Science.gov

Sample records for calculated harmonic vibrational

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

    NASA Astrophysics Data System (ADS)

    Hanson-Heine, Magnus W. D.

    2015-10-01

    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. Harmonic calculations and measurements of the irreversibility field using a vibrating sample magnetometer

    E-print Network

    Hampshire, Damian

    magnetometer Ian J. Daniel and Damian P. Hampshire Department of Physics, Superconductivity Group, University inhomogeneity of the magnet on a vibrating sample magnetometer VSM measure- ment of a superconductor measurements on superconductors using a Vi- brating Sample Magnetometer12 VSM . Harmonic VSM measurements

  3. Estimating the carbonyl anharmonic vibrational frequency from affordable harmonic frequency calculations.

    PubMed

    Buczek, Aneta; Kupka, Teobald; Sauer, Stephan P A; Broda, Ma?gorzata A

    2012-06-01

    A linear correlation between harmonic and anharmonic frequencies of water calculated at B3LYP level of theory was observed with a number of basis sets. Similar relationships were found in both the gas phase and solution for several small molecules. The best correlation was found for C = O stretch mode in formaldehyde, formamide and N-methylacetamide. The average difference between B3LYP harmonic and anharmonic ?(C = O) frequencies calculated with several basis sets in these molecules was 30 cm(-1). The ad hoc correction of -30 cm(-1), added to harmonic frequencies of two different carbonyl groups present in a structure of a larger molecule was tested as a fast way of predicting anharmonic frequencies without elaborated calculations. The proposed approach was tested successfully on a larger molecule of E and Z isomers of N-acetyl-?,?-dehydrophenylalanine N',N'-dimethylamide [Ac-(E/Z)-?Phe-NMe(2)] and the estimated anharmonic ?(C = O) frequencies were close to directly calculated results. PMID:22015591

  4. 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 ?* and ?* 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Index calculation by means of harmonic expansion

    E-print Network

    Yosuke Imamura

    2015-10-28

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

  10. Index calculation by means of harmonic expansion

    E-print Network

    Imamura, Yosuke

    2015-01-01

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

  11. Quasi-harmonic Calculations of the Thermal Expansion of Metals

    NASA Astrophysics Data System (ADS)

    Quong, Andrew A.; Liu, Amy Y.

    1997-03-01

    Many problems in material science, such as phase stablity, growth, and diffusion, require the determination of accurate energetics at finite temperature. Electronic structure calculations enable very accurate determinations of energies from first-principles for a wide range of systems. However, these calculations are performed at zero temperature. The vibrational contribution to the free energy can be obtained through the quasi-harmonic approximation, where the vibriational modes are determined from first-princples using linear response theory. We will present results for the thermal expansion and the temperature dependence of the bulk modulus for several s-p bonded metals.

  12. Quasi-harmonic Calculations of the Thermal Expansion of Metals

    NASA Astrophysics Data System (ADS)

    Quong, Andrew A.

    1997-08-01

    Electronic structure calculations enable very accurate determinations of energies from first-principles for a wide range of systems. However, these calculations are performed at zero temperature and many materials properties are very temperature dependent. In particular, the elastic constants of a material may vary significantly with temperature. Results for the temperature dependence of the elastic constants of Al will be presented. The vibrational contribution to the free energy is be obtained through the quasi-harmonic approximation, where the vibriational modes are determined from first-princples using linear response theory.

  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. Forced harmonic vibration of a Duffing oscillator with

    E-print Network

    5 Forced harmonic vibration of a Duffing oscillator with linear viscous damping Tamas Kalmar-Nagy1 of Mechanical Engineering, University of Maryland, USA 5.1 Introduction The Duffing oscillator has become- order models of complex mechanical systems ranging from microscales to macroscales [3

  15. Variational calculations of vibrational properties of ozone

    NASA Technical Reports Server (NTRS)

    Carney, G. D.; Curtiss, L. A.; Langhoff, S. R.

    1977-01-01

    A variational method is used to obtain vibrational-rotational properties for ozone from an experimental quartic force field. Band positions, average structures, matrix elements for calculating infrared intensities, and effective rotational constants are reported for (O-16)3 and its O-18 isotopic species. Also, the degree to which the vibrational energies and properties are converged is investigated as a function of the basis set parameters and basis set size, and of the method of obtaining the Hamiltonian matrix elements. A convenient procedure for assigning the vibrational states is developed for variational vibrational wavefunction expansions.

  16. 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.

  17. Intermolecular Vibrations in Hydrophobic Amino Acid Crystals: Experiments and Calculations

    E-print Network

    Intermolecular Vibrations in Hydrophobic Amino Acid Crystals: Experiments and Calculations Michael-8107, United States *S Supporting Information ABSTRACT: Intermolecular vibrations of amino acid crystals occur not previously been compared. Theoretical modeling of intermolecular vibrations in hydrophobic amino acids

  18. Enhancement of high-harmonic generation by laser-induced cluster vibration

    E-print Network

    Enhancement of high-harmonic generation by laser-induced cluster vibration Yen-Mu Chen,1,2 Ming a new tool for studying the vibrational dynamics of nanometer atomic clusters. © 2007 Optical Society vibration was reported [8], and the results indicate that HHG is a very sensitive probe for vibrational

  19. 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.

  20. Optimized coordinates in vibrational coupled cluster calculations

    NASA Astrophysics Data System (ADS)

    Thomsen, Bo; Yagi, Kiyoshi; Christiansen, Ove

    2014-04-01

    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.

  1. 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

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

    PubMed

    Xu, Xiangbo; Chen, Shao

    2015-01-01

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

  3. 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.

  4. Heat Conduction in a One-Dimensional Harmonic Chain with Three-Dimensional Vibrations

    E-print Network

    Li, Baowen

    Heat Conduction in a One-Dimensional Harmonic Chain with Three-Dimensional Vibrations Zonghua LIU1 chain connected by three-dimensional (3D) harmonic springs, the coefficient of heat conduction changes where the coefficient is independent of the lattice constant. KEYWORDS: heat conduction, harmonic chain

  5. Ground vibration due to a high-speed moving harmonic rectangular load on a

    E-print Network

    Avignon et des Pays de Vaucluse, Université de

    Ground vibration due to a high-speed moving harmonic rectangular load on a poroviscoelastic half'Avignon, Facult´e des Sciences, 33 rue Louis Pasteur, F-84000 Avignon, France RUNNING TITLE: Vibrations induced) #12;Abstract The transmission of vibrations in the ground, due to a high-speed moving vertical har

  6. Multiphoton ionization photoelectron spectroscopy of phenol: Vibrational frequencies and harmonic force field for the 281 cation

    E-print Network

    Multiphoton ionization photoelectron spectroscopy of phenol: Vibrational frequencies and harmonic 94305 (Recieved 1 February 1985; accepted 14 March 1985) A molecular beam of phenol, cooled vibrational frequencies for the 2BI phenol-h6cation and ten vibrational frequencies for phenol-d5. Of these

  7. Toward large scale vibrational configuration interaction calculations

    NASA Astrophysics Data System (ADS)

    Neff, Michael; Rauhut, Guntram

    2009-09-01

    The implementation of a state-specific configuration-selective vibrational configuration interaction (cs-VCI) approach based on a polynomial representation of the potential energy surface is presented. Advantages over grid-based algorithms are discussed. A combination of a configuration selection criterion, the simultaneous exclusion of irrelevant configurations, and an internal contraction scheme allow to handle large variational spaces. A modified version of the iterative Jacobi-Davidson diagonalization has been used to determine relevant internal eigenpairs of the cs-VCI matrices in the selected space. Benchmark calculations are provided for systems with up to 2×107 configurations and three-mode couplings in the expansion of the potential.

  8. Dynamical properties of an harmonic oscillator impacting a vibrating wall.

    PubMed

    de Alcantara Bonfim, O F

    2009-05-01

    The dynamics of a spring-mass system under repeated impact with a vibrating wall is investigated using the static wall approximation. The evolution of the harmonic oscillator is described by two coupled difference equations. These equations are solved numerically, and in some cases exact analytical expressions have also been found. For a periodically vibrating wall, Fermi acceleration is only found at resonance. There, the average rebounding velocity increases linearly with the number of collisions. Near resonance, the average rebounding velocity grows initially with the number of collisions and eventually reaches a plateau. In the vicinity of resonance, the motion of the oscillator exhibits scaling properties over a range of frequency ratios. The presence of dissipation at resonance destroys the Fermi-acceleration process and induces scaling behavior similar to that at near resonance. For a moving wall with a random amplitude at collisions, Fermi acceleration is observed independently of the ratio between the wall and oscillator frequencies. In this case the average rebounding velocity grows with the square root of the number of collisions with the wall. Also, in this latter case, dissipation suppresses the Fermi-acceleration mechanism and induces a scaling behavior with the same universality class as that of the dissipative bouncing ball model with random external perturbations. PMID:19518541

  9. Dynamical properties of an harmonic oscillator impacting a vibrating wall

    NASA Astrophysics Data System (ADS)

    de Alcantara Bonfim, O. F.

    2009-05-01

    The dynamics of a spring-mass system under repeated impact with a vibrating wall is investigated using the static wall approximation. The evolution of the harmonic oscillator is described by two coupled difference equations. These equations are solved numerically, and in some cases exact analytical expressions have also been found. For a periodically vibrating wall, Fermi acceleration is only found at resonance. There, the average rebounding velocity increases linearly with the number of collisions. Near resonance, the average rebounding velocity grows initially with the number of collisions and eventually reaches a plateau. In the vicinity of resonance, the motion of the oscillator exhibits scaling properties over a range of frequency ratios. The presence of dissipation at resonance destroys the Fermi-acceleration process and induces scaling behavior similar to that at near resonance. For a moving wall with a random amplitude at collisions, Fermi acceleration is observed independently of the ratio between the wall and oscillator frequencies. In this case the average rebounding velocity grows with the square root of the number of collisions with the wall. Also, in this latter case, dissipation suppresses the Fermi-acceleration mechanism and induces a scaling behavior with the same universality class as that of the dissipative bouncing ball model with random external perturbations.

  10. 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.

  11. Attosecond Probing of Vibrational Dynamics with High-Harmonic Generation Manfred Lein*

    E-print Network

    Lein, Manfred

    Attosecond Probing of Vibrational Dynamics with High-Harmonic Generation Manfred Lein* Max Planck into the time scale below one femtosecond. One method [1] utilizes attosecond light pulses obtained from high-order harmonic generation (HHG). In this scheme, the attosecond pulse triggers an atomic process which

  12. Abstract. Scaling factors for obtaining fundamental vibrational frequencies from harmonic frequencies

    E-print Network

    Schlegel, H. Bernhard

    Abstract. Scaling factors for obtaining fundamental vibrational frequencies from harmonic harmonic frequen- cy scaling factors for ®rst- and second-row molecules were derived from a comparison scaling factors for use with the Sadlej pVTZ basis set are 0.9066, 0.9946, 1.0047, 0.9726, 0.9674 and 0

  13. Beyond vibrational self-consistent-field methods: Benchmark calculations for the fundamental vibrations of ethylene

    NASA Astrophysics Data System (ADS)

    Christiansen, Ove; Luis, Josep M.

    A number of different methods for calculation of vibrational energies are reviewed and tested for calculation of the fundamental vibrational frequencies for ethylene. The methods tested for the description of the vibrational states are vibrational self-consistent field (VSCF), vibrational configuration interaction (VCI), vibrational Møller-Plesset theory (VMP), and vibrational coupled cluster (VCC). The convergence of the different methods toward the full vibrational configuration interaction (FVCI) result is discussed for a modest-sized one-mode basis. For larger one-mode basis sets results are presented for selected methods. Different representations of the potential energy surface are compared including full and partial quartic force field as well as expansions using up to sixth derivatives of the potential energy surface. Using MP2 electronic structure theory, the electronic structure basis set convergence is tested.

  14. 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.

  15. Calculation of oscillations generated by a vibrator in a boundary layer of an incompressible fluid

    NASA Astrophysics Data System (ADS)

    Manuilovich, S. V.

    Consideration is given to the problem of the excitation of small oscillations in flow of a viscous incompressible fluid by a vibrator generationg harmonic oscillations at the bottom of the boundary layer. The well posedness of the problem for a linearized system of Navier-Stokes equations is investigated by the Fourier method. An asymptotic analysis of the perturbed flow downstream makes it possible to determine the amplitude of the generated Tollmien-Schlichting wave. Calculations are made of the perturbation pressure in the vicinity of the vibrator.

  16. 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.

  17. Anharmonic calculation of the structure, vibrational frequencies and intensities of the NH3···trans-HONO complex.

    PubMed

    Bulychev, Valentin P; Buturlimova, Marina V; Tokhadze, Konstantin G

    2013-09-19

    The equilibrium geometry of the NH3···trans-HONO complex and the harmonic vibrational frequencies and intensities are calculated in the MP2/aug-cc-pVTZ approximation with the basis set superposition error taken into account. Effects of anharmonic interactions on spectroscopic parameters are studied by solving vibrational Schrödinger equations in 1-4 dimensions using the variational method. Anharmonic vibrational equations are formulated in the space of normal coordinates of the complex. Detailed analysis is performed for the H-bond stretching vibration and internal vibrations of the trans-HONO isomer in the complex. The intermode anharmonicity and anharmonic coupling between two, three, and four vibrational modes are studied on the basis of correct ab initio potential energy surfaces calculated in the above approximation. The combinations of normal modes of the complex most strongly coupled to one another are examined. The calculated frequencies and intensities of vibrational bands are compared with the experimental data on the NH3···trans-HONO complex in an argon matrix and results of earlier calculations of monomeric HONO. In this calculation the strong resonance between the first excited state of the OH stretching vibration and the doubly excited state of the NOH bending vibration of trans-HONO isomer in the complex is thoroughly studied by solving vibrational equations in two and four dimensions. PMID:23944642

  18. Full dimensional Franck-Condon factors for the acetylene [~ over A] [superscript 1]A[subscript u] — [~ over X] [superscript 1?[+ over g] transition. I. Method for calculating polyatomic linear—bent vibrational intensity factors and evaluation of calculated intensities for the gerade vibrational modes in acetylene

    E-print Network

    Park, Barratt

    Franck-Condon vibrational overlap integrals for the [~ over A] [superscript 1]A[subscript u] — [~ over X [superscript 1]?[+ over g] transition in acetylene have been calculated in full dimension in the harmonic normal mode ...

  19. 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.

  20. Efficient calculation of anharmonic vibrational spectra of large molecules with localized modes.

    PubMed

    Panek, Pawe? T; Jacob, Christoph R

    2014-10-20

    The analysis and interpretation of the vibrational spectra of complex (bio)molecular systems, such as polypeptides and proteins, requires support from quantum-chemical calculations. Such calculations are currently restricted to the harmonic approximation. Here, we show how one of the main bottlenecks in such calculations, the evaluation of the potential energy surface, can be overcome by using localized modes instead of the commonly employed normal modes. We apply such local vibrational self-consistent field (L-VSCF) and vibrational configuration interaction (L-VCI) calculations to a cyclic water tetramer and a helical hexa-alanine peptide. The results show that the use of localized modes is equivalent to the commonly used normal modes, but offers several advantages. First, a faster convergence with respect to the excitation level is observed in L-VCI calculations. Second, the localized modes provide a reduced representation of the couplings between modes that show a regular coupling pattern. This can be used to disregard a significant number of small two-mode potentials a priori. Several such reduced coupling approximations are explored, and we show that the number of single-point calculations required to evaluate the potential energy surface can be significantly reduced without introducing noticeable errors in the resulting vibrational spectra. PMID:25080397

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

    PubMed Central

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

    2015-01-01

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

  2. 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

    2015-01-01

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

  3. 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.

  4. 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 requirements by increasing harvested power, shifting optimal conditioning impedance, inducing significant voltage supply fluctuations and ultimately rendering idealized sinusoidal and random analyses insufficient.

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

    PubMed

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

    2015-01-01

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

  6. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  8. 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 operating in a transition flight regime and for an articulated rotor operating at the level-flight boundary (high speed and high thrust conditions) indicate that blade parameters including flap, lag, torsion stiffness distributions, linear pretwist, chordwise offset of center-of-mass from elastic axis and chordwise offset of elastic axis from aerodynamic center can be selected to minimize the actuator power requirements for HHC.

  9. Vibronic-structure tracking: a shortcut for vibrationally resolved UV/Vis-spectra calculations.

    PubMed

    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. PMID:25362280

  10. 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.

  11. 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.

  12. A harmonic balance method for the non-linear vibration of viscoelastic shells

    NASA Astrophysics Data System (ADS)

    Boutyour, El Hassan; Daya, El Mostafa; Potier-Ferry, Michel

    2006-01-01

    In this Note, we deal with the non-linear vibration of viscoelastic shell structures. Coupling a harmonic balance method with a one mode Galerkin's procedure, one obtains an amplitude equation depending on two complex coefficients. These are determined by solving a classical eigenvalue problem and two linear problems. This permits us to characterize the evolution of the loss factor with the vibration amplitude. To validate our approach, the amplitude-frequency and the amplitude-loss factor relationships are illustrated in the case of a circular ring. To cite this article: E.H. Boutyour et al., C. R. Mecanique 334 (2006).

  13. Vibrational spectra and density functional theoretical calculations on the anti-neurodegenerative drug: Orphenadrine hydrochloride

    NASA Astrophysics Data System (ADS)

    Edwin, Bismi; Hubert Joe, I.

    2012-11-01

    Vibrational spectral analysis and quantum chemical computations based on density functional theory have been performed on the anti-neuro-degenerative drug Orphenadrine hydrochloride. The geometry, intermolecular hydrogen bond, and harmonic vibrational frequencies of the title molecule have been investigated with the help of B3LYP method. The calculated molecular geometry has been compared with the experimental data. The various intramolecular interactions have been exposed by natural bond orbital analysis. The distribution of Mulliken atomic charges and bending of natural hybrid orbitals also reflect the presence of intramolecular hydrogen bonding. The analysis of the electron density of HOMO and LUMO gives an idea of the delocalization and low value of energy gap indicates electron transport in the molecule and thereby bioactivity. Effective docking of the drug molecule with NMDA receptor subunit 3A also enhances its bioactive nature.

  14. Electron-impact vibrational excitation of polyatomic gases: Exploratory calculations

    E-print Network

    Electron-impact vibrational excitation of polyatomic gases: Exploratory calculations M. Cascella, which have been directed to the development of specific particle beams, of selected molecular lasers, and to designing low-temperature multicomponent molecular plasmas for chemical vapor deposition technology.4

  15. REGULAR PAPER Vibrational mode frequency calculations of chlorophyll-d

    E-print Network

    Hastings, Gary

    REGULAR PAPER Vibrational mode frequency calculations of chlorophyll-d for assessing (P740+ -P740 that utilizes chlorophyll-d for light induced photochemistry. In photosystem I particles from Acary- ochloris marina, the primary electron donor is called P740, and it is thought that P740 consist of two chlorophyll

  16. 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.

  17. Harmonic two-phonon {gamma}-vibrational state in neutron-rich {sup 106}Mo

    SciTech Connect

    Guessous, A.; Schulz, N.; Phillips, W.R.; Ahmad, I.; Bentaleb, M.; Durell, J.L.; Jones, M.A.; Leddy, M.; Lubkiewicz, E.; Morss, L.R.; Piepenbring, R.; Smith, A.G.; Urban, W.; Varley, B.J.

    1995-09-18

    The neutron-rich {sup 106}Mo nucleus has been studied by prompt {gamma}-ray spectroscopy following the spontaneous fission of {sup 248}Cm. The characteristics of the rotational band built on a state at 1435 keV identifies the band head as the best candidate for a harmonic double-phonon {ital K}{sup {pi}}=4{sup +} {gamma}-vibrational state observed so far.

  18. 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.

  19. Investigation of the vibration of a blade with friction damper by HBM. [Harmonic Balance Method

    SciTech Connect

    Wang, J.H.; Chen, W.K. )

    1993-04-01

    The friction damper has been widely used to reduce the resonant vibration of blades. The most commonly used methods for studying the dynamic behavior of a blade with a friction damper are direct integration methods. Although the harmonic balance method (HBM) is a well-known method for studying nonlinear vibration problems, generally only a one-term approximation has been proposed to study the nonlinear vibration of a frictionally damped blade. In this work, a HMB procedure with a multiterm approximation is proposed. The results show that the steady-state response and other related behavior of a frictionally damped blade can be predicted accurately and quickly by an HBM with a multiterm approximation.

  20. 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.

  1. A theoretical vibrational spectroscopic study with density functional theory and force field refinement calculation methods on free 4-aminopyrimidine molecule

    NASA Astrophysics Data System (ADS)

    Balci, K.; Akyuz, S.

    2005-06-01

    A detailed investigation of the geometric structure, force field, electro-optical parameters, relative IR intensities and harmonic vibrational wavenumbers of free 4-aminopyrimidine molecule (4APM) in the electronically ground state has been carried out by using both the DFT-B3LYP (with 6-31++G(d,p) double and 6-311++G(d,p) triple basis sets) and force field refinement calculation methods. The vibrational wavenumbers calculated with DFT method were scaled by using two different methods: (1) scaling with dual scaling factors, (2) deriving the scaling factors from the graph of observed versus calculated wavenumbers. In the case of force field refinement method, the force constants of the pyrimidine were slightly refined so as to fit the calculated wavenumbers to the experimental ones. In order to define the contributions of the internal coordinates of the molecule on its each normal vibrational mode, P.E.D. calculations were performed. In wavenumber and PED calculations, both methods have yield results in agreement with the experimental assignment and also with each other, particularly for ring vibrations. The relative IR intensities calculated by the force field refinement method are considerably in good agreement with experimental ones, however, the results of the IR intensities, obtained from the DFT method are found to be significantly different from the experimental values.

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

    PubMed

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

    2015-11-01

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

  3. 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.

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

    NASA Astrophysics Data System (ADS)

    Jiang, Hao; Yeatman, Eric M.

    2013-12-01

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

  5. 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.

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

    SciTech Connect

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

    2011-10-28

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

  7. Large Vibrational Effects upon Calculated Phase Boundaries in Al-Sc

    SciTech Connect

    Ozolin s, 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.

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

    PubMed

    Ozoli?s, 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. PMID:11177852

  9. 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 ?, b = 8.477 ± 0.045 ?, c = 6.983 ± 0.015, ? = ? 90° and ? = 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.

  10. 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.

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

    NASA Astrophysics Data System (ADS)

    Kongsted, Jacob; Christiansen, Ove

    2006-09-01

    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 Møller-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.

  12. ORIGINAL PAPER Calculation of infrared and Raman vibration modes of magnesite

    E-print Network

    Cattin, Rodolphe

    ORIGINAL PAPER Calculation of infrared and Raman vibration modes of magnesite at high pressure) are used to obtain infrared (IR) and Raman magnesite vibration modes as they vary with pressure up to 50 approaches of vibrations in crystals based on empirical models suffer several drawbacks lead- ing

  13. 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.

  14. 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

    2015-10-01

    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. PMID:26450293

  15. 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)

  16. 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.

  17. 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.

  18. 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. PMID:22925973

  19. 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.

  20. 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 ?ab(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 line list can be used for modelling atmospheres of (exo)planets at elevated temperatures.

  1. 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.

  2. 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 effective way, which allows us to calculate matrix of the brackets up to a few hundred times more rapidly and more accurate than in a previous version. Solution method: Using external parallelization libraries and mutable precision we created a pack of numerical codes based on the methods of compact expressions of the three and four-particle harmonics oscillator brackets 3HOB, 4HOB, presented in [3]. Restrictions: For double precision version calculations can be done up to harmonic oscillator (HO) energy quanta e=28. For quadruple precision mantissa is equal to approximately 34 decimal digits, therefore calculations can be done up to HO energy quanta to e=52. Running time: The running time depends on the harmonic oscillator energy quanta, cluster size and the precision of intermediate calculations. More information on Table 1 for 3HOB and Table 2 for 4HOB. Reasons for a new version: The new program version expands the limits of harmonic oscillator energy quanta and gives shorter calculation time. Extend the limits of calculation of HOB First version was able to produce harmonic oscillator transformation brackets for three and four particles if E?HO energy quanta. With this version of our program, if quadruple or arbitrary precision functions are being used, it is possible to calculate three and four particle harmonic oscillator transformation brackets for greater values of energy and momenta, while sustaining tolerable margin of error. Calculation time As the code of previous version of program was redone using parallelism paradigma, it is now possible to reduce the calculation time of transformation matrices significantly, depending on the size of computing cluster, as the dimensions of matrices are growing very rapidly according to the energy and momenta values. subroutinematrix_4HOB_dimensionCalculates the dimension of 4HOB matrix. subroutinematrix_3HOB_dimensionCalculates the dimension of 3HOB matrix, subroutinematrix_3HOBCalculates the global state array which is used in parallel calculation of 3HOB matrix. subroutinematrix_4HOBCalculates the global sta

  3. 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 ?(*) and ?(*) 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 (?) and the first order hyperpolarizability (?) 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. PMID:24096066

  4. Fragment quantum chemical approach to geometry optimization and vibrational spectrum calculation of proteins.

    PubMed

    Liu, Jinfeng; Zhang, John Z H; He, Xiao

    2016-01-21

    Geometry optimization and vibrational spectra (infrared and Raman spectra) calculations of proteins are carried out by a quantum chemical approach using the EE-GMFCC (electrostatically embedded generalized molecular fractionation with conjugate caps) method (J. Phys. Chem. A, 2013, 117, 7149). The first and second derivatives of the EE-GMFCC energy are derived and employed in geometry optimization and vibrational frequency calculations for several test systems, including a polypeptide ((GLY)6), an ?-helix (AKA), a ?-sheet (Trpzip2) and ubiquitin (76 residues with 1231 atoms). Comparison of the present results with those obtained from full system QM (quantum mechanical) calculations shows that the EE-GMFCC approach can give accurate molecular geometries, vibrational frequencies and vibrational intensities. The EE-GMFCC method is also employed to simulate the amide I vibration of proteins, which has been widely used for the analysis of peptide and protein structures, and the results are in good agreement with the experimental observations. PMID:26686896

  5. A hybrid variational-perturbation calculation of the ro-vibrational spectrum of nitric acid

    E-print Network

    Pavlyuchko, A I; Tennyson, Jonathan

    2014-01-01

    Rotation-vibration spectra of the nitric acid molecule, HNO\\3, are calculated for wavenumbers up to 7000~\\cm. Calculations are performed using a Hamiltonian expressed in internal curvilinear vibrational coordinates solved using a hybrid variational-perturbation method. An initial potential energy surface (PES) and dipole moment function (DMF) are calculated {\\it ab initio} at the CCSD(T)/aug-cc-pVQZ level of theory. Parameters of the PES and DMF are varied to minimize differences between the calculated and experimental transition frequencies and intensities. The average, absolute deviation between calculated and experimental values is 0.2~\\cm\\ for frequencies in the fundamental bands and 0.4~\\cm\\ for those in the first overtone and lowest combination bands. For the intensities, the calculated and experimental values differ by 0.3\\% and 40\\% for the fundamentals and overtones, respectively. The optimized PES and DMF are used to calculate the room-temperature ro-vibrational spectrum. These calculation reproduce...

  6. On complex resonance vibration systems calculation S.B. Karavashkin and O.N. Karavashkina

    E-print Network

    On complex resonance vibration systems calculation S.B. Karavashkin and O.N. Karavashkina Special end elements, we will analyse the vibration pattern in systems having such structure. We will find: Mathematical physics, Wave physics, Many­body theory, Complex resonance sys­ tems, ODE, nonlinear dynamics

  7. 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.

  8. Microwave, structural, conformational, vibrational studies and ab initio calculations of fluoroacetyl chloride.

    PubMed

    Deodhar, Bhushan S; Brenner, Reid E; Klaassen, Joshua J; Tubergen, Michael J; Durig, James R

    2015-09-01

    The infrared and Raman spectra (3200-50 cm(-1)) of the gas, liquid or solution, and solid of fluoroacetyl chloride, FCH2COCl have been recorded. FT-microwave studies have also been carried out and 22 transitions were recorded for the trans conformer. Variable temperature (-50 to -105 °C) studies of the infrared and Raman spectra (3200-50 cm(-1)) of xenon solutions have been carried out. From these data, the trans, cis and gauche conformers have been identified and their relative stabilities obtained. The enthalpy difference has been determined to be 159±11 cm(-1) (1.90±0.14 kJ mol(-1)) with the trans conformer the more stable form than the cis. The energy difference between the cis and gauche form is 222±18 cm(-1) (2.66±0.21 kJ/mol) and the energy difference between the trans and gauche forms is 386±13 cm(-1) (4.61±0.16 kJ/mol). Vibrational assignments have been made for the observed bands for the three conformers with initial predictions by MP2(full)/6-31G(d) ab initio calculations to obtain harmonic force constants, wavenumbers, infrared intensities, and Raman activities for the three conformers. By utilizing the microwave rotational constants of two isotopomers for trans, combined with the structural parameters predicted from MP2(full)/6-311+G(d,p) calculations, adjusted r0 parameters have been obtained for the trans conformer. The results are discussed and compared to the corresponding properties of some related molecules. PMID:25909903

  9. Microwave, structural, conformational, vibrational studies and ab initio calculations of fluoroacetyl chloride

    NASA Astrophysics Data System (ADS)

    Deodhar, Bhushan S.; Brenner, Reid E.; Klaassen, Joshua J.; Tubergen, Michael J.; Durig, James R.

    2015-09-01

    The infrared and Raman spectra (3200-50 cm-1) of the gas, liquid or solution, and solid of fluoroacetyl chloride, FCH2COCl have been recorded. FT-microwave studies have also been carried out and 22 transitions were recorded for the trans conformer. Variable temperature (-50 to -105 °C) studies of the infrared and Raman spectra (3200-50 cm-1) of xenon solutions have been carried out. From these data, the trans, cis and gauche conformers have been identified and their relative stabilities obtained. The enthalpy difference has been determined to be 159 ± 11 cm-1 (1.90 ± 0.14 kJ mol-1) with the trans conformer the more stable form than the cis. The energy difference between the cis and gauche form is 222 ± 18 cm-1 (2.66 ± 0.21 kJ/mol) and the energy difference between the trans and gauche forms is 386 ± 13 cm-1 (4.61 ± 0.16 kJ/mol). Vibrational assignments have been made for the observed bands for the three conformers with initial predictions by MP2(full)/6-31G(d) ab initio calculations to obtain harmonic force constants, wavenumbers, infrared intensities, and Raman activities for the three conformers. By utilizing the microwave rotational constants of two isotopomers for trans, combined with the structural parameters predicted from MP2(full)/6-311+G(d,p) calculations, adjusted r0 parameters have been obtained for the trans conformer. The results are discussed and compared to the corresponding properties of some related molecules.

  10. Tunable harmonic vibrations of quasi one-dimensional conductors induced by sliding charge-density waves

    NASA Astrophysics Data System (ADS)

    Nikitin, M. V.; Zybtsev, S. G.; Pokrovskii, V. Ya.

    2012-07-01

    We demonstrate that samples of quasi one-dimensional compounds show torsional vibrations induced by the sliding charge-density wave (CDW). Narrowband noise at the fundamental frequency is found in the vibrations spectra. The result suggests an approach to studies of the CDW dynamics and presents CDW conductors as tunable (ultra)sonic acoustoelectronic generators—unique solids vibrating under dc voltage.

  11. 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. PMID:25579654

  12. Theoretical probation of FClCOCl2 molecular complex : Post Hartree-Fock studies on molecular structures, stabilities and vibrational harmonic frequencies

    NASA Astrophysics Data System (ADS)

    Nowek, Andrzej; Reddy, Shirisha; LeszczySki, Jerzy

    1994-12-01

    Potential energy surfaces of the weak FClCO⋯Cl 2 complex were studied using ab initio post Hartree-Fock theory at the MP2 and MP4 levels with 6-311G(d) and 6-311G(2d) basis sets. Two minimum energy conformations, first-order transition state and two second-order transition structures were found. The minimum energy forms (C and T) are separated by a small (less than 0.5 kcal/mol) barrier. At the MP2/6-311G(d) level their relative stabilities amount to -0.63 and -0.60 kcal/mol for C and T conformers, respectively, where at the MP2/6-311G(2d) approximation stabilities of both forms rise to -1.09 and -1.21 kcal/mol. The harmonic vibrational frequencies were calculated and compared with available experimental data.

  13. Infrared and Raman spectra, conformational stability, vibrational assignment and ab initio calculations of methylvinyl silyl chloride

    NASA Astrophysics Data System (ADS)

    Durig, James R.; Hur, Seung Won; Guirgis, Gamil A.

    2003-09-01

    The infrared spectra (3200-50 cm -1) of gaseous and solid and Raman spectra (3200-10 cm -1) of the liquid and solid methylvinyl silyl chloride, CH 2?CHSiH(CH 3)Cl, and the Si-d isotopomer have been recorded. The three expected stable conformers (the three different groups eclipsing the double bond) have been identified in the fluid phase, but it was not possible to obtain an annealed solid with a single conformer. 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 differences between the most stable conformer with the hydrogen atom (HE) eclipsing the double bond to that with the chlorine atom (ClE) and the methyl group (ME) eclipsing the double bond have been determined to be 17±4 cm -1 (203±48 J mol -1) and 80±12 cm -1 (957±144 J mol -1), respectively. However in the liquid state the ME conformer is the most stable form with enthalpy differences of 13±4 and 27±7 cm -1 to the HE and ClE rotamers, respectively. It is estimated that there is 39% of the HE conformer, 35% of the ClE conformer, and 26% of the ME conformer present at ambient temperature. A complete vibration assignment is proposed for the HE conformer which is based on infrared band contours and group frequencies, which is supported by normal coordinate calculations utilizing the force constants from ab initio MP2/6-31G(d) calculations. Additionally, several of the fundamentals for the other two conformers have been assigned. The optimal geometries, conformational stabilities, harmonic force fields, infrared intensities, Raman activities, depolarization ratios, and vibrational frequencies are reported for all three conformers from MP2/6-31G(d,p) ab initio calculations with full electron correlation. Optimized geometrical parameters and conformational stabilities have been obtained from MP2/6-311+G(d,p) calculations. At this highest level of calculations, the HE conformer is predicted to be more stable by 62 and 84 cm -1 than the ME and ClE conformers, respectively. The coefficients from the potential function governing the conformational interchange have been obtained from the MP2/6-31G(d) ab initio calculations. By utilizing the frequency of the SiH stretching mode, the r0 Si?H distance has been determined to be 1.481 Å for the HE conformer. The ab initio calculated quantities are compared to the experimentally determined values where applicable, as well as to some corresponding results for some similar molecules.

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

    PubMed

    Petrenko, Taras; Rauhut, Guntram

    2015-12-21

    The calculation of vibronic spectra and resonance Raman intensities can be performed on the basis of the Raman wavefunction (RWF) formalism. In general, the well-known sum-over-states (SOS) and time-dependent methods can be applied for calculating the RWF. We present an alternative route in which the RWF is determined pointwise in a spectral range on the basis of the inhomogeneous Schrödinger equation using an iterative subspace method, in which explicit state-by-state calculations of vibrational eigenstates are bypassed. We study this approach within the framework of vibrational configuration interaction theory in conjunction with high-level electronic structure calculations for the multidimensional Born-Oppenheimer potential energy surface. The method benefits from an implicit account of interference effects between vibrational states, so that its computational cost correlates with the required resolution in the spectra. The accuracy and efficiency of the method with respect to comparable SOS calculations are tested for the simulation of the photoelectron spectra of ClO2, HS2 (-), ZnOH(-), and Zn(H2O)(+). PMID:26696045

  15. 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.

  16. Lattice Monte Carlo calculations for unitary fermions in a harmonic trap

    SciTech Connect

    Endres, Michael G.; Kaplan, David B.; Lee, Jong-Wan; Nicholson, Amy N.

    2011-10-15

    We present a lattice Monte Carlo approach developed for studying large numbers of strongly interacting nonrelativistic fermions and apply it to a dilute gas of unitary fermions confined to a harmonic trap. In place of importance sampling, our approach makes use of high statistics, an improved action, and recently proposed statistical techniques. We show how improvement of the lattice action can remove discretization and finite volume errors systematically. For N=3 unitary fermions in a box, our errors in the energy scale as the inverse lattice volume, and we reproduce a previous high-precision benchmark calculation to within our 0.3% uncertainty; as additional benchmarks we reproduce precision calculations of N=3,...,6 unitary fermions in a harmonic trap to within our {approx}1% uncertainty. We then use this action to determine the ground-state energies of up to 70 unpolarized fermions trapped in a harmonic potential on a lattice as large as 64{sup 3}x72. In contrast to variational calculations, we find evidence for persistent deviations from the thermodynamic limit for the range of N considered.

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

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

    PubMed

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

    2011-12-28

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

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

    NASA Astrophysics Data System (ADS)

    Simbotin, Ion; Coté, Robin

    2006-05-01

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

  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. 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.

  2. 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.

  3. 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.

  4. Modelling of Rail Vehicles and Track for Calculation of Ground-Vibration Transmission Into Buildings

    NASA Astrophysics Data System (ADS)

    Hunt, H. E. M.

    1996-05-01

    A methodology for the calculation of vibration transmission from railways into buildings is presented. The method permits existing models of railway vehicles and track to be incorporated and it has application to any model of vibration transmission through the ground. Special attention is paid to the relative phasing between adjacent axle-force inputs to the rail, so that vibration transmission may be calculated as a random process. The vehicle-track model is used in conjunction with a building model of infinite length. The tracking and building are infinite and parallel to each other and forces applied are statistically stationary in space so that vibration levels at any two points along the building are the same. The methodology is two-dimensional for the purpose of application of random process theory, but fully three-dimensional for calculation of vibration transmission from the track and through the ground into the foundations of the building. The computational efficiency of the method will interest engineers faced with the task of reducing vibration levels in buildings. It is possible to assess the relative merits of using rail pads, under-sleeper pads, ballast mats, floating-slab track or base isolation for particular applications.

  5. R0 Structural parameters, conformational, vibrational studies and ab initio calculations of cyanocyclopentane.

    PubMed

    Sawant, Dattatray K; Klaassen, Joshua J; Gounev, Todor K; Durig, James R

    2015-12-01

    The infrared and Raman spectra (3100-50 cm(-1)) of the gas, liquid or solution, and solid have been recorded of cyanocyclopentane, c-C5H9CN. Variable temperature (-60 to -100°C) studies of the infrared spectra (3100-400cm(-1)) of the sample dissolved in liquid xenon have been carried out. From these data, both the envelope-equatorial (Eq) and Ax conformers have been identified and their relative stabilities obtained. The enthalpy difference has been determined to be 55 ± 12 cm(-1) (0.66 ± 0.14 kJ/mol) with the Eq conformer the more stable form. The percentage of the Ax conformer is estimated to be 45±1% at ambient temperature. The conformational stabilities have been predicted from ab initio calculations by utilizing several different basis sets up to aug-cc-pVTZ from both MP2(full) and density functional theory calculations by the B3LYP method. Vibrational assignments have been made for the observed bands for both conformers with initial predictions by MP2(full)/6-31G(d) ab initio calculations to obtain harmonic force constants, wavenumbers, infrared intensities, Raman activities and depolarization ratios for both conformers. The r0 structural parameter values for the Eq[Ax] form are; for the heavy atom distances (Å): CN=1.160 [1.160] (3); C?-C=1.463 [1.463] (3); C?-C?, C?'=1.543 [1.545] (3); C?-C?, C?'=1.540 [1.541] (3); C?-C?'=1.552 [1.553] (3) and angles (°): ?C?-CN=179.0 [178.9] (5); ?C?C?-C=113.1 [110.1] (5); ?C?C?C?'=103.0 [102.1] (5); ?C?C?C?=104.1 [104.8] (5); ?C?C?C?'=106.3 [106.0] (5). The results are discussed and compared to the corresponding properties of some related molecules. PMID:26151436

  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.

    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. PMID:21112810

  7. 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.

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

    PubMed

    Wang, Liang; Liu, Weimin; Fang, Chong

    2015-07-14

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

  9. 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.

  10. Transformation of potential energy surfaces for estimating isotopic shifts in anharmonic vibrational frequency calculations

    SciTech Connect

    Meier, Patrick; Oschetzki, Dominik; Rauhut, Guntram; Berger, Robert

    2014-05-14

    A transformation of potential energy surfaces (PES) being represented by multi-mode expansions is introduced, which allows for the calculation of anharmonic vibrational spectra of any isotopologue from a single PES. This simplifies the analysis of infrared spectra due to significant CPU-time savings. An investigation of remaining deviations due to truncations and the so-called multi-level approximation is provided. The importance of vibrational-rotational couplings for small molecules is discussed in detail. In addition, an analysis is proposed, which provides information about the quality of the transformation prior to its execution. Benchmark calculations are provided for a set of small molecules.

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

    NASA Astrophysics Data System (ADS)

    Keçeli, Murat; Hirata, So; Yagi, Kiyoshi

    2010-07-01

    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 ? 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 ?2(0) fundamental and ?8(?) first overtone in polyethylene.

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

    E-print Network

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

    2015-01-01

    We present calculated rate coefficients for ro-vibrational transitions of CO in collisions with H atoms for a gas temperature range of 10 K $\\leq T \\leq$ 3000 K, based on the recent three-dimensional ab initio H-CO interaction potential of Song et al(2013). Rate coefficients for ro-vibrational $v=1,j=0-30 \\rightarrow v'=0, j'$ transitions were obtained from scattering cross sections previously computed with the close-coupling method by Song et al(2015). Combining these with the rate coefficients for vibrational $v=1-5 \\rightarrow v' < v$ quenching obtained with the infinite-order sudden approximation, we propose a new extrapolation scheme that yields the rate coefficients for ro-vibrational $v=2-5,j=0-30 \\rightarrow v',j'$ de-excitation. Cross sections and rate coefficients for ro-vibrational $v=2, j=0-30 \\rightarrow v'=1,j'$ transitions calculated with the close-coupling method confirm the effectiveness of this extrapolation scheme. Our calculated and extrapolated rates are very different from those that ...

  13. Calculation of the Alpha--Particle Ground State within the Hyperspherical Harmonic Basis

    E-print Network

    M. Viviani; A. Kievsky; S. Rosati

    2004-08-06

    The problem of calculating the four--nucleon bound state properties for the case of realistic two- and three-body nuclear potentials is studied using the hyperspherical harmonic (HH) approach. A careful analysis of the convergence of different classes of HH functions has been performed. A restricted basis is chosen to allow for accurate estimates of the binding energy and other properties of the 4He ground state. Results for various modern two-nucleon and two- plus three-nucleon interactions are presented. The 4He asymptotic normalization constants for separation in 2+2 and 1+3 clusters are also computed.

  14. 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)

  15. Density functional theory based calculations of the vibrational properties of chlorophyll-a

    E-print Network

    Hastings, Gary

    Density functional theory based calculations of the vibrational properties of chlorophyll-a Ruili in revised form 8 March 2007; accepted 13 March 2007 Available online 23 March 2007 Abstract Chlorophyll organisms, such as plants algae and cyanobacteria. To study the chlorophyll-a species at the heart

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

    PubMed

    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. PMID:26723655

  17. 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/.

  18. Theoretical calculation and vibrational spectral analysis of L-arginine trifluoroacetate.

    PubMed

    Sun, Z H; Zhang, L; Xu, D; Wang, X Q; Liu, X J; Zhang, G H

    2008-11-15

    Fourier transform infrared and Raman spectra of the nonlinear optical crystal, L-arginine trifluoroacetate (L-arginine.CF3COOH, abbreviated as LATF) have been calculated by the first-principles calculation and investigated in experiment. The calculated results are slightly different from those experimental values because of the distinction resulted from the intermolecular hydrogen bonds. The role of this type of intermolecular interaction on the crystal vibrational spectra and nonlinear optical properties has been discussed. The absorption-edge on the IR side has been estimated by the theoretical approach on basis of the calculated infrared spectrum, which will be meaningful for further research on NLO crystal. PMID:18329334

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  20. Infrared and Raman spectra, ab initio calculations, force field refinement and vibrational assignment of 3-aminophenol

    NASA Astrophysics Data System (ADS)

    Buyukmurat, Y.; Akyuz, S.

    2005-06-01

    The molecular geometry and molecular vibrations of 3-aminophenol and its some deuterated derivatives have been investigated with the aid of quantum chemical calculations, normal coordinate analysis using force field refinement method and vibrational spectroscopy. The barrier of the OH group pointing in the direction of the amino group with respect to the anti conformer for 3-aminophenol was computed to be 2.44 kJ/mol. The spectroscopic and theoretical results are compared to the corresponding properties for some similar molecules.

  1. Variational Calculation on the Simple Harmonic Oscillator in Momentum Space The following normalized trial wave function is proposed for a variational calculation on the

    E-print Network

    Rioux, Frank

    normalized trial wave function is proposed for a variational calculation on the harmonic oscillator. x a = 0, indicating that the wave function is not wellbehaved and therefore cannot be used for quantum mechanical calculations. 5 0 5 x 1,( ) x Therefore, the wave function is Fourier transformed

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

    SciTech Connect

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

    2015-05-28

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

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

  4. Motion of a condensate in a shaken and vibrating harmonic trap

    E-print Network

    Y. Japha; Y. B. Band

    2002-04-14

    The dynamics of a Bose-Einstein condensate (BEC) in a time-dependent harmonic trapping potential is determined for arbitrary variations of the position of the center of the trap and its frequencies. The dynamics of the BEC wavepacket is soliton-like. The motion of the center of the wavepacket, and the spatially and temporally dependent phase (which affects the coherence properties of the BEC) multiplying the soliton-like part of the wavepacket, are analytically determined.

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

    PubMed

    McLachlan, Neil; Adams, Ryan; Burvill, Colin

    2012-01-01

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

  6. An Ab Initio Calculation of the Low-Frequency Vibrational Energies of the HCl Dimer

    NASA Astrophysics Data System (ADS)

    Gomez, P. C.; Bunker, P. R.; Karpfen, A.; Lischka, H.

    1994-08-01

    With the two HCl bond lengths held fixed at the monomer vibrational ground state value ( r0 = 1.284 Å) we have calculated a four-dimensional ab initio potential energy surface of the HCl dimer at 400 nuclear geometries covering energies within 1000 cm -1 of the minimum. The electronic basis set is larger than that used earlier (A. Karpfen, P.R. Bunker, and P. Jensen, Chem. Phys. 149, 299-309, (1991) to obtain a surface on which dynamical calculations were carried out. We calculate the lowest 33 vibrational energies (up to 230 cm -1) involving the four large-amplitude modes on this surface using an adiabatic separation of the van der Waals stretching coordinate from the three large-amplitude bending coordinates (following S.C. Althorpe, D.C. Clary, and P. R. Bunker, Chem, Phys. Lett. 187, 345-353, (1991), and we contrast the results with those obtained using electrostatic potentials.

  7. Optimal configuration for vibration frequencies in a ring of harmonic oscillators: The nonidentical mass effect

    NASA Astrophysics Data System (ADS)

    Liu, Shuai; Zhang, Guo-Yong; He, Zhiwei; Zhan, Meng

    2015-06-01

    The parameter diversity effect in coupled nonidentical elements has attracted persistent interest in nonlinear dynamics. Of fundamental importance is the so-called optimal configuration problem for how the spatial position of elements with different parameters precisely determines the dynamics of the whole system. In this work, we study the optimal configuration problem for the vibration spectra in the classical mass-spring model with a ring configuration, paying particular attention to how the configuration of different masses affects the second smallest vibration frequency ( ? 2) and the largest one ( ? N ). For the extreme values of ? 2 and ? N , namely, ( ? 2)min, ( ? 2)max, ( ? N )min, and ( ? N )max, we find some explicit organization rules for the optimal configurations and some approximation rules when the explicit organization rules are not available. The different distributions of ? 2 and ? N are compared. These findings are interesting and valuable for uncovering the underlying mechanism of the parameter diversity effect in more general cases.

  8. 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.

  9. Multidimensional local mode calculations for the vibrational spectra of OH(-)(H2O)2 and OH(-)(H2O)2·Ar.

    PubMed

    Morita, Masato; Takahashi, Kaito

    2013-09-28

    Multidimensional local mode calculations are performed for OH stretching vibrations of the gas phase OH(-)(H2O)2 and OH(-)(H2O)2·Ar clusters in the 1000-4000 cm(-1) energy range. The potential energies and the associated dipole moment values are calculated with MP2/6-311++G(3df,3pd). To fully take into account the anharmonic effects for the stretching vibrations of the ionic hydrogen bonded OHs (IHB OHs), those donating H to the O atom in OH(-), the vibrational Hamiltonian represented by the discrete variable representation (DVR) technique is diagonalized without using any truncation/contraction scheme for the basis. The necessary potential energies and dipole moment values at the DVR grid points are supplied by the polynomial inter- and extrapolations based on the values calculated at fine spatial grid points. We found that the peaks at 2700 cm(-1) should be assigned to the first overtone (?: 0 ? 2) of the IHB OH stretching vibrations rather than the previous assignment of the fundamental of the IHB OH based on harmonic frequencies. The relevant fundamental peaks should be observed around 1600-2000 cm(-1) where no experimental observation has been performed. This prediction of the fundamental peak positions leads to a simple correlation between the magnitude of the red-shift of the IHB OH stretching vibrational peak position and the cluster size of OH(-)(H2O)n for n = 1-3. Furthermore, to determine important contributions toward the assignment of the experimental spectrum, detailed analyses are performed from the following 3 viewpoints: (1) mode coupling between the inter water IHB OH stretching vibrations, (2) coupling between the IHB OH and the low-frequency OO stretching vibrations and (3) argon attachment to OH(-)(H2O)2. We found that the overall shape of the vibrational spectrum can be essentially described by considering only factor (1). However, fairly large peak shifts are caused by factors (2) and (3). PMID:23912845

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

    NASA Astrophysics Data System (ADS)

    Yoon, Jong-Yun; Singh, Rajendra

    2014-10-01

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

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

    SciTech Connect

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

    2014-01-21

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

  12. Vibrationally Averaged Long-Range Molecule-Molecule Dispersion Coefficients from Coupled-Cluster Calculations

    NASA Astrophysics Data System (ADS)

    Schmidt, Matthew; Nooijen, Marcel

    2011-06-01

    Recent years have seen increasing interest in the structure and dynamics of molecular clusters formed when a chromophore molecule such as CO_2, OCS or N_2O is solvated by number of He atoms and/or para-H_2 molecules. A key experimental probe of their behaviour is the shift of a chromophore's vibrational transition frequency which occurs when the solvent species are attached to it. Such shifts are driven by the changes in the solvent-chromophore interaction potential upon vibrational excitation of the probe molecule. While `conventional' supermolecule calculations can often provide realistic predictions of such changes in the potential well and repulsive wall region, they become increasingly unreliable for describing the weak interactions at long range where most of the solvent species in a large cluster are located. It is therefore important to have accurate relative-orientation and monomer-stretching dependent long-range C_6, C_8 and C10 dispersion coefficients to incorporate into the models for the interaction potential and for its dependence on the chromophore's vibrational state. This paper describes how those coefficients can be obtained from calculated monomer dipole, quadrupole, and octupole polarizabilities for imaginary frequencies, and by making use of the Casimir-Polder relation and angular momentum coupling to extract orientation-dependent quantities. The calculations are performed using a modified version of the ACES2 program system which allows the calculation of dipole, quadrupole and octupole polarizabilities at the EOM-CCSD level, and of static multipole moments using CCSD(T) calculations and adequate basis sets. For each relevant level of the chromophore, vibrational averaging is performed by calculating the imaginary frequency polarizabilities at judiciously chosen geometries and performing a numerical integration using the free-molecule vibrational wavefunction. Subsequent work will involve merging this long-range part of the potential with a short-range part obtained from 'conventional' CCSD(T) calculations and using it in PIMC simulations of cluster behaviour. H. Li, N. Blinov, P.-N. Roy and R.J. Le Roy, J. Chem. Phys. 130, 144305 (2009).

  13. Infrared and ultraviolet cutoffs in variational calculations with a harmonic oscillator basis

    E-print Network

    Sidney A Coon

    2013-03-26

    I abstract from a recent publication [1] the motivations for, analysis in and conclusions of a study of the ultraviolet and infrared momentum regulators induced by the necessary truncation of the model spaces formed by a variational trial wave function. This trial function is built systematically from a complete set of many-body basis states based upon three-dimensional harmonic oscillator (HO) functions. Each model space is defined by a truncation of the expansion characterized by a counting number (N) and by the intrinsic scale ($\\hbar\\omega$) of the HO basis. Extending both the uv cutoff to infinity and the ir cutoff to zero is prescribed for a converged calculation. In [1] we established practical procedures which utilize these regulators to obtain the extrapolated result from sequences of calculations with model spaces. Finally, I update this subject by mentioning recent work on our extrapolation prescriptions which have appeared since the submission of [1]. The numerical example chosen for this contribution consists of calculations of the ground state energy of the triton with the "bare" and "soft" Idaho N3LO nucleon-nucleon (NN) interaction.

  14. Vibrational spectroscopic studies and computational calculations of 5-chloro-2-(3-chlorophenylcarbamoyl)phenylacetate.

    PubMed

    Madhavan, V S; Mary, Y Sheena; Varghese, Hema Tresa; Panicker, C Yohannan; Mathew, Samuel; Van Alsenoy, Christian; Vinsova, Jarmila

    2012-04-01

    The FT-IR and FT-Raman spectra of 5-chloro-2-(3-chlorophenylcarbamoyl)phenylacetate were studied. The vibrational wave numbers and corresponding vibrational assignments were examined theoretically using the Gaussian 03 set of quantum chemistry codes and the normal modes are assigned by Potential Energy Distribution calculations. The synthesis, elemental analysis and NMR values are presented. The red shift of the NH stretching wave number in the infrared spectrum from the computed wave number indicates the weakening of the NH bond resulting in proton transfer to the neighboring oxygen atom. The first hyperpolarizability, infrared intensities and Raman activities are reported. The calculated first hyperpolarizability is comparable with the reported values of similar derivatives and is an attractive object for future studies of nonlinear optics. The geometrical parameters of the title compound are in agreement with that of similar reported derivatives. PMID:22297035

  15. Accurate quantum dynamics calculations of vibrational spectrum of dideuteromethane CH2D2.

    PubMed

    Yu, Hua-Gen

    2015-05-21

    We report a rigorous variational study of the infrared (IR) vibrational spectra of both CH2D2 and (13)CH2D2 isotopomers using an exact molecular Hamiltonian. Calculations are carried out using a recently developed multi-layer Lanczos algorithm based on the accurate refined Wang and Carrington potential energy surface of methane and the low-order truncated ab initio dipole moment surface of Yurchenko et al. [J. Mol. Spectrosc. 291, 69 (2013)]. All well converged 357 vibrational energy levels up to 6100 cm(-1) of CH2D2 are obtained, together with a comparison to previous calculations and 91 experimental bands available. The calculated frequencies are in excellent agreement with the experimental results and give a root-mean-square error of 0.67?cm(-1). In particular, we also compute the transition intensities from the vibrational ground state for both isotopomers. Based on the theoretical results, 20 experimental bands are suggested to be re-assigned. Surprisingly, an anomalous C isotopic effect is discovered in the n?5 modes of CH2D2. The predicted IR spectra provide useful information for understanding those unknown bands. PMID:26001461

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  17. Dispersion corrected DFT approaches for anharmonic vibrational frequency calculations: nucleobases and their dimers.

    PubMed

    Fornaro, Teresa; Biczysko, Malgorzata; Monti, Susanna; Barone, Vincenzo

    2014-06-01

    Computational spectroscopy techniques have become in the last few years an effective means to analyze and assign infrared (IR) spectra of molecular systems of increasing dimensions and in different environments. However, transition from compilation of harmonic data to fully anharmonic simulations of spectra is still underway. The most promising results for large systems have been obtained, in our opinion, by perturbative vibrational approaches based on potential energy surfaces computed by hybrid (especially B3LYP) density functionals and medium size (e.g. SNSD) basis sets. In this framework, we are actively developing a comprehensive and robust computational protocol aimed at quantitative reproduction of the spectra of nucleic acid base complexes and their adsorption on solid supports (organic/inorganic). In this contribution we report the essential results of the first step devoted to isolated monomers and dimers. It is well known that in order to model the vibrational spectra of weakly bound molecular complexes dispersion interactions should be taken into proper account. In this work we have chosen two popular and inexpensive approaches to model dispersion interactions, namely the semi-empirical dispersion correction (D3) and pseudopotential based (DCP) methodologies both in conjunction with the B3LYP functional. These have been used for simulating fully anharmonic IR spectra of nucleobases and their dimers through generalized second order vibrational perturbation theory (GVPT2). We have studied, in particular, isolated adenine, hypoxanthine, uracil, thymine and cytosine, the hydrogen-bonded and stacked adenine and uracil dimers, and the stacked adenine-naphthalene heterodimer. Anharmonic frequencies are compared with standard B3LYP results and experimental findings, while the computed interaction energies and structures of complexes are compared to the best available theoretical estimates. PMID:24531740

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

    PubMed

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

    2014-11-11

    In the present study structural properties of p-cresol, and 2-methoxy-p-cresol have been studied by using B3LYP/cc-pvdz and B3PW91/cc-pvdz of Density Functional Theory (DFT) utilizing Becke three exchange functional and Lee Yang Paar correlation functional. The Fourier transform infrared and Fourier transform Raman spectra of title molecules were recorded (solid phase). Optimized geometry, harmonic vibrational frequencies and various thermodynamic parameters of the title compounds were calculated with B3LYP/cc-pvdz, and B3PW91/cc-pvdz basis sets. Non-linear optical (NLO) behavior of the p-cresol and 2-methoxy-p-cresol were investigated by determining of electric dipole moment, polarizability ?, and hyperpolarizability ? using the above mentioned basis sets. The molecular properties such as ionization potential, electronegativity, chemical potential, electrophilicity have been deduced from HOMO-LUMO analysis employing the same basis sets. A detailed interpretation of the infrared and Raman spectra of title molecules were reported. UV spectrum was measured in different solvent. The energy and oscillator strength are calculated by Time Dependant Density Functional Theory (TD-DFT) results. The calculated HOMO and LUMO energies also confirm that charge transfer occurs within the molecule. The complete assignments were performed on the basis of the potential energy distribution (PED) of vibrational modes, calculated with scaled quantum mechanics (SQM) method. Finally the theoretical FT-IR, FT-Raman, and UV spectra of the title molecules have also been constructed. PMID:24892532

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

    PubMed

    Rashev, Svetoslav; Moule, David C

    2015-04-01

    In this work we present a full 6D quartic potential energy surface (PES) for S0 thiophosgene in curvilinear symmetrized bond-angle coordinates. The PES was refined starting from an ab initio field derived from acc-pVTZ basis set with CCSD(T) corrections for electron correlation. In the present calculations we used our variational method that was recently tested on formaldehyde and some of its isotopomers, along with additional improvements. The lower experimentally known vibrational levels for 35Cl2CS were reproduced quite well in the calculations, which can be regarded as a test for the feasibility of the obtained quartic PES. PMID:25615683

  20. On the correction of calculated vibrational frequencies for the effects of the counterions - ?,?-diamine dihydrochlorides.

    PubMed

    Fiuza, S M; Silva, T M; Marques, M P M; de Carvalho, L A E Batista; Amado, A M

    2015-10-01

    The present work provides sets of correction factors to adjust the calculated vibrational frequencies of a series of ?,?-diamines hydrochloride salts to account for the intermolecular interactions with the counterion. The study was performed using different theory levels for predicting the vibrational data of isolated dicationic ?,?-diamines and their hydrochloride forms, with and without the explicit account of the interactions with the chloride counterions. Different sets of correction factors were determined for each theory level considering the four smallest elements for the ?,?-diamines series, while their transferability and reliability was evaluated considering the larger elements of the series. The theory level simplification was also evaluated and was found to neither compromise the vibrational frequencies estimates nor the magnitude and accuracy of the pre-defined scaling factors. This suggests that transferability of the correction factors is possible not only for different diamines but also between different levels of theory with the averaged group correction factor, ? g (a) , being the best choice to account for the effects of the N-H?·?·?·?Cl interactions. The possibility of simplifying the theory level without compromising efficiency and accuracy is additionally of utmost importance. This computational approach can constitute a valuable tool in the future for studying the hydrochloride forms of larger and more complex diamine systems. Graphical Abstract A computational approach that may constitute a valuable tool for studying the hydrochloride forms of large and complex diamine systems. Correction factors to adjust the vibrational frequencies calculated for isolated dicationic primary diamines for the effects of the interactions with chloride counterions, without their explicit account in the calculations, are presented and evaluated for eficiency. PMID:26386957

  1. Iterative active-space selection for vibrational configuration interaction calculations using a reduced-coupling VSCF basis

    NASA Astrophysics Data System (ADS)

    Scribano, Yohann; Benoit, David M.

    2008-06-01

    We adapt a variation-perturbation method to perform vibrational configuration interaction (VCI) calculations on large molecular systems. Starting from a self-consistent vibrational wave function, we use the vibrational configuration interaction with perturbation selected interactions (VCIPSI) algorithm to select an active VCI space iteratively. We then extend this approach to use a reduced-coupling description of potential energy surfaces. The accuracy of the method is tested on methane and benzoic acid molecules. The significant reduction in the size of the VCI basis obtained using the VCIPSI scheme does not affect the quality of the computed vibrational frequencies and reduces computational time dramatically.

  2. Vibrationally resolved photoelectron imaging of Cu2H- and AgCuH- and theoretical calculations.

    PubMed

    Xie, Hua; Li, Xiaoyi; Zhao, Lijuan; Liu, Zhiling; Qin, Zhengbo; Wu, Xia; Tang, Zichao; Xing, Xiaopeng

    2013-02-28

    Vibrationally resolved photoelectron spectra have been obtained for Cu(2)H(-) and AgCuH(-) using photoelectron imaging at 355 nm. Two transition bands X and A are observed for each spectrum. The X bands in both spectra show the vibration progressions of the Cu-H stretching mode and the broad peaks of these progressions indicate significant structural changes from Cu(2)H(-) and AgCuH(-) to their neutral ground states. The A bands in the spectra of Cu(2)H(-) and CuAgH(-) show stretching progressions of Cu-Cu and Ag-Cu, respectively. The contours of these two progressions are pretty narrow, indicating relatively small structural changes from Cu(2)H(-) and AgCuH(-) to their neutral excited states. Calculations based on density functional theory indicate that the ground states of Cu(2)H(-) and AgCuH(-) and the first excited states of their neutrals are linear, whereas their neutral ground states are bent. The photoelectron detachment energies and vibrational frequencies from these calculations are in good agreement with the experimental observations. Especially, the theoretical predication of linear structures for the anions and the neutral excited states are supported by the spectral features of A bands, in which the bending modes are inactive. Comparisons among the vertical detachment energies of Cu(2)H(-), AgCuH(-), and their analogs help to elucidate electronic characteristics of coinage metal elements and hydrogen in small clusters. PMID:23388039

  3. 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.

  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. Convergence properties of {\\itshape ab initio} calculations of light nuclei in a harmonic oscillator basis

    E-print Network

    Sidney A. Coon; Matthew I. Avetian; Michael K. G. Kruse; Bira van Kolck; Pieter Maris; James P. Vary

    2012-05-15

    We study recently proposed ultraviolet and infrared momentum regulators of the model spaces formed by construction of a variational trial wavefunction which uses a complete set of many-body basis states based upon three-dimensional harmonic oscillator (HO) functions. These model spaces are defined by a truncation of the expansion characterized by a counting number ($\\mathcal{N}$) and by the intrinsic scale ($\\hbar\\omega$) of the HO basis; in short by the ordered pair ($\\mathcal{N},\\hbar\\omega$). In this study we choose for $\\mathcal{N}$ the truncation parameter $N_{max}$ related to the maximum number of oscillator quanta, above the minimum configuration, kept in the model space. The ultraviolet (uv) momentum cutoff of the continuum is readily mapped onto a defined uv cutoff in this finite model space, but there are two proposed definitions of the infrared (ir) momentum cutoff inherent in a finite-dimensional HO basis. One definition is based upon the lowest momentum difference given by $\\hbar\\omega$ itself and the other upon the infrared momentum which corresponds to the maximal radial extent used to encompass the many-body system in coordinate space. Extending both the uv cutoff to infinity and the ir cutoff to zero is prescribed for a converged calculation. We calculate the ground state energy of light nuclei with "bare" and "soft" $NN$ interactions. By doing so, we investigate the behaviors of the uv and ir regulators of model spaces used to describe $^2$H, $^3$H, $^4$He and $^6$He with $NN$ potentials Idaho N$^3$LO and JISP16. We establish practical procedures which utilize these regulators to obtain the extrapolated result from sequences of calculations with model spaces characterized by ($\\mathcal{N},\\hbar\\omega$).

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

    NASA Astrophysics Data System (ADS)

    Lamichhane, Hari; Hastings, Gary

    2009-11-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2001-01-01

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

  8. 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.

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

    NASA Astrophysics Data System (ADS)

    Stanke, Monika; Adamowicz, Ludwik

    2014-10-01

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

  10. The image source method for calculating the vibrations of simply supported convex polygonal plates

    NASA Astrophysics Data System (ADS)

    Cuenca, J.; Gautier, F.; Simon, L.

    2009-05-01

    The aim of this paper is to show that the image source method (ISM) can be used both for analytically calculating Green's functions of particular simply supported convex polygonal plates and for predicting medium and high frequency vibrations of arbitrarily shaped simply supported convex polygonal plates with controllable precision. In the first part of the paper, the method for obtaining the Green's function of a polygonal plate by ISM is developed. Examples for plates of different geometries (rectangle, isosceles right triangle, half-equilateral triangle and equilateral triangle) are given. In the second part of the paper, the pertinence of ISM for predicting medium and high frequency vibrations of arbitrarily shaped simply supported convex polygonal plates is investigated. An approximation based on the exclusion of image sources beyond a certain distance from the receiver is used in order to take advantage of the dissipation of vibrational energy through wave propagation. We investigate the influence of structural damping and truncation distance on the accuracy of such approximation. The computed responses are in good agreement with reference solutions, which are analytically known or obtained by the finite element method.

  11. 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].

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

    NASA Astrophysics Data System (ADS)

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

    2006-07-01

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

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

    SciTech Connect

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

    1998-12-01

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

  14. 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.

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

    E-print Network

    Leclerc, Arnaud

    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.

  16. 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.

  17. 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.

  18. 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. PMID:17299728

  19. Modeling and active vibration suppression of a single-walled carbon nanotube subjected to a moving harmonic load based on a nonlocal elasticity theory

    NASA Astrophysics Data System (ADS)

    Pirmohammadi, A. A.; Pourseifi, M.; Rahmani, O.; Hoseini, S. A. H.

    2014-07-01

    This paper investigates active vibration suppression of a single-walled carbon nanotube (SWCNT) under the action of a moving harmonic load using Eringen's nonlocal elasticity theory. The SWCNT is modeled according to the nonlocal Euler-Bernoulli beam theory. A Dirac-delta function is used to describe the position of the moving load along the SWCNT. Next, a linear classical optimal control algorithm with displacement-velocity feedback is used to suppress vibration in the SWCNT with control forces acting as actuators. The effects of a small-scale parameter, slenderness ratio, moving load velocity, and the excitation frequency of a moving load on the dynamic deflection of the SWCNT are examined. Finally, the ability of the control algorithm to suppress the response of the SWCNT under the effects of a moving load with a number of controlled modes and control forces is surveyed.

  20. Emission spectroscopy, harmonic vibrational frequencies, and improved ground state structures of jet-cooled monochloro- and monobromosilylene (HSiCl and HSiBr)

    NASA Astrophysics Data System (ADS)

    Hostutler, David A.; Ndiege, Nicholas; Clouthier, Dennis J.; Pauls, Steven W.

    2001-09-01

    The ground state harmonic frequencies of gas phase H/DSi35Cl and H/DSi79Br have been determined by exciting single vibronic bands of the à 1A?-X˜1A' electronic transition and recording the dispersed fluorescence. The jet-cooled radicals were produced in a pulsed discharge jet using H/DSiX3 (X=Cl or Br) precursors. The emission data were fitted to an anharmonic model and a normal coordinate analysis of the harmonic frequencies allowed the determination of five of the six force constants of each molecule. Using previously obtained v?=0 rotational constants and the improved force fields, average (rz) and estimated equilibrium (rez) structures were calculated for both monohalosilylenes. The validity of the force constants was evaluated by comparing calculated and observed zero-point inertial defects and by simulating the Franck-Condon profiles of the observed emission spectra in the harmonic approximation.

  1. 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.

  2. Vibrational investigation, molecular orbital studies and molecular electrostatic potential map analysis on 3-chlorobenzoic acid using hybrid computational calculations.

    PubMed

    Ramalingam, S; Babu, P David Suresh; Periandy, S; Fereyduni, E

    2011-12-15

    The FT-IR and FT-Raman spectra of 3-chlorobenzoic acid (3CBA) are recorded in the liquid state. The fundamental vibrational frequencies, intensity of vibrational bands and the optimized geometrical parameters of the compound are evaluated using HF and DFT (LSDA/B3LYP/B3PW91/MPW1PW91) methods with 6-311+G(d,p) basis set. The theoretical wave numbers are scaled down and compared with the experimental values which showed very good agreement. Comparison of stimulated spectra with the experimental spectra provides important information about the ability of the hybrid computational method to describe the vibrational modes. The HOMO, LUMO, chemical hardness (?), chemical potential (?), electrophilicity values (?) and maximum amount of electronic charge transfer (?N(max)) are calculated. The molecular electrostatic potential (MESP) is calculated and the corresponding graphs are drawn. Some thermodynamic parameters and physico-chemical properties are calculated and discussed. PMID:21993254

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

    NASA Astrophysics Data System (ADS)

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

    2008-03-01

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

  4. Vibrational spectra, DFT calculations, and conformations of 5?-chloro-1-isopropyl-7-azaindirubin-3?-oxime

    NASA Astrophysics Data System (ADS)

    Robbins, Timothy J.; Wang, Yongmei; Yao, Qi-Zheng; Wang, Zhao-Hui; Cheng, Jingcai; Li, Ying-Sing

    2013-09-01

    For centuries Danggui Longhui Wan has been used to treat chronic ailments, such as myelocytic leukemia. In the 1960s, the active ingredient in Danggui Longhui Wan was isolated and identified as indirubin. Indirubin has shown potent inhibition of cyclin-dependent kinase through binding to the ATP-binding site. However, indirubin shows poor solubility and low absorption, hence many derivatives have been developed to enhance these properties. One such derivative is 5?-chloro-1-isopropyl-7-azaindirubin-3?-oxime (CIADO), investigated in the current work. Infrared and Raman spectra were collected and compared with predicted spectra using density functional theory. Based on theoretical calculations, the most stable form of CIADO isomer is found to be cis (Z) and trans (E) with respect to the ring system linkage and the 3?-oxime functional group respectively. Also observed were two distinct internal rotational minima for the 1-isoprooyl group separated by a large energy barrier. The presence of two distinct isopropyl conformations observed in our calculations was confirmed with temperature-dependent IR experiments. Assignment of experimental vibrational modes was carried out based on functional group displacement observed in the calculations.

  5. The Classical Harmonic Vibrations of the Atomic Centers of Mass with Micro Amplitudes and Low Frequencies Monitored by the Entanglement between the Two Two-level Atoms in a Single mode Cavity

    E-print Network

    Yong-Yi Huang

    2013-12-08

    We study the entanglement dynamics of the two two-level atoms coupling with a single-mode polarized cavity field after incorporating the atomic centers of mass classical harmonic vibrations with micro amplitudes and low frequencies. We propose a quantitative vibrant factor to modify the concurrence of the two atoms states. When the vibrant frequencies are very low, we obtain that: (i) 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; (ii) the concurrence increases with the increase of the initial phases; (iii) the frequency of the harmonic vibration can be obtained by measuring the maximal value of the concurrence during a small time. These results indicate that even the extremely weak classical harmonic vibrations can be monitored by the entanglement of quantum states.

  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. Microwave and Infrared Spectra, Adjusted R_{0} Structural Parameters, Conformational Stabilities, Vibrational Assignments, and AB Initio Calculations of Cyclobutylcarboxylic Acid Chloride

    NASA Astrophysics Data System (ADS)

    Klaassen, Joshua J.; Groner, Peter; Durig, James R.

    2013-06-01

    The FT-microwave spectrum of cyclobutylcarboxylic acid chloride, c-C_{4}H_{7}C(O)Cl, has been recorded and 153 transitions for the ^{35}Cl and ^{37}Cl isotopologues have been assigned for the gauche-equatorial conformation. The ground state rotational constants were determined from these assignments with following values for ^{35}Cl [^{37}Cl]: A = 4349.84294(48) [4322.0555(56)], B = 1414.80319(36) [1384.50581(105)], C = 1148.24114(18) [1126.35465(101)]. From the determined microwave rotational constants and ab initio MP2(full)/6-311+G(d,p) predicted structural values, adjusted r_{0} parameters are reported. Variable temperature (-70 to -100^{o}C) infrared spectra (4000 to 400 cm^{-1}) were recorded in liquid xenon and gauche-equatorial conformer is the most stable form with an enthalpy differences of 91 ± 9 cm^{-1} (1.09 ± 0.05 kJ/mol) with gauche-axial and 173 ± 17 cm^{-1} (2.07 ± 0.04 kJ/mol) with the trans-equatorial conformer. The relative amounts present at an ambient temperature are 54% gauche-equatorial, 35 ± 1% gauche-axial and 12 ± 1% trans-equatorial. The conformational stabilities have been predicted from ab initio calculations utilizing several different basis sets up to aug-cc-pVTZ from both MP2(full) and density functional theory calculations by the B3LYP method. Vibrational assignments have been provided for the observed bands for all three conformers which are supported by ab initio calculations to predict harmonic force constants, vibrational wavenumbers, infrared intensities, Raman activities and depolarization ratios. The results are discussed and compared to the corresponding properties of some related molecules.

  8. Variational calculations of rotational-vibrational energies of CH{sub 4} and isotopomers using an adjusted ab initio potential

    SciTech Connect

    Carter, S.; Bowman, J.M.

    2000-03-23

    The authors report variational calculations of vibrational energies of CH{sub 4}, CH{sub 3}D, CH{sub 2}D{sub 2}, CHD{sub 3}, and CD{sub 4} using the code Multimode and the ab initio force field of Lee and co-workers [Lee, T.J.; Martin, J.M.L.; Taylor, P.R.--J.Chem.Phys. 1995, 102, 254], re-expressed using Morse variables in the stretch displacements. Comparisons are made with experimental energies for CH{sub 4} with this potential, and then small adjustments are made to the potential to improve agreement with experiment for CH{sub 4}. Calculations for the isotopomers are done using the adjusted potential and compared with experiment. Additional vibrational energies and assignments not reported experimentally are also given for CH{sub 4} and the isotopomers. Exact rotational-vibrational energies of CH{sub 4} are also reported for J = 1.

  9. A Refined Quartic Forcefield for Acetylene: Accurate Calculation of the Vibrational Spectrum

    NASA Astrophysics Data System (ADS)

    Bramley, M. J.; Carter, S.; Handy, N. C.; Mills, I. M.

    1993-02-01

    It is now possible to calculate the nine-dimensional rovibrational wavefunctions of sequentially bonded four-atom molecules variationally without dynamical approximation. In the case of HCCH, the simplest such molecule, many hundreds of rovibrational (J = 0, 1, 2) levels can be converged to better than 1.5 cm -1. Variational calculations of this kind are used here systematically to refine the well-known quartic valence-coordinate forcefleld of Strey and Mills [J.Mol. Spectrosc.59, 103-115 (1976)] against experimental term values up to three C-H stretch quanta for the principal and two deuterated isotopomers, yielding a new surface that reproduces the energies of all the known ?, ?, and ? states of these species up to the energy of two C-H stretch quanta with an rms error of 3 cm-1 . The refined forcefield is used to study the resonances associated with the accidental degeneracies (?2 + ?4 + ?5, ?3) and (?2 + 2?5, ?1) in the principal isotopomer, leading to a clarification of the assignment of she experimentally detected states in the 2?3 and 3?3, polyads, and to the finding that vibrational Coriolis (kinetic energy) terms, rather than quartic anharmonicities in the potential, are the primary cause of the resonant interactions. Using a new cubic ab initio electric dipole field to calculate IR absorption coefficients, 24 undetected ? and ? states of 1H12C12C1H and 5 undetected ? states of D12C12CD are identified as candidates for experimental study, and their calculated energies and assignments are given.

  10. Single crystal XRD, vibrational and quantum chemical calculation of pharmaceutical drug paracetamol: A new synthesis form.

    PubMed

    Anitha, R; Gunasekaran, M; Kumar, S Suresh; Athimoolam, S; Sridhar, B

    2015-11-01

    The common house hold pharmaceutical drug, paracetamol (PAR), has been synthesized from 4-chloroaniline as a first ever report. After the synthesis, good quality single crystals were obtained for slow evaporation technique under the room temperature. The crystal and molecular structures were re-determined by the single crystal X-ray diffraction. The vibrational spectral measurements were carried out using FT-IR and FT-Raman spectroscopy in the range of 4000-400 cm(-1). The single crystal X-ray studies shows that the drug crystallized in the monoclinic system polymorph (Form-I). The crystal packing is dominated by N-H?O and O-H?O classical hydrogen bonds. The ac diagonal of the unit cell features two chain C(7) and C(9) motifs running in the opposite directions. These two chain motifs are cross-linked to each other to form a ring R4(4)(22) motif and a chain C2(2)(6) motif which is running along the a-axis of the unit cell. Along with the classical hydrogen bonds, the methyl group forms a weak C-H?O interactions in the crystal packing. It offers the support for molecular assembly especially in the hydrophilic regions. Further, the strength of the hydrogen bonds are studied the shifting of vibrational bands. Geometrical optimizations of the drug molecule were done by the Density Functional Theory (DFT) using the B3LYP function and Hartree-Fock (HF) level with 6-311++G(d,p) basis set. The optimized molecular geometry and computed vibrational spectra are compared with experimental results which show significant agreement. The factor group analysis of the molecule was carried out by the various molecular symmetry, site and factor group species using the standard correlation method. The Natural Bond Orbital (NBO) analysis was carried out to interpret hyperconjugative interaction and intramolecular charge transfer (ICT). The chemical softness, chemical hardness, electro-negativity, chemical potential and electrophilicity index of the molecule were found out first time by HOMO-LUMO plot. The frontier orbitals shows lower band gap values signify the possible biological/pharmaceutical activity of the molecule. The thermodynamical properties are also obtained from the calculated frequencies of the optimized structures. PMID:26072380

  11. Effects of broad-banded higher harmonics on fatigue damage of risers due to vortex-induced vibrations

    E-print Network

    Price, Rachel Elizabeth

    2011-01-01

    Recent works have discussed "chaotic" or "Type-II" riser motion and suggested that it is a general feature of VIV riser response. Chaotic riser response contains broad-banded harmonics and a combination of standing and ...

  12. Calculation of the Vibrational Properties of Chlorophyll a in Solution Sreeja Parameswaran, Ruili Wang, and Gary Hastings*

    E-print Network

    Hastings, Gary

    Calculation of the Vibrational Properties of Chlorophyll a in Solution Sreeja Parameswaran, Ruili, Georgia 30303 ReceiVed: July 10, 2008; ReVised Manuscript ReceiVed: August 26, 2008 Chlorophyll a (Chl species at the heart of all solar capture and conversion processes is chlorophyll a (Chl-a), either

  13. 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})

  14. From small fullerenes to the graphene limit: A harmonic force-field method for fullerenes and a comparison to density functional calculations for Goldberg-Coxeter fullerenes up to C980.

    PubMed

    Wirz, Lukas N; Tonner, Ralf; Hermann, Andreas; Sure, Rebecca; Schwerdtfeger, Peter

    2016-01-01

    We introduce a simple but computationally very efficient harmonic force field, which works for all fullerene structures and includes bond stretching, bending, and torsional motions as implemented into our open-source code Fullerene. This gives accurate geometries and reasonably accurate vibrational frequencies with root mean square deviations of up to 0.05 Å for bond distances and 45.5 cm(-1) for vibrational frequencies compared with more elaborate density functional calculations. The structures obtained were used for density functional calculations of Goldberg-Coxeter fullerenes up to C980 . This gives a rather large range of fullerenes making it possible to extrapolate to the graphene limit. Periodic boundary condition calculations using density functional theory (DFT) within the projector augmented wave method gave an energy difference between -8.6 and -8.8 kcal/mol at various levels of DFT for the reaction C60 ?graphene (per carbon atom) in excellent agreement with the linear extrapolation to the graphene limit (-8.6 kcal/mol at the Perdew-Burke-Ernzerhof level of theory). © 2015 Wiley Periodicals, Inc. PMID:25821044

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

    NASA Astrophysics Data System (ADS)

    Kirillov, A. S.

    2014-05-01

    Calculated in (Kirillov, 2014) constants are applied for simulations of vibrational populations of Herzberg states in mixtures of O2 with CO2, CO, N2 gases for laboratory conditions. Results show very important role of electronic-vibrational processes in redistribution of electronic excitation energy among vibrational levels. It is shown that the interaction between O2(A?3?u) and O2 causes effective production O2(c1?u-,v = 0) observed in laboratory conditions. The inclusion of the interaction between O2(A?3?u) and CO2 molecules may explain high intensities of Herzberg II system observed in laboratory experiments with high CO2 concentrations and registered in the nightglow of Venusian atmosphere.

  16. 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.

  17. Theoretical calculations and vibrational spectra of 1,4-benzodioxan in its S 1(?, ? *) electronic excited state

    NASA Astrophysics Data System (ADS)

    Yang, Juan; Choo, Jaebum; Kwon, Ohyun; Laane, Jaan

    2007-12-01

    The structure and vibrational frequencies of 1,4-benzodioxan in its S 1(?, ? *) electronic state have been calculated using the GAUSSIAN 03 and TURBOMOLE programs. The results have been compared to experimental data and also to the ground state. Structural data for the T 1(?, ? *) state have also been calculated. The theoretical frequencies agree very well with the experimental values for the S 0 electronic ground state but are less accurate for the S 1 excited state. Nonetheless, they provide valuable guidance for excited state calculations.

  18. Calculation of Raman intensities for the ring-puckering vibrations of cyclopentene and 2,5-dihydrofuran

    NASA Astrophysics Data System (ADS)

    Bocian, David F.; Schick, G. Alan; Birge, Robert R.

    1981-10-01

    Raman intensities are calculated for the ring-puckering vibrations of cyclopentene and 2,5-dihydrofuran using an anisotropic atom-point dipole interaction model to calculate the elements of the molecular polarizability tensor. Large second-order terms are calculated for both molecules in the expansions of the molecular polarizability tensor elements in the ring-puckering coordinate [?(?2???/?Z2)0??0]. These terms result in intense calculated ?v = 2 overtone transitions, in agreement with experimental observations. The calculations predict that the ?v = 2 transitions of cyclopentene are one to two orders of magnitude more intense than the ?v = 1 fundamentals, while the two sets of transitions are comparable in intensity in 2,5-dihydrofuran. Although the shape of the band contours precludes observation of the ?v = 1 transitions for either molecule, the calculations suggest that the fundamental transitions of cyclopentene would not be observable even if the band shape were amenable to observation.

  19. 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).

  20. The silyl anion (SiH - 3): Harmonic vibrational frequencies and infrared intensities predicted at the SCF, CISD, and CCSD levels of theory with substantial basis sets

    NASA Astrophysics Data System (ADS)

    Shen, Mingzuo; Xie, Yaoming; Schaefer, Henry F., III

    1990-12-01

    Ab initio quantum mechanical methods have been applied to obtain harmonic vibrational frequencies and infrared intensities for the silyl anion (C3vSiH-3) in the gas phase. The best results in this study agree well with the limited experimental data of Ellison, although new experiments are required for an assessment of our predictions. The theoretical methods employed are the self-consistent field (SCF), configuration interaction with single and double excitations (CISD), and coupled cluster with single and double excitations (CCSD) methods. Basis sets used include double-zeta plus polarization (DZP), triple-zeta plus double polarization (TZ2P), and additional diffuse functions on the silicon atom [DZP+diff(Si), TZ2P+diff(Si)]. The umbrella mode of the silyl anion is most sensitive to basis set quality and electron correlation. Our best predicted vibrational frequency [CISD with TZ2P+diff(Si)] for this particular mode is 890 cm-1. At all levels of theory, the infrared (IR) intensities have been obtained. The planar transition state (D3hSiH-3) has also been studied with respect to its geometry and energy relative to the pyramidal structure.

  1. Vibrational spectra and chemical quantum calculations for 2-adamantylamino-5-nitropyridine crystals--a novel material for laser Raman converters.

    PubMed

    Lorenc, J; Hanuza, Jerzy; Maczka, Miros?aw; Kucharska, Edyta; Kaminskii, Alexander A; Kaino, Toshikuni; Yaima, Tetsuya; Yokoo, Atsushi

    2005-02-01

    Polycrystalline infrared and polarized FT-Raman spectra have been measured for 2-adamantylamino-5-nitropyridine, a novel organic material for laser Raman converters. The assignment of IR and Raman bands is given on the basis of DFT calculations. The spectroscopic studies have not indicated the presence of any significant intermolecular interactions in the crystal structure of this compound. The lines observed in the stimulated Raman spectrum of this crystal are assigned to the respective molecular vibrations. PMID:15649801

  2. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

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

  5. A complete assignment of the vibrational spectra of sucrose in aqueous medium based on the SQM methodology and SCRF calculations.

    PubMed

    Brizuela, Alicia Beatriz; Castillo, María Victoria; Raschi, Ana Beatriz; Davies, Lilian; Romano, Elida; Brandán, Silvia Antonia

    2014-03-31

    In the present study, a complete assignment of the vibrational spectra of sucrose in aqueous medium was performed combining Pulay's Scaled Quantum Mechanics Force Field (SQMFF) methodology with self-consistent reaction field (SCRF) calculations. Aqueous saturated solutions of sucrose and solutions at different molar concentrations of sucrose in water were completely characterized by infrared, HATR, and Raman spectroscopies. In accordance with reported data of the literature for sucrose, the theoretical structures of sucrose penta and sucrose dihydrate were also optimized in gas and aqueous solution phases by using the density functional theory (DFT) calculations. The solvent effects for the three studied species were analyzed using the solvation PCM/SMD model and, then, their corresponding solvation energies were predicted. The presence of pure water, sucrose penta-hydrate, and sucrose dihydrate was confirmed by using theoretical calculations based on the hybrid B3LYP/6-31G(?) method and the experimental vibrational spectra. The existence of both sucrose hydrate complexes in aqueous solution is evidenced in the IR and HATR spectra by means of the characteristic bands at 3388, 3337, 3132, 1648, 1375, 1241, 1163, 1141, 1001, 870, 851, 732, and 668cm(-1) while in the Raman spectrum, the groups of bands in the regions 3159-3053cm(-1), 2980, 2954, and 1749-1496cm(-1) characterize the vibration modes of those complexes. The inter and intra-molecular H bond formations in aqueous solution were studied by Natural Bond Orbital (NBO) and Atoms in Molecules theory (AIM) investigation. PMID:24632216

  6. 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.

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

    NASA Astrophysics Data System (ADS)

    Leadenham, S.; Erturk, A.

    2014-11-01

    Over the past few years, nonlinear oscillators have been given growing attention due to their ability to enhance the performance of energy harvesting devices by increasing the frequency bandwidth. Duffing oscillators are a type of nonlinear oscillator characterized by a symmetric hardening or softening cubic restoring force. In order to realize the cubic nonlinearity in a cantilever at reasonable excitation levels, often an external magnetic field or mechanical load is imposed, since the inherent geometric nonlinearity would otherwise require impractically high excitation levels to be pronounced. As an alternative to magnetoelastic structures and other complex forms of symmetric Duffing oscillators, an M-shaped nonlinear bent beam with clamped end conditions is presented and investigated for bandwidth enhancement under base excitation. The proposed M-shaped oscillator made of spring steel is very easy to fabricate as it does not require extra discrete components to assemble, and furthermore, its asymmetric nonlinear behavior can be pronounced yielding broadband behavior under low excitation levels. For a prototype configuration, linear and nonlinear system parameters extracted from experiments are used to develop a lumped-parameter mathematical model. Quadratic damping is included in the model to account for nonlinear dissipative effects. A multi-term harmonic balance solution is obtained to study the effects of higher harmonics and a constant term. A single-term closed-form frequency response equation is also extracted and compared with the multi-term harmonic balance solution. It is observed that the single-term solution overestimates the frequency of upper saddle-node bifurcation point and underestimates the response magnitude in the large response branch. Multi-term solutions can be as accurate as time-domain solutions, with the advantage of significantly reduced computation time. Overall, substantial bandwidth enhancement with increasing base excitation is validated experimentally, analytically, and numerically. As compared to the 3 dB bandwidth of the corresponding linear system with the same linear damping ratio, the M-shaped oscillator offers 3200, 5600, and 8900 percent bandwidth enhancement at the root-mean-square base excitation levels of 0.03g, 0.05g, and 0.07g, respectively. The M-shaped configuration can easily be exploited in piezoelectric and electromagnetic energy harvesting as well as their hybrid combinations due to the existence of both large strain and kinetic energy regions. A demonstrative case study is given for electromagnetic energy harvesting, revealing the importance of higher harmonics and the need for multi-term harmonic balance analysis for predicting the electrical power output accurately.

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

    SciTech Connect

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

    2014-05-07

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  10. Calculation of density functional theory (DFT) vibrational parameters of nucleotides for use in theoretical optical calculations: Herein applied to circular dichroism (CD) and absorption of polynucleotides

    NASA Astrophysics Data System (ADS)

    Ferber, Steven Dwight

    2005-11-01

    The Vibrational Circular Dichroism (VCD) of Nucleic Acids is a sensitive function of their conformation. DeVoe's classically derived polarizability theory allows the calculation of polymer absorption and circular dichroism spectra in any frequency range. Following the approach of Tinoco and Cech as modified by Moore and Self, calculations were done in the infrared (IR) region with theoretically derived monomer input parameters. Presented herein are calculated absorption and CD spectra for nucleic acid oligomers and polymers. These calculations improve upon earlier attempts, which utilized frequencies, intensities and normal modes from empirical analysis of the nitrogenous base of the monomers. These more complete input polarizability parameters include all contributions to specific vibrational normal modes for the entire nucleotide structure. They are derived from density functional theory (DFT) vibrational analysis on quasi-nucleotide monomers using the GAUSSIAN '98/'03 program. The normal modes are "integrated" for the first time into single virtual (DeVoe) oscillators by incorporating "fixed partial charges" in the manner of Schellman. The results include the complete set of monomer normal modes. All of these modes may be analyzed, in a manner similar to those demonstrated here (for the 1500-1800 cm-1 region). A model is utilized for the polymer/oligomer monomers which maintains the actual electrostatic charge on the adjacent protonated phosphoryl groups (hydrogen phosphate, a mono-anion). This deters the optimization from "collapsing" into a hydrogen-bonded "ball" and thereby maintains the extended (polymer-like) conformation. As well, the precise C2 "endo" conformation of the sugar ring is maintained in the DNA monomers. The analogous C3 "endo" conformation is also maintained for the RNA monomers, which are constrained by massive "anchors" at the phosphates. The complete IR absorbance spectra (0-4,000 cm-1) are calculated directly in Gaussian. Calculated VCD and Absorbance Spectra for the eight standard Ribonucleic and Deoxy-ribonucleic acid homo-polymers in the nitrogenous base absorbing region 1550-1750 cm-1 are presented. These spectra match measured spectra at least as well as spectra calculated from empirical parameters. These results demonstrate that the purely theoretical calculation, an example given herein, should serve to provide more transferable, universal parameters for the polarizability treatment of the optical properties of oligomers and polymers.

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

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

    NASA Astrophysics Data System (ADS)

    Thore, A.; Dahlqvist, M.; Alling, B.; Rosén, J.

    2014-09-01

    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.

  13. First-principles calculations of the electronic, vibrational, and elastic properties of the magnetic laminate Mn?GaC

    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 Mn?GaC. 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, Mn?GaC 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 M?AC phases where M?=?Ti, V, Cr, Zr, Nb, Ta, and A?=?Al, S, Ge, In, Sn.

  14. 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.

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

    PubMed

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

    2015-11-14

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

  16. 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.

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

    NASA Astrophysics Data System (ADS)

    Mielke, Steven L.; Truhlar, Donald G.

    2015-01-01

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

  18. 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 2? 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. PMID:25637967

  19. 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

    SciTech Connect

    Mielke, Steven L. E-mail: truhlar@umn.edu; Truhlar, Donald G. E-mail: truhlar@umn.edu

    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{sup ?6}) to O(P{sup ?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 2? 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.

  20. Vibrational Spectra, Theoretical Calculations, and Structures of Cyclic Silanes, 2,4,7-Trioxa(3.3.0)Octane and Botryococcenes 

    E-print Network

    Chun, Hye Jin

    2014-12-08

    The vibrational spectra and structures of several cyclic silanes and a bicyclic molecule have been investigated with high-level ab initio and density function theory (DFT) calculations. In addition, the Raman spectra of botryococcene hydrocarbons...

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

    NASA Astrophysics Data System (ADS)

    Toy, Mehmet; Tanak, Hasan

    2016-01-01

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

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

    PubMed

    Toy, Mehmet; Tanak, Hasan

    2016-01-01

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

  3. A new treatment for predicting the self-excited vibrations of nonlinear systems with frictional interfaces: The Constrained Harmonic Balance Method, with application to disc brake squeal

    NASA Astrophysics Data System (ADS)

    Coudeyras, N.; Sinou, J.-J.; Nacivet, S.

    2009-01-01

    Brake squeal noise is still an issue since it generates high warranty costs for the automotive industry and irritation for customers. Key parameters must be known in order to reduce it. Stability analysis is a common method of studying nonlinear phenomena and has been widely used by the scientific and the engineering communities for solving disc brake squeal problems. This type of analysis provides areas of stability versus instability for driven parameters, thereby making it possible to define design criteria. Nevertheless, this technique does not permit obtaining the vibrating state of the brake system and nonlinear methods have to be employed. Temporal integration is a well-known method for computing the dynamic solution but as it is time consuming, nonlinear methods such as the Harmonic Balance Method (HBM) are preferred. This paper presents a novel nonlinear method called the Constrained Harmonic Balance Method (CHBM) that works for nonlinear systems subject to flutter instability. An additional constraint-based condition is proposed that omits the static equilibrium point (i.e. the trivial static solution of the nonlinear problem that would be obtained by applying the classical HBM) and therefore focuses on predicting both the Fourier coefficients and the fundamental frequency of the stationary nonlinear system. The effectiveness of the proposed nonlinear approach is illustrated by an analysis of disc brake squeal. The brake system under consideration is a reduced finite element model of a pad and a disc. Both stability and nonlinear analyses are performed and the results are compared with a classical variable order solver integration algorithm. Therefore, the objectives of the following paper are to present not only an extension of the HBM (CHBM) but also to demonstrate an application to the specific problem of disc brake squeal with extensively parametric studies that investigate the effects of the friction coefficient, piston pressure, nonlinear stiffness and structural damping.

  4. 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 from: CPC Program Library, Queen's University of Belfast, N. Ireland Reference in CPC to previous version: 86 (1995) 175 Catalogue identifier of previous version: ADAK Authors of previous version: J. Tennyson, J.R. Henderson and N.G. Fulton Does the new version supersede the original program?: DVR3DRJZ supersedes DVR3DRJ Computer: PC running Linux Installation: desktop Other machines on which program tested: Compaq running True64 Unix; SGI Origin 2000, Sunfire V750 and V880 systems running SunOS, IBM p690 Regatta running AIX Programming language used in the new version: Fortran 90 Memory required to execute: case dependent No. of lines in distributed program, including test data, etc.: 4203 No. of bytes in distributed program, including test data, etc.: 30 087 Has code been vectorised or parallelised?: The code has been extensively vectorised. A parallel version of the code, PDVR3D has been developed [1], contact the first author for details Additional keywords: perpendicular embedding Distribution format: gz Nature of physical problem: DVR3DRJZ calculates the bound vibrational or Coriolis decoupled rotational-vibrational states of a triatomic system in body-fixed Jacobi (scattering) or Radau coordinates [2] Method of solution: All coordinates are treated in a discrete variable representation (DVR). The angular coordinate uses a DVR based on (associated) Legendre polynomials and the radial coordinates utilise a DVR based on either Morse oscillator-like or spherical oscillator functions. Intermediate diagonalisation and truncation is performed on the hierarchical expression of the Hamiltonian operator to yield the final secular problem. DVR3DRJ provides the vibrational wavefunctions necessary for ROTLEV3, ROLEV3B or ROTLEV3Z to calculate rotationally excited states, DIPOLE3 to calculate rotational-vibrational transition strengths and XPECT3 to compute expectation values Restrictions on the complexity of the problem: (1) The size of the final Hamiltonian matrix that can practically be diagonalised. (2) The order of integration in the radial coordinates that can b

  5. Conformational and Vibrational Studies of Triclosan

    NASA Astrophysics Data System (ADS)

    Özi?ik, Haci; Bayari, S. Haman; Sa?lam, 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.

  6. Ab initio calculations and INS measurements of phonons and molecular vibrations in a model peptide compound urea

    NASA Astrophysics Data System (ADS)

    Johnson, M. R.; Parlinski, K.; Natkaniec, I.; Hudson, B. S.

    2003-06-01

    Density functional theory (DFT) methods, as implemented in the V ASP code, are used to calculate the inelastic neutron scattering (INS) spectrum of urea, which has been measured on the T OSCA spectrometer at ISIS, UK and the NERA-PR spectrometer at Dubna, Russia. Urea presents an extended network of bifurcated hydrogen bonds resulting in significant dispersion of the vibrational excitations, both for external and internal modes. The small mass of the molecule also results in intense multiphonon contributions to the spectral profile. Recent, successful applications of DFT in molecular spectroscopy are extended here using the P HONON code to include dispersion and multiphonon contributions to the INS spectrum. Thus the whole spectral profile is calculated with only the crystal structure as input. The accuracy of the calculated normal modes is demonstrated for protonated and deuterated urea.

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

    NASA Technical Reports Server (NTRS)

    Chandra, N.; Temkin, A.

    1976-01-01

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

  8. Characterization of a Genuine Lron(V)-Nitrido Species By Nuclear Resonant Vibrational Spectroscopy Coupled to Density Functional Calculations

    SciTech Connect

    Petrenko, T.; George, S.D.; Aliaga-Alcalde, N.; Bill, E.; Mienert, B.; Xiao, Y.; Guo, Y.; Sturhahn, W.; Cramer, S.P.; Wieghardt, K.; Neese, F.; /Bonn U., LTC /SLAC, SSRL /Max Planck Inst., Mulheim /UC, Davis /Argonne /LBL, Berkeley

    2007-10-19

    The characterization of high-valent iron species is of interest due to their relevance to biological reaction mechanisms. Recently, we have synthesized and characterized an [Fe(V)-nitrido-cyclam-acetato]+ complex, which has been characterized by M{umlt o}ssbauer, magnetic susceptibility data, and XAS spectroscopies combined with DFT calculations. The results of this study indicated that the [Fe(V)-nitrido-cyclam-acetato]+ complex is an unusual d3 system with a nearly orbitally degenerate S = 1/2 ground state. Although the calculations predicted fairly different Fe-N stretching frequencies for the S = 1/2 and the competing S = 3/2 ground states, a direct experimental determination of this important fingerprint quantity was missing. Here we apply synchrotron-based nuclear resonance vibrational scattering (NRVS) to characterize the Fe-N stretching frequency of an Fe(V)-nitrido complex and its Fe(III)-azide precursor. The NRVS data show a new isolated band at 864 cm-1 in the Fe(V)-nitrido complex that is absent in the precursor. The NRVS spectra are fit and simulated using a DFT approach, and the new feature is unambiguously assigned to a Fe(V)-N stretch. The calculated Fe-N stretching frequency is too high by {approx}75 cm-1. Anharmonic contributions to the Fe-N stretching frequency have been evaluated and have been found to be small (-5.5 cm-1). The NRVS data provided a unique opportunity to obtain this vibrational information, which had eluded characterization by more traditional vibrational spectroscopies.

  9. 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. PMID:17664964

  10. 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 (?) and the first hyperpolarizability (?) that results in the nonlinearity of the molecule. PMID:24892542

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

    DOE PAGESBeta

    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 CH? 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

  12. 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? 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.

  13. An accurate {ital ab initio} HOCl potential energy surface, vibrational and rotational calculations, and comparison with experiment

    SciTech Connect

    Skokov, S.; Peterson, K.A.; Bowman, J.M.

    1998-08-01

    Accurate {ital ab initio} multireference configuration interaction (CI) calculations with large correlation-consistent basis sets are performed for HOCl. After extrapolation to the complete basis set limit, the {ital ab initio} data are precisely fit to give a semiglobal three-dimensional potential energy surface to describe HOCl{r_arrow}Cl+OH from high overtone excitation of the OH-stretch. The average absolute deviation between the {ital ab initio} and fitted energies is 4.2thinspcm{sup {minus}1} for energies up to 60 kcal/mol relative to the HOCl minimum. Vibrational energies of HOCl including the six overtones of the OH-stretch are computed using a vibrational-Cl method on the fitted potential and also on a slightly adjusted potential. Near-spectroscopic accuracy is obtained using the adjusted potential; the average absolute deviation between theory and experiment for 19 experimentally reported states is 4.8thinspcm{sup {minus}1}. Very good agreement with experiment is also obtained for numerous rotational energies for the ground vibrational state, the ClO-stretch fundamental, and the fifth overtone of the OH-stretch. {copyright} {ital 1998 American Institute of Physics.}

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  15. 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.

  16. 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. PMID:26168865

  17. First-principles calculations of the dielectric and vibrational properties of ferroelectric and paraelectric BaAl2O4

    NASA Astrophysics Data System (ADS)

    Xie, Congwei; Zeng, Qingfeng; Dong, Dong; Gao, Shuang; Cai, Yongqing; Oganov, Artem R.

    2014-05-01

    First-principles calculations have been conducted to study the structural, dielectric, and vibrational properties of ferroelectric and paraelectric BaAl2O4. High-frequency and static dielectric constants, and phonon frequencies at the Brillouin zone center are reported. Both BaAl2O4 polymorphs are promising infrared-transparent materials due to their low electronic dielectric constants. The ferroelectric and paraelectric BaAl2O4 have much smaller permittivity compared to the classical ferroelectric materials. From an atomic nanostructure standpoint, the abnormally low permittivity of BaAl2O4 polymorphs is mainly related to low coordination numbers of Ba (9) and Al (4).

  18. High-order-harmonic generation from H2+ molecular ions near plasmon-enhanced laser fields

    NASA Astrophysics Data System (ADS)

    Yavuz, I.; Tikman, Y.; Altun, Z.

    2015-08-01

    Simulations of plasmon-enhanced high-order-harmonic generation are performed for a H2+ molecular cation near the metallic nanostructures. We employ the numerical solution of the time-dependent Schrödinger equation in reduced coordinates. We assume that the main axis of H2+ is aligned perfectly with the polarization direction of the plasmon-enhanced field. We perform systematic calculations on plasmon-enhanced harmonic generation based on an infinite-mass approximation, i.e., pausing nuclear vibrations. Our simulations show that molecular high-order-harmonic generation from plasmon-enhanced laser fields is possible. We observe the dispersion of a plateau of harmonics when the laser field is plasmon enhanced. We find that the maximum kinetic energy of the returning electron follows 4 Up . We also find that when nuclear vibrations are enabled, the efficiency of the harmonics is greatly enhanced relative to that of static nuclei. However, the maximum kinetic energy 4 Up is largely maintained.

  19. A receptance harmonic balance technique for the computation of the vibration of a whole aero-engine model with nonlinear bearings

    NASA Astrophysics Data System (ADS)

    Bonello, Philip; Minh Hai, Pham

    2009-07-01

    Current frequency-domain techniques for the rapid computation of the steady-state periodic vibration of unbalanced rotordynamic systems with nonlinear bearings are not suitable for realistic engine structures like aero-engine assemblies. In this paper, a whole-engine receptance harmonic balance method (RHBM) is devised that, for the first time, allows the frequency domain analysis of such a structure. The method uses the receptance functions of the linear part of the structure under non-rotational conditions, obtained from a one-off eigenvalue analysis, to set up the equations for the rotating nonlinear assembly. The unknowns solved for are the Fourier coefficients of the relative displacements at the nonlinear bearings plus a few extra unknowns. These latter unknowns enable solution of the problem in the presence of statically indeterminate rotors that have just one linear point support or none at all. Simulation tests on a realistically sized representative twin-spool engine showed excellent correlation with time-marching results obtained from the recently developed impulsive receptance method (IRM). It is demonstrated that, when used in conjunction with a time-marching solver like the IRM, the RHBM is a very powerful tool that should greatly facilitate the hitherto highly restricted nonlinear dynamic analysis of realistic engine structures.

  20. Calculation of rotational--vibrational preionization in H/sub 2/ by multichannel quantum defect theory

    SciTech Connect

    Jungen, C.; Dill, D.

    1980-10-01

    Multichannel quantum defect theory is adapted to treat simultaneous rotational and vibrational preionization in H/sub 2/. The strongly preionized spectrum between the N/sup +/=0 and N/sup +/=2 rotational thresholds of photoionization of H/sub 2/X/sup 1/..sigma../sub g//sup +/(J''=0, v''=0) to produce H/sub 2//sup +/X/sup 2/..sigma../sub g//sup +/(N/sup +/, v/sup +/=0) is computed as example and good agreement is obtained with the photoionization data of Dehmer and Chupka.

  1. 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.

  2. Ab initio molecular dynamics with noisy and cheap quantum Monte Carlo forces: accurate calculation of vibrational frequencies

    NASA Astrophysics Data System (ADS)

    Luo, Ye; Sorella, Sandro

    2014-03-01

    We introduce a general and efficient method for the calculation of vibrational frequencies of electronic systems, ranging from molecules to solids. By performing damped molecular dynamics with ab initio forces, we show that quantum vibrational frequencies can be evaluated by diagonalizing the time averaged position-position or force-force correlation matrices, although the ionic motion is treated on the classical level within the Born-Oppenheimer approximation. The novelty of our approach is to evaluate atomic forces with QMC by means of a highly accurate and correlated variational wave function which is optimized simultaneously during the dynamics. QMC is an accurate and promising many-body technique for electronic structure calculation thanks to massively parallel computers. However, since infinite statistics is not feasible, property evaluation may be affected by large noise that is difficult to harness. Our approach controls the QMC stochastic bias systematically and gives very accurate results with moderate computational effort, namely even with noisy forces. We prove the accuracy and efficiency of our method on the water monomer[A. Zen et al., JCTC 9 (2013) 4332] and dimer. We are currently working on the challenging problem of simulating liquid water at ambient conditions.

  3. 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.

  4. Pushing the limits in accurate vibrational structure calculations: anharmonic frequencies of lithium fluoride clusters (LiF)n, n = 2-10.

    PubMed

    Oschetzki, Dominik; Rauhut, Guntram

    2014-08-21

    The vibrational spectra of a series of small lithium fluoride clusters, i.e. (LiF)n, n = 2-10, were studied by vibrational configuration interaction (VCI) calculations relying on potential energy surfaces including three-mode coupling terms and being obtained from explicitly correlated local coupled cluster calculations. Due to the account for anharmonicity effects, the simulated spectra allow for a direct comparison with experimental data and may thus help to identify clusters in the experiments. Even structurally closely related clusters can clearly be distinguished by infrared spectroscopy. The largest system in this study required more than 1000 basis functions in the electronic structure calculations and more than 10(7) configurations in the vibrational structure calculations and became computationally feasible only due to a combination of different approximations and highly parallelized algorithms. PMID:24981078

  5. 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.

  6. Calculation of vibrational (J=0) excitation energies and band intensities of formaldehyde using the recursive residue generation method

    NASA Astrophysics Data System (ADS)

    Poulin, Nicolas M.; Bramley, Matthew J.; Carrington, Tucker, Jr.; Kjaergaard, Henrik G.; Henry, Bryan R.

    1996-05-01

    We use the recursive residue generation method (RRGM) with an exact kinetic energy operator to calculate vibrational excitation energies and band intensities for formaldehyde. The basis is a product of one-dimensional potential optimized discrete variable representation (PO-DVR) functions for each coordinate. We exploit the symmetry by using symmetry adapted basis functions obtained by taking linear combinations of PO-DVR functions. Our largest basis set consists of 798 600 functions (per symmetry block). The Lanczos tridiagonal representation of the Hamiltonian is generated iteratively (without constructing matrix elements explicitly) by sequential transformations. We determine a six-dimensional dipole moment function from the ab initio dipole moment values computed at the QCISD level with a 6-311++G(d,p) basis set. We converged all A1, B2 and B1 vibrational states up to the combination band with two quanta in the C-O stretch and one quantum in a C-H stretch at about 6 350 cm-1 above zero point energy. We present a simulated (J=0) infrared spectrum of CH2O for transitions from the ground state.

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

    DOE PAGESBeta

    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 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

  8. Vibrational spectroscopic study of fluticasone propionate

    NASA Astrophysics Data System (ADS)

    Ali, H. R. H.; Edwards, H. G. M.; Kendrick, J.; Scowen, I. J.

    2009-03-01

    Fluticasone propionate is a synthetic glucocorticoid with potent anti-inflammatory activity that has been used effectively in the treatment of chronic asthma. The present work reports a vibrational spectroscopic study of fluticasone propionate and gives proposed molecular assignments on the basis of ab initio calculations using BLYP density functional theory with a 6-31G* basis set and vibrational frequencies predicted within the quasi-harmonic approximation. Several spectral features and band intensities are explained. This study generated a library of information that can be employed to aid the process monitoring of fluticasone propionate.

  9. Infrared and Raman Spectroscopy of Eugenol, Isoeugenol, and Methyl Eugenol: Conformational Analysis and Vibrational Assignments from Density Functional Theory Calculations of the Anharmonic Fundamentals.

    PubMed

    Chowdhry, Babur Z; Ryall, John P; Dines, Trevor J; Mendham, Andrew P

    2015-11-19

    IR and Raman spectra of eugenol, isoeugenol and methyl eugenol have been obtained in the liquid phase. Vibrational spectroscopic results are discussed in relation to computed structures and spectra of the low energy conformations of these molecules obtained from DFT calculations at the B3LYP/cc-pVTZ level. Although computed differences in vibrational spectra for the different conformers were generally small, close examination, in conjunction with the experimental spectra, enabled conformational analysis of all three molecules. Anharmonic contributions to computed vibrational spectra were obtained from calculations of cubic and quartic force constants at the B3LYP/DZ level. This permitted the determination of the anharmonic fundamentals for comparison with the experimental IR and Raman band positions, leading to an excellent fit between calculated and experimental spectra. Band assignments were obtained in terms of potential energy distributions (ped's). PMID:26496173

  10. 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. PMID:16788266

  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. 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}).

  13. Fourier grid Hamiltonian multiconfigurational self-consistent-field: A method to calculate multidimensional hydrogen vibrational

    E-print Network

    Hammes-Schiffer, Sharon

    Fourier grid Hamiltonian multiconfigurational self-consistent-field: A method to calculate Received 10 May 2000; accepted 28 June 2000 The Fourier Grid Hamiltonian Multiconfigurational Self that are products of one-dimensional wavefunctions, with a Fourier grid method that represents the one

  14. 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.

  15. 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.

  16. 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.

  17. 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, ? = 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 ?-? 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.

  18. Density functional theory study, FT-IR and FT-Raman spectra and SQM force field calculation for vibrational analysis of 1, 3-Bis (hydroxymethyl) benzimidazolin-2-one

    NASA Astrophysics Data System (ADS)

    Joseph, Lynnette; Sajan, D.; Chaitanya, K.; Devarajegowda, H. C.; Isac, Jayakumary

    2013-10-01

    FT-IR and FT-Raman spectra of 1, 3-Bis (hydroxymethyl) benzimidazolin-2-one were recorded and analyzed in the solid phase. The optimized molecular geometry and vibrational wavenumbers have also been calculated in optimized structure by using DFT method. Scaled quantum mechanical force fields have also been used to calculate potential energy distributions in order to make conspicuous vibrational assignments. The red shifting of the Osbnd H stretching wavenumber is due to the formation of Osbnd H⋯O intermolecular hydrogen bonding. The lowering and splitting of the carbonyl stretching vibrational modes is assigned to the intermolecular association based on Cdbnd O⋯H type hydrogen bonding in the molecule. Chemical interpretation of hyperconjugative interactions was done by natural bond orbital analysis.

  19. Storage capacity and vibration frequencies of guest molecules in CH4 and CO2 hydrates by first-principles calculations.

    PubMed

    Cao, Xiaoxiao; Su, Yan; Liu, Yuan; Zhao, Jijun; Liu, Changling

    2014-01-01

    Using first-principle calculations at B97-D/6-311++G(2d,2p) level, we systematically explore the gas capacity of five standard water cavities (5(12), 4(3)5(6)6(3), 5(12)6(2), 5(12)6(4), and 5(12)6(8)) in clathrate hydrate and study the inclusion complexes to infer general trends in vibrational frequencies of guest molecules as a function of cage size and number of guest molecules. In addition, the Raman spectra of hydrates from CO2/CH4 gases are simulated. From our calculations, the maximum cage occupancy of the five considered cages (5(12), 4(3)5(6)6(3), 5(12)6(2), 5(12)6(4), and 5(12)6(8)) is one, one, two, three, and seven for both CH4 and CO2 guest molecules, respectively. Meanwhile, the optimum cage occupancy are one, one, one, two, and four for CO2 molecules and one, one, two, three, and five for CH4 molecules, respectively. Both the C-H stretching frequency of CH4 and the C-O stretching frequency of CO2 gradually decrease as size of the water cages increases. Meanwhile, the C-H stretching frequency gradually increases as the amount of CH4 molecules in the water cavity (e.g., 5(12)6(8)) increases. PMID:24320601

  20. 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.

  1. MORSMATEL: a rapid and efficient code to calculate vibration-rotational matrix elements for r-dependent operators of two Morse oscillators

    NASA Astrophysics Data System (ADS)

    Lopez-Piñeiro, A.; Sanchez, M. L.; Moreno, B.

    1992-06-01

    The computer program MORSMATEL has been developed to calculate vibrational-rotational matrix elements of several r-dependent operators of two Morse oscillators. This code is based on a set of recurrence relations which are valid for any value of the power and of the quantum numbers v and J of each oscillator.

  2. Calculation of the harmonic spectrum for one and two-electron atoms in two-colour laser fields

    NASA Astrophysics Data System (ADS)

    Robinson, D. J.; Parker, J. S.; Moore, L. R.; Taylor, K. T.

    2012-11-01

    We study the behaviour of hydrogen and helium atoms in intense two-colour linearly-polarised laser fields. Two cases are considered - the case where both fields act with parallel axes of polarisation and the case where the polarisation axes are perpendicular. We report extensions of the HELIUM code and a related hydrogen code to study these two cases of the two-colour problem. The impact of the second laser pulse on the harmonic spectrum is explored.

  3. Molecular conformational analysis, vibrational spectra and normal coordinate analysis of trans-1,2-bis(3,5-dimethoxy phenyl)-ethene based on density functional theory calculations.

    PubMed

    Joseph, Lynnette; Sajan, D; Chaitanya, K; Isac, Jayakumary

    2014-03-25

    The conformational behavior and structural stability of trans-1,2-bis(3,5-dimethoxy phenyl)-ethene (TDBE) were investigated by using density functional theory (DFT) method with the B3LYP/6-311++G(d,p) basis set combination. The vibrational wavenumbers of TDBE were computed at DFT level and complete vibrational assignments were made on the basis of normal coordinate analysis calculations (NCA). The DFT force field transformed to natural internal coordinates was corrected by a well-established set of scale factors that were found to be transferable to the title compound. The infrared and Raman spectra were also predicted from the calculated intensities. The observed Fourier transform infrared (FTIR) and Fourier transform (FT) Raman vibrational wavenumbers were analyzed and compared with the theoretically predicted vibrational spectra. Comparison of the simulated spectra with the experimental spectra provides important information about the ability of the computational method to describe the vibrational modes. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecules has been obtained by mapping electron density isosurface with electrostatic potential surfaces (ESP). PMID:24317264

  4. Isomers and conformers of two push pull hydrazines studied by NMR and vibrational spectroscopy and by ab initio calculations

    NASA Astrophysics Data System (ADS)

    Gróf, M.; Polovková, J.; Gatial, A.; Milata, V.; ?ernuchová, P.; Prónayová, N.; Mat?jka, P.

    2007-05-01

    The isomers and conformers of two push-pull hydrazines: 3- N, N-dimethylhydrazino-2-acetyl propenenitrile [(H 3C) 2N sbnd NH sbnd CH dbnd C(CN)(COCH 3)] (DMHAP) and 3- N, N-dimethylhydrazino-2-methylsulfonyl propenenitrile [(H 3C) 2N sbnd NH sbnd CH dbnd C(CN)(SO 2CH 3)] (DMHSP) have been studied experimentally by NMR and vibrational spectroscopy and theoretically by the ab initio calculations at MP2 level in 6-31G** basis set. The IR and Raman spectra of both compounds as a solid and solute in various solvents have been recorded. The NMR spectra were obtained in chloroform and DMSO at room temperature. Both compounds have been prepared by the same way. NMR spectra revealed that DMHAP was prepared as a pure Z-isomer whereas in the case of DMHSP a pure E-isomer was obtained. Due to the low barrier for both compounds practically free isomerisation process occurred in the solutions but in opposite directions. Whereas DMHAP exists in the solid state and in the less polar solvent as Z-isomer, in more polar solvents the appearance of next two conformers of E-isomer was observed. On the contrary DMHSP exists in the solid state and in the more polar solvent as E-isomer only but in less polar solvent the presence of Z-isomer was observed as well. Conformational possibilities of both studied compounds are given by the rotation of dimethylhydrazino group with its anti- or syn-orientation towards the olefinic double bond. Moreover, by the rotation of the acetyl group with Z- and E-orientation of carbonyl bond towards olefinic double bond can occur in DMHAP. Vibrational and NMR spectra revealed the existence of single conformer with intramolecular hydrogen bond for Z-isomer in less polar solvent and next two conformers for E-isomer of DMHAP with Z-orientation of acetyl group and anti and syn orientation of dimethylhydrazine group in more polar solvents. For E-isomer of DMHSP two conformers with anti or syn orientations of dimethylhydrazino group have been also confirmed by NMR spectra in more polar solvents. Additionally the third DMHSP conformer with anti orientation of dimethylhydrazino group originating from Z-isomer was detected in less polar solvents. These experimental findings have been supported by ab initio calculations with solvent effect inclusion.

  5. Energy, contact, and density profiles of one-dimensional fermions in a harmonic trap via nonuniform-lattice Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Berger, C. E.; Anderson, E. R.; Drut, J. E.

    2015-05-01

    We determine the ground-state energy and Tan's contact of attractively interacting few-fermion systems in a one-dimensional harmonic trap, for a range of couplings and particle numbers. Complementing those results, we show the corresponding density profiles. The calculations were performed with a lattice Monte Carlo approach based on a nonuniform discretization of space, defined via Gauss-Hermite quadrature points and weights. This particular coordinate basis is natural for systems in harmonic traps, and can be generalized to traps of other shapes. In all cases, it yields a position-dependent coupling and a corresponding nonuniform Hubbard-Stratonovich transformation. The resulting path integral is performed with hybrid Monte Carlo as a proof of principle for calculations at finite temperature and in higher dimensions. We present results for N =4 ,...,20 particles (although the method can be extended beyond that) to cover the range from few- to many-particle systems. This method is exact up to statistical and systematic uncertainties, which we account for—and thus also represents an ab initio calculation of this system, providing a benchmark for other methods and a prediction for ultracold-atom experiments.

  6. Ion-orbital coupling in Car-Parrinello calculations of hydrogen-bond vibrational dynamics: Case study with the NH3-HCl dimer

    NASA Astrophysics Data System (ADS)

    Ong, S. W.; Lee, B. X. B.; Kang, H. C.

    2011-09-01

    We have performed Car-Parrinello molecular dynamics (CPMD) calculations of the hydrogen-bonded NH3-HCl dimer. Our main aim is to establish how ionic-orbital coupling in CPMD affects the vibrational dynamics in hydrogen-bonded systems by characterizing the dependence of the calculated vibrational frequencies upon the orbital mass in the adiabatic limit of Car-Parrinello calculations. We use the example of the NH3-HCl dimer because of interest in its vibrational spectrum, in particular the magnitude of the frequency shift of the H-Cl stretch due to the anharmonic interactions when the hydrogen bond is formed. We find that an orbital mass of about 100 a.u. or smaller is required in order for the ion-orbital coupling to be linear in orbital mass, and the results for which can be accurately extrapolated to the adiabatic limit of zero orbital mass. We argue that this is general for hydrogen-bonded systems, suggesting that typical orbital mass values used in CPMD are too high to accurately describe vibrational dynamics in hydrogen-bonded systems. Our results also show that the usual application of a scaling factor to the CPMD frequencies to correct for the effects of orbital mass is not valid. For the dynamics of the dimer, we find that the H-Cl stretch and the N-H-Cl bend are significantly coupled, suggesting that it is important to include the latter degree of freedom in quantum dynamical calculations. Results from our calculations with deuterium-substitution show that both these degrees of freedom have significant anharmonic interactions. Our calculated frequency for the H-Cl stretch using the Becke-exchange Lee-Yang-Parr correlation functional compares reasonably well with a previous second-order Møller-Plesset calculation with anharmonic corrections, although it is low compared to the experimental value for the dimer trapped in a neon-matrix.

  7. Calculation of exact vibrational spectra for P{sub 2}O and CH{sub 2}NH using a phase space wavelet basis

    SciTech Connect

    Halverson, Thomas Poirier, Bill

    2014-05-28

    ‘‘Exact” quantum dynamics calculations of vibrational spectra are performed for two molecular systems of widely varying dimensionality (P{sub 2}O and CH{sub 2}NH), using a momentum-symmetrized Gaussian basis. This basis has been previously shown to defeat exponential scaling of computational cost with system dimensionality. The calculations were performed using the new “SWITCHBLADE” black-box code, which utilizes both dimensionally independent algorithms and massive parallelization to compute very large numbers of eigenstates for any fourth-order force field potential, in a single calculation. For both molecules considered here, many thousands of vibrationally excited states were computed, to at least an “intermediate” level of accuracy (tens of wavenumbers). Future modifications to increase the accuracy to “spectroscopic” levels, along with other potential future improvements of the new code, are also discussed.

  8. Calculated vibrational frequencies for FeMo-co, the active site of nitrogenase, bearing hydrogen atoms and carbon monoxide.

    PubMed

    Dance, Ian

    2011-06-28

    The intramolecular hydrogenation paradigm for the reducing actions of the enzyme nitrogenase postulates that the iron-molybdenum cofactor (FeMo-co, Fe(7)MoS(9)N(homocitrate)) as active site contains H atoms bound to Fe and S during the catalytic cycle, and that these H atoms are the reducing agents. The reduction of N(2) and of all other non-physiological substrates is strongly inhibited by carbon monoxide, except for the formation of H(2) from protons. It has been recently reported that vanadium nitrogenase and modified molybdenum nitrogenase reduce CO to hydrocarbons. Therefore many questions now arise about relationships between CO and H on the nitrogenase cofactors. In order to assist the interpretation of kinetic infrared spectral data, vibrational frequencies and modes have been calculated for a variety of possible structures in which FeMo-co bears H atoms, or CO ligands, or both. Fe-H stretching frequencies occur in the same spectral window as the C-O stretching frequencies, with lesser intensity, and both stretches are strongly coupled in some structures. Symmetrical bridging of CO between two Fe atoms of FeMo-co is destabilised by the presence of other ligands on Fe, and the reason for this is evident. Two results for bound formyl, HCO, are reported. These calculations of reference structures allow some interpretation of existing experimental spectra, but, more significantly, they suggest further kinetic infrared experiments to elucidate the chemical mechanism of catalysis by nitrogenase under normal turnover conditions. PMID:21584340

  9. 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; Apra, Edoardo; Xantheas, Sotiris S.

    2013-09-21

    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 (??) are smaller than the MP2 ones, due to the fact that the former produces shorter elongations (?R) 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 - ?? = s ? ?R, with a rate of s = 20.3 cm-1 / 0.001 Å. The CCSD(T) harmonic frequencies, when corrected using the MP2 anharmonicities obtained from second order vibrational perturbation theory (VPT2), produce anharmonicCCSD(T) estimates that are within < 60 cm-1 from the measured infrared (IR) active bands of the n=2-6 clusters and furthermore trace the observed red shifts with respect to the monomer (??) quite accurately. The energetic order between the various hexamer isomers on the PES (prism has the lowest energy) previously reported at MP2 was found to be preserved at the CCSD(T) level, whereas the inclusion of anharmonic corrections further stabilizes the cage among the hexamer isomers.

  10. 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.

  11. 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.

  12. Molecular conformational analysis, vibrational spectra, NBO analysis and first hyperpolarizability of (2E)-3-phenylprop-2-enoic anhydride based on density functional theory calculations.

    PubMed

    Sheena Mary, Y; Raju, K; Panicker, C Yohannan; Al-Saadi, Abdulaziz A; Thiemann, Thies; Van Alsenoy, Christian

    2014-07-15

    The conformational behavior and structural stability of (2E)-3-phenylprop-2-enoic anhydride were investigated by using density functional theory. Seventeen possible stable conformations of the title compound were determined and verified with their calculated vibrational frequencies being all positive. The optimized molecular structure, vibrational wavenumbers, corresponding vibrational assignments of (2E)-3-phenylprop-2-enoic anhydride have been 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 first hyperpolarizability of the title compound is 12×10(-30) esu and is 92.31 times that of the standard NLO material urea and the title compound is an attractive object for future studies of nonlinear optical properties. MEP was performed by the DFT method and the predicted infrared intensities and Raman activities have also been reported. PMID:24704480

  13. Calculations of Nonlinear Wave-Packet Interferometry Signals in the Pump-Probe Limit as Tests for Vibrational Control over Electronic Excitation Transfer

    E-print Network

    Jason D. Biggs; Jeffrey A. Cina

    2009-10-12

    The preceding paper describes a strategy for externally influencing the course of short-time electronic excitation transfer (EET) in molecular dimers and observing the process by nonlinear wave-packet interferometry (nl-WPI). Within a sample of isotropically oriented dimers having a specified internal geometry, a vibrational mode internal to the acceptor chromophore can be preferentially driven by electronically nonresonant impulsive stimulated Raman (or resonant infrared) excitation with a short polarized control pulse. A subsequent electronically resonant polarized pump then preferentially excites the donor, and EET ensues. Here we test both the control strategy and its spectroscopic investigation-with some sacrifice of amplitude-level detail-by calculating the pump-probe difference signal. That signal is the limiting case of the control-influenced nl-WPI signal in which the two pulses in the pump pulse-pair coincide, as do the two pulses in the probe pulse-pair. We present calculated pump-probe difference signals for (1) a model excitation-transfer complex in which two equal-energy monomers each support one moderately Franck-Condon active intramolecular vibration; (2) a simplified model of the covalent dimer dithia-anthracenophane, representing its EET dynamics following selective impulsive excitation of the weakly Franck-Condon active anthracene vibration at 385 cm-1; and (3) a model complex featuring moderate electronic-vibrational coupling in which the site energy of the acceptor chromophore is lower than that of the donor.

  14. Accurate non-Born-Oppenheimer calculations of the complete pure vibrational spectrum of ditritium using all-particle explicitly correlated Gaussian functions

    NASA Astrophysics Data System (ADS)

    Bubin, Sergiy; Stanke, Monika; Adamowicz, Ludwik

    2014-04-01

    Very accurate variational calculations of the complete pure vibrational spectrum of the ditritium (T2) molecule are performed within the framework where the Born-Oppenheimer approximation is not assumed. After separating out the center-of-mass motion from the total laboratory-frame Hamiltonian, T2 becomes a three-particle problem. States corresponding to the zero total angular momentum, which are pure vibrational states, are spherically symmetric in this framework. The wave functions of these states are expanded in terms of all-particle, one-center, spherically symmetric explicitly correlated Gaussian functions multiplied by even non-negative powers of the internuclear distance. In the calculations the total energies, the dissociation energies, and expectation values of some operators dependent on interparticle distances are determined.

  15. Vibrational spectroscopy, ab initio calculations and Frontier Orbital analysis of 4,5,6,8,9-pentachloropyrimido-[1,2-a][1,8]naphthyridin-10-one.

    PubMed

    Nogueira, C E S; Caselli, P E S; Freire, P T C; Teixeira, A M R; Oliveira, I M M; Bento, R R F; Faria, J L B; Gusmão, G O M; Silva, L E

    2015-10-01

    In this work we present a study of the vibrational spectra of 4,5,6,8,9-pentachloropyrimido-[1,2-a][1,8]naphthyridin-10-one, C11H2Cl5N3O, a substance belonging to the important pharmacological class of 1,8-naphthyridine derivatives. The Fourier transform infrared and the Fourier transform Raman spectra of the crystal were recorded at room temperature in the regions 400-4000 and 50-4000 cm(-1), respectively. Vibrational wavenumbers were predicted using Density Functional Theory calculations with the B3LYP functional on 6-31G(d,p) and 6-311++G(d,p) basis sets. The descriptions of the normal modes were made after calculating the potential energy distribution. Additionally, potential reaction sites were evaluated through Mulliken population and Frontier Orbital analysis. PMID:25965513

  16. 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.

  17. Post-processing of EPR spectra by convolution filtering: Calculation of a harmonics’ series and automatic separation of fast-motion components from spin-label EPR spectra

    NASA Astrophysics Data System (ADS)

    Smirnov, Alex I.

    2008-01-01

    This communication reports on post-processing of continuous wave EPR spectra by a digital convolution with filter functions that are subjected to differentiation or the Kramers-Krönig transform analytically. In case of differentiation, such a procedure improves spectral resolution in the higher harmonics enhancing the relative amplitude of sharp spectral features over the broad lines. At the same time high-frequency noise is suppressed through filtering. These features are illustrated on an example of a Lorentzian filter function that has a principal advantage of adding a known magnitude of homogeneous broadening to the spectral shapes. Such spectral distortion could be easily and accurately accounted for in the consequent least-squares data modeling. Application examples include calculation of higher harmonics from pure absorption echo-detected EPR spectra and resolving small hyperfine coupling that are unnoticeable in conventional first derivative EPR spectra. Another example involves speedy and automatic separation of fast and broad slow-motion components from spin-label EPR spectra without explicit simulation of the slow motion spectrum. The method is illustrated on examples of X-band EPR spectra of partially aggregated membrane peptides.

  18. 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.

  19. 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 ? ? ?? 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.

  20. Molecular structure, vibrational spectra, HOMO, LUMO and NMR studies of 2,3,4,5,6-penta bromo toluene and bromo durene based on density functional calculations.

    PubMed

    Krishna Kumar, V; Suganya, S; Mathammal, R

    2014-05-01

    This work deals with the vibrational spectra of 2,3,4,5,6-Penta Bromo Toluene (PBT) and Bromo Durene (BD) by quantum chemical calculations. The solid phase FTIR and FT-Raman spectra of the title compounds were recorded in the regions 4000-400 cm(-1) and 4000-50 cm(-1), respectively. The spectra were interpreted with the aid of normal coordinate analysis based on density functional theory (DFT) using B3LYP/6-31G* level and basis set combinations and was scaled using various scale factors yielding a good agreement between observed and calculated frequencies. The infrared and Raman spectra were also predicted from the calculated intensities. Comparison of the simulated spectra with the experimental spectra provides important information about the ability of the computational method to describe the vibrational modes. The HOMO and LUMO energies were calculated within the molecule. (13)C and (1)H NMR chemical shifts results were also calculated and compared with the experimental values. Thermodynamical properties like entropy heat capacity, zero point energy have been calculated for the title molecules. PMID:24556128

  1. 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.

  2. Scaling Rules for Vibrational Energy Transport in Globular Proteins.

    PubMed

    Buchenberg, Sebastian; Leitner, David M; Stock, Gerhard

    2016-01-01

    Computational studies of vibrational energy flow in biomolecules have to date mapped out transport pathways on a case-by-case basis. To provide a more general approach, we derive scaling rules for vibrational energy transport in a globular protein, which are identified from extensive nonequilibrium molecular dynamics simulations of vibrational energy flow in the villin headpiece subdomain HP36. We parametrize a master equation based on inter-residue, residue-solvent, and heater-residue energy-transfer rates, which closely reproduces the results of the all-atom simulations. From that fit, two scaling rules emerge, one for energy transport along the protein backbone which relies on a diffusion model and another for energy transport between tertiary contacts, which is based on a harmonic model. Requiring only the calculation of mean and variance of relatively few atomic distances, the approach holds the potential to predict the pathways and time scales of vibrational energy flow in large proteins. PMID:26650387

  3. 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 (?) 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.

  4. 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.

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

    PubMed

    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. (1)H and (13)C 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 (?) 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. PMID:26278882

  6. Time-independent and time-dependent methods for the calculation of the vibrational spectra: H2CN as example

    NASA Astrophysics Data System (ADS)

    Carbonniere, Philippe; Pouchan, Claude

    Computed anharmonic transitions and intensities of H2CN are reported in a spectral range ranging from 900 to 2,900 cm-1. Four vibrational treatments were considered from a B3LYP/6-31+G(d,p) potential electronic surface: The second order perturbational method, the full configuration interaction, the discrete variable representation method and the vibrational analysis arising from a molecular dynamics trajectory. The four approaches yield basically the same results since the convergence of the values is achieved by about 15-20 cm-1.

  7. 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

    NASA Astrophysics Data System (ADS)

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

    2013-09-01

    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 coupled-cluster including single, double, and full perturbative triple excitations (CCSD(T))/aug-cc-pVDZ level of theory. All five examined hexamer isomer minima previously reported by Møller-Plesset perturbation theory (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) frequencies 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 CCSD(T) and MP2 are observed for the harmonic hydrogen bonded frequencies, for which the former produces larger absolute values than the latter. Their CCSD(T) redshifts from the monomer values (??) are smaller than the MP2 ones, due to the fact that CCSD(T) produces shorter elongations (?R) of the respective hydrogen bonded OH lengths from the monomer value with respect to MP2. Both the MP2 and CCSD(T) results for the hydrogen bonded frequencies were found to closely follow the relation -?? = s . ?R, with a rate of s = 20.2 cm-1/0.001 Å for hydrogen bonded frequencies with IR intensities >400 km/mol. The CCSD(T) harmonic frequencies, when corrected using the MP2 anharmonicities obtained from second order vibrational perturbation theory, produce anharmonic CCSD(T) estimates that are within <60 cm-1 from the measured infrared (IR) active bands of the n = 2-6 clusters. Furthermore, the CCSD(T) harmonic redshifts (with respect to the monomer) trace the measured ones quite accurately. The energetic order between the various hexamer isomers on the PES (prism has the lowest energy) previously reported at MP2 was found to be preserved at the CCSD(T) level, whereas the inclusion of anharmonic corrections further stabilizes the cage among the hexamer isomers.

  8. Quasiclassical trajectory calculations for Li(22PJ) + H2 ? LiH(X1?+) + H: Influence by vibrational excitation and translational energy

    NASA Astrophysics Data System (ADS)

    Hsiao, Ming-Kai; Lin, King-Chuen; Hung, Yu-Ming

    2011-01-01

    Ab initio potential energy surfaces and the corresponding analytical energy functions of the ground 1A' and excited 2A' states for the Li(22P) plus H2 reaction are constructed. Quasiclassical trajectory calculations on the fitted energy functions are performed to characterize the reactions of Li(22P) with H2(v = 0, j = 1) and H2(v = 1, j = 1) as well as the reaction when the vibrational energy is replaced by collision energy. For simplicity, the transition probability is assumed to be unity when the trajectories go through the crossing seam region and change to the lower surface. The calculated rotational distributions of LiH(v = 0) for both H2(v = 0, j = 1) and H2(v = 1, j = 1) reactions are single-peaked with the maximum population at j' = 7, consistent with the previous observation. The vibrational excitation of H2(v = 1) may enhance the reaction cross section of LiH(v' = 0) by about 200 times, as compared to a result of 93-107 reported in the experimental measurements. In contrast, the enhancement is 3.1, if the same amount of energy is deposited in the translational states. This endothermic reaction can be considered as an analog of late barrier. According to the trajectory analysis, the vibrational excitation enlarges the H-H distance in the entrance channel to facilitate the reaction, but the excess energy may not open up additional reaction configuration.

  9. Structural and vibrational study of maprotiline

    NASA Astrophysics Data System (ADS)

    Yavuz, A. E.; Haman Bayar?, S.; Kazanc?, 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.

  10. 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.

  11. 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.

  12. Calculations of nonlinear wave-packet interferometry signals in the pump-probe limit as tests for vibrational control over electronic excitation transfer

    NASA Astrophysics Data System (ADS)

    Biggs, Jason D.; Cina, Jeffrey A.

    2009-12-01

    The preceding paper [J. D. Biggs and J. A. Cina, J. Chem. Phys. 131, 224101 (2009)] (referred to here as Paper 1), describes a strategy for externally influencing the course of short-time electronic excitation transfer (EET) in molecular dimers and observing the process by nonlinear wave-packet interferometry (nl-WPI). External influence can, for example, be exerted by inducing coherent intramolecular vibration in one of the chromophores prior to short-pulse electronic excitation of the other. Within a sample of isotropically oriented dimers having a specified internal geometry, a vibrational mode internal to the acceptor chromophore can be preferentially driven by electronically nonresonant impulsive stimulated Raman (or resonant infrared) excitation with a short polarized "control" pulse. A subsequent electronically resonant polarized pump then preferentially excites the donor, and EET ensues. Paper 1 investigates control-pulse-influenced nl-WPI as a tool for the spectroscopic evaluation of the effect of coherent molecular vibration on excitation transfer, presenting general expressions for the nl-WPI difference signal from a dimer following the action of a control pulse of arbitrary polarization and shape. Electronic excitation is to be effected and its interchromophore transfer monitored by resonant pump and probe "pulses," respectively, each consisting of an optical-phase-controlled ultrashort pulse-pair having arbitrary polarization, duration, center frequency, and other characteristics. Here we test both the control strategy and its spectroscopic investigation—with some sacrifice of amplitude-level detail—by calculating the pump-probe difference signal. That signal is the limiting case of the control-influenced nl-WPI signal in which the two pulses in the pump pulse-pair coincide, as do the two pulses in the probe pulse-pair. We present calculated pump-probe difference signals for (1) a model excitation-transfer complex in which two equal-energy monomers each support one moderately Franck-Condon active intramolecular vibration; (2) a simplified model of the covalent dimer dithia-anthracenophane, representing its EET dynamics following selective impulsive excitation of the weakly Franck-Condon active ?12 anthracene vibration at 385 cm-1; and (3) a model complex featuring moderate electronic-vibrational coupling in which the site energy of the acceptor chromophore is lower than that of the donor.

  13. Molecular conformational analysis, vibrational spectra, NBO, NLO analysis and molecular docking study of bis[(E)-anthranyl-9-acrylic]anhydride based on density functional theory calculations.

    PubMed

    Mary, Y Sheena; Panicker, C Yohannan; Thiemann, Thies; Al-Azani, Mariam; Al-Saadi, Abdulaziz A; Van Alsenoy, C; Raju, K; War, Javeed Ahmad; Srivastava, S K

    2015-12-01

    FT-IR and FT-Raman spectra of bis[(E)-anthranyl-9-acrylic]anhydride were recorded and analyzed. The conformational behavior is also investigated. The vibrational wave numbers were calculated using density functional theory (DFT) quantum chemical calculations. The data obtained from wave number calculations are used to assign vibrational bands obtained in Infrared and Raman spectra. Potential energy distribution was done using GAR2PED program. The geometrical parameters are compared with related structures. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using Natural Bonding Orbital (NBO) analysis. The Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) analysis are used to determine the charge transfer within the molecule. Molecular Electrostatic Potential (MEP) was performed by the DFT method. The calculated first hyperpolarizability of the title compound is comparable with the reported values of similar derivatives and is 4.23 times that of the standard nonlinear optical (NLO) material urea and the title compound and its derivatives are an attractive object for future studies of nonlinear optical properties. To evaluate the in silico antitumor activity of the title compound molecular docking studies were carried out against protein Bcl-xL. The (1)H-NMR spectrum is also reported. PMID:26143327

  14. Journal of Sound and Vibration ] (

    E-print Network

    Shaw, Steven W.

    to harmonic excitation. The approach is an extension of the nonlinear normal mode (NNM) formulation previously. This dependence defines the invariant manifold for the nonlinear normal mode (NNM). The construction of the NNMJOURNAL OF SOUND AND VIBRATION Journal of Sound and Vibration ] (

  15. 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. PMID:23263358

  16. 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.

  17. 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-?-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-? and ?-D-glucopyranoside, as well as for the methyl-?-D-xylopyranoside.

  18. Heavy strain conditions in colloidal core-shell quantum dots and their consequences on the vibrational properties from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Han, Peng; Bester, Gabriel

    2015-09-01

    We perform large-scale ab initio density functional theory calculations to study the lattice strain and the vibrational properties of colloidal semiconductor core-shell nanoclusters with up to one thousand atoms (radii up to 15.6 Å). For all the group IV, III-V, and II-VI semiconductors studied, we find that the atom positions of the shell atoms seem unaffected by the core material. In particular, for group-IV core-shell clusters the shell material remains unstrained, while the core adapts to the large lattice mismatch (compressive or tensile strain). For InAs-InP and CdSe-CdS, both the cores and the shells are compressively strained corresponding to pressures up to 20 GPa. We show that this compression, which contributes a large blueshift of the vibrational frequencies, is counterbalanced, to some degree, by the undercoordination effect of the near-surface shell, which contributes a redshift to the vibrational modes. These findings lead to a different interpretation of the frequency shifts of recent Raman experiments, while they confirm the speculated interface nature of the low-frequency shoulder of the high-frequency Raman peak.

  19. 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-?-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 4000-500cm(-1) spectral region for the IR spectra, and in the 4000-20cm(-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-? and ?-d-glucopyranoside, as well as for the methyl-?-d-xylopyranoside. PMID:26342821

  20. Synthesis, structural and vibrational investigation on 2-phenyl-N-(pyrazin-2-yl)acetamide combining XRD diffraction, FT-IR and NMR spectroscopies with DFT calculations

    NASA Astrophysics Data System (ADS)

    Lukose, Jilu; Yohannan Panicker, C.; Nayak, Prakash S.; Narayana, B.; Sarojini, B. K.; Van Alsenoy, C.; Al-Saadi, Abdulaziz A.

    2015-01-01

    The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 2-phenyl-N-(pyrazin-2-yl)acetamide have been investigated experimentally and theoretically using Gaussian09 software package. The title compound was optimized by using the HF/6-31G(6D,7F) and B3LYP/6-31G(6D,7F) calculations. The geometrical parameters are in agreement with the XRD data. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. Gauge-including atomic orbital 1H-NMR chemical shifts calculations were carried out and compared with experimental data. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. Molecular electrostatic potential was performed by the DFT method. First hyperpolarizability is calculated in order to find its role in non linear optics. From the XRD data, in the crystal, molecules are held together by strong Csbnd H⋯O and Nsbnd H⋯O intermolecular interactions.

  1. Synthesis, structural and vibrational investigation on 2-phenyl-N-(pyrazin-2-yl)acetamide combining XRD diffraction, FT-IR and NMR spectroscopies with DFT calculations.

    PubMed

    Lukose, Jilu; Yohannan Panicker, C; Nayak, Prakash S; Narayana, B; Sarojini, B K; Van Alsenoy, C; Al-Saadi, Abdulaziz A

    2015-01-25

    The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 2-phenyl-N-(pyrazin-2-yl)acetamide have been investigated experimentally and theoretically using Gaussian09 software package. The title compound was optimized by using the HF/6-31G(6D,7F) and B3LYP/6-31G(6D,7F) calculations. The geometrical parameters are in agreement with the XRD data. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. Gauge-including atomic orbital (1)H-NMR chemical shifts calculations were carried out and compared with experimental data. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. Molecular electrostatic potential was performed by the DFT method. First hyperpolarizability is calculated in order to find its role in non linear optics. From the XRD data, in the crystal, molecules are held together by strong C-H?O and N-H?O intermolecular interactions. PMID:25124846

  2. Comparative Study Between GGA and LDA Approximation Using First- Principles Calculations of Structural, Electronic, Optical and Vibrational Properties of CaTiO3 Crystal

    NASA Astrophysics Data System (ADS)

    Medeiros, Subenia; Araujo, Maeva

    2015-03-01

    The structural, electronic, vibrational, and optical properties of perovskite CaTiO3 in the cubic, orthorhombic, and tetragonal phase are calculated in the framework of density functional theory (DFT) with different exchange-correlation potentials by CASTEP package. The calculated band structure shows an indirect band gap of 1.88 eV at the ?-R points in the Brillouin zone to the cubic structure, a direct band gap of 2.41 eV at the ?- ? points to the orthorhombic structure, and an indirect band gap of 2.31 eV at theM - ? points to the tetragonal phase. It is still known that the CaTiO3 has a static dielectric constant that extrapolates to a value greater than 300 at zero temperature, and the dielectric response is dominated by low frequency (? ~ 90cm-1) polar optical modes in which cation motion opposes oxygen motion. Our calculated lattice parameters, elastic constants, optical properties, and vibrational frequencies are found to be in good agreement with the available theoretical and experimental values. The results for the effective mass in the electron and hole carriers are also presented in this work.

  3. Ab initio variational calculations of the vibrational properties of Li + 3, Li2Na + , LiNa + 2, and KLiNa +

    NASA Astrophysics Data System (ADS)

    Searles, D. J.; von Nagy-Felsobuki, E. I.

    1991-07-01

    A rovibrational Hamiltonian has been derived in terms of rectilinear displacement coordinates which is based on the Watson Hamiltonian. Moreover, it is a generalization of the Carney and Porter analysis for D3h triatomic systems [J. Chem. Phys. 65, 3547 (1976)] and Carney et al. analysis for C2v triatomic systems [J. Chem. Phys. 66, 3724 (1977)]. It is therefore the most general form of the Watson Hamiltonian which is applicable to a bent triatomic system. Ab initio variational calculations using this Hamiltonian are presented for vibrational properties of Li+3, Li2Na+, LiNa+2, and KLiNa+.

  4. 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…

  5. 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.

  6. Vibrational spectra of tris(acetylacetonato)chromium(III)

    NASA Astrophysics Data System (ADS)

    Dolati, Fatemeh; Vakili, Mohammad; Ebrahimi, Ali; Tayyari, Sayyed Faramarz

    2015-11-01

    The molecular structure and vibrational spectra of tris(acetylacetonato)chromium(III), Cr (AA)3, its mono-deuterated, Cr (DAA)3, and per-deuterated analogous, Cr(D7AA)3, were investigated using density functional theory (DFT) calculations. The geometry of the titled compound was fully optimized at the B3LYP level using 6-311 + G* and 6-31G** basis sets. The harmonic vibrational frequencies were obtained at the B3LYP/6-311 + G** level. Raman scattering activities were calculated at the B3LYP/6-31G** level. The calculated frequencies are compared with the experimental IR and Raman spectra. All of the measured IR and Raman bands were interpreted in terms of the calculated vibrational modes and isotopic frequency shifts. The scaled theoretical frequencies and the structural parameters are in excellent agreement with the experimental data. Analysis of the vibrational spectra indicates a strong coupling between the chelated ring modes. Several bands at 933, 680, 611, 594, 495, 250, 224, and 179 cm-1 are found to be engaged in Cr-O vibrational movements. The IR bands at 611 and 594 cm-1 are attributed to the asymmetric Cr-O stretching and the very strong Raman band at 460 cm-1 is assigned to the totally symmetric Cr-O stretching mode (a1 species).

  7. 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.

  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

    2015-02-01

    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, ?=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. PMID:25315872

  9. 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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

    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, ? = 100.739(2)°, V = 677.31(3) Å3 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.

  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{sup -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. Reinvestigation of the crystal structure, vibrational spectroscopic studies and DFT calculations of 5-bromo-7-azaindole with dual N-H???N 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-H???N 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-H???N dimers of 7-azaindole and its halogeno derivatives.

  12. Vibrational dynamics of YPO4 and ScPO4 single crystals: An integrated study by polarized Raman spectroscopy and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Giarola, M.; Sanson, A.; Rahman, A.; Mariotto, G.; Bettinelli, M.; Speghini, A.; Cazzanelli, E.

    2011-06-01

    A thorough study of the vibrational dynamics of xenotime YPO4 and its isomorphs, pretulite ScPO4 single crystals, with tetragonal zircon structure, was carried out by means of an integrated approach consisting of both polarized micro-Raman scattering spectroscopy and first-principles calculations. Polarized Raman scattering experiments were performed at room temperature either in the 180° or in the 90° geometry on both samples under different crystal orientations set by a micromanipulator. All the 12 independent components of the polarizability tensor, expected on the basis of the group theory for both YPO4 and ScPO4, were selected in turn and assigned in symmetry. In particular, it was possible to unambiguously identify a B1g mode peaked at 316 cm-1 in YPO4 and two B1g modes peaked at 350 and 677 cm-1 in ScPO4, respectively, all of them never reported before. These observations were corroborated by the results of first-principles calculations, based on density functional theory in the generalized gradient approximation, performed to determine Raman and infrared vibrational modes. In fact, an excellent agreement between computational and experimental results has been found.

  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 ?, 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 spectra of ?-bromo and ?-chloro derivatives of tris(acetylacetonato)chromium(III)

    NASA Astrophysics Data System (ADS)

    Dolati, Fatemeh; Tayyari, Sayyed Faramarz; Vakili, Mohammad; Ebrahimi, Ali

    2016-01-01

    The molecular structure and vibrational spectra of ?-chloro and ?-bromo derivatives of tris(acetylacetonato)chromium(III), Cr(ClAA)3 and Cr(BrAA)3, were investigated using the density functional theory (DFT) calculations. The geometrical parameters and harmonic vibrational wavenumbers of the titled compounds were obtained at the B3LYP level, using 6-311 + G(d) and 6-31G** basis sets. The calculated vibrational wavenumbers were compared with the corresponding experimental results and those of tris(acetylacetonato)chromium(III), Cr(AA)3. The effects of chlorine and bromine substitutions at the ?-position on the vibrational spectra and geometry of Cr(AA)3 were studied. The ?-halo substitution effects were also investigated using the natural bond orbital, NBO, analysis.

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

    PubMed

    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. PMID:15268366

  16. Calculation of kinetic energy functions for the ring-puckering vibration of asymmetric five-membered rings

    NASA Astrophysics Data System (ADS)

    Schmude, R. W.; Harthcock, M. A.; Kelly, M. B.; Laane, J.

    1987-08-01

    The use of vectors simplifies the representation of the molecular structures resulting from the ring puckering of asymmetric five-membered rings. The kinetic energy (inverse reduced mass) functions have been calculated for several ring molecules including 2,3-dihydrofuran, 2,3-dihydrothiophene, 2-cyclopenten-1-one, and 2-phospholene. The structures used for the calculations were determined from molecular mechanics calculations. The accurate determination of the kinetic energy terms has made it possible to calculate the one-dimensional ring-puckering potential functions for these molecules in dimensional form.

  17. Study of structure-activity relationship of enantiomeric, protonated and deprotonated forms of warfarin via vibrational spectroscopy and DFT calculations.

    PubMed

    Mishra, Alok; Srivastava, Sunil Kumar; Swati, D

    2013-09-01

    The structure-activity relationship of the anticoagulant drug warfarin were studied by studying two enantiomeric forms (S-form and R-form) of warfarin and its protonated as well as deprotonated structures in aqueous media using density functional theory (DFT). Theoretically computed Raman and IR spectra of all the computed structures were compared and their specific vibrational spectroscopic signatures were discussed. The percentage contributions of individual normal modes of warfarin, which provides direct evidence of the different molecular activity due to change in relative atomic position of atoms in molecule, were investigated through potential energy distribution (PED). The optimized energy and molecular electrostatic potential (MEP) maps show that the S-form of the drug molecules warfarin is energetically more stable than R-form and provides higher docking opportunity for the molecular binding with the receptors in the bio-systems. PMID:23747386

  18. 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.

  19. 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...

  20. Conformational stability, structural parameters and vibrational assignment from variable temperature infrared spectra of xenon and krypton solutions and ab initio calculations of ethylisocyanate

    NASA Astrophysics Data System (ADS)

    Durig, James R.; Zhou, Sarah Xiaohua; Zheng, Chao; Durig, Douglas T.

    2010-05-01

    Variable temperature (-55 to -155 °C) studies of the infrared spectra (400-3500 cm -1) of ethylisocyanate, CH 3CH 2NCO, dissolved in liquid xenon and krypton have been recorded. Additionally the infrared spectra of the gas and solid have been re-investigated. These spectroscopic data indicate two conformers in the fluid states which are the cis and trans forms with a large proportion of molecules in the gas phase at ambient temperature in the excited states of the NCO torsional mode which has a very low barrier to conformational interchange. Variable temperature (-110 to -155 °C) studies of krypton solutions were carried out and by using two conformer pairs, an enthalpy difference of 100 ± 4 cm -1 (1.20 ± 0.05 kJ/mol) was obtained with the cis conformer the more stable form. 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 full electron correlation using a variety of basis sets up to 6-311+G(2df,2pd) and cc-PVQZ. With the basis sets 6-311+G(2d,2p) and larger, the barrier at the cis position ranged from a low value of 11 cm -1 to a high value of 31 cm -1 with a value of 19 cm -1 from the largest basis set of cc-PVQZ. Thus, the gauche well is probably so shallow that it does not contain a bound vibrational state. This results in the cis conformer as the most stable form which is consistent with the experimental rotational and vibrational data. The predicted energy difference from these calculations between the cis conformer and the transitional-state skew form is ˜100 cm -1 which is consistent with the assigned microwave lines for four excited states of the NCO torsion. Density functional theory calculation by the B3LYP method with many of the same basis sets provided little information. 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 r0 structural parameters have been obtained for the cis form. The determined heavy atom parameters are: r(C dbnd N) = 1.211(5), r(C dbnd O) = 1.167(5), r(C sbnd N) = 1.448(5), r(C sbnd C) = 1.516(5) Å for the distances and angles of ?CCN = 112.6(5), ?CNC = 137.5(5), ?NCO = 172.9(5)°. 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 quantities when available. These results are compared to the corresponding quantities of some similar molecules.

  1. Vibrational spectroscopic (FT-IR, FT-Raman) and quantum chemical calculations of 1-(5,5-dioxido-10H-phenothiazin-10-yl)ethanone.

    PubMed

    Kaur, Manpreet; Mary, Y Shyma; Panicker, C Yohannan; Varghese, Hema Tresa; Yathirajan, H S; Byrappa, K; Van Alsenoy, Christian

    2014-01-01

    FT-IR and FT-Raman spectra of 1-(5,5-dioxido-10H-phenothiazin-10-yl)ethanone were recorded and analyzed. The vibrational wavenumbers were computed using B3LYP/6-31G? and SDD basis. Potential energy distribution of normal modes of vibrations was done using GAR2PED program. The HOMO and LUMO analysis is 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. Molecular electrostatic potential was performed by the DFT method and infrared intensities and Raman activities are also reported. MEP shows that the negative potential sites are on oxygen atoms and the positive potential sites are around the nitrogen atoms. The geometrical parameters of the title compound (SDD) are in agreement with XRD crystal structure data. The calculated first hyperpolarizability is comparable with the reported values of similar derivatives and is an attractive object for future studies of nonlinear optics. PMID:24211803

  2. Vibrational coupled cluster theory

    NASA Astrophysics Data System (ADS)

    Christiansen, Ove

    2004-02-01

    The theory and first implementation of a vibrational coupled cluster (VCC) method for calculations of the vibrational structure of molecules is presented. Different methods for introducing approximate VCC methods are discussed including truncation according to a maximum number of simultaneous mode excitations as well as an interaction space order concept is introduced. The theory is tested on calculation of anharmonic frequencies for a three-mode model system and a formaldehyde quartic force field. The VCC method is compared to vibrational self-consistent-field, vibrational Møller-Plesset perturbation theory, and vibrational configuration interaction (VCI). A VCC calculation typically gives higher accuracy than a corresponding VCI calculation with the same number of parameters and the same formal operation count.

  3. Understanding and Manipulating Electrostatic Fields at the Protein-Protein Interface Using Vibrational Spectroscopy and Continuum Electrostatics Calculations.

    PubMed

    Ritchie, Andrew W; Webb, Lauren J

    2015-11-01

    Biological function emerges in large part from the interactions of biomacromolecules in the complex and dynamic environment of the living cell. For this reason, macromolecular interactions in biological systems are now a major focus of interest throughout the biochemical and biophysical communities. The affinity and specificity of macromolecular interactions are the result of both structural and electrostatic factors. Significant advances have been made in characterizing structural features of stable protein-protein interfaces through the techniques of modern structural biology, but much less is understood about how electrostatic factors promote and stabilize specific functional macromolecular interactions over all possible choices presented to a given molecule in a crowded environment. In this Feature Article, we describe how vibrational Stark effect (VSE) spectroscopy is being applied to measure electrostatic fields at protein-protein interfaces, focusing on measurements of guanosine triphosphate (GTP)-binding proteins of the Ras superfamily binding with structurally related but functionally distinct downstream effector proteins. In VSE spectroscopy, spectral shifts of a probe oscillator's energy are related directly to that probe's local electrostatic environment. By performing this experiment repeatedly throughout a protein-protein interface, an experimental map of measured electrostatic fields generated at that interface is determined. These data can be used to rationalize selective binding of similarly structured proteins in both in vitro and in vivo environments. Furthermore, these data can be used to compare to computational predictions of electrostatic fields to explore the level of simulation detail that is necessary to accurately predict our experimental findings. PMID:26375183

  4. 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.

  5. The evolution of harmonic Indian musical drums: A mathematical perspective

    NASA Astrophysics Data System (ADS)

    Gaudet, Samuel; Gauthier, Claude; Léger, Sophie

    2006-03-01

    We explain using mathematics how harmonic musical drums were discovered by Indian artisans and musicians more than 2000 years ago. To this end, we introduce a harmonic error function which measures the quality of the harmonic relationship and degeneracy of the first modes of vibration of a centrally symmetric loaded membrane. We explain that although the tabla configuration found by the ancient Indians is the most natural one, other configurations exist and some are harmonically superior to the classical one.

  6. 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.

  7. 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.

  8. Towards black-box calculations of tunneling splittings obtained from vibrational structure methods based on normal coordinates.

    PubMed

    Neff, Michael; Rauhut, Guntram

    2014-02-01

    Multidimensional potential energy surfaces obtained from explicitly correlated coupled-cluster calculations and further corrections for high-order correlation contributions, scalar relativistic effects and core-correlation energy contributions were generated in a fully automated fashion for the double-minimum benchmark systems OH3(+) and NH3. The black-box generation of the potentials is based on normal coordinates, which were used in the underlying multimode expansions of the potentials and the ?-tensor within the Watson operator. Normal coordinates are not the optimal choice for describing double-minimum potentials and the question remains if they can be used for accurate calculations at all. However, their unique definition is an appealing feature, which removes remaining errors in truncated potential expansions arising from different choices of curvilinear coordinate systems. Fully automated calculations are presented, which demonstrate, that the proposed scheme allows for the determination of energy levels and tunneling splittings as a routine application. PMID:23548204

  9. Microwave and vibrational spectra, ab initio calculations, conformational stabilities and assignments of the fundamentals of the C s conformer of n-butylgermane

    NASA Astrophysics Data System (ADS)

    LaPlante, Arthur J.; Stidham, Howard D.; Peebles, Sean A.; Peebles, Rebecca A.; Wurrey, Charles J.; Guirgis, Gamil A.

    2011-01-01

    The FT-microwave spectrum of n-butylgermane, CH 3CH 2CH 2CH 2GeH 3 has been investigated from 4000 to 18,000 MHz and the microwave spectra have been observed for all of the five naturally occurring germanium isotopologues for the anti-anti (aa) conformer. The dipole moment for the 74Ge containing species has been measured, giving a total dipole moment of 0.881 (26) D. In addition, the vibrational spectrum of n-butylgermane is described. Modestly complete assignments are made for the aa conformer. The relative stabilities of the five conformers are calculated, and the anti-anti (aa) conformer is found to be the most stable in all calculations done. This conclusion is confirmed by the infrared and Raman spectrum of the annealed crystal. The dipole moments of all conformers are calculated to be approximately equal and less than 1 D, ranging from approximately 0.8 to 0.9 D.

  10. Anharmonic vibrations of the dicarbon antisite defect in 4H-SiC

    SciTech Connect

    Yan, F.; Devaty, R. P.; Choyke, W. J.; Gali, A.; Kimoto, T.; Ohshima, T.; Pensl, G.

    2012-03-26

    Dicarbon antisite defects were created by either electron irradiation or ion implantation into 4H-SiC. The no-phonon lines from the dicarbon antisite defect center were observed with their phonon replicas. The stretch frequencies of the defect were observed up to the fifth harmonic. The Morse potential model accounts for the anharmonicity quite well and gives a very good prediction of the vibration energies up to the fifth harmonic with an error of less than 1%. First principles calculations show that the model of a dicarbon antisite defect along with its four nearest neighboring carbon atoms can explain the observed anharmonicity.

  11. 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.

  12. Vibrational spectra, structure, and theoretical calculations of 2-chloro- and 3-chloropyridine and 2-bromo- and 3-bromopyridine

    NASA Astrophysics Data System (ADS)

    Boopalachandran, Praveenkumar; Sheu, Hong-Li; Laane, Jaan

    2012-09-01

    The infrared and Raman spectra of 2-chloropyridine, 3-chloropyridine, 2-bromopyridine, and 3-bromopyridine have been recorded and assigned. Density functional theory calculations (B3LYP with 6-311++G(d,p) basis set) produce excellent agreement with the experimental values. Ab initio calculations (MP2 with the cc-pVTZ basis set) were utilized to compute the molecular structures, which were compared to those of pyridine and the corresponding fluoropyridines. All of the 2-halopyridines show a shortening of the N-C(2) bond resulting from the halogen substitution on the C(2) carbon atom. All of the other ring bond distances for the 2-halopyridines and 3-halopyridines are little different from pyridine itself.

  13. 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.

  14. Vibrational spectra obtained from high quality potential energy surfaces spanned by low level normal coordinates: application to CHFClI and CDFClI

    NASA Astrophysics Data System (ADS)

    Heislbetz, Sandra; Schwerdtfeger, Peter; Rauhut, Guntram

    2007-05-01

    The impact of approximate normal coordinates for spanning high level potential energy surfaces on vibrational frequencies is studied within the framework of vibrational SCF and configuration interaction calculations (VCI). The use of low level normal coordinates avoids expensive geometry optimizations and harmonic frequency calculations and thus allows for a significant reduction in CPU time. Benchmark calculations are provided for a set of molecules ranging from 5 to 7 atoms. An application to CHFClI and CDFClI shows that this approximation still allows for very accurate results. These molecules are of particular interest for studying parity violation effects.

  15. 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.

  16. Vibrational spectra and structures of urazole and 4-methylurazole: DFT calculations of the normal modes in aqueous solution and in the solid state, and the influence of hydrogen bonding

    NASA Astrophysics Data System (ADS)

    Ryall, John P.; Dines, Trevor J.; Chowdhry, Babur Z.; Leharne, Stephen A.; Withnall, Robert

    2010-08-01

    Solid-state IR and Raman as well as aqueous solution state Raman spectra are reported for urazole, 4-methylurazole and their deuterated derivatives. DFT calculations, at the B3-LYP/cc-pVTZ level, established that the structures and vibrational spectra of the molecules can be interpreted using models with hydrogen-bonded water molecules, in conjunction with the polarizable continuum solvation method. The vibrational spectra were computed at the optimised molecular geometry in each case, enabling normal coordinate analysis, which yielded satisfactory agreement with the experimental IR and Raman data. Computed potential energy distributions of the normal modes provided detailed vibrational assignments. Solid-state pseudopotential-plane-wave DFT calculations, using the PW91 functional were also carried out, reflecting the importance of intermolecular hydrogen bonding in the solid state.

  17. 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.

  18. Infrared, Raman and NMR spectral analysis, vibrational assignments, normal coordinate analysis, and quantum mechanical calculations of 2-Amino-5-ethyl-1,3,4-thiadiazole

    NASA Astrophysics Data System (ADS)

    Shaaban, Ibrahim A.; Hassan, Ahmed E.; Abuelela, Ahmed M.; Zoghaieb, Wajdi M.; Mohamed, Tarek A.

    2016-01-01

    Raman (3500-55 cm-1) and infrared (4000-300 cm-1) spectra of 2-Amino-5-ethyl-1,3,4-thiadiazole (AET; C4H7N3S) have been recorded in the solid phase. In addition, the 1H and 13C NMR spectra of AET were obtained in DMSO-d6. As a result of internal rotations of either methyl and/or ethyl groups around the C-C bonds with NH2 moiety being planar (sp2) and/or non-planar (sp3) eight structures are theoretically proposed (1-8). The conformational energies and vibrational frequencies have been calculated using Density Functional Theory (DFT) with the methods of B3LYP and B3PW91 utilizing 6-31G (d) and 6-311++G(d,p) basis sets. And then S-4 (the only conformer with real frequencies) was optimized, to yield S-9, however the Thiadiazole ring slightly twisted (tilt angle is 0.9°). The 1H and 13C NMR chemical shifts were also predicted using a GIAO approximation at 6-311++G(d,p) basis set utilizing B3LYP and B3PW91 methods with solvent effects using PCM method. The computational outcomes favor S-9; the methyl group being staggered to the lone pair of N4 and reside trans position to the S atom, whereas NH2 is non-planar in good agreement with the current study. Aided by the above mentioned DFT computations, a complete vibrational assignment of the observed infrared and Raman bands along with NMR chemical shifts has been proposed. The vibrational interpretations have been supported by normal coordinate analysis and potential energy distributions (PEDs). Finally, NH2, CH3 and C2H5 barriers to internal rotations were carried out using B3LYP/6-31G(d) optimized structural parameters (S-9). The results are reported herein and compared with X-ray structural parameters.

  19. Application of Vibrational Spectroscopy Supported by Theoretical Calculations in Identification of Amorphous and Crystalline Forms of Cefuroxime Axetil

    PubMed Central

    Lewandowska, Kornelia; Jeli?ska, Anna; Zalewski, Przemys?aw; Oszczapowicz, Irena; Sikora, Adam; Kozak, Maciej

    2015-01-01

    FT-IR and Raman scattering spectra of cefuroxime axetil were proposed for identification studies of its crystalline and amorphous forms. An analysis of experimental spectra was supported by quantum-chemical calculations performed with the use of B3LYP functional and 6-31G(d,p) as a basis set. The geometric structure of a cefuroxime axetil molecule, HOMO and LUMO orbitals, and molecular electrostatic potential were also determined by using DFT (density functional theory). The benefits of applying FT-IR and Raman scattering spectroscopy for characterization of drug subjected to degradation were discussed. PMID:25654137

  20. Vibrational properties and DFT calculations of the perovskite metal formate framework of [(CH3)2NH2][Ni(HCOO3)] system

    NASA Astrophysics Data System (ADS)

    M?czka, M.; Zierkiewicz, W.; Michalska, D.; Hanuza, J.

    2014-07-01

    Experimental Raman and IR spectra of multiferroic [(CH3)2NH2][Ni(HCOO)3] were recorded at room temperature. The three-parameter hybrid B3LYP density functional method has been used with the 6-31G(d, p) basis set to derive the equilibrium geometry, atomic spin densities, vibrational wavenumbers, infrared intensities and Raman scattering activities. Based on these calculations, the assignment of the observed bands to the respective internal and lattice modes is proposed. The performed calculations revealed that the ?(NH2) stretching, ?(NH2) rocking and ?(CH3) torsional modes are very sensitive to formation of the hydrogen bond between the DMA+ cation and Ni-formate framework. Therefore, these modes are suitable probes for strength of hydrogen bonds in this family of metal-formate frameworks and study of their temperature dependence may provide significant information on a role of the hydrogen bonds in mechanism of the ferroelectric phase transition occurring in these compounds at low temperatures.

  1. Vibrational properties and DFT calculations of the perovskite metal formate framework of [(CH3)2NH2][Ni(HCOO3)] system.

    PubMed

    M?czka, M; Zierkiewicz, W; Michalska, D; Hanuza, J

    2014-07-15

    Experimental Raman and IR spectra of multiferroic [(CH3)2NH2][Ni(HCOO)3] were recorded at room temperature. The three-parameter hybrid B3LYP density functional method has been used with the 6-31G(d, p) basis set to derive the equilibrium geometry, atomic spin densities, vibrational wavenumbers, infrared intensities and Raman scattering activities. Based on these calculations, the assignment of the observed bands to the respective internal and lattice modes is proposed. The performed calculations revealed that the ?(NH2) stretching, ?(NH2) rocking and ?(CH3) torsional modes are very sensitive to formation of the hydrogen bond between the DMA(+) cation and Ni-formate framework. Therefore, these modes are suitable probes for strength of hydrogen bonds in this family of metal-formate frameworks and study of their temperature dependence may provide significant information on a role of the hydrogen bonds in mechanism of the ferroelectric phase transition occurring in these compounds at low temperatures. PMID:24694997

  2. Method and apparatus for vibrating a substrate during material formation

    DOEpatents

    Bailey, Jeffrey A. (Richland, WA) [Richland, WA; Roger, Johnson N. (Richland, WA) [Richland, WA; John, Munley T. (Benton City, WA) [Benton City, WA; Walter, Park R. (Benton City, WA) [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.

  3. A First Principles Density-Functional Calculation of the Electronic and Vibrational Structure of the Key Melanin Monomers

    E-print Network

    B. J. Powell; T. Baruah; N. Bernstein; K. Brake; Ross H. McKenzie; P. Meredith; M. R. Pederson

    2004-01-23

    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 bio-macromolecules with important biological functions (including photoprotection) and with potential for certain bioengineering applications. We have used the DeltaSCF (difference of self consistent fields) method to study the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), 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 broad band 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 non-destructively 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 behaviour of the eumelanins.

  4. Thermal weights for semiclassical vibrational response functions.

    PubMed

    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. PMID:26328812

  5. Vibrational Heat Transport in Molecular Junctions

    E-print Network

    Segal, Dvira

    2015-01-01

    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 interplay 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 which incorporate molecular anharmonicities. Theoretical methods are described along with...

  6. Large scale exact quantum dynamics calculations: Ten thousand quantum states of acetonitrile

    NASA Astrophysics Data System (ADS)

    Halverson, Thomas; Poirier, Bill

    2015-03-01

    'Exact' quantum dynamics (EQD) calculations of the vibrational spectrum of acetonitrile (CH3CN) are performed, using two different methods: (1) phase-space-truncated momentum-symmetrized Gaussian basis and (2) correlated truncated harmonic oscillator basis. In both cases, a simple classical phase space picture is used to optimize the selection of individual basis functions-leading to drastic reductions in basis size, in comparison with existing methods. Massive parallelization is also employed. Together, these tools-implemented into a single, easy-to-use computer code-enable a calculation of tens of thousands of vibrational states of CH3CN to an accuracy of 0.001-10 cm-1.

  7. An unscaled quantum mechanical harmonic force field for p-benzoquinone

    NASA Astrophysics Data System (ADS)

    Nonella, Marco; Tavan, Paul

    1995-10-01

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

  8. 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.

  9. The role of vibrations in thermodynamic properties of Cu-Ni alloys

    NASA Astrophysics Data System (ADS)

    Onat, Berk; Durukano?lu, Sondan

    2014-11-01

    We report results of a systematic study for vibrational thermodynamic functions of Cu-Ni alloys, in the harmonic approximation, using interaction potentials based on the embedded atom method with improved optimization techniques. The vibrational density of states of the systems is calculated using real space Green's function method. From an investigation of local force fields we found that increasing Ni concentration in the alloy substantially stiffens the force experienced by Cu atoms compared to that of Ni atoms. Our calculations also reveal that vibrational entropy change between ordered and disordered crystals of Cu-Ni is negligible. However, the mixing entropy of the phonons and electronic states is found to be negative and favors un-mixing, and thus contributes to the miscibility gap.

  10. 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.

  11. Vibrational anharmonicity of small gold and silver clusters using the VSCF method.

    PubMed

    Mancera, Luis A; Benoit, David M

    2016-01-01

    We study the vibrational spectra of small neutral gold (Au2-Au10) and silver (Ag2-Au5) clusters using the vibrational self-consistent field method (VSCF) in order to account for anharmonicity. We report harmonic, VSCF, and correlation-corrected VSCF calculations obtained using a vibrational configuration interaction approach (VSCF/VCI). Our implementation of the method is based on an efficient calculation of the potential energy surfaces (PES), using periodic density functional theory (DFT) with a plane-wave pseudopotential basis. In some cases, we use an efficient technique (fast-VSCF) assisted by the Voter-Chen potential in order to get an efficient reduction of the number of pair-couplings between modes. This allows us to efficiently reduce the computing time of 2D-PES without degrading the accuracy. We found that anharmonicity of the gold clusters is very small with maximum rms deviations of about 1 cm(-1), although for some particular modes anharmonicity reaches values slightly larger than 2 cm(-1). Silver clusters show slightly larger anharmonicity. In both cases, large differences between calculated and experimental vibrational frequencies (when available) stem more likely from the quality of the electronic structure method used than from vibrational anharmonicity. We show that noble gas embedding often affects the vibrational properties of these clusters more than anharmonicity, and discuss our results in the context of experimental studies. PMID:26619274

  12. Optimized Structure and Vibrational Properties by Error Affected Potential Energy Surfaces

    PubMed Central

    Zen, Andrea; Zhelyazov, Delyan; Guidoni, Leonardo

    2013-01-01

    The precise theoretical determination of the geometrical parameters of molecules at the minima of their potential energy surface and of the corresponding vibrational properties are of fundamental importance for the interpretation of vibrational spectroscopy experiments. Quantum Monte Carlo techniques are correlated electronic structure methods promising for large molecules, which are intrinsically affected by stochastic errors on both energy and force calculations, making the mentioned calculations more challenging with respect to other more traditional quantum chemistry tools. To circumvent this drawback in the present work, we formulate the general problem of evaluating the molecular equilibrium structures, the harmonic frequencies, and the anharmonic coefficients of an error affected potential energy surface. The proposed approach, based on a multidimensional fitting procedure, is illustrated together with a critical evaluation of systematic and statistical errors. We observe that the use of forces instead of energies in the fitting procedure reduces the statistical uncertainty of the vibrational parameters by 1 order of magnitude. Preliminary results based on variational Monte Carlo calculations on the water molecule demonstrate the possibility to evaluate geometrical parameters and harmonic and anharmonic coefficients at this level of theory with an affordable computational cost and a small stochastic uncertainty (<0.07% for geometries and <0.7% for vibrational properties). PMID:24093004

  13. Vibrational Thermodynamics of Materials Brent Fultz

    E-print Network

    Fultz, Brent

    Vibrational Thermodynamics of Materials Brent Fultz California Institute of Technology, W. M. Keck Laboratory, Pasadena CA 91125 USA July 6, 2009 Abstract. The literature on vibrational thermodynamics of harmonic phonons in alloys are organized into thermodynamic models for unmixing and ordering

  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. A vibrational spectroscopy study on anserine and its aqueous solutions.

    PubMed

    Akkaya, Y; Balci, K; Goren, Y; Akyuz, S; Stricker, M C; Stover, D D; Ritzhaupt, G; Collier, W B

    2015-10-01

    In this study based on vibrational spectroscopic measurements and Density Functional Theory (DFT), we aimed for a reliable interpretation of the IR and Raman spectra recorded for anserine in the solid phase and water (H2O) and heavy water (D2O) solutions. Initial DFT calculations at the B3LYP/6-31G(d) searched possible conformers of the anserine zwitterion using a systematic conformational search. The corresponding equilibrium geometrical parameters and vibrational spectral data were determined for each of the stable conformers (in water) by the geometry optimization and hessian calculations performed at the same level of theory using the polarized continuum model (PCM). The same calculations were repeated to determine the most energetically preferred dimer structure for the molecule and the associated geometry, force field and vibrational spectral data. The harmonic force constants obtained from these calculations were scaled by the Scaled Quantum Mechanical Force Field (SQM) method and then used in the calculation of the refined wavenumbers, potential energy distributions, IR and Raman intensities. These refined theoretical data, which confirm the zwitterion structure for anserine in the solid phase or aqueous solvents, revealed the remarkable effects of intermolecular hydrogen bonding on the structural properties and observed IR and Raman spectra of this molecule. PMID:25997178

  16. Prediction of the fundamental vibrational frequencies for C{sub 60} by local density functional theory

    SciTech Connect

    Dixon, D.A.; Chase, B.E.; Fitzgerald, G.; Matsuzawa, Nobuyuki

    1995-03-30

    The harmonic vibrational frequencies of C{sub 60} have been calculated at the local density functional level by using analytic second derivatives. The calculated values for the observed infrared and Raman transitions are in good agreement with the experimental values and suggest that there are a number of misassigned bands based on thick film infrared and Raman measurements. The calculated transitions have been used to provide tentative assignments to the peaks observed by inelastic neutron scattering and high-resolution electron-energy-loss spectroscopy. 31 refs., 4 tabs.

  17. Quantum-chemical calculations of a long proton wire. Application of a harmonic model to analysis of the structure of an ionic defect in a water chain with an excess proton.

    PubMed

    Isaev, Alexander N

    2010-02-11

    Quantum-chemical calculations of molecular complexes (NH(3))(3)Zn(2+)...(H(2)O)(n)...NH(3) (C(n), n = 11, 16, 21, and 30) simulating a proton wire donor-water chain-acceptor were carried out. Earlier found periodicity in the length of the O-H bonds in water chain is explained within the framework of a one-component harmonic model. In complexes C(n), the geometry and electronic structure of ionic defect in water chain with an excess proton were studied. Calculations carried out at ab initio (B3LYP/6-31+G**) and semiempirical (PM3) levels of theory predict different patterns of distribution of the O-H bonds lengths and positive charge on the H-bond hydrogen atoms in the region of ionic defect. The obtained data show how a length of water chain and position of a protonated water link in the chain influence the ionic defect structure. To describe the observed structures of ionic defect, the harmonic model was used and the role of parameters of the H-bonded chain was investigated. The performed analysis explains different mechanisms (concerted and stepwise) of proton transfer along the H-bonded chain derived from ab initio and semiempirical calculation schemes. PMID:20085360

  18. Vibrations and reorientations of NH3 molecules in [Mn(NH3)6](ClO4)2 studied by infrared spectroscopy and theoretical (DFT) calculations

    NASA Astrophysics Data System (ADS)

    Hetma?czyk, Joanna; Hetma?czyk, ?ukasz; Migda?-Mikuli, Anna; Mikuli, Edward

    2015-02-01

    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 3385 cm-1, associated with: ?r(NH3) and ?as(N-H) modes, respectively, indicate that there exist fast (correlation times ?R ? 10-12-10-13 s) reorientational motions of NH3 ligands, with a mean values of activation energies: 7.8 and 4.5 kJ mol-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 TCc = 137.6 K (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.

  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. Estimation of formamide harmonic and anharmonic modes in the Kohn-Sham limit using the polarization consistent basis sets.

    PubMed

    Buczek, Aneta; Kupka, Teobald; Broda, Ma?gorzata A

    2011-09-01

    Formamide harmonic and anharmonic frequencies of fundamental vibrations in the gas phase and in several solvents were successfully estimated in the B3LYP Kohn-Sham complete basis set limit (KS CBS). CBS results were obtained by extrapolating a power function (two-parameter formula) to the results calculated with polarization-consistent basis sets. Anharmonic corrections using the second order perturbation treatment (PT2) and hybrid B3LYP functional combined with polarization consistent pc-n (n=0, 1, 2, 3, 4) and several Pople's basis sets were analyzed for all fundamental formamide vibrational modes in the gas phase and solution. Solvent effects were modeled within a PCM method. The anharmonic frequency of diagnostic amide vibration C=O in the gas phase and the CCl(4) solution calculated with the VPT2 method was significantly closer to experimental data than the corresponding harmonic frequency. Both harmonic and anharmonic frequencies of C=O stretching mode decreased linearly with solvent polarity, expressed by relative environment permittivity (?) ratio (?-1)/(2?+1). However, an unphysical behavior of solvent dependence of some low frequency anharmonic amide modes of formamide (e.g., CN stretch, NH(2) scissoring, and NH(2) in plane bend) was observed, probably due to the presence of severe anharmonicity and Fermi resonance. PMID:21267754

  1. 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.

  2. 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.

  3. Thickness vibrations of a piezoelectric plate with dissipation.

    PubMed

    Lee, Peter C Y; Liu, Ninghui; Ballato, Arthur

    2004-01-01

    The three-dimensional (3-D) equations of linear piezoelectricity with quasi-electrostatic approximation are extended to include losses attributed to the acoustic viscosity and electrical conductivity. These equations are used to investigate effects of dissipation on the propagation of plane waves in an infinite solid and forced thickness vibrations in an infinite piezoelectric plate with general symmetry. For a harmonic plane wave propagating in an arbitrary direction in an unbounded solid, the complex eigenvalue problem is solved from which the effective elastic stiffness, viscosity, and conductivity are computed. For the forced thickness vibrations of an infinite plate, the complex coupling factor K*, input admittance Y are derived and an explicit, approximate expression for K* is obtained in terms of material properties. Effects of the viscosity and conductivity on the resonance frequency, modes, admittance, attenuation coefficient, dynamic time constant, coupling factor, and quality factor are calculated and examined for quartz and ceramic barium titanate plates. PMID:14995016

  4. 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. PMID:24785092

  5. 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.

  6. Spectroscopic analysis and DFT calculations of a food additive Carmoisine

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

    FT-IR and Raman techniques were employed for the vibrational characterization of the food additive Carmoisine (E122). The equilibrium geometry, various bonding features, and harmonic vibrational wavenumbers have been investigated with the help of density functional theory (DFT) calculations. A good correlation was found between the computed and experimental wavenumbers. Azo stretching wavenumbers have been lowered due to conjugation and ?-electron delocalization. Predicted electronic absorption spectra from TD-DFT calculation have been analysed comparing with the UV-vis spectrum. The first hyperpolarizability of the molecule is calculated. Intramolecular charge transfer (ICT) responsible for the optical nonlinearity of the dye molecule has been discussed theoretically and experimentally. Stability of the molecule arising from hyperconjugative interactions, charge delocalization and C-H⋯O, improper, blue shifted hydrogen bonds have been analysed using natural bond orbital (NBO) analysis.

  7. Harmonic engine

    DOEpatents

    Bennett, Charles L. (Livermore, CA)

    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.

  8. Quantum steam tables. Free energy calculations for H2O, D2O, H2S, and H2Se by adaptively optimized Monte Carlo Fourier path integrals

    NASA Astrophysics Data System (ADS)

    Topper, Robert Q.; Zhang, Qi; Liu, Yi-Ping; Truhlar, Donald G.

    1993-03-01

    Converged quantum mechanical vibrational-rotational partition functions and free energies are calculated using realistic potential energy surfaces for several chalcogen dihydrides (H2O, D2O, H2S, H2Se) over a wide range of temperatures (600-4000 K). We employ an adaptively optimized Monte Carlo integration scheme for computing vibrational-rotational partition functions by the Fourier path-integral method. The partition functions and free energies calculated in this way are compared to approximate calculations that assume the separation of vibrational motions from rotational motions. In the approximate calculations, rotations are treated as those of a classical rigid rotator, and vibrations are treated by perturbation theory methods or by the harmonic oscillator model. We find that the perturbation theory treatments yield molecular partition functions which agree closely overall (within ˜7%) with the fully coupled accurate calculations, and these treatments reduce the errors by about a factor of 2 compared to the independent-mode harmonic oscillator model (with errors of ˜16%). These calculations indicate that vibrational anharmonicity and mode-mode coupling effects are significant, but that they may be treated with useful accuracy by perturbation theory for these molecules. The quantal free energies for gaseous water agree well with previously available approximate values for this well studied molecule, and similarly accurate values are also presented for the less well studied D2O, H2S, and H2Se.

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

    NASA Astrophysics Data System (ADS)

    Fedorov, Dmitry A.; Derevianko, Andrei; Varganov, Sergey A.

    2014-05-01

    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 X1?+ electronic state using the coupled cluster with singles doubles and triples method. All-electron quadruple-? basis sets with additional core functions are used for Li and Na, and small-core relativistic effective core potentials with quadruple-? 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.

  10. 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}?{sup +} electronic state using the coupled cluster with singles doubles and triples method. All-electron quadruple-? basis sets with additional core functions are used for Li and Na, and small-core relativistic effective core potentials with quadruple-? 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.

  11. Vibrational Spectra and Heat Capacity of Methane, and the Speed of Sound

    NASA Astrophysics Data System (ADS)

    Tennis, Ronald; Bailey, Ryan; Henderson, Giles

    2000-12-01

    A two-part physical chemistry laboratory experiment is described in which students evaluate statistical mechanical theory by comparing a measured speed of sound and heat capacity with values predicted from vibrational spectra. In part 1 students measure the IR spectrum of CH4(g) and the Raman spectrum of CH4(l) to determine quantized vibrational energy spacings. Strong Raman scattering of a pulsed nitrogen laser beam is observed with a liquid methane sample in a custom cryogenic cell constructed from two side-arm test tubes and a length of Pyrex tube. These data are used with the statistical mechanics of a harmonic oscillator to calculate vibrational heat capacities and CP/CV; of CH4(g) and the speed of sound in CH4(g). In part 2, the predicted speed of sound is compared with an experimental value measured with a simple acoustic resonance cavity (Kundt's tube) exhausted to a Bunsen burner.

  12. An experimental and theoretical study of the vibrational spectra and structure of Isosorbide dinitrate

    NASA Astrophysics Data System (ADS)

    Uma Maheswari, J.; Muthu, S.; Sundius, Tom

    2013-05-01

    The present work aims at exploring the vibrational spectra of Isosorbide dinitrate and its chemical activity in a five membered ring system. The FT-IR and FT-Raman spectral studies of the Isosorbide dinitrate (ISDN) were carried out. The equilibrium geometry, various bonding features and harmonic vibrational frequencies of ISDN have been calculated using B3LYP density functional theory (DFT) with 6-31G(d, p) as basis set. The calculated HOMO and LUMO energies and density of states (DOS) show the chemical activity of the molecule. Good correlations between the experimental 1H and 13C NMR chemical shifts in methanol-d and calculated GIAO shielding tensors were found. The potential energy surface was studied using the DFT method.

  13. 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. PMID:17243664

  14. Ab initio calculation and anharmonic force field of hypochlorous acid, HOCl

    NASA Astrophysics Data System (ADS)

    Halonen, L.; Ha, T.-K.

    1988-03-01

    Ab initio calculations on HOCl have been performed at the third-order Møller-Plesset perturbation theory level to determine the equilibrium structure and the anharmonic force field. An empirical anharmonic force field based on the ab initio results is obtained using available experimental vibration-rotation data. Four of the six harmonic and six of the ten cubic force constants have been determined experimentally, the remaining values being fixed at the ab initio values. A good fit to the experimental vibration-rotation data of four isotopic species is obtained.

  15. First-principle calculation and assignment for vibrational spectra of Ba(Mg{sub 1/3}Nb{sub 2/3})O{sub 3} microwave dielectric ceramic

    SciTech Connect

    Diao, Chuan-Ling; Wang, Chun-Hai; Lu, Jing; Luo, Neng-Neng; Jing, Xi-Ping E-mail: xpjing@pku.edu.cn; Qi, Ze-Ming; Shao, Tao; Wang, Yu-Yin; Wang, Quan-Chao; Kuang, Xiao-Jun; Fang, Liang; Shi, Feng E-mail: xpjing@pku.edu.cn

    2014-03-21

    1:2 B-site cation ordered Ba(Mg{sub 1/3}Nb{sub 2/3})O{sub 3} ceramic was synthesized using conventional solid-state reaction at 1600?°C for 12?h. The structure parameters were obtained through Rietveld refinement of X-ray diffraction data. The Raman peak frequencies were obtained by Lorenz fitting on Raman spectrum. Four-parameter semiquantum model was used to fit the infrared (IR) reflectivity spectrum, and the fitted parameters were used to calculate the dielectric permittivity ? and dielectric loss tan?. A total of 9 active Raman and 16 active IR modes were obtained using first-principle calculations based on density functional theory with local density approximation. All of the vibrational modes were assigned and represented by linear combinations of the symmetry coordinates deduced using group theory analysis. The Raman mode with the highest frequency A{sub 1g}{sup (4)} (789?cm{sup ?1}) can be described as the breathing vibration of NbO{sub 6}. The IR modes E{sub u}{sup (1)} (149?cm{sup ?1}) and A{sub 2u}{sup (2)} (212?cm{sup ?1}), which can be described as the twisting vibrations of Ba–MgO{sub 6}/Ba–NbO{sub 6} on the a–b plane and the stretching vibrations of Ba–MgO{sub 6}/Ba–NbO{sub 6} along the c direction, respectively, are the dominant contributing modes to ? and tan?. The dielectric property parameters obtained using IR spectrum fittings, first-principal calculations, and microwave measurements were compared.

  16. Superradiance of Harmonic Oscillators

    E-print Network

    Delanty, Michael; Twamley, Jason

    2011-01-01

    Superradiance, the enhanced collective emission of light from a coherent ensemble of quantum systems, has been typically studied in atomic ensembles. In this work we study the enhanced emission of energy from coherent ensembles of harmonic oscillators. We show that it should be possible to observe harmonic oscillator superradiance in a variety of physical platforms such as waveguide arrays in integrated photonics and resonator arrays in circuit QED. We find general conditions specifying when emission is superradiant and subradiant and find that superradiant, subradiant and dark states take the form of multimode squeezed coherent states and highly entangled multimode Fock states. The intensity, two-mode correlations and fraction of quanta trapped in the system after decay are calculated for a range of initial states including multimode Fock, squeezed, coherent and thermal states. In order to explore these effects, the Law and Eberly protocol [C. K. Law and J. H. Eberly, Phys. Rev. Lett. 76, 1055 (1996)] is gen...

  17. 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

    2016-01-01

    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. PMID:25468437

  18. 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.

  19. Polyatomic molecule vibrations

    NASA Technical Reports Server (NTRS)

    1976-01-01

    Polyatomic molecule vibrations are analyzed as harmonic vibrations along normal coordinates. The energy eigenvalues are found for linear and nonlinear symmetric triatomic molecules for valence bond models of the potential function with arbitrary coupling coefficients; such models can usually be fitted to observed energy levels with reasonably good accuracy. Approximate normal coordinates for the H2O molecule are discussed. Degenerate vibrational modes such as occur in CO2 are analyzed and expressions for Fermi resonance between close-lying states of the same symmetry are developed. The bending modes of linear triatomic molecules are expressed in terms of Laguerre polynomials in cylindrical coordinates as well as in terms of Hermite polynomials in Cartesian coordinates. The effects of large-amplitude bending such as occur in the C3 molecule are analyzed, along with anharmonic effects, which split the usually degenerate bending mode energy levels. Finally, the vibrational frequencies, degeneracies, and symmetry properties of XY3, X2Y2, and XY4 type molecules are discussed.

  20. 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.

  1. The Harmonic Oscillator Influenced by Gravitational Wave in Noncommutative Quantum Phase Space

    NASA Astrophysics Data System (ADS)

    Yakup, Rehimhaji; Dulat, Sayipjamal; Li, Kang; Hekim, Mamatabdulla

    2014-04-01

    Dynamical property of harmonic oscillator affected by linearized gravitational wave (LGW) is studied in a particular case of both position and momentum operators which are noncommutative to each other. By using the generalized Bopp's shift, we, at first, derived the Hamiltonian in the noncommutative phase space (NPS) and, then, calculated the time evolution of coordinate and momentum operators in the Heisenberg representation. Tiny vibration of flat Minkowski space and effect of NPS let the Hamiltonian of harmonic oscillator, moving in the plain, get new extra terms from it's original and noncommutative space partner. At the end, for simplicity, we take the general form of the LGW into gravitational plain wave, obtain the explicit expression of coordinate and momentum operators.

  2. 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.

  3. HARMONIC CYCLOTRON HEATING IN THE TOROIDAL OCTUPOLE

    E-print Network

    Sprott, Julien Clinton

    HARMONIC CYCLOTRON HEATING IN THE TOROIDAL OCTUPOLE J. C. Sprott October 1976 Plasma Studies PLP without consent of the author and maj or professor. #12;-2- Previous calculations of cyclotron resonance the harmonic cyclotron heating of both electrons and ions. It is well known (see, for example, O. Eldridge

  4. High-Accuracy Vibrational Computations for Transition-Metal Complexes Including Anharmonic Corrections: Ferrocene, Ruthenocene, and Osmocene as Test Cases.

    PubMed

    Latouche, Camille; Palazzetti, Federico; Skouteris, Dimitrios; Barone, Vincenzo

    2014-10-14

    Density functional theory calculations of infrared spectra at harmonic and anharmonic levels of theory have been carried out in order to define a reliable yet feasible strategy to perform accurate computations on metal complexes starting from metallocenes. We present different possibilities to compute with unprecedented accuracy either the ligand vibrations or vibrations where the metal atom is involved or even to obtain the entire spectrum without invoking any scaling factor. Anharmonic calculations employing second-order vibrational perturbation theory provide very good results when performed using the B3PW91 hybrid functional associated with an extended basis set and are able to reproduce quantitatively the entire spectrum of ferrocene, including the presence of overtones at ?1700 cm(-1). Furthermore, our results confirm that B3LYP is the best functional to reproduce ligand vibrations, but, unfortunately, it provides unreliable results for vibrations involving the metal atom. Conversely, the PBE0 functional gives accurate results for metal-ligand vibrational frequencies, but it is quite far from the experiment for intraligand ones. PMID:26588150

  5. Nonlinear harmonic generation by diurnal tides

    NASA Astrophysics Data System (ADS)

    Wunsch, Scott

    2015-09-01

    Recent observations from the South China Sea have demonstrated that semi-diurnal tides sometimes generate a double-frequency harmonic. Similar harmonic generation has been found in laboratory experiments and numerical simulations of internal wave beams refracting into a pycnocline. Here, a weakly nonlinear theory of internal wave refraction is applied to oceanic internal tides in an idealized stratification profile. The steady state harmonic amplitude is calculated as a function of the tidal frequency and the pycnocline characteristics. The results indicate that harmonic generation by nonlinear refraction of semi-diurnal tides is consistent with the South China Sea observations.

  6. Complex Energy of Harmonic Oscillator under Non-Hermitian transformation of momentum with real wave function

    E-print Network

    Biswanath Rath

    2015-05-19

    For the first time in the literature of Quantum Physics, we present complex energy eigenvalues of non-Hermitian Harmonic Oscillator $H=\\frac{(p+iLx)}^{2}}{2} + W^{2} \\frac{x^{2}}{2}$ with real wave function having positive frequency of vibration $(w)$ under some selective choice of $L$ and $W$ .Interestingly for the same values of $L$ and $W$, if the frequency of vibration $w$ in the real wave function is (some how) related as $w=L\\pmW$ or $w=W-L$ then the same oscillator can reflect either pure positive or negative energy eigenvalues.The real energy levels are in conformity with the perturbative calculation. PACS :03.65.Db;11.39.Er. Key words: Positive frequency, real wave function, complex energy, real positive energy,negative energy.

  7. Coupled rotor/airframe vibration analysis

    NASA Technical Reports Server (NTRS)

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

    1982-01-01

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

  8. Coupling between plate vibration and acoustic radiation

    NASA Technical Reports Server (NTRS)

    Frendi, Abdelkader; Maestrello, Lucio; Bayliss, Alvin

    1992-01-01

    A detailed numerical investigation of the coupling between the vibration of a flexible plate and the acoustic radiation is performed. The nonlinear Euler equations are used to describe the acoustic fluid while the nonlinear plate equation is used to describe the plate vibration. Linear, nonlinear, and quasi-periodic or chaotic vibrations and the resultant acoustic radiation are analyzed. We find that for the linear plate response, acoustic coupling is negligible. However, for the nonlinear and chaotic responses, acoustic coupling has a significant effect on the vibration level as the loading increases. The radiated pressure from a plate undergoing nonlinear or chaotic vibrations is found to propagate nonlinearly into the far-field. However, the nonlinearity due to wave propagation is much weaker than that due to the plate vibrations. As the acoustic wave propagates into the far-field, the relative difference in level between the fundamental and its harmonics and subharmonics decreases with distance.

  9. VIBRATIONALLY EXCITED C{sub 6}H

    SciTech Connect

    Gottlieb, C. A.; McCarthy, M. C.; Thaddeus, P.

    2010-08-15

    Rotational spectra of the linear carbon chain radical C{sub 6}H in two low-lying excited vibrational states were observed both at millimeter wavelengths in a low-pressure glow discharge and at centimeter wavelengths in a supersonic molecular beam. Two series of harmonically related lines with rotational constants within 0.3% of the {sup 2{Pi}} ground state were assigned to the {sup 2{Sigma}} and {sup 2{Delta}} vibronic components of an excited bending vibrational level. Measurements of the intensities of the lines in the glow discharge indicate that the {sup 2{Sigma}} component lies very close to ground, but the {sup 2{Delta}} component is much higher in energy. The standard Hamiltonian for an isolated {sup 2{Delta}} state with five spectroscopic constants reproduces the observed rotational spectrum, but several high-order distortion terms in the spin-rotation interaction are needed to reproduce the spectrum of the {sup 2{Sigma}} component in C{sub 6}H and C{sub 6}D. The derived spectroscopic constants allow astronomers to calculate the rotational spectra of the {sup 2{Sigma}} and {sup 2{Delta}} states up to 260 GHz to within 0.1 km s{sup -1} or better in equivalent radial velocity.

  10. 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.

  11. Molecular vibrational states during a collision

    NASA Technical Reports Server (NTRS)

    Recamier, Jose A.; Jauregui, Rocio

    1995-01-01

    Alternative algebraic techniques to approximate a given Hamiltonian by a harmonic oscillator are described both for time-independent and time-dependent systems. We apply them to the description of a one dimensional atom-diatom collision. From the resulting evolution operator, we evaluate vibrational transition probabilities as well as other time-dependent properties. As expected, the ground vibrational state becomes a squeezed state during the collision.

  12. Molecular conformational analysis, vibrational spectra, NBO, NLO, HOMO-LUMO and molecular docking studies of ethyl 3-(E)-(anthracen-9-yl)prop-2-enoate based on density functional theory calculations.

    PubMed

    Mary, Y Sheena; Varghese, Hema Tresa; Panicker, C Yohannan; Thiemann, Thies; Al-Saadi, Abdulaziz A; Popoola, Saheed A; Van Alsenoy, C; Al Jasem, Yosef

    2015-11-01

    FT-IR and FT-Raman spectra of ethyl 3-(E)-(anthracen-9-yl)prop-2-enoate were recorded and analyzed. The conformational behavior of the molecule was also investigated. The vibrational wavenumbers were calculated using DFT quantum chemical calculations. The data obtained from the wavenumber calculations were used to assign vibrational bands obtained experimentally. The geometrical parameters are in agreement with XRD data. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The HOMO and LUMO analysis were used to determine the charge transfer within the molecule and quantum chemical parameters related to the title compound. From the MEP analysis, it is clear that the negative electrostatic potential regions are mainly localized over the carbonyl groups and anthracene ring and are possible sites for electrophilic attack and the positive regions are localized at all the hydrogen atoms as possible sites for nucleophilic attack. NLO and NMR studies are also reported. Molecular docking studies suggest that the title compound might exhibit inhibitory activity against IDE and may act as an insulysin inhibitor. Conformational analysis is also reported. PMID:26079511

  13. Vibrational and Thermophysical Properties of PETN from First Principles

    NASA Astrophysics Data System (ADS)

    Gonzalez, Joseph; Landerville, Aaron; Oleynik, Ivan

    2015-06-01

    Thermophysical properties are urgently sought as input for meso- and continuum-scale modeling of energetic materials (EMs). However, empirical data in this regard are often limited to specific pressures and temperatures. Such modeling of EMs can be greatly improved by inclusion of thermophysical properties over a wide range of pressures and temperatures, provided such data could be reliably obtained from theory. We demonstrate such a capability by calculating the equation of state, heat capacities, coefficients of thermal expansion, and Gruneissen parameters for pentaerythritol tetranitrate (PETN) using first-principles density functional theory, which includes proper description of van der Waals interactions and zero-point and thermal free energy contributions to pressure, the latter being calculated using the quasi-harmonic approximation. Further, we investigate the evolution of the vibration spectrum of PETN as a function of pressure.

  14. Structure, Anharmonic Vibrational Frequencies, and Intensities of NNHNN(.).

    PubMed

    Yu, Qi; Bowman, Joel M; Fortenberry, Ryan C; Mancini, John S; Lee, Timothy J; Crawford, T Daniel; Klemperer, William; Francisco, Joseph S

    2015-11-25

    A semiglobal potential energy surface (PES) and quartic force field (QFF) based on fitting high-level electronic structure energies are presented to describe the structures and spectroscopic properties of NNHNN(+). The equilibrium structure of NNHNN(+) is linear with the proton equidistant between the two nitrogen groups and thus of D?h symmetry. Vibrational second-order perturbation theory (VPT2) calculations based on the QFF fails to describe the proton "rattle" motion, i.e., the antisymmetric proton stretch, due to the very flat nature of PES around the global minimum but performs properly for other modes with sharper potential wells. Vibrational self-consistent field/virtual state configuration interaction (VSCF/VCI) calculations using a version of MULTIMODE without angular momentum terms successfully describe this motion and predict the fundamental to be at 759 cm(-1). This is in good agreement with the value of 746 cm(-1) from a fixed-node diffusion Monte Carlo calculation and the experimental Ar-tagged result of 743 cm(-1). Other VSCF/VCI energies are in good agreement with other experimentally reported ones. Both double-harmonic intensity and rigorous MULTIMODE intensity calculations show the proton-transfer fundamental has strong intensity. PMID:26529262

  15. Intermolecular charge transfer and vibrational analysis of hydrogen bonding in acetazolamide

    NASA Astrophysics Data System (ADS)

    Chaturvedi, Deepika; Gupta, Vineet; Tandon, Poonam; Sharma, Anamika; Baraldi, C.; Gamberini, M. C.

    2012-12-01

    In the present work the structural and spectral characteristics of acetazolamide have been studied by methods of infrared, Raman spectroscopy and quantum chemistry. Electrostatic potential surface, optimized geometry, harmonic vibrational frequencies, infrared intensities and activities of Raman scattering were calculated by density functional theory (DFT) employing B3LYP with complete relaxation in the potential energy surface using 6-311++G(d,p) basis set. Based on these results, we have discussed the correlation between the vibrational modes and the structure of the dimers of acetazolamide. The calculated vibrational spectra of three dimers of acetazolamide have been compared with observed spectra, and the assignment of observed bands was carried out using potential energy distribution. The observed spectra agree well with the values computed from the DFT. A comparison of observed and calculated vibrational spectra clearly shows the effect of hydrogen bonding. The frequency shifts observed for the different dimers are in accord with the hydrogen bonding in acetazolamide. Natural bond orbital (NBO) analyses reflect the charge transfer interaction in the individual hydrogen bond units and the stability of different dimers of acetazolamide.

  16. PREFACE: Vibrations at surfaces Vibrations at surfaces

    NASA Astrophysics Data System (ADS)

    Rahman, Talat S.

    2011-12-01

    This special issue is dedicated to the phenomenon of vibrations at surfaces—a topic that was indispensible a couple of decades ago, since it was one of the few phenomena capable of revealing the nature of binding at solid surfaces. For clean surfaces, the frequencies of modes with characteristic displacement patterns revealed how surface geometry, as well as the nature of binding between atoms in the surface layers, could be different from that in the bulk solid. Dispersion of the surface phonons provided further measures of interatomic interactions. For chemisorbed molecules on surfaces, frequencies and dispersion of the vibrational modes were also critical for determining adsorption sites. In other words, vibrations at surfaces served as a reliable means of extracting information about surface structure, chemisorption and overlayer formation. Experimental techniques, such as electron energy loss spectroscopy and helium-atom-surface scattering, coupled with infra-red spectroscopy, were continually refined and their resolutions enhanced to capture subtleties in the dynamics of atoms and molecules at surfaces. Theoretical methods, whether based on empirical and semi-empirical interatomic potential or on ab initio electronic structure calculations, helped decipher experimental observations and provide deeper insights into the nature of the bond between atoms and molecules in regions of reduced symmetry, as encountered on solid surfaces. Vibrations at surfaces were thus an integral part of the set of phenomena that characterized surface science. Dedicated workshops and conferences were held to explore the variety of interesting and puzzling features revealed in experimental and theoretical investigations of surface vibrational modes and their dispersion. One such conference, Vibrations at Surfaces, first organized by Harald Ibach in Juelich in 1980, continues to this day. The 13th International Conference on Vibrations at Surfaces was held at the University of Central Florida, Orlando, in March 2010. Several speakers at this meeting were invited to contribute to the special section in this issue. As is clear from the articles in this special section, the phenomenon of vibrations at surfaces continues to be a dynamic field of investigation. In fact, there is a resurgence of effort because the insights provided by surface dynamics are still fundamental to the development of an understanding of the microscopic factors that control surface structure formation, diffusion, reaction and structural stability. Examination of dynamics at surfaces thus complements and supplements the wealth of information that is obtained from real-space techniques such as scanning tunneling microscopy. Vibrational dynamics is, of course, not limited to surfaces. Surfaces are important since they provide immediate deviation from the bulk. They display how lack of symmetry can lead to new structures, new local atomic environments and new types of dynamical modes. Nanoparticles, large molecules and nanostructures of all types, in all kinds of local environments, provide further examples of regions of reduced symmetry and coordination, and hence display characteristic vibrational modes. Given the tremendous advance in the synthesis of a variety of nanostructures whose functionalization would pave the way for nanotechnology, there is even greater need to engage in experimental and theoretical techniques that help extract their vibrational dynamics. Such knowledge would enable a more complete understanding and characterization of these nanoscale systems than would otherwise be the case. The papers presented here provide excellent examples of the kind of information that is revealed by vibrations at surfaces. Vibrations at surface contents Poisoning and non-poisoning oxygen on Cu(410)L Vattuone, V Venugopal, T Kravchuk, M Smerieri, L Savio and M Rocca Modifying protein adsorption by layers of glutathione pre-adsorbed on Au(111)Anne Vallée, Vincent Humblot, Christophe Méthivier, Paul Dumas and Claire-Marie Pradier Relating temperature dependence of atom

  17. Vibrational spectroscopic investigations and computational study of 5-tert-butyl-N-(4-trifluoromethylphenyl)pyrazine-2-carboxamide.

    PubMed

    Joseph, Tomy; Varghese, Hema Tresa; Yohannan Panicker, C; Viswanathan, K; Dolezal, Martin; Manojkumar, T K; Van Alsenoy, Christian

    2013-09-01

    Pyrazine and its derivatives form an important class of compounds present in several natural flavors and complex organic molecules. Quantum chemical calculations of the equilibrium geometry, harmonic vibrational frequencies, infrared intensities and Raman activities of 5-tert-Butyl-N-(4-trifluoromethylphenyl)pyrazine-2-carboxamide in the ground state were carried out by using density functional methods. Potential energy distribution of normal modes of vibrations was done using GAR2PED program. Nonlinear optical behavior of the examined molecule was investigated by the determination of first hyperpolarizability. The calculated HOMO and LUMO energies show the chemical activity of 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 that of similar derivatives. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. PMID:23727674

  18. Vibrational analysis of isonicotinamide

    NASA Astrophysics Data System (ADS)

    Akalin, E.; Yilmaz, A.; Akyuz, S.

    2005-06-01

    The FT-IR and FT-Raman spectra of isonicotinamide (in solid phase) have been recorded in the regions 4000-400 and 4000-70 cm -1, respectively. The geometry optimizations and vibrational spectrum calculations of isonicotinamide have been carried out at the DFT/B3LYP level with 6-31++G(d,p) basis set. With the SQM approach, the force field of isonicotinamide obtained by DFT calculations has been corrected by a set of scaling factors to get a good agreement between observed and calculated wavenumbers. Isonicotinamide interacting with Al(OH) 3 has also been studied by B3LYP/6-31++G(d,p) calculations and the SQM results of both molecules have been compared to investigate how the coordination through the ring nitrogen effects the isonicotinamide vibrational wavenumbers.

  19. Vibrational Coupling

    SciTech Connect

    2011-01-01

    By homing in on the distribution patterns of electrons around an atom, a team of scientists team with Berkeley Lab's Molecular Foundry showed how certain vibrations from benzene thiol cause electrical charge to "slosh" onto a gold surface (left), while others do not (right). The vibrations that cause this "sloshing" behavior yield a stronger SERS signal.

  20. Vertical vibration and shape oscillation of acoustically levitated water drops

    SciTech Connect

    Geng, D. L.; Xie, W. J.; Yan, N.; Wei, B.

    2014-09-08

    We present the vertical harmonic vibration of levitated water drops within ultrasound field. The restoring force to maintain such a vibration mode is provided by the resultant force of acoustic radiation force and drop gravity. Experiments reveal that the vibration frequency increases with the aspect ratio for drops with the same volume, which agrees with the theoretical prediction for those cases of nearly equiaxed drops. During the vertical vibration, the floating drops undergo the second order shape oscillation. The shape oscillation frequency is determined to be twice the vibration frequency.

  1. The Renner-Teller effect in HCCCN + ( X ˜ 2 ? ) studied by zero-kinetic energy photoelectron spectroscopy and theoretical calculations

    NASA Astrophysics Data System (ADS)

    Dai, Zuyang; Sun, Wei; Wang, Jia; Mo, Yuxiang

    2015-08-01

    The spin-vibronic energy levels of the cyanoacetylene cation have been measured using the one-photon zero-kinetic energy (ZEKE) photoelectron spectroscopic method. All three degenerate vibrational modes showing vibronic coupling, i.e., Renner-Teller (RT) effect, have been observed. All the splitting spin-vibronic energy levels of the fundamental H—C?C bending vibration (v5) have been determined. The spin-vibronic energy levels of the degenerate vibrational modes have also been calculated using a diabatic model in which the harmonic terms as well as all the second-order vibronic coupling terms are used. The theoretical predictions are in good agreement with the experimental data and are used to assign the ZEKE spectrum. It is found that the RT effects for the H—(CC)—CN bending (v7) and the C—C?N bending (v6) vibrations are weak, whereas they are strong for the H—C?C bending (v5) vibration. The cross-mode RT couplings between any of the two degenerate vibrations are strong. The spin-orbit resolved fundamental vibrational energy levels of the C?N stretching (v2) and C—H stretching (v1) vibrations have also been observed. The spin-orbit energy splitting of the ground state has been determined for the first time as 43 ± 2 cm-1, and the ionization energy of HCCCN is found to be 93 903.5 ± 2 cm-1.

  2. Vibration Analysis of Composite Laminate Plate Excited by Piezoelectric Actuators

    PubMed Central

    Her, Shiuh-Chuan; Lin, Chi-Sheng

    2013-01-01

    Piezoelectric materials can be used as actuators for the active vibration control of smart structural systems. In this work, piezoelectric patches are surface bonded to a composite laminate plate and used as vibration actuators. A static analysis based on the piezoelectricity and elasticity is conducted to evaluate the loads induced by the piezoelectric actuators to the host structure. The loads are then employed to develop the vibration response of a simply supported laminate rectangular plate excited by piezoelectric patches subjected to time harmonic voltages. An analytical solution of the vibration response of a simply supported laminate rectangular plate under time harmonic electrical loading is obtained and compared with finite element results to validate the present approach. The effects of location and exciting frequency of piezoelectric actuators on the vibration response of the laminate plate are investigated through a parametric study. Numerical results show that modes can be selectively excited, leading to structural vibration control. PMID:23529121

  3. FT-IR, FT-Raman, NMR spectra, density functional computations of the vibrational assignments (for monomer and dimer) and molecular geometry of anticancer drug 7-amino-2-methylchromone

    NASA Astrophysics Data System (ADS)

    Mariappan, G.; Sundaraganesan, N.

    2014-04-01

    Vibrational assignments for the 7-amino-2-methylchromone (abbreviated as 7A2MC) molecule using a combination of experimental vibrational spectroscopic measurements and ab initio computational methods are reported. The optimized geometry, intermolecular hydrogen bonding, first order hyperpolarizability and harmonic vibrational wavenumbers of 7A2MC have been investigated with the help of B3LYP density functional theory method. The calculated molecular geometry parameters, the theoretically computed vibrational frequencies for monomer and dimer and relative peak intensities were compared with experimental data. DFT calculations using the B3LYP method and 6-31 + G(d,p) basis set were found to yield results that are very comparable to experimental IR and Raman spectra. Detailed vibrational assignments were performed with DFT calculations and the potential energy distribution (PED) obtained from the Vibrational Energy Distribution Analysis (VEDA) program. Natural Bond Orbital (NBO) study revealed the characteristics of the electronic delocalization of the molecular structure. 13C and 1H NMR spectra have been recorded and 13C and 1H nuclear magnetic resonance chemical shifts of the molecule have been calculated using the gauge independent atomic orbital (GIAO) method. Furthermore, All the possible calculated values are analyzed using correlation coefficients linear fitting equation and are shown strong correlation with the experimental data.

  4. Franck-Condon factors based on anharmonic vibrational wave functions of polyatomic molecules

    NASA Astrophysics Data System (ADS)

    Rodriguez-Garcia, Valerie; Yagi, Kiyoshi; Hirao, Kimihiko; Iwata, Suehiro; Hirata, So

    2006-07-01

    Franck-Condon (FC) integrals of polyatomic molecules are computed on the basis of vibrational self-consistent-field (VSCF) or configuration-interaction (VCI) calculations capable of including vibrational anharmonicity to any desired extent (within certain molecular size limits). The anharmonic vibrational wave functions of the initial and final states are expanded unambiguously by harmonic oscillator basis functions of normal coordinates of the respective electronic states. The anharmonic FC integrals are then obtained as linear combinations of harmonic counterparts, which can, in turn, be evaluated by established techniques taking account of the Duschinsky rotations, geometry displacements, and frequency changes. Alternatively, anharmonic wave functions of both states are expanded by basis functions of just one electronic state, permitting the FC integral to be evaluated directly by the Gauss-Hermite quadrature used in the VSCF and VCI steps [Bowman et al., Mol. Phys. 104, 33 (2006)]. These methods in conjunction with the VCI and coupled-cluster with singles, doubles, and perturbative triples [CCSD(T)] method have predicted the peak positions and intensities of the vibrational manifold in the X˜B12 photoelectron band of H2O with quantitative accuracy. It has revealed that two weakly visible peaks are the result of intensity borrowing from nearby states through anharmonic couplings, an effect explained qualitatively by VSCF and quantitatively by VCI, but not by the harmonic approximation. The X˜B22 photoelectron band of H2CO is less accurately reproduced by this method, likely because of the inability of CCSD(T)/cc-pVTZ to describe the potential energy surface of open-shell H2CO+ with the same high accuracy as in H2O+.

  5. Structural, vibrational, electronic, NMR, NLO and reactivity analyses of (3Z)-3-(2-oxo-2-phenylethylidene)-1,3-dihydro-2H-indol-2-one (OPEDI) by ab initio HF and DFT calculations.

    PubMed

    Sridevi, C; Velraj, G

    2013-04-15

    This study represents the vibrational, electronic, NMR, NLO, reactivity and structural aspects of (3Z)-3-(2-oxo-2-phenylethylidene)-1,3-dihydro-2H-indol-2-one (OPEDI). A detailed interpretation of the FT-IR, FT-Raman, UV and NMR spectra were reported. Theoretical calculations were performed by ab initio HF and density functional theory (DFT)/B3LYP method using 6-311++G(d,p) basis sets. The most preferred Z isomer (cis-configuration) was confirmed through PES scan studies. The vibrational wavenumbers and potential energy distribution (PED) of various normal modes were calculated. The lower frontier orbital energy gap and high dipole moment of OPEDI illustrates the high reactivity. The stability and charge delocalization of the molecule was studied by natural bond orbital (NBO) analysis. OPEDI exhibited good nonlinear optical activity and was 13 times greater than that of urea. Molecular electrostatic potential (MEP) was carried out for predicting the reactive sites. The NMR results indicated that the observed chemical shifts depend not only on the structure of the molecule being studied, but also on the solvent used. PMID:23434562

  6. Vibrational properties, crystal X-ray diffraction structure and quantum chemical calculations on a divalent sulfur substituted phthalimide: 1H-Isoindole-1,3(2H)-dione, 2-[(methoxycarbonyl)thio

    NASA Astrophysics Data System (ADS)

    Torrico-Vallejos, Sonia; Erben, Mauricio F.; Piro, Oscar E.; Castellano, Eduardo E.; Della Védova, Carlos O.

    2010-06-01

    Structural and conformational properties of 1H-Isoindole-1,3(2H)-dione, 2-[(methoxycarbonyl)thio] ( S-phthalimido O-methyl thiocarbonate) are analyzed using a combined approach including X-ray diffraction, vibrational spectra and theoretical calculation methods. The vibrational properties have been studied by infrared and Raman spectroscopies along with quantum chemical calculations (B3LYP and B3PW91 functional in connection with the 6-311++G ** and aug-cc-pVDZ basis sets). The crystal structure was determined by X-ray diffraction methods. The substance crystallizes in the monoclinic P2 1/c space group with a = 6.795(1), b = 5.109(1), c = 30.011(3) Å, ? = 90.310(3)° and Z = 4 molecules per unit cell. The conformation adopted by the N sbnd S sbnd C dbnd O group is syn (C dbnd O double bond in synperiplanar orientation with respect to the N sbnd S single bond). The experimental molecular structure is well reproduced by the MP2/aug-cc-pVDZ method.

  7. Vibration by relativistic effects

    E-print Network

    Enrique Oradaz Romay

    2005-12-27

    Relativity, time reversal invariance in mechanics and principle of causality can be in the bases of a type of vibration of the extensive objects. It is because, the detailed analysis of the relativistic movement of an extensive body entail that all the objects must have inherent a vibratory movement to their own size. Such effect does not happen when it works with point particles thus is not stranger who happens unnoticed in the traditional studies. Also we can find relation between the form of vibration of the extensive objects and the energy that calculates by quantum considerations.

  8. SHTOOLS: Tools for Working with Spherical Harmonics

    NASA Astrophysics Data System (ADS)

    Wieczorek, Mark

    2011-10-01

    SHTOOLS is an archive of fortran 95 based software that can be used to perform (among others) spherical harmonic transforms and reconstructions, rotations of spherical harmonic coefficients, and multitaper spectral analyses on the sphere. While several collections of code currently exist for working with data expressed in spherical harmonics, this one is unique for several reasons: It can accommodate any standard normalization of the spherical harmonic functions ("geodesy" 4? normalized, Schmidt semi-normalized, orthonormalized, and unnormalized).Either real or complex spherical harmonics can be employed.Spherical harmonic transforms are calculated by exact quadrature rules using either (1) the sampling theorem of Driscoll and Healy (1994) where data are equally sampled (or spaced) in latitude and longitude, or (2) Gauss-Legendre quadrature. A least squares inversion routine for irregularly sampled data is included as well.One can choose to use or exclude the Condon-Shortley phase factor of (-1)m with the associated Legendre functions.The spherical harmonic transforms are proven to be accurate to approximately degree 2800, corresponding to a spatial resolution of better than 4 arc minutes.Routines are included for performing localized multitaper spectral analyses.Routines are included for performing standard gravity calculations, such as computation of the geoid and the determination of the potential associated with finite-amplitude topography.The routines are fast. Spherical harmonic transforms and reconstructions take on the order of 1 second for bandwidths less than 600 and about 3 minutes for bandwidths close to 2800.

  9. Fast calculation of the infrared spectra of large biomolecules.

    PubMed

    Mott, A J; Thirumuruganandham, S P; Thorpe, M F; Rez, P

    2013-12-01

    Vibrational spectra of proteins potentially give insight into biologically significant molecular motion and the proportions of different types of secondary structure. Vibrational spectra can be calculated either from normal modes obtained by diagonalizing the mass-weighted Hessian or from the time autocorrelation function derived from molecular dynamics trajectories. The Hessian matrix is calculated from force fields because it is not practical to calculate the Hessian from quantum mechanics for large molecules. As an alternative to molecular dynamics the spectral response can be calculated from a time autocorrelation derived from numerical solution of the harmonic equations of motion, resulting in calculations at least 4 times faster. Because the calculation also scales linearly with number of atoms, N, it is faster than normal-mode calculations that scale as N (3) for proteins with more then 4,700 atoms. Using this method it is practical to perform all-atom calculations for large biological systems, for example viral capsids, with the order of 10(5) atoms. PMID:24037120

  10. Ultrasound Vibrometry Using Orthogonal Frequency Based Vibration Pulses

    PubMed Central

    Zheng, Yi; Yao, Aiping; Chen, Shigao; Urban, Matthew W.; Lin, Haoming; Chen, Xin; Guo, Yanrong; Chen, Ke; Wang, Tianfu; Chen, Shiping

    2014-01-01

    New vibration pulses are developed for shear wave generation in a tissue region with preferred spectral distributions for ultrasound vibrometry applications. The primary objective of this work is to increase the frequency range of detectable harmonics of the shear wave. The secondary objective is to reduce the required peak intensity of transmitted pulses that induce the vibrations and shear waves. Unlike the periodic binary vibration pulses, the new vibration pulses have multiple pulses in one fundamental period of the vibration. The pulses are generated from an orthogonal-frequency wave composed of several sinusoidal signals of which the amplitudes increase with frequency to compensate for higher loss at higher frequency in tissues. The new method has been evaluated by studying the shear wave propagation in in vitro chicken and swine liver. The experimental results show that the new vibration pulses significantly increase tissue vibration with a reduced peak ultrasound intensity, compared with the binary vibration pulses. PMID:24158291

  11. FTIR, Raman spectra and ab initio calculations of 2-mercaptobenzothiazole.

    PubMed

    Rai, Amareshwar K; Singh, Rachana; Singh, K N; Singh, V B

    2006-02-01

    FTIR and Raman spectra of a rubber vulcanization accelerator, 2-mercaptobenzothiazole (MBT), were recorded in the solid phase. The harmonic vibrational wavenumbers, for both the toutomeric forms of MBT, as well as for its dimeric complex, have been calculated, using ab initio RHF and density functional B3LYP methods invoking different basis sets upto RHF/6-31G** and B3LYP/6-31G** and the results were compared with the experimental values. Conformational studies have been also carried out regarding its toutomeric monomer forms and its dimer form. With all the basis sets the thione form of MBT (II) is predicted to be more stable than thiol form (I) and dimeric conformation (III) is predicted to be more stable with monomeric conformations (I) and (II). Vibrational assignments have been made, and it has been found that the calculated normal mode frequencies of dimeric conformation (III) are required for the analysis of IR and Raman bands of the MBT. The predicted shift in NH- stretching vibration towards the lower wave number side with the B3LYP/6-31G** calculations for the most stable dimer form (III), is in better agreement with experimental results. The intermolecular sulfur-nitrogen distance in N-H...S hydrogen bond was found to be 3.35 angstroms from these calculations, is also in agreement to the experimental value. PMID:16098806

  12. Improved continuous-time higher harmonic control using [Eta] [infinity] methods

    E-print Network

    Fan, Frank H. (Frank Hsiao)

    2013-01-01

    The helicopter is a versatile aircraft that can take-off and land vertically, hover efficiently, and maneuver in confined space. This versatility is enabled by the main rotor, which also causes undesired harmonic vibration ...

  13. Full counting statistics of vibrationally-assisted electronic conduction: transport and fluctuations of the thermoelectric efficiency

    E-print Network

    Agarwalla, Bijay Kumar; Segal, Dvira

    2015-01-01

    We study the statistical properties of charge and energy transport in electron conducting junctions with electron-phonon interactions, specifically, the thermoelectric efficiency and its fluctuations. The system comprises donor and acceptor electronic states, representing a two-site molecule or a double quantum dot system. Electron transfer between metals through the two molecular sites is coupled to a particular vibrational mode which is taken to be either harmonic or anharmonic- a truncated (two-state) spectrum. Considering these models we derive the cumulant generating function in steady state for charge and energy transfer, correct to second-order in the electron-phonon interaction, but exact to all orders in the metal-molecule coupling strength. This is achieved by using the non-equilibrium Green's function approach (harmonic mode) and a kinetic quantum master equation method (anharmonic mode). From the cumulant generating function we calculate the charge current and its noise and the large deviation fun...

  14. 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.

  15. Intramolecular hydrogen bonding in N-salicylideneaniline: FT-IR spectrum and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Moosavi-Tekyeh, Zainab; Dastani, Najmeh

    2015-12-01

    FT-IR and FT-Raman spectra of N-salicylideneaniline (SAn) and its deuterated analogue (D-SAn) are recorded, and the theoretical calculations are performed on their molecular structures and vibrational frequencies. The same calculations are performed for SAn in different solutions using the polarizable conductor continuum model (CPCM) method. Comparisons between the spectra obtained and the corresponding theoretical calculations are used to assign the vibrational frequencies for these compounds. The spectral behavior of SAn upon deuteration is also used to distinguish the positions of OH vibrational frequencies. The hydrogen bond strength of SAn is investigated by applying the atoms-in-molecules (AIM) theory, natural bond orbital (NBO) analysis, and geometry calculations. The harmonic vibrational frequencies of SAn are calculated at B3LYP and X3LYP levels of theory using 6-31G*, 6-311G**, and 6-311++G** basis sets. The AIM results support a medium hydrogen bonding in SAn. The observed ?OH/?OD and ?OH/?OD for SAn appear at 2940/2122 and 830/589 cm-1, respectively.

  16. Vibration sensors

    NASA Astrophysics Data System (ADS)

    Gupta, Amita; Singh, Ranvir; Ahmad, Amir; Kumar, Mahesh

    2003-10-01

    Today, vibration sensors with low and medium sensitivities are in great demand. Their applications include robotics, navigation, machine vibration monitoring, isolation of precision equipment & activation of safety systems e.g. airbags in automobiles. Vibration sensors have been developed at SSPL, using silicon micromachining to sense vibrations in a system in the 30 - 200 Hz frequency band. The sensing element in the silicon vibration sensor is a seismic mass suspended by thin silicon hinges mounted on a metallized glass plate forming a parallel plate capacitor. The movement of the seismic mass along the vertical axis is monitored to sense vibrations. This is obtained by measuring the change in capacitance. The movable plate of the parallel plate capacitor is formed by a block connected to a surrounding frame by four cantilever beams located on sides or corners of the seismic mass. This element is fabricated by silicon micromachining. Several sensors in the chip sizes 1.6 cm x 1.6 cm, 1 cm x 1 cm and 0.7 cm x 0.7 cm have been fabricated. Work done on these sensors, techniques used in processing and silicon to glass bonding are presented in the paper. Performance evaluation of these sensors is also discussed.

  17. Dynamics of the [4Fe-4S] Cluster in Pyrococcus furiosus D14C Ferredoxin via Nuclear Resonance Vibrational and Resonance Raman Spectroscopies, Force Field Simulations, and Density Functional Theory Calculations

    PubMed Central

    Mitra, Devrani; Pelmenschikov, Vladimir; Guo, Yisong; Case, David A.; Wang, Hongxin; Dong, Weibing; Tan, Ming-Liang; Ichiye, Toshiko; Jenney, Francis E.; Adams, Michael W. W.; Yoda, Yoshitaka; Zhao, Jiyong; Cramer, Stephen P.

    2011-01-01

    We have used 57Fe nuclear resonance vibrational spectroscopy (NRVS) to study oxidized and reduced forms of the [4Fe-4S] cluster in the D14C variant ferredoxin from Pyrococcus furiosus (Pf D14C Fd). To assist the normal mode assignments, we recorded the NRVS of D14C ferredoxin samples with 36S substituted into the [4Fe-4S] cluster bridging sulfide positions, and a model compound without ligand side chains: (Ph4P)2[Fe4S4Cl4]. Several distinct regions of NRVS intensity are identified, ranging from `protein' and torsional modes below 100 cm?1, through bending and breathing modes near 150 cm?1, to strong bands from Fe-S stretching modes between 250 cm?1 and ~400 cm?1. The oxidized ferredoxin samples were also investigated by resonance Raman (RR) spectroscopy. We found good agreement between NRVS and RR frequencies, but because of different selection rules, the intensities vary dramatically between the two types of spectra. The 57Fe partial vibrational densities of states (PVDOS) for the oxidized samples were interpreted by normal mode analysis with optimization of Urey-Bradley force fields for local models of the [4Fe-4S] clusters. Full protein model calculations were also conducted using a supplemented CHARMM force field, and these calculations revealed low frequency modes that may be relevant to electron transfer with Pf Fd partners. Density functional theory (DFT) calculations complemented these empirical analyses, and DFT was used to estimate the reorganization energy associated with the [Fe4S4]2+/1+ redox cycle. Overall, the NRVS technique demonstrates great promise for the observation and quantitative interpretation of the dynamical properties of Fe-S proteins. PMID:21500788

  18. Vibrational spectral analysis of anti-neurodegenerative drug Levodopa: A DFT study

    NASA Astrophysics Data System (ADS)

    Edwin, Bismi; Hubert Joe, I.

    2013-02-01

    The Fourier transform Raman and infrared spectra of anti-neurodegenerative drug Levodopa (L-3,4-dihydroxy phenyl alanine) in crystalline form have been recorded and analyzed. The optimized geometry, intermolecular hydrogen bonding, and harmonic vibrational wavenumbers of Levodopa have been investigated with the help of B3LYP density functional theory method. The calculated molecular geometry has been compared with the experimental data. The assignments of the vibrational spectra have been carried out with the aid of normal co-ordinate analysis following the scaled quantum mechanical force field methodology. The strong doubly hydrogen bonded interface of the dimerized system is well demonstrated by the natural bond orbital analysis. The biological activity of substituents like carboxylic acid, hydroxyl groups of the catechol ring and amino group are evident from the hydrogen bonds through which the target amino acids are linked to the drug as evidenced from molecular docking.

  19. 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)

  20. FT-IR, FT-Raman spectra, and DFT computations of the vibrational spectra and molecular geometry of chlorzoxazone.

    PubMed

    Yurdakul, Senay; Yurdakul, Murat

    2014-05-21

    Far-IR, mid-IR, and FT-Raman spectra of the chlorzoxazone (CZX) were recorded. The observed vibrational wavenumbers were analyzed and assigned to different normal modes of vibration of the molecule. Density functional calculations were performed to support wavenumber assignments of the observed bands. The equilibrium geometry and harmonic wavenumbers of CZX were calculated by the DFT B3LYP method. All tautomeric forms and dimer form of CZX were determined and optimized. Additionally, experimental FT-IR spectrum in ethanol solution was recorded and compared with solid phase experimental data for the first time. The combination of the DFT B3LYP with polarized continuum model (PCM) was employed to characterize the solvent effects in ethanol solution. PMID:24684869

  1. 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.

  2. Random Vibrations

    NASA Technical Reports Server (NTRS)

    Messaro. Semma; Harrison, Phillip

    2010-01-01

    Ares I Zonal Random vibration environments due to acoustic impingement and combustion processes are develop for liftoff, ascent and reentry. Random Vibration test criteria for Ares I Upper Stage pyrotechnic components are developed by enveloping the applicable zonal environments where each component is located. Random vibration tests will be conducted to assure that these components will survive and function appropriately after exposure to the expected vibration environments. Methodology: Random Vibration test criteria for Ares I Upper Stage pyrotechnic components were desired that would envelope all the applicable environments where each component was located. Applicable Ares I Vehicle drawings and design information needed to be assessed to determine the location(s) for each component on the Ares I Upper Stage. Design and test criteria needed to be developed by plotting and enveloping the applicable environments using Microsoft Excel Spreadsheet Software and documenting them in a report Using Microsoft Word Processing Software. Conclusion: Random vibration liftoff, ascent, and green run design & test criteria for the Upper Stage Pyrotechnic Components were developed by using Microsoft Excel to envelope zonal environments applicable to each component. Results were transferred from Excel into a report using Microsoft Word. After the report is reviewed and edited by my mentor it will be submitted for publication as an attachment to a memorandum. Pyrotechnic component designers will extract criteria from my report for incorporation into the design and test specifications for components. Eventually the hardware will be tested to the environments I developed to assure that the components will survive and function appropriately after exposure to the expected vibration environments.

  3. Enhancing tidal harmonic analysis: Robust (hybrid L1 ) solutions

    E-print Network

    Hickey, Barbara

    Enhancing tidal harmonic analysis: Robust (hybrid L1 =L2 ) solutions Keith E. Leffler Ã, David A 24 February 2008 Accepted 28 April 2008 Keywords: Tides Tidal analysis Harmonic analysis Robust is calculated from the power spectrum of the residual, a calculation that filters broad spectrum noise

  4. Applicability of Density Functional Theory in Reproducing Accurate Vibrational Spectra of Surface Bound Species

    SciTech Connect

    Matanovic, Ivana; Atanassov, Plamen; Kiefer, Boris; Garzon, Fernando; Henson, Neil J.

    2014-10-05

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

  5. On the uniqueness of harmonic coordinates

    E-print Network

    Jiri Bicak; Joseph Katz

    2005-03-04

    Harmonic coordinate conditions in stationary asymptotically flat spacetimes with matter sources have more than one solution. The solutions depend on the degree of smoothness of the metric and its first derivatives, which we wish to impose across the material boundary, and on the conditions at infinity and at a suitable point inside the matter. This is illustrated in detail by simple fully solvable examples of static spherically symmetric spacetimes in global harmonic coordinates. Examples of stationary electrovacuum spacetimes described simply in harmonic coordinates are also given. They can represent the exterior fields of material discs. The use of an appropriate background metric considerably simplifies the calculations.

  6. Electronic structures of organometallic complexes of f elements LXXXII: comparison of assigned experimental and calculated (on the basis of density functional theory) frequencies of normal vibrations of the first homoleptic organometallic complex of the lanthanides: tris(?(5)-tetramethylcyclopentadienyl)lanthanum.

    PubMed

    Amberger, Hanns-Dieter; Reddmann, Hauke

    2014-04-24

    The far and mid infrared spectra of powdered La(?(5)-C5Me4H)3 as well as polarized Raman spectra of an oriented single crystal (where the principal axes of the two molecules per unit cell are uniformly oriented) have been recorded. Applying the selection rules of C3h symmetry to the experimental data, numerous signals were assigned which agree well with the predictions of a calculation based on density functional theory. Neglecting ?C-H and ?Cp-H (out of plane) modes, an r.m.s. deviation of 21.9 cm(-1) for 71 assignments was achieved. Skeletal and intra-ligand vibrations were separated and an inspection of the vibronic sidebands of the purely electronic hypersensitive absorption transitions (4)I9/2?(4)G5/2 of Nd(?(5)-C5Me4H)3 showed that mainly the latter are coupled. PMID:24508890

  7. Photothermal Study of Free and Forced Elastic Vibrations of Microcantilevers

    NASA Astrophysics Data System (ADS)

    Todorovic, D. M.; Cretin, B.; Vairac, P.; Song, Y.; Rabasovic, M. D.; Markushev, D. D.

    2015-06-01

    Dynamic free (spontaneous) and forced (optically excited) elastic vibration spectra of a cantilever (CL) were studied. The amplitude and phase elastic displacements of silicon CLs were measured as a function of the modulation frequency with and without optical excitation. Typically, four obvious peaks can be observed in the elastic vibration spectrum. The first peak represents the forced vibrations at the same frequency as the modulation of laser excitation, while two other peaks are the third and fifth harmonics. One small peak is the first natural resonance of the CL (free vibrations, spontaneous vibrations). The amplitude of elastic vibrations without optical excitation changes with frequency, and it is possible to distinguish two frequency regions. In the high frequency range above 10 kHz, the amplitude elastic vibration spectra are not a function of the frequency which is typically for white noise. The white noise level, which corresponds to the thermomechanical noise, was found. The forced vibrations are precisely studied by modulated optical excitation where the frequency is varied from 3 kHz to 45 kHz and by measuring the response with a lock-in-amplifier (measuring the amplitude and phase of the elastic vibrations). The optically excited elastic vibrations are the consequence of thermal and electronic elastic effects in the silicon CL. The mechanical response of the optically excited CL was modeled with good approximation by a damped harmonic oscillator. The experimental amplitude and phase spectra were fitted with theoretical curves, and the quality factor near the natural (resonance) frequency was obtained.

  8. Conformational stability, vibrational and NMR analysis, chemical potential and thermodynamical parameter of 3-tert-butyl-4-hydroxyanisole.

    PubMed

    Balachandran, V; Karpagam, V; Revathi, B; Kavimani, M; Santhi, G

    2015-01-25

    The FT-IR and FT-Raman spectra of 3-tert-butyl-4-hydroxyanisole (TBHA) molecule have been recorded in the region 4000-400 cm(-1) and 3500-100 cm(-1), respectively. Optimized geometrical structure, harmonic vibrational frequencies has been computed by B3LYP level using 6-31G (d,p) and 6-311+G (d,p) basis sets. The observed FT-IR and FT-Raman vibrational frequencies are analyzed and compared with theoretically predicted vibrational frequencies. The geometries and normal modes of vibration obtained from DFT method are in good agreement with the experimental data. The Mulliken charges, the natural bonding orbital (NBO) analysis, the first-order hyperpolarizability of the investigated molecule were computed using DFT calculations. Besides, charge transfer occurring in the molecule between HOMO and LUMO energies, frontier energy gap, molecular electrostatic potential (MEP) were calculated and analyzed. The isotropic chemical shift computed by (1)H and (13)C nuclear magnetic resonance (NMR) chemical shifts of the TBHA calculated using the gauge invariant atomic orbital (GIAO) method also shows good agreement with experimental observations. PMID:25173520

  9. Dynamics of an [Fe4S4(SPh)4]2- cluster explored via IR, Raman, and nuclear resonance vibrational spectroscopy (NRVS)-analysis using 36S substitution, DFT calculations, and empirical force fields.

    PubMed

    Xiao, Yuming; Koutmos, Markos; Case, David A; Coucouvanis, Dimitri; Wang, Hongxin; Cramer, Stephen P

    2006-05-14

    We have used four vibrational spectroscopies--FT-IR, FT-Raman, resonance Raman, and 57Fe nuclear resonance vibrational spectroscopy (NRVS)--to study the normal modes of the Fe-S cluster in [(n-Bu)4N]2[Fe4S4(SPh)4]. This [Fe4S4(SR)4]2- complex serves as a model for the clusters in 4Fe ferredoxins and high-potential iron proteins (HiPIPs). The IR spectra exhibited differences above and below the 243 K phase transition. Significant shifts with 36S substitution into the bridging S positions were also observed. The NRVS results were in good agreement with the low temperature data from the conventional spectroscopies. The NRVS spectra were interpreted by normal mode analysis using optimized Urey-Bradley force fields (UBFF) as well as from DFT theory. For the UBFF calculations, the parameters were refined by comparing calculated and observed NRVS frequencies and intensities. The frequency shifts after 36S substitution were used as an additional constraint. A D 2d symmetry Fe4S4S'4 model could explain most of the observed frequencies, but a better match to the observed intensities was obtained when the ligand aromatic rings were included for a D 2d Fe4S4(SPh)4 model. The best results were obtained using the low temperature structure without symmetry constraints. In addition to stretching and bending vibrations, low frequency modes between approximately 50 and 100 cm(-1) were observed. These modes, which have not been seen before, are interpreted as twisting motions with opposing sides of the cube rotating in opposite directions. In contrast with a recent paper on a related Fe4S4 cluster, we find no need to assign a large fraction of the low frequency NRVS intensity to 'rotational lattice modes'. We also reassign the 430 cm(-1) band as primarily an elongation of the thiophenolate ring, with approximately 10% terminal Fe-S stretch character. This study illustrates the benefits of combining NRVS with conventional Raman and IR analysis for characterization of Fe-S centers. DFT theory is shown to provide remarkable agreement with the experimental NRVS data. These results provide a reference point for the analysis of more complex Fe-S clusters in proteins. PMID:16673033

  10. FT-IR, FT-Raman and DFT quantum chemical study on the molecular conformation, vibrational and electronic transitions of 1-(m-(trifluoromethyl)phenyl)piperazine.

    PubMed

    Prabavathi, N; Nilufer, A; Krishnakumar, V

    2014-01-01

    The FTIR and FT-Raman spectra of 1-(m-(trifluoromethyl)phenyl)piperazine [TFMPP] have been recorded in the region 4000-400 cm(-1) and 3500-100 cm(-1), respectively. The optimized geometry, frequency and intensity of the vibrational bands of the compound was obtained by the density functional theory using 6-311++G(d,p) basis set. The harmonic vibrational frequencies were calculated and the scaled values have been compared with experimental FTIR and FT-Raman spectra. The observed and the calculated frequencies are found to be in good agreement. A detailed interpretation of the infrared and Raman spectra were also reported based on potential energy distribution (PED). UV-Vis spectrum of the compound was recorded and the electronic properties HOMO and LUMO energies were measured by TD-DFT approach. Furthermore, molecular electrostatic potential is performed and also the calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. PMID:24291424

  11. Computational vibrational study on coordinated nicotinamide

    NASA Astrophysics Data System (ADS)

    Bolukbasi, Olcay; Akyuz, Sevim

    2005-06-01

    The molecular structure and vibrational spectra of zinc (II) halide complexes of nicotinamide (ZnX 2(NIA) 2; X=Cl or Br; NIA=Nicotinamide) were investigated by computational vibrational study and scaled quantum mechanical (SQM) analysis. The geometry optimisation and vibrational wavenumber calculations of zinc halide complexes of nicotinamide were carried out by using the DFT/RB3LYP level of theory with 6-31G(d,p) basis set. The calculated wavenumbers were scaled by using scaled quantum mechanical (SQM) force field method. The fundamental vibrational modes were characterised by their total energy distribution. The coordination effects on nicotinamide through the ring nitrogen were discussed.

  12. Simulation of a tetramer form of 5-chlorouracil: the vibrational spectra and molecular structure in the isolated and in the solid state by using DFT calculations.

    PubMed

    Ortiz, S; Alcolea Palafox, M; Rastogi, V K; Akitsu, T; Hubert Joe, I; Kumar, Satendra

    2013-06-01

    A Raman and FT-IR study of the biomolecule 5-chlorouracil in the solid state was carried out. The unit cell found in the crystal was simulated as a tetramer form by density functional calculations. They were performed to clarify the assignments of the experimentally observed bands in the spectra. Calculations in the monomer form and comparisons with the experimental data in Ar matrix were also carried out. The error in the calculated frequencies was analyzed and reduced by using scaling equations and scaling factors deduced from the uracil molecule. The calculations with the B3LYP method and with the 6-31G(d,p) and 6-311+G(2d,p) basis set, appear in general to be useful, when combining with a scaling equation procedure or with the specific scale factors, for interpretation of the general features of the IR and Raman spectra. The scaled values were used in the reassignment of the IR and Raman experimental bands. Comparison of the results with those determined in uracil and 5-halogenated derivatives were performed. The substitution at 5-position of the uracil ring by a chlorine atom has a little effect on the geometric parameters. PMID:23583877

  13. Analysis of vibration effects on holographic data storage system

    NASA Astrophysics Data System (ADS)

    Ishii, Toshiki; Shimada, Ken-ichi; Hoshizawa, Taku; Takashima, Yuzuru

    2015-09-01

    It is crucial to understand the effects of random mechanical vibration on holographic data storage system, but such effects have not yet been formalized. Therefore, we developed a generalized formalization of vibration effects using a concept of time-averaged holography. Normalized intensity as a function of a statistical measure of vibration waveforms is simulated by simple harmonic oscillation, then normalized intensity is predicted well even for random vibration waveforms. Servo and mechanical systems will be designed solely by specifying the required signal level, which enables efficient product development.

  14. Vibrational study, first hyperpolarizability and HOMO-LUMO analyses on the structure of 2-hydroxy-6-nitro toluene.

    PubMed

    Arivazhagan, M; Thilagavathi, G

    2012-06-01

    Vibrational spectral measurements, namely, FT-infrared (4000-400 cm(-1)) and FT-Raman (3500-50 cm(-1)) spectra have been made for 2-hydroxy-6-nitrotoluene (HNT) and assigned to different normal modes of the molecule. Quantum chemical calculations of energies, geometrical structure, harmonic vibrational frequencies intensities and vibrational wavenumbers of HNT were carried out by ab initio HF and density functional theory (DFT/B3LYP) method with 6-311++G(d,p) basis set. The differences between the observed and scaled wave number values of most of the fundamentals are very small. The values of the total dipole moment (?) and first hyperpolarizability (?) of the investigated molecule were computed by using ab initio HF and density functional theory (DFT/B3LYP) methods with 6-311++G(d,p) basis set quantum mechanical calculations. The calculated results also show that the HNT molecule might have microscopic nonlinear optical (NLO) behavior with non-zero values. A detailed interpretation of the infrared and Raman spectra of HNT is also reported based on total energy distribution (TED). The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. The results of the calculations were applied to simulated infrared and Raman spectra of the title compound which showed excellent agreement with the observed spectra. PMID:22402481

  15. The Study of Damped Harmonic Oscillations Using an Electronic Counter

    ERIC Educational Resources Information Center

    Wadhwa, Ajay

    2009-01-01

    We study damped harmonic oscillations in mechanical systems like the loaded spring and simple pendulum with the help of an oscillation measuring electronic counter. The experimental data are used in a software program that solves the differential equation for damped vibrations of any system and determines its position, velocity and acceleration as…

  16. Structure and vibrations of different charge Ge impurity in ?-quartz

    SciTech Connect

    Kislov, A. N. Mikhailovich, A. P. Zatsepin, A. F.

    2014-10-21

    Atomic structure and localized vibrations of ??SiO{sub 2}:Ge are studied using computer modeling techniques. The simulation was carried out by the lattice dynamics calculation of the local density of vibrational states. Local structures parameters are calculated, localized symmetrized vibrations frequency caused by Ge impurity in different charge states are defined. The movements of atoms located near Ge impurity are analyzed and their contribution into localized vibrations of different type is evaluated.

  17. Modeling Motion Oscillations Worksheet Solutions 1. A particle executes simple harmonic motion. When the velocity of the particle is a maximum

    E-print Network

    Modeling Motion Oscillations Worksheet Solutions Part I 1. A particle executes simple harmonic mass rests on a horizontal platform which vibrates vertically in simple harmonic motion with period 0 harmonic motion the position is given by the expression x = A cos (t + ). We have A = 0.062 m and = 2/T =

  18. The vibrational spectrum of H2O3: An ab initio investigation

    NASA Technical Reports Server (NTRS)

    Jackels, Charles F.

    1991-01-01

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

  19. Temperature effects in first-principles solid state calculations of the chemical shielding tensor made simple.

    PubMed

    Monserrat, Bartomeu; Needs, Richard J; Pickard, Chris J

    2014-10-01

    We study the effects of atomic vibrations on the solid-state chemical shielding tensor using first principles density functional theory calculations. At the harmonic level, we use a Monte Carlo method and a perturbative expansion. The Monte Carlo method is accurate but computationally expensive, while the perturbative method is computationally more efficient, but approximate. We find excellent agreement between the two methods for both the isotropic shift and the shielding anisotropy. The effects of zero-point quantum mechanical nuclear motion are important up to relatively high temperatures: at 500 K they still represent about half of the overall vibrational contribution. We also investigate the effects of anharmonic vibrations, finding that their contribution to the zero-point correction to the chemical shielding tensor is small. We exemplify these ideas using magnesium oxide and the molecular crystals L-alanine and ?-aspartyl-L-alanine. We therefore propose as the method of choice to incorporate the effects of temperature in solid state chemical shielding tensor calculations using the perturbative expansion within the harmonic approximation. This approach is accurate and requires a computational effort that is about an order of magnitude smaller than that of dynamical or Monte Carlo approaches, so these effects might be routinely accounted for. PMID:25296790

  20. Communication: Creation of molecular vibrational motions via the rotation-vibration coupling

    SciTech Connect

    Shu, Chuan-Cun; Henriksen, Niels E.

    2015-06-14

    Building on recent advances in the rotational excitation of molecules, we show how the effect of rotation-vibration coupling can be switched on in a controlled manner and how this coupling unfolds in real time after a pure rotational excitation. We present the first examination of the vibrational motions which can be induced via the rotation-vibration coupling after a pulsed rotational excitation. A time-dependent quantum wave packet calculation for the HF molecule shows how a slow (compared to the vibrational period) rotational excitation leads to a smooth increase in the average bond length whereas a fast rotational excitation leads to a non-stationary vibrational motion. As a result, under field-free postpulse conditions, either a stretched stationary bond or a vibrating bond can be created due to the coupling between the rotational and vibrational degrees of freedom. The latter corresponds to a laser-induced breakdown of the adiabatic approximation for rotation-vibration coupling.

  1. Algebraic methods in vibrational spectroscopy

    SciTech Connect

    Lemus, Renato

    2011-03-21

    These lectures review some advances in the algebraic description of molecules from two point of views: structure and dynamics. We start by presenting the basic ideas involved in the traditional description of molecular structure in configuration space, where the Born-Oppenheimer and rotor-rigid approximations are assumed to be valid. We then focus on the vibrational degrees of freedom in order to introduce the traditional algebraic realization in terms of bosonic operators of harmonic oscillators. This analysis allows the algebraic methods based on dynamical unitary groups to be introduced as a anharmonization procedure where the local bosonic operators are translated into operators satisfying the su(2) commutation relations. Some examples of the vibrational spec-troscopic description are presented. Concerned with the dynamical point of view an algebraic model to describe collinear collisions in the semiclassical approximation is presented.

  2. Vibrational and electronic spectroscopic studies of melatonin

    NASA Astrophysics Data System (ADS)

    Singh, Gurpreet; Abbas, J. M.; Dogra, Sukh Dev; Sachdeva, Ritika; Rai, Bimal; Tripathi, S. K.; Prakash, Satya; Sathe, Vasant; Saini, G. S. S.

    2014-01-01

    We report the infrared absorption and Raman spectra of melatonin recorded with 488 and 632.8 nm excitations in 3600-2700 and 1700-70 cm-1 regions. Further, we optimized molecular structure of the three conformers of melatonin within density functional theory calculations. Vibrational frequencies of all three conformers have also been calculated. Observed vibrational bands have been assigned to different vibrational motions of the molecules on the basis of potential energy distribution calculations and calculated vibrational frequencies. Observed band positions match well with the calculated values after scaling except Nsbnd H stretching mode frequencies. It is found that the observed and calculated frequencies mismatch of Nsbnd H stretching is due to intermolecular interactions between melatonin molecules.

  3. Lab 5: Damped simple harmonic motion Simple harmonic oscillation

    E-print Network

    Gustafsson, Torgny

    Lab 5: Damped simple harmonic motion · Simple harmonic oscillation · Damped harmonic oscillation;Friction: retarding motion (energy dissipation) Damped simple harmonic oscillation 1 2 Hooke's law: Damping 381 Mechanics #12;Ideal case: no friction Simple harmonic oscillation Hooke's law: Newton's 2nd law: F

  4. Understanding Vibration Spectra of Planetary Gear Systems for Fault Detection

    NASA Technical Reports Server (NTRS)

    Mosher, Marianne

    2003-01-01

    An understanding of the vibration spectra is very useful for any gear fault detection scheme based upon vibration measurements. The vibration measured from planetary gears is complicated. Sternfeld noted the presence of sidebands about the gear mesh harmonics spaced at the planet passage frequency in spectra measured near the ring gear of a CH-47 helicopter. McFadden proposes a simple model of the vibration transmission that predicts high spectral amplitudes at multiples of the planet passage frequency, for planetary gears with evenly spaced planets. This model correctly predicts no strong signal at the meshing frequency when the number of teeth on the ring gear is not an integer multiple of the number of planets. This paper will describe a model for planetary gear vibration spectra developed from the ideas started in reference. This model predicts vibration to occur only at frequencies that are multiples of the planet repetition passage frequency and clustered around gear mesh harmonics. Vibration measurements will be shown from tri-axial accelerometers mounted on three different planetary gear systems and compared with the model. The model correctly predicts the frequencies with large components around the first several gear mesh harmonics in measurements for systems with uniformly and nonuniformly spaced planet gears. Measurements do not confirm some of the more detailed features predicted by the model. Discrepancies of the ideal model to the measurements are believed due to simplifications in the model and will be discussed. Fault detection will be discussed applying the understanding will be discussed.

  5. Inelastic and elastic neutron scattering studies of the vibrational and reorientational dynamics, crystal structure and solid-solid phase transition in [Mn(OS(CH3)2)6](ClO4)2 supported by theoretical (DFT) calculations

    NASA Astrophysics Data System (ADS)

    Szostak, El?bieta; Hetma?czyk, Joanna; Migda?-Mikuli, Anna

    2015-06-01

    The vibrational and reorientational dynamics of CH3 groups from (CH3)2SO ligands in the high- and low-temperature phases of [Mn(OS(CH3)2)6](ClO4)2 were investigated by quasielastic and inelastic incoherent neutron scattering (QENS and IINS) methods. The results show that above the phase transition temperature (detected earlier by differential scanning calorimetry (DSC) at TC5c = 222.9 K on cooling and at TC5h = 225.4 K on heating) the CH3 groups perform fast (?R ? 10-12-10-13 s) reorientational motions. These motions start to slow down below TC5c Neutron powder diffraction (NPD) measurements, performed simultaneously with QENS and IINS, indicated that this phase transition is associated with a change of the crystal structure, too. Theoretical infrared absorption, Raman and inelastic incoherent neutron scattering spectra were calculated using DFT method (B3LYP functional, LANL2DZ ECP basis set (on Mn atom) and 6-311+G(d,p) basis set (on C, H, S, O atoms) for the isolated equilibrium model (isolated [Mn(DMSO)6]2+ cation and ClO4- anion). Calculated spectra show a good agreement with the experimental spectra (FT-IR, RS and IINS). The comparison of the results obtained by these complementary methods was made.

  6. Lowest Vibrational States of Acrylonitrile

    NASA Astrophysics Data System (ADS)

    Kisiel, Zbigniew; Martin-Drumel, Marie-Aline; Pirali, Olivier

    2015-06-01

    Recent studies of the broadband rotational spectrum of acrylonitrile, H_2C=CHC?N, revealed the presence of multiple resonances between rotational levels in different vibrational states. The resonances affect even the ground state transitions and their analysis allowed determination of vibrational term values for the first three excited states above the ground state and of vibrational energy differences in several polyads above these states. At that time there was no infrared data of sufficient resolution to assess the reliability of the resonance based vibrational energy determinations. We presently report results based on a 40-700 cm-1 high-resolution spectrum of acrylonitrile recorded at the AILES beamline of the SOLEIL synchrotron. This spectrum was reduced by using the AABS packagea, and allowed assignment of vibration-rotation transitions in four fundamentals, five hot bands, and one overtone band. The infrared data and previous measurements made with microwave techniques have been combined into a single global fit encompassing over 31000 measured transitions. Precise vibrational term values have been determined for the eight lowest excited vibrational states. The new results validate the previous estimates from rotational perturbations and are also compared with results of ab~initio anharmonic force field calculations. Z. Kisiel, et al., J. Mol. Spectrosc. 280 134 (2012). A. López, et al., Astron. & Astrophys. 572, A44 Z. Kisiel, et al., J. Mol. Spectrosc. 233 231 (2005).

  7. Aeroelastic analysis for helicopter rotors with blade appended pendulum vibration absorbers. Mathematical derivations and program user's manual

    NASA Technical Reports Server (NTRS)

    Bielawa, R. L.

    1982-01-01

    Mathematical development is presented for the expanded capabilities of the United Technologies Research Center (UTRC) G400 Rotor Aeroelastic Analysis. This expanded analysis, G400PA, simulates the dynamics of teetered rotors, blade pendulum vibration absorbers and the higher harmonic excitations resulting from prescribed vibratory hub motions and higher harmonic blade pitch control. Formulations are also presented for calculating the rotor impedance matrix appropriate to these higher harmonic blade excitations. This impedance matrix and the associated vibratory hub loads are intended as the rotor blade characteristics elements for use in the Simplified Coupled Rotor/Fuselage Vibration Analysis (SIMVIB). Sections are included presenting updates to the development of the original G400 theory, and material appropriate to the user of the G400PA computer program. This material includes: (1) a general descriptionof the tructuring of the G400PA FORTRAN coding, (2) a detaild description of the required input data and other useful information for successfully running the program, and (3) a detailed description of the output results.

  8. 2011 Vibrations -1 VIBRATION OF PLATES & BARS

    E-print Network

    Gustafsson, Torgny

    2011 Vibrations - 1 VIBRATION OF PLATES & BARS The objectives of this experiment are: To observe and short flat bars, Chladni plates, salt, salt trays INTRODUCTION he equations of vibrational motion;2011 Vibrations - 2 2f 6.27 1f 3f 17.55 1f etc. Where y = transverse displacement of bar element x = distance

  9. Quantum chemical vibrational study, molecular property, FTIR, FT-Raman spectra, NBO, HOMO-LUMO energies and thermodynamic properties of 1-methyl-2-phenyl benzimidazole

    NASA Astrophysics Data System (ADS)

    Karnan, M.; Balachandran, V.; Murugan, M.; Murali, M. K.

    2014-09-01

    The solid phase FT-IR and FT-Raman spectra of 1-methyl-2-phenyl benzimidazole (MPBZ) have been recorded in the condensed state. In this work, experimental and theoretical study on the molecular structure, quantum chemical calculations of energies and vibrational wavenumbers of MPBZ is presented. The vibrational frequencies of the title compound were obtained theoretically by DFT/B3LYP calculations employing the standard 6-311+G(d,p) and 6-311++G(d,p) basis set for optimized geometry and were compared with Fourier transform infrared spectrum (FTIR) in the region of 4000-400 cm-1 and with Fourier transform Raman spectrum in the region of 4000-100 cm-1. Complete vibrational assignments, analysis and correlation of the fundamental modes for the title compound were carried out. The vibrational harmonic frequencies were scaled using scale factor, yielding a good agreement between the experimentally recorded and the theoretically calculated values. The study is extended to calculate the HOMO-LUMO energy gap, NBO, mapped molecular electrostatic potential (MEP) surfaces, polarizability, Mulliken charges and thermodynamic properties of the title compound.

  10. Quantum chemical vibrational study, molecular property, FTIR, FT-Raman spectra, NBO, HOMO-LUMO energies and thermodynamic properties of 1-methyl-2-phenyl benzimidazole.

    PubMed

    Karnan, M; Balachandran, V; Murugan, M; Murali, M K

    2014-09-15

    The solid phase FT-IR and FT-Raman spectra of 1-methyl-2-phenyl benzimidazole (MPBZ) have been recorded in the condensed state. In this work, experimental and theoretical study on the molecular structure, quantum chemical calculations of energies and vibrational wavenumbers of MPBZ is presented. The vibrational frequencies of the title compound were obtained theoretically by DFT/B3LYP calculations employing the standard 6-311+G(d,p) and 6-311++G(d,p) basis set for optimized geometry and were compared with Fourier transform infrared spectrum (FTIR) in the region of 4000-400 cm(-1) and with Fourier transform Raman spectrum in the region of 4000-100 cm(-1). Complete vibrational assignments, analysis and correlation of the fundamental modes for the title compound were carried out. The vibrational harmonic frequencies were scaled using scale factor, yielding a good agreement between the experimentally recorded and the theoretically calculated values. The study is extended to calculate the HOMO-LUMO energy gap, NBO, mapped molecular electrostatic potential (MEP) surfaces, polarizability, Mulliken charges and thermodynamic properties of the title compound. PMID:24785089

  11. Vibrational Dynamics of Tricyanomethanide

    NASA Astrophysics Data System (ADS)

    Weidinger, Daniel; Houchins, Cassidy; Owrutsky, Jeffrey C.

    2011-06-01

    Time-resolved and steady-state IR spectroscopy have been used to characterize vibrational spectra and energy relaxation dynamics of the CN stretching band of the tricyanomethanide (TCM, C(CN)3-) anion near 2170 Cm-1 in solutions of water, heavy water, methanol, formamide, dimethyl sulfoxide (DMSO) and the ionic liquid 1-butyl methyl imidazolium tetrafluoroborate ([BMIM][BF4]). The band intensity is strong (˜1500 M-1Cm-1) and the vibrational energy relaxation times are relatively long (˜5 ps in water, 12 ps in heavy water, and ˜30 ps in DMSO and [BMIM][BF4]). They are longer than those previously reported for dicyanamide in the same solvents. Although the static TCM frequency generally shifts to higher frequency with more strongly interacting solvents, the shift does not follow the same trend as the vibrational dynamics. The results for the experimental frequencies and intensities agree well with results from ab initio calculations. Proton and electron affinities for TCM are also calculated because they are relevant to potential applications of this anion in low viscosity ionic liquids.

  12. Workshop on Harmonic Oscillators

    NASA Technical Reports Server (NTRS)

    Han, D. (editor); Kim, Y. S. (editor); Zachary, W. W. (editor)

    1993-01-01

    Proceedings of a workshop on Harmonic Oscillators held at the College Park Campus of the University of Maryland on March 25 - 28, 1992 are presented. The harmonic oscillator formalism is playing an important role in many branches of physics. This is the simplest mathematical device which can connect the basic principle of physics with what is observed in the real world. The harmonic oscillator is the bridge between pure and applied physics.

  13. Harmonic quarks and their precise masses

    E-print Network

    Oleg A. Teplov

    2003-07-02

    An examination of charged two-quark meson masses hinted that the mass ratio of neighboring quarks could simply be a constant. The concept of a harmonic quark oscillator based on a quark-antiquark pair is introduced. Unstable symmetric state of the harmonic quark oscillator can be broken to an asymmetric state with the formation the neighboring quark of lesser mass due to a weak reaction. A new recurrent equation of quark masses is obtained and the model of harmonic quark family is developed. The quark masses in the model are bound together into one rigid chain. With the electromagnetic contribution taken into account the quark masses are calculated with the 0.03 percent inaccuracy. It follows from the model that the muon is a single u-quark mass state fixed as a lepton. The neutral pion is probably a stable harmonic oscillator based on a quark-antiquark u-pair.

  14. Separation of High Order Harmonics with Fluoride Windows

    SciTech Connect

    Allison, Tom; van Tilborg, Jeroen; Wright, Travis; Hertlein, Marcus; Falcone, Roger; Belkacem, Ali

    2010-08-02

    The lower orders produced in high order harmonic generation can be effciently temporally separated into monochromatic pulses by propagation in a Fluoride window while still preserving their femtosecond pulse duration. We present calculations for MgF2, CaF2, and LiF windows for the third, fifth, and seventh harmonics of 800 nm. We demonstrate the use of this simple and inexpensive technique in a femtosecond pump/probe experiment using the fifth harmonic.

  15. Quantum-mechanical study of energies, structures, and vibrational spectra of the H(D)Cl complexed with dimethyl ether.

    PubMed

    Boda, ?ukasz; Boczar, Marek; G?ug, Maciej; Wójcik, Marek J

    2015-11-28

    Interaction energies, molecular structure and vibrational frequencies of the binary complex formed between H(D)Cl and dimethyl ether have been obtained using quantum-chemical methods. Equilibrium and vibrationally averaged structures, harmonic and anharmonic wavenumbers of the complex and its deuterated isotopomer were calculated using harmonic and anharmonic second-order perturbation theory procedures with Density Functional Theory B3LYP and B2PLYP-D and ab initio Møller-Plesset second-order methods, and a 6-311++G(3d,3p) basis set. A phenomenological model describing anharmonic-type vibrational couplings within hydrogen bonds was developed to explain the unique broadening and fine structure, as well as the isotope effect of the Cl-H and Cl-D stretching IR absorption bands in the gaseous complexes with dimethyl ether, as an effect of hydrogen bond formation. Simulations of the rovibrational structure of the Cl-H and Cl-D stretching bands were performed and the results were compared with experimental spectra. PMID:26627954

  16. Quantum-mechanical study of energies, structures, and vibrational spectra of the H(D)Cl complexed with dimethyl ether

    NASA Astrophysics Data System (ADS)

    Boda, ?ukasz; Boczar, Marek; G?ug, Maciej; Wójcik, Marek J.

    2015-11-01

    Interaction energies, molecular structure and vibrational frequencies of the binary complex formed between H(D)Cl and dimethyl ether have been obtained using quantum-chemical methods. Equilibrium and vibrationally averaged structures, harmonic and anharmonic wavenumbers of the complex and its deuterated isotopomer were calculated using harmonic and anharmonic second-order perturbation theory procedures with Density Functional Theory B3LYP and B2PLYP-D and ab initio Møller-Plesset second-order methods, and a 6-311++G(3d,3p) basis set. A phenomenological model describing anharmonic-type vibrational couplings within hydrogen bonds was developed to explain the unique broadening and fine structure, as well as the isotope effect of the Cl-H and Cl-D stretching IR absorption bands in the gaseous complexes with dimethyl ether, as an effect of hydrogen bond formation. Simulations of the rovibrational structure of the Cl-H and Cl-D stretching bands were performed and the results were compared with experimental spectra.

  17. Enhanced vibration energy harvesting using nonlinear oscillations

    NASA Astrophysics Data System (ADS)

    Engel, Emily; Wei, Jiaying; Lee, Christopher L.

    2015-05-01

    Results for the design and testing of an electromagnetic device that converts ambient mechanical vibration into electricity are presented. The design of the device is based on an L-shaped beam structure which is tuned so that the first two natural frequencies have a near two-to-one ratio which is referred to as an internal resonance or autoparametic condition. It is shown that in contrast to single degree-of-freedom, linear-dynamics-based vibration harvesters which convert energy in a very narrow frequency band the prototype can generate power over an extended frequency range when subject to harmonic, base displacement excitation.

  18. Structural features of the adenosine conjugate in means of vibrational spectroscopy and DFT.

    PubMed

    Malek, Kamilla; Podstawka, Edyta; Milecki, Jan; Schroeder, Grzegorz; Proniewicz, Leonard M

    2009-06-01

    Vibrational spectra of adenosine bearing benzo-15-crown ether moiety [N(6)-4'-(benzo-15-crown-5)-adenosine, AC] have been recorded in solid phase (FT-IR, FT-Raman) and in aqueous solution on the silver colloid surface (SERS). To interpret a very complex vibrational pattern of experimental data, geometrical parameters (molecular structure) as well as harmonic frequencies of the isolated molecule were calculated at the density functional theory level [B3LYP/6-31G(d)]. Assignment of the observed vibrational modes is discussed on the basis of the theoretical results obtained for N(6)-4'-(benzo-15-crown-5)-adenosine as well as its molecular isolated fragments, i.e. adenosine and benzo-15-crown ether. Our analysis of SERS spectrum indicates that adenine and benzo-15-crown ether take tilted orientation while the imino group and ribose adopt almost vertical position in respect to the metal surface. Moreover, calculated atomic charge distribution gives interesting insights into changes of electron density allocation in investigated fragments. PMID:19344993

  19. Vibrational study, molecular properties and first-order molecular hyperpolarizability of Methyl 2-amino 5-bromobenzoate using DFT method

    NASA Astrophysics Data System (ADS)

    Saxena, Avinay; Agrawal, Megha; Gupta, Archana

    2015-08-01

    The molecular structure of Methyl 2-amino 5-bromobenzoate (M2A5B) was investigated by density functional theory employing Becke's three parameter hybrid exchange functional with Lee-Yang-Parr (B3LYP) co-relational functional involving 6-311++G(d,p) basis set. Harmonic vibrational wavenumber calculation along with the normal mode analysis has been carried out in order to obtain a complete description of molecular dynamics. A detailed interpretation of the Infrared and Raman spectra of M2A5B have been reported. Complete vibrational assignments of the vibrational modes have been done on the basis of the potential energy distribution (PED) in terms of internal coordinates. The scaled vibrational wavenumbers corrected by a recommended set of scaling factors were compared with the experimental results and a fairly good agreement was obtained. The molecular electrostatic potential mapped onto total density surface has been obtained. A study on the electronic properties, such as absorption wavelength, excitation energy and frontier molecular orbitals energy, was performed by time dependent DFT (TD-DFT) approach. Additionally, major contribution from molecular orbitals to the electronic transition was investigated theoretically. The stability of the molecule arising from hyper conjugative interactions and accompanying charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The theoretical 1H and 13C NMR chemical shifts have been calculated by GIAO method and compared with experimentally measured ones. The polarizability and first order hyperpolarizability of the title molecule were calculated and interpreted. The energy gap between frontier orbitals has been used along with electric moments and first order hyperpolarizability, to understand the non linear optical (NLO) activity of the molecule. The prominent vibrational modes contributing to the NLO activity have been identified and examined from the concurrent IR and Raman activity. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures have been calculated.

  20. Vibrational spectral characterization, NLO studies and charge transfer analysis of the organometallic material L-Alanine cadmium chloride

    NASA Astrophysics Data System (ADS)

    Arun Sasi, B. S.; Bright, K. C.; James, C.

    2016-01-01

    An organometallic nonlinear crystal, L-Alanine Cadmium Chloride (LACC) was synthesized by slow evaporation technique. The effects of hydrogen bonding on the structure, binding of ligand to metal ion, natural orbital occupancies, and vibrational frequencies were investigated using density functional theory (DFT) with the combined B3LYP and LANL2DZ basis set. Vibrational assignments were made on the basis of calculated potential energy distribution values from MOLVIB program. The topological analysis of electron localization function (ELF) provides basin population N (integrated density over the attractor basin), standard deviation (?), and their relative fluctuation, defined as ? = ?2/N, which are sensitive criteria of delocalization. The molecular stability, electronic exchange interaction, and bond strength of the molecule were studied by natural bond orbital (NBO) analysis. The second harmonic generation (SHG) efficiency was determined using Kurtz and Perry method. Natural bond orbital analysis was carried out to study various intramolecular interactions that are responsible for the stabilization of the molecule.

  1. Component mode synthesis and large deflection vibration of complex structures. Volume 2: Single-mode large deflection vibrations of beams and plates using finite element method

    NASA Technical Reports Server (NTRS)

    Mei, Chuh

    1987-01-01

    A finite element method is presented for the large amplitude vibrations of complex structures that can be modelled with beam and rectangular plate elements subjected to harmonic excitation. Both inplane deformation and inertia are considered in the formulation. Derivation of the harmonic force and nonlinear stiffness matrices for a beam and a rectangular plate element are presented. Solution procedures and convergence characteristics of the finite element method are described. Nonlinear response to uniform and concentrated harmonic loadings and improved nonlinear free vibration results are presented for beams and rectangular plates of various boundary conditions.

  2. Covariant harmonic oscillators and coupled harmonic oscillators

    NASA Technical Reports Server (NTRS)

    Han, Daesoo; Kim, Young S.; Noz, Marilyn E.

    1995-01-01

    It is shown that the system of two coupled harmonic oscillators shares the basic symmetry properties with the covariant harmonic oscillator formalism which provides a concise description of the basic features of relativistic hadronic features observed in high-energy laboratories. It is shown also that the coupled oscillator system has the SL(4,r) symmetry in classical mechanics, while the present formulation of quantum mechanics can accommodate only the Sp(4,r) portion of the SL(4,r) symmetry. The possible role of the SL(4,r) symmetry in quantum mechanics is discussed.

  3. Note: real time control of a tunable vibration absorber based on magnetorheological elastomer for suppressing tonal vibrations.

    PubMed

    Kim, Young-Keun; Bae, Hyo-In; Koo, Jeong-Hoi; Kim, Kyung-Soo; Kim, Soohyun

    2012-04-01

    An adaptive tunable vibration absober based on magnetorheological elastomer (MRE) is designed as an intelligent device for auto-tuning itself to the time-varying harmonic disturbance force to reduce the unwanted vibration of the primary system in the steady state. The objectives of this note are to develop and implement a continuous control method for a MRE tunable vibration absorber (TVA) and to evaluate its performance in suppressing time-varying tonal vibrations. In the proposed control, the stiffness of MREs is continuously varied based on a nonlinear tuning function that relates the response of the system to the input magnetic field density. Through experiments, it will be shown that the proposed MRE TVA reduces in real time the transmission of a time-varying excited vibration of 48-55 Hz, which shows the potential applicability of the MRE in reducing unwanted vibration to precision devices. PMID:22559594

  4. Note: Real time control of a tunable vibration absorber based on magnetorheological elastomer for suppressing tonal vibrations

    NASA Astrophysics Data System (ADS)

    Kim, Young-Keun; Bae, Hyo-In; Koo, Jeong-Hoi; Kim, Kyung-Soo; Kim, Soohyun

    2012-04-01

    An adaptive tunable vibration absober based on magnetorheological elastomer (MRE) is designed as an intelligent device for auto-tuning itself to the time-varying harmonic disturbance force to reduce the unwanted vibration of the primary system in the steady state. The objectives of this note are to develop and implement a continuous control method for a MRE tunable vibration absorber (TVA) and to evaluate its performance in suppressing time-varying tonal vibrations. In the proposed control, the stiffness of MREs is continuously varied based on a nonlinear tuning function that relates the response of the system to the input magnetic field density. Through experiments, it will be shown that the proposed MRE TVA reduces in real time the transmission of a time-varying excited vibration of 48-55 Hz, which shows the potential applicability of the MRE in reducing unwanted vibration to precision devices.

  5. Harmonic spheres conjecture

    NASA Astrophysics Data System (ADS)

    Sergeev, A. G.

    2010-09-01

    We discuss the harmonic spheres conjecture that the space of harmonic maps of the Riemann sphere into the loop space of a compact Lie group G are related to the moduli space of Yang-Mills G-fields on the four-dimensional Euclidean space.

  6. How do nuclei really vibrate or rotate

    SciTech Connect

    Andresen, H.G.; Kunz, J.; Mosel, U.; Mueller, M.; Schuh, A.; Wust, U.

    1983-01-01

    By means of the adiabatic cranking model the properties of the current and velocity fields of nuclear quadrupole vibrations for even-even nuclei in the rare-earth region are investigated. BCS correlated wave functions based on the Nilsson single particle Hamiltonian have been used. The current fields are analyzed in terms of vector spherical harmonics. The realistic microscopic currents show a vortex structure not present in the classical irrotational flow. The microscopic origin of the vortex structure is investigated.

  7. Quantum chemical approach for condensed-phase thermochemistry: Proposal of a harmonic solvation model

    NASA Astrophysics Data System (ADS)

    Nakai, Hiromi; Ishikawa, Atsushi

    2014-11-01

    We propose a novel quantum chemical method, called the harmonic solvation model (HSM), for calculating thermochemical parameters in the condensed phase, particularly in the liquid phase. The HSM represents translational and rotational motions of a solute as vibrations interacting with a cavity wall of solvent molecules. As examples, the HSM and the ideal-gas model (IGM) were used for the standard formation reaction of liquid water, combustion reactions of liquid formic acid, methanol, and ethanol, vapor-liquid equilibration of water and ethanol, and dissolution of gaseous CO2 in water. The numerical results confirmed the reliability and applicability of the HSM. In particular, the temperature dependence of the Gibbs energy of liquid molecules was accurately reproduced by the HSM; for example, the boiling point of water was reasonably determined using the HSM, whereas the conventional IGM treatment failed to obtain a crossing of the two Gibbs energy curves for gaseous and liquid water.

  8. Quantum chemical approach for condensed-phase thermochemistry: Proposal of a harmonic solvation model

    SciTech Connect

    Nakai, Hiromi; Ishikawa, Atsushi

    2014-11-07

    We propose a novel quantum chemical method, called the harmonic solvation model (HSM), for calculating thermochemical parameters in the condensed phase, particularly in the liquid phase. The HSM represents translational and rotational motions of a solute as vibrations interacting with a cavity wall of solvent molecules. As examples, the HSM and the ideal-gas model (IGM) were used for the standard formation reaction of liquid water, combustion reactions of liquid formic acid, methanol, and ethanol, vapor–liquid equilibration of water and ethanol, and dissolution of gaseous CO{sub 2} in water. The numerical results confirmed the reliability and applicability of the HSM. In particular, the temperature dependence of the Gibbs energy of liquid molecules was accurately reproduced by the HSM; for example, the boiling point of water was reasonably determined using the HSM, whereas the conventional IGM treatment failed to obtain a crossing of the two Gibbs energy curves for gaseous and liquid water.

  9. Quantum chemical approach for condensed-phase thermochemistry: proposal of a harmonic solvation model.

    PubMed

    Nakai, Hiromi; Ishikawa, Atsushi

    2014-11-01

    We propose a novel quantum chemical method, called the harmonic solvation model (HSM), for calculating thermochemical parameters in the condensed phase, particularly in the liquid phase. The HSM represents translational and rotational motions of a solute as vibrations interacting with a cavity wall of solvent molecules. As examples, the HSM and the ideal-gas model (IGM) were used for the standard formation reaction of liquid water, combustion reactions of liquid formic acid, methanol, and ethanol, vapor-liquid equilibration of water and ethanol, and dissolution of gaseous CO2 in water. The numerical results confirmed the reliability and applicability of the HSM. In particular, the temperature dependence of the Gibbs energy of liquid molecules was accurately reproduced by the HSM; for example, the boiling point of water was reasonably determined using the HSM, whereas the conventional IGM treatment failed to obtain a crossing of the two Gibbs energy curves for gaseous and liquid water. PMID:25381501

  10. Harmonic analysis of spacecraft power systems using a personal computer

    NASA Technical Reports Server (NTRS)

    Williamson, Frank; Sheble, Gerald B.

    1989-01-01

    The effects that nonlinear devices such as ac/dc converters, HVDC transmission links, and motor drives have on spacecraft power systems are discussed. The nonsinusoidal currents, along with the corresponding voltages, are calculated by a harmonic power flow which decouples and solves for each harmonic component individually using an iterative Newton-Raphson algorithm. The sparsity of the harmonic equations and the overall Jacobian matrix is used to an advantage in terms of saving computer memory space and in terms of reducing computation time. The algorithm could also be modified to analyze each harmonic separately instead of all at the same time.

  11. Study of molecular vibration by coupled cluster method: Bosonic approach

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

    The vibrational coupled cluster method in bosonic representation is formulated to describe the molecular anharmonic vibrational spectra. The vibrational coupled cluster formalism is based on Watson Hamiltonian in normal coordinates. The vibrational excited states are described using coupled cluster linear response theory (CCLRT). The quality of the coupled cluster wave function is analyzed. Specifically, the mean displacement values of the normal coordinates and expectation values of the square of the normal coordinates of different vibrational states are calculated. A good agreement between the converged full CI results and coupled cluster results is found for the lower lying vibrational states.

  12. Making space for harmonic oscillators

    SciTech Connect

    Michelotti, Leo; /Fermilab

    2004-11-01

    If we restrict the number of harmonic oscillator energy eigenstates to some finite value, N, then the discrete spectrum of the corresponding position operator comprise the roots of the Hermite polynomial H{sub N+1}. Its range is just large enough to accommodate classical motion at high energy. A negative energy term must be added to the Hamiltonian which affects only the last eigenstate, |N>, suggesting it is concentrated at the extrema of this finite ''space''. Calculations support a conjecture that, in the limit of large N, the global distribution of points approaches the differential form for classical action.

  13. Infrared and Raman spectra, DFT-calculations and spectral assignments of 1,1,3,3,5,5-hexafluoro-1,3,5-trisilacyclohexane

    NASA Astrophysics Data System (ADS)

    Nielsen, Claus J.; Klaeboe, Peter; Andersen, Niels H.; Guirgis, Gamil A.; Hickman, Daniel V.; Morris, Tamia B.

    2015-11-01

    The infrared and Raman spectra of 1,1,3,3,5,5-hexafluoro-1,3,5-trisilacyclohexane (c-C3H6Si3F6) as a solid powder have been recorded. The vibrational spectra reveal that the crystalline compound exists as a chair conformer with C3v symmetry at ambient temperature. Additional conformers such as twist or boat were not detected although quantum chemical calculations indicated a negligible energy difference between chair, twist and boat forms. The wavenumbers of the IR and Raman bands were measured and the assignments were initially supported by quantum chemical B3LYP/cc-pVTZ calculations in the harmonic approximation. These vibrational modes were scaled with a common factor of 0.98, and the 11 totally symmetric A1 and 16 doubly degenerate E fundamentals were assigned on the basis of the infrared and Raman intensities. An average relative deviation of ca. 2.9% between the observed and the scaled harmonic calculations was found. Additional calculations were made in the anharmonic approximation, in which the symmetry was reduced to Cs symmetry by a slight distortion of the hexagonal ring. Employing these calculations without scaling, a better agreement between the observed and calculated wavenumbers was obtained (1.5%). Further calculations, involving a twist conformer was not consistent with the spectral results, neither in terms of the number of modes nor their wavenumbers.

  14. Dual Time Stepping Algorithms With the High Order Harmonic Balance Method for Contact Interfaces With Fretting-Wear

    E-print Network

    Salles, Loic; Gouskov, Alexandre; Jean, Pierrick; Thouverez, Fabrice

    2014-01-01

    Contact interfaces with dry friction are frequently used in turbomachinery. Dry friction damping produced by the sliding surfaces of these interfaces reduces the amplitude of bladed-disk vibration. The relative displacements at these interfaces lead to fretting-wear which reduces the average life expectancy of the structure. Frequency response functions are calculated numerically by using the multi-harmonic balance method (mHBM). The dynamic Lagrangian frequency-time method is used to calculate contact forces in the frequency domain. A new strategy for solving nonlinear systems based on dual time stepping is applied. This method is faster than using Newton solvers. It was used successfully for solving Nonlinear CFD equations in the frequency domain. This new approach allows identifying the steady state of worn systems by integrating wear rate equations a on dual time scale. The dual time equations are integrated by an implicit scheme. Of the different orders tested, the first order scheme provided the best re...

  15. A combined variational and perturbational study on the vibrational spectrum of P 2F 4

    NASA Astrophysics Data System (ADS)

    Rauhut, Guntram; Hrenar, Tomica

    2008-05-01

    The structure and vibrational spectrum of tetrafluorodiphosphine, P 2F 4, were studied by calculating large fractions of the multidimensional potential energy surface at the coupled-cluster level. Vibrational corrections to the geometrical parameters were accounted for by calculating the vibrational wave function using configuration interaction theory (VCI). Fundamental modes, first vibrational overtones and low lying combination bands were computed at the same level and were compared with results from vibrational perturbation theory. A comparison with experimental results is provided.

  16. Collisional line shapes for low frequency vibrations of adsorbates on a metal surface

    E-print Network

    Guantes, Raúl

    the relaxation of a vibrationally excited atom or molecule within a model of a damped quantum harmonic oscillator in a temperature dependent damping mechanism or with electron-hole pairs.3,4 The cor- responding vibrational bilinearly coupled to a bath of lattice oscillators. The collisional time correlation function is generalized

  17. On the homology of the Harmonic Archipelago

    E-print Network

    Karimov, Umed H; 10.2478/s11533-012-0038-2

    2012-01-01

    We calculate the singular homology and \\v{C}ech cohomology groups of the Harmonic archipelago. As a corollary, we prove that this space is not homotopy equivalent to the Griffiths space. This is interesting in view of Eda's proof that the first singular homology groups of these spaces are isomorphic.

  18. Lab 6: Forced Harmonic Motion Driven harmonic oscillation

    E-print Network

    Gustafsson, Torgny

    Lab 6: Forced Harmonic Motion Driven harmonic oscillation Example: Atomic force microscope watch;Lab 6: Forced Harmonic Motion · For each measurement allow enough time for the system to reach steady, circuit, ... #12;A constant energy flow at steady state ( )F t dF Rx= - 0oin ut PP + = #12;Forced harmonic

  19. Downhole vibration sensing by vibration energy harvesting

    E-print Network

    Trimble, A. Zachary

    2007-01-01

    This thesis outlines the design of a prototype electromagnetic induction vibration energy harvesting device for use in a downhole environment. First order models of the necessary components for a generic vibration energy ...

  20. Vibration Analysis Reduces Computer Time

    NASA Technical Reports Server (NTRS)

    Engels, R. C.

    1983-01-01

    Improved calculation method promises to reduce computer time by factor of 10 for vibration analysis of complex structures. Method originally developed to predict mechanical response of spacecraft to maneuvers in various cases in which same booster is used with different payloads. Method is more exact than conventional normal-mode methods; it involves no initial approximations of assumptions. Calculation cost is reduced without loss of accuracy.

  1. Spectroscopic (FT-IR, FT-Raman) investigations and quantum chemical calculations of 4-hydroxy-2-oxo-1,2-dihydroquinoline-7-carboxylic acid.

    PubMed

    Ulahannan, Rajeev T; Panicker, C Yohannan; Varghese, Hema Tresa; Van Alsenoy, C; Musiol, Robert; Jampilek, Josef; Anto, P L

    2014-01-01

    Quinoline derivatives have good nonlinear optical properties and have been extensively studied due to their great potential application in the field of organic light emitting diodes. Quantum chemical calculations of the equilibrium geometry, harmonic vibrational frequencies, infrared intensities and Raman activities of 4-hydroxy-2-oxo-1,2-dihydroquinoline-7-carboxylic acid in the ground state were reported. Potential energy distribution of normal modes of vibrations was done using GAR2PED program. The synthesis, (1)H NMR and PES scan results are also discussed. Nonlinear optical behavior of the examined molecule was investigated by the determination of first hyperpolarizability. The calculated HOMO and LUMO energies show the chemical activity of the molecule. The stability of the molecule arising from hyperconjugative interaction and charge delocalization has been analyzed using NBO analysis. The calculated geometrical parameters are in agreement with that of similar derivatives. PMID:24287049

  2. Vibrational nonequilibrium effects on diatomic dissociation rates

    NASA Technical Reports Server (NTRS)

    Hansen, C. F.

    1993-01-01

    The collision-induced dissociation rate of diatomic molecules from a ladder of rotational and anharmonic vibrational states is developed, and the correction for vibrational nonequilibrium is considered. The result is similar to an analytic correction derived by Hammerling et al. (1959) for harmonic oscillators. An empirical correction algorithm suggested by Park (1987, 1990) gives similar results when vibrational temperature is comparable to kinetic temperature but underestimates the dissociation rate when vibrational temperature is small compared with the kinetic temperature. This algorithm uses an effective temperature in the experimentally determined Arrhenius expression for the rate coefficient, which is a weighted average of the vibrational and kinetic temperature, whereas theory indicates that kinetic temperature should appear only in the exponential term of the Arrhenius expression. Nevertheless, an effective temperature can always be found that will numerically duplicate the proper rate coefficient at any given condition, but a constant weighting factor cannot be expected to provide this. However, the algorithm can he adjusted to give reasonable results over a range of conditions if the geometric weighting factor is taken to be a simple linear function of the ratio of vibrational to kinetic temperature in the gas.

  3. Structural and vibrational studies on 1-(5-methyl-[1,3,4] thiadiazol-2-yl)-pyrolidin-2-ol.

    PubMed

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

    2016-01-01

    FT-Raman and FT-IR spectra were recorded for1-(5-methyl-[1,3,4]thiadiazol-2-yl)-pyrolidin-2-ol (MTPN) sample in solid state. The equilibrium geometries, harmonic vibrational frequencies, IR and the Raman scattering intensities were computed using DFT/6-311++G (d,p) level. Results obtained at this level of theory were used for a detailed interpretation of the IR and Raman spectra, based on the TED of the normal modes. Molecular parameters such as bond lengths, bond angles and dihedral angles were calculated. The intra-molecular charge transfer was calculated by means of NBO. Hyperconjugative interaction energy was more during the ?-?(?) transition. Energy gap of the molecule has been found using HOMO and LUMO calculation, hence the less band gap, which seems to be more stable. PMID:26219020

  4. Structural and vibrational studies on 1-(5-methyl-[1,3,4] thiadiazol-2-yl)-pyrolidin-2-ol

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

    FT-Raman and FT-IR spectra were recorded for1-(5-methyl-[1,3,4]thiadiazol-2-yl)-pyrolidin-2-ol (MTPN) sample in solid state. The equilibrium geometries, harmonic vibrational frequencies, IR and the Raman scattering intensities were computed using DFT/6-311++G (d,p) level. Results obtained at this level of theory were used for a detailed interpretation of the IR and Raman spectra, based on the TED of the normal modes. Molecular parameters such as bond lengths, bond angles and dihedral angles were calculated. The intra-molecular charge transfer was calculated by means of NBO. Hyperconjugative interaction energy was more during the ?-?? transition. Energy gap of the molecule has been found using HOMO and LUMO calculation, hence the less band gap, which seems to be more stable.

  5. Energy repartition for a harmonic chain with local reservoirs.

    PubMed

    Falasco, Gianmaria; Baiesi, Marco; Molinaro, Leo; Conti, Livia; Baldovin, Fulvio

    2015-08-01

    We exactly analyze the vibrational properties of a chain of harmonic oscillators in contact with local Langevin heat baths. Nonequilibrium steady-state fluctuations are found to be described by a set of mode temperatures, independent of the strengths of both the harmonic interaction and the viscous damping. Energy is equally distributed between the conjugate variables of a given mode but differently among different modes, in a manner which depends exclusively on the bath temperatures and on the boundary conditions. We outline how bath-temperature profiles can be designed to enhance or reduce fluctuations at specific frequencies in the power spectrum of the chain length. PMID:26382366

  6. [Vibration studies on high-speed angular handpieces].

    PubMed

    Gütschow, F

    1989-01-01

    In the course of preparation the inner structure of the hard tooth substance may be damaged by frictioninduced vibrations. This aspect was examined in 30 KaVo high-speed angular handpieces of the new type 2304 LD/24 L by frequency analysis. The individual handpieces showed major differences in the amplitude of the 3rd and 4th harmonic. Above approx. 120,000 revs/min they lead to vibrations in the natural frequency range resulting in measurably smoother running. Solutions are discussed to eliminate these vibrations probably originating in the head of the handpiece. PMID:2689148

  7. Simple harmonic motion displacement x

    E-print Network

    Bertulani, Carlos A. - Department of Physics and Astronomy, Texas A&M University

    1 Simple harmonic motion time (s) displacement x 5cm -5cm 2 4 6 8 10 a) what is the amplitude () of the corresponding circular motion? b) What is the period (T) of the harmonic motion? c) What is the frequency (f)? d of the harmonic oscillation? b) what is the period of the harmonic oscillation? c) what is the frequency

  8. Three-dimensional analytic probabilities of coupled vibrational-rotational-translational energy transfer for DSMC modeling of nonequilibrium flows

    SciTech Connect

    Adamovich, Igor V.

    2014-04-15

    A three-dimensional, nonperturbative, semiclassical analytic model of vibrational energy transfer in collisions between a rotating diatomic molecule and an atom, and between two rotating diatomic molecules (Forced Harmonic Oscillator–Free Rotation model) has been extended to incorporate rotational relaxation and coupling between vibrational, translational, and rotational energy transfer. The model is based on analysis of semiclassical trajectories of rotating molecules interacting by a repulsive exponential atom-to-atom potential. The model predictions are compared with the results of three-dimensional close-coupled semiclassical trajectory calculations using the same potential energy surface. The comparison demonstrates good agreement between analytic and numerical probabilities of rotational and vibrational energy transfer processes, over a wide range of total collision energies, rotational energies, and impact parameter. The model predicts probabilities of single-quantum and multi-quantum vibrational-rotational transitions and is applicable up to very high collision energies and quantum numbers. Closed-form analytic expressions for these transition probabilities lend themselves to straightforward incorporation into DSMC nonequilibrium flow codes.

  9. Multidimensional high harmonic spectroscopy

    NASA Astrophysics Data System (ADS)

    Bruner, Barry D.; Soifer, Hadas; Shafir, Dror; Serbinenko, Valeria; Smirnova, Olga; Dudovich, Nirit

    2015-09-01

    High harmonic generation (HHG) has opened up a new frontier in ultrafast science where attosecond time resolution and Angstrom spatial resolution are accessible in a single measurement. However, reconstructing the dynamics under study is limited by the multiple degrees of freedom involved in strong field interactions. In this paper we describe a new class of measurement schemes for resolving attosecond dynamics, integrating perturbative nonlinear optics with strong-field physics. These approaches serve as a basis for multidimensional high harmonic spectroscopy. Specifically, we show that multidimensional high harmonic spectroscopy can measure tunnel ionization dynamics with high precision, and resolves the interference between multiple ionization channels. In addition, we show how multidimensional HHG can function as a type of lock-in amplifier measurement. Similar to multi-dimensional approaches in nonlinear optical spectroscopy that have resolved correlated femtosecond dynamics, multi-dimensional high harmonic spectroscopy reveals the underlying complex dynamics behind attosecond scale phenomena.

  10. Nonempirical ab initio calculations on DNA base pairs

    NASA Astrophysics Data System (ADS)

    Šponer, Ji?í; Hobza, Pavel

    1996-04-01

    28 H-bonded DNA base pairs formed by guanine, adenine, thymine and cytosine were optimized by the gradient method at the ab initio HF/MINI-1 level. 10 pairs were found to be nonplanar with propeller structure. Harmonic vibration analysis indicates that all the stationary points found correspond to energy minima. The calculated interaction enthalpies (sum of the SCF interaction energy, the dispersion energy and the zero-point energy) are larger than the respective experimental data due to overestimation of the MINI-1 SCF interaction energy. Buckling and propeller vibrations were found to be the lowest for all the pairs; it is therefore possible to expect that all the pairs are flexible toward buckle and propeller vibrations. The H-bonded structure of the cytosine dimer was found to be considerably more stable than the stacked structures; both structures were studied at the higher MP2/6-31G ? level. The reliability of the procedure used (MP2/6-31G ?) was tested for model clusters (formamide … formamidine, benzene … Ar) at higher levels (MP4, CCSD(T)).

  11. Theory and Techniques for Vibration-Induced Conductivity Fluctuation testing of Soils

    E-print Network

    Hung-Chih Chang; Laszlo B. Kish; Andrea Kishne; Cristine Morgan; Chiman Kwan

    2009-01-22

    First we present and theoretically analyze the phenomenological physical picture behind Vibration-Induced Conductivity Fluctuations. We identify the relevant tensors characterizing the electromechanical response against the vibrations for both longitudinal and transversal responses. We analyze the conductivity response with acceleration type vibrations and a new scheme, measurements with more advantageous compression type vibrations that are first introduced here. Compression vibrations provide sideband spectral lines shifted by the frequency of the vibration instead of its second harmonics; moreover the application of this method is less problematic with loose electrodes. Concerning geometry and electrodes, the large measurement errors in earlier experiment indicated electrode effects which justify using four-electrode type measurements. We propose and analyze new arrangements for the longitudinal and transversal measurements with both compression vibration and acceleration vibration for laboratory and field conditions.

  12. Molecular structure and vibrational spectroscopic studies of prothionamide by density functional theory

    NASA Astrophysics Data System (ADS)

    Yilmaz, A.; Bolukbasi, O.

    2016-01-01

    Prothionamide (PTH) is the secondary drug used against Mycobacterium tuberculosis bacteria and leprosy. The aim of this work was to investigate the potential energy surface map, anharmonic and harmonic vibrational spectra, NBO analysis and ELF (Electron Localization Function) of the title compound using DFT approach with the B3LYP (Becke, three-parameter, Lee-Yang-Parr) exchange-correlation functional with the 6-31G++(d, p) and the Z3POLX basis sets were employed. In the experimental part of this study, FT-Mid IR, FT-Far IR and FT-Raman spectra of the molecule were recorded in the regions 4000-450 cm-1, 700-30 cm-1 and 4000-100 cm-1 respectively in the solid phase. The comparison between calculated and experimental vibrational spectra (infrared and Raman spectra) and assignments of fundamental vibrational modes were characterized by total energy distribution (TED). Theoretical spectra were seen to be in good agreement with those of the experimental ones.

  13. Molecular structure and vibrational spectroscopic studies of prothionamide by density functional theory.

    PubMed

    Yilmaz, A; Bolukbasi, O

    2016-01-01

    Prothionamide (PTH) is the secondary drug used against Mycobacterium tuberculosis bacteria and leprosy. The aim of this work was to investigate the potential energy surface map, anharmonic and harmonic vibrational spectra, NBO analysis and ELF (Electron Localization Function) of the title compound using DFT approach with the B3LYP (Becke, three-parameter, Lee-Yang-Parr) exchange-correlation functional with the 6-31G++(d,p) and the Z3POLX basis sets were employed. In the experimental part of this study, FT-Mid IR, FT-Far IR and FT-Raman spectra of the molecule were recorded in the regions 4000-450cm(-1), 700-30cm(-1) and 4000-100cm(-1) respectively in the solid phase. The comparison between calculated and experimental vibrational spectra (infrared and Raman spectra) and assignments of fundamental vibrational modes were characterized by total energy distribution (TED). Theoretical spectra were seen to be in good agreement with those of the experimental ones. PMID:26219021

  14. [Study on the spectroscopic data and vibrational levels of the ground SiH+ molecular ion].

    PubMed

    Zhao, Jun; Zeng, Hui

    2014-12-01

    The ground electronic state and the reasonable dissociation limit of SiH+ molecular ion have been correctly determined based on group theory and atomic and molecular reaction statics. The energy, equilibrium geometry and harmonic frequency of the ground electronic state of SiH+ molecular ion have been calculated using the method QCISD(T)/cc-pVQZ. The whole potential curves for the ground electronic state is further scanned using the above method, the potential energy functions and relevant spectroscopic constants of this state are then first obtained by least square fitting to the Murrell-Sorbie function (n=9) and the modified Murrell-Sorbie+c6 function, respectively. The present results showed that the calculated results based on the Murrell-Sorbie function (n=9) are in better agreement with the experimental values, with the relative errors between spectroscopic constants and the experimental values being 0.13%, 3.07%, 0.38%, 5.25% and 0.52% respectively. With the potential obtained at the QCISD(T)/cc-pVQZ level of theory, the total of 27 vibrational states are predicted when J=0 by numerically solving the radial Schrodinger equation of nuclear motion. The complete vibrational levels, inertial rotation and six centrifugal distortion constants are obtained for the ground electronic state of SiH+ molecular ion for the first time. Calculation results in the present work may provide theoretical supports for the further study of SiH+ molecular ion. PMID:25881406

  15. Trajectory study of supercollision relaxation in highly vibrationally excited pyrazine and CO2.

    PubMed

    Li, Ziman; Sansom, Rebecca; Bonella, Sara; Coker, David F; Mullin, Amy S

    2005-09-01

    Classical trajectory calculations were performed to simulate state-resolved energy transfer experiments of highly vibrationally excited pyrazine (E(vib) = 37,900 cm(-1)) and CO(2), which were conducted using a high-resolution transient infrared absorption spectrometer. The goal here is to use classical trajectories to simulate the supercollision energy transfer pathway wherein large amounts of energy are transferred in single collisions in order to compare with experimental results. In the trajectory calculations, Newton's laws of motion are used for the molecular motion, isolated molecules are treated as collections of harmonic oscillators, and intermolecular potentials are formed by pairwise Lennard-Jones potentials. The calculations qualitatively reproduce the observed energy partitioning in the scattered CO(2) molecules and show that the relative partitioning between bath rotation and translation is dependent on the moment of inertia of the bath molecule. The simulations show that the low-frequency modes of the vibrationally excited pyrazine contribute most to the strong collisions. The majority of collisions lead to small DeltaE values and primarily involve single encounters between the energy donor and acceptor. The large DeltaE exchanges result from both single impulsive encounters and chattering collisions that involve multiple encounters. PMID:16834139

  16. Noncontact Electromagnetic Vibration Source

    NASA Technical Reports Server (NTRS)

    Namkung, Min; Fulton, James P.; Wincheski, Buzz A.

    1994-01-01

    Metal aircraft skins scanned rapidly in vibration tests. Relatively simple combination of permanent magnets and electromagnet serves as noncontact vibration source for nondestructive testing of metal aircraft skins. In test, source excites vibrations, and vibration waveforms measured, then analyzed for changes in resonances signifying cracks and other flaws.

  17. Vibration and noise analysis of a gear transmission system

    NASA Technical Reports Server (NTRS)

    Choy, F. K.; Qian, W.; Zakrajsek, J. J.; Oswald, F. B.

    1993-01-01

    This paper presents a comprehensive procedure to predict both the vibration and noise generated by a gear transmission system under normal operating conditions. The gearbox vibrations were obtained from both numerical simulation and experimental studies using a gear noise test rig. In addition, the noise generated by the gearbox vibrations was recorded during the experimental testing. A numerical method was used to develop linear relationships between the gearbox vibration and the generated noise. The hypercoherence function is introduced to correlate the nonlinear relationship between the fundamental noise frequency and its harmonics. A numerical procedure was developed using both the linear and nonlinear relationships generated from the experimental data to predict noise resulting from the gearbox vibrations. The application of this methodology is demonstrated by comparing the numerical and experimental results from the gear noise test rig.

  18. Flow-induced vibration

    SciTech Connect

    Blevins, R.D.

    1990-01-01

    This book reports on dimensional analysis; ideal fluid models; vortex-induced vibration; galloping and flutter; instability of tube and cylinder arrays; vibrations induced by oscillating flow; vibration induced by turbulence and sound; damping of structures; sound induced by vortex shedding; vibrations of a pipe containing a fluid flow; indices. It covers the analysis of the vibrations of structures exposed to fluid flows; explores applications for offshore platforms and piping; wind-induced vibration of buildings, bridges, and towers; and acoustic and mechanical vibration of heat exchangers, power lines, and process ducting.

  19. Low-energy vibrations of the group 10 metal monocarbonyl MCO (M = Ni, Pd, and Pt): rotational spectroscopy and force field analysis.

    PubMed

    Okabayashi, Toshiaki; Yamamoto, Takuya; Okabayashi, Emi Y; Tanimoto, Mitsutoshi

    2011-03-17

    The rotational spectra of NiCO and PdCO in the ground and ?(2) excited vibrational states were observed by employing a source-modulated microwave spectrometer. The NiCO and PdCO molecules were generated in a free space cell by the sputtering reaction of nickel and palladium sheets, respectively, lining the inner surface of a stainless steel cathode with a dc glow plasma of CO and Ar. The molecular constants of NiCO and PdCO were determined by least-squares analysis. By force field analysis for the molecular constants of not only NiCO and PdCO but also of PtCO as previously reported, the harmonic force constants were determined for these three group 10 metal monocarbonyls. The vibrational wavenumbers derived for the lower M-C stretching vibrations were in good agreement with those obtained from the IR spectra in noble gas matrices and those predicted by several quantum chemical calculations published in the past. The bending vibrational wavenumbers derived by the force field analysis were also consistent with most quantum chemical calculations previously reported, but showed systematic discrepancies from the matrix IR values by about 40 cm(-1), even after reassignment (?(2) band ? 2?(2) band) of the matrix IR spectra of PdCO and PtCO. PMID:21332227

  20. On the intermolecular vibrational modes of the guanine⋯cytosine, adenine⋯thymine and formamide⋯formamide H-bonded dimers

    NASA Astrophysics Data System (ADS)

    Florián, Jan; Leszczynski, Jerzy; Johnson, Benny G.

    1995-04-01

    Harmonic force fields, frequencies, and IR and Raman intensities of the intermolecular vibrational modes in the cyclic formamide dimer and the guanine-cytosine and adenine-thymine DNA base pairs were calculated using several ab initio methods, including Hartree-Fock, MP2 and gradient-corrected density functional theory (DFT), with various basis sets. A polar environment was modeled using the polarizable continuum model (SCRF). The effect of electron correlation upon calculated Raman intensities was investigated using DFT. The normal coordinate analysis was carried out in internal coordinates observing C 2h symmetry of the formamide dimer. These coordinates were also generalized for the DNA base pairs, allowing force constants, frequencies and intensities of the characteristic intermolecular vibrational modes to be compared among the H-bonded complexes studied. In addition, coordinates defined in this way are directly related to standard DNA interbase structural parameters as pseudodyad, tilt and propeller twist angles. Extensive coupling of the intramolecular wagging vibrations of the amino groups participating in H-bonding with the tilt and propeller twist vibrations was obtained for the lowest frequency normal modes.

  1. Ab initio and density functional study of the geometrical, electronic and vibrational properties of 3,4'-bi-1,2,4-triazole.

    PubMed

    Guédira, F; Castellà-Ventura, M; Zaydoun, S; Elhajji, A; Lautié, A; Saidi Idrissi, M

    2009-08-15

    The conventional ab initio method at the closed restricted Hartree-Fock level (RHF) and the density functional theory (DFT) approach at the B3-LYP level, using the 6-31+G* basis set, are applied to predict the molecular structure and the energetic and the vibrational properties (harmonic wave numbers, force fields and potential energy distributions) of the 3,4'-bi-1,2,4-triazole and of two deuterated derivatives (ND and ND(CD)(3)). The theoretical results are compared to the Raman and infrared vibrational data. Using both methods, there is a very good agreement between theory and experiment concerning not only the wave numbers but also the isotopic shifts. This accordance allows us to validate the calculated structure of bTA. This molecule is characterized by an aromatic structure in which two triazolic rings are linked by a CN bond, intermediary between a single and double bond, in a planar conformation. From a methodological point of view, the B3-LYP method predicts more accurate structure and harmonic vibrational wave numbers than the RHF method. PMID:19411187

  2. Ab initio and density functional study of the geometrical, electronic and vibrational properties of 3,4'-bi-1,2,4-triazole

    NASA Astrophysics Data System (ADS)

    Guédira, F.; Castellà-Ventura, M.; Zaydoun, S.; Elhajji, A.; Lautié, A.; Saidi Idrissi, M.

    2009-08-01

    The conventional ab initio method at the closed restricted Hartree-Fock level (RHF) and the density functional theory (DFT) approach at the B3-LYP level, using the 6-31+G* basis set, are applied to predict the molecular structure and the energetic and the vibrational properties (harmonic wave numbers, force fields and potential energy distributions) of the 3,4'-bi-1,2,4-triazole and of two deuterated derivatives (ND and ND(CD) 3). The theoretical results are compared to the Raman and infrared vibrational data. Using both methods, there is a very good agreement between theory and experiment concerning not only the wave numbers but also the isotopic shifts. This accordance allows us to validate the calculated structure of bTA. This molecule is characterized by an aromatic structure in which two triazolic rings are linked by a CN bond, intermediary between a single and double bond, in a planar conformation. From a methodological point of view, the B3-LYP method predicts more accurate structure and harmonic vibrational wave numbers than the RHF method.

  3. Quantum mechanical study of the structure and vibrational spectroscopic (FT-IR and FT-Raman), first-order hyperpolarizability, NBO and HOMO-LUMO studies of 4-bromo-3-nitroanisole

    NASA Astrophysics Data System (ADS)

    Balachandran, V.; Karunakaran, V.

    2013-04-01

    The FT-IR and FT-Raman spectra of 4-bromo-3-nitroanisole (BNA) molecule have been recorded in the region 4000-400 cm-1 and 3500-100 cm-1, respectively. Optimized geometrical structure, harmonic vibrational frequencies, intensities, reduced mass, force constants and depolarization ratio have been computed by ab initio HF and the B3LYP density functional levels using 6-311++G (d,p) basis set. The observed FT-IR and FT-Raman vibrational frequencies are analyzed and compared with theoretically predicted vibrational frequencies. The geometries and normal modes of vibration obtained from DFT method are in good agreement with the experimental data. The first-order hyperpolarizability (?) of the investigated molecule were computed using DFT calculations. Besides, charge transfer occurring in the molecule between HOMO and LUMO energies, frontier energy gap, molecular electrostatic potential (MEP) were calculated and analyzed. The influences of bromine atom, nitrile group and methyl group on the geometry of benzene and its normal modes of vibrations have also been discussed.

  4. Quantum mechanical study of the structure and vibrational spectroscopic (FT-IR and FT-Raman), first-order hyperpolarizability, NBO and HOMO-LUMO studies of 4-bromo-3-nitroanisole.

    PubMed

    Balachandran, V; Karunakaran, V

    2013-04-01

    The FT-IR and FT-Raman spectra of 4-bromo-3-nitroanisole (BNA) molecule have been recorded in the region 4000-400 cm(-1) and 3500-100 cm(-1), respectively. Optimized geometrical structure, harmonic vibrational frequencies, intensities, reduced mass, force constants and depolarization ratio have been computed by ab initio HF and the B3LYP density functional levels using 6-311++G (d,p) basis set. The observed FT-IR and FT-Raman vibrational frequencies are analyzed and compared with theoretically predicted vibrational frequencies. The geometries and normal modes of vibration obtained from DFT method are in good agreement with the experimental data. The first-order hyperpolarizability (?) of the investigated molecule were computed using DFT calculations. Besides, charge transfer occurring in the molecule between HOMO and LUMO energies, frontier energy gap, molecular electrostatic potential (MEP) were calculated and analyzed. The influences of bromine atom, nitrile group and methyl group on the geometry of benzene and its normal modes of vibrations have also been discussed. PMID:23416886

  5. High-harmonic spectroscopy of molecular isomers

    SciTech Connect

    Wong, M. C. H.; Brichta, J.-P.; Bhardwaj, V. R.; Spanner, M.; Patchkovskii, S.

    2011-11-15

    We demonstrate that high-order-harmonic generation (HHG) spectroscopy can be used to probe stereoisomers of randomly oriented 1,2-dichloroethylene (C{sub 2}H{sub 2}Cl{sub 2}) and 2-butene (C{sub 4}H{sub 8}). The high-harmonic spectra of these isomers are distinguishable over a range of laser intensities and wavelengths. Time-dependent numerical calculations of angle-dependent ionization yields for 1,2-dichloroethylene suggest that the harmonic spectra of molecular isomers reflect differences in their strong-field ionization. The subcycle ionization yields for the cis isomer are an order of magnitude higher than those for the trans isomer. The sensitivity in discrimination of the harmonic spectra of cis- and trans- isomers is greater than 8 and 5 for 1,2-dichloroethylene and 2-butene, respectively. We show that HHG spectroscopy cannot differentiate the harmonic spectra of the two enantiomers of the chiral molecule propylene oxide (C{sub 3}H{sub 6}O).

  6. The origin of harmonic tremor at Old Faithful geyser

    NASA Astrophysics Data System (ADS)

    Kedar, Sharon; Sturtevant, Bradford; Kanamori, Hiroo

    1996-02-01

    VOLCANIC eruptions are sometimes accompanied by a characteristic type of seismicity known as harmonic tremor, in which the signal is dominated by discrete vibration frequencies1-4. This harmonic structure could reflect resonance behaviour in the excitation source4-6 or filtering of the seismic waves as they propagate through the surrounding rocks7-10 but complexity and variability in the properties of volcanic systems make it difficult to discriminate between such mechanisms. To address this question, we have analysed the source and propagation characteristics of seismicity at Old Faithful geyser (Yellowstone National Park), the cyclic behaviour and accessibility of which make it an ideal natural laboratory for studying harmonic tremor associated with near-surface sources. We find that sharp pressure pulses inside the water column trigger distinct seismic events that give rise to a harmonic ground response whose frequency varies spatially but not temporally. A superposition of these seismic events creates the appearance of continuous harmonic tremor. The absence of resonance within the water column suggests that the harmonic motion must arise from the interaction of the seismic waves with heterogeneities in the surrounding elastic medium-most probably a near-surface soft layer.

  7. Improved Continuous-Time Higher Harmonic Control Using Hinfinity Methods

    NASA Astrophysics Data System (ADS)

    Fan, Frank H.

    The helicopter is a versatile aircraft that can take-off and land vertically, hover efficiently, and maneuver in confined space. This versatility is enabled by the main rotor, which also causes undesired harmonic vibration during operation. This unwanted vibration has a negative impact on the practicality of the helicopter and also increases its operational cost. Passive control techniques have been applied to helicopter vibration suppression, but these methods are generally heavy and are not robust to changes in operating conditions. Feedback control offers the advantages of robustness and potentially higher performance over passive control techniques, and amongst the various feedback schemes, Shaw's higher harmonic control algorithm has been shown to be an effective method for attenuating harmonic disturbance in helicopters. In this thesis, the higher harmonic disturbance algorithm is further developed to achieve improved performance. One goal in this thesis is to determine the importance of periodicity in the helicopter rotor dynamics for control synthesis. Based on the analysis of wind tunnel data and simulation results, we conclude the helicopter rotor can be modeled reasonably well as linear and time-invariant for control design purposes. Modeling the helicopter rotor as linear time-invariant allows us to apply linear control theory concepts to the higher harmonic control problem. Another goal in this thesis is to find the limits of performance in harmonic disturbance rejection. To achieve this goal, we first define the metrics to measure the performance of the controller in terms of response speed and robustness to changes in the plant dynamics. The performance metrics are incorporated into an Hinfinity control problem. For a given plant, the resulting Hinfinity controller achieves the maximum performance, thus allowing us to identify the performance limitation in harmonic disturbance rejection. However, the Hinfinity controllers are of high order, and may have unstable poles, leading us to develop a design method to generate stable, fixed-order, and high performance controllers. Both the Hinfinity and the fixed-order controllers are designed for constant flight conditions. A gain-scheduled control law is used to reduce the vibration throughout the flight envelope. The gain-scheduling is accomplished by blending the outputs from fixed-order controllers designed for different flight conditions. The structure of the fixed-order controller allows the usage of a previously developed anti-windup scheme, and the blending function results in a bumpless full flight envelope control law. (Copies available exclusively from MIT Libraries, libraries.mit.edu/docs - docs mit.edu)

  8. Nuclear motion effects on the density matrix of crystals: An ab initio Monte Carlo harmonic approach

    NASA Astrophysics Data System (ADS)

    Pisani, Cesare; Erba, Alessandro; Ferrabone, Matteo; Dovesi, Roberto

    2012-07-01

    In the frame of the Born-Oppenheimer approximation, nuclear motions in crystals can be simulated rather accurately using a harmonic model. In turn, the electronic first-order density matrix (DM) can be expressed as the statistically weighted average over all its determinations each resulting from an instantaneous nuclear configuration. This model has been implemented in a computational scheme which adopts an ab initio one-electron (Hartree-Fock or Kohn-Sham) Hamiltonian in the CRYSTAL program. After selecting a supercell of reasonable size and solving the corresponding vibrational problem in the harmonic approximation, a Metropolis algorithm is adopted for generating a sample of nuclear configurations which reflects their probability distribution at a given temperature. For each configuration in the sample the "instantaneous" DM is calculated, and its contribution to the observables of interest is extracted. Translational and point symmetry of the crystal as reflected in its average DM are fully exploited. The influence of zero-point and thermal motion of nuclei on such important first-order observables as x-ray structure factors and Compton profiles can thus be estimated.

  9. Structural and vibrational spectroscopic studies on charge transfer and ionic hydrogen bonding interactions of melaminium benzoate dihydrate.

    PubMed

    Kanagathara, N; Marchewka, M K; Drozd, M; Gunasekaran, S; Rajakumar, P R; Anbalagan, G

    2015-06-15

    Single crystals of melaminium benzoate dihydrate (MBDH) have been grown from aqueous solution by the slow solvent evaporation method at room temperature. Crystalline nature of the grown crystal has been confirmed by X-ray powder diffraction studies. The optimized geometry, frequency and intensity of the vibrational bands of MBDH were obtained by the Hartree-Fock and density functional theory using B3LYP/cam-B3LYP with 6-311++G(d,p) basis set. The harmonic vibrational frequencies were calculated and the scaled values have been compared with the experimental FT-IR and FT-Raman spectral values. The obtained vibrational wavenumbers and optimized geometric parameters are found to be in good agreement with the experimental data. UV-Visible spectrum was recorded in the region 200-400 nm and the electronic properties, HOMO-LUMO energies and other related electronic parameters are calculated. The isotropic chemical shifts computed by (1)H and (13)C NMR analysis also show good agreement with experimental observation. Natural bond orbital (NBO) analysis has been performed on MBDH compound to analyze the stability of the molecule arising from hyperconjugative interactions and charge delocalization. Molecular electrostatic potential surface (MEP) has also been performed by DFT/cam-B3LYP method with 6-311++G(d,p) basis set. Differential scanning calorimetric measurements performed on the powder sample indicate the phase transition point approximately at 368 and 358K for heating and cooling, respectively. PMID:25796010

  10. Structural and vibrational spectroscopic studies on charge transfer and ionic hydrogen bonding interactions of melaminium benzoate dihydrate

    NASA Astrophysics Data System (ADS)

    Kanagathara, N.; Marchewka, M. K.; Drozd, M.; Gunasekaran, S.; Rajakumar, P. R.; Anbalagan, G.

    2015-06-01

    Single crystals of melaminium benzoate dihydrate (MBDH) have been grown from aqueous solution by the slow solvent evaporation method at room temperature. Crystalline nature of the grown crystal has been confirmed by X-ray powder diffraction studies. The optimized geometry, frequency and intensity of the vibrational bands of MBDH were obtained by the Hartree-Fock and density functional theory using B3LYP/cam-B3LYP with 6-311++G(d,p) basis set. The harmonic vibrational frequencies were calculated and the scaled values have been compared with the experimental FT-IR and FT-Raman spectral values. The obtained vibrational wavenumbers and optimized geometric parameters are found to be in good agreement with the experimental data. UV-Visible spectrum was recorded in the region 200-400 nm and the electronic properties, HOMO-LUMO energies and other related electronic parameters are calculated. The isotropic chemical shifts computed by 1H and 13C NMR analysis also show good agreement with experimental observation. Natural bond orbital (NBO) analysis has been performed on MBDH compound to analyze the stability of the molecule arising from hyperconjugative interactions and charge delocalization. Molecular electrostatic potential surface (MEP) has also been performed by DFT/cam-B3LYP method with 6-311++G(d,p) basis set. Differential scanning calorimetric measurements performed on the powder sample indicate the phase transition point approximately at 368 and 358 K for heating and cooling, respectively.

  11. Quantum-chemical modeling of the effect of microhydration and media on the vibrational spectra of 2-(2'-pyridyl)-benzimidazole and its 1-methylsubstituted analogue

    NASA Astrophysics Data System (ADS)

    Vakula, O. A.; Vakula, N. I.; Kuramshina, G. M.; Pentin, Yu. A.

    2013-09-01

    Quantum-chemical calculations of the optimized structures, harmonic force fields, and frequencies of 1 : 1 and 1 : 2 complexes of 2-(2'-pyridyl)-benzimidazole and 1-methyl-2-pyridine-2-yl-1H-benzimidazole are performed by means of DFT (B3LYP/6-31+G**). The shifts in the frequencies of the vibrational spectra of the investigated complexes are considered with allowance for the conformational structure and effect of the medium. Analytical bands (spectral marks) are proposed that can be used to identify complexes of 2-(2'-pyridyl)-benzimidazole and 1-methyl-2-pyridine-2-yl-1H-benzimidazole with water. It is concluded that considering the environment within a model of a polarized continuum allows the forecasting of possible shifts in the frequencies in the vibrational spectra of the studied compounds in aqueous media and DMF.

  12. Optical harmonic generator

    DOEpatents

    Summers, M.A.; Eimerl, D.; Boyd, R.D.

    1982-06-10

    A pair of uniaxial birefringent crystal elements are fixed together to form a serially arranged, integral assembly which, alternatively, provides either a linearly or elliptically polarized second-harmonic output wave or a linearly polarized third-harmonic output wave. The extraordinary or e directions of the crystal elements are oriented in the integral assembly to be in quadrature (90/sup 0/). For a second-harmonic generation in the Type-II-Type-II angle tuned case, the input fundamental wave has equal amplitude o and e components. For a third-harmonic generation, the input fundamental wave has o and e components whose amplitudes are in a ratio of 2:1 (o:e reference first crystal). In the typical case of a linearly polarized input fundamental wave this can be accomplished by simply rotating the crystal assembly about the input beam direction by 10/sup 0/. For both second and third harmonic generation input precise phase-matching is achieved by tilting the crystal assembly about its two sensitive axeses (o).

  13. Booster double harmonic setup notes

    SciTech Connect

    Gardner, C. J.

    2015-02-17

    The motivation behind implementing a booster double harmonic include the reduced transverse space charge force from a reduced peak beam current and reduced momentum spread of the beam, both of which can be achieved from flattening the RF bucket. RF capture and acceleration of polarized protons (PP) is first set up in the single harmonic mode with RF harmonic h=1. Once capture and acceleration have been set up in the single harmonic mode, the second harmonic system is brought on and programmed to operate in concert with the single harmonic system.

  14. Thermoelectricity in molecular junctions with harmonic and anharmonic modes

    PubMed Central

    Agarwalla, Bijay Kumar; Jiang, Jian-Hua

    2015-01-01

    Summary We study charge and energy transfer in two-site molecular electronic junctions in which electron transport is assisted by a vibrational mode. To understand the role of mode harmonicity/anharmonicity in transport behavior, we consider two limiting situations: (i) the mode is assumed harmonic, (ii) we truncate the mode spectrum to include only two levels, to represent an anharmonic mode. Based on the cumulant generating functions of the models, we analyze the linear-response and nonlinear performance of these junctions and demonstrate that while the electrical and thermal conductances are sensitive to whether the mode is harmonic/anharmonic, the Seebeck coefficient, the thermoelectric figure-of-merit, and the thermoelectric efficiency beyond linear response, conceal this information. PMID:26665085

  15. Vibrational spectra and first order hyperpolarizability studies of dimethyl amino pyridinium 4-nitrophenolate 4-nitrophenol

    NASA Astrophysics Data System (ADS)

    John, C. Jesintha; Amalanathan, M.; Twinkle, A. R.; Srinivasan, P.; Joe, I. Hubert

    2011-10-01

    Vibrational spectra of the organic nonlinear optical crystallized dimethyl amino pyridinium 4-nitrophenolate 4-nitrophenol have been recorded and analyzed. The spectral interpretation has been done based on the density functional theory using the standard B3LYP/LANL2DZ basis set. Total energy distribution is calculated using the scaled quantum mechanic program. Natural bond orbital analysis is also used to explain the inter and intra molecular hydrogen bonding. The relative second harmonic efficiency of the compound is found to be 15 times greater than that of KDP. The effect of intermolecular hydrogen bonding between the phenolate ion of 4-nitrophenol with N-atom of pyridine ring is sufficiently more, enhancing the ? value which is the required property of a system to be NLO active.

  16. Harmonic prime movers

    NASA Astrophysics Data System (ADS)

    Rice, Ian; Smith, Gordon

    2005-09-01

    Western Kentucky University is undertaking the development of a thermoacoustically powered acoustic agglomerator as a means of pretreating exhaust from coal generators before entering standard industrial electrostatic precipitators. In order to fulfill the design requirement of maintaining a clean, isolated environment for the thermoacoustic components, it will be necessary to operate a thermoacoustic prime mover in a harmonic mode, which normally is not a desirable feature in typical devices. Details of a harmonic-mode prime mover will be presented. [Work supported by KY EPSCoR and the Western Kentucky Office of Sponsored Programs.

  17. Multi-reference vibration correlation methods

    SciTech Connect

    Pfeiffer, Florian; Rauhut, Guntram

    2014-02-14

    State-specific vibration correlation methods beyond the vibrational multi-configuration self-consistent field (VMCSCF) approximation have been developed, which allow for the accurate calculation of state energies for systems suffering from strong anharmonic resonances. Both variational multi-reference configuration interaction approaches and an implementation of approximate 2nd order vibrational multi-reference perturbation theory are presented. The variational approach can be significantly accelerated by a configuration selection scheme, which leads to negligible deviations in the final results. Relaxation effects due to the partitioning of the correlation space and the performance of a VMCSCF modal basis in contrast to a standard modal basis obtained from vibrational self-consistent field theory have been investigated in detail. Benchmark calculations based on high-level potentials are provided for the propargyl cation and cis-diazene.

  18. Direct simulation with vibration-dissociation coupling

    NASA Technical Reports Server (NTRS)

    Hash, David B.; Hassan, H. A.

    1992-01-01

    The majority of implementations of the Direct Simulation Monte Carlo (DSMC) method of Bird do not account for vibration-dissociation coupling. Haas and Boyd have proposed the vibrationally-favored dissociation model to accomplish this task. This model requires measurements of induction distance to determine model constants. A more general expression has been derived that does not require any experimental input. The model is used to calculate one-dimensional shock waves in nitrogen and the flow past a lunar transfer vehicle (LTV). For the conditions considered in the simulation, the influence of vibration-dissociation coupling on heat transfer in the stagnation region of the LTV can be significant.

  19. Expansion Hamiltonian model for a diatomic molecule adsorbed on a surface: Vibrational states of the CO/Cu(100) system including surface vibrations

    NASA Astrophysics Data System (ADS)

    Meng, Qingyong; Meyer, Hans-Dieter

    2015-10-01

    Molecular-surface studies are often done by assuming a corrugated, static (i.e., rigid) surface. To be able to investigate the effects that vibrations of surface atoms may have on spectra and cross sections, an expansion Hamiltonian model is proposed on the basis of the recently reported [R. Marquardt et al., J. Chem. Phys. 132, 074108 (2010)] SAP potential energy surface (PES), which was built for the CO/Cu(100) system with a rigid surface. In contrast to other molecule-surface coupling models, such as the modified surface oscillator model, the coupling between the adsorbed molecule and the surface atoms is already included in the present expansion SAP-PES model, in which a Taylor expansion around the equilibrium positions of the surface atoms is performed. To test the quality of the Taylor expansion, a direct model, that is avoiding the expansion, is also studied. The latter, however, requests that there is only one movable surface atom included. On the basis of the present expansion and direct models, the effects of a moving top copper atom (the one to which CO is bound) on the energy levels of a bound CO/Cu(100) system are studied. For this purpose, the multiconfiguration time-dependent Hartree calculations are carried out to obtain the vibrational fundamentals and overtones of the CO/Cu(100) system including a movable top copper atom. In order to interpret the results, a simple model consisting of two coupled harmonic oscillators is introduced. From these calculations, the vibrational levels of the CO/Cu(100) system as function of the frequency of the top copper atom are discussed.

  20. Expansion Hamiltonian model for a diatomic molecule adsorbed on a surface: Vibrational states of the CO/Cu(100) system including surface vibrations.

    PubMed

    Meng, Qingyong; Meyer, Hans-Dieter

    2015-10-28

    Molecular-surface studies are often done by assuming a corrugated, static (i.e., rigid) surface. To be able to investigate the effects that vibrations of surface atoms may have on spectra and cross sections, an expansion Hamiltonian model is proposed on the basis of the recently reported [R. Marquardt et al., J. Chem. Phys. 132, 074108 (2010)] SAP potential energy surface (PES), which was built for the CO/Cu(100) system with a rigid surface. In contrast to other molecule-surface coupling models, such as the modified surface oscillator model, the coupling between the adsorbed molecule and the surface atoms is already included in the present expansion SAP-PES model, in which a Taylor expansion around the equilibrium positions of the surface atoms is performed. To test the quality of the Taylor expansion, a direct model, that is avoiding the expansion, is also studied. The latter, however, requests that there is only one movable surface atom included. On the basis of the present expansion and direct models, the effects of a moving top copper atom (the one to which CO is bound) on the energy levels of a bound CO/Cu(100) system are studied. For this purpose, the multiconfiguration time-dependent Hartree calculations are carried out to obtain the vibrational fundamentals and overtones of the CO/Cu(100) system including a movable top copper atom. In order to interpret the results, a simple model consisting of two coupled harmonic oscillators is introduced. From these calculations, the vibrational levels of the CO/Cu(100) system as function of the frequency of the top copper atom are discussed. PMID:26520516