluidic circuit of the engine. The engine is especially designed to operate with very high temperature input to the expander and very low temperature input to the compressor, to produce very high thermal conversion efficiency.

  11. Spectra and structure of small ring compounds. LXVII vibrational spectra, variable temperature FT-IR spectra of krypton solutions, conformational stability and ab initio calculations of 1-bromosilacyclobutane.

    PubMed

    Gounev, T K; Guirgis, G A; Zhen, P; Durig, J R

    2000-11-15

    The infrared (3,200-30 cm(-1) spectra of gaseous and solid 1-bromosilacyclobutane, c-C3H6SiBrH, have been recorded. Additionally, the Raman spectra of the liquid (3,200- 30 cm(-1) with quantitative depolarization values and the solid have been recorded. Both the equatorial and the axial conformers have been identified in the fluid phases, Variable temperature ( - 105 to - 150 degrees C) studies of the infrared spectra of the sample dissolved in liquid krypton have been carried out. From these data the enthalpy difference has been determined to be 182 +/- 18 cm(-1) (2.18 +/- 0.22 kJ/mol) with the equatorial conformer the more stable rotamer and only conformer remaining in the annealing solid. At ambient temperature there is approximately 22% of the axial conformer present in the vapor phase. A complete vibrational assignment is proposed for both conformers based on infrared contours, relative intensities, depolarization values and group frequencies. The vibrational assignments are supported by normal coordinate calculations utilizing the force constants from ab initio MP2/6-31G(d) calculations. From the frequencies of the Si-H stretch, the Si-H bond distance of 1.483 A has been determined for both the equatorial and the axial conformers. Complete equilibrium geometries have been determined for both rotamers by ab initio calculations employing the 6-31G(d) and 6-311 +/- G(d,p) basis sets at levels of Hartree Fock (RHF) and/or Moller- Plesset with full electron correlation by the perturbation method to the second order (MP2). The results are discussed and compared to those obtained for some similar molecules.

  12. Use of the Riesz method to calculate axisymmetric vibrations of composite shells of revolution supported by rings and filled with a liquid

    NASA Astrophysics Data System (ADS)

    Grishanina, T. V.; Shklyarchuk, F. N.

    2016-05-01

    We consider the axisymmetric vibrations of a composite structure shaped as a system of thin shells of revolution connected by rings and filled with an ideal incompressible liquid. The structure is divided into independent shell blocks and frame rings. According to the Riesz method, the displacements of each free block treated as a momentless shell are represented as a series in prescribed functions supplemented with local functions of the shell boundary bending. According to the method of variations in displacements, the axisymmetric vibrations of a liquid in an elastic shell of revolution are described by plane displacement and deplanation of the liquid cross-sections. The plane displacement of the liquid is integrally expressed in terms of the shell normal displacements, and the deplanation is represented as a series in prescribed functions of the axial coordinate. The potential and kinetic energies of the system are first written in terms of generalized coordinates of independent free shell and frame blocks filled with the liquid and with free surfaces at the ends. Then the kinematic conditions of conjugation of the shell edges with the frame and the liquid surfaces are used to eliminate a part of generalized coordinates. Moreover, the generalized coordinates representing the deplanation of the liquid cross-sections in the cavities are also eliminated as cyclic coordinates. As a result, the potential and kinetic energies of the systemare written in terms of the basic generalized coordinates of the composite structure as a whole. As an example, the natural axisymmetric vibrations are calculated for a tank filled with a liquid, which consists of a cylindrical shell, spherical bottom shell, and the frame connecting these shells. The Riesz method convergence is estimated by the number of prescribed functions, as well as the influence of the deplanation of the liquid cross-sections and the shape of the transverse cross-section of the frame.

  13. Deducing the molecular properties of zwitterionic, protonated, deprotonated, and double-deprotonated forms of L-cysteine from vibrational spectroscopy (IR, Raman, VCD) and quantum chemical calculations.

    PubMed

    Quesada-Moreno, María Mar; Avilés-Moreno, Juan Ramón; Márquez-García, A A; López-González, Juan Jesús

    2014-06-01

    The behavior of L-cysteine (C3H7NO2S, (2R)-2-amino-3-sulfanylpropanoic acid) in water at different pH values was analyzed both experimentally and theoretically. The behavior was studied at pH values of 5.21 (at this pH, L-cysteine is a zwitterionic species), 1.00 (protonated species), 8.84 (monodeprotonated species), and 13.00 (dideprotonated species). We carried out a vibrational study using nonchiroptical (IR-Raman) and chiroptical (VCD) techniques complemented by quantum chemical calculations. We adopted a dual strategy, as follows. (i) The hybrid density functionals B3LYP and M062X and the ab initio MP2 method were employed, with the same 6-311++G (d,p) basis set, in order to characterize the relative energies and structures of an extensive set of conformers of L-cysteine. The presence of water was included by utilizing the IEF-PCM implicit solvation model. (ii) The vibrational analysis was made using a chirality-sensitive using a chirality-sensitive technique (VCD) and chirality-insensitive techniques (IR, including MIR and FIR, and Raman), especially in aqueous solution. The results obtained theoretically and experimentally were compared in order to deduce the most stable structures at each pH. Moreover, for the first time, the monodeprotonated anion of L-cysteine was detected in aqueous solution by means of IR, Raman and vibrational circular dichroism (VCD). Finally, analysis of the low-frequency region using the IR and Raman techniques was shown to be a very important way to understanding the conformational preference of the zwitterionic species.

  14. Chemical synthesis, crystal structure, vibrational spectroscopy, non-linear optical properties and DFT calculation of bis (2,6-diaminopyridinium) sulfate monohydrate

    NASA Astrophysics Data System (ADS)

    Ben Hassen, Chaouki; Dammak, Thameur; Chniba-Boudjada, Nassira; Mhiri, Tahar; Boujelbene, Mohamed

    2017-01-01

    Single crystals of a new organic inorganic hybrid compound "bis (2,6-diaminopyridinium) sulfate monohydrate [C5H8N3]2SO4·H2O ([2,6-HDAP]2SO4·H2O)" was synthesized by slow evaporation method at room temperature and characterized by X-ray single crystal diffraction, infrared spectroscopy and DFT calculation. The new hybrid compound crystallizes in the orthorhombic system with the non-centro symmetric space group Pna21 and the following parameters a = 14.759(2) Å, b = 7.076 (2) Å and c = 28.159 (2) Å. The atomic arrangement can be described as inorganic chains following the b axis connected with the organic groups by means of Nsbnd H⋯O hydrogen bonds to form 3D network. Antiparallelly π-π stacked 2,6-HDAP cations form molecular columns in the spaces between the chains. The optimized molecular structure, vibrational spectra and the optical properties were calculated by the density functional theory (DFT) method using the B3LYP function with the LanL2DV basis set. The wavenumber calculated are in good agreement with the observed frequency values. The calculated hyperpolarizability βtot is about 4.5 times more than that of the reference crystal KDP. Hence, the large β value shows that the title compound is an attractive object for future studies of nonlinear optical properties.

  15. Ab initio molecular dynamics with noisy forces: Validating the quantum Monte Carlo approach with benchmark calculations of molecular vibrational properties

    SciTech Connect

    Luo, Ye Sorella, Sandro; Zen, Andrea

    2014-11-21

    We present a systematic study of a recently developed ab initio simulation scheme based on molecular dynamics and quantum Monte Carlo. In this approach, a damped Langevin molecular dynamics is employed by using a statistical evaluation of the forces acting on each atom by means of quantum Monte Carlo. This allows the use of an highly correlated wave function parametrized by several variational parameters and describing quite accurately the Born-Oppenheimer energy surface, as long as these parameters are determined at the minimum energy condition. However, in a statistical method both the minimization method and the evaluation of the atomic forces are affected by the statistical noise. In this work, we study systematically the accuracy and reliability of this scheme by targeting the vibrational frequencies of simple molecules such as the water monomer, hydrogen sulfide, sulfur dioxide, ammonia, and phosphine. We show that all sources of systematic errors can be controlled and reliable frequencies can be obtained with a reasonable computational effort. This work provides convincing evidence that this molecular dynamics scheme can be safely applied also to realistic systems containing several atoms.

  16. Ab-initio and DFT calculations on molecular structure, NBO, HOMO-LUMO study and a new vibrational analysis of 4-(Dimethylamino) Benzaldehyde.

    PubMed

    Rocha, Mariana; Di Santo, Alejandro; Arias, Juan Marcelo; Gil, Diego M; Ben Altabef, Aída

    2015-02-05

    The experimental and theoretical study on the molecular structure and a new vibrational analysis of 4-(Dimethylamino) Benzaldehyde (DMABA) is presented. The IR and Raman spectra were recorded in solid state. Optimized geometry, vibrational frequencies and various thermodynamic parameters of the title compound were calculated using DFT methods and are in agreement with the experimental values. A detailed interpretation of the IR and Raman spectra of the title compound were reported. The stability of the molecule arising from hyper-conjugative interactions and charge delocalization has been analyzed using NBO analysis and AIM approach. The HOMO and LUMO analysis were used to determine the charge transfer within the molecule and some molecular properties such as ionization potential, electron affinity, electronegativity, chemical potential, hardness, softness and global electrophilicity index. The TD-DFT approach was applied to assign the electronic transitions observed in the UV-visible spectrum measured experimentally. Molecular electrostatic potential map was performed by the DFT method. According to DSC measurements, the substance presents a melting point of 72.34°C and decomposes at temperatures higher than 193°C.

  17. (H2O)2(g): Monomer/dimer vibrational frequency shifts in Bopp-Jancsó-Heinzinger- and Matsuoka-Clementi-Yoshimine-Lie-type flexible potentials

    NASA Astrophysics Data System (ADS)

    Slanina, Zdeněk

    1991-01-01

    Harmonic vibrational analysis of the water dimer is reported for four BJH- and four MCYL-type flexible water-water potentials. The calculated monomer/dimer frequency shifts correspond reasonably well to the available observed terms, the BJH-type flexible potentials (with the gas-phase intramolecular potential) yielding a slightly better agreement.

  18. Conformational stability, structural parameters and vibrational assignment from variable temperature infrared spectra of krypton solutions and ab initio calculations of ethylisothiocyanate.

    PubMed

    Durig, James R; Zheng, Chao

    2007-11-01

    Variable temperature (-105 to -150 degrees C) studies of the infrared spectra (3500-400 cm(-1)) of ethylisothiocyanate, CH(3)CH(2)NCS, dissolved in liquid krypton have been recorded. Additionally the infrared spectra of the gas and solid have been re-investigated. These spectroscopic data indicate a single conformer in all physical states with a large number of molecules in the gas phase at ambient temperature in excited states of the CN torsional mode which has a very low barrier to conformational interchange. To aid in the analyses of the vibrational and rotational spectra, ab initio calculations have been carried out by the perturbation method to the second order (MP2) with valence and core electron correlation using a variety of basis sets up to 6-311+G(2df,2pd). With the smaller basis sets up to 6-311+G(d,p) and cc-PVDZ, the cis conformer is indicated as a transition state with all larger basis sets the cis conformer is the only stable form. The predicted energy difference from these calculations between the cis form and the higher energy trans conformer is about 125 cm(-1) which represents essentially the barrier to internal rotation of the NCS group (rotation around NC axis). Density functional theory calculation by the B3LYP method with the same basis sets predicts this barrier to be about 25 cm(-1). By utilizing the previously reported microwave rotational constants with the structural parameters predicted by the ab initio MP2(full)/6-311+G(d,p) calculations, adjusted r(0) structural parameters have been obtained for the cis form. The determined heavy atom parameters are: r(NC)=1.196(5), r(CS)=1.579(5), r(CN)=1.439(5), r(CC)=1.519(5)A for the distances and angles of angleCCN=112.1(5), angleCNC=146.2(5), angleNCS=174.0(5) degrees . The centrifugal distortion constants, dipole moments, conformational stability, vibrational frequencies, infrared intensities and Raman activities have been predicted from ab initio calculations and compared to experimental

  19. Combined IR/NIR and density functional theory calculations analysis of the solvent effects on frequencies and intensities of the fundamental and overtones of the C ═ O stretching vibrations of acetone and 2-hexanone.

    PubMed

    Chen, Yujing; Morisawa, Yusuke; Futami, Yoshisuke; Czarnecki, Mirosław A; Wang, Hai-Shui; Ozaki, Yukihiro

    2014-04-10

    Vibrational overtone studies primarily focus on X-H stretching overtone transitions, where X is an atom like C, O, N, or S. In contrast, the studies on the C ═ O stretching overtones are very scattered. To advance the research in this field, we measured the fundamental, first, and second overtones of the C ═ O stretching vibration of acetone and 2-hexanone in n-hexane, CCl4, and CHCl3, as well as in the vapor phase using FT-IR/FT-NIR spectroscopy. Density functional theory (DFT) calculations have also been performed to help the assignment of the C ═ O stretching bands and to guide interpretation of the experimental results. It was found that the wavenumbers, absorption intensities, and oscillator strengths of the C ═ O stretching bands show marked solvent dependence. In the fundamental and the first overtone regions, the intensities of the C ═ O stretching vibration were found to be pronouncedly more intense than those of the C-H stretching vibration. In the second overtone region, the intensities of the C-H stretching vibration are comparable to those of the C ═ O stretching vibration. The theoretical and observed decrease in integrated intensity upon going from the fundamental to the first overtone of the C ═ O stretching vibration is around 50, which is significantly larger than those of the O-H, C-H, and S-H stretching vibration. Both the calculated and experimental results suggest that excessive weakness in the C ═ O stretching overtone was shown to be a result of both a low anharmonicity and a substantial reduction in the oscillator strength. These results provide new insight into our understanding of the C ═ O stretching vibration.

  20. Raman spectrum, quantum mechanical calculations and vibrational assignments of (95% α-TeO 2/5% Sm 2O 3) glass

    NASA Astrophysics Data System (ADS)

    Shaltout, I.; Mohamed, Tarek A.

    2007-06-01

    Chozen system of tellurite glasses doped with rare earth oxides (95% α-TeO 2 + 5% Sm 2O 3) was prepared by melt quenching. Consequently, the Raman spectrum (150-1250 cm -1) of the modified tellurite have been recorded. As a continuation to our normal coordinate analysis, force constants and quantum mechanical (QM) calculations for tbp TeO 44- (triagonal bipyramid, C2v) and TeO 3+1; Te 2O 76- (bridged tetrahedral), we have carried out ab initio frequency calculations for tpy TeO 32- (triagonal pyramidal, C3v and Cs) and tp TeO 32- (triagonal planar, D3h) ions. The quantum mechanical calculations at the levels of RHF, B3LYP and MP2 allow confident vibrational assignments and structural identification in the binary oxide glass (95% α-TeO 2 + 5% Sm 2O 3). The dominant three-dimensional network structures in the modified glass are triagonal pyramidal TeO 3 with minor features of short range distorted tbp TeO 4 and bridged tetrahedral unit of TeO 3+1, leading to a structure of infinite chain. Therefore, α-TeO 2/Sm 2O 3 (95/5%) glass experience structural changes from TeO 4 (tbp); Te 2O 7 (TeO 3+1) → TeO 3 (tpy).

  1. Vibrational spectroscopic studies (FT-IR, FT-Raman) and quantum chemical calculations on 5-(Adamantan-1-yl)-3-[(4-fluoroanilino)methyl]-2,3-dihydro-1,3,4-oxadiazole-2-thione, a potential chemotherapeutic agent

    NASA Astrophysics Data System (ADS)

    Al-Abdullah, Ebtehal S.; Roseline, Sebastian S. H., Sr.; Al-Wabli, Reem I.; El-Emam, Ali A.; Panicker, C. Yohannan; Van Alsenoy, Christian

    2014-12-01

    The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 5-(Adamantan-1-yl)-3-[(4-fluoroanilino)methyl]-2,3-dihydro-1,3,4-oxadiazole-2-thione are investigated experimentally and theoretically using Gaussian09 software package. Potential energy distribution of normal modes vibrations was done using GAR2PED program. The HOMO and LUMO analysis are used to determine the charge transfer within the molecule. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The calculated geometrical parameters are in agreement with the XRD data. The calculated first hyperpolarizability is high and the title compound is an attractive candidate for further studies in non-linear optical applications. To estimate the chemical reactivity of the molecule, the molecular electrostatic potential is calculated for the optimized geometry of the molecule.

  2. Vibrational spectroscopic studies (FT-IR, FT-Raman) and quantum chemical calculations on 5-(Adamantan-1-yl)-3-[(4-fluoroanilino)methyl]-2,3-dihydro-1,3,4-oxadiazole-2-thione, a potential chemotherapeutic agent.

    PubMed

    Al-Abdullah, Ebtehal S; Sebastian, Sr S H Roseline; Al-Wabli, Reem I; El-Emam, Ali A; Panicker, C Yohannan; Van Alsenoy, Christian

    2014-12-10

    The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 5-(Adamantan-1-yl)-3-[(4-fluoroanilino)methyl]-2,3-dihydro-1,3,4-oxadiazole-2-thione are investigated experimentally and theoretically using Gaussian09 software package. Potential energy distribution of normal modes vibrations was done using GAR2PED program. The HOMO and LUMO analysis are used to determine the charge transfer within the molecule. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The calculated geometrical parameters are in agreement with the XRD data. The calculated first hyperpolarizability is high and the title compound is an attractive candidate for further studies in non-linear optical applications. To estimate the chemical reactivity of the molecule, the molecular electrostatic potential is calculated for the optimized geometry of the molecule.

  3. Conformational analysis and vibrational spectroscopic studies on dapsone

    NASA Astrophysics Data System (ADS)

    Ildiz, Gulce Ogruc; Akyuz, Sevim

    2012-11-01

    In this study, the theoretical conformation analysis of free dapsone has been performed by single point energy calculations at both semi-empirical PM3 and DFT/B3LYP-3-21G theory levels and three stable conformers were determined. Both the IR and Raman spectra of the molecule in solid phase have been recorded. The IR intensities and harmonic vibrational wavenumbers of each conformer were calculated by DFT method at B3LYP/6-31++G(d,p) theory level. For the fundamental characterization, the total energy distribution (TED) calculations of the vibrational modes were done using parallel quantum mechanic solution program (SQM) and the fundamental modes were assigned. The theoretical results are in agreement with the experimental ones.

  4. Numerical analysis of the hybrid transducer ultrasonic motor: comparison of characteristics calculated by transmission-line and lumped-element models.

    PubMed

    Satonobu, Jun; Friend, James R; Nakamura, Kentaro; Ueha, Sadayuki

    2002-06-01

    In this paper, a hybrid transducer ultrasonic motor is numerically analyzed by using two equivalent electrical circuit models. A transmission-line model for the torsional vibration in the stator, which can model any torsional vibration mode and their combinations, was introduced and compared with a lumped-element model, which modeled the fundamental torsional resonance mode in the stator. The calculation result by using the transmission-line model demonstrated that the second harmonic torsional vibration increased either with the static spring force by which the rotor was pressed to the stator or with the load torque placed on the rotor. The difference in the calculated motor performance between the two models appeared when the second harmonic torsional vibration became large at a sufficient static spring force.

  5. Harmonic engine

    DOEpatents

    Bennett, Charles L.; Sewall, Noel; Boroa, Carl

    2014-08-19

    An engine based on a reciprocating piston engine that extracts work from pressurized working fluid. The engine includes a harmonic oscillator inlet valve capable of oscillating at a resonant frequency for controlling the flow of working fluid into of the engine. In particular, the inlet valve includes an inlet valve head and a spring arranged together as a harmonic oscillator so that the inlet valve head is moveable from an unbiased equilibrium position to a biased closed position occluding an inlet. Upon releasing the inlet valve the inlet valve head undergoes a single oscillation past the equilibrium positio to a maximum open position and returns to a biased return position close to the closed position to choke the flow and produce a pressure drop across the inlet valve causing the inlet valve to close. Protrusions carried either by the inlet valve head or piston head are used to bump open the inlet valve from the closed position and initiate the single oscillation of the inlet valve head, and protrusions carried either by the outlet valve head or piston head are used to close the outlet valve ahead of the bump opening of the inlet valve.

  6. Vibrational overtone stretching transitions in sarin

    NASA Astrophysics Data System (ADS)

    Petryk, Michael W. P.

    2006-10-01

    The CH stretching overtone transitions of the nerve agent sarin (O-isopropyl methylphosphonofluoridate) are of interest to the standoff detection of chemical warfare agents, as many of these transitions occur near regions where small, efficient, portable diode lasers (originally developed for use in the telecommunications industry) operate. However, the interpretation of experimental vibrational overtone spectra is often difficult, and the computational simulation of overtone transitions in a molecule is challenging. Presented herein are the simulated CH overtone stretching transitions in sarin. Spectral regions are simulated from overtone transition energies and intensities, both of which are calculated within the harmonically coupled anharmonic oscillator (HCAO) model. Data for HCAO calculations are obtained from ab initio calculations, without any recourse to experimental data.

  7. A first-principles density-functional calculation of the electronic and vibrational structure of the key melanin monomers

    NASA Astrophysics Data System (ADS)

    Powell, B. J.; Baruah, T.; Bernstein, N.; Brake, K.; McKenzie, Ross H.; Meredith, P.; Pederson, M. R.

    2004-05-01

    We report first-principles density-functional calculations for hydroquinone (HQ), indolequinone (IQ), and semiquinone (SQ). These molecules are believed to be the basic building blocks of the eumelanins, a class of biomacromolecules with important biological functions (including photoprotection) and with the potential for certain bioengineering applications. We have used the difference of self-consistent fields method to study the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, ΔHL. We show that ΔHL is similar in IQ and SQ, but approximately twice as large in HQ. This may have important implications for our understanding of the observed broadband optical absorption of the eumelanins. The possibility of using this difference in ΔHL to molecularly engineer the electronic properties of eumelanins is discussed. We calculate the infrared and Raman spectra of the three redox forms from first principles. Each of the molecules have significantly different infrared and Raman signatures, and so these spectra could be used in situ to nondestructively identify the monomeric content of macromolecules. It is hoped that this may be a helpful analytical tool in determining the structure of eumelanin macromolecules and hence in helping to determine the structure-property-function relationships that control the behavior of the eumelanins.

  8. A first-principles density-functional calculation of the electronic and vibrational structure of the key melanin monomers.

    PubMed

    Powell, B J; Baruah, T; Bernstein, N; Brake, K; McKenzie, Ross H; Meredith, P; Pederson, M R

    2004-05-08

    We report first-principles density-functional calculations for hydroquinone (HQ), indolequinone (IQ), and semiquinone (SQ). These molecules are believed to be the basic building blocks of the eumelanins, a class of biomacromolecules with important biological functions (including photoprotection) and with the potential for certain bioengineering applications. We have used the difference of self-consistent fields method to study the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, Delta(HL). We show that Delta(HL) is similar in IQ and SQ, but approximately twice as large in HQ. This may have important implications for our understanding of the observed broadband optical absorption of the eumelanins. The possibility of using this difference in Delta(HL) to molecularly engineer the electronic properties of eumelanins is discussed. We calculate the infrared and Raman spectra of the three redox forms from first principles. Each of the molecules have significantly different infrared and Raman signatures, and so these spectra could be used in situ to nondestructively identify the monomeric content of macromolecules. It is hoped that this may be a helpful analytical tool in determining the structure of eumelanin macromolecules and hence in helping to determine the structure-property-function relationships that control the behavior of the eumelanins.

  9. Effects of Fe substitution on B3-B1 phase transition and structural, vibrational, and electronic properties of ZnS from DFT calculations

    NASA Astrophysics Data System (ADS)

    Das, Pratik Kr.; Mandal, Nibir; Arya, A.

    2017-02-01

    Naturally occurring zinc sulfide (ZnS) contains a substantial amount of iron (Fe) in its crystal structure. This study explores the possible effects of such Fe impurity on the physical properties of its two phases: B3 and B1, crystallizing in a cubic system with zinc blend (ZB, space group: F-43m) and rock salt (RS, space group: Fm-3m) structures. We have performed ab-initio calculations within density functional theory (DFT) to determine the equilibrium volumes of B3- and B1-ZnS phases, doped with Fe in varying concentrations (0% to 25%), and their corresponding lattice structures. Using the enthalpy cross-over, we determine the pressure-dependent B3 to B1 transition as a function of Fe concentration. Our DFT calculations suggest an inverse relation of the transition pressure with Fe content. For pure ZnS, the transition occurs at 17 GPa, which drops to ˜12 GPa for 25% Fe. This study also provides a first-hand analysis of the elastic constants (C11, C12, and C44) to show the effects of Fe impurity on the mechanical properties of ZnS phases. Their values generally drop due to Fe and the differences widen with increasing pressure. Fe causes large softening of C44, especially for the B1 phase. We have also performed phonon calculations to characterize the vibrational properties and explain the pressure dependent structural instability of the B3- ZnS. Finally, our calculations of the electronic structures show a transition of semi-conductor to conductor behavior of ZnS with incorporation of Fe impurity.

  10. Conformational stability from variable temperature infrared spectra of krypton solutions, ab initio calculations, vibrational assignment, and r0 structural parameters of 1,3-difluoropropane.

    PubMed

    Durig, James R; Zheng, Chao; Williams, Michael J; Stidham, Howard D; Guirgis, Gamil A

    2004-06-01

    The infrared spectra (3200-400 cm(-1)) of krypton solutions of 1,3-difluoropropane, FCH2CH2CH2F, at variable temperatures (-105 to -150 degrees C) have been recorded. Additionally, the infrared spectra (3200-50 cm(-1)) of the gas and solid have been recorded as well as the Raman spectrum of the liquid. From a comparison of the spectra of the fluid phases with that in the solid, all of the fundamental vibrations of the C2 conformer (gauche-gauche) where the first gauche indicates the form for one of the CH2F groups and the second gauche the other CH2F, and many of those for the C1 form (trans-gauche) have been identified. Tentative assignments have been made for a few of the fundamentals of the other two conformers, i.e. C2v (trans-trans) and Cs (gauche-gauche'). By utilizing six pairs of fundamentals for these two conformers in the krypton solutions, an enthalpy difference of 277 +/- 28 cm(-1) (3.31 +/- 0.33 kJ mol(-1)) has been obtained for the C2 versus C1 conformer with the C2 conformer the more stable form. For the C2v conformer, the enthalpy difference has been determined to be 716 +/- 72 cm(-1) (8.57 +/- 0.86 kJ mol(-1)) and for the Cs form 971 +/- 115 cm(-1) (11.6 +/- 1.4 kJ mol(-1)). It is estimated that there is 64 +/- 3% of the C2 form, 34 +/-3% of the C1 form, 1% of the C2v form and 0.6% of the Cs conformer present at ambient temperature. Equilibrium geometries and total energies of the four stable conformers have been determined from ab initio calculations with full electron correlation by the perturbation method to second order as well as by hybrid density functional theory calculations with the B3LYP method using a number of basis sets. The MP2 calculations predict the C1 conformer stability to be slightly higher than the experimentally determined value whereas for the C2v and Cs conformers the predicted energy difference is much larger than the experimental value. The B3LYP calculations predict a better energy difference for both the C1 and C2v as

  11. Vibrational spectroscopic study, structural analysis, photophysical properties and theoretical calculations of cis-(±)-2,4,5-tris(pyridin-2-yl)imidazoline

    NASA Astrophysics Data System (ADS)

    Baldenebro-López, Jesús; Báez-Castro, Alberto; Glossman-Mitnik, Daniel; Höpfl, Herbert; Cruz-Enríquez, Adriana; Miranda-Soto, Valentín; Parra-Hake, Miguel; Campos-Gaxiola, José J.

    2017-02-01

    cis-(±)-2,4,5-tris(pyridin-2-yl)imidazoline has been fully characterized by FT-IR, FT-Raman, UV-Vis and fluorescence spectroscopy, one- and two-dimensional NMR spectroscopy (1H, 1H-1H gCOSY, 1H-1H gNOESY,13C{1H} ATP, 1H-13C and 1H-15N gHSQC and 1H-13C gHMBC), high-resolution mass spectrometry (HR-FAB+), TG-DSC analysis and low-temperature single-crystal X-ray diffraction analysis. Additionally, the molecular geometry and the vibrational infrared and Raman frequencies were calculated by density functional theory using the M06/6-31G(d) level of theory, showing good agreement with the experimental results. The title compound showed interesting photophysical properties, which were studied experimentally in solution and in the solid state by UV-Vis and fluorescence spectroscopy and compared to the theoretically obtained parameters using TD-DFT calculations. Natural and Mulliken atomic charges and the molecular electrostatic potential (MEP) have been mapped.

  12. Fourier-transform infrared and Raman spectra of cysteine dichloride cadmium(II) anion DFT: B3LYP/3-21G(d) structural and vibrational calculations.

    PubMed

    Faget, Grisset; Felcman, Judith; Giannerini, Tiago; Téllez, Claudio A

    2005-07-01

    The cysteine dichloride cadmium(II) potassium was synthesized and the structural analysis was carried out through the following methods: determination of the C, H, N, S and O contents, thermogravimetry, infrared and Raman spectra. Assuming Cd-S, Cd-O (O-carboxilate) and Cd-N bonds, several hypothetical structures were calculated by means DFT: B3LYP/3-21G(d) quantum mechanical method. The calculations shows that the Cd-S and Cd-N central bonds are favoured in the anion complex formation [Cd(Cys)Cl2]-, being the stabilization energy 55.52 kcal mol(-1) lower than isotopomers with Cd-S and Cd-O central bonds. Features of the infrared and Raman spectra confirm the theoretical structural prediction. Full assignment of the vibrational spectra is proposed based on the DFT procedure, and in order to confirm the C-H, N-H, C-C, C-N, Cd-N, Cd-S and Cd-Cl stretching and the HNH and HCH bending, a normal coordinate analysis based on local symmetry force field for -SC(H2)C-, -CdN(H2)C- and -SCd(Cl2)N- fragments was carried out.

  13. Structural characterization, vibrational study, NLO and DFT calculations of a novel organic sulfate monohydrate templated with (S)-(-)-2,6-diammonium-4,5,6,7-tetrahydrobenzothiazole

    NASA Astrophysics Data System (ADS)

    Barhoumi, Abir; Mhiri, Tahar; Dammak, Thameur; Suñol, Joan Josep; Belhouchet, Mohamed

    2017-01-01

    A single crystal of (S)-(-)-2,6-diammonium-4,5,6,7-tetrahydrobenzothiazole sulfate monohydrate has been synthesized and grown at room temperature by slow evaporation of aqueous solution. The studied compound crystallizes in the space group P212121 of the orthorhombic system with cell parameters a = 7.0014(12), b = 8.7631(15), c = 19.773(3) Å. We report the molecular structure and the theoretical and experimental vibrational spectra of the synthesized compound. The atomic arrangement, which is an alternation of organic inorganic layers linked together through hydrogen bonds, gives rise to three types of rings formed by the interconnection of organic-inorganic entities. The experimental FT-IR and the Raman spectra the synthesized compound were recorded and analyzed. The peaks assignment has been made unambiguously from the literature. To confirm the assignment, the experimental spectra were compared with theoretical spectra obtained with the Gaussian 98 program by the Density Functional Theory (DFT) method using B3LYP function with the LanL2DZ basis set. Moreover, to study the nonlinear optical (NLO) property of this compound, the hyperpolarizability βtot, the electric dipole μtot and the polarizability αtot were calculated using the DFT. Based on our calculation the synthesized compound has a non-zero hyperpolarizability suggesting that it may be used in some NLO applications.

  14. Conformational stability, vibrational assignments, and normal coordinate analysis from FT-IR spectra of xenon solutions and ab initio calculations of epichlorohydrin

    NASA Astrophysics Data System (ADS)

    Lee, Min Joo; Hur, Seung Won; Durig, James R.

    1998-03-01

    Infrared spectra (3500-400 cm -1) of epichlorohydrin (chloromethyloxirane), c-OC 2H 3C(Cl)H 2, dissolved in liquid xenon have been recorded at several temperatures from -40 to -105°C. Additionally, the Raman spectrum of the liquid has been obtained from 23 to -39°C. These spectra are consistent with three stable conformers existing in both phases at ambient temperature. The data have been interpreted on the basis that the gauche-2 conformer is the most stable form and the gauche-1 rotamer (most polar) is the second most stable form in the xenon solution whereas the gauche-1 conformer is the most stable form and the cis conformer is the second most stable form in the liquid. Utilizing well separated triplets of three fundamentals due to all three conformers, the enthalpy differences have been determined to be 51 ± 14 cm -1 (146 ± 40 cal mol -1) (gauche-2 to gauche-1) and 213 ± 97 cm -1 (609 ± 277 cal mol -1) (gauche-2 to cis) in the xenon solution and 383 ± 28 cm -1 (gauche-1 to gauche-2) and 358 ± 12 cm -1 (gauche-1 to cis) in the liquid. The structural parameters, dipole moments, conformational stability, and vibrational frequencies have been determined by ab initio calculations with two basis sets up to MP2/6-31G∗. Vibrational assignments for the 24 normal modes for both the gauche-2 and gauche-1 conformers are proposed with several of the fundamentals assigned for the cis conformer. In addition, some of the fundamental frequencies for motions of the 37Cl isotope have been observed at 2-3 cm -1 lower frequency than the corresponding modes of the 35Cl isotope.

  15. DFT computation and experimental analysis of vibrational and electronic spectra of phenoxy acetic acid herbicides

    NASA Astrophysics Data System (ADS)

    Arul Dhas, D.; Hubert Joe, I.; Roy, S. D. D.; Balachandran, S.

    2013-05-01

    An absolute vibrational analysis has been attempted on the basis of experimental FTIR and NIR-FT Raman spectra with calculated vibrational wavenumbers and intensities of phenoxy acetic acids. The equilibrium geometry, bonding features and harmonic vibrational wavenumbers have been calculated with the help of B3LYP method with Dunning correlation consistent basis set aug-cc-pVTZ. The electronic structures of molecular fragments were described in terms of natural bond orbital analysis, which shows intermolecular Osbnd H⋯O and intramolecular Csbnd H⋯O hydrogen bonds. The electronic absorption spectra with different solvents have been investigated in combination with time-dependent density functional theory calculation. The pKa values of phenoxy acetic acids were compared.

  16. Ab initio and DFT studies of the structure and vibrational spectra of anhydrous caffeine.

    PubMed

    Srivastava, Santosh K; Singh, Vipin B

    2013-11-01

    Vibrational spectra and molecular structure of anhydrous caffeine have been systematically investigated by second order Moller-Plesset (MP2) perturbation theory and density functional theory (DFT) calculations. Vibrational assignments have been made and many previous ambiguous assignments in IR and Raman spectra are amended. The calculated DFT frequencies and intensities at B3LYP/6-311++G(2d,2p) level, were found to be in better agreement with the experimental values. It was found that DFT with B3LYP functional predicts harmonic vibrational wave numbers more close to experimentally observed value when it was performed on MP2 optimized geometry rather than DFT geometry. The calculated TD-DFT vertical excitation electronic energies of the valence excited states of anhydrous caffeine are found to be in consonance to the experimental absorption peaks.

  17. Ab initio and DFT studies of the structure and vibrational spectra of anhydrous caffeine

    NASA Astrophysics Data System (ADS)

    Srivastava, Santosh K.; Singh, Vipin B.

    2013-11-01

    Vibrational spectra and molecular structure of anhydrous caffeine have been systematically investigated by second order Moller-Plesset (MP2) perturbation theory and density functional theory (DFT) calculations. Vibrational assignments have been made and many previous ambiguous assignments in IR and Raman spectra are amended. The calculated DFT frequencies and intensities at B3LYP/6-311++G(2d,2p) level, were found to be in better agreement with the experimental values. It was found that DFT with B3LYP functional predicts harmonic vibrational wave numbers more close to experimentally observed value when it was performed on MP2 optimized geometry rather than DFT geometry. The calculated TD-DFT vertical excitation electronic energies of the valence excited states of anhydrous caffeine are found to be in consonance to the experimental absorption peaks.

  18. Vibration Analysis of AN Induction Motor

    NASA Astrophysics Data System (ADS)

    WANG, C.; LAI, J. C. S.

    1999-07-01

    With the advent of power electronics, variable speed induction motors are finding increasing use in industries because of their low cost and potential savings in energy consumption. However, the acoustic noise emitted by the motor increases due to switching harmonics introduced by the electronic inverters. Consequently, the vibro-acoustic behaviour of the motor structure has attracted more attention. In this paper, considerations given to modelling the vibration behaviour of a 2·2 kW induction motor are discussed. By comparing the calculated natural frequencies and the mode shapes with the results obtained from experimental modal testing, the effects of the teeth of the stator, windings, outer casing, slots, end-shields and support on the overall vibration behaviour are analyzed. The results show that when modelling the vibration behaviour of a motor structure, the laminated stator should be treated as an orthotropic structure, and the teeth of the stator could be neglected. As the outer casing, end-shields and the support all affect the vibration properties of the whole structure, these substructures should be incorporated in the model to improve the accuracy.

  19. Aeroelastic Computations of a Compressor Stage Using the Harmonic Balance Method

    NASA Technical Reports Server (NTRS)

    Reddy, T. S. R.

    2010-01-01

    The aeroelastic characteristics of a compressor stage were analyzed using a computational fluid dynamic (CFD) solver that uses the harmonic balance method to solve the governing equations. The three dimensional solver models the unsteady flow field due to blade vibration using the Reynolds-Averaged Navier-Stokes equations. The formulation enables the study of the effect of blade row interaction through the inclusion of coupling modes between blade rows. It also enables the study of nonlinear effects of high amplitude blade vibration by the inclusion of higher harmonics of the fundamental blade vibration frequency. In the present work, the solver is applied to study in detail the aeroelastic characteristics of a transonic compressor stage. Various parameters were included in the study: number of coupling modes, blade row axial spacing, and operating speeds. Only the first vibration mode is considered with amplitude of oscillation in the linear range. Both aeroelastic stability (flutter) of rotor blade and unsteady loading on the stator are calculated. The study showed that for the stage considered, the rotor aerodynamic damping is not influenced by the presence of the stator even when the axial spacing is reduced by nearly 25 percent. However, the study showed that blade row interaction effects become important for the unsteady loading on the stator when the axial spacing is reduced by the same amount.

  20. Molecular structural, non-linear optical, second order perturbation and Fukui studies of Indole-3-Aldehyde using density functional calculations.

    PubMed

    Muthu, S; Maheswari, J Uma; Sundius, Tom

    2013-04-01

    Indole-3-Aldehyde is a new organic non-linear material having good second harmonic generation. The optimized molecular geometry, harmonic vibrational frequencies, infrared intensities of Indole-3-Aldehyde (I3A, C9H7NO) in the ground state were carried out by using density functional theory (B3LYP) method with 6-31G(d,p) basis set. A detailed interpretation of the infrared spectrum of Indole-3-Aldehyde is reported. The vibrational frequencies are calculated and compared with experimental FT-IR spectra. The theoretical spectrograms of FT-IR of the title compound have been constructed in addition, theoretical information like ONIOM, potential energy surface, NBO, and Fukui function are also calculated. Unambiguous vibrational assignment of all the fundamentals was made using the potential energy distribution.

  1. Large amplitude vibrations and damage detection of rectangular plates

    NASA Astrophysics Data System (ADS)

    Manoach, Emil; Trendafilova, Irina

    2008-08-01

    In this work, geometrically nonlinear vibrations of fully clamped rectangular plates are used to study the sensitivity of some nonlinear vibration response parameters to the presence of damage. The geometrically nonlinear version of the Mindlin plate theory is used to model the plate behaviour. Damage is represented as a stiffness reduction in a small area of the plate. The plate is subjected to harmonic loading with a frequency of excitation close to the first natural frequency leading to large amplitude vibrations. The plate vibration response is obtained by a pseudo-load mode superposition method. The main results are focussed on establishing the influence of damage on the vibration response of the plate and the change in the time-history diagrams and the Poincaré maps caused by the damage. Finally, a criterion and a damage index for detecting the presence and the location of the damage is proposed. The criterion is based on analysing the points in the Poincaré sections of the damaged and healthy plate. Numerical results for large amplitude vibrations of damaged and healthy rectangular and square plates are presented and the proposed damage index for the considered cases is calculated. The criterion demonstrates quite good abilities to detect and localize damage.

  2. Numerical analysis of strongly nonlinear extensional vibrations in elastic rods.

    PubMed

    Vanhille, Christian; Campos-Pozuelo, Cleofé

    2007-01-01

    In the framework of transduction, nondestructive testing, and nonlinear acoustic characterization, this article presents the analysis of strongly nonlinear vibrations by means of an original numerical algorithm. In acoustic and transducer applications in extreme working conditions, such as the ones induced by the generation of high-power ultrasound, the analysis of nonlinear ultrasonic vibrations is fundamental. Also, the excitation and analysis of nonlinear vibrations is an emergent technique in nonlinear characterization for damage detection. A third-order evolution equation is derived and numerically solved for extensional waves in isotropic dissipative media. A nine-constant theory of elasticity for isotropic solids is constructed, and the nonlinearity parameters corresponding to extensional waves are proposed. The nonlinear differential equation is solved by using a new numerical algorithm working in the time domain. The finite-difference numerical method proposed is implicit and only requires the solution of a linear set of equations at each time step. The model allows the analysis of strongly nonlinear, one-dimensional vibrations and can be used for prediction as well as characterization. Vibration waveforms are calculated at different points, and results are compared for different excitation levels and boundary conditions. Amplitude distributions along the rod axis for every harmonic component also are evaluated. Special attention is given to the study of high-amplitude damping of vibrations by means of several simulations. Simulations are performed for amplitudes ranging from linear to nonlinear and weak shock.

  3. Analysis of vibrational-translational energy transfer using the direct simulation Monte Carlo method

    NASA Technical Reports Server (NTRS)

    Boyd, Iain D.

    1991-01-01

    A new model is proposed for energy transfer between the vibrational and translational modes for use in the direct simulation Monte Carlo method (DSMC). The model modifies the Landau-Teller theory for a harmonic oscillator and the rate transition is related to an experimental correlation for the vibrational relaxation time. Assessment of the model is made with respect to three different computations: relaxation in a heat bath, a one-dimensional shock wave, and hypersonic flow over a two-dimensional wedge. These studies verify that the model achieves detailed balance, and excellent agreement with experimental data is obtained in the shock wave calculation. The wedge flow computation reveals that the usual phenomenological method for simulating vibrational nonequilibrium in the DSMC technique predicts much higher vibrational temperatures in the wake region.

  4. Vibration measurement based on the optical cross-correlation technique with femtosecond pulsed laser

    NASA Astrophysics Data System (ADS)

    Han, Jibo; Wu, Tengfei; Zhao, Chunbo; Li, Shuyi

    2016-10-01

    Two vibration measurement methods with femtosecond pulsed laser based on the optical cross-correlation technique are presented independently in this paper. The balanced optical cross-correlation technique can reflect the time jitter between the reference pluses and measurement pluses by detecting second harmonic signals using type II phase-matched nonlinear crystal and balanced amplified photo-detectors. In the first method, with the purpose of attaining the vibration displacement, the time difference of the reference pulses relative to the measurement pluses can be measured using single femtosecond pulsed laser. In the second method, there are a couple of femtosecond pulsed lasers with high pulse repetition frequency. Vibration displacement associated with cavity length can be calculated by means of precisely measuring the pulse repetition frequency. The results show that the range of measurement attains ±150μm for a 500fs pulse. These methods will be suited for vibration displacement measurement, including laboratory use, field testing and industrial application.

  5. Influence of molecular vibrations on the valence electron momentum distributions of adamantane

    NASA Astrophysics Data System (ADS)

    Morini, Filippo; Watanabe, Noboru; Kojima, Masataka; Deleuze, Michael Simon; Takahashi, Masahiko

    2017-03-01

    We report an electron momentum spectroscopy study of vibrational effects on the electron momentum distributions of the outer valence orbitals of adamantane (C10H16). The symmetric noncoplanar (e, 2e) experiment has been carried out at an incident electron energy of 1.2 keV. Furthermore, theoretical calculations of the electron momentum distributions with vibrational effects being involved have been performed using the harmonic analytical quantum mechanical and Born-Oppenheimer molecular dynamics approaches. In spite of the complex nature of the vibrational structure of this large molecule, both approaches provide overall quantitative insights into the results of the experiment. Comparisons between experiment and theory have shown that ground state nuclear dynamics appreciably affects the momentum profiles of the 7t2, {2t1 + 3e}, and {5t2 + 5a1} orbitals. It has been demonstrated that changes in the momentum profiles are mainly due to the vibrational motions associated with the CH bonds.

  6. Experimental and computational study on molecular structure and vibrational analysis of an antihyperglycemic biomolecule: gliclazide.

    PubMed

    Karakaya, Mustafa; Kürekçi, Mehmet; Eskiyurt, Buse; Sert, Yusuf; Çırak, Çağrı

    2015-01-25

    In present study, the experimental and theoretical harmonic vibrational frequencies of gliclazide molecule have been investigated. The experimental FT-IR (400-4000 cm(-1)) and Laser-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) have been calculated using ab initio Hartree Fock (HF), density functional theory (B3LYP hybrid function) methods with 6-311++G(d,p) and 6-31G(d,p) basis sets by Gaussian 09W program. The assignments of the vibrational frequencies were performed by potential energy distribution (PED) analysis by using VEDA 4 program. Theoretical optimized geometric parameters and vibrational frequencies have been compared with the corresponding experimental data, and they have been shown to be in a good agreement with each other. Also, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies have been found.

  7. Experimental and computational study on molecular structure and vibrational analysis of an antihyperglycemic biomolecule: Gliclazide

    NASA Astrophysics Data System (ADS)

    Karakaya, Mustafa; Kürekçi, Mehmet; Eskiyurt, Buse; Sert, Yusuf; Çırak, Çağrı

    2015-01-01

    In present study, the experimental and theoretical harmonic vibrational frequencies of gliclazide molecule have been investigated. The experimental FT-IR (400-4000 cm-1) and Laser-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) have been calculated using ab initio Hartree Fock (HF), density functional theory (B3LYP hybrid function) methods with 6-311++G(d,p) and 6-31G(d,p) basis sets by Gaussian 09W program. The assignments of the vibrational frequencies were performed by potential energy distribution (PED) analysis by using VEDA 4 program. Theoretical optimized geometric parameters and vibrational frequencies have been compared with the corresponding experimental data, and they have been shown to be in a good agreement with each other. Also, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies have been found.

  8. Synthesis, characterization and vibrational studies of p-chlorosulfinylaniline

    NASA Astrophysics Data System (ADS)

    Chemes, Doly M.; Alonso de Armiño, Diego J.; Cutin, Edgardo H.; Oberhammer, Heinz; Robles, Norma L.

    2017-01-01

    p-Cholorosulfinylaniline was prepared by the reaction of p-chloroaniline and SOCl2. The structural, conformational and configurational properties of the obtained liquid compound were studied by Raman and infrared spectroscopy in the liquid state. The assignment of the vibrational spectra was carried out with the help of data obtained by quantum chemical calculations at the harmonic oscillator approximation and using anharmonic vibrational self-consistent field (VSCF) method as well. The 1H and 13C NMR chemical shifts of the molecule were calculated by Gauge including orbital (GIAO) method (DFT/B3LYP approximation using 6-311 + G (df), 6-311++G (df,pd) and cc-pVTZ basis sets) and compared to the experimental values. Natural Bond Orbital analysis provides an explanation of the stability of the molecule and its electronic properties upon charge delocalization.

  9. A computer program to calculate zeroes, extrema, and interval integrals for the associated Legendre functions. [for estimation of bounds of truncation error in spherical harmonic expansion of geopotential

    NASA Technical Reports Server (NTRS)

    Payne, M. H.

    1973-01-01

    A computer program is described for the calculation of the zeroes of the associated Legendre functions, Pnm, and their derivatives, for the calculation of the extrema of Pnm and also the integral between pairs of successive zeroes. The program has been run for all n,m from (0,0) to (20,20) and selected cases beyond that for n up to 40. Up to (20,20), the program (written in double precision) retains nearly full accuracy, and indications are that up to (40,40) there is still sufficient precision (4-5 decimal digits for a 54-bit mantissa) for estimation of various bounds and errors involved in geopotential modelling, the purpose for which the program was written.

  10. Sunspots and Their Simple Harmonic Motion

    ERIC Educational Resources Information Center

    Ribeiro, C. I.

    2013-01-01

    In this paper an example of a simple harmonic motion, the apparent motion of sunspots due to the Sun's rotation, is described, which can be used to teach this subject to high-school students. Using real images of the Sun, students can calculate the star's rotation period with the simple harmonic motion mathematical expression.

  11. Thermal weights for semiclassical vibrational response functions

    SciTech Connect

    Moberg, Daniel R.; Alemi, Mallory; Loring, Roger F.

    2015-08-28

    Semiclassical approximations to response functions can allow the calculation of linear and nonlinear spectroscopic observables from classical dynamics. Evaluating a canonical response function requires the related tasks of determining thermal weights for initial states and computing the dynamics of these states. A class of approximations for vibrational response functions employs classical trajectories at quantized values of action variables and represents the effects of the radiation-matter interaction by discontinuous transitions. Here, we evaluate choices for a thermal weight function which are consistent with this dynamical approximation. Weight functions associated with different semiclassical approximations are compared, and two forms are constructed which yield the correct linear response function for a harmonic potential at any temperature and are also correct for anharmonic potentials in the classical mechanical limit of high temperature. Approximations to the vibrational linear response function with quantized classical trajectories and proposed thermal weight functions are assessed for ensembles of one-dimensional anharmonic oscillators. This approach is shown to perform well for an anharmonic potential that is not locally harmonic over a temperature range encompassing the quantum limit of a two-level system and the limit of classical dynamics.

  12. Raman and IR studies and DFT calculations of the vibrational spectra of 2,4-Dithiouracil and its cation and anion.

    PubMed

    Singh, R; Yadav, R A

    2014-09-15

    Raman and FTIR spectra of solid 2,4-Dithiouracil (DTU) at room temperature have been recorded. DFT calculations were carried out to compute the optimized molecular geometries, GAPT charges and fundamental vibrational frequencies along with their corresponding IR intensities, Raman activities and depolarization ratios of the Raman bands for the neutral DTU molecule and its cation (DTU+) and anion (DTU-) using the Gaussian-03 software. Addition of one electron leads to increase in the atomic charges on the sites N1 and N3 and decrease in the atomic charges on the sites S8 and S10. Due to ionization of DTU molecule, the charge at the site C6 decreases in the cationic and anionic radicals of DTU as compared to its neutral species. As a result of anionic radicalization, the C5C6 bond length increases and loses its double bond character while the C4C5 bond length decreases. In the case of the DTU+ ion the IR and Raman band corresponding to the out-of-phase coupled NH stretching mode is strongest amongst the three species. The anionic DTU radical is found to be the most stable. The two NH out-of-plane bending modes are found to originate due to out-of-phase and in-phase coupling of the two NH bonds in the anion and cation contrary to the case of the neutral DTU molecule in which the out-of-plane bending motions of the two NH bonds are not coupled.

  13. Vibrations and reorientations of NH3 molecules in [Mn(NH3)6](ClO4)2 studied by infrared spectroscopy and theoretical (DFT) calculations.

    PubMed

    Hetmańczyk, Joanna; Hetmańczyk, Łukasz; Migdał-Mikuli, Anna; Mikuli, Edward

    2015-02-05

    The vibrational and reorientational motions of NH3 ligands and ClO4(-) anions were investigated by Fourier transform middle-infrared spectroscopy (FT-IR) in the high- and low-temperature phases of [Mn(NH3)6](ClO4)2. The temperature dependencies of full width at half maximum (FWHM) of the infrared bands at: 591 and 3385cm(-1), associated with: ρr(NH3) and νas(N-H) modes, respectively, indicate that there exist fast (correlation times τR≈10(-12)-10(-13)s) reorientational motions of NH3 ligands, with a mean values of activation energies: 7.8 and 4.5kJmol(-1), in the phase I and II, respectively. These reorientational motions of NH3 ligands are only slightly disturbed in the phase transition region and do not significantly contribute to the phase transition mechanism. Fourier transform far-infrared and middle-infrared spectra with decreasing of temperature indicated characteristic changes at the vicinity of PT at TC(c)=137.6K (on cooling), which suggested lowering of the crystal structure symmetry. Infrared spectra of [Mn(NH3)6](ClO4)2 were recorded and interpreted by comparison with respective theoretical spectra calculated using DFT method (B3LYP functional, LANL2DZ ECP basis set (on Mn atom) and 6-311+G(d,p) basis set (on H, N, Cl, O atoms) for the isolated equilibrium two models (Model 1 - separate isolated [Mn(NH3)6](2+) cation and ClO4(-) anion and Model 2 - [Mn(NH3)6(ClO4)2] complex system). Calculated optical spectra show a good agreement with the experimental infrared spectra (FT-FIR and FT-MIR) for the both models.

  14. Communication: Ro-vibrational control of chemical reactivity in H+CH{sub 4}→ H{sub 2}+CH{sub 3} : Full-dimensional quantum dynamics calculations and a sudden model

    SciTech Connect

    Welsch, Ralph Manthe, Uwe

    2014-08-07

    The mode-selective chemistry of the title reaction is studied by full-dimensional quantum dynamics simulation on an accurate ab initio potential energy surface for vanishing total angular momentum. Using a rigorous transition state based approach and multi-configurational time-dependent Hartree wave packet propagation, initial state-selected reaction probabilities for many ro-vibrational states of methane are calculated. The theoretical results are compared with experimental trends seen in reactions of methane. An intuitive interpretation of the ro-vibrational control of the chemical reactivity provided by a sudden model based on the quantum transition state concept is discussed.

  15. Vibrational spectroscopic studies and ab initio calculations of a substituted amide of pyrazine-2-carboxylic acid--C12H10ClN3O.

    PubMed

    Mary, Y Sheeena; Varghese, Hema Tresa; Panicker, C Yohannan; Dolezal, Martin

    2008-11-15

    A substituted amide of pyrazine-2-carboxylic acid was prepared and the IR spectrum is recorded and analysed. The vibrational frequencies and corresponding vibrational assignments are examined theoretically using the Gaussian03 set of quantum chemistry codes. Predicted infrared and Raman intensities are reported.

  16. Method and apparatus for vibrating a substrate during material formation

    DOEpatents

    Bailey, Jeffrey A [Richland, WA; Roger, Johnson N [Richland, WA; John, Munley T [Benton City, WA; Walter, Park R [Benton City, WA

    2008-10-21

    A method and apparatus for affecting the properties of a material include vibrating the material during its formation (i.e., "surface sifting"). The method includes the steps of providing a material formation device and applying a plurality of vibrations to the material during formation, which vibrations are oscillations having dissimilar, non-harmonic frequencies and at least two different directions. The apparatus includes a plurality of vibration sources that impart vibrations to the material.

  17. Structural and vibrational studies and molecular force field of zinc difluoromethanesulfinate

    NASA Astrophysics Data System (ADS)

    Romano, Elida; Davies, Lilian Emilia; Brandán, Silvia Antonia

    2013-07-01

    The new compound zinc difluoromethanesulfinate salt, Zn(SO2CF2H)2 (recently synthesized by Fujiwara et al. [12]) was characterized by infrared and Raman spectroscopies. The ab initio calculations were used to study the structures and vibrational properties of the compound and its SO2CF2H- anion. Employing the HF and B3LYP levels of theory, the molecular structures of both species were theoretically determined in gas phase and the harmonic vibrational frequencies were evaluated at the same levels. Also, the structure of a monohydrated complex in accordance with the observed experimental structure was optimized. The calculated harmonic vibrational frequencies for zinc difluoromethanesulfinate 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 difluoromethanesulfinate groups of this compound as monodentate and bidentate ligands. A complete assignment of all the observed bands in the IR and Raman spectra for zinc difluoromethanesulfinate was performed. The nature of the CF, SO and Zn ← 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.

  18. Vibrational Schroedinger Cats

    NASA Technical Reports Server (NTRS)

    Kis, Z.; Janszky, J.; Vinogradov, An. V.; Kobayashi, T.

    1996-01-01

    The optical Schroedinger cat states are simple realizations of quantum states having nonclassical features. It is shown that vibrational analogues of such states can be realized in an experiment of double pulse excitation of vibrionic transitions. To track the evolution of the vibrational wave packet we derive a non-unitary time evolution operator so that calculations are made in a quasi Heisenberg picture.

  19. Full-dimensional quantum calculations of vibrational levels of NH4+ and isotopomers on an accurate ab initio potential energy surface

    SciTech Connect

    Hua -Gen Yu; Han, Huixian; Guo, Hua

    2016-03-29

    Vibrational energy levels of the ammonium cation (NH4+) and its deuterated isotopomers are calculated using a numerically exact kinetic energy operator on a recently developed nine-dimensional permutation invariant semiglobal potential energy surface fitted to a large number of high-level ab initio points. Like CH4, the vibrational levels of NH4+ and ND4+ exhibit a polyad structure, characterized by a collective quantum number P = 2(v1 + v3) + v2 + v4. As a result, the low-lying vibrational levels of all isotopomers are assigned and the agreement with available experimental data is better than 1 cm–1.

  20. Analysis of a high Tc superconducting levitation system with vibration isolation control

    SciTech Connect

    Nagaya, Kosuke

    1996-03-01

    This paper presents a method for controlling vibrations of a levitated high Tc superconducting body subjected to base disturbances. To have the control forces, an actuator consisting of a permanent magnet with an electromagnet was presented. The analytical solution for calculating levitation forces due to the permanent magnet and the control currents in the electromagnet was obtained. The levitation forces obtained coincide with the previously published results. The equation of motion of the levitated body subjected to base disturbances under the control was presented. Nonlinear vibrations of the body were first discussed; then the method of vibration isolation control using the direct disturbance cancellation combining the velocity feedback control was investigated. Numerical calculations were carried out for the levitation forces, with respect to the levitated body subjected to harmonic or pulse base excitations. It was clarified that the present method is valid for controlling nonlinear systems like the magnetic levitated superconducting body.

  1. Vibrational contribution to molecular polarizabilities and hyperpolarizabilities

    NASA Astrophysics Data System (ADS)

    Pandey, P. K. K.; Santry, D. P.

    1980-09-01

    The vibrational averaging theory of Kern and Matcha is extended, at the harmonic level of approximation, to the case where the molecular property under investigation can itself lead indirectly to a perturbation of the vibrational levels of the molecule. It is found that contributions arising from this perturbation can be significant, especially for molecular hyperpolarizabilities.

  2. Direct non-Born-Oppenheimer variational calculations of all bound vibrational states corresponding to the first rotational excitation of D{sub 2} performed with explicitly correlated all-particle Gaussian functions

    SciTech Connect

    Sharkey, Keeper L.; Kirnosov, Nikita; Adamowicz, Ludwik

    2015-05-07

    Direct variational calculations where the Born-Oppenheimer approximation is not assumed are done for all rovibrational states of the D{sub 2} molecule corresponding to first excited rotational level (the N = 1 states). All-particle explicitly correlated Gaussian basis functions are used in the calculations. The exponential parameters of the Gaussians are optimized with the aid of analytically calculated energy gradient determined with respect to these parameters. The results allow to determine the ortho-para spin isomerization energies as a function of the vibrational quantum number.

  3. Absorption intensity changes and frequency shifts of fundamental and first overtone bands for OH stretching vibration of methanol upon methanol-pyridine complex formation in CCl4: analysis by NIR/IR spectroscopy and DFT calculations.

    PubMed

    Futami, Yoshisuke; Ozaki, Yasushi; Ozaki, Yukihiro

    2016-02-21

    Infrared (IR) and near infrared (NIR) spectra were measured for methanol and the methanol-pyridine complex in carbon tetrachloride. Upon the formation of the methanol-pyridine complex, the frequencies of both the fundamental and first overtone bands of the OH stretching vibration shifted to lower frequencies, and the absorption intensity of the fundamental increased significantly, while that of the first overtone decreased markedly. By using quantum chemical calculations, we estimated the absorption intensities and frequencies of the fundamental and first overtone bands for the OH stretching vibration based on the one-dimensional Schrödinger equation. The calculated results well reproduced the experimental results. The molecular vibration potentials and dipole moment functions of the OH stretching vibration modes were compared between methanol and the methanol-pyridine complex in terms of absorption intensity changes and frequency shifts. The large change in the dipole moment function was found to be the main cause for the variations in absorption intensity for the fundamental and first overtone bands.

  4. Multidimentional Normal Mode Calculations for the OH Vibrational Spectra of (H_2O)_3^+, (H_2O)_3^+Ar, H^+(H_2O)_3, and H^+(H_2O)_3Ar

    NASA Astrophysics Data System (ADS)

    Li, Ying-Cheng; Chuang, Hsiao-Han; Tan, Jake Acedera; Takahashi, Kaito; Kuo, Jer-Lai

    2014-06-01

    Recent experimental observations of (H_2O)_3^+, (H_2O)_3^+Ar, H^+(H_2O)_3, and H^+(H_2O)_3Ar clusters in the region 1400-3800 wn show that the OH stretching vibration has distinct characteristics. Multidimensional normal mode calculations were carried out for OH stretching vibrations in the 1200-4000 wn photon energy range. The potential energy and dipole surfaces were evaluated by using first-principles methods. By comparing the calculated frequencies and intensities of OH stretching vibration with experimental spectra, we found that the assignment of OH strecthing of H_3O^+ moiety and free OH strectching vibration have resonable agreement with experimental data. Jeffrey M. Headrick, Eric G. Diken, Richard S. Walters, Nathan I. Hammer, Richard A. Christie, Jun Cui, Evgeniy M. Myshakin, Michael A. Duncan, Mark A. Johnson, Kenneth D. Jordan, Science, 2005, 17, 1765. Kenta Mizuse, Jer-Lai Kuo and Asuka Fujii, Chem. Sci., 2011, 2, 868 Kenta Mizuse and Asuka Fujii, J. Phys. Chem. A, 2013, 117, 929.

  5. Color harmonization for images

    NASA Astrophysics Data System (ADS)

    Tang, Zhen; Miao, Zhenjiang; Wan, Yanli; Wang, Zhifei

    2011-04-01

    Color harmonization is an artistic technique to adjust a set of colors in order to enhance their visual harmony so that they are aesthetically pleasing in terms of human visual perception. We present a new color harmonization method that treats the harmonization as a function optimization. For a given image, we derive a cost function based on the observation that pixels in a small window that have similar unharmonic hues should be harmonized with similar harmonic hues. By minimizing the cost function, we get a harmonized image in which the spatial coherence is preserved. A new matching function is proposed to select the best matching harmonic schemes, and a new component-based preharmonization strategy is proposed to preserve the hue distribution of the harmonized images. Our approach overcomes several shortcomings of the existing color harmonization methods. We test our algorithm with a variety of images to demonstrate the effectiveness of our approach.

  6. Clock Spectroscopy of Interacting Fermions in a Harmonic Trap

    NASA Astrophysics Data System (ADS)

    Koller, Andrew; Rey, Ana

    2013-05-01

    We investigate the dynamics during Ramsey interrogation of interacting fermions in a harmonic trap. We consider the effect of both s-wave and p-wave collisions during the dynamics, including processes that change the spatial modes of particles. Prior theoretical treatments utilize the so-called spin model,, which includes processes that change the internal states of atoms, but leave the vibrational modes unchanged. We discuss how the inclusion of these mode-changing processes modifies the predicted density-dependent frequency shifts and contrast of Ramsey fringes, both of which are relevant for the precision of optical lattice clocks using fermionic alkaline-earth atoms. We also discuss how the frequency shifts and contrast depend on the pulse areas, interaction strength, and temperature - and how these dependences are affected by the inclusion of mode-changing collisions in the calculations. Supported by AFOSR, DARPA-OLE, NSF, and NDSEG.

  7. Cross-correlation trajectory study of vibrational relaxation of HF (v=1--7) by HF (v=0)

    SciTech Connect

    Coltrin, M.E.; Marcus, R.A.

    1980-11-01

    Results are presented for a three-dimensional quasiclassical trajectory study of the vibrational deactivation of vibrationally excited HF (v=1--7) by ground vibrational HF. A cross-correlation method of analysis is used to calculate probabilities and rate constants for V--V and V--RT transitions using trajectory results. Comparisons are made of calculated total deactivation rate constants (V--V plus V--RT) with experimental values. The V--RT dominates the relaxation for higher v states, and increases particularly rapidly with increasing v. Comparisons are made with recent classical-path calculations for this system, and in the use of Morse versus equivalent harmonic oscillator potentials.

  8. Vibrational and thermal properties of β-HMX and TATB from dispersion corrected density functional theory

    NASA Astrophysics Data System (ADS)

    Landerville, Aaron C.; Oleynik, Ivan I.

    2017-01-01

    Dispersion Corrected Density Functional Theory (DFT+vdW) calculations are performed to predict vibrational and thermal properties of the bulk energetic materials (EMs) β-octahydrocyclotetramethylene-tetranitramine (β-HMX) and triaminotrinitrobenzene (TATB). DFT+vdW calculations of pressure-dependent crystal structure and the hydrostatic equation of state are followed by frozen-phonon calculations of their respective vibration spectra at each pressure. These are then used under the quasi-harmonic approximation to obtain zero-point and thermal free energy contributions to the pressure, resulting in pressure-volume-temperature (PVT) EOS for each material that are in excellent agreement with experiment. Heat capacities, and coefficients of thermal expansion as functions of temperature are also calculated and compared with experiment.

  9. Vibration manual

    NASA Technical Reports Server (NTRS)

    Green, C.

    1971-01-01

    Guidelines of the methods and applications used in vibration technology at the MSFC are presented. The purpose of the guidelines is to provide a practical tool for coordination and understanding between industry and government groups concerned with vibration of systems and equipments. Topics covered include measuring, reducing, analyzing, and methods for obtaining simulated environments and formulating vibration specifications. Methods for vibration and shock testing, theoretical aspects of data processing, vibration response analysis, and techniques of designing for vibration are also presented.

  10. Vibrational spectroscopic (FT-IR, FT-Raman, SERS) and quantum chemical calculations of 3-(10,10-dimethyl-anthracen-9-ylidene)-N,N,N-trimethylpropanaminiium chloride (Melitracenium chloride).

    PubMed

    Mary, Y Shyma; Jojo, P J; Van Alsenoy, Christian; Kaur, Manpreet; Siddegowda, M S; Yathirajan, H S; Nogueira, Helena I S; Cruz, Sandra M A

    2014-01-01

    FT-IR, FT-Raman spectra of Melitracenium chloride were recorded and analyzed. SERS spectrum was recorded in silver colloid. The vibrational wavenumbers were computed using DFT quantum chemical calculations. The data obtained from wavenumber calculations are used to assign vibrational bands obtained in infrared and Raman spectra as well as in SERS of the studied molecule. Potential energy distribution was done using GAR2PED program. The geometrical parameters (SDD) of the title compound are in agreement with the XRD results. The presence anthracene ring modes in the SERS spectrum suggest a tilted orientation with respect to the metal surface. The methyl groups in the title molecule are also close to the metal surface. The first hyperpolarizability, NBO analysis and molecular electrostatic potential results are also reported.

  11. Harmonic motion microwave Doppler imaging: a simulation study using a simple breast model.

    PubMed

    Top, Can Bariş; Gençer, Nevzat G

    2014-02-01

    A hybrid method for tissue imaging using dielectric and elastic properties is proposed and investigated with simple bi-layered breast model. In this method, local harmonic motion is generated in the tissue using a focused ultrasound probe. A narrow-band microwave signal is transmitted to the tissue. The Doppler component of the scattered signal, which depends on the dielectric and elastic properties of the vibrating region, is sensed. A plane-wave spectrum technique is used together with reciprocity theorem for calculating the response of a vibrating electrically small spherical tumor in breast tissue. The effects of operating frequency, antenna alignment and distance, and tumor depth on the received signal are presented. The effect of harmonic motion frequency on the vibration amplitude and displacement distribution is investigated with mechanical simulations using the finite element method. The safety of the method is analyzed in terms of microwave and ultrasound exposure of the breast tissue. The results show that the method has a potential in detecting tumors inside fibro-glandular breast tissue.

  12. Solvent effects on zero-point vibrational corrections to optical rotations and nuclear magnetic resonance shielding constants

    NASA Astrophysics Data System (ADS)

    Kongsted, Jacob; Ruud, Kenneth

    2008-01-01

    We present a study of solvent effects on the zero-point vibrational corrections (ZPVC) to optical rotations and nuclear magnetic resonance shielding constants of solvated molecules. The model used to calculate vibrational corrections rely on an expansion of the potential and property surfaces around an effective molecular geometry and includes both harmonic and anharmonic corrections. Numerical examples are presented for ( S)-propylene oxide in various solvents as well as for acetone and the three diazene molecules. We find that solvent effects on the ZPVCs may be significant and in some cases crucial to accurately predict solvent shifts on molecular properties.

  13. Density-functional theory study of vibrational relaxation of CO stretching excitation on Si(100)

    NASA Astrophysics Data System (ADS)

    Sakong, Sung; Kratzer, Peter; Han, Xu; Laß, Kristian; Weingart, Oliver; Hasselbrink, Eckart

    2008-11-01

    A first-principles theory is presented for calculating the lifetime of adsorbate vibrations on semiconductor or insulator surfaces, where dissipation of the vibrational energy to substrate phonons is the dominant relaxation mechanism. As an example, we study the stretching vibration of CO/Si(100), where a lifetime of 2.3 ns has been measured recently [K. Laß, X. Han, and E. Hasselbrink, J. Chem. Phys. 123, 051102 (2005)]. Density-functional theory (DFT) calculations for the local modes of the adsorbate, including their anharmonic coupling, are combined with force field calculations for the substrate phonons. Using the DFT-Perdew-Burke-Ernzerhof functional, we have determined the most stable adsorption site for CO on top of the lower Si atom of the Si surface dimer, the local normal modes of CO, and the multidimensional potential energy surface for the CO vibrations. The anharmonic stretching frequency of adsorbed CO obtained in DFT-PBE is 5% lower than the experimental value, while the B3LYP functional reproduces the CO stretching frequency with only 1.4% error. The coupling between the anharmonic vibrational modes and the phonon continuum is evaluated within first-order perturbation theory, and transition rates for the CO vibrational relaxation are calculated using Fermi's golden rule. The lifetime of 0.5 ns obtained with DFT-PBE is in qualitative agreement with experiment, while using vibrational frequencies from the B3LYP functional gives a much too long lifetime as compared to experiment. We find that the numerical value of the lifetime is very sensitive to the harmonic frequencies used as input to the calculation of the transition rate. An empirical adjustment of these frequencies yields excellent agreement between our theory and experiment. From these calculations we conclude that the most probable microscopic decay channel of the CO stretching mode is into four lateral shift/bending quanta and one phonon.

  14. Simple Harmonic Motion in Harmonic Plane Waves.

    ERIC Educational Resources Information Center

    Benumof, Reuben

    1980-01-01

    Discusses the distribution of kinetic and potential energy in transverse and longitudinal waves and examines the transmission of power and momentum. This discussion is intended to aid in understanding the simple harmonic motion of a particle involved in the propagation of a harmonic mechanical plane wave. (HM)

  15. Theoretical structural and experimental vibrational study of niobyl nitrate

    NASA Astrophysics Data System (ADS)

    Castillo, M. V.; Romano, E.; Lanús, H. E.; Díaz, S. B.; Ben Altabef, A.; Brandán, S. A.

    2011-05-01

    We have prepared niobyl nitrate, Nb(NO 3) 3 and characterized it by infrared and Raman spectroscopies. The Density functional theory (DFT) has been used to study its structure and vibrational properties. We have made a comparative work for this compound to evaluate not only the best level of theory but also the best basis set to be used to reproduce the experimental wavenumbers. These calculations gave us a precise knowledge of the normal modes of vibration taking into account the type of coordination adopted by nitrate groups of this compound as monodentate and bidentate ligands. The calculated harmonic vibrational frequencies for niobyl nitrate are consistent with the experimental vibrational spectra. An assignment of the observed spectral features is proposed. The nature of the Nb sbnd O and Nb ← O bonds and the topological properties of electronic charge density in the compound were systematically and quantitatively investigated by means of Natural Bond Order (NBO) and the Bader's Atoms in Molecules theory (AIM), respectively.

  16. DFT calculation of the chromyl nitrate, CrO2(NO3)2 The molecular force field.

    PubMed

    Brandán, S A; Roldán, M L; Socolsky, C; Ben Altabef, A

    2008-03-01

    We have carried out a structural and vibrational theoretical study for chromyl nitrate. The density functional theory has been used to study its structure and vibrational properties. The geometries were fully optimised at the B3LYP/Lanl2DZ, B3LYP/6-31G* and B3LYP/6-311++G levels of theory and the harmonic vibrational frequencies were evaluated at the same levels. The calculated harmonic vibrational frequencies for chromyl nitrate are consistent with the experimental IR and Raman spectra in the solid and liquid phases. These calculations gave us a precise knowledge of the normal modes of vibration taking into account the type of coordination adopted by nitrate groups of this compound as monodentate and bidentate. We have also made the assignment of all the observed bands in the vibrational spectra for chromyl nitrate. The nature of the Cr-O and Cr<--O bonds in the compound were quantitatively investigated by means of Natural Bond Order (NBO) analysis. The topological properties of electronic charge density are analysed employing Bader's Atoms in Molecules theory (AIM).

  17. OECD Maximum Residue Limit Calculator

    EPA Pesticide Factsheets

    With the goal of harmonizing the calculation of maximum residue limits (MRLs) across the Organisation for Economic Cooperation and Development, the OECD has developed an MRL Calculator. View the calculator.

  18. Asymmetric Gaussian harmonic steering in second-harmonic generation

    NASA Astrophysics Data System (ADS)

    Olsen, M. K.

    2013-11-01

    Intracavity second-harmonic generation is one of the simplest of the quantum optical processes and is well within the expertise of most optical laboratories. It is well understood and characterized, both theoretically and experimentally. We show that it can be a source of continuous-variable asymmetric Gaussian harmonic steering with fields which have a coherent excitation, hence combining the important effects of harmonic entanglement and asymmetric steering in one easily controllable device, adjustable by the simple means of tuning the cavity loss rates at the fundamental and harmonic frequencies. We find that whether quantum steering is available via the standard measurements of the Einstein-Podolsky-Rosen correlations can depend on which quadrature measurements are inferred from output spectral measurements of the fundamental and the harmonic. Altering the ratios of the cavity loss rates can be used to tune the regions where symmetric steering is available, with the results becoming asymmetric over all frequencies as the cavity damping at the fundamental frequency becomes significantly greater than at the harmonic. This asymmetry and its functional dependence on frequency is a potential new tool for experimental quantum information science, with possible utility for quantum key distribution. Although we show the effect here for Gaussian measurements of the quadratures, and cannot rule out a return of the steering symmetry for some class of non-Gaussian measurements, we note here that the system obeys Gaussian statistics in the operating regime investigated and Gaussian inference is at least as accurate as any other method for calculating the necessary correlations. Perhaps most importantly, this system is simpler than any other methods we are aware of which have been used or proposed to create asymmetric steering.

  19. Laser-induced fluorescence study of the S1 state of doubly-substituted 13C acetylene and harmonic force field determination.

    PubMed

    Jiang, Jun; Baraban, Joshua H; Park, G Barratt; Clark, Michelle L; Field, Robert W

    2013-12-19

    In the first half of this study, rotational and vibrational constants of six Franck-Condon bright vibrational levels of S1 doubly-substituted (13)C acetylene are determined from laser-induced fluorescence spectra and an updated geometry of the trans conformer of S1 acetylene is obtained. In the second half, we determine the quadratic force field of S1 acetylene on the basis of the harmonic frequencies of four isotopologues of acetylene. The effects of both diagonal and off-diagonal x(ij) anharmonicities are removed from the input harmonic frequencies. Results from both experimental and theoretical studies of various isotopologues of acetylene (including those from the first half of this paper) are used to obtain a set of force constants that agrees well with ab initio calculations. Our set of force constants for S1 acetylene is an improvement over previous work by Tobiason et al., which did not include off-diagonal anharmonicities.

  20. Harmonization of Biodiesel Specifications

    SciTech Connect

    Alleman, T. L.

    2008-02-01

    Worldwide biodiesel production has grown dramatically over the last several years. Biodiesel standards vary across countries and regions, and there is a call for harmonization. For harmonization to become a reality, standards have to be adapted to cover all feedstocks. Additionally, all feedstocks cannot meet all specifications, so harmonization will require standards to either tighten or relax. For harmonization to succeed, the biodiesel market must be expanded with the alignment of test methods and specification limits, not contracted.

  1. 3D field harmonics

    SciTech Connect

    Caspi, S.; Helm, M.; Laslett, L.J.

    1991-03-30

    We have developed an harmonic representation for the three dimensional field components within the windings of accelerator magnets. The form by which the field is presented is suitable for interfacing with other codes that make use of the 3D field components (particle tracking and stability). The field components can be calculated with high precision and reduced cup time at any location (r,{theta},z) inside the magnet bore. The same conductor geometry which is used to simulate line currents is also used in CAD with modifications more readily available. It is our hope that the format used here for magnetic fields can be used not only as a means of delivering fields but also as a way by which beam dynamics can suggest correction to the conductor geometry. 5 refs., 70 figs.

  2. Molecular docking, spectroscopic studies and quantum calculations on nootropic drug.

    PubMed

    Uma Maheswari, J; Muthu, S; Sundius, Tom

    2014-04-05

    A systematic vibrational spectroscopic assignment and analysis of piracetam [(2-oxo-1-pyrrolidineacetamide)] have been carried out using FT-IR and FT-Raman spectral data. The vibrational analysis was aided by an electronic structure calculation based on the hybrid density functional method B3LYP using a 6-311G++(d,p) basis set. Molecular equilibrium geometries, electronic energies, IR and Raman intensities, and harmonic vibrational frequencies have been computed. The assignments are based on the experimental IR and Raman spectra, and a complete assignment of the observed spectra has been proposed. The UV-visible spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies and the maximum absorption wavelengths λmax were determined by the time-dependent DFT (TD-DFT) method. The geometrical parameters, vibrational frequencies and absorption wavelengths were compared with the experimental data. The complete vibrational assignments are performed on the basis of the potential energy distributions (PED) of the vibrational modes in terms of natural internal coordinates. The simulated FT-IR, FT-Raman, and UV spectra of the title compound have been constructed. Molecular docking studies have been carried out in the active site of piracetam by using Argus Lab. In addition, the potential energy surface, HOMO and LUMO energies, first-order hyperpolarizability and the molecular electrostatic potential have been computed.

  3. Raman and infrared spectroscopy, DFT calculations, and vibrational assignment of the anticancer agent picoplatin: performance of long-range corrected/hybrid functionals for a platinum(II) complex.

    PubMed

    Malik, Magdalena; Wysokiński, Rafał; Zierkiewicz, Wiktor; Helios, Katarzyna; Michalska, Danuta

    2014-08-28

    Picoplatin, cis-[PtCl2(NH3)(2-picoline)], is a new promising anticancer agent undergoing clinical trials, which reveals high efficacy against many tumors and greatly reduced toxicity, in comparison to cisplatin. In this work, we present for the first time the Fourier-transform Raman and infrared spectra of picoplatin, in the region of 3500-50 cm(-1). The comprehensive theoretical studies on the molecular structure, the nature of Pt-ligand bonding, vibrational frequencies, and intensities were performed by employing different DFT methods, including hybrid (PBE0, mPW1PW, and B3LYP) and long-range-corrected hybrid density functionals (LC-ωPBE, CAM-B3LYP). Various effective core potentials (ECP) and basis sets have been used. In the prediction of the molecular structure of picoplatin, the best results have been obtained by LC-ωPBE, followed by PBE0, mPW1PW, and CAM-B3LYP density functionals, while the least accurate is B3LYP. The use of the LanL2TZ(f) ECP/basis set for Pt, in conjunction with all tested DFT methods, improves the calculated geometry of the title complex. The PBE0, mPW1PW, and CAM-B3LYP methods have shown the best performance in the calculations of the frequencies of Pt-ligand vibrations. A clear-cut assignment of all the bands in the IR and Raman spectra have been made on the basis of the calculated potential energy distribution (PED). The nature of the "vibrational signatures" of picoplatin have been determined. These results are indispensable for further investigation on drug-target interactions using vibrational spectroscopy.

  4. Single-order laser high harmonics in XUV for ultrafast photoelectron spectroscopy of molecular wavepacket dynamics

    PubMed Central

    Fushitani, Mizuho; Hishikawa, Akiyoshi

    2016-01-01

    We present applications of extreme ultraviolet (XUV) single-order laser harmonics to gas-phase ultrafast photoelectron spectroscopy. Ultrashort XUV pulses at 80 nm are obtained as the 5th order harmonics of the fundamental laser at 400 nm by using Xe or Kr as the nonlinear medium and separated from other harmonic orders by using an indium foil. The single-order laser harmonics is applied for real-time probing of vibrational wavepacket dynamics of I2 molecules in the bound and dissociating low-lying electronic states and electronic-vibrational wavepacket dynamics of highly excited Rydberg N2 molecules. PMID:27795976

  5. Theory of harmonic dissipation in disordered solids

    NASA Astrophysics Data System (ADS)

    Damart, T.; Tanguy, A.; Rodney, D.

    2017-02-01

    Mechanical spectroscopy, i.e., cyclic deformations at varying frequencies, is used theoretically and numerically to compute dissipation in model glasses. From a normal mode analysis, we show that in the high-frequency terahertz regime where dissipation is harmonic, the quality factor (or loss angle) can be expressed analytically. This expression is validated through nonequilibrium molecular dynamics simulations applied to a model of amorphous silica (SiO2). Dissipation is shown to arise from nonaffine relaxations triggered by the applied strain through the excitation of vibrational eigenmodes that act as damped harmonic oscillators. We discuss an asymmetry vector field, which encodes the information about the structural origin of dissipation computed by mechanical spectroscopy. In the particular case of silica, we find that the motion of oxygen atoms, which induce a deformation of the Si-O-Si bonds, is the main contributor to harmonic energy dissipation.

  6. The harmonic oscillator and nuclear physics

    NASA Technical Reports Server (NTRS)

    Rowe, D. J.

    1993-01-01

    The three-dimensional harmonic oscillator plays a central role in nuclear physics. It provides the underlying structure of the independent-particle shell model and gives rise to the dynamical group structures on which models of nuclear collective motion are based. It is shown that the three-dimensional harmonic oscillator features a rich variety of coherent states, including vibrations of the monopole, dipole, and quadrupole types, and rotations of the rigid flow, vortex flow, and irrotational flow types. Nuclear collective states exhibit all of these flows. It is also shown that the coherent state representations, which have their origins in applications to the dynamical groups of the simple harmonic oscillator, can be extended to vector coherent state representations with a much wider range of applicability. As a result, coherent state theory and vector coherent state theory become powerful tools in the application of algebraic methods in physics.

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

    NASA Technical Reports Server (NTRS)

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

    1989-01-01

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

  8. Vibrationally resolved UV/Vis spectroscopy with time-dependent density functional based tight binding.

    PubMed

    Rüger, Robert; Niehaus, Thomas; van Lenthe, Erik; Heine, Thomas; Visscher, Lucas

    2016-11-14

    We report a time-dependent density functional based tight-binding (TD-DFTB) scheme for the calculation of UV/Vis spectra, explicitly taking into account the excitation of nuclear vibrations via the adiabatic Hessian Franck-Condon method with a harmonic approximation for the nuclear wavefunction. The theory of vibrationally resolved UV/Vis spectroscopy is first summarized from the viewpoint of TD-DFTB. The method is benchmarked against time-dependent density functional theory (TD-DFT) calculations for strongly dipole allowed excitations in various aromatic and polar molecules. Using the recent 3ob:freq parameter set of Elstner's group, very good agreement with TD-DFT calculations using local functionals was achieved.

  9. Vibrationally resolved UV/Vis spectroscopy with time-dependent density functional based tight binding

    NASA Astrophysics Data System (ADS)

    Rüger, Robert; Niehaus, Thomas; van Lenthe, Erik; Heine, Thomas; Visscher, Lucas

    2016-11-01

    We report a time-dependent density functional based tight-binding (TD-DFTB) scheme for the calculation of UV/Vis spectra, explicitly taking into account the excitation of nuclear vibrations via the adiabatic Hessian Franck-Condon method with a harmonic approximation for the nuclear wavefunction. The theory of vibrationally resolved UV/Vis spectroscopy is first summarized from the viewpoint of TD-DFTB. The method is benchmarked against time-dependent density functional theory (TD-DFT) calculations for strongly dipole allowed excitations in various aromatic and polar molecules. Using the recent 3ob:freq parameter set of Elstner's group, very good agreement with TD-DFT calculations using local functionals was achieved.

  10. Molecular structure and vibrational assignment of 1-[N-(2-pyridyl) aminomethylidene}-2(1H)-Naphtalenone by density functional theory (DFT) and ab initio Hartree-Fock (HF) calculations

    NASA Astrophysics Data System (ADS)

    Tanak, Hasan; Toy, Mehmet

    2016-01-01

    The molecular geometry and vibrational frequencies of 1-[N-(2-pyridyl)aminomethylidene}-2(1H)-Naphtalenone in the ground state have been calculated by using the Hartree-Fock (HF) and density functional method (B3LYP) with 6-311++G(d,p) basis set. The results of the optimized molecular structure are presented and compared with the experimental X-ray diffraction. The computed vibrational frequencies were used to determine the types of molecular motions associated with each of the experimental bands observed. In addition, calculated results are related to the linear correlation plot of computed data versus experimental geometric parameters and IR data. From the results it was concluded that the B3LYP method is superior to the HF method for the vibrational frequencies. Using the time-dependent density functional theory (TD-DFT) and Hartree-Fock (TD-HF) methods, electronic absorption spectra of the title compound have been predicted and a good agreement with the TD-DFT method and experimental ones is determined.

  11. Molecular structure and vibrational assignment of 1-[N-(2-pyridyl) aminomethylidene}-2(1H)-Naphtalenone by density functional theory (DFT) and ab initio Hartree-Fock (HF) calculations.

    PubMed

    Tanak, Hasan; Toy, Mehmet

    2016-01-05

    The molecular geometry and vibrational frequencies of 1-[N-(2-pyridyl)aminomethylidene}-2(1H)-Naphtalenone in the ground state have been calculated by using the Hartree-Fock (HF) and density functional method (B3LYP) with 6-311++G(d,p) basis set. The results of the optimized molecular structure are presented and compared with the experimental X-ray diffraction. The computed vibrational frequencies were used to determine the types of molecular motions associated with each of the experimental bands observed. In addition, calculated results are related to the linear correlation plot of computed data versus experimental geometric parameters and IR data. From the results it was concluded that the B3LYP method is superior to the HF method for the vibrational frequencies. Using the time-dependent density functional theory (TD-DFT) and Hartree-Fock (TD-HF) methods, electronic absorption spectra of the title compound have been predicted and a good agreement with the TD-DFT method and experimental ones is determined.

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

    SciTech Connect

    Fedorov, Dmitry A.; Varganov, Sergey A.; Derevianko, Andrei

    2014-05-14

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

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

    PubMed

    Fedorov, Dmitry A; Derevianko, Andrei; Varganov, Sergey A

    2014-05-14

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

  14. Vibrational analysis of amino acids and short peptides in hydrated media. I. L-glycine and L-leucine.

    PubMed

    Derbel, Najoua; Hernández, Belén; Pflüger, Fernando; Liquier, Jean; Geinguenaud, Frédéric; Jaïdane, Nejmeddine; Lakhdar, Zohra Ben; Ghomi, Mahmoud

    2007-02-15

    Raman scattering and Fourier-transform infrared (FT-IR) attenuated transmission reflectance (ATR) spectra of two alpha-amino acids (alpha-AAs), i.e., glycine and leucine, were measured in H2O and D2O (at neutral pH and pD). This series of observed vibrational data gave us the opportunity to analyze vibrational features of both AAs in hydrated media by density functional theory (DFT) calculations at the B3LYP/6-31++G* level. Harmonic vibrational modes calculated after geometry optimization on the clusters containing each AA and 12 surrounding water molecules, which represent primary models for hydration scheme of amino acids, allowed us to assign the main observed peaks.

  15. Novel zinc(II) and copper(II) complexes of a Mannich base derived from lawsone: Synthesis, single crystal X-ray analysis, ab initio density functional theory calculations and vibrational analysis

    NASA Astrophysics Data System (ADS)

    Neves, Amanda P.; Vargas, Maria D.; Soto, Claudio A. Téllez; Ramos, Joanna M.; Visentin, Lorenzo do C.; Pinheiro, Carlos B.; Mangrich, Antônio S.; de Rezende, Edivaltrys I. P.

    Zinc(II) and copper(II) complexes of a tridentate Mannich base L1 derived from 2-hydroxy-1,4-naphthoquinone, pyridinecarboxyaldehyde and 2-aminomethylpyridine, [ZnL1Cl2]·H2O 1 and [CuL1Cl2]·2H2O 2, have been synthesized and fully characterized. The structure of complex 1 has been elucidated by a single crystal X-ray diffraction study: the zinc atom is pentacoordinate and the coordination geometry is a distorted square base pyramid, with a geometric structural parameter τ equal to 0.149. Vibrational spectroscopy and ab initio DFT calculations of both compounds have confirmed that the two complexes exhibit similar structures. Full assignment of the vibrational spectra was also supported by careful analysis of the distorted geometries generated by the normal modes

  16. Vibrational and rotational excitation of CO in comets. Part 1: Non-equilibrium calculations. Part 2: Results of the calculation for standard bright comet, comet Iras-Araki-Alcock and comet Halley

    NASA Technical Reports Server (NTRS)

    Chin, G.; Weaver, H. A.

    1984-01-01

    The vibrational and rotational excitation of the CO molecule in cometary comae were investigated using a model which includes IR vibrational pumping by the solar flux, vibrational and rotational radiative decay, and collisional coupling among rotational states. Steady state was not assumed in solving the rate equations. The evolution of a shell of CO gas was monitored as it expanded from the nucleus into the outer coma. Collisional effects were treated using a kinetic temperature profile derived from theoretical work on the coma energy balance. The kinetic temperature was assumed to be extremely cold in the inner coma; this has significant consequences for the CO excitation. If optical depth effects are ignored, only low J transitions will be significantly excited in comets observed at high spatial resolution. Ground-based observations of CO co-vibrational and rotational transitions will be extremely difficult due to lack of sensitivity and/or terrestrial absorption. However, CO should be detectable from a large comet with favorable observing geometry if the CO is a parent molecule present at the 10% level (or greater) relative to H2O. Observations using cooled, spaceborne instruments should be capable of detecting CO emission from even moderately bright comets.

  17. Tautomeric purine forms of 2-amino-6-chloropurine (N9H10 and N7H10): Structures, vibrational assignments, NBO analysis, hyperpolarizability, HOMO-LUMO study using B3 based density functional calculations

    NASA Astrophysics Data System (ADS)

    Balachandran, V.; Parimala, K.

    2012-10-01

    Two purine tautomers of 2-amino-6-chloropurine (ACP), in labeled as N9H10 and N7H10, were investigated by vibrational spectroscopy and quantum chemical method. The FT-IR and FT-Raman spectra of ACP have been recorded in the regions 4000-400 cm-1 and 3500-100 cm-1, respectively. The measured spectra were interpreted by aid of a normal coordinate analysis following DFT full geometry optimization and vibrational frequency calculations at B3LYP/6-311++G(d,p) level. First-order hyperpolarizability, HOMO and LUMO energies were calculated at same level of theory. The calculated molecular geometry has been compared with the X-ray data. The observed and calculated frequencies were found in good agreement. The obtained NBO data and second-order perturbation energy values to elucidate the Lewis and non-Lewis types of bonding structures in the purine tautomer N9H10, have indicated the presence of an intramolecular hyperconjucative interaction between lone pair N and N-C bond orbital.

  18. Tautomeric purine forms of 2-amino-6-chloropurine (N9H10 and N7H10): structures, vibrational assignments, NBO analysis, hyperpolarizability, HOMO-LUMO study using B3 based density functional calculations.

    PubMed

    Balachandran, V; Parimala, K

    2012-10-01

    Two purine tautomers of 2-amino-6-chloropurine (ACP), in labeled as N(9)H(10) and N(7)H(10), were investigated by vibrational spectroscopy and quantum chemical method. The FT-IR and FT-Raman spectra of ACP have been recorded in the regions 4000-400 cm(-1) and 3500-100 cm(-1), respectively. The measured spectra were interpreted by aid of a normal coordinate analysis following DFT full geometry optimization and vibrational frequency calculations at B3LYP/6-311++G(d,p) level. First-order hyperpolarizability, HOMO and LUMO energies were calculated at same level of theory. The calculated molecular geometry has been compared with the X-ray data. The observed and calculated frequencies were found in good agreement. The obtained NBO data and second-order perturbation energy values to elucidate the Lewis and non-Lewis types of bonding structures in the purine tautomer N(9)H(10), have indicated the presence of an intramolecular hyperconjucative interaction between lone pair N and N-C bond orbital.

  19. Vibrational averages along thermal lines

    NASA Astrophysics Data System (ADS)

    Monserrat, Bartomeu

    2016-01-01

    A method is proposed for the calculation of vibrational quantum and thermal expectation values of physical properties from first principles. Thermal lines are introduced: these are lines in configuration space parametrized by temperature, such that the value of any physical property along them is approximately equal to the vibrational average of that property. The number of sampling points needed to explore the vibrational phase space is reduced by up to an order of magnitude when the full vibrational density is replaced by thermal lines. Calculations of the vibrational averages of several properties and systems are reported, namely, the internal energy and the electronic band gap of diamond and silicon, and the chemical shielding tensor of L-alanine. Thermal lines pave the way for complex calculations of vibrational averages, including large systems and methods beyond semilocal density functional theory.

  20. Analysis of potential helicopter vibration reduction concepts

    NASA Technical Reports Server (NTRS)

    Landgrebe, A. J.; Davis, M. W.

    1985-01-01

    Results of analytical investigations to develop, understand, and evaluate potential helicopter vibration reduction concepts are presented in the following areas: identification of the fundamental sources of vibratory loads, blade design for low vibration, application of design optimization techniques, active higher harmonic control, blade appended aeromechanical devices, and the prediction of vibratory airloads. Primary sources of vibration are identified for a selected four-bladed articulated rotor operating in high speed level flight. The application of analytical design procedures and optimization techniques are shown to have the potential for establishing reduced vibration blade designs through variations in blade mass and stiffness distributions, and chordwise center-of-gravity location.