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

    SciTech Connect

    Hanson-Heine, Magnus W. D.

    2015-10-28

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

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

    SciTech Connect

    Miliordos, Evangelos; Xantheas, Sotiris S.

    2013-08-15

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

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

    PubMed

    Miliordos, Evangelos; Xantheas, Sotiris S

    2013-08-15

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

  5. Harmonic Vibrational Analysis in Delocalized Internal Coordinates.

    PubMed

    Jensen, Frank; Palmer, David S

    2011-01-11

    It is shown that a principal component analysis of a large set of internal coordinates can be used to define a nonredundant set of delocalized internal coordinates suitable for the calculation of harmonic vibrational normal modes. The selection of internal coordinates and the principal component analysis provide large degrees of freedom in extracting a nonredundant set of coordinates, and thus influence how the vibrational normal modes are described. It is shown that long-range coordinates may be especially suitable for describing low-frequency global deformation modes in proteins.

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

    NASA Astrophysics Data System (ADS)

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

    2013-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Powers, R. W.

    1978-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-03-01

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

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

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

  11. 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.

  12. Harmonic motion detection in a vibrating scattering medium.

    PubMed

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

    2008-09-01

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

  13. Harmonic Motion Detection in a Vibrating Scattering Medium

    PubMed Central

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

    2008-01-01

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

  14. Calculation of the vibrational spectra of cytosine derivatives by the CNDO/2 force method. Part III. Planar vibrations of cytosine

    NASA Astrophysics Data System (ADS)

    Kuczera, Krzysztof; Szczesniak, Marian; Szczepaniak, Krystyna

    1988-02-01

    Calculations of harmonic force constants by the CNDO/2 FORCE method with Pulay's empirical correction are performed for the amino-keto-N 4H and amino-enol tautomeric forms of cytosine. Frequencies, normal modes and fundamental transition absorption intensities for in-plane vibrations are found. On the bases of the calculations assignments of IR absorption bands of nitrogen and argon matrix spectra of cytosine to normal vibrational modes of the two tautomers are proposed.

  15. Calculating Buckling And Vibrations Of Lattice Structures

    NASA Technical Reports Server (NTRS)

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

    1989-01-01

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

  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. First principles semiclassical calculations of vibrational eigenfunctions.

    PubMed

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

    2011-06-21

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

  18. First principles semiclassical calculations of vibrational eigenfunctions

    NASA Astrophysics Data System (ADS)

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

    2011-06-01

    Vibrational eigenfunctions are calculated on-the-fly using semiclassical methods in conjunction with ab initio density functional theory classical trajectories. Various semiclassical approximations based on the time-dependent representation of the eigenfunctions are tested on an analytical potential describing the chemisorption of CO on Cu(100). Then, first principles semiclassical vibrational eigenfunctions are calculated for the CO2 molecule and its accuracy evaluated. The multiple coherent states initial value representations semiclassical method recently developed by us has shown with only six ab initio trajectories to evaluate eigenvalues and eigenfunctions at the accuracy level of thousands trajectory semiclassical initial value representation simulations.

  19. 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

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

    PubMed

    Xu, Xiangbo; Chen, Shao

    2015-08-31

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

  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. Vibrational spectroscopic studies and DFT calculations of 4-aminoantipyrine

    NASA Astrophysics Data System (ADS)

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

    2009-08-01

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

  3. Intermediate vibrational coordinate localization with harmonic coupling constraints

    NASA Astrophysics Data System (ADS)

    Hanson-Heine, Magnus W. D.

    2016-05-01

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

  4. Local ergodicity in coupled harmonic vibrators: classical and quantal treatments

    NASA Astrophysics Data System (ADS)

    Englman, R.

    2016-03-01

    Ensemble-time ergodicity is proven under some restrictive assumptions for a classical system, comprising interacting harmonic oscillators. An atom in a monatomic chain or lattice is shown to behave ergodically, in the sense that the time average behavior of a lattice point is identical to the ensemble average of the behavior of a lattice point at any long time (in large excess of the inverse vibrational frequencies). This equivalence (for ‘local observables’) differs from the Fermi-Pasta-Ulam result for mode energies (which are non-local). Then, the analogous quantal result is derived, with extensions to wider instances. Relationships to canonical typicality and to the eigenstate thermalization hypothesis are discussed and possibilities of experimental verifications of the results are indicated.

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

    PubMed

    Joutsuka, Tatsuya; Ando, Koji

    2011-05-28

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

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

    PubMed

    Tanimura, Yoshitaka; Ishizaki, Akihito

    2009-09-15

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

  7. Quantum Monte Carlo Algorithms for Diagrammatic Vibrational Structure Calculations

    NASA Astrophysics Data System (ADS)

    Hermes, Matthew; Hirata, So

    2015-06-01

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

  8. 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.

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

    SciTech Connect

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

    1990-04-05

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

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

    SciTech Connect

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

    1982-09-01

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

  11. 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.

  12. 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.

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

    PubMed

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

    2015-10-09

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

  14. 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

  15. 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

  16. 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

  17. Intermolecular vibrations in hydrophobic amino acid crystals: experiments and calculations.

    PubMed

    Williams, Michael R C; Aschaffenburg, Daniel J; Ofori-Okai, Benjamin K; Schmuttenmaer, Charles A

    2013-09-12

    Intermolecular vibrations of amino acid crystals occur in the THz, or far-infrared, region of the electromagnetic spectrum. We have measured the THz and Raman spectra of DL-leucine as well as two polymorphs of DL-valine, the spectroscopic properties of which have not previously been compared. Theoretical modeling of intermolecular vibrations in hydrophobic amino acids is challenging because the van der Waals interactions between molecules are not accounted for in standard density functional theory. Therefore, to calculate the vibrational modes, we used a recently developed approach that includes these nonlocal electron correlation forces. We discuss methods for comparing results from different theoretical models using metrics other than calculated vibrational frequency and intensity, and we also report a new approach enabling concise comparison of vibrational modes that involve complicated mixtures of inter- and intramolecular displacements.

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

    NASA Technical Reports Server (NTRS)

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

    1980-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  20. 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.

  1. Ab initio molecular orbital calculations of the vibrational frequencies of XY4/sup -n/ anions

    NASA Astrophysics Data System (ADS)

    Curtiss, L. A.; Nichols, R.

    The vibrational frequencies of a seris of XY4/sup -n/ anions (BeF4(-2), BF4(-), AlF4(-), MgCl4(-2), and AlCl4(-)) have been calculated by ab initio molecular orbital theory using the 3-21G and 6-31G* basis sets. The predicted harmonic frequencies are for the most part in good agreement with the observed frequencies of these anions in molten alkali halide mixtures. At the 3-21G basis set level the average difference between the observed and predicted frequencies is 12% while at the 6-31G* basis set level the average difference is 6%. Calculations of this type may be helpful in predicting the vibrational frequencies of other anions in molten salts.

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

    PubMed

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

    2015-08-01

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

  3. 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.

  4. Harmonic-resonator-based triboelectric nanogenerator as a sustainable power source and a self-powered active vibration sensor.

    PubMed

    Chen, Jun; Zhu, Guang; Yang, Weiqing; Jing, Qingshen; Bai, Peng; Yang, Ya; Hou, Te-Chien; Wang, Zhong Lin

    2013-11-13

    A harmonic-resonator-based triboelectric nanogenerator (TENG) is presented as a sustainable power source and an active vibration sensor. It can effectively respond to vibration frequencies ranging from 2 to 200 Hz with a considerably wide working bandwidth of 13.4 Hz. This work not only presents a new principle in the field of vibration energy harvesting but also greatly expands the applicability of TENGs.

  5. 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.

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

    NASA Astrophysics Data System (ADS)

    Barton, Dennis; König, Carolin; Neugebauer, Johannes

    2014-10-01

    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.

  7. Analytic calculations of anharmonic infrared and Raman vibrational spectra

    PubMed Central

    Louant, Orian; Ruud, Kenneth

    2016-01-01

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

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

    PubMed

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

    2016-05-01

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

  9. Calculating vibrational spectra of molecules using tensor train decomposition

    NASA Astrophysics Data System (ADS)

    Rakhuba, Maxim; Oseledets, Ivan

    2016-09-01

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

  10. 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.

  11. Calculation of mechanical vibration frequencies of stiffened superconducting cavities

    SciTech Connect

    Black, S.J.; Spalek, G.

    1992-09-01

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

  12. Calculation of mechanical vibration frequencies of stiffened superconducting cavities

    SciTech Connect

    Black, S.J.; Spalek, G.

    1992-01-01

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

  13. Harmonic resonance structure and chaotic dynamics in the earth-vibrator system

    SciTech Connect

    Walker, D.

    1995-05-01

    Source-generated energy in seismic vibrator records includes ultraharmonics, sub-harmonics, ultra-subharmonics and possibly chaotic oscillatory behavior. Non-linear behaviors can be modeled using a ``hard-spring`` form of the Duffing equation. Modeling indicates that a qualitatively similar harmonic resonance structure is present for a broad range of possible mathematical descriptions. Qualitative global system behaviors may be examined without knowledge of actual earth parameters. Non-linear resonances become stronger, relative to fundamental sweep frequencies, as the driving force increases or damping decreases. System response energy levels are highest when non-linear resonances are strong. The presence of chaotic energy can indicate the highest energy state of a system response. Field data examples are consistent with behaviors predicted by modeling. Conventional correlation and stack uses a fraction of the energy produced in the earth-vibrator system. A correlation and filtering process that uses a representation of the source dynamics based on the system response can reduce signal degradation due to non-linear resonance.

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

    PubMed

    Urban, Matthew W; Greenleaf, James F

    2008-01-01

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

  15. 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.

  16. Molecular structure and vibrational spectra of ibuprofen using density function theory calculations

    NASA Astrophysics Data System (ADS)

    Liu, Lekun; Gao, Hongwei

    2012-04-01

    The molecular geometry and the theoretical harmonic frequencies and infrared intensities of ibuprofen were calculated for all the molecules using five different density functional methods (mPW1PW91, B3PW91, B3LYP, HCTH and LSDA) with five basic sets, including 6-311G, 6-311++G, 6-311+G (d, p), 6-311++G (d, p) and 6-311++G (2d, 2p). The purpose of this research was to compare the performance of different DFT methods at different basis sets in predicting geometry and vibration spectrum of ibuprofen. The optimized geometric band lengths and bond angles obtained by using mPW1PW91 at 6-311++G (d, p) and 6-311++G (2d, 2p) basic sets show the best agreement with the experimental data. Comparison of the observed fundamental vibrational frequencies of ibuprofen with calculated results indicates that the B3PW91/6-311++G (2d, 2p) level is superior to all the remaining levels for predicting all the vibration spectra on average for ibuprofen.

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

    NASA Astrophysics Data System (ADS)

    Garrett, P. E.; Green, K. L.; Bangay, J.; Varela, A. Diaz; Sumithrarachchi, C. S.; Austin, R. A. E.; Ball, G. C.; Bandyopadhyay, D. S.; Bianco, L.; Colosimo, S.; Cross, D. S.; Demand, G. A.; Finlay, P.; Garnsworthy, A. B.; Grinyer, G. F.; Hackman, G.; Kulp, W. D.; Leach, K. G.; Morton, A. C.; Orce, J. N.; Pearson, C. J.; Phillips, A. A.; Schumaker, M. A.; Svensson, C. E.; Triambak, S.; Wong, J.; Wood, J. L.; Yates, S. W.

    2011-10-01

    The stable Cd isotopes have long been used as paradigms for spherical vibrational motion. Extensive investigations with in-beam γ 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 β decay using the 8π spectrometer at the TRIUMF radioactive beam facility. The decays of 112In and 112Ag 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+ or 2+ three-phonon candidates has been revealed. Further, the sum of the B(E2) strength from spin 0+ and 2+ 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.

  18. 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.

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

    PubMed

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

    2015-11-01

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

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

    NASA Astrophysics Data System (ADS)

    Penn, G.; Reinsch, M.

    2011-09-01

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

  1. Calculation of ground vibration spectra from heavy military vehicles

    NASA Astrophysics Data System (ADS)

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

    2010-07-01

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

  2. Assessing the accuracy of some popular DFT methods for computing harmonic vibrational frequencies of water clusters

    NASA Astrophysics Data System (ADS)

    Howard, J. Coleman; Enyard, Jordan D.; Tschumper, Gregory S.

    2015-12-01

    A wide range of density functional theory (DFT) methods (37 altogether), including pure, hybrid, range-separated hybrid, double-hybrid, and dispersion-corrected functionals, have been employed to compute the harmonic vibrational frequencies of eight small water clusters ranging in size from the dimer to four different isomers of the hexamer. These computed harmonic frequencies have been carefully compared to recently published benchmark values that are expected to be very close to the CCSD(T) complete basis set limit. Of the DFT methods examined here, ωB97 and ωB97X are the most consistently accurate, deviating from the reference values by less than 20 cm-1 on average and never more than 60 cm-1. The performance of double-hybrid methods including B2PLYP and mPW2-PLYP is only slightly better than more economical approaches, such as the M06-L pure functional and the M06-2X hybrid functional. Additionally, dispersion corrections offer very little improvement in computed frequencies.

  3. On the calculation of classical vibrational energy exchange

    NASA Astrophysics Data System (ADS)

    Gibbons, John P.; Stettler, John D.

    1982-07-01

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

  4. 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.

  5. Calculation of Vibrational Spectra for Coordinated Thiocyanate Ion in Acetonitrile

    NASA Astrophysics Data System (ADS)

    Mikhailov, G. P.

    2016-07-01

    The impact of the association of lithium cation with NCS- ion in acetonitrile on the vibrational spectrum was studied by the density-functional method in the B3LYP/6-31+G(d,p) approximation. The best agreement between experimental and calculated ionic association data was achieved taking into account the nonspecific solvation, oversolvation, and solubility of ionic complexes within the discrete-continuum model. The microstructures of the thiocyanate ion in a contact ion pair with lithium cation and ion-pair dimer and trimer in acetonitrile were established.

  6. Rotor blade-vortex interaction noise reduction and vibration using higher harmonic control

    NASA Technical Reports Server (NTRS)

    Brooks, Thomas F.; Booth, Earl R., Jr.

    1990-01-01

    The use of higher harmonic control (HHC) of blade pitch to reduce blade-vortex interaction (BVI) noise is examined by means of a rotor acoustic test. A dynamically scaled, four-bladed, articulated rotor model was tested in a heavy gas (Freon-12) medium. Acoustic and vibration measurements were made for a large range of matched flight conditions where prescribed (open loop) HHC pitch schedules were superimposed on the normal (baseline) collective and cyclic trim pitch. A novel sound power measurement technique was developed to take advantage of the reverberance in the hard walled tunnel. Quantitative sound power results are presented for a 4/rev (4P) collective pitch HHC. By comparing the results using 4P HHC to corresponding baseline (no HHC) conditions, significant midfrequency noise reductions of 5-6 dB are found for low-speed descent conditions where BVI is most intense. For other flight conditions, noise is found to increase with the use of HHC. LF loading noise, as well as fixed and rotating frame vibration levels, show increased levels.

  7. Relationship between dipole moments and harmonic vibrational frequencies in diatomic molecules.

    PubMed

    Hou, Shilin; Bernath, Peter F

    2015-02-26

    Electric dipole moments and harmonic vibrational frequencies are two of the most important molecular properties in many fields of chemistry and physics. With the aid of classical physics, an empirical relationship between them was obtained for diatomic molecules as μd = kq(2)/(ReμAωe(2))(1/2), where k is a constant and μd, q, Re, μA, and ωe are the dipole moment, atomic charge, equilibrium bond length, reduced mass, and equilibrium vibrational frequency, respectively. This relation also provides the atomic charge q as a function of molecular dipole moment. Comparisons with over 60 molecules were made to test this relationship. For typical ionic molecules such as the alkali halides, the predicted dipole moments are in good agreement with the observed data assuming the atomic charges are 1 e. For general polar molecules, the estimated atomic charges obtained from the electric dipole moments are in good agreement with ab initio results for natural bond orbital and/or Mulliken populations.

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

    PubMed

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

    2016-01-01

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

  9. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

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

    NASA Technical Reports Server (NTRS)

    Jarzembski, Maurice A.; Srivastava, Vandana

    1999-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Tennyson, Jonathan

    2016-09-01

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

  13. 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

  14. Influence on isotope effect calculations of the method of obtaining force constants from vibrational data

    SciTech Connect

    Goodson, D.Z.; Sarpal, S.K.; Bopp, P.; Wolfsberg, M.

    1982-01-01

    Reduced isotopic partition function ratios (s/sub 2//s/sub 1/)f are employed in the calculation of isotope effects on thermodynamic equilibrium constrants. The quadratic force constants of the molecular force field are needed to evaluate (s/sub 2//s/sub 1/)f. Often these force constants are directly deduced from observed fundamentals in vibrational spectra and the (s/sub 2//s/sub 1/)f values so obtained are labeled (ANHARM). In a theroretically more valid procedure that is more difficult, one corrects observed fundamentals for anharmonicity on the basis of observed overtone and combination bands and then deduces force constants from these observed harmonic frequencies. The (s/sub 2//s/sub 1/)f values obtained from these force constants are labeled (HARM). (HARM) values and (ANHARM) values are evaluated and the isotope effects calculated with these values are discussed. It is concluded that the consistent use of (ANHARM) values in such calculations is a valid procedure.

  15. Calculated vibrational states of ozone up to dissociation

    NASA Astrophysics Data System (ADS)

    Ndengué, Steve; Dawes, Richard; Wang, Xiao-Gang; Carrington, Tucker; Sun, Zhigang; Guo, Hua

    2016-02-01

    A new accurate global potential energy surface for the ground electronic state of ozone [R. Dawes et al., J. Chem. Phys. 139, 201103 (2013)] was published fairly recently. The topography near dissociation differs significantly from previous surfaces, without spurious submerged reefs and corresponding van der Waals wells. This has enabled significantly improved descriptions of scattering processes, capturing the negative temperature dependence and large kinetic isotope effects in exchange reaction rates. The exchange reactivity was found to depend on the character of near-threshold resonances and their overlap with reactant and product wavefunctions, which in turn are sensitive to the potential. Here we present global "three-well" calculations of all bound vibrational states of three isotopic combinations of ozone (48O3, 16O218O, 16O217O) for J = 0 and J = 1 with a focus on the character and density of highly excited states and discuss their impact on the ozone isotopic anomaly. The calculations were done using a parallel symmetry-adapted Lanczos method with the RV3 code. Some comparisons were made with results obtained with the improved relaxation method implemented in the Heidelberg multi-configuration time-dependent Hartree code.

  16. Calculated vibrational states of ozone up to dissociation.

    PubMed

    Ndengué, Steve; Dawes, Richard; Wang, Xiao-Gang; Carrington, Tucker; Sun, Zhigang; Guo, Hua

    2016-02-21

    A new accurate global potential energy surface for the ground electronic state of ozone [R. Dawes et al., J. Chem. Phys. 139, 201103 (2013)] was published fairly recently. The topography near dissociation differs significantly from previous surfaces, without spurious submerged reefs and corresponding van der Waals wells. This has enabled significantly improved descriptions of scattering processes, capturing the negative temperature dependence and large kinetic isotope effects in exchange reaction rates. The exchange reactivity was found to depend on the character of near-threshold resonances and their overlap with reactant and product wavefunctions, which in turn are sensitive to the potential. Here we present global "three-well" calculations of all bound vibrational states of three isotopic combinations of ozone ((48)O3, (16)O2 (18)O, (16)O2 (17)O) for J = 0 and J = 1 with a focus on the character and density of highly excited states and discuss their impact on the ozone isotopic anomaly. The calculations were done using a parallel symmetry-adapted Lanczos method with the RV3 code. Some comparisons were made with results obtained with the improved relaxation method implemented in the Heidelberg multi-configuration time-dependent Hartree code.

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

    PubMed

    Kongsted, Jacob; Christiansen, Ove

    2006-09-28

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

  18. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-09-01

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

  20. Calculation of harmonic generation during the multiphoton ionization of the hydrogen atom

    SciTech Connect

    DeVries, P.L. )

    1990-04-01

    The response of a hydrogen atom to an intense nonresonant laser field is investigated by direct numerical solution of the time-dependent Schroedinger equation. This calculation is nonperturbative and does not involve the eigenstates of the field-free atom. An ionization rate for three-photon ionization is calculated and found to be in excellent agreement with previous values. The time-dependent electric dipole moment is calculated; its Fourier transform yields the spectrum of scattered light. Odd-order harmonic peaks through at least the 25th order are present in the spectrum.

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

    PubMed

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

    2015-05-01

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

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

    NASA Astrophysics Data System (ADS)

    Bačić, Z.

    1991-09-01

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

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

    NASA Astrophysics Data System (ADS)

    Petrenko, Taras; Rauhut, Guntram

    2015-12-01

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

  4. Mixed quartic-harmonic oscillators: a study of the ring puckering vibration of a cyclic amino acid dimer

    NASA Astrophysics Data System (ADS)

    Withnall, Robert; Andrews, David L.; Mendham, Andrew P.; Chowdhry, Babur Z.

    2001-10-01

    A band at ca. 150 cm-1 in the far infrared spectrum of diketopiperazine (DKP) is assigned to a ring puckering vibration. The multiplet structure reported for this band in the low temperature (77 K) far IR spectrum can be interpreted if the vibration is assumed to have quartic character. By means of Rayleigh-Schrodinger perturbation theory, a new vibrational selection rule, (Delta) n equals +/- 1, +/- 3, has been derived for mixed quartic-quadratic vibrations in the near harmonic region for the case of zero electrical anharmonicity. Assignments of the multiplet components have been made in the light of this vibrational selection rule. A two-parameter potential energy function of the ring puckering coordinate has been derived for the DKP molecule. This has enabled a value of ca. 355 cm-1 to be estimated for the energy barrier to interconversion of enantiomeric boat forms of DKP. The 0 - 1 transition has been estimated to have a wavenumber value of 0.033 cm-1 (1 GHz) in excellent agreement with the value of approximately 1 GHz obtained from a gas phase microwave spectroscopic study.

  5. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-02-01

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

  7. Dynamical calculation of third-harmonic generation in a semiconductor quantum well

    NASA Astrophysics Data System (ADS)

    Guazzotti, Stefano; Pusch, Andreas; Reiter, Doris E.; Hess, Ortwin

    2016-09-01

    Nonlinear phenomena in optically excited semiconductor structures are of high interest. Here we develop a model capable of studying the dynamics of the photoexcited carriers, including Coulomb interaction on a Hartree-Fock level, on the same footing as the dynamics of the light field impinging on an arbitrary photonic structure. Applying this method to calculate the third-harmonic generation in a semiconductor quantum well embedded in a Bragg mirror structure, we find that the power-law exponent of the intensity dependence of the third-harmonic generation depends on the frequency of the exciting pulse. Off-resonant pulses follow the expected cubic dependence, while the exponent is smaller for resonant pulses due to saturation effects in the induced carrier density. Our study provides a detailed understanding of the carrier and light field dynamics during nonlinear processes.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    SciTech Connect

    Tang, Xiaoli; Dong, Jianjun

    2009-06-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1982-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Pakos, Wojciech

    2015-09-01

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

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

    NASA Astrophysics Data System (ADS)

    Balachandran, V.; Parimala, K.

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    PubMed

    Wang, Liang; Liu, Weimin; Fang, Chong

    2015-07-14

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

  15. 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

  16. Vibrationally and rotationally nonadiabatic calculations on H3+ using coordinate-dependent vibrational and rotational masses

    NASA Astrophysics Data System (ADS)

    Diniz, Leonardo G.; Mohallem, José Rachid; Alijah, Alexander; Pavanello, Michele; Adamowicz, Ludwik; Polyansky, Oleg L.; Tennyson, Jonathan

    2013-09-01

    Using the core-mass approach, we have generated a vibrational-mass surface for the triatomic H3+. The coordinate-dependent masses account for the off-resonance nonadiabatic coupling and permit a very accurate determination of the rovibrational states using a single potential energy surface. The new, high-precision measurements of 12 rovibrational transitions in the ν2 bending fundamental of H3+ by Wu [Phys. Rev. A1050-294710.1103/PhysRevA.88.032507 88, 032507 (2013)] are used to scale this surface empirically and to derive state-dependent vibrational and rotational masses that reproduce the experimental transition energies to 10-3cm-1. Rotational term values for J≤10 are presented for the two lowest vibrational states and equivalent transitions in D3+ considered.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    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 1H and 13C nuclear magnetic resonance (NMR) chemical shift of the molecules are calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results.

  18. Self-Consistent Calculation of Half-Harmonics Emission Generated by the Two-Plasmon-Decay Instability

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

    Half-harmonics emission can be used as an effective diagnostic tool for the two-plasmon-decay (TPD) instability. However, interpretation of the half-harmonics spectrum is difficult because of its complicated generation mechanism. We have developed a code that can calculate half-harmonics emission self-consistently with the TPD instability. The results would be useful to interpret experimental data and help design experiments. This material is based upon work supported by the Department of Energy National Nuclear Security Administration under Award Number DE-NA0001944.

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

    PubMed

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

    2014-08-14

    The molecular structure of 2-(tert-butoxycarbonyl (Boc) -amino)-5-bromopyridine (BABP) was optimized by the DFT/B3LYP method with 6-311G (d,p), 6-311++G (d,p) and cc-pVTZ basis sets using the Gaussian 09 program. The most stable optimized structure of the molecule was predicted by the DFT/B3LYP method with cc-pVTZ basis set. The vibrational frequencies, Mulliken atomic charge distribution, frontier molecular orbitals and thermodynamical parameters were calculated. These calculations were done at the ground state energy level of BABP without applying any constraint on the potential energy surface. The vibrational spectra were experimentally recorded using Fourier Transform-Infrared (FT-IR) and micro-Raman spectrometer. The computed vibrational frequencies were scaled by scale factors to yield a good agreement with observed experimental vibrational frequencies. The complete theoretically calculated and experimentally observed vibrational frequencies were assigned on the basis of Potential Energy Distribution (PED) calculation using the VEDA 4.0 program. The vibrational modes assignments were performed by using the animation option of GaussView 05 graphical interface for Gaussian program. The Mulliken atomic charge distribution was calculated for BABP molecule. The molecular reactivity and stability of BABP were also studied by frontier molecular orbitals (FMOs) analysis. PMID:24727165

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1984-01-01

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

  2. 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.

  3. Structures and vibrational spectra of pinacol.. 1. Infrared and matrix infrared spectra of monomeric pinacol. Ab initio calculations on conformers and vibrational frequencies

    NASA Astrophysics Data System (ADS)

    Dahlqvist, Martti; Hotokka, Matti; Räsänen, Markku

    1998-04-01

    -temperature argon matrix. This is due to the high energy barrier to internal rotation around the central C-C bond as demonstrated by ab initio calculations. Assignments of the vibrational bands were made with the aid of computer animations of the ab initio calculated harmonic vibrations, common group frequencies, and analogy conclusions from related compounds. The deuterium derivatives [(CD 3) 2C(OH)C(OH)(CD 3) 2 and (CH 3) 2C(OD)C(OD)(CH 3) 2] of pinacol were also utilized even though their spectra were recorded only in the condensed phases.

  4. Nonlinear vibrational excitations in molecular crystals molecular mechanics calculations

    NASA Astrophysics Data System (ADS)

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

    1992-03-01

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

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

    SciTech Connect

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

    2009-11-15

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

  6. 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

  7. 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

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-09-01

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

  10. 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.

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

    SciTech Connect

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

    2007-08-15

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

  12. 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.

  13. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    NASA Astrophysics Data System (ADS)

    Moutinho, Carlos

    2015-05-01

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

  16. Calculated vibrational properties of pigments in protein binding sites.

    PubMed

    Lamichhane, Hari Prasad; Hastings, Gary

    2011-06-28

    FTIR difference spectroscopy is widely used to probe molecular bonding interactions of protein-bound electron transfer cofactors. The technique is particularly attractive because it provides information on both neutral and radical cofactor states. Such dual information is not easily obtainable using other techniques. Although FTIR difference spectroscopy has been used to study cofactors in biological protein complexes, in nearly all cases interpretation of the spectra has been purely qualitative. Virtually no computational work has been undertaken in an attempt to model the spectra. To address this problem we have developed the use of ONIOM (our own N-layered integrated molecular Orbital + Molecular mechanics package) (quantum mechanical:molecular mechanics) methods to calculate FTIR difference spectra associated with protein-bound cofactors. As a specific example showing the utility of the approach we have calculated isotope edited FTIR difference spectra associated with unlabeled and labeled ubiquinones in the Q(A) binding site in Rhodobacter sphaeroides photosynthetic reaction centers. The calculated spectra are in remarkable agreement with experiment. Such agreement cannot be obtained by considering ubiquinone molecules in the gas phase or in solution. A calculation including the protein environment is required. The ONIOM calculated spectra agree well with experiment but indicate a very different interpretation of the experimental data compared to that proposed previously. In particular the calculations do not predict that one of the carbonyl groups of Q(A) is very strongly hydrogen bonded. We show that a computational-based interpretation of FTIR difference spectra associated with protein-bound cofactors is now possible. This approach will be applicable to FTIR studies of many cofactor-containing proteins.

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

    PubMed

    Baudry, Matthieu; Micheau, Philippe; Berry, Alain

    2006-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    SciTech Connect

    Josef, J.A.

    1997-12-01

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

  20. Pyridine N-oxide/trichloroacetic acid complex in acetonitrile: FTIR spectra, anharmonic calculations and computations of 1-3D potential surfaces of O-H vibrations.

    PubMed

    Pitsevich, G; Malevich, A; Doroshenko, I; Kozlovskaya, E; Pogorelov, V; Sablinskas, V; Balevicius, V

    2014-01-01

    FTIR spectra of pyridine N-oxide and trichloroacetic acid H-bonded complex in acetonitrile were studied at 20 and 50°C. The calculations of equilibrium configurations of the complex and their IR spectra in harmonic- and anharmonic approximations were carried out at the level of B3LYP/cc-pVTZ/PCM. However both approximations turned out to be incompetent determining the frequency of the O-Н stretching vibration. In order to reveal the causes of essential discrepancies between calculated and experimental data one-, two- and three-dimensional potential energy surfaces (PES) of the O-H…O bridge proton motion in the frame of fixed other atoms in the complex were calculated. The frequencies of O-H…O stretching and bending vibrations were calculated by numerical solution of the Schrödinger equation. It is shown that only the approach of proton motion on the 3D PES allows obtaining a good agreement between the calculated and the experimental values of the frequencies of the О-Н stretching vibrations. PMID:24373980

  1. 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.

  2. 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.

  3. 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.

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

    PubMed

    Keçeli, Murat; Hirata, So; Yagi, Kiyoshi

    2010-07-21

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

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

    NASA Astrophysics Data System (ADS)

    Ramalingam, S.; Periandy, S.

    2011-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

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

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

    PubMed

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

    2015-05-15

    The FT-IR, FT-Raman and UV-Vis spectra of the Schiff base compound (E)-N'-(4-methoxybenzylidene) benzohydrazide (MBBH) have been recorded and analyzed. The optimized geometrical parameters were calculated. The complete vibrational assignments were performed on the basis of TED of the vibrational modes, calculated with the help of SQM method. NBO analysis has been carried out to explore the hyperconjugative interactions and their second order stabilization energy within the molecule. The molecular orbitals (MO's) and its energy gap were studied. The first order hyperpolarizability (β0) and related properties (β, α0, Δα) of MBBH are also calculated. All theoretical calculations were performed on the basis of B3LYP/6-311++G(d,p) level of theory. PMID:25733250

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

    NASA Astrophysics Data System (ADS)

    Ishida, Kazuhiro

    1999-09-01

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

  9. 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/.

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

    NASA Astrophysics Data System (ADS)

    Panek, Paweł T.; Jacob, Christoph R.

    2016-04-01

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

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

    PubMed

    Panek, Paweł T; Jacob, Christoph R

    2016-04-28

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

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

    SciTech Connect

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

    2015-12-28

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

  15. 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.

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

    SciTech Connect

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

    2015-05-28

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

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

    PubMed

    Suresh, S; Gunasekaran, S; Srinivasan, S

    2014-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

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

  19. Vibrational spectra, DFT calculations, conformational stabilities and assignments of the fundamentals of the 1-butylpiperazine

    NASA Astrophysics Data System (ADS)

    Bağlayan, Özge; Kaya, Mehmet Fatih; Güneş, Esma; Şenyel, Mustafa

    2016-10-01

    FT-IR and FT-Raman spectra of 1-butylpiperazine (1bpa) were experimentally recorded in the region of 4000-10 cm-1 and 4000-100 cm-1, respectively. The optimized geometric parameters, conformational equilibria, normal mode frequencies and corresponding vibrational assignments of 1bpa (C8H18N2) are theoretically examined by means of B3LYP hybrid density functional theory (DFT) method together with 6-31++G(d,p) basis set. Also, reliable conformational investigation and vibrational assignments have been performed by the potential energy surface (PES) and potential energy distribution (PED) analysis, respectively. Calculations are made for four possible conformations. According to the experimental and theoretical data, density functional B3LYP method provides reliable results for predicting vibrational wavenumbers and equatorial-equatorial conformer is considered to be the most stable form of 1bpa.

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

    SciTech Connect

    Josef, J.A.

    1996-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2008-10-01

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

  2. 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

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

    NASA Astrophysics Data System (ADS)

    Hansen, K.

    2008-05-01

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

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

    PubMed

    Aieta, Chiara; Gabas, Fabio; Ceotto, Michele

    2016-07-14

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

  5. Thermodynamic functions of liquid water calculated from the temperature evolution of the vibration spectrum contour.

    PubMed

    Efimov, Yu Ya; Naberukhin, Yu I

    2005-06-01

    Configurational contributions of hydrogen bonds to thermodynamic properties of water (internal energy, entropy, and heat capacity) are calculated on the basis of statistical distributions of frequencies of the OH vibrations of liquid water, calculated earlier from the experimental Raman spectra in frameworks of the fluctuation theory of hydrogen bonding. Distributions of the energy of hydrogen bonds are determined. It is shown by comparison with computer experiments that previously established dependence of energy on frequency, E(nu), must be considered in this formalism as the effective energy of hydrogen bonding averaged over those configurations of hydrogen bridge O-H...O which lead to the given frequency nu in the vibrational spectrum. Contribution of van der Waals interactions not affecting the frequency shift to heat capacity is evaluated.

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

    SciTech Connect

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

    2014-01-21

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

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

    PubMed

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

    2015-06-15

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

  8. 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 α, and hyperpolarizability β using the above mentioned basis sets. The molecular properties such as ionization potential, electronegativity, chemical potential, electrophilicity have been deduced from HOMO-LUMO analysis employing the same basis sets. A detailed interpretation of the infrared and Raman spectra of title molecules were reported. UV spectrum was measured in different solvent. The energy and oscillator strength are calculated by Time Dependant Density Functional Theory (TD-DFT) results. The calculated HOMO and LUMO energies also confirm that charge transfer occurs within the molecule. The complete assignments were performed on the basis of the potential energy distribution (PED) of vibrational modes, calculated with scaled quantum mechanics (SQM) method. Finally the theoretical FT-IR, FT-Raman, and UV spectra of the title molecules have also been constructed.

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

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

    PubMed

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

    2016-01-01

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

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

    PubMed

    Rashev, Svetoslav; Moule, David C

    2015-04-01

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

  12. Extraction of the vibrational dynamics from the spectra of highly excited molecules and periodic orbit quantization by harmonic inversion

    NASA Astrophysics Data System (ADS)

    Atilgan, Erdinc

    Part I. The effective spectroscopic Hamiltonian fitted to experiment by Troellsch and Temps {A. Troellsch, F. Temps Zeitschrift fuer Physikalische Chemie 215, 207, (2001)} and describing high vibrational excitation to bound and resonant states, is used in conjunction with methods of nonlinear classical dynamics and semiclassical mechanics to extract for all the observed highly excited resonance levels in Polyad 8, the molecular motions upon which they are quantized. Two types of interlaced dynamically distinct ladders of states are revealed. The rungs of these ladders intersperse making the spectra complex. The resonant 2:2:1 frequency ratio of the DC, CO stretches and the bend respectively is what causes the complexity and is what caused past attempts at interpretation to be at best incomplete. All states are assigned with physically meaningful quantum numbers corresponding to quasiconserved quantities. Most interestingly it is pointed out that much of the information and assignment can be done without any calculations at all, using only the qualitative ideas from nonlinear, semiclassical and quantum mechanics along with the information supplied by the experimentalist. Part II. In systems with few degrees of freedom modern quantum calculations are, in general, numerically more efficient than semiclassical methods. However, this situation can be reversed with increasing dimension of the problem. For a three-dimensional system, viz. the hyperbolic four-sphere scattering system, we demonstrate the superiority of semiclassical versus quantum calculations. Semiclassical resonances can easily be obtained even in energy regions which are unattainable with the currently available quantum techniques.

  13. 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.

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

    NASA Astrophysics Data System (ADS)

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

    1990-09-01

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

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

    NASA Astrophysics Data System (ADS)

    Yang, Yue; Gao, Hongwei

    2012-01-01

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

  16. 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.

  17. 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.

  18. 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

  19. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-05-01

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

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

    PubMed

    Davis, Sergio; Gutiérrez, Gonzalo

    2011-12-14

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

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

    NASA Astrophysics Data System (ADS)

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

    1986-04-01

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

  3. 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.

  4. 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.

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

    NASA Astrophysics Data System (ADS)

    Salvi, Jonathan; Giaralis, Agathoklis

    2016-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

  7. Quantum Mechanical Calculations to Interpret Vibrational and NMR Spectra of Organic Compounds Adsorbed onto Mineral Surfaces

    NASA Astrophysics Data System (ADS)

    Kubicki, J. D.

    2008-12-01

    Vibrational (e.g., ATR FTIR and Raman) and nuclear magnetic resonance (NMR) spectroscopies provide excellent information on the bonding and atomic environment of adsorbed organic compounds. However, interpretation of observed spectra collected for organic compounds adsorbed onto mineral surfaces can be complicated by the lack of comparable analogs of known structure and uncertainties about the mineral surface structure. Quantum mechanical calculations provide a method for testing interpretations of observed spectra because models can be built to mimic predicted structures, and the results are independent of experimental parameters (i.e., no fitting to data is necessary). In this talk, methodologies for modeling vibrational frequencies and NMR chemical shifts of adsorbed organic compounds are discussed. Examples included salicylic acid (as an analog for important binding functional groups in humic acids) adsorbed onto aluminum oxides, organic phosphoryl compounds that represent herbicides and bacterial extracellular polymeric substances (EPS), and ofloxacin (a common agricultural antibiotic). The combination of the ability of quantum mechanical calculations to predict structures, spectroscopic parameters and energetics of adsorption with experimental data on these same properties allows for more definitive construction of surface complex models.

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

    SciTech Connect

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

    2013-07-14

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

  9. First-principles calculation of geometry and anharmonic vibrational spectra of thioformamide and thioformamide-d2.

    PubMed

    Kowal, Andrzej T

    2006-01-01

    The equilibrium geometry of thioformamide HCSNH2 has been determined at the MP2 and CCSD(T) electron correlation levels under C(s) symmetry constraints using triple-zeta basis sets up to cc-pVTZ. All optimized planar structures are true minima on the potential-energy surface and are characterized by the C-N bond length within 1.353-1.343 A, C-S distances of 1.656-1.628 A, and NCS angle between 125.7 degrees and 125.9 degrees . The wave number of the NH2 out-of-plane wagging mode computed in the harmonic approximation shows stronger dependence on the basis set rather than the electron correlation level and varies from 85.9 cm(-1) at CCSD(T)cc-pVDZ level to 335 cm(-1) at MP2/aug-cc-pVTZ level. Anharmonic vibrational spectra of HCSNH2 and HCSND2 have been determined directly from the potential-energy surfaces computed at MP2 level in triple-zeta valence (TZV)(2df,2p) and TZV+(2df,2p) basis sets using vibrational self-consistent-field (VSCF) and correlation-corrected VSCF (CC-VSCF) methods. CC-VSCF wave numbers of fundamental, first overtone, and most intense combination transitions are reported for thioformamide and those of fundamentals for thioformamide-d2. The NH2 wagging (nu12) mode is strongly anharmonic and its fundamentals have been computed at 406.9 cm(-1) [TZV(2df,2p)] and 399.5 cm(-1) [TZV+(2df,2p)], which is remarkably close to the experimental energy of 393 cm(-1). Anharmonically computed fundamentals of this mode in thioformamide-d2, 299.7 cm(-1) [TZV(2df,2p)] and 299.6 cm(-1) [TZV+(2df,2p)], are only approximately 7 cm(-1) higher than the transition energy (293 cm(-1)) observed in the gas phase spectrum of HCSND2. The first overtone of the NH2 wagging mode of thioformamide (nu12 (02)) has been calculated by CC-VSCF procedure at 830.8 cm(-1) [TZV(2df,2p)] and 880.0 cm(-1) [TZV+(2df,2p)], which implies "negative" (nu12 (02)>2*nu12 (01)) anharmonicity of this mode.

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

    PubMed

    Mielke, Steven L; Truhlar, Donald G

    2009-04-23

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

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

    PubMed

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

    2015-02-01

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

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

    PubMed

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

    2014-09-14

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

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

    NASA Astrophysics Data System (ADS)

    Radhika Devi, V.; Shrivastava, Keshav N.

    2012-09-01

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

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

    PubMed

    Radhika Devi, V; Shrivastava, Keshav N

    2012-09-01

    We have calculated the vibrational frequencies of clusters of Ga and As atoms from the first principles using the density-functional theory (DFT) method and the local-density approximation (LDA). We find that the calculated value of 286.2 cm(-1) for a linear cluster of Ga(2)As(2) is very near the experimental value of 292 ± 4 cm(-1). The calculated value of 289.4 cm(-1) for Ga(2)As(6) (dumb bell) cluster is indeed very near the experimental value. There are strong phonon correlations so that the cluster frequency is within the dispersion relation of the crystal LO value. There is a weak line in the experimental Raman spectrum at 268 cm(-1) which is very near the value of 267.3 cm(-1) calculated for the Ga(2)As (triangular) cluster. The weak lines corresponding to the linear bonds provide the strength to the amorphous samples. There are clusters of atoms in the glassy state of GaAs.

  15. 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.

  16. The spectrum of vibration modes in soft opals.

    PubMed

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

    2005-09-22

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

  17. 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.

  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 α, and hyperpolarizability β using the above mentioned basis sets. The molecular properties such as ionization potential, electronegativity, chemical potential, electrophilicity have been deduced from HOMO-LUMO analysis employing the same basis sets. A detailed interpretation of the infrared and Raman spectra of title molecules were reported. UV spectrum was measured in different solvent. The energy and oscillator strength are calculated by Time Dependant Density Functional Theory (TD-DFT) results. The calculated HOMO and LUMO energies also confirm that charge transfer occurs within the molecule. The complete assignments were performed on the basis of the potential energy distribution (PED) of vibrational modes, calculated with scaled quantum mechanics (SQM) method. Finally the theoretical FT-IR, FT-Raman, and UV spectra of the title molecules have also been constructed. PMID:24892532

  19. Orbital-optimized coupled-electron pair theory and its analytic gradients: Accurate equilibrium geometries, harmonic vibrational frequencies, and hydrogen transfer reactions

    NASA Astrophysics Data System (ADS)

    Bozkaya, Uǧur; Sherrill, C. David

    2013-08-01

    Orbital-optimized coupled-electron pair theory [or simply "optimized CEPA(0)," OCEPA(0), for short] and its analytic energy gradients are presented. For variational optimization of the molecular orbitals for the OCEPA(0) method, a Lagrangian-based approach is used along with an orbital direct inversion of the iterative subspace algorithm. The cost of the method is comparable to that of CCSD [O(N6) scaling] for energy computations. However, for analytic gradient computations the OCEPA(0) method is only half as expensive as CCSD since there is no need to solve the λ2-amplitude equation for OCEPA(0). The performance of the OCEPA(0) method is compared with that of the canonical MP2, CEPA(0), CCSD, and CCSD(T) methods, for equilibrium geometries, harmonic vibrational frequencies, and hydrogen transfer reactions between radicals. For bond lengths of both closed and open-shell molecules, the OCEPA(0) method improves upon CEPA(0) and CCSD by 25%-43% and 38%-53%, respectively, with Dunning's cc-pCVQZ basis set. Especially for the open-shell test set, the performance of OCEPA(0) is comparable with that of CCSD(T) (ΔR is 0.0003 Å on average). For harmonic vibrational frequencies of closed-shell molecules, the OCEPA(0) method again outperforms CEPA(0) and CCSD by 33%-79% and 53%-79%, respectively. For harmonic vibrational frequencies of open-shell molecules, the mean absolute error (MAE) of the OCEPA(0) method (39 cm-1) is fortuitously even better than that of CCSD(T) (50 cm-1), while the MAEs of CEPA(0) (184 cm-1) and CCSD (84 cm-1) are considerably higher. For complete basis set estimates of hydrogen transfer reaction energies, the OCEPA(0) method again exhibits a substantially better performance than CEPA(0), providing a mean absolute error of 0.7 kcal mol-1, which is more than 6 times lower than that of CEPA(0) (4.6 kcal mol-1), and comparing to MP2 (7.7 kcal mol-1) there is a more than 10-fold reduction in errors. Whereas the MAE for the CCSD method is only 0.1 kcal

  20. Orbital-optimized coupled-electron pair theory and its analytic gradients: accurate equilibrium geometries, harmonic vibrational frequencies, and hydrogen transfer reactions.

    PubMed

    Bozkaya, Uğur; Sherrill, C David

    2013-08-01

    Orbital-optimized coupled-electron pair theory [or simply "optimized CEPA(0)," OCEPA(0), for short] and its analytic energy gradients are presented. For variational optimization of the molecular orbitals for the OCEPA(0) method, a Lagrangian-based approach is used along with an orbital direct inversion of the iterative subspace algorithm. The cost of the method is comparable to that of CCSD [O(N(6)) scaling] for energy computations. However, for analytic gradient computations the OCEPA(0) method is only half as expensive as CCSD since there is no need to solve the λ2-amplitude equation for OCEPA(0). The performance of the OCEPA(0) method is compared with that of the canonical MP2, CEPA(0), CCSD, and CCSD(T) methods, for equilibrium geometries, harmonic vibrational frequencies, and hydrogen transfer reactions between radicals. For bond lengths of both closed and open-shell molecules, the OCEPA(0) method improves upon CEPA(0) and CCSD by 25%-43% and 38%-53%, respectively, with Dunning's cc-pCVQZ basis set. Especially for the open-shell test set, the performance of OCEPA(0) is comparable with that of CCSD(T) (ΔR is 0.0003 Å on average). For harmonic vibrational frequencies of closed-shell molecules, the OCEPA(0) method again outperforms CEPA(0) and CCSD by 33%-79% and 53%-79%, respectively. For harmonic vibrational frequencies of open-shell molecules, the mean absolute error (MAE) of the OCEPA(0) method (39 cm(-1)) is fortuitously even better than that of CCSD(T) (50 cm(-1)), while the MAEs of CEPA(0) (184 cm(-1)) and CCSD (84 cm(-1)) are considerably higher. For complete basis set estimates of hydrogen transfer reaction energies, the OCEPA(0) method again exhibits a substantially better performance than CEPA(0), providing a mean absolute error of 0.7 kcal mol(-1), which is more than 6 times lower than that of CEPA(0) (4.6 kcal mol(-1)), and comparing to MP2 (7.7 kcal mol(-1)) there is a more than 10-fold reduction in errors. Whereas the MAE for the CCSD method is

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

    NASA Astrophysics Data System (ADS)

    Ishida, Kazuhiro

    1998-07-01

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

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

    SciTech Connect

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

    1995-10-01

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

  3. Elastic properties of self-supported circular thin copper films calculated from equilibrium thermal vibration.

    PubMed

    Chang, Hsi-Hung; Hwang, Chi-Chuan; Shen, Yue-Ling

    2011-06-01

    Thermomechanical vibration of ultrathin, self-supported copper films due to thermal fluctuations is studied via the molecular dynamics simulation at room temperature. The elastodynamic theory with pre-stress is adopted to extract the physical properties of the films by comparing with the molecular dynamics data. The edge-clamped circular films consist of several atomic layers of fcc copper with the [100] direction normal to the film surface. From the time-history trajectories of atoms and their Fourier frequency spectrums, it was found that the fundamental resonant frequency non-monotonically varies with the film thickness due to the existence of residual stress in the film. Multiple resonant modes are adopted for modulus calculation and residual stress determination. The value of Young's modulus increases with increasing thickness of the film and the residual stress decreases with increasing thickness. Thicker films exhibit less residual stress, indicating the equilibrium distance between copper atoms changes with the film thickness.

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

    NASA Astrophysics Data System (ADS)

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

    2006-01-01

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

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

    PubMed

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

    2006-01-28

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

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

    PubMed

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

    2016-03-14

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

  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

  8. Combinatorial Vibration-Mode Assignment for the FTIR Spectrum of Crystalline Melamine: A Strategic Approach toward Theoretical IR Vibrational Calculations of Triazine-Based Compounds.

    PubMed

    Yuan, Xiaohong; Luo, Kun; Zhang, Keqin; He, Julong; Zhao, Yuanchun; Yu, Dongli

    2016-09-29

    Although polymeric graphitic carbon nitride (g-C3N4) has been widely studied as metal-free photocatalyst, the description of its structure still remains a great challenge. Fourier transform infrared (FTIR) spectroscopy can provide complementary structural information. In this paper, we reconsider the representative crystalline melamine and develop a strategic approach to theoretically calculate the IR vibrations of this triazine-based nitrogen-rich system. IR calculations were based on three different models: a single molecule, a 4-molecule unit cell, and a 32-molecule cluster, respectively. By this comparative study the contribution of the intermolecular weak interactions were elucidated in detail. An accurate and visualized description on the experimental FTIR spectrum has been further presented by a combinatorial vibration-mode assignment based on the calculated potential energy distribution of the 32-molecule cluster. The theoretical approach reported in this study opens the way to the facile and accurate assignment for IR vibrational modes of other complex triazine-based compounds, such as g-C3N4. PMID:27598419

  9. A comment on recent proposals for the calculation of vibration-rotation energies in more-than-three atom molecules

    NASA Astrophysics Data System (ADS)

    Chapuisat, Xavier; Belafhal, Abdelmajid; Nauts, André; Iung, Christophe

    In a recent paper (Molec. Phys. 1991, 73, 1183), Bramley et al. analysed the physical and mathematical context in which the vibrational rotational Hamiltonian operator for a molecule is expressed in terms of Euler angles for the rotation and internal curvilinear coordinates for the vibration. In the case of a generic tetra-atomic molecule, they derived a few rules which determine the choice of the basis functions, in order (i) to ensure continuity and single-valuedness of the eigenfunctions and (ii) to cancel out the singularities (infinite integrals) that unavoidably crop up in the matrix representation of the vibration-rotation kinetic energy operator. In another recent paper (Phys. Rev.A, 1992, 45, 6217), Chapuisat and lung considered the vibration-rotation of a polyatomic molecule as resulting from the rotational-vibrational motion of coupled relative vectors; with the help of a standard representation for the angular motion of each vector viewed in the moving frame resulting from the first two Euler rotations, i.e. for the whole molecule a direct product of spherical harmonics, they have shown that it is possible to get rid of the singularities and to derive, after completing the third Euler rotation, analytical expressions of the kinetic energy operator matrix elements in the usual bending-torsion-rotation basis. In implementing this approach, the rules derived for tetraatomics by Bramley et al. are confirmed and are next generalized to the case of the N-atom molecule. The restrictions to the direct product representation which must be explicitly taken into account are established on the basis of a purely physical analysis of the coupled vector motion.

  10. The molecular structures, vibrational spectroscopies (FT-IR and Raman) and quantum chemical calculations of n-alkyltrimethylammonium bromides

    NASA Astrophysics Data System (ADS)

    Gökce, Halil; Bahçeli, Semiha

    2013-11-01

    The FT-IR and micro-Raman spectra of three n-alkyltrimethylammonium bromides (dodecyltrimethylammonium bromide (DTAB), tetradecyltrimethylammonium bromide (TTAB) and hexadecyl(cetyl)trimethylammonium bromide (CTAB)) in powder form were recorded in the regions 4000-550 cm-1 and 3200-300 cm-1, respectively. The optimized geometries and vibrational frequencies of DTAB, TTAB and CTAB have been carried out with ab initio Hartree-Fock (HF) and density functional theory method B3LYP calculations with the 6-31 G (d, p) basis set in the ground state. The comparison of the observed fundamental vibrational frequencies and calculated results for the fundamental vibrational frequencies of DTAB, TTAB and CTAB indicate that the scaled B3LYP method is superior compared to the scaled HF method.

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

    NASA Astrophysics Data System (ADS)

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

    2008-11-01

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

  12. The vibrational spectrum and rotational constants of difluoroethyne FC 3/4 CF. Matrix and high resolution infrared studies and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Bürger, H.; Schneider, W.; Sommer, S.; Thiel, W.; Willner, H.

    1991-10-01

    Infrared spectra of the short-lived difluoroethyne molecule have been recorded in neon and argon matrices between 200 and 5000 cm-1. Fourier transform infrared spectra with a resolution of 0.004 cm-1 have been measured in the gas phase around 1350 cm-1 (ν3, ν2+ν4+ν5, hot bands) and 2150 cm-1 (ν2+ν3, ν1-ν5, hot bands). The high resolution study yields rotational parameters of the ground and all singly excited vibrational states. The interpretation of the experimental data has been guided by ab initio calculations at the SCF (self-consistent-field) level and the correlated MP2 level (Moller-Plesset second order perturbation theory) employing three different large basis sets. The theoretical calculations provide the SCF and MP2 harmonic fields as well as the SCF anharmonic force field of FCCF. The agreement between the available theoretical and experimental results is generally quite good, with the exception of the spectroscopic constants involving the trans-bending mode ν4 where more theoretical work is required. The combined use of theoretical and experimental information leads to an estimate of the equilibrium structure [D∞h, re(CC)=1.1865 Å, re(CF)=1.2832 Å] and to recommended ``best'' values for the wave numbers of all fundamental vibrations based on the matrix and high resolution infrared data and some ab initio anharmonicity constants. The present study demonstrates the advantages of a combined theoretical and experimental approach to the spectroscopy of short-lived molecules.

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

    PubMed

    Paulo, Pedro M R

    2010-03-21

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

  14. Method in calculating own vibration frequencies of open sections bars with thin walls

    NASA Astrophysics Data System (ADS)

    Mihuț, N.

    2016-08-01

    Dynamic stability of thin-walled bars of open sections, as well as the stability of elastic systems dynamics in general, is studying closely with their vibrations. This, because, areas of dynamics instability is around twice the frequency of free vibration of the bar or elastic system in all cases excitation parametric, on the one hand, and on the other hand matrices involved in the matrix equation of free vibration are matrices of matrix equation of dynamic stability. In this paper we settled differential equations of parametric vibrations of thin-walled straight bars open sections constant as a system with a triple infinity of second order differential equations, linear coefficients homogeneous and periodicals. In the end of work, by customizing differential equations of forced vibration parameters have been obtained differential equations of own vibration of bars with thin wall and open sections as a system with a triple infinity of differential equations of second order, linear, homogeneous with constant coefficients and, using it, the algebraic equation of own vibrations pulsations.

  15. 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.

  16. Franck-Condon transitions in a system with large-amplitude anharmonic vibrations coupled to a harmonic-oscillator bath: Application to the C 1s photoelectron spectrum of ethanol

    SciTech Connect

    Abu-samha, M.; Boerve, K. J.

    2006-10-15

    A vibrational adiabatic approach to Franck-Condon analysis is presented for systems with a few highly displaced oscillators coupled to a bath of harmonic oscillators. The model reduces the many-coupled-oscillator problem to few-body problems, albeit with corrections due to coupling to harmonic modes. The theory is applied with very good results to the carbon 1s photoelectron spectrum of ethanol, which is strongly influenced by change in conformation from gauche to anti when ethanol is ionized at the methyl site.

  17. Coupled calculation of vibrational frequencies and intensities. Part VI. IR and Raman spectra of crotonaldehyde, methacrolein and methyl-vinylketone

    NASA Astrophysics Data System (ADS)

    Oelichmann, H.-J.; Bougeard, D.; Schrader, B.

    1981-12-01

    The vibrational spectra of trans-crotonaldehyde, methacrolein and methylvinylketone have been reinvestigated and the bands assigned. Normal coordinate analyses of these molecules based on the given assignments have been carried out in the valence force field approximation. A transferable force field for α, β-unsaturated aldehydes and ketones was obtained leading to good agreement between observed and calculated frequencies. The relative cartesian displacements of the atoms given in the L matrices were used to compute the IR and Raman intensities of each mode by a modified CNDO/2 procedure. The intensity calculations confirm the assignments and support the calculated force constants.

  18. Vibrational spectroscopic studies and density functional theory calculations of speciation in the CO2-water system.

    PubMed

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

    2006-02-01

    Raman spectra of CO(2) dissolved in water and heavy water were measured at 22 degrees C, and the Fermi doublet of CO(2), normally at 1285.45 and 1388.15 cm(-1) in the gaseous state, revealed differences in normal water and heavy water, although no symmetry lowering of the hydrated CO(2) could be detected. Raman spectra of crystalline KHCO(3) and KDCO(3) were measured at 22 degrees C and compared with the infrared data from the literature. In these solids, (H(D)CO(3))(2)(2-) dimers exist and the spectra reveal strong intramolecular coupling. The vibrational data of the dimer (C(2h) symmetry) were compared with the values from density functional theory (DFT) calculations and the agreement is fair. Careful measurements were made of the Raman spectra of aqueous KHCO(3), and KDCO(3) solutions in D(2)O down to 50 cm(-1) and, in some cases, down to very low concentrations (> or =0.0026 mol/kg). In order to complement the spectroscopic assignments, infrared solution spectra were also measured. The vibrational spectra of HCO(3)(-)(aq) and DCO(3)(-)(D(2)O) were assigned, and the measured data compared well with data derived from DFT calculations. The symmetry for HCO(3)(-)(aq) is C(1), while the gas-phase structure of HCO(3)(-) possesses Cs symmetry. No dimers could be found in aqueous solutions, but at the highest KHCO(3) concentration (3.270 mol/kg) intermolecular coupling between HCO(3)(-)(aq) anions could be detected. KHCO(3) solutions do not dissolve congruently, and with increasing concentrations of the salt increasing amounts of carbonate could be detected. Raman and infrared spectra of aqueous Na(2) -, K(2) -, and Cs(2)CO(3) solutions in water and heavy water were measured down to 50 cm(-1) and in some cases down to extremely low concentrations (0.002 mol/kg) and up to the saturation state. For carbonate in aqueous solution a symmetry breaking of the D(3h) symmetry could be detected similar to the situation in aqueous nitrate solutions. Strong hydration of carbonate

  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. Communication: MULTIMODE calculations of low-lying vibrational states of NO3 using an adiabatic potential energy surface

    NASA Astrophysics Data System (ADS)

    Homayoon, Zahra; Bowman, Joel M.

    2014-10-01

    A semi-global, permutationally invariant potential energy surface for NO3 is constructed from a subset of roughly 5000 Multi-State CASPT2 calculations (MS-CAS(17e,13o)PT2/aug-cc-pVTZ) reported by Morokuma and co-workers [H. Xiao, S. Maeda, and K. Morokuma, J. Chem. Theory Comput. 8, 2600 (2012)]. The PES, with empirical adjustments to modify the energies of two fundamentals and a hot-band transition, is used in full-dimensional vibrational self-consistent field/virtual state configuration interaction calculations using the code MULTIMODE. Vibrational energies and assignments are given for the fundamentals and low-lying combination states, including two that have been the focus of some controversy. Energies of a number of overtone and combinations are shown to be in good agreement with experiment and previous calculations using a model vibronic Hamiltonian [C. S. Simmons, T. Ichino, and J. F. Stanton, J. Phys. Chem. Lett. 3, 1946 (2012)]. Notably, the fundamental v3 is calculated to be at 1099 cm-1 in accord with the prediction from the vibronic analysis, although roughly 30 cm-1 higher. The state at 1493 cm-1 is assigned as v3 + v4, which is also in agreement with the vibronic analysis and some experiments. Vibrational energies for 15NO3 are also presented and these are also in good agreement with experiment.

  1. The crystal structure, vibrational spectra, thermal behaviour and second harmonic generation of aminoguanidinium(1+) hydrogen L-tartrate monohydrate

    NASA Astrophysics Data System (ADS)

    Macháčková, Zorka; Němec, Ivan; Teubner, Karel; Němec, Petr; Vaněk, Přemysl; Mička, Zdeněk

    2007-04-01

    Aminoguanidinium(1+) hydrogen L-tartrate monohydrate was prepared by crystallisation from aqueous solution and X-ray structural analysis was carried out. The substance crystallises in the orthorhombic system in space group P2 12 12 1, a = 7.1380(2) Å, b = 9.9700(4) Å, c = 14.0790(6) Å, V = 1001.94(7) Å 3, Z = 4, R = 0.0271 for 2272 observed reflections. The crystal structure consists of a 3D framework formed by hydrogen tartrate anions and water molecules with incorporated aminoguanidinium(1+) cations connected by a system of hydrogen bonds. The FTIR and FT Raman spectra of natural and N,O-deuterated compounds were measured and discussed at laboratory temperature. DSC measurements were carried out in the temperature range from 95 to 380 K. A weak anomaly was observed at a temperature of 268 K. Quantitative measurements of second harmonic generation of powdered aminoguanidinium(1+) hydrogen tartrate monohydrate at 800 nm were performed relative to KDP and a relative efficiency of 14% was observed.

  2. Vibrational spectra, theoretical calculations, and two-dimensional potential energy surface for the ring-puckering vibrations of 2,4,7-trioxa[3.3.0]octane.

    PubMed

    Chun, Hye Jin; Meinander, Niklas; Villarreal, John R; Laane, Jaan

    2015-01-15

    2,4,7-Trioxa[3.3.0]octane (247TOO) is an unusual bicyclic molecule which can exist in four different conformational forms which are determined by the directions of the two ring- puckering motions. The vibrational assignments of 247TOO have been made based on its infrared and Raman spectra and theoretical density functional theory (DFT) calculations. The two ring-puckering motions (in-phase and out-of-phase) were observed in the Raman spectra of the liquid at 249 and 205 cm(-1) and these values correspond well to the DFT values of 247 and 198 cm(-1). Ab initio calculations were utilized to calculate the structures and conformational energies for the four energy minima and the barriers to interconversion and the data was utilized to generate a two-dimensional potential energy surface (PES) for the two ring-puckering motions. The resulting quantum state energies for this PES were then calculated in order to better understand the patterns that are produced when the PES has four energy minima at different energy values. The wave functions corresponding to the different quantum states were also calculated. The NMR spectrum of 247TOO showed the presence of the two lowest energy conformations, consistent with the results of the ab initio calculations. PMID:25514365

  3. Vibrational spectra, theoretical calculations, and two-dimensional potential energy surface for the ring-puckering vibrations of 2,4,7-trioxa[3.3.0]octane.

    PubMed

    Chun, Hye Jin; Meinander, Niklas; Villarreal, John R; Laane, Jaan

    2015-01-15

    2,4,7-Trioxa[3.3.0]octane (247TOO) is an unusual bicyclic molecule which can exist in four different conformational forms which are determined by the directions of the two ring- puckering motions. The vibrational assignments of 247TOO have been made based on its infrared and Raman spectra and theoretical density functional theory (DFT) calculations. The two ring-puckering motions (in-phase and out-of-phase) were observed in the Raman spectra of the liquid at 249 and 205 cm(-1) and these values correspond well to the DFT values of 247 and 198 cm(-1). Ab initio calculations were utilized to calculate the structures and conformational energies for the four energy minima and the barriers to interconversion and the data was utilized to generate a two-dimensional potential energy surface (PES) for the two ring-puckering motions. The resulting quantum state energies for this PES were then calculated in order to better understand the patterns that are produced when the PES has four energy minima at different energy values. The wave functions corresponding to the different quantum states were also calculated. The NMR spectrum of 247TOO showed the presence of the two lowest energy conformations, consistent with the results of the ab initio calculations.

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

    NASA Astrophysics Data System (ADS)

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

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  6. 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.

  7. Molecular structure, vibrational spectra, first hyperpolarizability and HOMO-LUMO analysis of p-acetylbenzonitrile using quantum chemical calculation

    NASA Astrophysics Data System (ADS)

    Nataraj, A.; Balachandran, V.; Karthick, T.

    2013-04-01

    The FT-IR and FT-Raman spectra of p-acetylbenzonitrile (p-ABN) are recorded in the solid phase. The fundamental vibrational frequencies, intensity of vibrational bands and the optimized geometrical parameters of the compound are evaluated using MP2 and DFT (B3PW91) methods with 6-31G basis set. The theoretical frequencies are scaled down and compared with experimental values which showed good agreement. Comparison of the simulated spectra with experimental spectra provides important information about ability of the hybrid computational method to describe the vibrational modes. The investigation of non-linear optical properties, the electric dipole moment μ, polarizability α, anisotropy of polarizability Δα, and molecular first hyperpolarizability β were computed. The linear polarizabilities and first hyperpolarizabilities of the studied molecule indicate that the molecule can be a candidate of non-linear optical material. The HOMO, LUMO, chemical hardness (η), chemical potential (μ), electrophilicity value (ω), total energy, and dipole moment are calculated by MP2 and DFT/B3PW91 using 6-31G basis set. The molecular electrostatic potential (MESP) is also calculated and corresponding graphs are drawn. Stability of the molecule arising from hyper conjugative interactions, charge delocalization has been analyzed using natural bond orbital analysis. Finally, some thermodynamic parameters are also calculated and discussed.

  8. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2008-11-01

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

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

    PubMed

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

    2015-06-15

    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. PMID:25766474

  11. 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.

  12. Calculation of vibrational frequencies of atoms adsorbed on metal surfaces: H, O, and S on Ni(100) and Ni(111) as examples

    SciTech Connect

    Black, J.E.; Bopp, P.; Luetzenkirchen, K.; Wolfsberg, M.

    1982-06-15

    We present vibrational frequencies calculated for H, O, and S atoms adsorbed on Ni(111) and Ni(100) surfaces. The calculations are done for a single atom adsorbed on nickel clusters, and also for a single atom and periodic arrangements of atoms on an infinite nickel substrate. We are able to indicate under what conditions a simple cluster calculation will yield vibrational frequencies suitable for comparison with experiment.

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

    PubMed

    Mielke, Steven L; Truhlar, Donald G

    2015-01-28

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

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

    PubMed

    Mielke, Steven L; Truhlar, Donald G

    2015-01-28

    We present an improved version of our "path-by-path" enhanced same path extrapolation scheme for Feynman path integral (FPI) calculations that permits rapid convergence with discretization errors ranging from O(P(-6)) to O(P(-12)), where P is the number of path discretization points. We also present two extensions of our importance sampling and stratified sampling schemes for calculating vibrational-rotational partition functions by the FPI method. The first is the use of importance functions for dihedral angles between sets of generalized Jacobi coordinate vectors. The second is an extension of our stratification scheme to allow some strata to be defined based only on coordinate information while other strata are defined based on both the geometry and the energy of the centroid of the Feynman path. These enhanced methods are applied to calculate converged partition functions by FPI methods, and these results are compared to ones obtained earlier by vibrational configuration interaction (VCI) calculations, both calculations being for the Jordan-Gilbert potential energy surface. The earlier VCI calculations are found to agree well (within ∼1.5%) with the new benchmarks. The FPI partition functions presented here are estimated to be converged to within a 2σ statistical uncertainty of between 0.04% and 0.07% for the given potential energy surface for temperatures in the range 300-3000 K and are the most accurately converged partition functions for a given potential energy surface for any molecule with five or more atoms. We also tabulate free energies, enthalpies, entropies, and heat capacities. PMID:25637967

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

    SciTech Connect

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

    2014-09-14

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

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

    SciTech Connect

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

    2015-11-14

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

  17. Calculation of vibrational and electronic excited state absorption spectra of arsenic-water complexes using density functional theory

    NASA Astrophysics Data System (ADS)

    Huang, L.; Lambrakos, S. G.; Shabaev, A.; Massa, L.

    2016-05-01

    Calculations are presented of vibrational and electronic excited-state absorption spectra for As-H2O complexes using density function theory (DFT) and time-dependent density functional theory (TD-DFT). DFT and TD-DFT can provide interpretation of absorption spectra with respect to molecular structure for excitation by electromagnetic waves at frequencies within the IR and UV-visible ranges. The absorption spectrum corresponding to excitation states of As-H2O complexes consisting of relatively small numbers of water molecules should be associated with response features that are intermediate between that of isolated molecules and that of a bulk system. DFT and TD-DFT calculated absorption spectra represent quantitative estimates that can be correlated with additional information obtained from laboratory measurements and other types of theory based calculations. The DFT software GAUSSIAN was used for the calculations of excitation states presented here.

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

    NASA Astrophysics Data System (ADS)

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

    2005-02-01

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

  19. 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

  20. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  2. Theoretical investigations on molecular structure, vibrational spectra, HOMO, LUMO, NBO analysis and hyperpolarizability calculations of thiophene-2-carbohydrazide

    NASA Astrophysics Data System (ADS)

    Balachandran, V.; Janaki, A.; Nataraj, A.

    2014-01-01

    The Fourier-Transform infrared and Fourier-Transform Raman spectra of thiophene-2-carbohydrazide (TCH) was recorded in the region 4000-400 cm-1 and 3500-100 cm-1. Quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers of TCH were carried out by DFT (B3LYP) method with 6-311++G(d,p) as basis set. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. Stability of the molecule arising from hyper conjugative interaction and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. 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 molecule have also been constructed.

  3. Theoretical investigations on molecular structure, vibrational spectra, HOMO, LUMO, NBO analysis and hyperpolarizability calculations of thiophene-2-carbohydrazide.

    PubMed

    Balachandran, V; Janaki, A; Nataraj, A

    2014-01-24

    The Fourier-Transform infrared and Fourier-Transform Raman spectra of thiophene-2-carbohydrazide (TCH) was recorded in the region 4000-400 cm(-1) and 3500-100 cm(-1). Quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers of TCH were carried out by DFT (B3LYP) method with 6-311++G(d,p) as basis set. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. Stability of the molecule arising from hyper conjugative interaction and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. 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 molecule have also been constructed. PMID:24060478

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

    NASA Astrophysics Data System (ADS)

    Wang, Xiaowei; Wang, Qiang

    2011-02-01

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

  5. 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.

  6. 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.

  7. Complete pure vibrational spectrum of HD calculated without the Born-Oppenheimer approximation and including relativistic corrections

    SciTech Connect

    Bubin, Sergiy; Stanke, Monika; Adamowicz, Ludwik

    2011-04-15

    All 18 bound pure vibrational levels of the HD molecule have been calculated within the framework that does not assume the Born-Oppenheimer (BO) approximation. The nonrelativistic energies of the states have been corrected for the relativistic effects of the order of {alpha}{sup 2} (where {alpha} is the fine structure constant), calculated using the perturbation theory with the nonrelativistic non-BO wave functions being the zero-order approximation. The calculations were performed by expanding the non-BO wave functions in terms of one-center explicitly correlated Gaussian functions multiplied by even powers of the internuclear distance and by performing extensive optimization of the Gaussian nonlinear parameters. Up to 10 000 basis functions were used for each state.

  8. 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

  9. Progress Towards the Accurate Calculation of Anharmonic Vibrational States of Fluxional Molecules and Clusters Without a Potential Energy Surface

    NASA Astrophysics Data System (ADS)

    Petit, Andrew S.; McCoy, Anne B.

    2011-06-01

    The accurate calculation of anharmonic vibrational states of highly fluxional systems is complicated by the need to first obtain the full-dimensional potential energy surface(PES). Although commonly exploited as a way around this problem, grid-based methodologies scale exponentially with system size while reduced dimensional approaches are highly system dependent, both in terms of the details of their application and in terms of their suitability. Moreover, the achievement of converged variational calculations of highly anharmonic systems is complicated by the necessity of using a very large basis and hence the construction and diagonalization of enormous Hamiltonian matrices. We report here our recent efforts to develop an algorithm capable of accurately calculating anharmonic vibrational energies, even for very floppy systems, without first obtaining a PES and using only a handful of basis functions per degree of freedom. More specifically, the potential energy and G-matrix elements are calculated on a set of points obtained from a Monte Carlo sampling of the most important regions of configuration space, allowing for a significant reduction in the number of required sampling points. The Hamiltonian matrix is then constructed using an evolving basis which, with each iteration, captures the effect of building H from an ever-expanding basis despite the fact that the actual dimensionality of H is fixed throughout the calculation. This latter property of the algorithm also greatly reduces the size of basis needed for the calculation relative to more traditional variational approaches. The results obtained from the application of our method to several test systems, including ion water complexes, will be reported along with its observed convergence properties.

  10. Crystal structure, vibrational studies, optical properties and DFT calculations of 2-amino-5-diethyl-aminopentanium tetrachlorocadmate (II).

    PubMed

    Baklouti, Yosra; chaari, Najla; Feki, Habib; Chniba-Boudjada, Nassira; Zouari, Fatma

    2015-02-01

    Single crystals of a new organic-inorganic compound (C9H24N2) CdCl4 were grown by the slow evaporation technique and characterized by X-ray diffraction, infrared absorption Raman spectroscopy scattering, optical absorption, differential scanning calorimetry (DSC) analysis and dielectric measurements. The title compound belongs to the orthorhombic space group Pbca with the following unit cell parameters: a=11.397(7), b=13.843(4), c=22.678(5)Å and Z=8. In crystal structure, the tetrachlorocadmate anion is connected to organic cations through N-H⋯Cl hydrogen bonds. Theoretical calculations were performed using density functional theory (DFT) with the B3LYP/LanL2DZ level of theory for studying the molecular structure and vibrational spectra of the title compound. Good consistency is found between the calculated results and the experimental structure, IR, and Raman spectra. The detailed interpretation of the vibrational modes was carried out on the basis on our DFT calculations as primary source of assignment and by comparison with spectroscopic studies of similar compounds. The optical properties were investigated by optical absorption and show three bands at 300, 329 and 513 nm. PMID:25311521

  11. Vibrational spectroscopic and DFT calculation studies of a new organic-inorganic compound of bis (4-acetylanilinium) tetrachlorocadmiate (II)

    NASA Astrophysics Data System (ADS)

    Jellibi, A.; Chaabane, I.; Guidara, K.

    2016-10-01

    The FT-IR and Raman vibrational spectra of bis (4-acetylanilinium) tetrachlorocadmiate (II) compound have been measured at room temperature by FT-infrared spectroscopy (4000-400 cm-1) on polycrystalline samples, and by Raman spectroscopy (3600-30 cm-1) on monocrystals. The structure of the [C8H10NO] 2CdCl4 formed by two cations [C8H10NO]+ of same type and one type of anion [CdCl4]2- was optimized by density functional theory (DFT) using the B3LYP method. The theoretical wavenumbers spectra were scaled by multiple scaling factors, yielding a good agreement between the experimentally recorded and the theoretically calculated values. Root mean square (rms) value was calculated and the small difference between experimental and calculated modes has been interpreted by intermolecular interactions in the crystal. The comparison between the [C8H9NO] ligand and the [C8H10NO]2[CdCl4] compound of the Raman spectra showed a decrease in the wavenumber of the bands assigned to the stretching vibration of (NH3) group in the compound due to the effect of the protonation of the nitrogen.

  12. Empirical maps for the calculation of amide I vibrational spectra of proteins from classical molecular dynamics simulations.

    PubMed

    Małolepsza, Edyta; Straub, John E

    2014-07-17

    New sets of parameters (maps) for calculating amide I vibrational spectra for proteins through a vibrational exciton model are proposed. The maps are calculated as a function of electric field and van der Waals forces on the atoms of peptide bonds, taking into account the full interaction between peptide bonds and the surrounding environment. The maps are designed to be employed using data obtained from standard all-atom molecular simulations without any additional constraints on the system. Six proteins representing a wide range of sizes and secondary structure complexity were chosen as a test set. Spectra calculated for these proteins reproduce experimental data both qualitatively and quantitatively. The proposed maps lead to spectra that capture the weak second peak observed in proteins containing β-sheets, allowing for clear distinction between α-helical and β-sheet proteins. While the parametrization is specific to the CHARMM force field, the methodology presented can be readily applied to any empirical force field. PMID:24654732

  13. Empirical Maps For The Calculation of Amide I Vibrational Spectra of Proteins From Classical Molecular Dynamics Simulations

    PubMed Central

    2015-01-01

    New sets of parameters (maps) for calculating amide I vibrational spectra for proteins through a vibrational exciton model are proposed. The maps are calculated as a function of electric field and van der Waals forces on the atoms of peptide bonds, taking into account the full interaction between peptide bonds and the surrounding environment. The maps are designed to be employed using data obtained from standard all-atom molecular simulations without any additional constraints on the system. Six proteins representing a wide range of sizes and secondary structure complexity were chosen as a test set. Spectra calculated for these proteins reproduce experimental data both qualitatively and quantitatively. The proposed maps lead to spectra that capture the weak second peak observed in proteins containing β-sheets, allowing for clear distinction between α-helical and β-sheet proteins. While the parametrization is specific to the CHARMM force field, the methodology presented can be readily applied to any empirical force field. PMID:24654732

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

    DOE PAGES

    Yu, Hua-Gen

    2015-01-28

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

  15. Calculation of Vibrational Shifts of Nitrile Probes in the Active Site of Ketosteroid Isomerase upon Ligand Binding

    PubMed Central

    Layfield, Joshua P.

    2012-01-01

    The vibrational Stark effect provides insight into the roles of hydrogen bonding, electrostatics, and conformational motions in enzyme catalysis. In a recent application of this approach to the enzyme ketosteroid isomerase (KSI), thiocyanate probes were introduced in site-specific positions throughout the active site. This paper implements a quantum mechanical/molecular mechanical (QM/MM) approach for calculating the vibrational shifts of nitrile (CN) probes in proteins. This methodology is shown to reproduce the experimentally measured vibrational shifts upon binding of the intermediate analog equilinen to KSI for two different nitrile probe positions. Analysis of the molecular dynamics simulations provides atomistic insight into the roles that key residues play in determining the electrostatic environment and hydrogen-bonding interactions experienced by the nitrile probe. For the M116C-CN probe, equilinen binding reorients an active site water molecule that is directly hydrogen bonded to the nitrile probe, resulting in a more linear CNH angle and increasing the CN frequency upon binding. For the F86C-CN probe, equilinen binding orients the Asp103 residue, decreasing the hydrogen-bonding distance between the Asp103 backbone and the nitrile probe and slightly increasing the CN frequency. This QM/MM methodology is applicable to a wide range of biological systems and has the potential to assist in the elucidation of the fundamental principles underlying enzyme catalysis. PMID:23210919

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

    SciTech Connect

    Yu, Hua-Gen

    2015-01-28

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

  18. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2006-01-01

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

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

    SciTech Connect

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

    2011-02-15

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

  1. Conformational and Vibrational Studies of Triclosan

    NASA Astrophysics Data System (ADS)

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

    2010-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1995-01-01

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

  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. The C3-bending vibrational levels of the C3-Kr and C3-Xe van der Waals complexes studied by their Ã-X̃ electronic transitions and by ab initio calculations.

    PubMed

    Chao, Jun-Mei; Tham, Keng Seng; Zhang, Guiqiu; Merer, Anthony J; Hsu, Yen-Chu; Hu, Wei-Ping

    2011-02-21

    Fluorescence excitation spectra and wavelength-resolved emission spectra of the C(3)-Kr and C(3)-Xe van der Waals (vdW) complexes have been recorded near the 2(2-)(0), 2(2+)(0), 2(4-)(0), and 1(1)(0) bands of the Ã(1)Π(u)-X̃(1)Σ(g)(+) system of the C(3) molecule. In the excitation spectra, the spectral features of the two complexes are red-shifted relative to those of free C(3) by 21.9-38.2 and 34.3-36.1 cm(-1), respectively. The emission spectra from the à state of the Kr complex consist of progressions in the two C(3)-bending vibrations (ν(2), ν(4)), the vdW stretching (ν(3)), and bending vibrations (ν(6)), suggesting that the equilibrium geometry in the X̃ state is nonlinear. As in the Ar complex [Zhang et al., J. Chem. Phys. 120, 3189 (2004)], the C(3)-bending vibrational levels of the Kr complex shift progressively to lower energy with respect to those of free C(3) as the bending quantum number increases. Their vibrational structures could be modeled as perturbed harmonic oscillators, with the dipole-induced dipole terms of the Ar and Kr complexes scaled roughly by the polarizabilities of the Ar and Kr atoms. Emission spectra of the Xe complex, excited near the Ã, 2(2-) level of free C(3), consist only of progressions in even quanta of the C(3)-bending and vdW modes, implying that the geometry in the higher vibrational levels (υ(bend) ≥ 4, E(vib) ≥ 328 cm(-1)) of the X̃ state is (vibrationally averaged) linear. In this structure the Xe atom bonds to one of the terminal carbons nearly along the inertial a-axis of bent C(3). Our ab initio calculations of the Xe complex at the level of CCSD(T)∕aug-cc-pVTZ (C) and aug-cc-pVTZ-PP (Xe) predict that its equilibrium geometry is T-shaped (as in the Ar and Kr complexes), and also support the assignment of a stable linear isomer when the amplitude of the C(3) bending vibration is large (υ(4) ≥ 4).

  5. Vibrational spectra, optical properties, NBO and HOMO-LUMO analysis of L-Phenylalanine L-Phenylalaninium Perchlorate: DFT calculations.

    PubMed

    Elleuch, Nabil; Ben Ahmed, Ali; Feki, Habib; Abid, Younes; Minot, Christian

    2014-01-01

    In this work, we report a combined experimental and theoretical study of a nonlinear optical material, L-Phenylalanine L-Phenylalaninium Perchlorate. Single crystals of the title compound have been grown by slow evaporation of an aqueous solution at room temperature. Theoretical calculations were preceded by redetermination of the crystal X-ray structure. The compound crystallizes in the non-centro symmetric space group P2(1)2(1)2(1) of the orthorhombic system. The FT-IR and Raman spectra of the crystal were recorded and analyzed. The density functional theory (DFT) computations have been performed at B3LYP/6-31G(d) level to derive equilibrium geometry, vibrational wavenumbers, intensity and NLO properties. All observed vibrational bands have been discussed and assigned to normal mode or to combinations on the basis of our DFT calculations as a primary source of attribution and also by comparison with the previous results for similar compounds. Natural bond orbital analysis was carried out to demonstrate the various inter-and intramolecular interaction that are responsible of the stabilization of the compound. The lowering of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy gap appears to be the cause of its enhanced charge transfer interaction leading to high NLO activity.

  6. Vibrational spectra and molecular mechanics and ab initio calculations for 1,3-dioxole. Confirmation of non-planarity

    NASA Astrophysics Data System (ADS)

    Cortez, Enriqueta; Laane, Jaan

    1995-02-01

    Infrared and Raman spectra of the vapor, liquid, and solid phases of 1,3-dioxole have been recorded and analyzed. Much of the spectra can be interpreted assuming C2v symmetry. However, several combination bands with the ring-puckering vibration along with the observation of an otherwise inactive mode confirm the non-planarity of this molecule. The observed frequencies are compared with predicted values from molecular mechanics (MM3) and ab initio (STO3-21G∗) calculations. These calculated values provide useful estimates but about half of them differ from the observed values by more than 50 cm -1. Several predicted values disagree by more than 200 cm -1.

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

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1995-01-01

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

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

    DOE PAGES

    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

  10. Two-photon vibrational excitation of air by long-wave infrared laser pulses

    NASA Astrophysics Data System (ADS)

    Palastro, J. P.; Peñano, J.; Johnson, L. A.; Hafizi, B.; Wahlstrand, J. K.; Milchberg, H. M.

    2016-08-01

    Ultrashort long-wave infrared (LWIR) laser pulses can resonantly excite vibrations in N2 and O2 through a two-photon transition. The absorptive vibrational component of the ultrafast optical nonlinearity grows in time, starting smaller than but quickly surpassing the electronic, rotational, and vibrational refractive components. The growth of the vibrational component results in a novel mechanism of third-harmonic generation, providing an additional two-photon excitation channel, fundamental + third harmonic. The original and emergent two-photon excitations drive the resonance exactly out of phase, causing spatial decay of the absorptive vibrational nonlinearity. This nearly eliminates two-photon vibrational absorption. Here we present simulations and analytical calculations demonstrating how these processes modify the ultrafast optical nonlinearity in air. The results reveal nonlinear optical phenomena unique to the LWIR regime of ultrashort pulse propagation in the atmosphere.

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

    SciTech Connect

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

    1998-02-01

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

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

    SciTech Connect

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

    1997-12-01

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

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

    PubMed

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

    2015-02-25

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

  15. Molecular structure, vibrational spectral assignments (FT-IR and FT-RAMAN), NMR, NBO, HOMO-LUMO and NLO properties of O-methoxybenzaldehyde based on DFT calculations

    NASA Astrophysics Data System (ADS)

    Vennila, P.; Govindaraju, M.; Venkatesh, G.; Kamal, C.

    2016-05-01

    Fourier transform - Infra red (FT-IR) and Fourier transform - Raman (FT-Raman) spectroscopic techniques have been carried out to analyze O-methoxy benzaldehyde (OMB) molecule. The fundamental vibrational frequencies and intensity of vibrational bands were evaluated using density functional theory (DFT). The vibrational analysis of stable isomer of OMB has been carried out by FT-IR and FT-Raman in combination with theoretical method simultaneously. The first-order hyperpolarizability and the anisotropy polarizability invariant were computed by DFT method. The atomic charges, hardness, softness, ionization potential, electronegativity, HOMO-LUMO energies, and electrophilicity index have been calculated. The 13C and 1H Nuclear magnetic resonance (NMR) have also been obtained by GIAO method. Molecular electronic potential (MEP) has been calculated by the DFT calculation method. Electronic excitation energies, oscillator strength and excited states characteristics were computed by the closed-shell singlet calculation method.

  16. Efficient method for calculations of ro-vibrational states in triatomic molecules near dissociation threshold: Application to ozone

    NASA Astrophysics Data System (ADS)

    Teplukhin, Alexander; Babikov, Dmitri

    2016-09-01

    A method for calculations of rotational-vibrational states of triatomic molecules up to dissociation threshold (and scattering resonances above it) is devised, that combines hyper-spherical coordinates, sequential diagonalization-truncation procedure, optimized grid DVR, and complex absorbing potential. Efficiency and accuracy of the method and new code are tested by computing the spectrum of ozone up to dissociation threshold, using two different potential energy surfaces. In both cases good agreement with results of previous studies is obtained for the lower energy states localized in the deep (˜10 000 cm-1) covalent well. Upper part of the bound state spectrum, within 600 cm-1 below dissociation threshold, is also computed and is analyzed in detail. It is found that long progressions of symmetric-stretching and bending states (up to 8 and 11 quanta, respectively) survive up to dissociation threshold and even above it, whereas excitations of the asymmetric-stretching overtones couple to the local vibration modes, making assignments difficult. Within 140 cm-1 below dissociation threshold, large-amplitude vibrational states of a floppy complex O⋯O2 are formed over the shallow van der Waals plateau. These are assigned using two local modes: the rocking-motion and the dissociative-motion progressions, up to 6 quanta in each, both with frequency ˜20 cm-1. Many of these plateau states are mixed with states of the covalent well. Interestingly, excitation of the rocking-motion helps keeping these states localized within the plateau region, by raising the effective barrier.

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

    DOE PAGES

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

    2016-03-29

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

  18. Full-Dimensional Quantum Calculations of Vibrational Levels of NH4(+) and Isotopomers on An Accurate Ab Initio Potential Energy Surface.

    PubMed

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

    2016-04-14

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

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

    PubMed

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

    2006-03-01

    The harmonic balance method (HBM) was originally developed for finding periodic solutions of electronical and mechanical systems under a periodic force, but has been adapted to self-sustained musical instruments. Unlike time-domain methods, this frequency-domain method does not capture transients and so is not adapted for sound synthesis. However, its independence of time makes it very useful for studying any periodic solution, whether stable or unstable, without care of particular initial conditions in time. A computer program for solving general problems involving nonlinearly coupled exciter and resonator, HARMBAL, has been developed based on the HBM. The method as well as convergence improvements and continuation facilities are thoroughly presented and discussed in the present paper. Applications of the method are demonstrated, especially on problems with severe difficulties of convergence: the Helmholtz motion (square signals) of single-reed instruments when no losses are taken into account, the reed being modeled as a simple spring. PMID:16583920

  20. 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.

  1. Vibrational spectroscopic, first-order hyperpolarizability and HOMO, LUMO studies of 4-chloro-2-(trifluoromethyl) aniline based on DFT calculations

    NASA Astrophysics Data System (ADS)

    Arivazhagan, M.; Subhasini, V. P.; Austine, A.

    2012-02-01

    The Fourier-transform infrared and FT-Raman spectra of 4-chloro-2-(trifluoromethyl) aniline (4C2TFA) were recorded in the region 4000-400 cm -1 and 3500-50 cm -1 respectively. Quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers of 4C2TFA were carried out by density functional theory (DFT/B3LYP) method with 6-311+G(d,p) and 6-311++G(d,p) basis sets. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The values of the total dipole moment ( μ) and the first order hyperpolarizability ( β) of the investigated compound were computed using B3LYP/6-311++G(d,p) calculations. The calculated results also show that 4C2TFA might have microscopic non-linear optical (NLO) behavior with non-zero values. A detailed interpretation of infrared and Raman spectra of 4C2TFA is also reported. The calculated HOMO-LUMO energy gap shows that charge transfer occurs within the molecule.

  2. Ab initio calculations of the elastic, electronic, optical, and vibrational properties of PdGa compound under pressure

    NASA Astrophysics Data System (ADS)

    Koc, H.; Yildirim, A.; Deligoz, E.

    2012-09-01

    The structural, elastic, electronic, optical, and vibrational properties of cubic PdGa compound are investigated using the norm-conserving pseudopotentials within the local density approximation (LDA) in the framework of the density functional theory. The calculated lattice constant has been compared with the experimental value and has been found to be in good agreement with experimental data. The obtained electronic band structures show that PdGa compound has no band gap. The second-order elastic constants have been calculated, and the other related quantities such as the Young's modulus, shear modulus, Poisson's ratio, anisotropy factor, sound velocities, and Debye temperature have also been estimated. Our calculated results of elastic constants show that this compound is mechanically stable. Furthermore, the real and imaginary parts of the dielectric function and the optical constants such as the electron energy-loss function, the optical dielectric constant and the effective number of electrons per unit cell are calculated and presented in the study. The phonon dispersion curves are also derived using the direct method.

  3. 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.

  4. Ab Initio Calculation of Accurate Vibrational Frequencies for Molecules of Interest in Atmospheric Chemistry

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Langhoff, Stephen R. (Technical Monitor)

    1996-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  6. Calculation of rotation-vibration energy levels of the ammonia molecule based on an ab initio potential energy surface

    NASA Astrophysics Data System (ADS)

    Polyansky, Oleg L.; Ovsyannikov, Roman I.; Kyuberis, Aleksandra A.; Lodi, Lorenzo; Tennyson, Jonathan; Yachmenev, Andrey; Yurchenko, Sergei N.; Zobov, Nikolai F.

    2016-09-01

    An ab initio potential energy surface (PES) for gas-phase ammonia NH3 has been computed using the methodology pioneered for water (Polyansky et al., 2013). Multireference configuration interaction calculations are performed at about 50 000 points using the aug-cc-pCVQZ and aug-cc-pCV5Z basis sets and basis set extrapolation. Relativistic and adiabatic surfaces are also computed. The points are fitted to a suitable analytical form, producing the most accurate ab initio PES for this molecule available. The rotation-vibration energy levels are computed using nuclear motion program TROVE in both linearised and curvilinear coordinates. Better convergence is obtained using curvilinear coordinates. Our results are used to assign the visible spectrum of 14NH3 recorded by Coy and Lehmann (1986). Rotation-vibration energy levels for the isotopologues NH2D, NHD2, ND3 and 15NH3 are also given. An ab initio value for the dissociation energy D0 of 14NH3 is also presented.

  7. Raman and infrared spectra, structure, vibrational assignment, normal coordinate analysis, and ab initio calculations of trifluoromethyl isocyanate

    NASA Astrophysics Data System (ADS)

    Durig, J. R.; Guirgis, G. A.; Eltayeb, S.

    1994-07-01

    The Raman (2500 to 30 cm -1) and infrared (2500 to 60 cm 1) spectra of gaseous and solid trifluoromethyl isocyanate, CF 3NCO, have been recorded. The Raman spectrum of the liquid has also been obtained and qualitative depolarization ratios have been measured. The CNC bend has been observed in the low-frequency Raman spectrum of the gas at 130 cm -1 as a relatively strong line which is split in the spectrum of the solid. However, the CF 3 torsional mode was not observed. The infrared spectrum of CF 3NCO dissolved in liquid xenon was also obtained and the observed spectrum indicates a very small barrier to internal rotation. With the exception of the torsion, a complete assignment of the vibrational fundamentals is proposed. The structural parameters, force constants, and vibrational frequencies have been determined from ab initio calculations utilizing a variety of basis sets and the theoretical results are compared to the experimental values when appropriate. These results have been compared with the corresponding quantities obtained for some similar molecules.

  8. Vibrational, NMR and UV-visible spectroscopic investigation and NLO studies on benzaldehyde thiosemicarbazone using computational calculations

    NASA Astrophysics Data System (ADS)

    Moorthy, N.; Prabakar, P. C. Jobe; Ramalingam, S.; Pandian, G. V.; Anbusrinivasan, P.

    2016-04-01

    In order to investigate the vibrational, electronic and NLO characteristics of the compound; benzaldehyde thiosemicarbazone (BTSC), the XRD, FT-IR, FT-Raman, NMR and UV-visible spectra were recorded and were analysed with the calculated spectra by using HF and B3LYP methods with 6-311++G(d,p) basis set. The XRD results revealed that the stabilized molecular systems were confined in orthorhombic unit cell system. The cause for the change of chemical and physical properties behind the compound has been discussed makes use of Mulliken charge levels and NBO in detail. The shift of molecular vibrational pattern by the fusing of ligand; thiosemicarbazone group with benzaldehyde has been keenly observed. The occurrence of in phase and out of phase molecular interaction over the frontier molecular orbitals was determined to evaluate the degeneracy of the electronic energy levels. The thermodynamical studies of the temperature region 100-1000 K to detect the thermal stabilization of the crystal phase of the compound were investigated. The NLO properties were evaluated by the determination of the polarizability and hyperpolarizability of the compound in crystal phase. The physical stabilization of the geometry of the compound has been explained by geometry deformation analysis.

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

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1987-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1987-09-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

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

  13. 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.

  14. The isomers and conformers of some push pull enamines studied by vibrational and NMR spectroscopy and by ab initio calculations

    NASA Astrophysics Data System (ADS)

    Pigošová, J.; Gatial, A.; Milata, V.; Černuchová, P.; Prónayová, N.; Liptaj, T.; Matějka, P.

    2005-06-01

    The isomers and conformers of six push-pull enamines: 3-dimethylamino-, 3-methylamino- and 3-amino-2-acetyl propenenitrile [(H 3C) 2N-CH dbnd6 C(CN)(COCH 3), H 3C-NH-CH dbnd6 C(CN)(COCH 3) and H 2N-CH dbnd6 C(CN)(COCH 3)] and 3-dimethylamino-, 3-methylamino- and 3-amino-2-methylsulfonyl propenenitrile [(H 3C) 2N-CH dbnd6 C(CN)(SO 2CH 3), H 3C-NH-CH dbnd6 C(CN)(SO 2CH 3) and H 2N-CH dbnd6 C(CN)(SO 2CH 3)] have been studied experimentally by vibrational and NMR spectroscopy and theoretically by the ab initio calculations at MP2 level in 6-31G** basis set. The IR and Raman spectra of all compounds as a solid and solute in various solvents have been recorded in the region 4000-50 cm -1. The NMR spectra were obtained in chloroform and DMSO at room temperature. All six compounds have been prepared by the same way. NMR spectra revealed that both dimethylamino compounds were prepared as a pure E isomers whereas in the case of methylamino compounds the 3-methylamino-2-methylsulfonyl propenenitrile was prepared also as a pure E isomer but 3-methylamino-2-acetyl propenenitrile as a pure Z isomer. Also 3-amino-2-methylsulfonyl propenenitrile was obtained as a pure the E isomer, but 3-amino-2-acetyl propenenitrile as a mixture of both E and Z isomers. Confomational possibilities of studied compounds are given only by the rotation of the acetyl and methylamino groups. Vibrational spectra revealed existence of two conformers with Z and E orientation of acetyl group for 3-dimethylamino-2-acetyl propenenitrile. Two conformers with anti or syn orientation of methylamino group for 3-methylamino-2-methylsulfonyl propenenitrile have been confirmed by vibrational and NMR spectra, but only one conformer with anti orientation of methylamino group for 3-methylamino-2-acetyl propenenitrile in chloroform solution and in solid phase was found. For latter compound the additional isomer/conformer was detected in more polar solvents (acetonitrile/DMSO). These experimental findings have been

  15. 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}).

  16. Combined QM/MM calculations of active-site vibrations in binding process of P450cam to putidaredoxin.

    PubMed

    Freindorf, Marek; Shao, Yihan; Kong, Jing; Furlani, Thomas R

    2008-03-01

    Combined QM/MM calculations of the active-site of cytochrome P450cam have been performed before and after the binding of P450cam to putidaredoxin. The calculations were carried out for both a 5-coordinated and a 6-coordinated active-site of cytochrome P450cam, with either a water molecule or a carbon monoxide molecule as a 6th distal ligand. An experimentally observed increase in the Fe-S stretching frequency that occurs after cytochrome P450cam binds to putidaredoxin, has been reproduced in our study. Experimentally observed changes in the Fe-C and C-O vibration frequencies that occur after binding of both proteins, have also been reproduced in our study. The computed increase of the Fe-S and Fe-C stretching frequencies is correlated with a corresponding decrease of the Fe-S and Fe-C interatomic distances. According to our calculations, for the active-site with carbon monoxide in the triplet electronic state, the binding process increases the spin densities on the iron and sulfur atoms, which changes the Fe-C and C-O stretching frequencies in opposite directions, in agreement with experimental data.

  17. FTIR and FT-Raman spectra, vibrational assignments and density functional theory calculations of 2,6-dibromo-4-nitroaniline and 2-(methylthio)aniline.

    PubMed

    Krishnakumar, V; Balachandran, V

    2005-06-01

    The FTIR and FT-Raman spectra of 2,6-dibromo-4-nitroaniline (2,6-DB4NA) in solid phase and 2-(methylthio)aniline (2-MTA) in liquid phase were measured. The geometry and normal vibrations have been obtained from the density functional theory (DFT) with the B3LYP method employing the 6-31G* basis set. Scale factors, which bring computational frequencies in closer agreement with the experimental data, have been calculated for predominant vibrational motions of the normal modes. The effects of the amino, bromine, nitro, thio and methyl substituents on vibrational frequencies have been investigated. The infrared and Raman spectra were also predicted from the calculated intensities. The observed and the calculated spectra were found to be in good agreement. PMID:15863052

  18. FTIR and FT-Raman spectra, vibrational assignments and density functional theory calculations of 2,6-dibromo-4-nitroaniline and 2-(methylthio)aniline

    NASA Astrophysics Data System (ADS)

    Krishnakumar, V.; Balachandran, V.

    2005-06-01

    The FTIR and FT-Raman spectra of 2,6-dibromo-4-nitroaniline (2,6-DB4NA) in solid phase and 2-(methylthio)aniline (2-MTA) in liquid phase were measured. The geometry and normal vibrations have been obtained from the density functional theory (DFT) with the B3LYP method employing the 6-31G* basis set. Scale factors, which bring computational frequencies in closer agreement with the experimental data, have been calculated for predominant vibrational motions of the normal modes. The effects of the amino, bromine, nitro, thio and methyl substituents on vibrational frequencies have been investigated. The infrared and Raman spectra were also predicted from the calculated intensities. The observed and the calculated spectra were found to be in good agreement.

  19. 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.

  20. 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.

  1. Microwave, infrared and Raman spectra, r0 structural parameters, ab initio calculations and vibrational assignment of 1-fluoro-1-silacyclopentane.

    PubMed

    Durig, James R; Panikar, Savitha S; Obenchain, Daniel A; Bills, Brandon J; Lohan, Patrick M; Peebles, Rebecca A; Peebles, Sean A; Groner, Peter; Guirgis, Gamil A; Johnston, Michael D

    2012-01-28

    The microwave spectrum (6500-18 ,500 MHz) of 1-fluoro-1-silacyclopentane, c-C(4)H(8)SiHF has been recorded and 87 transitions for the (28)Si, (29)Si, (30)Si, and (13)C isotopomers have been assigned for a single conformer. Infrared spectra (3050-350 cm(-1)) of the gas and solid and Raman spectrum (3100-40 cm(-1)) of the liquid have also been recorded. The vibrational data indicate the presence of a single conformer with no symmetry which is consistent with the twist form. Ab initio calculations with a variety of basis sets up to MP2(full)/aug-cc-pVTZ predict the envelope-axial and envelope-equatorial conformers to be saddle points with nearly the same energies but much lower energy than the planar conformer. By utilizing the microwave rotational constants for seven isotopomers ((28)Si, (29)Si, (30)Si, and four (13)C) combined with the structural parameters predicted from the MP2(full)/6-311+G(d,p) calculations, adjusted r(0) structural parameters have been obtained for the twist conformer. The heavy atom distances in Å are: r(0)(SiC(2)) = 1.875(3); r(0)(SiC(3)) = 1.872(3); r(0)(C(2)C(4)) = 1.549(3); r(0)(C(3)C(5)) = 1.547(3); r(0)(C(4)C(5)) = 1.542(3); r(0)(SiF) = 1.598(3) and the angles in degrees are: [angle]CSiC = 96.7(5); [angle]SiC(2)C(4) = 103.6(5); [angle]SiC(3)C(5) = 102.9(5); [angle]C(2)C(4)C(5) = 108.4(5); [angle]C(3)C(5)C(4) = 108.1(5); [angle]F(6)Si(1)C(2) = 110.7(5); [angle]F(6)Si(1)C(3) = 111.6(5). The heavy atom ring parameters are compared to the corresponding r(s) parameters. Normal coordinate calculations with scaled force constants from MP2(full)/6-31G(d) calculations were carried out to predict the fundamental vibrational frequencies, infrared intensities, Raman activities, depolarization values, and infrared band contours. These experimental and theoretical results are compared to the corresponding quantities of some other five-membered rings.

  2. Interactions of Hydrogen Molecules with Halogen-Containing Diatomics from Ab Initio Calculations: Spherical-Harmonics Representation and Characterization of the Intermolecular Potentials.

    PubMed

    Albernaz, Alessandra F; Aquilanti, Vincenzo; Barreto, Patricia R P; Caglioti, Concetta; Cruz, Ana Claudia P S; Grossi, Gaia; Lombardi, Andrea; Palazzetti, Federico

    2016-07-14

    For the prototypical diatomic-molecule-diatomic-molecule interactions H2-HX and H2-X2, where X = F, Cl, Br, quantum-chemical ab initio calculations are carried out on grids of the configuration space, which permit a spherical-harmonics representation of the potential energy surfaces (PESs). Dimer geometries are considered for sets of representative leading configurations, and the PESs are analyzed in terms of isotropic and anisotropic contributions. The leading configurations are individuated by selecting a minimal set of mutual orientations of molecules needed to build the spherical-harmonic expansion on geometrical and symmetry grounds. The terms of the PESs corresponding to repulsive and bonding dimer geometries and the averaged isotropic term, for each pair of interacting molecules, are compared with representations in terms of a potential function proposed by Pirani et al. (see Chem. Phys. Lett. 2004, 394, 37-44 and references therein). Connections of the involved parameters with molecular properties provide insight into the nature of the interactions.

  3. Vibrational Dynamics and Thermodynamics of AgCu nanoparticles

    NASA Astrophysics Data System (ADS)

    Kara, Abdelkader; Yildirim, Handan; Rahman, Talat S.; Ferrando, Ricardo

    2006-03-01

    We present results of a systematic study of the structure, vibrational dynamics and thermodynamics of AgnCu34-n nanoparticles including. The starting structure were generated using a structural optimization using a genetic algorithm [1]. Using the embedded atom method potentials, we have calculated the vibrational densities of states for all stoichiometries and the corresponding vibrational free energies, in the harmonic approximations. At 300K, the vibrational free energy is found to behave linearly with the increasing number of Ag atoms in the nanoparticles. The vibrational contributions to the free energy increase from 5.5% for Ag0Cu34 to 8.3% Ag34Cu0. Selected force constants for several nanoparticles were calculated using density functional theory (DFT) and were found to be very close to those determined using EAM potentials. [1] G. Rossi, A. Rapallo, C. Mottet, A. Fortunelli, F. Baletto and R. Ferrando Phys. Rev. Lett, 93, 105503 (2004)

  4. Molecular structure and vibrational assignment of melaminium phthalate by density functional theory (DFT) and ab initio Hartree-Fock (HF) calculations.

    PubMed

    Tarcan, Erdoğan; Altindağ, Ozgü; Avci, Davut; Atalay, Yusuf

    2008-11-01

    The molecular geometry, the normal mode frequencies and corresponding vibrational assignment of melaminium phthalate (C3H7N6+.C8H5O4(-)) in the ground state were performed by HF and B3LYP levels of theory using the 6-31G(d) basis set. The optimized bond length numbers with bond angles are in good agreement with the X-ray data. The vibrational spectra of melaminium phthalate which is calculated by HF and B3LYP methods, reproduces vibrational wave numbers with an accuracy which allows reliable vibrational assignments. The title compound has been studied in the 4000-100 cm(-1) region where the theoretical evaluation and assignment of all observed bands were made.

  5. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  7. 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.

  8. Vibrational spectroscopic studies and DFT calculations on tribromoacetate and tribromoacetic acid in aqueous solution.

    PubMed

    Rudolph, Wolfram W; Irmer, Gert

    2011-09-01

    Aqueous solutions of sodium tribromoacetate (NaCBr3CO2) and its corresponding acid (CBr3COOH) have been studied using Raman and infrared spectroscopy. The spectra of the species in solution were assigned according to symmetry Cs. Characteristic bands of CBr3CO2-(aq) and the tribromoacetic acid, CBr3COOH(aq), are discussed. For the hydrated anion, the CO2 group, the symmetric CO2 stretching mode at 1332 cm(-1) and the asymmetric stretching mode at 1651 cm(-1) are characteristic while the CO mode at 1730 cm(-1) is characteristic for the spectra of the acid. The stretching mode, νC-C at 912cm(-1) for CBr3CO2-(aq) is 10 cm(-1) lower in the anion compared with that of the acid. These characteristic modes are compared to those in acetate, CH3CO2-(aq). Coupling of the modes are fairly extensive and therefore DFT calculations have been carried out in order to compare the measured spectra with the calculated ones. The geometrical parameters such as bond length and bond angles of the tribromoacetate, and tribromoacetic acid have been obtained and may be compared with the ones published for other acetates and their conjugated acids. CBr3COOH(aq) is a moderately strong acid and the pKa value derived from quantitative Raman measurements is equal to -0.23 at 23°C. The deuterated acid CBr3COOD in heavy water has been measured as well and the assignments were given.

  9. Structural, vibrational, and thermodynamic properties of ordered and disordered Ni1-xPtx alloys from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Shang, S. L.; Wang, Y.; Kim, D. E.; Zacherl, C. L.; Du, Y.; Liu, Z. K.

    2011-04-01

    In terms of first-principles phonon calculations and the quasiharmonic approach, the structural, vibrational, and thermodynamic properties have been investigated for the ordered and disordered Ni1-xPtx alloys, with the main focus being on disordered Ni0.5Pt0.5. To gain insight into the disordered alloys, we use special quasirandom structures (SQSs) and demonstrate their capabilities in predicting (i) the bond-length distributions, (ii) the phonon spectra, and (iii) the elastic stiffness constants of the disordered alloys. It is found that the Pt-Pt atomic pairs possess the longest bond lengths relative to the Ni-Pt and Ni-Ni ones in the disordered alloys, the predicted force constants indicate that the Pt-Pt bond is stiffer when compared to the Ni-Pt and the Ni-Ni ones for both the ordered and disordered alloys, and the phonon density of states of the disordered alloys are similar to the broadened versions of the ordered cases. Based on the results of the ordered and disordered alloys, a slightly positive deviation from Vegard's law is found for the volume variation of Ni1-xPtx, and correspondingly, a negative deviation is predicted for the change of bulk modulus. With increasing Pt content, the bulk modulus derivative relative to pressure increases approximately linearly, whereas the magnetic moment decreases. In addition, the SQS-predicted relative energies (enthalpies of formation) for the disordered Ni1-xPtx are also compared to cluster expansion predictions. As an application of the finite temperature thermodynamic properties, the phase transition between the ordered L10 and the disordered Ni0.5Pt0.5 is predicted to be 755 ± 128 K, which agrees reasonably well with the measurement ˜900 K, demonstrating that the driving force of the phase transition stems mainly from the configurational entropy rather than the vibrational entropy.

  10. 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.

  11. 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.

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

    PubMed

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

    2005-01-22

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

  13. 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.

  14. 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.

    PubMed

    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 O-H stretching wavenumber is due to the formation of O-H···O intermolecular hydrogen bonding. The lowering and splitting of the carbonyl stretching vibrational modes is assigned to the intermolecular association based on C=O···H type hydrogen bonding in the molecule. Chemical interpretation of hyperconjugative interactions was done by natural bond orbital analysis. PMID:23792238

  15. Vibrational spectroscopy and DFT calculations of the di-amino acid peptide L-aspartyl-L-glutamic acid in the zwitterionic state.

    PubMed

    Kausar, Nighat; Dines, Trevor J; Chowdhry, Babur Z; Alexander, Bruce D

    2009-08-14

    Solid state IR and Raman as well as aqueous solution state Raman spectra are reported for the linear di-amino acid peptide L-aspartyl-L-glutamic acid (L-Asp-L-Glu); the solution state Raman spectrum has also been obtained for the N,O-deuterated derivative. SCF-DFT calculations at the B3-LYP/cc-pVDZ level established that the structure and vibrational spectra of L-Asp-L-Glu can be interpreted using a model of the peptide with ten hydrogen-bonded water molecules, in conjunction with the conductor-like polarizable continuum solvation method. The DFT calculations resulted in the computation of a stable zwitterionic structure, which displays trans-amide conformation. The vibrational spectra were computed at the optimised molecular geometry, 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.

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

    NASA Astrophysics Data System (ADS)

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

    2009-06-01

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

  17. 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

  18. 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.; Černuchová, P.; Prónayová, N.; Matějka, 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

  19. 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).

  20. Vibrational rainbows

    SciTech Connect

    Drolshagen, G.; Mayne, H.R.; Toennies, J.P.

    1981-07-01

    We extend the theory of inelastic rainbows to include vibrationally inelastic scattering, showing how the existence of vibrational rainbows can be deduced from collinear classical scattering theory. Exact close-coupling calculations are carried out for a breathing sphere potential, and rainbow structures are, in fact, observed. The location of the rainbows generally agrees well with the classical prediction. In addition, the sensitivity of the location of the rainbow to changes in the vibrational coupling has been investigated. It is shown that vibrational rainbows persist in the presence of anisotropy. Experimental results (R. David, M. Faubel, and J. P. Toennies, Chem. Phys. Lett. 18, 87 (1973)) are examined for evidence of vibrational rainbow structure, and it is shown that vibrational rainbow theory is not inconsistent with these results.

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

    PubMed

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

    2011-08-15

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-08-01

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

  3. Communication: Ro-vibrational control of chemical reactivity in H+CH₄→ H₂+CH₃: full-dimensional quantum dynamics calculations and a sudden model.

    PubMed

    Welsch, Ralph; Manthe, Uwe

    2014-08-01

    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.

  4. Time-domain calculations of the 1D and 2D spectra of resonantly-coupled vibrations in liquids and proteins

    NASA Astrophysics Data System (ADS)

    Torii, Hajime

    2012-12-01

    A time-domain computational method for calculating 1D and 2D spectra of resonantly-coupled vibrations in condensed-phase systems is presented. This method simultaneously takes into account the diagonal frequency modulations, the off-diagonal vibrational couplings, and the dynamics of the system, and is applicable to systems of wide interest, e.g., the O-H stretching modes of water and alcohols, and the amide I modes of proteins. The case of the amide I mode of (Ala-d)4 in D2O solution is shown as an example.

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

    PubMed

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

    2016-05-28

    Full quantum mechanical calculations of vibrational energies of methane and fluoromethane are carried out using a polyspherical description combining Radau and Jacobi coordinates. The Hamiltonian is built in a potential-optimized discrete variable representation, and vibrational energies are solved using an iterative eigensolver. This new approach can be applied to a large variety of molecules. In particular, we show that it is able to accurately and efficiently compute eigenstates for four different molecules : CH4, CHD3, CH2D2, and CH3F. Very good agreement is obtained with the results reported previously in the literature with different approaches and with experimental data. PMID:27250301

  6. Coupled rotor-body vibrations with inplane degrees of freedom

    NASA Technical Reports Server (NTRS)

    Ming-Sheng, H.; Peters, D. A.

    1985-01-01

    In an effort to understand the vibration mechanisms of helicopters, the following basic studies are considered. A coupled rotor-fuselage vibration analysis including inplane degrees of freedom of both rotor and airframe is performed by matching of rotor and fuselage impedances at the hub. A rigid blade model including hub motion is used to set up the rotor flaplag equations. For the airframe, 9 degrees of freedom and hub offsets are used. The equations are solved by harmonic balance. For a 4-bladed rotor, the coupled responses and hub loads are calculated for various parameters in forward flight. The results show that the addition of inplane degrees of freedom does not significantly affect the vertical vibrations for the cases considered, and that inplane vibrations have similar resonance trends as do flapping vibrations.

  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. 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.

  9. Microwave and infrared spectra, adjusted r0 structural parameters, conformational stabilities, vibrational assignments, and theoretical calculations of cyclobutylcarboxylic acid chloride.

    PubMed

    Klaassen, Joshua J; Darkhalil, Ikhlas D; Deodhar, Bhushan S; Gounev, Todor K; Gurusinghe, Ranil M; Tubergen, Michael J; Groner, Peter; Durig, James R

    2013-08-01

    The FT-microwave spectrum of cyclobutylcarboxylic acid chloride, c-C4H7C(O)Cl, has been recorded and 153 transitions for the (35)Cl and (37)Cl isotopologues have been assigned for the gauche-equatorial (g-Eq) conformation. The ground state rotational constants were determined for (35)Cl [(37)Cl]: A = 4349.8429(25) [4322.0555(56)] MHz, B = 1414.8032(25) [1384.5058(25)] MHz, and C = 1148.2411(25) [1126.3546(25)] MHz. From these rotational constants and ab initio predicted parameters, adjusted r0 parameters are reported with distances (Å) rCα-C = 1.491(4), rC═O = 1.193(3), rCα-Cβ = 1.553(4), rCα-Cβ' = 1.540(4), rCγ-Cβ = 1.547(4), rCγ-Cβ' = 1.546(4), rC-Cl = 1.801(3) and angles (deg) τCγCβCβ'Cα = 30.9(5). Variable temperature (-70 to -100 °C) infrared spectra (4000 to 400 cm(-1)) were recorded in liquid xenon and the g-Eq conformer was determined the most stable form, with enthalpy differences of 91 ± 9 cm(-1) (1.09 ± 0.11 kJ/mol) for the gauche-axial (g-Ax) form and 173 ± 17 cm(-1) (2.07 ± 0.20 kJ/mol) for the trans-equatorial (t-Eq) conformer. The relative amounts at ambient temperature are 54% g-Eq, 35 ± 1% g-Ax, and 12 ± 1% t-Eq forms. Vibrational assignments have been provided for the three conformers and theoretical calculations were carried out. The results are discussed and compared to corresponding properties of related molecules.

  10. Simple systematization of vibrational excitation cross-section calculations for resonant electron-molecule scattering in the boomerang and impulse models.

    PubMed

    Sarma, Manabendra; Adhikari, S; Mishra, Manoj K

    2007-01-28

    Vibrational excitation (nu(f)<--nu(i)) cross-sections sigma(nu(f)<--nu(i) )(E) in resonant e-N(2) and e-H(2) scattering are calculated from transition matrix elements T(nu(f),nu(i) )(E) obtained using Fourier transform of the cross correlation function , where psi(nu(i))(R,t) approximately =e(-iH(A(2))-(R)t/h phi(nu(i))(R) with time evolution under the influence of the resonance anionic Hamiltonian H(A(2) (-))(A(2) (-)=N(2)(-)/H(2) (-)) implemented using Lanczos and fast Fourier transforms. The target (A(2)) vibrational eigenfunctions phi(nu(i))(R) and phi(nu(f))(R) are calculated using Fourier grid Hamiltonian method applied to potential energy (PE) curves of the neutral target. Application of this simple systematization to calculate vibrational structure in e-N(2) and e-H(2) scattering cross-sections provides mechanistic insights into features underlying presence/absence of structure in e-N(2) and e-H(2) scattering cross-sections. The results obtained with approximate PE curves are in reasonable agreement with experimental/calculated cross-section profiles, and cross correlation functions provide a simple demarcation between the boomerang and impulse models.

  11. Low frequency vibrational spectra, barrier to internal rotation, and RHF/STO-3G * ab initio calculations of 3-bromopropene

    NASA Astrophysics Data System (ADS)

    Durig, J. R.; Tang, Qun; Little, T. S.

    1992-06-01

    The far-infrared spectrum of gaseous 3-bromopropene, CH 2CHCH 2Br, has been recorded from 350 to 35 cm -1 at a resolution of 0.1 cm -1. The fundamental asymmetric torsional frequencies of the more stable gauche (dihedral angle ∢ CCCBr = 118.0 ± 0.2°) and higher energy cis (bromine atom eclipsing the double bond and dihedral angle ∢ CCCBr = 0°) conformers have been observed at about 93 and 113.3 cm -1 in the low frequency Raman and far-infrared spectra of the gas respectively. Three excited state torsional transitions falling to lower frequency have also been observed for the cis conformer. From studies of the Raman spectrum of the gas at variable temperatures, a value of 257 ± 50 cm -1 (735 ± 143 cal mol -1) has been determined for the enthalpy difference between the conformers. From these data the asymmetric torsional potential governing internal rotation about the CC has been determined and the potential coefficients are: V1 = -293 ± 18; V2 = -106 ± 26; V3 = 825 ± 12; V4 = 85 ± 13; V6 = -53 ± 6 cm -1. This potential function gives cis to gauche, gauche to gauche and gauche to cis barriers of 749, 770 and 986 cm -1 respectively, and an enthalpy difference between the conformers of 237 ± 56 cm -1 (672 ± 160 cal mol -1). The r0 structural parameters for the heavy atom skeleton of the gauche conformer have been determined from previously reported microwave rotational constants along with a fixed CBr distance taken from the electron diffraction study. The determined parameters (distances in »ngströms, angles in degrees) are: r(C 1 = C 2) = 1.335 ± 0.003; r(C 2C 3) = 1.492 ± 0.002; ∢ C 1C 2C 3 = 122.6 ± 0.1; ∢ BrC 3C 2 = 110.1 ± 0.1; ∢ C 1C 2C 3Br = 118.0 ± 0.2. The asymmetric torsional potential surface, complete equilibrium geometries and vibrational frequencies have been calculated using restricted Hartree-Fock calculations with the STO-3G * basis set. All of these results are discussed and compared with the corresponding

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

    PubMed

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

    2014-02-01

    This study introduces an improved hybrid MP2/MP4 ab initio potential for vibrational spectroscopy calculations which is very accurate, yet without high computational demands. The method uses harmonic vibrational calculations with the MP4(SDQ) potential to construct an improved MP2 potential by coordinate scaling. This improved MP2 potential is used for the anharmonic VSCF calculation. The method was tested spectroscopically for four molecules: butane, acetone, ethylene and glycine. Very good agreement with experiment was found. For most of the systems, the more accurate harmonic treatment considerably improved the MP2 anharmonic results. PMID:23838574

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

    NASA Astrophysics Data System (ADS)

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

    2011-11-01

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

  14. 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.

  15. Experimental and calculation aspects of vibrational spectra and optimized geometry of 2,3,4-tri-fluoro-benzoic acid dimer.

    PubMed

    Mukherjee, V; Singh, N P; Yadav, R A

    2009-12-01

    Raman and FTIR spectra for 2,3,4-tri-fluoro-benzoic acid molecules have been recorded in the regions 50-4000 cm(-1) and 400-4000 cm(-1) respectively. The geometrical parameters have been optimized in both the monomeric and dimeric forms while vibrational frequencies have been calculated in optimum state in the dimeric form by employing DFT method. SQM force fields have also been used to calculate potential energy distributions in order to make conspicuous vibrational assignments. Raman activities calculated by DFT method have been converted to the corresponding Raman intensities using Raman scattering theory. Optimized geometries of the molecule have been interpreted and compared with the earlier reported experimental values for benzoic acid and some mono and di-fluorinated benzoic acids. Some of the vibrational frequencies of the title molecule are effected upon profusely with the fluorine substitutions in comparison to benzoic acid and these differences have been interpreted. The strong doubly hydrogen-bonded interface of the dimerized system is well demonstrated by the red shift in OH stretching frequency concomitant with the elongation of bond length.

  16. 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.

  17. 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.

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

    PubMed

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

    2015-07-21

    In previous works, we have introduced an alternative perturbation scheme to find approximate solutions of the spectral problem for the rotation-vibration molecular Hamiltonian. An important feature of our approach is that the zero order Hamiltonian is the direct product of a purely vibrational Hamiltonian with the identity on the rotational degrees of freedom. The convergence of our method for the methane vibrational ground state was very satisfactory and our predictions were quantitative. In the present article, we provide further details on the implementation of the method in the degenerate and quasi-degenerate cases. The quasi-degenerate version of the method is tested on excited polyads of methane, and the results are assessed with respect to a variational treatment. The optimal choice of the size of quasi-degenerate spaces is determined by a trade-off between speed of convergence of the perturbation series and the computational effort to obtain the effective super-Hamiltonian. PMID:26203014

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

    SciTech Connect

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

    2015-07-21

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

  20. 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.

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

    PubMed

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

    2008-08-21

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

  2. Complex vibrational analysis of an antiferroelectric liquid crystal based on solid-state oriented quantum chemical calculations and experimental molecular spectroscopy.

    PubMed

    Drużbicki, Kacper; Mikuli, Edward; Kocot, Antoni; Ossowska-Chruściel, Mirosława Danuta; Chruściel, Janusz; Zalewski, Sławomir

    2012-08-01

    The experimental and theoretical vibrational spectroscopic study of one of a novel antiferroelectric liquid crystals (AFLC), known under the MHPSBO10 acronym, have been undertaken. The interpretation of both FT-IR and FT-Raman spectra was focused mainly on the solid-state data. To analyze the experimental results along with the molecular properties, density functional theory (DFT) computations were performed using several modern theoretical approaches. The presented calculations were performed within the isolated molecule model, probing the performance of modern exchange-correlations functionals, as well as going beyond, i.e., within hybrid (ONIOM) and periodic boundary conditions (PBC) methodologies. A detailed band assignment was supported by the normal-mode analysis with SQM ab initio force field scaling. The results are supplemented by the noncovalent interactions analysis (NCI). The relatively noticeable spectral differences observed upon Crystal to AFLC phase transition have also been reported. For the most prominent vibrational modes, the geometries of the transition dipole moments along with the main components of vibrational polarizability were analyzed in terms of the molecular frame. One of the goals of the paper was to optimize the procedure of solid-state calculations to obtain the results comparable with the all electron calculations, performed routinely for isolated molecules, and to test their performance. The presented study delivers a complex insight into the vibrational spectrum with a noticeable improvement of the theoretical results obtained for significantly attracting mesogens using modern molecular modeling approaches. The presented modeling conditions are very promising for further description of similar large molecular crystals. PMID:22709148

  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 (β) and molecular electrostatic potential of the molecule was computed using DFT calculations. The electron density based local reactivity descriptor such as Fukui functions were calculated to explain the chemically reactive site in the molecule.

  4. 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 (β) and molecular electrostatic potential of the molecule was computed using DFT calculations. The electron density based local reactivity descriptor such as Fukui functions were calculated to explain the chemically reactive site in the molecule.

  5. 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.

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

    SciTech Connect

    McGuire, John Andrew

    2004-11-24

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

  7. An ab initioCalculation of the Dipole Moment Surfaces and the Vibrational Transition Moments of the H 2Te Molecule

    NASA Astrophysics Data System (ADS)

    Kozin, Igor N.; Jensen, Per; Li, Yan; Buenker, Robert J.; Hirsch, Gerhard; Klee, Stefan

    1997-01-01

    The present work reports an ab initioMRD-CI calculation of the dipole moment surfaces for the electronic ground state of the H 2Te molecule. Using the ab initioresults, we calculate the vibrational transition moments, and we simulate the far-infrared spectrum of H 2Te by means of the MORBID program system. We obtain the equilibrium value of the dipole moment from the ab initiocalculation as 0.377 Debye based on our initial theoretical treatment which was employed over a wide range of molecular geometries. However, the use of an improved AO basis at the equilibrium geometry of H 2Te lowers this result to 0.298 Debye. The comparison of our simulated far-infrared spectrum with the experimental spectrum suggests that this value is too large, and that the correct value is certainly larger than 0.19 Debye and very probably smaller than 0.26 Debye. From the ab initiodata, we predict many vibrational transition moments for H 2Te, D 2Te, and HDTe. We hope that these results will be of assistance in the interpretation of the rotation-vibration spectrum of these molecules.

  8. 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.

  9. 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.

  10. 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

    2015-01-01

    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

  11. Calculation of Rotation-Vibration Energy Levels of the Water Molecule with Near-Experimental Accuracy Based on an ab Initio Potential Energy Surface

    NASA Astrophysics Data System (ADS)

    Polyansky, Oleg L.; Ovsyannikov, Roman I.; Kyuberis, Aleksandra A.; Lodi, Lorenzo; Tennyson, Jonathan; Zobov, Nikolai F.

    2013-10-01

    A recently computed, high-accuracy ab initio Born-Oppenheimer (BO) potential energy surface (PES) for the water molecule is combined with relativistic, adiabatic, quantum electrodynamics, and, crucially, nonadiabatic corrections. Calculations of ro-vibrational levels are presented for several water isotopologues and shown to have unprecedented accuracy. A purely ab initio calculation reproduces some 200 known band origins associated with seven isotopologues of water with a standard deviation (σ) of about 0.35 cm-1. Introducing three semiempirical scaling parameters, two affecting the BO PES and one controlling nonadiabatic effects, reduces σ below 0.1 cm-1. Introducing one further rotational nonadiabatic parameter gives σ better than 0.1 cm-1 for all observed ro-vibrational energy levels up to J = 25. We conjecture that the energy levels of closed-shell molecules with roughly the same number of electrons as water, such as NH3, CH4, and H3O+, could be calculated to this accuracy using an analogous procedure. This means that near-ab initio calculations are capable of predicting transition frequencies with an accuracy only about a factor of 5 worse than high resolution experiments.

  12. 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

    2015-01-01

    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.

  13. Corrections to the Born-Oppenheimer approximation for a harmonic oscillator

    NASA Astrophysics Data System (ADS)

    Patterson, Chris W.

    1993-02-01

    We derive simple expressions for the energy corrections to the Born-Oppenheimer approximation valid for a harmonic oscillator. We apply these corrections to the electronic and rotational ground state of H+2 and show that the diabatic energy corrections are linearly dependent on the vibrational quantum numbers as seen in recent variational calculations [D. A. Kohl and E. J. Shipsey, J. Chem. Phys. 84, 2707 (1986)].

  14. Vibrational Heat Transport in Molecular Junctions.

    PubMed

    Segal, Dvira; Agarwalla, Bijay Kumar

    2016-05-27

    We review studies of vibrational energy transfer in a molecular junction geometry, consisting of a molecule bridging two heat reservoirs, solids or large chemical compounds. This setup is of interest for applications in molecular electronics, thermoelectrics, and nanophononics, and for addressing basic questions in the theory of classical and quantum transport. Calculations show that system size, disorder, structure, dimensionality, internal anharmonicities, contact interaction, and quantum coherent effects are factors that combine to determine the predominant mechanism (ballistic/diffusive), effectiveness (poor/good), and functionality (linear/nonlinear) of thermal conduction at the nanoscale. We review recent experiments and relevant calculations of quantum heat transfer in molecular junctions. We recount the Landauer approach, appropriate for the study of elastic (harmonic) phononic transport, and outline techniques that incorporate molecular anharmonicities. Theoretical methods are described along with examples illustrating the challenge of reaching control over vibrational heat conduction in molecules. PMID:27215814

  15. Vibrational Heat Transport in Molecular Junctions

    NASA Astrophysics Data System (ADS)

    Segal, Dvira; Agarwalla, Bijay Kumar

    2016-05-01

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

  16. Vibrations of the carbon dioxide dimer

    NASA Astrophysics Data System (ADS)

    Chen, Hua; Light, J. C.

    2000-03-01

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

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

    NASA Astrophysics Data System (ADS)

    Kruglova, T. V.

    2004-01-01

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

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

    PubMed

    Zhang, Xianxi; Zhang, Yuexing; Jiang, Jianzhuang

    2004-08-01

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

  20. 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.

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

    NASA Astrophysics Data System (ADS)

    Govindarasu, K.; Kavitha, E.

    2015-05-01

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

  2. 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 Γ-R points in the Brillouin zone to the cubic structure, a direct band gap of 2.41 eV at the Γ- Γ points to the orthorhombic structure, and an indirect band gap of 2.31 eV at theM - Γ 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 (ν ~ 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. Vibrational normal modes calculation in the crystalline state of methylated monosaccharides: Anomers of the methyl-D-glucopyranoside and methyl-D-xylopyranoside molecules

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  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 calculation and spectroscopic analysis of the intramolecular vibrational redistribution in 1,1,1,2-tetrafluoroiodoethane CF3CHFI

    NASA Astrophysics Data System (ADS)

    Pochert, Jörg; Quack, Martin; Stohner, Jürgen; Willeke, Martin

    2000-08-01

    We report a new mechanism for intramolecular vibrational redistribution (IVR) in CF3CHFI which couples the CH chromophore vibrations through a strong Fermi resonance to the formal CF stretching normal mode (a heavy atom frame mode) involving the trans F-atom across the CC bond. The analysis is made possible by comparing spectroscopic results with extensive ab initio calculations of the vibrational fundamental and overtone spectra in the range extending to 12 000 cm-1. Potential energy and electric dipole moment hypersurfaces are calculated ab initio by second order Møller-Plesset perturbation theory (MP2) on a grid involving the CH stretching, two CH bending modes and one high frequency CF stretching normal mode. The potentials are scaled to obtain agreement between the experimental spectrum and the theoretical spectrum calculated by a discrete variable representation technique on this grid. Both spectra are then analyzed in terms of three-dimensional (3D) and four-dimensional (4D) effective vibrational Hamiltonians including Fermi- and Darling-Dennison-type resonances between the CH stretching mode and the CH bending modes and the CF stretching mode. The interaction between the CH modes and the CF mode is clearly visible in the experimental and calculated (4D) spectra. The effective Fermi resonance coupling constants [ksff'≃(40±10) cm-1 and ksaf'≃(55±10) cm-1] coupling the CH and CF mode subspaces are of about the same magnitude as the intra-CH chromophore Fermi resonances (ksaa'≃56 cm-1 and ksbb'≃42 cm-1, coupling CH stretching mode "s" with the two CH bending modes "a" and "b"). The chiral, pseudo-Cs symmetry breaking coupling (ksab'≃11 cm-1) is complemented by an equally strong coupling through the CF mode (ksfb'≃15 cm-1). It is demonstrated that low order perturbation theoretical analysis using potential constants from a polynomial expansion to represent effective coupling constants gives inadequate results with discrepancies ranging about from

  7. Calculation of the Transition from Pairing Vibrational to Pairing Rotational Regimes between Magic Nuclei {sup 100}Sn and {sup 132}Sn via Two-Nucleon Transfer Reactions

    SciTech Connect

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

    2011-08-26

    Absolute values of two-particle transfer cross sections along the Sn-isotopic chain are calculated. They agree with measurements within errors and without free parameters. Within this scenario, the predictions concerning the absolute value of the two-particle transfer cross sections associated with the excitation of the pairing vibrational spectrum expected around the recently discovered closed shell nucleus {sub 50}{sup 132}Sn{sub 82} and the very exotic nucleus {sub 50}{sup 100}Sn{sub 50} can be considered quantitative, opening new perspectives in the study of pairing in nuclei.

  8. Multi-Frequency Harmonics Technique for HIFU Tissue Treatment

    NASA Astrophysics Data System (ADS)

    Rybyanets, Andrey N.; Lugovaya, Maria A.; Rybyanets, Anastasia A.

    2010-03-01

    New technique for enhancing of tissue lysis and enlarging treatment volume during one HIFU sonification is proposed. The technique consists in simultaneous or alternative (at optimal repetition frequency) excitation of single element HIFU transducer on a frequencies corresponding to odd natural harmonics of piezoceramic element at ultrasound energy levels sufficient for producing cavitational, thermal or mechanical damage of fat cells at each of aforementioned frequencies. Calculation and FEM modeling of transducer vibrations and acoustic field patterns for different frequencies sets were performed. Acoustic pressure in focal plane was measured in water using calibrated hydrophone and 3D acoustic scanning system. In vitro experiments on different tissues and phantoms confirming the advantages of multifrequency harmonic method were performed.

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

  10. Benchmark Quantum Mechanical Calculations of Vibrationally Resolved Cross Sections and Rate Constants on ab Initio Potential Energy Surfaces for the F + HD Reaction: Comparisons with Experiments.

    PubMed

    De Fazio, Dario; Cavalli, Simonetta; Aquilanti, Vincenzo

    2016-07-14

    Quantum scattering calculations within the time-independent approach in an extended interval of energies were performed for the title reaction on four ab initio potential energy surfaces. The calculated integral cross sections, vibrational branching ratios, and rate constants are compared with scattering experiments as well as with chemical kinetics rate data available for this system for both the HF and DF channels. The calculations on the CSZ (J. Chem. Phys. 2015, 142, 024303) and LWAL (J. Chem. Phys. 2007, 127, 174302) surfaces are in close agreement between them and reproduce satisfactorily the experimental measurements. The agreement with the experiments is improved with respect to calculations on the earlier SW (J. Chem. Phys. 1996, 104, 6515) and FXZ (J. Chem. Phys. 2008, 129, 011103) surfaces. The results presented here witness the remarkable progress made by quantum chemistry calculations in describing the interatomic interactions governing the dynamics and kinetics of this reaction. They also suggest that comparison with translationally and rotationally averaged experimental observables is not sufficient to assess the relative accuracy of highly accurate potential energy surfaces. The dynamics and kinetics calculations show that temperatures lower than 50 K or molecular beam energy spread below 1 meV must be reached to discriminate the accuracy of the LWAL and the CSZ surfaces.

  11. 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…

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

    PubMed

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

    2011-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

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

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

    PubMed

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

    2011-05-01

    We report the structure and spectroscopic characteristics for the Xe:HI van der Waals binary isomers determined from variational solutions of two-dimensional and three-dimensional (3D) vibrational Schrödinger equations. The solutions are based on a potential energy surface computed at the coupled-cluster level of theory including single and double excitations and a non-iterative perturbation treatment of triple excitations [CCSD(T)]. The dipole moment surface was calculated using quadratic configuration interaction (QCISD). The global potential minimum is shown to be located at the anti-hydrogen-bonded Xe-IH isomer, 21 cm(-1) below the secondary local minimum associated with the hydrogen-bonded Xe-HI isomeric form. The dissociation energy from the global minimum is 245.9 cm(-1). 3D Schrödinger equations are solved for the rotational quantum numbers J = k = 0, 1, and 2, without invoking an adiabatic separation of high- and low-frequency degrees of freedom. The vibrational ground state resides in the Xe-HI potential well, while the first excited state, 8.59 cm(-1) above the ground, occupies the Xe-IH well. We find that intra-complex dynamics exhibits a sudden transformation upon increase of the r(HI) bond length, accompanied by abrupt changes in the geometric and dipole parameters. A similar chaotic behavior is predicted to occur for Xe:DI at a shorter r(DI) bond length, which implies stronger coupling between low- and high-frequency motions in the heavier complex. Our calculations confirm a strong enhancement for the r(HI) stretch fundamental and a significant weakening for the first overtone vibrational transitions in Xe:HI, as compared to those in the free HI molecule. A qualitative explanation of this, earlier experimentally detected effect is suggested. PMID:21548682

  15. Theoretical calculation of the OH vibrational overtone spectra of 1-n alkane diols (n = 2-4): origin of disappearing hydrogen-bonded OH peak.

    PubMed

    Cheng, Yu-Lung; Chen, Hui-Yi; Takahashi, Kaito

    2011-06-01

    In this theoretical study, we simulated the vibrational overtone spectrum of ethylene glycol (EG), 1-3 propanediol (PD), and 1-4 butanediol (BD). Using the local mode model along with the potential energy curve and dipole moment function calculated by B3LYP/6-31+G(d,p) and QCISD/6-311++G(3df,3pd), we obtained the theoretical peak position and integrated absorption coefficient. Furthermore, the vibrational spectra was simulated using a Voigt function using homogeneous and inhomogenous width obtained from quantum chemical calculation methods. Previously, Howard and Kjaergaard recorded the second and third overtone photoacoustic spectra of the three aforementioned alkane diols in the gas phase and observed that the intramolecular hydrogen bonded OH peak becomes difficult to observe as the intramolecular hydrogen bonding strength increased, that is, as the chain length was increased. In this paper we show that the disappearance of the hydrogen-bonded OH peak for the OH stretching overtone excitation for BD is partly due to the increase in homogeneous width due to the increase in the hydrogen bond strength and partly due to the decrease in the relative population of the intramolecular hydrogen-bonded conformers as the chain length is increased. This latter feature is a consequence of the unfavorable strained geometry needed to form the intramolecular hydrogen bond in longer alkane chains. PMID:21568300

  16. Correlation of observed and model vibrational frequencies for aqueous organic acids: UV resonance Raman spectra and molecular orbital calculations of benzoic, salicylic, and phthalic acids.

    PubMed

    Trout, Chad C; Tambach, T J; Kubicki, James D

    2005-09-01

    The aromatic carboxylic acids benzoic, salicylic and phthalic acid were used to study the interaction of soluble organics compounds with metal cations. To accomplish this, we have developed methods for studying the carboxylic acids using UV resonance Raman (UVRR) combined with molecular orbital density functional theory calculations. The pH values of the acid solutions were based on the pK(a)'s for the different acids to examine the neutral and charged species. Deprotonation of the organic acids was detectable down to 10(-4)M using UVRR (two orders of magnitude lower than previous vibrational spectroscopy studies). Limitations to decreasing the concentration lower using the current UVRR facilities are discussed. Two methods were used to calculate the optimized geometry and frequencies of the acids: explicit and continuum solvation. The frequencies from the experimental spectra were then compared to the theoretical results obtained from the two methods.

  17. Correlation of observed and model vibrational frequencies for aqueous organic acids: UV resonance Raman spectra and molecular orbital calculations of benzoic, salicylic, and phthalic acids

    NASA Astrophysics Data System (ADS)

    Trout, Chad C.; Tambach, T. J.; Kubicki, James D.

    2005-09-01

    The aromatic carboxylic acids benzoic, salicylic and phthalic acid were used to study the interaction of soluble organics compounds with metal cations. To accomplish this, we have developed methods for studying the carboxylic acids using UV resonance Raman (UVRR) combined with molecular orbital density functional theory calculations. The pH values of the acid solutions were based on the p Ka's for the different acids to examine the neutral and charged species. Deprotonation of the organic acids was detectable down to 10 -4 M using UVRR (two orders of magnitude lower than previous vibrational spectroscopy studies). Limitations to decreasing the concentration lower using the current UVRR facilities are discussed. Two methods were used to calculate the optimized geometry and frequencies of the acids: explicit and continuum solvation. The frequencies from the experimental spectra were then compared to the theoretical results obtained from the two methods.

  18. 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.

  19. Theoretical prediction of vibrational spectra

    NASA Astrophysics Data System (ADS)

    Niu, Zefu; Dunn, Kevin M.; Boggs, James E.

    The complete harmonic force field and the diagonal and first off-diagonal cubic constants of aniline have been calculated ab initio using a 4-21 basis set augmented by addition of d functions to the nitrogen atom. The force constants were then scaled using scale factors optimized previously to give the best fit to the similarly computed vibrational spectra of benzene and its deuterated isotopomers. The vibrational spectra of aniline, aniline-NHD, and aniline-ND2 were then calculated from this scaled quantum mechanical (SQM) force field and compared with experimentally observed spectra. Several corrections were made to previously proposed empirical spectral assignments. Because of computational difficulties, no definitive statement can be made about the torsion or inversion modes of the amino group. Aside from these and the C-H stretching frequencies for which the detailed assignment is still quite uncertain, the average deviation between the observed frequencies and those obtained entirely from the scaled computed force field is 9·1 cm-1. Dipole moment derivatives and infrared absorption intensities were also calculated, but these are of lower accuracy.

  20. Electronic [UV-Visible] and vibrational [FT-IR, FT-Raman] investigation and NMR-mass spectroscopic analysis of terephthalic acid using quantum Gaussian calculations

    NASA Astrophysics Data System (ADS)

    Karthikeyan, N.; Joseph Prince, J.; Ramalingam, S.; Periandy, S.

    2015-03-01

    In this research work, the vibrational IR, polarization Raman, NMR and mass spectra of terephthalic acid (TA) were recorded. The observed fundamental peaks (IR, Raman) were assigned according to their distinctiveness region. The hybrid computational calculations were carried out for calculating geometrical and vibrational parameters by DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the corresponding results were tabulated. The molecular mass spectral data related to base molecule and substitutional group of the compound was analyzed. The modification of the chemical property by the reaction mechanism of the injection of dicarboxylic group in the base molecule was investigated. The 13C and 1H NMR spectra were simulated by using the gauge independent atomic orbital (GIAO) method and the absolute chemical shifts related to TMS were compared with experimental spectra. The study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, were performed by hybrid Gaussian calculation methods. The orbital energies of different levels of HOMO and LUMO were calculated and the molecular orbital lobe overlapping showed the inter charge transformation between the base molecule and ligand group. From the frontier molecular orbitals (FMO), the possibility of electrophilic and nucleophilic hit also analyzed. The NLO activity of the title compound related to Polarizability and hyperpolarizability were also discussed. The present molecule was fragmented with respect to atomic mass and the mass variation depends on the substitutions have also been studied.

  1. Electronic [UV-Visible] and vibrational [FT-IR, FT-Raman] investigation and NMR-mass spectroscopic analysis of terephthalic acid using quantum Gaussian calculations.

    PubMed

    Karthikeyan, N; Prince, J Joseph; Ramalingam, S; Periandy, S

    2015-03-15

    In this research work, the vibrational IR, polarization Raman, NMR and mass spectra of terephthalic acid (TA) were recorded. The observed fundamental peaks (IR, Raman) were assigned according to their distinctiveness region. The hybrid computational calculations were carried out for calculating geometrical and vibrational parameters by DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the corresponding results were tabulated. The molecular mass spectral data related to base molecule and substitutional group of the compound was analyzed. The modification of the chemical property by the reaction mechanism of the injection of dicarboxylic group in the base molecule was investigated. The (13)C and (1)H NMR spectra were simulated by using the gauge independent atomic orbital (GIAO) method and the absolute chemical shifts related to TMS were compared with experimental spectra. The study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, were performed by hybrid Gaussian calculation methods. The orbital energies of different levels of HOMO and LUMO were calculated and the molecular orbital lobe overlapping showed the inter charge transformation between the base molecule and ligand group. From the frontier molecular orbitals (FMO), the possibility of electrophilic and nucleophilic hit also analyzed. The NLO activity of the title compound related to Polarizability and hyperpolarizability were also discussed. The present molecule was fragmented with respect to atomic mass and the mass variation depends on the substitutions have also been studied.

  2. Ab Initio XAS Debye-Waller Factors Beyond the Harmonic Approximation

    NASA Astrophysics Data System (ADS)

    Vila, Fernando; Rossner, H. H.; Krappe, H. J.; Rehr, J. J.

    2007-03-01

    We introduce an ab initio approach to calculate the temperature dependent vibrational effects in x-ray absorption spectra beyond the harmonic approximation. Instead of relying on empirical models, we apply electronic structure theory to determine the dynamical matrix of the system, from which the appropriate vibrational densities of state can be obtained using a Lanczos recursion algorithm [2]. By combining thermodynamic perturbation theory and the quasi-harmonic approximation we obtain x-ray absorption fine structure (XAFS) cumulants such as the mean square relative displacement (2nd cumulant), the thermal expansion (first cumulant), the asymmetry of the distribution (third cumulant) and the perpendicular motion contribution to the DW factor. Other quantities of interest such as mean square atomic displacements are also discussed. [2]H.J. Krappe and H.H. Rossner, Phys. Rev. B70, 104102 (2004).

  3. Structural and vibrational spectral investigations of melaminium maleate monohydrate by FTIR, FT-Raman and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Arjunan, V.; Kalaivani, M.; Marchewka, M. K.; Mohan, S.

    2013-04-01

    The structural investigations of the molecular complex of melamine with maleic acid, namely melaminium maleate monohydrate have been carried out by quantum chemical methods in addition to FTIR, FT-Raman and far-infrared spectral studies. The quantum chemical studies were performed with DFT (B3LYP) method using 6-31G**, cc-pVDZ and 6-311++G** basis sets to determine the energy, structural and thermodynamic parameters of melaminium maleate monohydrate. The hydrogen atom from maleic acid was transferred to the melamine molecule giving the singly protonated melaminium cation. The ability of ions to form spontaneous three-dimensional structure through weak Osbnd H⋯O and Nsbnd H⋯O hydrogen bonds shows notable vibrational effects.

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

    NASA Astrophysics Data System (ADS)

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

    2008-11-01

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

  5. The harmonic frequencies of benzene

    NASA Astrophysics Data System (ADS)

    Handy, Nicholas C.; Maslen, Paul E.; Amos, Roger D.; Andrews, Jamie S.; Murray, Christopher W.; Laming, Gregory J.

    1992-09-01

    We report calculations for the harmonic frequencies of C 6H 6 and C 6D 6. Our most sophisticated quantum chemistry values are obtained with the MP2 method and a TZ2P+f basis set (288 basis functions), which are the largest such calculations reported on benzene to date. Using the SCF density, we also calculate the frequencies using the exchange and correlation expressions of density functional theory. We compare our calculated harmonic frequencies with those deduced from experiment by Goodman, Ozkabak and Thakur. The density functional frequencies appear to be more reliable predictions than the MP2 frequencies and they are obtained at significantly less cost.

  6. Harmonic engine

    DOEpatents

    Bennett, Charles L.

    2009-10-20

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

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

    PubMed

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

    2012-06-01

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

  8. 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.

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

    PubMed

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

    2000-11-15

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

  10. Three-photon absorption and vibrational spectroscopic study of 2-methylamino-5-chlorobenzophenone.

    PubMed

    Sajan, D; Chaitanya, K; Safakath, K; Philip, Reji; Suthan, T; Rajesh, N P

    2013-04-01

    In this paper, the vibrational spectral analysis and three-photon absorption properties of an organic material of 2-methylamino-5-chlorobenzophenone have been reported. The geometry and harmonic vibrational wavenumbers are calculated with the help of B3LYP density functional theory method. The detailed interpretation of the vibrational spectra has been carried out with the aid of normal coordinate analysis following the scaled quantum mechanical force field methodology (SQM). SQM force fields have also been used to calculate potential energy distribution (PED) in order to make conspicuous vibrational assignments. The nonlinear absorption properties have been investigated in ethanol solution at 532nm using the Z-scan technique employing laser pulses of 5ns duration. Open aperture Z-scan data reveal the presence of effective three-photon absorption for ns pulses at 532nm resulting in a strong optical limiting behavior, indicating possible photonic applications. PMID:23410921

  11. 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.

  12. Vibrational and Thermal Properties of β-HMX and TATB from Dispersion Corrected Density Functional Theory

    NASA Astrophysics Data System (ADS)

    Landerville, Aaron; Oleynik, Ivan

    2015-06-01

    Dispersion Corrected Density Functional Theory (DFT+vdW) calculations are performed to predict vibrational and thermal properties of the bulk energetic materials (EMs) β-octahydrocyclotetramethylene-tetranitramine (β-HMX) and triaminotrinitrobenzene (TATB). DFT+vdW calculations of optimized unit cells along the hydrostatic equation of state are followed by frozen-phonon calculations of their respective vibration spectra. These are then used under the quasi-harmonic approximation to obtain zero-point and thermal free energy contributions to the pressure, resulting in PVT equations of state for each material that is in excellent agreement with experiment. Further, heat capacities, thermal expansion coefficients, and Gruneissen parameters as functions of temperature are calculated and compared with experiment. The vibrational properties, including phonon densities of states and pressure dependencies of individual modes, are also analyzed and compared with experiment.

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

    PubMed

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

    2015-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

  15. 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 μ-tensor within the Watson operator. Normal coordinates are not the optimal choice for describing double-minimum potentials and the question remains if they can be used for accurate calculations at all. However, their unique definition is an appealing feature, which removes remaining errors in truncated potential expansions arising from different choices of curvilinear coordinate systems. Fully automated calculations are presented, which demonstrate, that the proposed scheme allows for the determination of energy levels and tunneling splittings as a routine application.

  16. Calculation of the vibrational excited states of malonaldehyde and their tunneling splittings with the multi-configuration time-dependent Hartree method

    SciTech Connect

    Schröder, Markus Meyer, Hans-Dieter

    2014-07-21

    We report energies and tunneling splittings of vibrational excited states of malonaldehyde which have been obtained using full dimensional quantum mechanical calculations. To this end we employed the multi configuration time-dependent Hartree method. The results have been obtained using a recently published potential energy surface [Y. Wang, B. J. Braams, J. M. Bowman, S. Carter, and D. P. Tew, J. Chem. Phys. 128, 224314 (2008)] which has been brought into a suitable form by a modified version of the n-mode representation which was used with two different arrangements of coordinates. The relevant terms of the expansion have been identified with a Metropolis algorithm and a diffusion Monte-Carlo technique, respectively.

  17. Calculation of the vibrational excited states of malonaldehyde and their tunneling splittings with the multi-configuration time-dependent Hartree method

    NASA Astrophysics Data System (ADS)

    Schröder, Markus; Meyer, Hans-Dieter

    2014-07-01

    We report energies and tunneling splittings of vibrational excited states of malonaldehyde which have been obtained using full dimensional quantum mechanical calculations. To this end we employed the multi configuration time-dependent Hartree method. The results have been obtained using a recently published potential energy surface [Y. Wang, B. J. Braams, J. M. Bowman, S. Carter, and D. P. Tew, J. Chem. Phys. 128, 224314 (2008)] which has been brought into a suitable form by a modified version of the n-mode representation which was used with two different arrangements of coordinates. The relevant terms of the expansion have been identified with a Metropolis algorithm and a diffusion Monte-Carlo technique, respectively.

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

    PubMed

    Durig, James R; Zheng, Chao

    2007-11-01

    Variable temperature (-105 to -150 degrees C) studies of the infrared spectra (3500-400 cm(-1)) of ethylisothiocyanate, CH(3)CH(2)NCS, dissolved in liquid krypton have been recorded. Additionally the infrared spectra of the gas and solid have been re-investigated. These spectroscopic data indicate a single conformer in all physical states with a large number of molecules in the gas phase at ambient temperature in excited states of the CN torsional mode which has a very low barrier to conformational interchange. To aid in the analyses of the vibrational and rotational spectra, ab initio calculations have been carried out by the perturbation method to the second order (MP2) with valence and core electron correlation using a variety of basis sets up to 6-311+G(2df,2pd). With the smaller basis sets up to 6-311+G(d,p) and cc-PVDZ, the cis conformer is indicated as a transition state with all larger basis sets the cis conformer is the only stable form. The predicted energy difference from these calculations between the cis form and the higher energy trans conformer is about 125 cm(-1) which represents essentially the barrier to internal rotation of the NCS group (rotation around NC axis). Density functional theory calculation by the B3LYP method with the same basis sets predicts this barrier to be about 25 cm(-1). By utilizing the previously reported microwave rotational constants with the structural parameters predicted by the ab initio MP2(full)/6-311+G(d,p) calculations, adjusted r(0) structural parameters have been obtained for the cis form. The determined heavy atom parameters are: r(NC)=1.196(5), r(CS)=1.579(5), r(CN)=1.439(5), r(CC)=1.519(5)A for the distances and angles of angleCCN=112.1(5), angleCNC=146.2(5), angleNCS=174.0(5) degrees . The centrifugal distortion constants, dipole moments, conformational stability, vibrational frequencies, infrared intensities and Raman activities have been predicted from ab initio calculations and compared to experimental

  19. Thermal weights for semiclassical vibrational response functions

    NASA Astrophysics Data System (ADS)

    Moberg, Daniel Roger

    Semiclassical approximations to response functions can provide quantum mechanical effects for linear and nonlinear spectroscopic observables to be calculated from only classical trajectories as input. The two major components needed to evaluate a response function are the thermal weights for the system's initial conditions, and the calculation of the dynamics from those conditions. One such class of approximations for vibrational response functions utilizes classical trajectories at quantized values of classical action variables, with the effects of the radiation-matter interaction represented by discontinuous transitions. An alternative weight to the classical distribution is investigated and attempts to incorporate this both with and without this quantized action approach are presented. Two forms are constructed that 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 and coupled 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.

  20. Molecular vibrational investigation [FT-IR, FT-Raman, UV-Visible and NMR] on Bis(thiourea) Nickel chloride using HF and DFT calculations

    NASA Astrophysics Data System (ADS)

    Anand, S.; Sundararajan, R. S.; Ramachandraraja, C.; Ramalingam, S.; Durga, R.

    2015-03-01

    In the present research work, the FT-IR, FT-Raman spectra of the Bis(thiourea) Nickel chloride (BTNC) were recorded and analyzed. The observed fundamental frequencies in finger print and functional group regions were assigned according to their uniqueness region. The computational calculations were carried out by HF and DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the corresponding results were tabulated. The present organo-metallic compound was made up of covalent and coordination covalent bonds. The modified vibrational pattern of the complex molecule associated with ligand group was analyzed. Furthermore, the 13C NMR and 1H NMR spectral data were calculated by using the gauge independent atomic orbital (GIAO) method with B3LYP/6-311++G(d,p) basis set and their spectra were simulated and the chemical shifts linked to TMS were compared. A investigation on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies were carried out. The kubo gap of the present compound was calculated related to HOMO and LUMO energies which confirm the occurring of charge transformation between the base and ligand. Besides frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) was performed. The NLO properties related to Polarizability and hyperpolarizability based on the finite-field approach were also discussed.

  1. Structure of 1-methyl-6-oxyquinolinium betaine dihydrate studied by X-ray diffraction, DFT calculations, vibrational and NMR spectra

    NASA Astrophysics Data System (ADS)

    Barczyński, P.; Ratajczak-Sitarz, M.; Katrusiak, A.; Szafran, M.

    2010-07-01

    The crystals of 1-methyl-6-oxyquinolinium betaine dihydrate, 6QB·2H 2O, are triclinic, space group P1¯. The oxygen atom of 6QB exhibits an extremely rare capability of accepting four hydrogen bonds. It is engaged in four hydrogen bonds to water molecules of the 2.823, 2.825, 2.833 and 2.849 Å; each water molecule interacts with two neighbouring 6QB molecules linking them into infinite sheets. Differences in geometrical parameters between the X-ray and calculated molecules reflect changes in their structures between zwitterion and quinonoid forms. The probable assignments of the experimental FTIR solid spectrum have been made on the basis of B3LYP/6-311G(d,p) calculated frequencies in vacuum. Both 1H and 13C chemical shifts are solvent dependent. Linear correlations between the experimental 1H and 13C NMR chemical shifts of 6QB·2H 2O in solutions and the GIAO/B3LYP/6-311G(d,p) calculated magnetic isotropic shielding tensors ( σcal) using the screening solvation model, δexp = a + bσcal, are reported.

  2. Harmonic engine

    SciTech Connect

    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.

  3. Application of vibrational spectroscopy supported by theoretical calculations in identification of amorphous and crystalline forms of cefuroxime axetil.

    PubMed

    Talaczyńska, Alicja; Lewandowska, Kornelia; Jelińska, Anna; Garbacki, Piotr; Podborska, Agnieszka; Zalewski, Przemysław; Oszczapowicz, Irena; Sikora, Adam; Kozak, Maciej; Cielecka-Piontek, Judyta

    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.

  4. Numerical analysis of the hybrid transducer ultrasonic motor: comparison of characteristics calculated by transmission-line and lumped-element models.

    PubMed

    Satonobu, Jun; Friend, James R; Nakamura, Kentaro; Ueha, Sadayuki

    2002-06-01

    In this paper, a hybrid transducer ultrasonic motor is numerically analyzed by using two equivalent electrical circuit models. A transmission-line model for the torsional vibration in the stator, which can model any torsional vibration mode and their combinations, was introduced and compared with a lumped-element model, which modeled the fundamental torsional resonance mode in the stator. The calculation result by using the transmission-line model demonstrated that the second harmonic torsional vibration increased either with the static spring force by which the rotor was pressed to the stator or with the load torque placed on the rotor. The difference in the calculated motor performance between the two models appeared when the second harmonic torsional vibration became large at a sufficient static spring force.

  5. 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.

  6. 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.

  7. Conformational stability from variable temperature infrared spectra of krypton solutions, ab initio calculations, vibrational assignment, and r0 structural parameters of 1,3-difluoropropane.

    PubMed

    Durig, James R; Zheng, Chao; Williams, Michael J; Stidham, Howard D; Guirgis, Gamil A

    2004-06-01

    The infrared spectra (3200-400 cm(-1)) of krypton solutions of 1,3-difluoropropane, FCH2CH2CH2F, at variable temperatures (-105 to -150 degrees C) have been recorded. Additionally, the infrared spectra (3200-50 cm(-1)) of the gas and solid have been recorded as well as the Raman spectrum of the liquid. From a comparison of the spectra of the fluid phases with that in the solid, all of the fundamental vibrations of the C2 conformer (gauche-gauche) where the first gauche indicates the form for one of the CH2F groups and the second gauche the other CH2F, and many of those for the C1 form (trans-gauche) have been identified. Tentative assignments have been made for a few of the fundamentals of the other two conformers, i.e. C2v (trans-trans) and Cs (gauche-gauche'). By utilizing six pairs of fundamentals for these two conformers in the krypton solutions, an enthalpy difference of 277 +/- 28 cm(-1) (3.31 +/- 0.33 kJ mol(-1)) has been obtained for the C2 versus C1 conformer with the C2 conformer the more stable form. For the C2v conformer, the enthalpy difference has been determined to be 716 +/- 72 cm(-1) (8.57 +/- 0.86 kJ mol(-1)) and for the Cs form 971 +/- 115 cm(-1) (11.6 +/- 1.4 kJ mol(-1)). It is estimated that there is 64 +/- 3% of the C2 form, 34 +/-3% of the C1 form, 1% of the C2v form and 0.6% of the Cs conformer present at ambient temperature. Equilibrium geometries and total energies of the four stable conformers have been determined from ab initio calculations with full electron correlation by the perturbation method to second order as well as by hybrid density functional theory calculations with the B3LYP method using a number of basis sets. The MP2 calculations predict the C1 conformer stability to be slightly higher than the experimentally determined value whereas for the C2v and Cs conformers the predicted energy difference is much larger than the experimental value. The B3LYP calculations predict a better energy difference for both the C1 and C2v as

  8. 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.

  9. Explicitly correlated MRCI-F12 potential energy surfaces for methane fit with several permutation invariant schemes and full-dimensional vibrational calculations

    NASA Astrophysics Data System (ADS)

    Majumder, Moumita; Hegger, Samuel E.; Dawes, Richard; Manzhos, Sergei; Wang, Xiao-Gang; Tucker, Carrington, Jr.; Li, Jun; Guo, Hua

    2015-07-01

    A data-set of nearly 100,000 symmetry unique multi-configurational ab initio points for methane were generated at the (AE)-MRCI-F12(Q)/CVQZ-F12 level, including energies beyond 30,000 cm-1 above the minimum and fit into potential energy surfaces (PESs) by several permutation invariant schemes. A multi-expansion interpolative fit combining interpolating moving least squares (IMLS) fitting and permutation invariant polynomials (PIP) was able to fit the complete data-set to a root-mean-square deviation of 1.0 cm-1 and thus was used to benchmark the other fitting methods. The other fitting methods include a single PIP expansion and two neural network (NN) based approaches, one of which combines NN with PIP. Full-dimensional variational vibrational calculations using a contracted-iterative method (and a Lanczos eigensolver) were used to assess the spectroscopic accuracy of the electronic structure method. The results show that the NN-based fitting approaches are able to fit the data-set remarkably accurately with the PIP-NN method producing levels in remarkably close agreement with the PIP-IMLS benchmark. The (AE)-MRCI-F12(Q)/CVQZ-F12 electronic structure method produces vibrational levels of near spectroscopic accuracy and a superb equilibrium geometry. The levels are systematically slightly too high, beginning at ∼ 1-2 cm-1 above the fundamentals and becoming correspondingly higher for overtones. The PES is therefore suitable for small ab initio or empirical corrections and since it is based on a multi-reference method, can be extended to represent dynamically relevant dissociation channels.

  10. Adsorption of F2Cdbnd CFCl on TiO2 nano-powder: Structures, energetics and vibrational properties from DRIFT spectroscopy and periodic quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Tasinato, Nicola; Moro, Daniele; Stoppa, Paolo; Pietropolli Charmet, Andrea; Toninello, Piero; Giorgianni, Santi

    2015-10-01

    Photodegradation over titanium dioxide (TiO2) is a very appealing technology for removing environmental pollutants from the air, the adsorption interaction being the first step of the whole reaction pathway. In the present work the adsorption of F2Cdbnd CFCl (chlorotrifluoroethene, halon 1113), a compound used by industry and detected in the atmosphere, on a commercial TiO2 nano-powder is investigated experimentally by in situ DRIFT spectroscopy and theoretically through periodic ab initio calculations rooted in DFT. The spectra of the adsorbed molecule suggest that the anchoring to the surface mainly takes place through F atoms. Theoretically, five adsorption configurations for the molecule interacting with the anatase (1 0 1) surface are simulated at B3LYP level and for each of them, structures, binding energies and vibrational frequencies are derived. The interplay between theory and experiments shows the coexistence of different adsorption configurations, the foremost ones featuring the interaction of one F atom with a fivefold coordinated Ti4+ of the surface. These two adsorption models, which mostly differ for the orientation of the adsorbate with respect to the surface, feature a binding energy of -45.6 and -41.0 kJ mol-1 according to dispersion corrected DFT calculations. The favorable adsorption interaction appears as an important requirement toward the application of titanium dioxide technologies for the photocatalytic degradation of halon 1113.

  11. α- And β Pahases of oxalic acid, H 2C 2O 4: Vibrational spectra, normal-coordinate calculations, and intermolecular forces

    NASA Astrophysics Data System (ADS)

    De Villepin, J.; Novak, A.; Bougeard, D.

    1982-12-01

    Infrared (4000-30 cm -1) and Raman (4000-0 cm -) spectra of single crystals of α-oxalic acid (Pcab, Z=4) have been investigated at 100 and 300 K. A complete assignment of all modes in terms of symmetry species and to internal, librational, translational, and hydrogen bond motions is given. In order to interpret the spectra and to determine the crystal field, several normal-coordinate calculations (free molecule, rigid body model, unit cell as a supermolecule) have been carried out. The calculations are in good agreement with the experimental results and show the importance of different intermolecular forces: OH … O hydrogen bonds and very short C … O interactions lead to both unusually strong correlation field splitting and high lattice frequencies while quadrupole-quadrupole and CO dipole-dipole interactions influence lattice and some internal vibrations, respectively. The intermolecular potentials obtained for α-oxalic acid are transferable to the β form having a different crystal structure (P2 1/c, Z = 2) and stronger hydrogen bonds.

  12. Effects of wave function modifications on calculated CF and CCl vibrational frequencies and infrared intensities of the dihaloethylenes

    NASA Astrophysics Data System (ADS)

    Ramos, Mozart N.; da Silva, João Bosco P.; Bruns, Roy E.

    1997-09-01

    The CF and CCl calculated stretching frequencies are shown to obey different factorial models. On average, Møller-Plesset 2 treatment lowers the CF stretching frequencies by 100 cm -1 whereas it only lowers the CCl ones by 37 cm -1. Diffuse functions have negligible effects on these CCl frequencies but lower the CF stretching values by 24 cm -1. However, inclusion of polarization functions in the basis set increases both the CF and CCl stretching frequencies by 90 cm -1. The use of Møller-Plesset 2 treatment also lowers the bending frequencies and the inclusion of polarization functions increases them, although these effects are smaller than those for the stretching frequencies. The stretching and bending mode fundamental intensities of these dihaloethylenes all follow very different factorial models. Low dimensional principal component projections are shown to provide accurate representations of the agreement of the calculated frequencies and intensities with the experimental values. Wave function modifications leading to more accurate characteristic frequency values appear to be relatively insensitive to the vibration's symmetry or the molecular environment of the characteristic CF or CCI groups.

  13. Structural and vibrational investigation on species derived from the cyclamic acid in aqueous solution by using HATR and Raman spectroscopies and SCRF calculations

    NASA Astrophysics Data System (ADS)

    Brizuela, Alicia B.; Raschi, Ana B.; Castillo, María V.; Davies, Lilian; Romano, Elida; Brandán, Silvia A.

    2014-09-01

    In this study, aqueous solutions at different molar concentrations of sodium cyclamate in water were completely characterized by HATR (Horizontal Attenuated Total Reflectance) and Raman spectroscopies. The theoretical structures of cyclamate ion, the zwitterionic and neutral forms of the cyclamic acid and its dimer were optimized in gas and aqueous solution phases by using the hybrid B3LYP/6-31G* method. The solvent effects for the four species in aqueous solutions were simulated by using self-consistent reaction field (SCRF) calculations employing the integral equation formalism variant (IEFPCM) model. The complete assignments of the vibrational spectra of all the forms of cyclamic acid were performed taking into account the factor group analysis with the Scaled Quantum Mechanics Force Field (SQMFF) methodology. The existence of the zwitterionic and neutral forms of the cyclamic acid and its dimer in a solution of cyclamate in water is evidenced by characteristic bands in the HATR and Raman spectra. The dimerization of cyclamate in aqueous solution was previously reported by conductimetric method. The natural population analysis (NPA) and Merz-Kollman (MK) charges, molecular electrostatic potential (MEP), natural bond orbital (NBO) and atoms in molecules (AIM) calculations predict for all the species the principal donor and acceptor sites for the H bonds formation in aqueous solution. The SQM force fields for the cyclamate ion, the zwitterionic and neutral species of the cyclamic acid were obtained and their corresponding force constants in both phases were reported. Additionally, the solvation energies for those species were reported.

  14. The vibrationally averaged, temperature-dependent structure of polyatomic molecules. I - CO2

    NASA Astrophysics Data System (ADS)

    Mawhorter, R. J.; Fink, M.; Archer, B. T.

    1983-07-01

    A new high-temperature nozzle has been added to our counting electron diffraction apparatus, enabling precise studies of the vibrationally averaged structure of molecules at temperatures between 300 and 1000 K. Our results for CO2 are compared with the harmonic theory and the recent variational wave function calculation of Kohl and Hilderbrandt. The new nozzle system is described, and differences between the data and the theories are discussed.

  15. Philosophy of scaling the quantum mechanical molecular force field versus philosophy of solving the inverse vibrational problem

    NASA Astrophysics Data System (ADS)

    Panchenko, Yurii N.; De Maré, George R.

    2002-06-01

    The peculiarities characterising the traditional approach used in calculational vibrational spectroscopy and the approach based on using scaled quantum mechanical force fields are considered. Some results on the determination of the equilibrium geometry of benzene in both the harmonic approximation and in the approximation taking into account the kinematic and dynamic anharmonicity corrections by solving the inverse vibrational problem are discussed. Using the quantum mechanical force fields of the C 2F 6 molecule, calculated at three different theoretical levels as an example, the results of the determination of scale factors by different mathematical techniques are compared.

  16. 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.

  17. Vibrational spectra and normal coordinate analysis of plant growth regulator 1-naphthalene acetamide

    NASA Astrophysics Data System (ADS)

    Ravikumar, C.; Padmaja, L.; Hubert Joe, I.

    2010-02-01

    FT Raman and IR spectra of the biologically active molecule, 1-naphthalene acetamide (NA) have been recorded and analyzed. The equilibrium geometry, bonding features and harmonic vibrational wavenumbers of NA have been calculated with the help of B3LYP density functional theory (DFT) method. 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 downshifting of NH 2 stretching wavenumber indicates the formation of intermolecular N-H⋯O hydrogen bonding. The NBO analysis confirms the occurrence of strong intermolecular hydrogen bonding in the molecule.

  18. Conformational, Optoelectronic and Vibrational Properties of the Entacapone Molecule: A Quantum Chemistry Study.

    PubMed

    Frazão, N F; Albuquerque, E L; Fulco, U L; Mauriz, P W; Azevedo, D L

    2016-05-01

    A quantum chemistry study were carried out looking for the conformational, optoelectronic and vibrational properties of the entacapone molecule, an efficient drug used in the Parkinson's disease treatment. Classical annealing was performed to explore the entacapone's molecular configurations, searching for optimal geometries. The quantum optimization calculations were made using three different functional combination levels of the density functional theory (DFT). The structural data (bond length, bond and torsion angles), charge population analysis (absorption spectra) and molecular orbital study (HOMO and LUMO) were obtained considering the lower energy optimized conformation of the entacapone molecule. Furthermore, a complete assignment of the harmonic vibrational frequencies were achieved through their infrared (IR) and Raman spectra.

  19. The vibrational progressions of the N-->V electronic transition of ethylene: a test case for the computation of Franck-Condon factors of highly flexible photoexcited molecules.

    PubMed

    Borrelli, Raffaele; Peluso, Andrea

    2006-11-21

    The vibrational progressions of the N-->V electronic transition of ethylene--a test case for the computation of Franck-Condon factors between electronic states exhibiting very different equilibrium geometries--have been calculated by using both the Cartesian and the curvilinear internal coordinate representations of the normal modes of vibration. The comparison of the theoretical spectra with the experimental one shows that the Cartesian representation yields vibrational progressions which are not observed in the experimental spectrum, whereas the curvilinear one gives a very satisfying agreement, even in harmonic approximation.

  20. 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.

  1. FT-Raman and FTIR spectra, DFT investigation of the structure and vibrational assignment of mefenacet

    NASA Astrophysics Data System (ADS)

    Clemy Monicka, J.; James, C.

    2015-09-01

    FTIR and Raman spectral techniques were employed for the vibrational characterization of the herbicide mefenacet. The equilibrium geometry, various bonding features and harmonic vibrational wavenumbers were investigated with the help of density functional theory calculations. A detailed assignment of the vibrational spectra was made with the aid of theoretically predicted vibrational frequencies. Natural bond orbital analysis on mefenacet was carried out to reveal the nature of different interactions responsible for electron delocalization and the charge transfer between the orbitals (n → π∗, n → σ∗, π → π∗). Structural changes in the molecule due to the substitution of highly electronegative oxygen atom, conjugation and resonance effect were analyzed.

  2. Thermal weights for semiclassical vibrational response functions

    SciTech Connect

    Moberg, Daniel R.; Alemi, Mallory; Loring, Roger F.

    2015-08-28

    Semiclassical approximations to response functions can allow the calculation of linear and nonlinear spectroscopic observables from classical dynamics. Evaluating a canonical response function requires the related tasks of determining thermal weights for initial states and computing the dynamics of these states. A class of approximations for vibrational response functions employs classical trajectories at quantized values of action variables and represents the effects of the radiation-matter interaction by discontinuous transitions. Here, we evaluate choices for a thermal weight function which are consistent with this dynamical approximation. Weight functions associated with different semiclassical approximations are compared, and two forms are constructed which yield the correct linear response function for a harmonic potential at any temperature and are also correct for anharmonic potentials in the classical mechanical limit of high temperature. Approximations to the vibrational linear response function with quantized classical trajectories and proposed thermal weight functions are assessed for ensembles of one-dimensional anharmonic oscillators. This approach is shown to perform well for an anharmonic potential that is not locally harmonic over a temperature range encompassing the quantum limit of a two-level system and the limit of classical dynamics.

  3. 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.

  4. Calculation of multi-layer plate damper under one-axial load

    NASA Astrophysics Data System (ADS)

    Hui, Yan; Lu, Zhang; Hong-Yuan, Jiang; Alexander, M. Ulanov

    2016-02-01

    A multi-layer damper with waved plates under one-axial load is considered. A method of theoretical calculation of its energy dissipation coefficient is proposed. An experimental research of own frequencies and vibration transfer ratios for different parameters of damper structure, harmonic vibration load and random load is performed. Results of this research are approximated by functions; it is possible to use these functions for the calculation of the damper too. Project supported by the Programme of Introducing Talents of Discipline to Universities (Grant No. B07018).

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

    DOEpatents

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

    2008-10-21

    A method and apparatus for affecting the properties of a material include vibrating the material during its formation (i.e., "surface sifting"). The method includes the steps of providing a material formation device and applying a plurality of vibrations to the material during formation, which vibrations are oscillations having dissimilar, non-harmonic frequencies and at least two different directions. The apparatus includes a plurality of vibration sources that impart vibrations to the material.

  6. 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.

  7. 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.

  8. Towards an understanding of the vibrational spectrum of the neutral Au7 cluster.

    PubMed

    Mancera, Luis A; Benoit, David M

    2013-02-14

    We present a detailed theoretical study of the vibrational spectrum of the neutral Au(7) cluster, aimed at understanding its reported experimental spectrum [P. Gruene et al., Science, 2008, 321, 674]. We study the effect of vibrational anharmonicity, polymorphism, noble gas embedding, and the use of various electronic-structure methods. We use a vibrational configuration-interaction approach (VCI) with a vibrational self-consistent field (VSCF) basis, in order to study the effect of vibrational anharmonicity for the density functional theory (DFT) global minimum energy structure. Our implementation of the VSCF/VCI method is based on the direct calculation of the potential energy surface (PES) using pseudo potential plane-wave DFT. An efficient reduction of the number of mode-mode couplings between vibrational modes (fast-VSCF/VCI) is used to speed up calculations. We show that the rather small anharmonicity does not account for the difference between harmonic and experimental frequencies and consequently for the large global scaling factor, reported by the authors of the experiment. Instead, the use of different electronic structure methods allows for a significant reduction of the scaling factor. We also show that krypton embedding does not significantly change the vibrational frequencies of the Au(7) cluster.

  9. 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.

  10. 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.

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

    PubMed

    Hetmańczyk, Joanna; Hetmańczyk, Łukasz; Migdał-Mikuli, Anna; Mikuli, Edward

    2015-02-01

    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 3385cm(-1), associated with: ρr(NH3) and νas(N-H) modes, respectively, indicate that there exist fast (correlation times τR≈10(-12)-10(-13)s) reorientational motions of NH3 ligands, with a mean values of activation energies: 7.8 and 4.5kJmol(-1), in the phase I and II, respectively. These reorientational motions of NH3 ligands are only slightly disturbed in the phase transition region and do not significantly contribute to the phase transition mechanism. Fourier transform far-infrared and middle-infrared spectra with decreasing of temperature indicated characteristic changes at the vicinity of PT at TC(c)=137.6K (on cooling), which suggested lowering of the crystal structure symmetry. Infrared spectra of [Mn(NH3)6](ClO4)2 were recorded and interpreted by comparison with respective theoretical spectra calculated using DFT method (B3LYP functional, LANL2DZ ECP basis set (on Mn atom) and 6-311+G(d,p) basis set (on H, N, Cl, O atoms) for the isolated equilibrium two models (Model 1 - separate isolated [Mn(NH3)6](2+) cation and ClO4(-) anion and Model 2 - [Mn(NH3)6(ClO4)2] complex system). Calculated optical spectra show a good agreement with the experimental infrared spectra (FT-FIR and FT-MIR) for the both models. PMID:25459713

  12. 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)

    Hetmańczyk, Joanna; Hetmańczyk, Łukasz; Migdał-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: ρr(NH3) and νas(N-H) modes, respectively, indicate that there exist fast (correlation times τR ≈ 10-12-10-13 s) reorientational motions of NH3 ligands, with a mean values of activation energies: 7.8 and 4.5 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.

  13. Vibrational analysis for the nuclear-electronic orbital method

    NASA Astrophysics Data System (ADS)

    Iordanov, Tzvetelin; Hammes-Schiffer, Sharon

    2003-06-01

    The methodology for a vibrational analysis within the nuclear-electronic orbital (NEO) framework is presented. In the NEO approach, specified nuclei are treated quantum mechanically on the same level as the electrons, and mixed nuclear-electronic wave functions are calculated variationally with molecular orbital methods. Both electronic and nuclear molecular orbitals are expressed as linear combinations of Gaussian basis functions. The NEO potential energy surface depends on only the classical nuclei, and each point on this surface is optimized variationally with respect to all molecular orbitals as well as the centers of the nuclear basis functions. The NEO vibrational analysis involves the calculation, projection, and diagonalization of a numerical Hessian to obtain the harmonic vibrational frequencies corresponding to the classical nuclei. This analysis allows the characterization of stationary points on the NEO potential energy surface. It also enables the calculation of zero point energy corrections and thermodynamic properties such as enthalpy, entropy, and free energy for chemical reactions on the NEO potential energy surface. Illustrative applications of this vibrational analysis to a series of molecules and to a nucleophilic substitution reaction are presented.

  14. 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

  15. 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.

  16. Vibrational spectroscopy of triacetone triperoxide (TATP): Anharmonic fundamentals, overtones and combination bands

    NASA Astrophysics Data System (ADS)

    Brauer, Brina; Dubnikova, Faina; Zeiri, Yehuda; Kosloff, Ronnie; Gerber, R. Benny

    2008-12-01

    The vibrational spectrum of triacetone triperoxide (TATP) is studied by the correlation-corrected vibrational self-consistent field (CC-VSCF) method which incorporates anharmonic effects. Fundamental, overtone, and combination band frequencies are obtained by using a potential based on the PM3 method and yielding the same harmonic frequencies as DFT/cc-pVDZ calculations. Fundamentals and overtones are also studied with anharmonic single-mode (without coupling) DFT/cc-pVDZ calculations. Average deviations from experiment are similar for all methods: 2.1-2.5%. Groups of degenerate vibrations form regions of numerous combination bands with low intensity: the 5600-5800 cm -1 region contains ca. 70 overtones and combinations of CH stretches. Anharmonic interactions are analyzed.

  17. Molecular geometry, vibrational spectra, atomic charges, frontier molecular orbital and Fukui function analysis of antiviral drug zidovudine.

    PubMed

    Ramkumaar, G R; Srinivasan, S; Bhoopathy, T J; Gunasekaran, S

    2012-12-01

    The solid phase FT-IR and FT-Raman spectra of zidovudine (AZT) were recorded in the regions 4000-400 and 3500-100 cm(-1), respectively. The optimized geometry, frequency and intensity of the vibrational bands of zidovudine were obtained by the Restricted Hartree-Fock (RHF) density functional theory (DFT) with complete relaxation in the potential energy surface using 6-31G(d,p) basis set. The harmonic vibrational frequencies for zidovudine were calculated and the scaled values have been compared with experimental values of FTIR and FT-Raman spectra. The observed and the calculated frequencies are found to be in good agreement. The harmonic vibrational wave numbers and intensities of vibrational bands of zidovudine with its cation and anion were calculated and compared with the neutral AZT. The DFT calculated HOMO and LUMO energies shows that charge transfer occurs within the molecule. The electron density-based local reactivity descriptors such as Fukui functions were calculated to explain the chemical selectivity or reactivity site in AZT.

  18. Molecular geometry, vibrational spectra, atomic charges, frontier molecular orbital and Fukui function analysis of antiviral drug zidovudine

    NASA Astrophysics Data System (ADS)

    Ramkumaar, G. R.; Srinivasan, S.; Bhoopathy, T. J.; Gunasekaran, S.

    2012-12-01

    The solid phase FT-IR and FT-Raman spectra of zidovudine (AZT) were recorded in the regions 4000-400 and 3500-100 cm-1, respectively. The optimized geometry, frequency and intensity of the vibrational bands of zidovudine were obtained by the Restricted Hartree-Fock (RHF) density functional theory (DFT) with complete relaxation in the potential energy surface using 6-31G(d,p) basis set. The harmonic vibrational frequencies for zidovudine were calculated and the scaled values have been compared with experimental values of FTIR and FT-Raman spectra. The observed and the calculated frequencies are found to be in good agreement. The harmonic vibrational wave numbers and intensities of vibrational bands of zidovudine with its cation and anion were calculated and compared with the neutral AZT. The DFT calculated HOMO and LUMO energies shows that charge transfer occurs within the molecule. The electron density-based local reactivity descriptors such as Fukui functions were calculated to explain the chemical selectivity or reactivity site in AZT.

  19. 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

  20. 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

    2015-01-01

    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

  1. Vibrational (FT-IR and FT-Raman) spectra and quantum chemical studies on the molecular orbital calculations, chemical reactivity and thermodynamic parameters of 2-chloro-5-(trifluoromethyl) aniline

    NASA Astrophysics Data System (ADS)

    Karthick, T.; Balachandran, V.; Perumal, S.; Nataraj, A.

    2013-04-01

    In this work, the vibrational characteristics of 2-chloro-5-(trifluoromethyl) aniline have been investigated and both the experimental and theoretical vibrational data indicate the presence of various functional groups within the title molecule. The influence of chlorine substituent on the vibrational wavenumbers of a molecule in comparison with aniline and trifluoromethyl aniline has been discussed in detail. The density functional theoretical (DFT) computations were performed at the B3LYP/6-31++G(3df,3pd)/6-31G(3df,3pd) levels to derive the optimized geometry, vibrational wavenumbers with IR and Raman intensities. Furthermore, the molecular orbital calculations such as; natural bond orbitals (NBOs) and HOMO-LUMO energy gap and mapped molecular electrostatic potential (MEP) surfaces were also performed with the same level of DFT. The temperature dependence thermodynamic parameters of a molecule were illustrated on the basis of their correlation graphs. The detailed interpretation of the vibrational spectra has been carried out with the aid of potential energy distribution (PED) results obtained from MOLVIB program. The delocalization of electron density in various constituents of the molecule has been discussed with the aid of NBO and HOMO-LUMO energy gap analysis.

  2. Harmonic polynomials, hyperspherical harmonics, and atomic spectra

    NASA Astrophysics Data System (ADS)

    Avery, John Scales

    2010-01-01

    The properties of monomials, homogeneous polynomials and harmonic polynomials in d-dimensional spaces are discussed. The properties are shown to lead to formulas for the canonical decomposition of homogeneous polynomials and formulas for harmonic projection. Many important properties of spherical harmonics, Gegenbauer polynomials and hyperspherical harmonics follow from these formulas. Harmonic projection also provides alternative ways of treating angular momentum and generalised angular momentum. Several powerful theorems for angular integration and hyperangular integration can be derived in this way. These purely mathematical considerations have important physical applications because hyperspherical harmonics are related to Coulomb Sturmians through the Fock projection, and because both Sturmians and generalised Sturmians have shown themselves to be extremely useful in the quantum theory of atoms and molecules.

  3. The microwave spectrum, harmonic force field and structure of chlorodifluoromethane, CHF 2Cl

    NASA Astrophysics Data System (ADS)

    Cramb, D. T.; Bos, Y.; Jemson, H. M.; Gerry, M. C. L.; Marsden, C. J.

    1988-11-01

    Rotational spectra of four isotopic species of chlorodifluoromethane, CHF 235Cl, CHF 237Cl, CDF 235Cl and CDF 237Cl, have been extensively measured, and have been analysed for rotational constants, centrifugal distortion constants and chlorine nuclear quadrupole coupling constants. The distortion constants have been combined with vibrational wavenumbers from the literature and with ab initio force constants calculated in the present work to refine the harmonic force field. Ground state effective ( r0), substitution ( rs) and ground state average ( rz) structures have been evaluated for the molecule.

  4. Direct non-Born-Oppenheimer variational calculations of all bound vibrational states corresponding to the first rotational excitation of D{sub 2} performed with explicitly correlated all-particle Gaussian functions

    SciTech Connect

    Sharkey, Keeper L.; Kirnosov, Nikita; Adamowicz, Ludwik

    2015-05-07

    Direct variational calculations where the Born-Oppenheimer approximation is not assumed are done for all rovibrational states of the D{sub 2} molecule corresponding to first excited rotational level (the N = 1 states). All-particle explicitly correlated Gaussian basis functions are used in the calculations. The exponential parameters of the Gaussians are optimized with the aid of analytically calculated energy gradient determined with respect to these parameters. The results allow to determine the ortho-para spin isomerization energies as a function of the vibrational quantum number.

  5. Color harmonization for images

    NASA Astrophysics Data System (ADS)

    Tang, Zhen; Miao, Zhenjiang; Wan, Yanli; Wang, Zhifei

    2011-04-01

    Color harmonization is an artistic technique to adjust a set of colors in order to enhance their visual harmony so that they are aesthetically pleasing in terms of human visual perception. We present a new color harmonization method that treats the harmonization as a function optimization. For a given image, we derive a cost function based on the observation that pixels in a small window that have similar unharmonic hues should be harmonized with similar harmonic hues. By minimizing the cost function, we get a harmonized image in which the spatial coherence is preserved. A new matching function is proposed to select the best matching harmonic schemes, and a new component-based preharmonization strategy is proposed to preserve the hue distribution of the harmonized images. Our approach overcomes several shortcomings of the existing color harmonization methods. We test our algorithm with a variety of images to demonstrate the effectiveness of our approach.

  6. 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.

  7. Raman and IR studies and DFT calculations of the vibrational spectra of 2,4-Dithiouracil and its cation and anion

    NASA Astrophysics Data System (ADS)

    Singh, R.; Yadav, R. A.

    2014-09-01

    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 C5sbnd C6 bond length increases and loses its double bond character while the C4sbnd C5 bond length decreases. In the case of the DTU+ ion the IR and Raman band corresponding to the out-of-phase coupled Nsbnd H 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.

  8. 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.

  9. a Computational Study of the Vibrational - Stretching and - Bending Spectrum of the Water Trimer

    NASA Astrophysics Data System (ADS)

    Salmi, Teemu; Halonen, Lauri

    2011-06-01

    We have studied the vibrational O--H stretching and H--O--H angle bending spectrum of the water trimer computationally around the cyclic minimum energy structure. We obtain the energies and intensities of the fundamental and overtone transitions. Earlier we have modeled the water trimer as three individually vibrating monomer units. In this work we have improved our previous model by including the potential energy coupling between the three hydrogen bonded O--H stretching modes. An internal coordinate Hamiltonian is constructed for each water unit using a kinetic energy operator, which is exact within the Born-Oppenheimer approximation for a triatomic molecule. The potential energy coupling terms between the hydrogen bonded O--H stretching modes are added in the model. The O--H distances and the H--O--H bending angles are used as the vibrational coordinates. The potential energy grid is calculated using the coupled cluster method with single, double and perturbative triple excitations (CCSD(T)) with correlation consistent aug-cc-pVTZ basis set around the optimized geometry. The potential energy surface (PES) is obtained by fitting an analytical function to the potential energy grid. The dipole moment surface is calculated using the finite differences method. The vibrational problem has been solved with the variational method with a harmonic oscillator basis for all the vibrational coordinates. We calculate the transition intensities using the wavefunctions obtained from the variational calculation.

  10. 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 π-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.

  11. Current analysis for rotating and vibrating heavy nuclei

    NASA Astrophysics Data System (ADS)

    Kunz, J.; Schuh, A.; Mosel, U.; Wuest, E.

    Microscopic current distributions are calculated for rotations and quadrupole vibrations of heavy nuclei in the cranking model using the Nilsson Hamiltonian and pairing correlations. The currents are analyzed in terms of vector spherical harmonics; symmetry relations are taken into account. In the case of collective rotations magnetic and electric current contributions occur. The two dominant contributions correspond to rigid and irrotational flow. The strong influence of pairing on the rotational currents is demonstrated. It can be understood by investigating the delta N = 0 and delta N = 2 contributions to the currents. For collective quadrupole vibrations only electric current contributions occur. In contrast to the irrotational Bohr-Tassie flow the realistic current fields show a vortex structure.

  12. Non-equilibrium Casimir force between vibrating plates.

    PubMed

    Hanke, Andreas

    2013-01-01

    We study the fluctuation-induced, time-dependent force between two plates confining a correlated fluid which is driven out of equilibrium mechanically by harmonic vibrations of one of the plates. For a purely relaxational dynamics of the fluid we calculate the fluctuation-induced force generated by the vibrating plate on the plate at rest. The time-dependence of this force is characterized by a positive lag time with respect to the driving. We obtain two distinctive contributions to the force, one generated by diffusion of stress in the fluid and another related to resonant dissipation in the cavity. The relation to the dynamic Casimir effect of the electromagnetic field and possible experiments to measure the time-dependent Casimir force are discussed. PMID:23326401

  13. Harmonic motion microwave Doppler imaging: a simulation study using a simple breast model.

    PubMed

    Top, Can Bariş; Gençer, Nevzat G

    2014-02-01

    A hybrid method for tissue imaging using dielectric and elastic properties is proposed and investigated with simple bi-layered breast model. In this method, local harmonic motion is generated in the tissue using a focused ultrasound probe. A narrow-band microwave signal is transmitted to the tissue. The Doppler component of the scattered signal, which depends on the dielectric and elastic properties of the vibrating region, is sensed. A plane-wave spectrum technique is used together with reciprocity theorem for calculating the response of a vibrating electrically small spherical tumor in breast tissue. The effects of operating frequency, antenna alignment and distance, and tumor depth on the received signal are presented. The effect of harmonic motion frequency on the vibration amplitude and displacement distribution is investigated with mechanical simulations using the finite element method. The safety of the method is analyzed in terms of microwave and ultrasound exposure of the breast tissue. The results show that the method has a potential in detecting tumors inside fibro-glandular breast tissue.

  14. Simple Harmonic Motion in Harmonic Plane Waves.

    ERIC Educational Resources Information Center

    Benumof, Reuben

    1980-01-01

    Discusses the distribution of kinetic and potential energy in transverse and longitudinal waves and examines the transmission of power and momentum. This discussion is intended to aid in understanding the simple harmonic motion of a particle involved in the propagation of a harmonic mechanical plane wave. (HM)

  15. Role of vibrational anharmonicity in atmospheric radical hydrogen-bonded complexes.

    PubMed

    Torrent-Sucarrat, M; Anglada, J M; Luis, J M

    2009-08-14

    Harmonic and anharmonic vibrational frequency calculations are reported for the most stable hydrogen bonded complexes formed between the hydroperoxyl radical and formic, acetic, nitric, and sulfuric acids which are of atmospheric interest. A comparison between the calculated IR spectra of the hydrogen bonded complexes with the corresponding separate monomers is also reported with the aim to facilitate a possible experimental identification of these complexes. The calculations have been carried out using the second-order vibrational perturbative treatment implemented by Barone applied to the PES obtained with the B3LYP functional using the 6-31+G(d,p) and 6-311+G(2d,2p) basis sets. Our calculations for the separate monomers predict vibrational frequencies with quite a good agreement with the experimental values. The anharmonic contribution results in differences of around 40 cm(-1) with respect to the harmonic values; although in some cases involving highly anharmonic modes, these differences can rise up to 300 and 450 cm(-1). PMID:19809669

  16. State-to-state vibration-translation and vibration-vibration rate constants in H{sub 2}-H{sub 2} and HD-HD collisions

    SciTech Connect

    Cacciatore, M.; Billing G.D.

    1992-01-09

    The authors present calculations of vibration-vibration and vibration-translation energy transfer rate constants in diatom-diatom collisions. The results are compared to recent experimental measurements.

  17. Structural changes upon reduction of dipyrido[2,3-a:3',2'-c]phenazine probed by vibrational spectroscopy, ab initio calculations, and deuteration studies.

    PubMed

    Howell, Sarah L; Matthewson, Benjamin J; Polson, Matthew I J; Burrell, Anthony K; Gordon, Keith C

    2004-05-01

    A series of bridging ligands, dipyrido[2,3-a:3',2'-c]phenazine (ppb), dipyrido[2,3-a:3',2'-c]-6,7-dichlorophenazine (ppbCl2), and dipyrido[2,3-a:3',2'-c]-6,7-dimethylphenazine (ppbMe2), and their binuclear copper(I) complexes have been synthesized, and their spectral properties were measured. The single-crystal structure of the complex, [(PPh3)2Cu(mu-ppbCl2)Cu(PPh3)2](BF4)2 in the monoclinic space group P21/c, 18.2590(1), 21.1833(3), 23.2960(3) A with Z = 4 is reported. The copper(I) complexes are deeply colored through MLCT transitions in the visible region. The vibrational spectra of the ligands have been modeled using ab initio hybrid density functional theory (DFT) methods (B3LYP/6-31G(d)) and compared to experimental FT-Raman and IR data. The DFT calculations are used to interpret the resonance Raman spectra, and thus the electronic spectra, of the complexes. The preferential enhancement of modes associated with the phenanthroline section of the ligands with blue excitation (lambda(exc) = 457.9 nm) over phenazine-based modes with redder excitation (lambda(exc) = 514.5 and 632.8 nm) suggests the 2 MLCT transitions terminated on different unoccupied MOs are present under the visible absorption envelope. The radical anion species of the ligands are prepared by the electrochemical reduction of the binuclear copper(I) complexes; no evidence of dechelation prevalent in other copper(I) complexes is observed. The resonance Raman spectra of the reduced complexes are dramatically different from those of the parent species. Across the series common bands are observed at about 1590 and 1570 cm(-1) which do not shift with reduction but are altered in intensity. The normal-mode analysis of the radical anion species suggests that these normal modes primarily involve bond length distortions that are unaffected by reduction.

  18. 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 ε and dielectric loss tanδ. 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 ε and tanδ. The dielectric property parameters obtained using IR spectrum fittings, first-principal calculations, and microwave measurements were compared.

  19. Single-order laser high harmonics in XUV for ultrafast photoelectron spectroscopy of molecular wavepacket dynamics

    PubMed Central

    Fushitani, Mizuho; Hishikawa, Akiyoshi

    2016-01-01

    We present applications of extreme ultraviolet (XUV) single-order laser harmonics to gas-phase ultrafast photoelectron spectroscopy. Ultrashort XUV pulses at 80 nm are obtained as the 5th order harmonics of the fundamental laser at 400 nm by using Xe or Kr as the nonlinear medium and separated from other harmonic orders by using an indium foil. The single-order laser harmonics is applied for real-time probing of vibrational wavepacket dynamics of I2 molecules in the bound and dissociating low-lying electronic states and electronic-vibrational wavepacket dynamics of highly excited Rydberg N2 molecules. PMID:27795976

  20. Experimental and DFT studies on the vibrational and electronic spectra of 9-anthracenemethanol

    NASA Astrophysics Data System (ADS)

    Kou, Shanshan; Zhou, Hu; Tang, Guodong; Li, Rongqing; Zhang, Yu; Zhao, Jianying; Wei, Changmei

    2012-10-01

    Vibrational spectral measurements were made for 9-anthracenemethanol. Optimized geometrical structure and harmonic vibration frequencies were computed based on ab initio and density functional theory B3LYP methods using 6-311G∗∗ and LANL2DZ basis sets. The equilibrium geometries got from all of the methods and basis were compared with X-ray diffraction results. The IR and UV-vis spectra of the title compound were computed using all of the methods and choose the most appropriate way to discuss. And the absorption spectra were calculated both in gas phase and in CH3CH2OH and CH3CN solution. The calculated results matched well with the experimental values. On the basis, the first excited state electronic transition energy has been calculated using time-dependent density functional theory.

  1. 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.

  2. 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.

  3. Free vibrations of delaminated beams

    NASA Technical Reports Server (NTRS)

    Shen, M.-H. H.; Grady, J. E.

    1992-01-01

    Free vibration of laminated composite beams is studied. The effect of interply delaminations on natural frequencies and mode shapes is evaluated both analytically and experimentally. A generalized vibrational principle is used to formulate the equation of motion and associated boundary conditions for the free vibration of a composite beam with a delamination of arbitrary size and location. The effect of coupling between longitudinal vibration and bending vibration is considered. This coupling effect is shown to significantly affect the calculated natural frequencies and mode shapes of the delaminated beam.

  4. Vibrational averages along thermal lines

    NASA Astrophysics Data System (ADS)

    Monserrat, Bartomeu

    2016-01-01

    A method is proposed for the calculation of vibrational quantum and thermal expectation values of physical properties from first principles. Thermal lines are introduced: these are lines in configuration space parametrized by temperature, such that the value of any physical property along them is approximately equal to the vibrational average of that property. The number of sampling points needed to explore the vibrational phase space is reduced by up to an order of magnitude when the full vibrational density is replaced by thermal lines. Calculations of the vibrational averages of several properties and systems are reported, namely, the internal energy and the electronic band gap of diamond and silicon, and the chemical shielding tensor of L-alanine. Thermal lines pave the way for complex calculations of vibrational averages, including large systems and methods beyond semilocal density functional theory.

  5. Theoretical study of anharmonicity in the vibrational spectrum of the perfluorocyclopropenyl cation

    NASA Astrophysics Data System (ADS)

    Xie, Yaoming; Boggs, James E.

    1989-07-01

    Complete theoretical calculations for the structure, anharmonic force field up to partial sixth order, and anharmonic vibrational frequencies of C3F+3 have been carried out. The procedure included ab initio calculation of the vibrational potential-energy surface at the 6-311G plus double polarization plus local MP4(SDQ) level, followed by a complete, 12-mode variational solution of the vibrational Schrödinger equation using a configuration-interaction (CI) expansion from a large, well-selected harmonic oscillator basis. The geometric parameters of C3F+3 (D3h) were optimized as 1.3796 Å for the CC bond lengths and 1.2615 Å for the CF distances. Localized orbitals show strong π-bond character for the CF linkages, conjugated with the ring π orbital. The fundamental vibrational frequencies of C3F+3 are 1999.5, 742.8 (a'1); 767.3 (a2); 1596.9, 998.9, 271.3 (e'); 250.0 (a`2); and 664.1 (e`). These frequencies agree with condensed phase measurements of Raman and infrared spectra with a ±11.5 cm-1 average deviation, the largest difference appearing for the CF bending and wagging frequencies. The first vibrational overtone frequencies of C3F+3 are also predicted. This completely ab initio calculation of anharmonic frequencies also leads to detailed bond characterization and full information on all intermode interactions.

  6. Analysis of potential helicopter vibration reduction concepts

    NASA Technical Reports Server (NTRS)

    Landgrebe, A. J.; Davis, M. W.

    1985-01-01

    Results of analytical investigations to develop, understand, and evaluate potential helicopter vibration reduction concepts are presented in the following areas: identification of the fundamental sources of vibratory loads, blade design for low vibration, application of design optimization techniques, active higher harmonic control, blade appended aeromechanical devices, and the prediction of vibratory airloads. Primary sources of vibration are identified for a selected four-bladed articulated rotor operating in high speed level flight. The application of analytical design procedures and optimization techniques are shown to have the potential for establishing reduced vibration blade designs through variations in blade mass and stiffness distributions, and chordwise center-of-gravity location.

  7. Molecular docking, spectroscopic studies and quantum calculations on nootropic drug.

    PubMed

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

    2014-04-01

    A systematic vibrational spectroscopic assignment and analysis of piracetam [(2-oxo-1-pyrrolidineacetamide)] have been carried out using FT-IR and FT-Raman spectral data. The vibrational analysis was aided by an electronic structure calculation based on the hybrid density functional method B3LYP using a 6-311G++(d,p) basis set. Molecular equilibrium geometries, electronic energies, IR and Raman intensities, and harmonic vibrational frequencies have been computed. The assignments are based on the experimental IR and Raman spectra, and a complete assignment of the observed spectra has been proposed. The UV-visible spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies and the maximum absorption wavelengths λmax were determined by the time-dependent DFT (TD-DFT) method. The geometrical parameters, vibrational frequencies and absorption wavelengths were compared with the experimental data. The complete vibrational assignments are performed on the basis of the potential energy distributions (PED) of the vibrational modes in terms of natural internal coordinates. The simulated FT-IR, FT-Raman, and UV spectra of the title compound have been constructed. Molecular docking studies have been carried out in the active site of piracetam by using Argus Lab. In addition, the potential energy surface, HOMO and LUMO energies, first-order hyperpolarizability and the molecular electrostatic potential have been computed.

  8. 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

  9. 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.

  10. Temperature dependence of electronic eigenenergies in the adiabatic harmonic approximation

    NASA Astrophysics Data System (ADS)

    Poncé, S.; Antonius, G.; Gillet, Y.; Boulanger, P.; Laflamme Janssen, J.; Marini, A.; Côté, M.; Gonze, X.

    2014-12-01

    The renormalization of electronic eigenenergies due to electron-phonon interactions (temperature dependence and zero-point motion effect) is important in many materials. We address it in the adiabatic harmonic approximation, based on first principles (e.g., density-functional theory), from different points of view: directly from atomic position fluctuations or, alternatively, from Janak's theorem generalized to the case where the Helmholtz free energy, including the vibrational entropy, is used. We prove their equivalence, based on the usual form of Janak's theorem and on the dynamical equation. We then also place the Allen-Heine-Cardona (AHC) theory of the renormalization in a first-principles context. The AHC theory relies on the rigid-ion approximation, and naturally leads to a self-energy (Fan) contribution and a Debye-Waller contribution. Such a splitting can also be done for the complete harmonic adiabatic expression, in which the rigid-ion approximation is not required. A numerical study within the density-functional perturbation theory framework allows us to compare the AHC theory with frozen-phonon calculations, with or without the rigid-ion approximation. For the two different numerical approaches without non-rigid-ion terms, the agreement is better than 7 μ eV in the case of diamond, which represent an agreement to five significant digits. The magnitude of the non-rigid-ion terms in this case is also presented, distinguishing specific phonon modes contributions to different electronic eigenenergies.

  11. Orientation dependence of high-order harmonic generation in molecules

    NASA Astrophysics Data System (ADS)

    Lein, M.; Corso, P. P.; Marangos, J. P.; Knight, P. L.

    2003-02-01

    We present two- and three-dimensional model calculations of high-order harmonic generation in H+2. The harmonic spectra exhibit clear signatures of intramolecular interference. An interference minimum appears at a harmonic order that depends on the molecular orientation. Harmonic generation in three-center molecules is studied on the basis of two-dimensional calculations for a H2+3 model system. From analytical considerations, the orientation dependence of the harmonic intensities in three-center molecules exhibits a double minimum due to intramolecular interference. In the numerical results, the double minimum is broadened into a single wide minimum. The effect of nonzero laser ellipticity on harmonic generation is investigated by means of two-dimensional simulations for H+2. We find that harmonic generation with elliptical polarization is governed by interference effects similar to linear polarization.

  12. Novel zinc(II) and copper(II) complexes of a Mannich base derived from lawsone: Synthesis, single crystal X-ray analysis, ab initio density functional theory calculations and vibrational analysis.

    PubMed

    Neves, Amanda P; Vargas, Maria D; Téllez Soto, Claudio A; Ramos, Joanna M; Visentin, Lorenzo do C; Pinheiro, Carlos B; Mangrich, Antônio S; de Rezende, Edivaltrys I P

    2012-08-01

    Zinc(II) and copper(II) complexes of a tridentate Mannich base L1 derived from 2-hydroxy-1,4-naphthoquinone, pyridinecarboxyaldehyde and 2-aminomethylpyridine, [ZnL1Cl(2)]·H(2)O 1 and [CuL1Cl(2)]·2H(2)O 2, have been synthesized and fully characterized. The structure of complex 1 has been elucidated by a single crystal X-ray diffraction study: the zinc atom is pentacoordinate and the coordination geometry is a distorted square base pyramid, with a geometric structural parameter τ equal to 0.149. Vibrational spectroscopy and ab initio DFT calculations of both compounds have confirmed that the two complexes exhibit similar structures. Full assignment of the vibrational spectra was also supported by careful analysis of the distorted geometries generated by the normal modes. PMID:22513170

  13. Semiclassical approaches to below-threshold harmonics

    SciTech Connect

    Hostetter, James A.; Tate, Jennifer L.; Schafer, Kenneth J.; Gaarde, Mette B.

    2010-08-15

    We study the generation of below-threshold harmonics in a model atom by extending the three-step semiclassical model of harmonic generation to include effects of the atomic potential. We explore the generalization of semiclassical trajectories of the electron in the presence of the combined laser-atom potential and calculate the intensity-dependent dipole phase associated with these trajectories. Our results are in good agreement with fully quantum mechanical calculations, as well as with recent experimental observations. We show that the so-called long trajectory readily generalizes to below-threshold harmonic generation and is relatively insensitive to the choice of initial conditions. We also find that the short trajectory can only lead to low-energy harmonics for electrons that have been released close to the ion core in a process that is closer to multiphoton than to tunnel ionization.

  14. Harmonics generated from a DC biased transformer

    SciTech Connect

    Shu Lu; Yilu Liu; Ree, J. De La . The Bradley Dept. of Electrical Engineering)

    1993-04-01

    The paper presents harmonic characteristics of transformer excitation currents under DC bias caused by geomagnetically induced currents (GIC). A newly developed saturation model of a single phase shell form transformer based on 3D finite element analysis is used to calculate the excitation currents. As a consequence, the complete variations of excitation current harmonics with respect to an extended range of GIC bias are revealed. The results of this study are useful in understanding transformers as harmonic sources and the impact on power systems during a solar magnetic disturbance.

  15. Anharmonic Calculation of the Structure, Vibrational Frequencies, and Intensities of the NH3···cis-HONO and NH3···cis-DONO Complexes.

    PubMed

    Bulychev, V P; Buturlimova, M V; Tokhadze, K G

    2016-08-25

    The geometrical parameters, the frequencies, and absolute intensities for transitions between vibrational states of NH3···cis-HONO and NH3···cis-DONO hydrogen-bonded complexes are calculated using the approach earlier tested in calculations of isolated molecules of nitrous acid and the NH3···trans-HONO and NH3··trans-DONO complexes. Vibrational wave functions and energy values of the complexes are derived from variational solutions of anharmonic equations in one to four dimensions. The equilibrium nuclear configuration and potential energy surfaces are calculated by the MP2/aug-cc-pVTZ method with the basis set superposition error taken into account. Comparison of the obtained results with the analogous data calculated in the same approximation for isolated cis- and trans-HONO (DONO) molecules and the NH3···trans-HONO (DONO) complexes provides information about the changes in the spectroscopic and geometrical parameters of nitrous acid upon cis-trans transition, H/D substitution, and H-bond formation. PMID:27472262

  16. Experimental and numerical investigation of parametric resonance of flexible hose conveying non-harmonic fluid flow

    NASA Astrophysics Data System (ADS)

    Łuczko, Jan; Czerwiński, Andrzej

    2016-07-01

    The article presents an analysis of a model describing transverse vibrations of an elastic hose induced by non-harmonic fluid flow pulsation. The equation of motion is given as a nonlinear partial differential equation with periodically variable coefficients. The Galerkin method is employed, utilising orthogonal polynomials as shape functions. The effect of selected parameters on increased vibration intensity range and the character and form of vibrations is investigated. It is demonstrated that sub-harmonic and quasi-periodic vibrations can be induced in the simple and combination parametric resonance range. The occurrence of the parametric resonance phenomenon is evidenced by experimental data.

  17. Characteristic of torsional vibration of mill main drive excited by electromechanical coupling

    NASA Astrophysics Data System (ADS)

    Zhang, Yifang; Yan, Xiaoqiang; Lin, Qihui

    2016-01-01

    In the study of electromechanical coupling vibration of mill main drive system, the influence of electrical system on the mechanical transmission is considered generally, however the research for the mechanism of electromechanical interaction is lacked. In order to research the electromechanical coupling resonance of main drive system on the F3 mill in a plant, the cycloconverter and synchronous motor are modeled and simulated by the MTLAB/SIMULINK firstly, simulation result show that the current harmonic of the cycloconverter can lead to the pulsating torque of motor output. Then the natural characteristics of the mechanical drive system are calculated by ANSYS, the result show that the modal frequency contains the component which is close to the coupling vibration frequency of 42Hz. According to the simulation result of the mechanical and electrical system, the closed loop feedback model including the two systems are built, and the mechanism analysis of electromechanical coupling presents that there is the interaction between the current harmonic of electrical system and the speed of the mechanical drive system. At last, by building and computing the equivalent nonlinear dynamics model of the mechanical drive system, the dynamic characteristics of system changing with the stiffness, damping coefficient and the electromagnetic torque are obtained. Such electromechanical interaction process is suggested to consider in research of mill vibration, which can induce strong coupling vibration behavior in the rolling mill drive system.

  18. A combined dynamic analysis method for geometrically nonlinear vibration isolators with elastic rings

    NASA Astrophysics Data System (ADS)

    Hu, Zhan; Zheng, Gangtie

    2016-08-01

    A combined analysis method is developed in the present paper for studying the dynamic properties of a type of geometrically nonlinear vibration isolator, which is composed of push-pull configuration rings. This method combines the geometrically nonlinear theory of curved beams and the Harmonic Balance Method to overcome the difficulty in calculating the vibration and vibration transmissibility under large deformations of the ring structure. Using the proposed method, nonlinear dynamic behaviors of this isolator, such as the lock situation due to the coulomb damping and the usual jump resulting from the nonlinear stiffness, can be investigated. Numerical solutions based on the primary harmonic balance are first verified by direct integration results. Then, the whole procedure of this combined analysis method is demonstrated and validated by slowly sinusoidal sweeping experiments with different amplitudes of the base excitation. Both numerical and experimental results indicate that this type of isolator behaves as a hardening spring with increasing amplitude of the base excitation, which makes it suitable for isolating both steady-state vibrations and transient shocks.

  19. Targeting intermediates of [FeFe]-hydrogenase by CO and CN vibrational signatures.

    PubMed

    Yu, Lian; Greco, Claudio; Bruschi, Maurizio; Ryde, Ulf; De Gioia, Luca; Reiher, Markus

    2011-05-01

    In this work, we employ density functional theory to assign vibrational signatures of [FeFe]-hydrogenase intermediates to molecular structures. For this purpose, we perform an exhaustive analysis of structures and harmonic vibrations of a series of CN and CO containing model clusters of the [FeFe]-hydrogenase enzyme active site considering also different charges, counterions, and solvents. The pure density functional BP86 in combination with a triple-ζ polarized basis set produce reliable molecular structures as well as harmonic vibrations. Calculated CN and CO stretching vibrations are analyzed separately. Scaled vibrational frequencies are then applied to assign intermediates in [FeFe]-hydrogenase's reaction cycle. The results nicely complement the previous studies of Darensbourg and Hall, and Zilberman et al. The infrared spectrum of the H(ox) form is in very good agreement with the calculated spectrum of the Fe(I)Fe(II) model complex featuring a free coordination site at the distal Fe atom, as well as, with the calculated spectra of the complexes in which H(2) or H(2)O are coordinated at this site. The spectrum of H(red) measured from Desulfovibrio desulfuricans is compatible with a mixture of a Fe(I)Fe(I) species with all terminal COs, and a Fe(I)Fe(I) species with protonated dtma ligand, while the spectrum of H(red) recently measured from Chlamydomonas reinhardtii is compatible with a mixture of a Fe(I)Fe(I) species with a bridged CO, and a Fe(II)Fe(II) species with a terminal hydride bound to the Fe atom.

  20. Conformational and vibrational studies of isomeric hydrogen cyanide tetramers by quantum chemical methods

    NASA Astrophysics Data System (ADS)

    Gupta, V. P.; Tandon, Poonam

    2012-04-01

    The results of structural studies and detailed harmonic and anharmonic vibrational analysis on two hydrogen cyanide (HCN) tetramers diaminomaleonitrile (DAMN) and diaminofumaronitrile (DAFN), which are important molecules for understanding the chemistry of interstellar space and nitrile rich environments, are being reported on the basis of density functional theory using second-order perturbation theory. Both the molecules are found to have C1 symmetry. While all the heavy atoms of DAMN lie in the same plane (maximum deviation 6°), the two nitrogen atoms in DAFN are out of plane by about 15°. The two amino groups are tetrahedral and do not have significant bond angle anisotropy. Detailed conformational studies are reported on the two molecules and their possible rotational isomers are identified. Complete vibrational analysis based on harmonic and anharmonic frequencies, intensity of infrared and activity of Raman bands and potential energy distribution over the internal coordinates has been provided for the two molecules. Affect of hydrogen bonding on molecular geometry and frequencies of the Nsbnd H stretch modes has been studied by calculations on the dimers of the two molecules. A close agreement has been observed between the experimental and calculated frequencies. Vibrational-rotational constants such as rotational constants in the ground vibrational state (A0, B0, C0) and the effective rotational constants (Ae, Be and Ce), including terms due to quartic centrifugal distortion constants, rotation-vibration coupling constants, Wilson and Nielsen's centrifugal distortion constants have been calculated using B3LYP and B97-1 functionals and 6-31G**, 6-311+G** and TZVP basis sets.

  1. Vibrational spectroscopic study and NBO analysis on tranexamic acid using DFT method

    NASA Astrophysics Data System (ADS)

    Muthu, S.; Prabhakaran, A.

    2014-08-01

    In this work, we reported the vibrational spectra of tranexamic acid (TA) by experimental and quantum chemical calculation. The solid phase FT-Raman and FT-IR spectra of the title compound were recorded in the region 4000 cm-1 to 100 cm-1 and 4000 cm-1 to 400 cm-1 respectively. The molecular geometry, harmonic vibrational frequencies and bonding features of TA in the ground state have been calculated by using density functional theory (DFT) B3LYP method with standard 6-31G(d,p) basis set. The scaled theoretical wavenumber showed very good agreement with the experimental values. The vibrational assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes. Stability of the molecule, arising from hyperconjugative interactions and charge delocalization, has been analyzed using Natural Bond Orbital (NBO) analysis. The results show that ED in the σ* and π* antibonding orbitals and second order delocalization energies E(2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. The electrostatic potential mapped onto an isodensity surface has been obtained. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the title compound at different temperatures were calculated in gas phase.

  2. 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.

  3. NIS, IR and Raman spectra with quantum mechanical calculations for analyzing the force field of hypericin model compounds

    SciTech Connect

    Ulicny, Jozef; Leulliot, Nicolas; Ghomi, Mahmoud; Grajcar, Lydie; Baron, Marie-Helene; Jobic, Herve

    1999-06-15

    Geometry optimization as well as harmonic force field calculations at HF and DFT levels of theory have been performed in order to elucidate the ground state properties of anthrone and emodin, two polycyclic conjugated molecules considered as hypericin model compounds. NIS, IR and FT-Raman spectra of these compounds have been recorded to validate the calculated results (geometry and vibrational modes). Calculated NIS spectra using the lowest energy conformers are in agreement with experiment. In addition, the intramolecular H-bonds in emodin predicted by the calculations can be evidenced using IR spectra as a function of temperature.

  4. The electronic origin and vibrational levels of the first excited singlet state of isocyanic acid (HNCO)

    SciTech Connect

    Berghout, H. Laine; Crim, F. Fleming; Zyrianov, Mikhail; Reisler, Hanna

    2000-04-15

    The combination of vibrationally mediated photofragment yield spectroscopy, which excites molecules prepared in single vibrational states, and multiphoton fluorescence spectroscopy, which excites molecules cooled in a supersonic expansion, provides detailed information on the energetics and vibrational structure of the first excited singlet state (S{sub 1}) of isocyanic acid (HNCO). Dissociation of molecules prepared in individual vibrational states by stimulated Raman excitation probes vibrational levels near the origin of the electronically excited state. Detection of fluorescence from dissociation products formed by multiphoton excitation through S{sub 1} of molecules cooled in a supersonic expansion reveals the vibrational structure at higher energies. Both types of spectra show long, prominent progressions in the N-C-O bending vibration built on states with different amounts of N-C stretching excitation and H-N-C bending excitation. Analyzing the spectra locates the origin of the S{sub 1} state at 32 449{+-}20 cm{sup -1} and determines the harmonic vibrational frequencies of the N-C stretch ({omega}{sub 3}=1034{+-}20 cm{sup -1}), the H-N-C bend ({omega}{sub 4}=1192{+-}19 cm{sup -1}), and the N-C-O bend ({omega}{sub 5}=599{+-}7 cm{sup -1}), values that are consistent with several ab initio calculations. The assigned spectra strongly suggest that the N-C stretching vibration is a promoting mode for internal conversion from S{sub 1} to S{sub 0}. (c) 2000 American Institute of Physics.

  5. 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.

  6. Vibrational spectroscopy of resveratrol

    NASA Astrophysics Data System (ADS)

    Billes, Ferenc; Mohammed-Ziegler, Ildikó; Mikosch, Hans; Tyihák, Ernő

    2007-11-01

    In this article the authors deal with the experimental and theoretical interpretation of the vibrational spectra of trans-resveratrol (3,5,4'-trihydroxy- trans-stilbene) of diverse beneficial biological activity. Infrared and Raman spectra of the compound were recorded; density functional calculations were carried out resulting in the optimized geometry and several properties of the molecule. Based on the calculated force constants, a normal coordinate analysis yielded the character of the vibrational modes and the assignment of the measured spectral bands.

  7. Numerical Description of Acoustic Vibrations of a Vapor-Gas-Droplet Mixture in a Closed Channel Based on a One-Velocity, One-Temperature Model

    NASA Astrophysics Data System (ADS)

    Bayanov, R. I.; Tukmakov, A. L.

    2015-05-01

    The paper describes a mathematical model and the results of numerical calculations of resonance acoustic vibrations of a vapor-gas-droplet mixture in a closed volume under the action of periodic acoustic waves generated by a harmonically vibrating piston. The numerical method of solving the equations of the model is based on MacCormack's scheme. The model of equilibrium phase transitions used in the numerical scheme has allowed a chart of regimes of the vapor-gas-droplet mixture vibrations to be constructed depending on the initial vapor content. In accordance with the piston vibration amplitude, the limit of the critical vapor content below which vapor condensation is impossible has been found.

  8. 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.

  9. 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.

  10. Additional calculations of triton moments

    NASA Astrophysics Data System (ADS)

    Lally, D. F.; Levinger, J. S.

    1982-02-01

    The formalism of hyperspherical harmonics is used to calculate several moments of the triton photoeffect for a Volkov potential with Serber exchange. The accuracy of Clare's calculations of moments σ0 and σ1 is improved by including more terms in the hyperspherical harmonic expansion of the potential and of the ground state wave function. The moment σ2=8.9×104 MeV3 mb is calculated using one term in the hyperspherical harmonic expansions of the potential and wave function. We invert four moments and find reasonable agreement with Gorbunov's measurements of the 3He photoeffect. NUCLEAR REACTIONS Triton photoeffect, hyperspherical harmonics, moments of photoeffect, inversion of moments.

  11. An Accurate Quartic Force Field and Vibrational Frequencies for HNO and DNO

    NASA Technical Reports Server (NTRS)

    Dateo, Christopher E.; Lee, Timothy J.; Schwenke, David W.

    1994-01-01

    An accurate ab initio quartic force field for HNO has been determined using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, CCSD(T), in conjunction with the correlation consistent polarized valence triple zeta (cc-pVTZ) basis set. Improved harmonic frequencies were determined with the cc-pVQZ basis set. Fundamental vibrational frequencies were determined using a second-order perturbation theory analysis and also using variational calculations. The N-0 stretch and bending fundamentals are determined well from both vibrational analyses. The H-N stretch, however, is shown to have an unusually large anharmonic correction, and is not well determined using second-order perturbation theory. The H-N fundamental is well determined from the variational calculations, demonstrating the quality of the ab initio quartic force field. The zero-point energy of HNO that should be used in isodesmic reactions is also discussed.

  12. Interpreting nonlinear vibrational spectroscopy with the classical mechanical analogs of double-sided Feynman diagrams.

    PubMed

    Noid, W G; Loring, Roger F

    2004-10-15

    Observables in coherent, multiple-pulse infrared spectroscopy may be computed from a vibrational nonlinear response function. This response function is conventionally calculated quantum-mechanically, but the challenges in applying quantum mechanics to large, anharmonic systems motivate the examination of classical mechanical vibrational nonlinear response functions. We present an approximate formulation of the classical mechanical third-order vibrational response function for an anharmonic solute oscillator interacting with a harmonic solvent, which establishes a clear connection between classical and quantum mechanical treatments. This formalism permits the identification of the classical mechanical analog of the pure dephasing of a quantum mechanical degree of freedom, and suggests the construction of classical mechanical analogs of the double-sided Feynman diagrams of quantum mechanics, which are widely applied to nonlinear spectroscopy. Application of a rotating wave approximation permits the analytic extraction of signals obeying particular spatial phase matching conditions from a classical-mechanical response function. Calculations of the third-order response function for an anharmonic oscillator coupled to a harmonic solvent are compared to numerically correct classical mechanical results.

  13. 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.

  14. Monitoring Bearing Vibrations For Signs Of Damage

    NASA Technical Reports Server (NTRS)

    Martinez, Carol L.

    1991-01-01

    Real-time spectral analysis of vibrations being developed for use in monitoring conditions of critical bearings in rotating machinery. Underlying concept simple and fairly well established: appearance and growth of vibrations at frequencies associated with rotations of various parts of bearing system indicate wear, damage, and imperfections of manufacture. Frequencies include fundamental and harmonics of frequency of rotation of ball cage, frequency of passage of balls, and frequency of rotation of shaft.

  15. 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.

  16. Experimental and DFT studies on the vibrational and electronic spectra of 2-(4,5-phenyl-1H-imidazole-2-yl)-phenol

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

    The compound 2-(4,5-phenyl-1H-imidazole-2-yl-phenol (PIP) was synthesized, followed by structure determination by X-ray diffraction, the results of which agree well with the calculated optimized, lowest energy geometrical structure. Vibrational information was obtained by FT-IR and Raman spectroscopy which also agree well with calculations (of harmonic vibration frequencies). The calculations were carried out with density functional theory B3LYP methods using 6-311++G** and LANL2DZ basis sets. Absorption UV-Vis experiments of PIP in CH3CH2OH solution reveal three maximum peaks at 245, 292 and 317 nm, which are in agreement with calculated electronic transitions using TD-B3LYP/6-311++G** in CH3CH2OH solution, and agree to the gas-phase calculations.

  17. 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

  18. 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…

  19. Computer analysis of railcar vibrations

    NASA Technical Reports Server (NTRS)

    Vlaminck, R. R.

    1975-01-01

    Computer models and techniques for calculating railcar vibrations are discussed along with criteria for vehicle ride optimization. The effect on vibration of car body structural dynamics, suspension system parameters, vehicle geometry, and wheel and rail excitation are presented. Ride quality vibration data collected on the state-of-the-art car and standard light rail vehicle is compared to computer predictions. The results show that computer analysis of the vehicle can be performed for relatively low cost in short periods of time. The analysis permits optimization of the design as it progresses and minimizes the possibility of excessive vibration on production vehicles.

  20. Resonance vibrations of aircraft propellers

    NASA Technical Reports Server (NTRS)

    Liebers, Fritz

    1932-01-01

    On the basis of the consideration of various possible kinds of propeller vibrations, the resonance vibrations caused by unequal impacts of the propeller blades appear to be the most important. Their theoretical investigation is made by separate analysis of torsional and bending vibrations. This method is justified by the very great difference in the two natural frequencies of aircraft propeller blades. The calculated data are illustrated by practical examples. Thereby the observed vibration phenomenon in the given examples is explained by a bending resonance, for which the bending frequency of the propeller is equal to twice the revolution speed.

  1. 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.

  2. Vibrational spectral investigation and Natural Bond Orbital analysis of anti-rheumatoid drug Ethyl 4-nitrophenylacetate - DFT approach

    NASA Astrophysics Data System (ADS)

    Suresh, D. M.; Amalanathan, M.; Sebastian, S.; Sajan, D.; Hubert Joe, I.; Bena Jothy, V.

    2012-12-01

    Vibrational analysis of ethyl 4-nitrophenylacetate (ENPA) molecule was carried out using FT-IR and FT-Raman spectroscopic techniques. The equilibrium geometry, harmonic vibrational wave numbers, various bonding features have been computed using density functional theory. The calculated molecular geometry parameters have been compared with XRD data. The detailed interpretation of the vibrational spectra has been carried out by computing Potential Energy Distribution (PED). Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using Natural Bond Orbital (NBO) analysis. The results show that the charge in the electron density (ED) in the σ∗ and π∗ antibonding orbitals and second order delocalization energies (E2) confirm the occurrence of ICT (intramolecular charge transfer) within the molecule. The simulated spectra satisfactorily coincide with the experimental spectra.

  3. 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.

  4. VIBRATION COMPACTION

    DOEpatents

    Hauth, J.J.

    1962-07-01

    A method of compacting a powder in a metal container is described including the steps of vibrating the container at above and below the resonant frequency and also sweeping the frequency of vibration across the resonant frequency several times thereby following the change in resonant frequency caused by compaction of the powder. (AEC)

  5. Vibration analysis of composite laminate plate excited by piezoelectric actuators.

    PubMed

    Her, Shiuh-Chuan; Lin, Chi-Sheng

    2013-03-01

    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.

  6. 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

  7. 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.

  8. Vibrational frequency scaling factors for correlation consistent basis sets and the methods CC2 and MP2 and their spin-scaled SCS and SOS variants

    SciTech Connect

    Friese, Daniel H.; Törk, Lisa; Hättig, Christof

    2014-11-21

    We present scaling factors for vibrational frequencies calculated within the harmonic approximation and the correlated wave-function methods coupled cluster singles and doubles model (CC2) and Møller-Plesset perturbation theory (MP2) with and without a spin-component scaling (SCS or spin-opposite scaling (SOS)). Frequency scaling factors and the remaining deviations from the reference data are evaluated for several non-augmented basis sets of the cc-pVXZ family of generally contracted correlation-consistent basis sets as well as for the segmented contracted TZVPP basis. We find that the SCS and SOS variants of CC2 and MP2 lead to a slightly better accuracy for the scaled vibrational frequencies. The determined frequency scaling factors can also be used for vibrational frequencies calculated for excited states through response theory with CC2 and the algebraic diagrammatic construction through second order and their spin-component scaled variants.

  9. Accurate vibrational frequencies using the self-consistent-charge density-functional tight-binding method

    NASA Astrophysics Data System (ADS)

    Małolepsza, Edyta; Witek, Henryk A.; Morokuma, Keiji

    2005-09-01

    An optimization technique for enhancing the quality of repulsive two-body potentials of the self-consistent-charge density-functional tight-binding (SCC-DFTB) method is presented and tested. The new, optimized potentials allow for significant improvement of calculated harmonic vibrational frequencies. Mean absolute deviation from experiment computed for a group of 14 hydrocarbons is reduced from 59.0 to 33.2 cm -1 and maximal absolute deviation, from 436.2 to 140.4 cm -1. A drawback of the new family of potentials is a lower quality of reproduced geometrical and energetic parameters.

  10. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

    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.

  12. 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

  13. Variational study on the vibrational level structure and vibrational level mixing of highly vibrationally excited S₀ D₂CO.

    PubMed

    Rashev, Svetoslav; Moule, David C; Rashev, Vladimir

    2012-11-01

    We perform converged high precision variational calculations to determine the frequencies of a large number of vibrational levels in S(0) D(2)CO, extending from low to very high excess vibrational energies. For the calculations we use our specific vibrational method (recently employed for studies on H(2)CO), consisting of a combination of a search/selection algorithm and a Lanczos iteration procedure. Using the same method we perform large scale converged calculations on the vibrational level spectral structure and fragmentation at selected highly excited overtone states, up to excess vibrational energies of ∼17,000 cm(-1), in order to study the characteristics of intramolecular vibrational redistribution (IVR), vibrational level density and mode selectivity. PMID:22750345

  14. Analysis of Vibration and Acoustic Noise in Permanent Magnet Motors.

    NASA Astrophysics Data System (ADS)

    Hwang, Sangmoon

    The drive motor is a frequent source of vibration and acoustic noise in many precision spindle motors. One of the electromagnetic sources of vibration in permanent magnet motors is the torque ripple, consisting of the reluctance torque and electromagnetic torque fluctuation. This type of vibration is becoming more serious with the advent of new high-grade magnets with increased flux density. Acoustic noise of electromagnetic origin is difficult to predict and its exact mechanism is unclear. The mechanism of noise generation should be revealed to design a quieter motor which is the modern customer's demand. For motor operation at low speeds and loads, torque ripple due to the reluctance torque is often a source of vibration and control difficulty. The reluctance torque in a motor was calculated from the flux density by a finite element method and the Maxwell stress method. Effects of design parameters, such as stator slot width, permanent slot width, airgap length and magnetization direction, were investigated. Magnet pole shaping, by gradually decreasing the magnet thickness toward edges, yields a sinusoidal shape of the reluctance torque with reduced harmonics, thus reducing the vibration. This dissertation also presents two motor design techniques: stator tooth notching and rotor pole skewing with magnet pole shaping, and the effect of each method on the output torque. The analysis shows that the reluctance torque can be nearly eliminated by the suggested designs, with minimal sacrifice of the output torque. In permanent magnet DC motors, the most popular design type is the trapezoidal back electro-motive force (BEMF), for switched DC controllers. It is demonstrated that the output torque profile of one phase energized is qualitatively equivalent to the BEMF profile for motors with reduced reluctance torque. It implies that design of BEMF profile is possible by magnetic modeling of a motor, without expensive and time-consuming experiments for different designs

  15. Investigation of Student Reasoning about Harmonic Motions

    NASA Astrophysics Data System (ADS)

    Tongnopparat, N.; Poonyawatpornkul, J.; Wattanakasiwich, P.

    This study aimed to investigate student reasoning about harmonic oscillations. We conducted a semi-structured interview based on three situations of harmonic motions—(1) a mass attaching to spring and horizontally oscillating without damping, (2) the same situation but vertically oscillating and (3) a mass attaching to spring and oscillating in viscous liquid. Forty-five second-year students taking a vibrations and wave course at Chiang Mai University, Thailand participated in a fifteen-minute interview, which was video-recorded. The videos were transcribed and analyzed by three physics instructors. As results, we found that most students had misconceptions about angular frequency and energy mostly in the second and third situations.

  16. Experimental estimation of the statistical parameters of vibrations of a shell (using a digital computer), 2

    NASA Technical Reports Server (NTRS)

    Kanayev, B. A.; Lyubashevskiy, G. S.; Tartakovskiy, B. D.

    1973-01-01

    The statistical characteristics of complex variation amplitudes of shells excited by harmonic force sources in the sound frequency range are examined. Vibrations were measured with a multichannel unit, permitting the component values of a complex vibration amplitude for the i-th measurement point to be obtained at each measured point. An estimation was also made of the nature of the vibration field structure.

  17. Variational study on the vibrational level structure and IVR behavior of highly vibrationally excited S0 formaldehyde.

    PubMed

    Rashev, Svetoslav; Moule, David C

    2012-02-15

    We perform large scale converged variational vibrational calculations on S(0) formaldehyde up to very high excess vibrational energies (E(v)), E(v)∼17,000cm(-1), using our vibrational method, consisting of a specific search/selection/Lanczos iteration procedure. Using the same method we investigate the vibrational level structure and intramolecular vibrational redistribution (IVR) characteristics for various vibrational levels in this energy range in order to assess the onset of IVR. PMID:22185953

  18. 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

  19. Harmonization Initiatives in Europe

    PubMed Central

    2016-01-01

    Introduction Modern medicine is more and more based on protocols and guidelines; clinical laboratory data play very often a relevant role in these documents and for this reason the need for their harmonization is increasing. To achieve harmonized results the harmonization process must not be limited to only the analytical part, but has to include the pre- and the post-analytical phases. Results To fulfill this need the European Federation of Clinical Chemistry and Laboratory Medicine (EFLM) has started several initiatives. A Working Group on harmonization of the total testing process (WG-H) has been created with the aims of: 1) surveying and summarizing national European and pan European harmonization initiatives; 2) promoting and coordinating the dissemination of especially promising harmonization initiatives among the EFLM member societies; and 3) taking initiatives to harmonize nomenclature, units and reference intervals at a European level. The activity of the WG started this year with a questionnaire targeted at surveying the status of various harmonization activities, especially those in the pre- and post-analytical phase categories, among the European laboratory medicine societies. Conclusions Based on the results of the questionnaire, some activities promoting the dissemination of best practice in blood sampling, sample storage and transportation, in collaboration with WG on the pre-analytical phase, will be promoted, and initiatives to spread to all the European countries the use of SI units in reporting, will be undertaken. Moreover, EFLM has created a Task and Finish Group on standardization of the color coding for blood collection tube closures that is actively working to accomplish this difficult task through collaboration with manufacturers. PMID:27683503

  20. Ultrasound vibrometry using orthogonal- frequency-based vibration pulses.

    PubMed

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

    2013-11-01

    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, the amplitudes of which 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.