Sebastian, S; Sylvestre, S; Jayarajan, D; Amalanathan, M; Oudayakumar, K; Gnanapoongothai, T; Jayavarthanan, T
2013-01-15
In this work, we report harmonic vibrational frequencies, molecular structure, NBO and HOMO, LUMO analysis of Umbelliferone also known as 7-hydroxycoumarin (7HC). The optimized geometric bond lengths and bond angles obtained by computation (monomer and dimmer) shows good agreement with experimental XRD data. Harmonic frequencies of 7HC were determined and analyzed by DFT utilizing 6-311+G(d,p) as basis set. The assignments of the vibrational spectra have been carried out with the help of Normal Coordinate Analysis (NCA) following the Scaled Quantum Mechanical Force Field Methodology (SQMFF). The change in electron density (ED) in the ?* and ?* antibonding orbitals and stabilization energies E(2) have been calculated by Natural Bond Orbital (NBO) analysis to give clear evidence of stabilization originating in the hyperconjugation of hydrogen-bonded interaction. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) complements with the experimental findings. The simulated spectra satisfactorily coincides with the experimental spectra. Microbial activity of studied compounds was tested against Staphylococcus aureus, Streptococcus pyogenes, Bacillus subtilis, Escherichia coli, Psuedomonas aeruginosa, Klebsiella pneumoniae, Proteus mirabilis, Shigella flexneri, Salmonella typhi and Enterococcus faecalis. PMID:23123244
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.
Tiltrotor Vibration Reduction Through Higher Harmonic Control
NASA Technical Reports Server (NTRS)
Nixon, Mark W.; Kvaternik, Raymond G.; Settle, T. Ben
1997-01-01
The results of a joint NASA/Army/Bell Helicopter Textron wind-tunnel test to assess the potential of higher harmonic control (HHC) for reducing vibrations in tiltrotor aircraft operating in the airplane mode of flight, and to evaluate the effectiveness of a Bell-developed HHC algorithm called MAVSS (Multipoint Adaptive Vibration Suppression System) are presented. The test was conducted in the Langley Transonic Dynamics Tunnel using an unpowered 1/5-scale semispan aeroelastic model of the V-22 which was modified to incorporate an HHC system employing both the rotor swashplate and the wing flaperon. The effectiveness of the swashplate and the flaperon acting either singly or in combination in reducing IP and 3P wing vibrations over a wide range of tunnel airspeeds and rotor rotational speeds was demonstrated. The MAVSS algorithm was found to be robust to variations in tunnel airspeed and rotor speed, requiring only occasional on-line recalculations of the system transfer matrix. HHC had only a small (usually beneficial) effect on blade loads but increased pitch link loads by 25%. No degradation in aeroelastic stability was noted for any of the conditions tested.
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.
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.
Potential models and local mode vibrational eigenvalue calculations for acetylene
L. Halonen; M. S. Child; S. Carter
1982-01-01
Two potential models for acetylene are developed and tested by comparison between variational calculations for the stretching vibrational term values and available spectroscopic data. The first model based on local bond potentials with harmonic interbond coupling gives root mean square deviations of 6 cm-1 for C2H2 and 3 cm-1 for C2D2. The second model is more ambitious, being designed to
Influence of nuclear vibration on harmonic generation in molecules
NASA Astrophysics Data System (ADS)
Chiril?, Ciprian C.; Lein, Manfred
2006-07-01
The effect of vibrational motion on harmonic generation in molecules is studied within the strong-field approximation. Simple expressions are given for the cut-off energy and for the ratio of spectral intensities from two isotopes. The latter is based on electronic trajectories from the simple-man's model. The influence of vibration is given by a correlation function that is sensitive to the overlap between the initial vibrational wave packet and the wave packet after the evolution in the Born-Oppenheimer potential of the ionized molecule.
Anharmonic and harmonic intermolecular vibrational modes of the DNA base pairs
NASA Astrophysics Data System (ADS)
Špirko, Vladimír; Šponer, Ji?í; Hobza, Pavel
1997-01-01
Intermolecular vibrational modes of the H-bonded adenine…thymine Watson-Crick (AT) base pair were studied for the first time using multidimensional nonharmonic treatment. Relying on a Born-Oppenheimer-like separation of the fast and slow vibrational motions, the complete multidimensional vibrational problem is reduced to a six-dimensional subproblem in which all rearrangements between the pair fragments (i.e., adenine and thymine) can be described. Following the Hougen-Bunker-Johns approach and using appropriate vibrational coordinates, a nonrigid reference is defined which covers all motions on the low-lying part of the intermolecular potential surface and which facilitates the derivation of a suitable model Hamiltonian. The potential energy surface is determined at the ab initio Hartree-Fock level with minimal basis set (HF/MINI-1) and an analytic potential energy function is obtained by fitting to the ab initio data. This function is used to calculate vibrational energy levels and effective geometries within the framework of the model Hamiltonian, disregarding the role of the kinematic and potential (in-plane)-(out-of-plane) interactions. The calculations are in reasonable agreement with the normal coordinate analysis (harmonic treatment) thus indicating physical correctness of this standard approach for an approximate description of the lowest vibrational states of the AT base pair. In addition, to get a deeper insight, harmonic vibrational frequencies of the AT pair and 28 other base pairs are evaluated at the same and higher levels of theory [ab initio Hartree-Fock level with split-valence basis set (HF/6-31G**)]. The HF/MINI-1 and HF/6-31G** intermolecular harmonic vibrational frequencies differ by less than 30%. For all the base pairs, the buckle and propeller vibrational modes [for definition and nomenclature see R. E. Dickerson et al., EMBO J. 8, 1 (1989)] are the lowest ones, all being in the narrow interval (from 4 to 30 cm-1 in the harmonic approximation). Although most of the evaluated harmonic frequencies are qualitatively correct approximations to the genuine vibrational frequencies, in some cases due to a strong nonharmonic behavior of the buckle motion, they become physically meaningless. To get physically correct results in such cases, apparently, the standard harmonic oscillator approach should be replaced by a more adequate approach, for instance, by the approach we used in the case of the adenine…thymine pair.
Harmonic Motion Detection in a Vibrating Scattering Medium
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
Variational calculations of vibrational properties of ozone
NASA Technical Reports Server (NTRS)
Carney, G. D.; Curtiss, L. A.; Langhoff, S. R.
1977-01-01
A variational method is used to obtain vibrational-rotational properties for ozone from an experimental quartic force field. Band positions, average structures, matrix elements for calculating infrared intensities, and effective rotational constants are reported for (O-16)3 and its O-18 isotopic species. Also, the degree to which the vibrational energies and properties are converged is investigated as a function of the basis set parameters and basis set size, and of the method of obtaining the Hamiltonian matrix elements. A convenient procedure for assigning the vibrational states is developed for variational vibrational wavefunction expansions.
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.
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.
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.
Harmonic influence lines in structural dynamics calculated by use of Müller-Breslau's theorem
NASA Astrophysics Data System (ADS)
Åkesson, B. Å.
1990-10-01
Müller-Breslau's theorem is formulated and proved for certain linear structures in forced stationary harmonic vibration. The theorem provides the structural analyst with a computationally attractive method for finding, in one and the same calculation, all coefficients (generally complex-valued) describing the influence on a reactive or sectional force in a fixed position by an external harmonic unit load acting in any position. Critical and dimensioning combinations of loads can thereby easily be found. Three numerical examples demonstrate applications to systems that are discrete and continuous, undamped and damped, and finite and infinite. It is shown how a standard computer program for the analysis of beam and frame vibration can be employed to calculate and plot harmonic influence lines by use of the Müller-Breslau technique. Physical experiments based on the same technique are discussed.
Enhancement of high-harmonic generation by laser-induced cluster vibration
Enhancement of high-harmonic generation by laser-induced cluster vibration Yen-Mu Chen,1,2 Ming a new tool for studying the vibrational dynamics of nanometer atomic clusters. Â© 2007 Optical Society vibration was reported [8], and the results indicate that HHG is a very sensitive probe for vibrational
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
Optimized coordinates in vibrational coupled cluster calculations
Thomsen, Bo; Christiansen, Ove; Yagi, Kiyoshi
2014-04-21
The use of variationally optimized coordinates, which minimize the vibrational self-consistent field (VSCF) ground state energy with respect to orthogonal transformations of the coordinates, has recently been shown to improve the convergence of vibrational configuration interaction (VCI) towards the exact full VCI [K. Yagi, M. Keçeli, and S. Hirata, J. Chem. Phys. 137, 204118 (2012)]. The present paper proposes an incorporation of optimized coordinates into the vibrational coupled cluster (VCC), which has in the past been shown to outperform VCI in approximate calculations where similar restricted state spaces are employed in VCI and VCC. An embarrassingly parallel algorithm for variational optimization of coordinates for VSCF is implemented and the resulting coordinates and potentials are introduced into a VCC program. The performance of VCC in optimized coordinates (denoted oc-VCC) is examined through pilot applications to water, formaldehyde, and a series of water clusters (dimer, trimer, and hexamer) by comparing the calculated vibrational energy levels with those of the conventional VCC in normal coordinates and VCI in optimized coordinates. For water clusters, in particular, oc-VCC is found to gain orders of magnitude improvement in the accuracy, exemplifying that the combination of optimized coordinates localized to each monomer with the size-extensive VCC wave function provides a supreme description of systems consisting of weakly interacting sub-systems.
Lein, Manfred
2010-01-01
PHYSICAL REVIEW A 81, 023412 (2010) Vibrational-state and isotope dependence of high-order harmonic generation in water molecules Mirjam Falge,1 Volker Engel,1 and Manfred Lein2 1 Universit¨at W calculations on high-order harmonic generation in water molecules. Spectra are determined for various initial
Dynamical properties of an harmonic oscillator impacting a vibrating wall
NASA Astrophysics Data System (ADS)
de Alcantara Bonfim, O. F.
2009-05-01
The dynamics of a spring-mass system under repeated impact with a vibrating wall is investigated using the static wall approximation. The evolution of the harmonic oscillator is described by two coupled difference equations. These equations are solved numerically, and in some cases exact analytical expressions have also been found. For a periodically vibrating wall, Fermi acceleration is only found at resonance. There, the average rebounding velocity increases linearly with the number of collisions. Near resonance, the average rebounding velocity grows initially with the number of collisions and eventually reaches a plateau. In the vicinity of resonance, the motion of the oscillator exhibits scaling properties over a range of frequency ratios. The presence of dissipation at resonance destroys the Fermi-acceleration process and induces scaling behavior similar to that at near resonance. For a moving wall with a random amplitude at collisions, Fermi acceleration is observed independently of the ratio between the wall and oscillator frequencies. In this case the average rebounding velocity grows with the square root of the number of collisions with the wall. Also, in this latter case, dissipation suppresses the Fermi-acceleration mechanism and induces a scaling behavior with the same universality class as that of the dissipative bouncing ball model with random external perturbations.
Gain-Scheduled Higher Harmonic Control for Full Flight Envelope Vibration Reduction
Fan, Frank H.
This paper investigates the dynamics of the SMART rotor, and presents a method to design a gain-scheduled controller to reduce the harmonic vibration throughout the flight envelope. The dynamics of the SMART rotor was ...
Schneider, W.; Thiel, W. (Bergische Universitaet-Gesamthochschule, Wuppertal (West Germany)); Komornicki, A. (Polyatomics Research Institute, Mountain View, CA (USA))
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.
Algebraic-matrix calculation of vibrational levels of triatomic molecules.
Sedivcová-Uhlíková, T; Abdullah, Hewa Y; Manini, Nicola
2009-05-28
We introduce an accurate and efficient algebraic technique for the computation of the vibrational spectra of triatomic molecules, of both linear and bent equilibrium geometry. The full three-dimensional potential energy surface (PES), which can be based on entirely ab initio data, is parametrized as a product Morse-cosine expansion, expressed in bond angle internal coordinates, and includes explicit interactions among the local modes. We describe the stretching degrees of freedom in the framework of a Morse-type expansion on a suitable algebraic basis, which provides exact analytical expressions for the elements of a sparse Hamiltonian matrix. Likewise, we use a cosine power expansion on a spherical harmonics basis for the bending degree of freedom. The resulting matrix representation in the product space is very sparse, and vibrational levels and eigenfunctions can be obtained by efficient diagonalization techniques. We apply this method to carbonyl sulfide, hydrogen cyanide, water, and nitrogen dioxide. When we base our calculations on high-quality PESs tuned to the experimental data, the computed spectra are in very good agreement with the observed band origins. PMID:19419231
Chakraborty, Arindam; Truhlar, Donald G; Bowman, Joel M; Carter, Stuart
2004-08-01
The rovibration partition function of CH4 was calculated in the temperature range of 100-1000 K using well-converged energy levels that were calculated by vibrational-rotational configuration interaction using the Watson Hamiltonian for total angular momenta J = 0-50 and the MULTIMODE computer program. The configuration state functions are products of ground-state occupied and virtual modals obtained using the vibrational self-consistent field method. The Gilbert and Jordan potential energy surface was used for the calculations. The resulting partition function was used to test the harmonic oscillator approximation and the separable-rotation approximation. The harmonic oscillator, rigid-rotator approximation is in error by a factor of 2.3 at 300 K, but we also propose a separable-rotation approximation that is accurate within 2% from 100 to 1000 K. PMID:15260761
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.
Park, Barratt
Franck-Condon vibrational overlap integrals for the [~ over A] [superscript 1]A[subscript u] — [~ over X [superscript 1]?[+ over g] transition in acetylene have been calculated in full dimension in the harmonic normal mode ...
Efficient calculation of anharmonic vibrational spectra of large molecules with localized modes.
Panek, Pawe? T; Jacob, Christoph R
2014-10-20
The analysis and interpretation of the vibrational spectra of complex (bio)molecular systems, such as polypeptides and proteins, requires support from quantum-chemical calculations. Such calculations are currently restricted to the harmonic approximation. Here, we show how one of the main bottlenecks in such calculations, the evaluation of the potential energy surface, can be overcome by using localized modes instead of the commonly employed normal modes. We apply such local vibrational self-consistent field (L-VSCF) and vibrational configuration interaction (L-VCI) calculations to a cyclic water tetramer and a helical hexa-alanine peptide. The results show that the use of localized modes is equivalent to the commonly used normal modes, but offers several advantages. First, a faster convergence with respect to the excitation level is observed in L-VCI calculations. Second, the localized modes provide a reduced representation of the couplings between modes that show a regular coupling pattern. This can be used to disregard a significant number of small two-mode potentials a priori. Several such reduced coupling approximations are explored, and we show that the number of single-point calculations required to evaluate the potential energy surface can be significantly reduced without introducing noticeable errors in the resulting vibrational spectra. PMID:25080397
Variational calculation of vibrational linear and nonlinear optical properties.
Torrent-Sucarrat, Miquel; Luis, Josep M; Kirtman, Bernard
2005-05-22
A variational approach for reliably calculating vibrational linear and nonlinear optical properties of molecules with large electrical and/or mechanical anharmonicity is introduced. This approach utilizes a self-consistent solution of the vibrational Schrodinger equation for the complete field-dependent potential-energy surface and, then, adds higher-level vibrational correlation corrections as desired. An initial application is made to static properties for three molecules of widely varying anharmonicity using the lowest-level vibrational correlation treatment (i.e., vibrational Møller-Plesset perturbation theory). Our results indicate when the conventional Bishop-Kirtman perturbation method can be expected to break down and when high-level vibrational correlation methods are likely to be required. Future improvements and extensions are discussed. PMID:15945714
NASA Astrophysics Data System (ADS)
Budarz, Timo Erkki Brian
Biologically significant heme protein model compounds are studied via normal mode analysis using both a conventional harmonic approach and a self consistent harmonic approximation (SCHA) approach in order to model anharmonicities. The SCHA calculation allows us to investigate and predict the temperature dependence of vibrational modes and bond amplitudes---something that no other theoretical method can accomplish without either prohibitive computational cost or unreasonable and non-physical results such as premature bond dissociation or conformational change. Considering temperature dependence of dynamics is important as most biological compounds perform their functions at temperatures (room temperature) much greater than those used during experimental spectroscopic measurements (usually liquid nitrogen or liquid helium temperatures). Our findings indicate that an increase in temperature will selectively amplify certain bond amplitudes in a, complex fashion that is not possible to predict from geometry, bond strengths or standard normal mode frequencies and amplitudes. In the end, intuition is in some sense verified by finding that the most amplified motions tend to be rotational motions of groups which are weakly bound and weakly coupled to the rest of the molecule---such as phenyl groups at the heme periphery. From both standard normal mode and SCHA calculations, density of states is obtained and compared with experimental density of states arising from a novel experimental technique called nuclear resonance vibrational spectroscopy (NRVS). Standard harmonic parameters are calculated and refined to match experimental data in Fe(OEP)Cl and Fe(TPP)NO(1-MeIm). Fe(TPP)NO(1-MeIm) is further modeled by use of a set of anharmonic interatomic potentials. Use of these potentials in a SCHA calculation allows prediction of the temperature dependence of the vibrational spectrum which compares favorably with experimental data.
Vibrational and thermodynamic properties of Ni3S2 polymorphs from first-principles calculations
NASA Astrophysics Data System (ADS)
Yu, Yonggang G.; Ross, Nancy L.
2011-03-01
We have calculated the compressional, vibrational, and thermodynamic properties of Ni3S2 heazlewoodite and the high-pressure orthorhombic phase (with Cmcm symmetry) using the generalized gradient approximation to the density functional theory in conjunction with the quasi-harmonic approximation. The predicted Raman frequencies of heazlewoodite are in good agreement with room-temperature measurements. The calculated thermodynamic properties of heazlewoodite at room conditions agree very well with experiments, but at high temperatures (especially above 500 K) the heat capacity data from experiments are significantly larger than the quasi-harmonic results, indicating that heazlewoodite is anharmonic. On the other hand, the obtained vibrational density of states of the orthorhombic phase at 20 GPa reveals a group of low-frequency vibrational modes which are absent in heazlewoodite. These low-frequency modes contribute substantially to thermal expansivity, heat capacity, entropy, and Grüneisen parameter of the orthorhombic phase. The calculated phase boundary between heazlewoodite and the orthorhombic phase is consistent with high-pressure experiments; the predicted transition pressure is 17.9 GPa at 300 K with a negative Clapeyron slope of -8.5 MPa/K.
-optical double resonance,7 infrared difference-frequency laser spectrosco- py,8,9 velocity modulation infraredMultiphoton ionization photoelectron spectroscopy of phenol: Vibrational frequencies and harmonic 94305 (Recieved 1 February 1985; accepted 14 March 1985) A molecular beam of phenol, cooled
Cryns, Jackson W.; Hatchell, Brian K.; Santiago-Rojas, Emiliano; Silvers, Kurt L.
2013-07-01
Formal journal article Experimental analysis of a piezoelectric energy harvesting system for harmonic, random, and sine on random vibration Abstract: Harvesting power with a piezoelectric vibration powered generator using a full-wave rectifier conditioning circuit is experimentally compared for varying sinusoidal, random and sine on random (SOR) input vibration scenarios. Additionally, the implications of source vibration characteristics on harvester design are discussed. Studies in vibration harvesting have yielded numerous alternatives for harvesting electrical energy from vibrations but piezoceramics arose as the most compact, energy dense means of energy transduction. The rise in popularity of harvesting energy from ambient vibrations has made piezoelectric generators commercially available. Much of the available literature focuses on maximizing harvested power through nonlinear processing circuits that require accurate knowledge of generator internal mechanical and electrical characteristics and idealization of the input vibration source, which cannot be assumed in general application. In this manuscript, variations in source vibration and load resistance are explored for a commercially available piezoelectric generator. We characterize the source vibration by its acceleration response for repeatability and transcription to general application. The results agree with numerical and theoretical predictions for in previous literature that load optimal resistance varies with transducer natural frequency and source type, and the findings demonstrate that significant gains are seen with lower tuned transducer natural frequencies for similar source amplitudes. Going beyond idealized steady state sinusoidal and simplified random vibration input, SOR testing allows for more accurate representation of real world ambient vibration. It is shown that characteristic interactions from more complex vibrational sources significantly alter power generation and power processing requirements by increasing harvested power, shifting optimal conditioning impedance, inducing significant voltage supply fluctuations and ultimately rendering idealized sinusoidal and random analyses insufficient.
NASA Astrophysics Data System (ADS)
Ayyappan, S.; Sundaraganesan, N.; Aroulmoji, V.; Murano, E.; Sebastian, S.
2010-09-01
The FT-IR and FT-Raman spectral studies of the Methotrexate (MTX) were carried out. The equilibrium geometry, various bonding features and harmonic vibrational frequencies of MTX have been investigated with the help of B3LYP density functional theory (DFT) using 6-31G(d) as basis set. Detailed analysis of the vibrational spectra has been made with the aid of theoretically predicted vibrational frequencies. The vibrational analysis confirms the differently acting ring modes, steric repulsion, conjugation and back-donation. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) results complement with the experimental findings. The calculated HOMO and LUMO energies show that charge transfer occur within the molecule. Good correlations between the experimental 1H and 13C NMR chemical shifts in DMSO solution and calculated GIAO shielding tensors were found.
Ab initio and DFT calculations of the structure and vibrational spectra of trigonelline
NASA Astrophysics Data System (ADS)
Szafran, M.; Koput, J.; Dega-Szafran, Z.; Pankowski, M.
2002-09-01
The geometries, frequencies and infrared intensities of the vibrational bands of trigonelline its monohydrate and dimer have been computed by the MP2 and B3LYP approaches using the cc-pVDZ and 6-31G(d,p) basis sets. The computed geometry of the pyridine ring is slightly affected by hydration and dimerization, and satisfactorily agrees with the X-ray data. In contrast, the geometry of the COO group changes significantly on hydration and dimerization. All the measured IR bands were assigned in terms of the calculated vibrational modes. Most computed bands are predicted to lie at higher wavenumbers than the experimental bands. R.M.S. deviation between the experimental and the calculated harmonic frequencies is 69 cm -1 for all of the bands, and 46 cm -1 for all bands except those corresponding to ?(OH), ?(OH) and ?(CH).
Ab initio calculations and vibrational structure of sulfanilamide
NASA Astrophysics Data System (ADS)
Topacli, C.; Topacli, A.
2003-01-01
A complete infrared spectrum analysis of the sulfanilamide is performed in this paper. Observed frequencies for normal modes are compared with those calculated from normal mode coordinated analysis carried out on the basis of ab initio force fields using the 3-21G basis set theoretical optimized geometry. Assignment of all vibrational bands has been performed taking into account the results of the ab initio vibrational analysis.
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
Ab initio calculation of the rotational spectrum of methane vibrational ground state
NASA Astrophysics Data System (ADS)
Cassam-Chenaï, P.; Liévin, J.
2012-05-01
In a previous article we have introduced an alternative perturbation scheme to the traditional one starting from the harmonic oscillator, rigid rotator Hamiltonian, to find approximate solutions of the spectral problem for rotation-vibration molecular Hamiltonians. The convergence of our method for the methane vibrational ground state rotational energy levels was quicker than that of the traditional method, as expected, and our predictions were quantitative. In this second article, we study the convergence of the ab initio calculation of effective dipole moments for methane within the same theoretical frame. The first order of perturbation when applied to the electric dipole moment operator of a spherical top gives the expression used in previous spectroscopic studies. Higher orders of perturbation give corrections corresponding to higher centrifugal distortion contributions and are calculated accurately for the first time. Two potential energy surfaces of the literature have been used for solving the anharmonic vibrational problem by means of the vibrational mean field configuration interaction approach. Two corresponding dipole moment surfaces were calculated in this work at a high level of theory. The predicted intensities agree better with recent experimental values than their empirical fit. This suggests that our ab initio dipole moment surface and effective dipole moment operator are both highly accurate.
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.
Vibronic-structure tracking: A shortcut for vibrationally resolved UV/Vis-spectra calculations
Barton, Dennis; König, Carolin; Neugebauer, Johannes, E-mail: j.neugebauer@uni-muenster.de [Theoretische Organische Chemie, Organisch-Chemisches Institut and Center for Multiscale Theory and Computation, Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149 Münster (Germany)
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.
Lein, Manfred
Effect of dressing on high-order harmonic generation in vibrating H2 molecules C. C. Chiril and M of the molecule. We show that the field dressing becomes important at long laser wavelengths 2 m , leading
Harmonic two-phonon {gamma}-vibrational state in neutron-rich {sup 106}Mo
Guessous, A.; Schulz, N.; Phillips, W.R.; Ahmad, I.; Bentaleb, M.; Durell, J.L.; Jones, M.A.; Leddy, M.; Lubkiewicz, E.; Morss, L.R.; Piepenbring, R.; Smith, A.G.; Urban, W.; Varley, B.J. [Centre de Recherches Nucleaires, IN2P3-CNRS/Universite Louis Pasteur, 67037 Strasbourg (France)] [Centre de Recherches Nucleaires, IN2P3-CNRS/Universite Louis Pasteur, 67037 Strasbourg (France); [Department of Physics, University of Manchester, M13 9PL (United Kingdom); [Argonne National Laboratory, Argonne, Illinois 60439 (United States); [Institut des Sciences Nucleaires, IN2P3-CNRS/UJF, 38026 Grenoble (France)
1995-09-18
The neutron-rich {sup 106}Mo nucleus has been studied by prompt {gamma}-ray spectroscopy following the spontaneous fission of {sup 248}Cm. The characteristics of the rotational band built on a state at 1435 keV identifies the band head as the best candidate for a harmonic double-phonon {ital K}{sup {pi}}=4{sup +} {gamma}-vibrational state observed so far.
Peiran Yang; C. M. Rodkiewicz
1996-01-01
The bearing performance of a centrally supported tilting square pad, subjected to harmonic vibration, is analysed numerically. Thermo-elastohydrodynamic lubrication analysis considers simultaneously the heat transfer, elastic deformation of the pad's working surface, side leakage, and the inlet pressure build-up effect. Governing equations with their boundary conditions are transformed into non-dimensional forms so that the problem's non-dimensional parameters are obtained. An
Fully automated microcomputer calculation of vibrational spectra
NASA Astrophysics Data System (ADS)
Dowty, Eric
1987-01-01
A fully automated method for computing frequencies and atomic displacements of normal modes, giving synthetic infrared and Raman spectra, has been developed for use on small computers. No expertise in group theory or the mathematics of normal-mode calculation are required to use the computer program. The method takes full account of symmetry and is applicable to any crystal or molecule. Force constants can be specified in terms of any two-atom “bonds” or three-atom angles. The essential steps in the computer program are: (1) Locate all atoms in the unit cell or molecule and compute displacement vectors for each internal coordinate; (2) Convert the basis of the force constants from bonds and angles to cartesian displacements; (3) Construct the full-matrix irreducible representations of the point or factor group in question, using appropriate symmetry matrices and polynomial basis functions; (4) Derive the symmetry coordinates in terms of cartesian displacements using the projection/transfer-operator technique; (5) construct secular equations for each species with Wilson's f g method; (6) solve for frequencies and atomic motions; and (7) use simple models of infrared and Raman intensities to calculate spectra.
REGULAR PAPER Vibrational mode frequency calculations of chlorophyll-d
Hastings, Gary
REGULAR PAPER Vibrational mode frequency calculations of chlorophyll-d for assessing (P740+ -P740 that utilizes chlorophyll-d for light induced photochemistry. In photosystem I particles from Acary- ochloris marina, the primary electron donor is called P740, and it is thought that P740 consist of two chlorophyll
Calculation of unsteady linearized Euler flows in cascades using harmonically deforming grids
NASA Technical Reports Server (NTRS)
Hall, Kenneth C.; Clark, William S.
1991-01-01
A method for calculating unsteady, inviscid, compressible flows in cascades is presented. Using the linearized Euler technique, the flow is decomposed into a steady or mean flow plus a harmonically varying small disturbance flow. The equations that describe the small disturbance flow are linear variable coefficient equations, and are solved using a pseudo-time time marching Lax-Wendroff technique. Unlike previous linearized methods, however, the solution is computed on a harmonically deforming computational grid that conforms to the motion of the vibrating airfoils. The mean flow and perturbation flow solutions are defined in the deforming coordinate system rather than in a coordinate system fixed in space. Hence, no extrapolation terms are required to implement the upwash boundary conditions at the airfoil surfaces, significantly improving the accuracy of the method. For transonic flow calculations, unsteady shock motions are modelled using shock capturing. The unsteady loads due to the shock motion are then seen as pressure impulses. Representative computational results are presented for transonic channel flows and subsonic and transonic cascade flows.
Diabatic Versus Adiabatic Calculation of Torsion-Vibration Interactions
NASA Astrophysics Data System (ADS)
Hougen, Jon T.
2013-06-01
The introductory part of this talk will deal briefly with two historical topics: (i) use of the words adiabatic, nonadiabatic, and diabatic in thermodynamics and quantum mechanics, and (ii) application of diabatic and adiabatic ideas to vibrational energy level calculations for a pair of diatomic-molecule potential energy curves exhibiting an avoided crossing. The main part of the talk will be devoted to recent work with Li-Hong Xu and Ron Lees on how ab initio projected frequency calculations for small-amplitude vibrations along the large-amplitude internal rotation path in methanol can best be used to help guide experimental assignments and fits in the IR vibrational spectrum. The three CH stretching vibrations for CH_{3}OH can conveniently be represented as coefficients multiplying three different types of basis vibrations, i.e., as coefficients of: (i) the local mode C-H_i bond displacements ?r_{i} for hydrogens H_{1}, H_{2} and H_{3} of the methyl top, (ii) symmetrized linear combinations of the three ?r_{i} of species A_{1} oplus E in the permutation-inversion group G_{6} = C_{3v} appropriate for methanol, or (iii) symmetrized linear combinations of the three ?r_{i} of species 2A_{1} oplus A_{2} in the permutation-inversion group G_{6}. In this talk, we will focus on diabatic and adiabatic computations for the A_{1} oplus E basis vibrations of case (ii) above. We will briefly explain how Jahn-Teller-like and Renner-Teller-like torsion-vibration interaction terms occurring in the potential energy expression in the diabatic calculation become torsion-vibration Coriolis interaction terms occurring in the kinetic energy expression of the adiabatic calculations, and also show how, for algebraically solvable parameter choices, the same energy levels are obtained from either calculation. A final conclusion as to which approach is computationally superior for the numerical data given in a quantum chemistry output file has not yet been arrived at.
NASA Astrophysics Data System (ADS)
Jacques, N.; Daya, E. M.; Potier-Ferry, M.
2010-09-01
This paper deals with geometrically nonlinear vibrations of sandwich beams with viscoelastic materials. For this purpose, a new finite element formulation has been developed, in which a zig-zag model is used to describe the displacement field. The viscoelastic behaviour is handled by using hereditary integrals and their relationships with complex moduli. An efficient solution procedure based on the harmonic balance method is also developed. To demonstrate its abilities, various problems of nonlinear vibrations of sandwich beams are considered. First, the results derived from the proposed approach are compared with those of nonlinear dynamic analyses using direct time integration and to experimental data. Then, the influence of the vibration amplitude on the damping properties of sandwich beams is investigated. The effect of an initial axial strain is also examined.
Karpagam, J; Sundaraganesan, N; Kalaichelvan, S; Sebastian, S
2010-09-01
In this work, we will report a combined experimental and theoretical study on molecular structure and vibrational analysis of 3,4-diaminopyridine (3,4-DAP) and 3-aminopyridine (3-AP). The Fourier transform infrared and Fourier transform Raman spectra of 3,4-DAP were recorded in the solid phase. The molecular geometry, harmonic vibrational wavenumbers of 3-AP and 3,4-DAP in the ground-state have been calculated by using MP2 and density functional methods (B3LYP) using 6-311++G(d,p) as basis set. Predicted electronic absorption spectra 3,4-DAP from TD-DFT calculation have been analyzed comparing with the experimental UV-vis spectrum. The calculated HOMO and LUMO energies show that charge transfer occur in the molecule. A detailed interpretation of the infrared spectra of 3-AP and 3,4-DAP is reported. The theoretical spectrograms for FTIR and FT-Raman spectra of the title molecules have also been constructed. Comparison of the experimental spectra with anharmonic vibrational wavenumbers indicates that B3LYP results are more accurate. PMID:20483656
Do, Hainam; Besley, Nicholas A
2015-02-01
Vibrational frequencies for carbon clusters, fullerenes and nanotubes evaluated using empirical carbon-carbon potentials are presented. For linear and cyclic clusters, frequencies evaluated with the reactive empirical bond order (REBO) potential provide the closest agreement with experiment. The mean absolute deviation (MAD) between experiment and the calculated harmonic frequencies is 79 cm(-1) for the bending modes and 76 cm(-1) for the stretching modes. The effects of anharmonicity are included via second order vibrational perturbation theory and tend to increase the frequency of the bending modes while the stretching modes have negative shifts in the region of 20-60 cm(-1), with larger shifts for the higher frequency modes. This results in MADs for the bending and stretching modes of 84 cm(-1) and 58 cm(-1), respectively. For the fullerene molecule C60, the high frequency modes are predicted to have harmonic frequencies that are significantly higher than experiment, and this is not corrected by accounting for anharmonicity. This overestimation of experimental observed frequencies is also evident in the calculated frequencies of the G band in nanotubes. This suggests that the REBO potential is not optimal for these larger systems and it is shown that adjustment of the parameters within the potential leads to closer agreement with experiment, particularly if higher and lower frequency modes are considered separately. PMID:25559973
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.
Calculation of mechanical vibration frequencies of stiffened superconducting cavities
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.
Calculation of mechanical vibration frequencies of stiffened superconducting cavities
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.
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.
Vibrational and structural study of onopordopicrin based on the FTIR spectrum and DFT calculations.
Chain, Fernando E; Romano, Elida; Leyton, Patricio; Paipa, Carolina; Catalán, César A N; Fortuna, Mario; Brandán, Silvia Antonia
2015-11-01
In the present work, the structural and vibrational properties of the sesquiterpene lactone onopordopicrin (OP) were studied by using infrared spectroscopy and density functional theory (DFT) calculations together with the 6-31G(?) basis set. The harmonic vibrational wavenumbers for the optimized geometry were calculated at the same level of theory. The complete assignment of the observed bands in the infrared spectrum was performed by combining the DFT calculations with Pulay's scaled quantum mechanical force field (SQMFF) methodology. The comparison between the theoretical and experimental infrared spectrum demonstrated good agreement. Then, the results were used to predict the Raman spectrum. Additionally, the structural properties of OP, such as atomic charges, bond orders, molecular electrostatic potentials, characteristics of electronic delocalization and topological properties of the electronic charge density were evaluated by natural bond orbital (NBO), atoms in molecules (AIM) and frontier orbitals studies. The calculated energy band gap and the chemical potential (?), electronegativity (?), global hardness (?), global softness (S) and global electrophilicity index (?) descriptors predicted for OP low reactivity, higher stability and lower electrophilicity index as compared with the sesquiterpene lactone cnicin containing similar rings. PMID:26057092
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.
NASA Astrophysics Data System (ADS)
Grolet, Aurelien; Thouverez, Fabrice
2015-02-01
This paper is devoted to the study of vibration of mechanical systems with geometric nonlinearities. The harmonic balance method is used to derive systems of polynomial equations whose solutions give the frequency component of the possible steady states. Groebner basis methods are used for computing all solutions of polynomial systems. This approach allows to reduce the complete system to an unique polynomial equation in one variable driving all solutions of the problem. In addition, in order to decrease the number of variables, we propose to first work on the undamped system, and recover solution of the damped system using a continuation on the damping parameter. The search for multiple solutions is illustrated on a simple system, where the influence of the retained number of harmonic is studied. Finally, the procedure is applied on a simple cyclic system and we give a representation of the multiple states versus frequency.
A piezoelectric pulse generator for low frequency non-harmonic vibration
NASA Astrophysics Data System (ADS)
Jiang, Hao; Yeatman, Eric M.
2013-12-01
This paper reports a new piezoelectric prototype for pulse generation by energy harvesting from low frequency non-harmonic vibration. The pulse generator presented here consists of two parts: the electromechanical part and the load circuit. A metal rolling rod is used as the proof mass, moving along the substrate to achieve both actuating of the piezoelectric cantilever by magnetic coupling and self-synchronous switching of the circuit. By using this new approach, the energy from the piezoelectric transduction mechanism is regulated simultaneously when it is extracted. This allows a series of tuneable pulses to be generated, which can be applied to self-powered RF wireless sensor network (WSN) nodes.
Biswanath Rath
2015-06-09
We notice through a direct calculation that any variational based calculation on $PT$ symmetrized complex Harmonic Oscillator can lead to breakdown of $PT$ symmetry condition on real spectra. Two different types of oscillators have been tested yielding an uniform conclusion.
Rioux, Frank
Visualizing the Formally Forbidden Overtone Vibrational Transitions in HCl Using the harmonic for the Morse oscillator model for HCl is integrated numerically for the first five energy states. (Integration atomic units): n 150:= xmin 1.4:= xmax 8:= xmax xmin- n 1- := Enter the Morse parameters for HCl (in
On the effect of acoustic coupling on random and harmonic plate vibrations
NASA Technical Reports Server (NTRS)
Frendi, A.; Robinson, J. H.
1993-01-01
The effect of acoustic coupling on random and harmonic plate vibrations is studied using two numerical models. In the coupled model, the plate response is obtained by integration of the nonlinear plate equation coupled with the nonlinear Euler equations for the surrounding acoustic fluid. In the uncoupled model, the nonlinear plate equation with an equivalent linear viscous damping term is integrated to obtain the response of the plate subject to the same excitation field. For a low-level, narrow-band excitation, the two models predict the same plate response spectra. As the excitation level is increased, the response power spectrum predicted by the uncoupled model becomes broader and more shifted towards the high frequencies than that obtained by the coupled model. In addition, the difference in response between the coupled and uncoupled models at high frequencies becomes larger. When a high intensity harmonic excitation is used, causing a nonlinear plate response, both models predict the same frequency content of the response. However, the level of the harmonics and subharmonics are higher for the uncoupled model. Comparisons to earlier experimental and numerical results show that acoustic coupling has a significant effect on the plate response at high excitation levels. Its absence in previous models may explain the discrepancy between predicted and measured responses.
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 ? 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 ? decay using the 8? 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.
NASA Astrophysics Data System (ADS)
Brandán, S. A.; Ero?lu, E.; Ledesma, A. E.; Oltulu, O.; Yalç?nkaya, O. B.
2011-05-01
We have studied the 5-acetamido-1,3,4-thiadiazole-2-sulphonamide compound and characterized it by infrared and Raman spectroscopy in the solid phase. The Density Functional Theory (DFT) method together with Pople's basis set show that two stable molecules for the compound have been theoretically determined in the gas phase, and that only the more stable conformation is present in the solid phase, as was experimentally observed. The harmonic vibrational wavenumbers for the optimized geometry were calculated at B3LYP/6-31G ? and B3LYP/6-311++G ?? levels at the proximity of the isolated molecule. For a complete assignment of the vibrational spectra in the compound solid, DFT calculations were combined with Pulaýs Scaled Quantum Mechanics Force Field (SQMFF) methodology in order to fit the theoretical wavenumber values to the experimental ones. In this way, a complete assignment of all of the observed bands in the infrared spectrum for the compound was performed. The natural bond orbital (NBO) study reveals the characteristics of the electronic delocalization of the two structures, while the corresponding topological properties of electronic charge density are analysed by employing Bader's Atoms in the Molecules theory (AIM).
Calculation of low frequency vibrational resonances of submerged structures
NASA Technical Reports Server (NTRS)
Everstine, Gordon C.
1989-01-01
Numerical techniques for calculating the low frequency vibrational resonances of submerged structures are reviewed. Both finite element and boundary element approaches for calculating fully-coupled added mass matrices for use in NASTRAN analysis are described and illustrated. The finite element approach is implemented using existing capability in NASTRAN. The boundary element approach uses the NASHUA structural-acoustics program to compute the added mass matrix. The two procedures are compared to each other for the case of a submerged cylindrical shell with flat end closures. It is concluded that both procedures are capable of computing accurate submerged resonances and that the more elegant boundary element procedure is easier to use but may be more expensive computationally.
Chu, Shih-I
2014-01-01
PHYSICAL REVIEW A 90, 063412 (2014) Effect of nuclear vibration on high-order-harmonic generation of aligned H2 + molecules Dmitry A. Telnov,1,* John Heslar,2, and Shih-I Chu2,3, 1 Department of Physics, St. Petersburg State University, St. Petersburg 198504, Russia 2 Department of Physics, Center for Quantum
NASA Astrophysics Data System (ADS)
Sangeetha, V.; Govindarajan, M.; Kanagathara, N.; Gunasekaran, S.; Rajakumar, P. R.; Anbalagan, G.
2014-06-01
Single crystals of melaminium bis (hydrogen oxalate) (MOX) were grown by slow evaporation method. X-ray powder diffraction analysis indicates that MOX crystallizes in monoclinic system (space group C2/c) and the calculated lattice constants are a = 20.075 ± 0.123 ?, b = 8.477 ± 0.045 ?, c = 6.983 ± 0.015, ? = ? 90° and ? = 102.6 ± 0.33°. Thermal analysis confirms that MOX is thermally stable up to 250 °C. A detailed interpretation of the FT-IR, FT-Raman and NMR spectra were reported. The equilibrium geometry, bonding features, and harmonic vibrational frequencies have been investigated with the help of PM6, HF and DFT/B3LYP methods. The potential energy curve shows that MOX molecule has two stable structures and the computational results diagnose that Rot I is the most stable conformer. The 1H and 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the Gauge-Invariant Atomic Orbital (GIAO) method. Stability of the molecule, arising from hyperconjugative interactions and charge delocalization, has been analyzed using Natural Bond Orbital (NBO) analysis. The electronic properties, such as HOMO and LUMO energies, were calculated by Time-Dependent DFT (TD-DFT) approach. To estimate chemical reactivity of the molecule, the molecular electrostatic potential (MEP) surface map is calculated for the optimized geometry of the molecule.
Comparative Study on Calculation Methods of Blasting Vibration Velocity
NASA Astrophysics Data System (ADS)
Liang, Qingguo; An, Yafang; Zhao, Lei; Li, Dewu; Yan, Liping
2011-01-01
Due to the extreme complexities in rock blasting and difficulties in theoretical or numerical analysis, and the enormous consumption of explosives in mining and construction operations, empirical or semi-empirical formulae for blasting vibration velocity (BVV) were obtained from observations and measurements in field blast tests and are still widely used all over the world. This paper investigates the fitting degree and characteristics of several calculation methods for BVV based on 34 sets of data samples from 27 projects belonging to 4 types. The results indicate that both the cube-root scaling formula and the square-root scaling formula have relatively good fitting degree, while the multiple regression analysis can give the best fitting outcome if the sample space satisfies certain requirements. Whether the cube-root scaling formula or the square-root scaling formula is chosen to analyze the relationship between BVV and scaled distance depends on the average scaled distance under cubic-root scaling. If the average scaled distance is over 0.1, the cube-root scaling formula should be used; otherwise, the square-root scaling formula should be used. Bigger samples integrated from data samples of different projects but in the same type were then analyzed to get the empirical relations for different types of projects. The correlation coefficients of these relations are quite good, thus these relations can be used for reference in other similar projects. This paper then discusses the physical meanings of parameters in different formulae, sample selection and parameter choice for BVV. It suggests that the current calculation methods for explosive charge, blasting-to-monitoring distance and scaled distance need to be improved. It also concludes that the integrated BVV from velocity components in three-dimensions is more reasonable on a theoretical basis. It can yield good results in predicting the blasting vibration, and should be used as widely as possible.
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.
ORIGINAL PAPER Calculation of infrared and Raman vibration modes of magnesite
Cattin, Rodolphe
ORIGINAL PAPER Calculation of infrared and Raman vibration modes of magnesite at high pressure) are used to obtain infrared (IR) and Raman magnesite vibration modes as they vary with pressure up to 50 approaches of vibrations in crystals based on empirical models suffer several drawbacks lead- ing
Large Vibrational Effects upon Calculated Phase Boundaries in AlSc
V. Ozolins; M. Asta
2001-01-01
The fcc portion of the Al-Sc phase diagram is calculated from first principles including contributions to alloy free energies associated with ionic vibrations. It is found that vibrational entropy accounts for a 27-fold increase in the calculated solubility limits for Sc in fcc Al at high temperatures, bringing calculated and measured values into very good agreement. The present work gives
An improved filtered spherical harmonic method for transport calculations
Ahrens, C. [Department of Applied Mathematics and Statistics, Colorado School of Mines, Golden, CO 80401 (United States); Merton, S. [Computational Physics Group, AWE Aldermaston, Berkshire (United Kingdom)
2013-07-01
Motivated by the work of R. G. McClarren, C. D. Hauck, and R. B. Lowrie on a filtered spherical harmonic method, we present a new filter for such numerical approximations to the multi-dimensional transport equation. In several test problems, we demonstrate that the new filter produces results with significantly less Gibbs phenomena than the filter used by McClarren, Hauck and Lowrie. This reduction in Gibbs phenomena translates into propagation speeds that more closely match the correct propagation speed and solutions that have fewer regions where the scalar flux is negative. (authors)
Detection Enhancement of Protein Structural Vibrations: Measurements and Calculations
NASA Astrophysics Data System (ADS)
Niessen, Katherine; Xu, Mengyang; Snell, Edward; Cody, Vivian; Pace, James; Schmidt, Marius; Markelz, Andrea
2015-03-01
Narrow band intramolecular protein vibrations have been successfully measured using crystal anisotropy THz microscopy (CATM), a near-field technique, on protein crystals. To address the question of how these motions are related to protein function we developed a variation of this technique to rapidly measure a variety of protein crystals. The variation anisotropy measurement consists of introducing a wire-grid polarizer in the THz path and rotating the polarizer between measurements, instead of the sample. While the resulting anisotropic spectra confirm reproducibility and protein specific nature of the response the signal is not directly related to the absorption spectra and in fact shows more structure than CATM. This is due to the polarization sensitivity of the electro-optical detection crystal and the changing THz polarization direction and amplitude at the detector. This combination leads to an enhancement of specific resonances and increased sensitivity to rotation of the THz polarization from the sample itself. Preliminary calculations suggest that the technique is sensitive to the birefringence associated with anisotropic absorbance. The results and significance of these measurements on protein and sucrose crystals and the calculated expected response will be discussed.
Nicholas J. Wright; R. Benny Gerber
2000-01-01
Potential energy surface points computed from variants of density functional theory (DFT) are used to calculate directly the anharmonic vibrational frequencies of H2O,Cl?H2O, and (H2O)2. The method is an adaptation to DFT of a recent algorithm for direct calculations of anharmonic vibrational frequencies using ab initio electronic structure codes. The DFT calculations are performed using the BLYP and the B3LYP
Nicholas J. Wright; R. Benny Gerber
2000-01-01
Potential energy surface points computed from variants of density functional theory (DFT) are used to calculate directly the anharmonic vibrational frequencies of H2O, Cl-H2O, and (H2O)2. The method is an adaptation to DFT of a recent algorithm for direct calculations of anharmonic vibrational frequencies using ab initio electronic structure codes. The DFT calculations are performed using the BLYP and the
Variational Calculations of IR Ro-Vibrational Spectra for Nitric Acid
NASA Astrophysics Data System (ADS)
Pavlyuchko, A. I.; Yurchenko, S. N.; Tennyson, J.
2013-09-01
To model the atmospheric composition of the potentially habitable planets, it is essential to have comprehensive data on the spectroscopic properties of the main molecular absorbers. This is especially true in the infrared region which is dominated by transitions of polyatomic molecules [1]. Nitric acid (HNO3) is an important constituent of the Earth atmosphere where it is a prominent bio-signature. Here we present simulations of the absorption spectra for HNO3. We have developed a variational method to solve the ro-vibrational Schrödinger equation for a general polyatomic molecule. The ro-vibrational Hamiltonian is given by [2] where the internal curvilinear vibrational coordinates qi are used to represent the displacements of the bond lengths and bond angles, ?ij(q) are elements of the matrix of the kinematic coefficients, t is the determinant of this matrix, 'a are the Euler angles, and ?ab(q) is the inverse matrix of the tensor of inertia. The potential energy function, V (q), is given by a fourthorder polynomial expansion in terms of Morse variables xi = 1 - e-iqi for the stretching coordinates and xi = qi for the bending coordinates. The dipole moment of the molecule is presented in the form of a Taylor series of the 2nd order in terms of qi. The parameters of the potential energy and the dipole moment functions of HNO3 were calculated by the quantum chemical method at the CCSD(T)/aug-cc-pVQZ level of theory. With this potential energy function, agreement between the calculated and experimental fundamental frequencies of vibrations is within 5 cm -1. The harmonic part of the potential function was then optimized by fitting to the experimental fundamental frequencies and used to simulate the IR spectra of HNO3. The results are in good agreement with the experimental data. The figure shows an example of the simulated spectra of HNO3 in the area of the strong Fermi resonance between the -5 and 2-9 bands along with an experimental counterpart. The resulting line list can be used for modelling atmospheres of (exo)planets at elevated temperatures.
Calculation of Raman optical activity spectra for vibrational analysis.
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. PMID:25646177
Stella Papasavva; Stephanie Tai; Amy Esslinger; Karl H. Illinger; Jonathan E. Kenny
1995-01-01
We have investigated the feasibility of using ab initio molecular orbital methods for predicting the global warming potential of the proposed chlorofluorocarbon (CFC) substitute CFâCHâF, 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
NASA Astrophysics Data System (ADS)
Polome, J.
2012-07-01
This paper presents the performance methodology and the achieved results of a vibration test campaign. The test performed by shaker simulates an unusual acoustic excitation containing a harmonic serial superimposed on random noise seen by electronic flight equipment. The paper is focused on main experimental aspects resulting of “helicopter simulation” capability applied on (representative) dummy electronic equipment. Wide internal instrumentation shows that the equipment is effectively answering to the stimuli by resonances excitation.
Calculated second-harmonic susceptibilities of BN, AlN, and GaN Jian Chen,a)
Wilkins, John
Calculated second-harmonic susceptibilities of BN, AlN, and GaN Jian Chen,a) Zachary H. Levine September 1994; accepted for publication 15 December 1994 We report calculations for the dielectric constant-harmonic susceptibility for three of the com- pounds; BN, AlN, and GaN. Our calculation uses pseudopotentials with plane
NASA Astrophysics Data System (ADS)
Renuga, S.; Muthu, S.
2014-01-01
Density functional theory (DFT) computations have become an efficient tool in the prediction of molecular structure, harmonic force fields, vibrational wave numbers as well as the IR and Raman intensities of pharmaceutically important molecule. In this work, we report harmonic vibrational frequencies, molecular structure, NBO and HOMO, LUMO analysis and detonation properties of (S)-2-(2-oxopyrrolidin-1-yl) butanamide. The solid phase FT-IR and FT-Raman spectra of (S)-2-(2-oxopyrrolidin-1-yl) butanamide were recorded in the region 4000-450 cm-1 and 4000-50 cm-1 respectively. Harmonic frequencies of this compound were determined and analyzed by DFT utilizing 6-31G(d,p), 6-31+G(d,p) basis sets. The assignments of the vibrational spectra have been carried out with the help of Normal Coordinate Analysis (NCA) following the Scaled Quantum Mechanical Force Field Methodology (SQMFF). The calculated infrared and Raman spectra of the title compounds were also stimulated utilizing the scaled force fields and the computed dipole derivatives for IR intensities and polarizability derivatives for Raman intensities. The change in electron density (ED) in the ?* and ?* antibonding orbital's and stabilization energies E(2) have been calculated by Natural Bond Orbital (NBO) analysis to give clear evidence of stabilization originating in the hyperconjugation of hydrogen-bonded interaction. Heat of formation (HOF) and calculated density were estimated to evaluate detonation properties using Kamlet-Jacobs equations. The linear polarizability (?) and the first order hyperpolarizability (?) values of the investigated molecule have been computed using DFT calculations. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. The observed and calculated wave numbers are found to be in good agreement. On the basis of vibrational analyses, the thermodynamic properties of title compound at different temperatures have been calculated.
Renuga, S; Muthu, S
2014-01-24
Density functional theory (DFT) computations have become an efficient tool in the prediction of molecular structure, harmonic force fields, vibrational wave numbers as well as the IR and Raman intensities of pharmaceutically important molecule. In this work, we report harmonic vibrational frequencies, molecular structure, NBO and HOMO, LUMO analysis and detonation properties of (S)-2-(2-oxopyrrolidin-1-yl) butanamide. The solid phase FT-IR and FT-Raman spectra of (S)-2-(2-oxopyrrolidin-1-yl) butanamide were recorded in the region 4000-450 cm(-1) and 4000-50 cm(-1) respectively. Harmonic frequencies of this compound were determined and analyzed by DFT utilizing 6-31G(d,p), 6-31+G(d,p) basis sets. The assignments of the vibrational spectra have been carried out with the help of Normal Coordinate Analysis (NCA) following the Scaled Quantum Mechanical Force Field Methodology (SQMFF). The calculated infrared and Raman spectra of the title compounds were also stimulated utilizing the scaled force fields and the computed dipole derivatives for IR intensities and polarizability derivatives for Raman intensities. The change in electron density (ED) in the ?(*) and ?(*) antibonding orbital's and stabilization energies E(2) have been calculated by Natural Bond Orbital (NBO) analysis to give clear evidence of stabilization originating in the hyperconjugation of hydrogen-bonded interaction. Heat of formation (HOF) and calculated density were estimated to evaluate detonation properties using Kamlet-Jacobs equations. The linear polarizability (?) and the first order hyperpolarizability (?) values of the investigated molecule have been computed using DFT calculations. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. The observed and calculated wave numbers are found to be in good agreement. On the basis of vibrational analyses, the thermodynamic properties of title compound at different temperatures have been calculated. PMID:24096066
NASA Astrophysics Data System (ADS)
Palmer, Michael H.; Nelson, Alistair D.
2006-01-01
The ground vibrational state and equilibrium structures of the halogen (F to I) azides, isocyanates and isothiocyanates have been determined, and compared with spectral and diffraction data. We present results from Möller-Plesset (MP2) and DFT (B3LYP) methodologies, with similar basis sets (TZVP and cc-pVTZ), such that detailed comparisons of each with experiment is possible. In the case for iodine, this necessitated the generation of a new basis set. The bond lengths and angles for both MP2 and B3LYP methodologies are compared, and in the majority of cases, the MP2 series is marginally closer to experiment than B3LYP. The harmonic and anharmonic frequencies have been compared with experimental vibrational spectral data using both methodologies. In this case, the B3LYP method produces anharmonic and harmonic frequencies closer to experimental data, but both methods and both series of calculated frequencies scale well against the experimental data.
Yang Jingbo; Li Zheng
2008-01-01
A simplified model, which is composed of one tower and two spans of conductors, is given for overhead transmission line system. With tower regarded as cantilever beam and conductor as string, analytical calculation method of wind-induced vibration response of the mechanics system are studied based on the random vibration theory. A factor called dynamic load factor is introduced to the
NASA Astrophysics Data System (ADS)
Leyton, Patricio; Paipa, Carolina; Berrios, Andrés; Zárate, Antonio; Castillo, María Victoria; Brandán, Silvia Antonia
2013-01-01
We have studied 2-[[5-amino-5-oxo-2-(phenylmethoxycarbonylamino) pentanoyl] amino] acetic acid and characterized it by infrared and Raman spectroscopies in the solid phase. The Density Functional Theory (DFT) method and Pople's basis set have been used to study its structure and vibrational properties. These calculations have given us a precise understanding of the normal modes of vibration, taking into account the neutral and zwitterionic forms of the compound. The harmonic vibrational wavenumbers for the optimized geometries of both structures were calculated at the B3LYP/6-31G*and B3LYP/6-311G** levels for an isolated molecule. For a complete assignment of the vibrational spectra, DFT calculations were combined with Pulaýs Scaled Quantum Mechanics Force Field (SQMFF) methodology to fit the theoretical and experimental wavenumber values. In this context, an assignment of the observed spectral features is proposed. Four intense bands in the infrared spectrum at 3332, 1734, 1654 and 1534 cm-1 and three bands in the Raman spectrum at 3332, 2928 and 985 cm-1 are reported to characterize both forms of the compound. The theoretical vibrational calculations allowed us to obtain a set of scaled force constants. A Natural Bond Orbital (NBO) study revealed the characteristics of the electronic delocalization of both structures, while the corresponding topological properties of electronic charge density were analyzed by employing Bader's Atoms in the Molecules theory (AIM).
Vibrational spectroscopic studies and ab initio calculations of sulfanilamide
NASA Astrophysics Data System (ADS)
Varghese, Hema Tresa; Panicker, C. Yohannan; Philip, Daizy
2006-09-01
FT-Raman and FT-IR spectra of sulfanilamide were recorded and analyzed. The vibrational frequencies of the compound have been computed using the Hartree-Fock/6-21G * basis and compared with the experimental values. The assignments of the observed bands were made on the basis of available literature.
NASA Astrophysics Data System (ADS)
Arivazhagan, M.; Kavitha, R.; Subhasini, V. P.
2014-07-01
The FT-IR and FT-Raman spectra of 6-amino-1-methylpurine (AMP) have been recorded in the region 4000-400 cm-1 and 3500-50 cm-1 respectively. The optimized geometry, frequency and intensity of the vibrational bands of AMP have been obtained by DFT level of theory using B3LYP method with 6-311++G(d,p) basis set. A complete vibrational assignment aided by the theoretical harmonic frequency analysis has been proposed. Purines, including substituted purines and their tautomers, are the most widely occurring nitrogen-containing heterocyclic in nature. Purines and pyrimidines make up the two groups of nitrogenous bases, including the two groups of nucleotide bases. Two of the four deoxyribonucleotides and two of the four ribonucleotides, the respective building-blocks of DNA and RNA, are purines. The calculated vibrational values are in good agreement when they are compared with IR and Raman experimental data. Amine-imine tautomerism of 6-amino-1-methyl purine is studied in detail. In agreement with experimental results, it was found that imine tautomer is more stable than amine tautomer.
NASA Astrophysics Data System (ADS)
Deodhar, Bhushan S.; Brenner, Reid E.; Klaassen, Joshua J.; Tubergen, Michael J.; Durig, James R.
2015-09-01
The infrared and Raman spectra (3200-50 cm-1) of the gas, liquid or solution, and solid of fluoroacetyl chloride, FCH2COCl have been recorded. FT-microwave studies have also been carried out and 22 transitions were recorded for the trans conformer. Variable temperature (-50 to -105 °C) studies of the infrared and Raman spectra (3200-50 cm-1) of xenon solutions have been carried out. From these data, the trans, cis and gauche conformers have been identified and their relative stabilities obtained. The enthalpy difference has been determined to be 159 ± 11 cm-1 (1.90 ± 0.14 kJ mol-1) with the trans conformer the more stable form than the cis. The energy difference between the cis and gauche form is 222 ± 18 cm-1 (2.66 ± 0.21 kJ/mol) and the energy difference between the trans and gauche forms is 386 ± 13 cm-1 (4.61 ± 0.16 kJ/mol). Vibrational assignments have been made for the observed bands for the three conformers with initial predictions by MP2(full)/6-31G(d) ab initio calculations to obtain harmonic force constants, wavenumbers, infrared intensities, and Raman activities for the three conformers. By utilizing the microwave rotational constants of two isotopomers for trans, combined with the structural parameters predicted from MP2(full)/6-311+G(d,p) calculations, adjusted r0 parameters have been obtained for the trans conformer. The results are discussed and compared to the corresponding properties of some related molecules.
Accurate calculation of vibrational frequencies using explicitly correlated coupled-cluster theory
NASA Astrophysics Data System (ADS)
Rauhut, Guntram; Knizia, Gerald; Werner, Hans-Joachim
2009-02-01
The recently proposed explicitly correlated CCSD(T)-F12x (x =a,b) approximations [T. B. Adler, G. Knizia, and H.-J. Werner, J. Chem. Phys. 127, 221106 (2007)] are applied to compute equilibrium structures and harmonic as well as anharmonic vibrational frequencies for H2O, HCN, CO2, CH2O, H2O2, C2H2, CH2NH, C2H2O, and the trans-isomer of 1,2-C2H2F2. Using aug-cc-pVTZ basis sets, the CCSD(T)-F12a equilibrium geometries and harmonic vibrational frequencies are in very close agreement with CCSD(T)/aug-cc-pV5Z values. The anharmonic frequencies are evaluated using vibrational self-consistent field and vibrational configuration interaction methods based on automatically generated potential energy surfaces. The mean absolute deviation of the CCSD(T)-F12a/aug-cc-pVTZ anharmonic frequencies from experimental values amounts to only 4.0 cm-1.
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.
Mathammal, R; Monisha, N R; Yasaswini, S; Krishnakumar, V
2015-03-15
In this work, the vibrational spectral analysis is carried out by using Raman and infrared spectroscopy in the range 4000-400 cm(-1) and 4000-50 cm(-1) respectively for N,N-Diphenyl Formamide (DPF) molecule. The optimized molecular structures, vibrational frequencies and corresponding vibrational assignments, nuclear magnetic resonance (NMR) and ultraviolet-visible (UV-VIS) spectra of the title molecule are evaluated using density functional theory (DFT) with standard B3LYP/6-31G(d,p) basis set. The harmonic vibrational frequencies are calculated and the scaled values have been compared with experimental FT-IR and FT-Raman spectra. The observed and calculated frequencies are found to be in good agreement. The stability of the molecule arising from hyper conjugative interactions and the charge delocalization has been analyzed using natural bond (NBO) analysis. The possible electronic transitions are determined by HOMO-LUMO orbital shapes and their energies. Thermodynamic properties (heat capacity, entropy and enthalpy) and the first hyperpolarizability of the title compound are calculated. The Mulliken charges and electric dipole moment of the molecule are computed using DFT calculations. The (1)H and (13)C nuclear magnetic resonance (NMR) chemical shift of the molecules are calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. PMID:25579654
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 ?2 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.
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.
NASA Astrophysics Data System (ADS)
Mancini, John S.; Bowman, Joel M.
2013-10-01
We present an on-the-fly quantum mechanical method to obtain anharmonic vibrational frequencies for molecular clusters. The basis for the method is the local-monomer model, a "divide and conquer" approach to theoretical spectroscopy, previously applied using full-dimensional surfaces [Y. Wang and J. M. Bowman, J. Chem. Phys. 134, 154510 (2011)]. The model consists of performing a local normal-mode analysis for each monomer in a cluster in the field of the surrounding monomers. Anharmonic vibrational frequencies are then determined for each monomer by numerically solving the Schrödinger equation in terms of the local coordinates using ab initio energies obtained directly. Residual monomer-monomer coupling is accounted for using the Hückel-coupling extension [Y. Wang and J. M. Bowman, J. Chem. Phys. 136, 144113 (2012)]. In addition to the direct local-monomer approach, we propose and demonstrate a composite ab initio technique to reduce computational costs for calculating the anharmonic frequencies of large clusters. This technique utilizes two ab initio methods, a lower level of theory to compute geometries and perform harmonic analyses and a subsequent higher level of theory to compute the energies used in the anharmonic frequency calculations. We demonstrate the on-the-fly approach on hydrogen chloride clusters ranging in size from the dimer to the hexamer. Comparisons of the theoretical frequencies are made to previous experiments. We find the method to be an effective and computationally efficient approach to compute anharmonic frequencies.
Lattice Monte Carlo calculations for unitary fermions in a harmonic trap
Endres, Michael G.; Kaplan, David B.; Lee, Jong-Wan; Nicholson, Amy N.
2011-10-15
We present a lattice Monte Carlo approach developed for studying large numbers of strongly interacting nonrelativistic fermions and apply it to a dilute gas of unitary fermions confined to a harmonic trap. In place of importance sampling, our approach makes use of high statistics, an improved action, and recently proposed statistical techniques. We show how improvement of the lattice action can remove discretization and finite volume errors systematically. For N=3 unitary fermions in a box, our errors in the energy scale as the inverse lattice volume, and we reproduce a previous high-precision benchmark calculation to within our 0.3% uncertainty; as additional benchmarks we reproduce precision calculations of N=3,...,6 unitary fermions in a harmonic trap to within our {approx}1% uncertainty. We then use this action to determine the ground-state energies of up to 70 unpolarized fermions trapped in a harmonic potential on a lattice as large as 64{sup 3}x72. In contrast to variational calculations, we find evidence for persistent deviations from the thermodynamic limit for the range of N considered.
NASA Astrophysics Data System (ADS)
Pavlyuchko, A. I.; Yurchenko, S. N.; Tennyson, Jonathan
2015-07-01
A procedure for calculation of rotation-vibration states of medium sized molecules is presented. It combines the advantages of variational calculations and perturbation theory. The vibrational problem is solved by diagonalizing a Hamiltonian matrix, which is partitioned into two sub-blocks. The first, smaller sub-block includes matrix elements with the largest contribution to the energy levels targeted in the calculations. The second, larger sub-block comprises those basis states which have little effect on these energy levels. Numerical perturbation theory, implemented as a Jacobi rotation, is used to compute the contributions from the matrix elements of the second sub-block. Only the first sub-block needs to be stored in memory and diagonalized. Calculations of the vibrational-rotational energy levels also employ a partitioning of the Hamiltonian matrix into sub-blocks, each of which corresponds either to a single vibrational state or a set of resonating vibrational states, with all associated rotational levels. Physically, this partitioning is efficient when the Coriolis coupling between different vibrational states is small. Numerical perturbation theory is used to include the cross-contributions from different vibrational states. Separate individual sub-blocks are then diagonalized, replacing the diagonalization of a large Hamiltonian matrix with a number of small matrix diagonalizations. Numerical examples show that the proposed hybrid variational-perturbation method greatly speeds up the variational procedure without significant loss of precision for both vibrational-rotational energy levels and transition intensities. The hybrid scheme can be used for accurate nuclear motion calculations on molecules with up to 15 atoms on currently available computers.
Hall, K.C.; Lorence, C.B. (Duke Univ., Durham, NC (United States). Dept. of Mechanical Engineering and Materials Science)
1993-10-01
An efficient three-dimensional Euler analysis of unsteady flows in turbomachinery is presented. The unsteady flow is modeled as the sun of a steady or mean flow field plus a harmonically varying small perturbation flow. The linearized Euler equations, which describe the small perturbation unsteady flow, are found to be linear, variable coefficient differential equations whose coefficients depend on the mean flow. A pseudo-time time-marching finite-volume Lax-Wendroff scheme is used to discretize and solve the linearized equations for the unknown perturbation flow quantities. Local time stepping and multiple-grid acceleration techniques are used to speed convergence. For unsteady flow problems involving blade motion, a harmonically deforming computational grid, which conforms to the motion of the vibrating blades, is used to eliminate large error-producing extrapolation terms that would otherwise appear in the airfoil surface boundary conditions and in the evaluation of the unsteady surface pressure. Results are presented for both linear and annular cascade geometries, and for the latter, both rotating and nonrotating blade row.
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
NASA Astrophysics Data System (ADS)
Hu, Ting; Zhou, Jian; Dong, Jinming
2013-01-01
The vibrational properties and Raman spectra of graphene nanoribbons with six different edges have been studied by using the first-principles calculations. It is found that edge reconstruction leads to the emergence of localized vibrational modes and new topological defect modes, making the different edges identified by polarized Raman spectra. The radial breathing-like modes are found to be independent of the edge structures, while the G-band-related modes are affected by different edge structures. Our results suggest that the polarized Raman spectrum could be a powerful experimental tool for distinguishing the GNRs with different edge structures due to their different vibrational properties.
NASA Technical Reports Server (NTRS)
Wood, E. R.; Powers, R. W.; Hammond, C. E.
1978-01-01
The paper presents data which confirm the effectiveness of higher harmonic blade pitch control in substantially reducing helicopter rotor vibratory hub loads. The data are the result of recent tests on a 2.7-m model conducted in the Langley Research Center's transonic dynamics wind tunnel. Several predictive analyses developed in support of the NASA program are shown capable of accurately predicting both amplitude and phase of the higher harmonic control input required to nullify a single 4/rev force or moment input. The use of multiple blade feathering inputs in the design of a flightworthy higher harmonic control system is discussed.
Improved calculations of the lowest vibrational transitions in HeH{sup +}
Bubin, Sergiy [Department of Chemistry, University of Arizona, Tucson, Arizona 85721 (United States); Stanke, Monika [Department of Chemistry, University of Arizona, Tucson, Arizona 85721 (United States); Institute of Physics, Nicholas Copernicus University, ulica Grudziadzka 5, PL 87-100 Torun (Poland); Kedziera, Dariusz [Department of Chemistry, Nicholas Copernicus University, ulica Gagarina 7, PL 87-100 Torun (Poland); Adamowicz, Ludwik [Department of Chemistry, University of Arizona, Tucson, Arizona 85721 (United States); Department of Physics, University of Arizona, Tucson, Arizona 85721 (United States)
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)].
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.
A hybrid variational-perturbation calculation of the ro-vibrational spectrum of nitric acid.
Pavlyuchko, A I; Yurchenko, S N; Tennyson, Jonathan
2015-03-01
Rotation-vibration spectra of the nitric acid molecule, HNO3, are calculated for wavenumbers up to 7000 cm(-1). Calculations are performed using a Hamiltonian expressed in internal curvilinear vibrational coordinates employing a hybrid variational-perturbation method. An initial potential energy surface (PES) and dipole moment function (DMF) are calculated ab initio at the CCSD(T)/aug-cc-pVQZ level of theory. Parameters of the PES and DMF are varied to minimize differences between the calculated and experimental transition frequencies and intensities. The average, absolute deviation between calculated and experimental values is 0.2 cm(-1) for frequencies in the fundamental bands and 0.4 cm(-1) for those in the first overtone and lowest combination bands. For the intensities, the calculated and experimental values differ by 0.3% and 40% for the fundamentals and overtones, respectively. The optimized PES and DMF are used to calculate the room-temperature ro-vibrational spectrum. These calculation reproduce both the form of the absorption bands and fine details of the observed spectra, including the rotational structure of the vibrational bands and the numerous hot absorption band. Many of these hot bands are found to be missing from the compilation in HITRAN. A room temperature line list comprising 2 × 10(9) lines is computed. PMID:25747083
Calculation of vibrational spectra of an icosahedral quasicrystal AlCuFe
Rudenko, A. N., E-mail: ran@infoteck.ru; Mazurenko, V. G. [Ural State University (Russian Federation)
2007-11-15
Vibrational spectra of an icosahedral quasicrystal AlCuFe have been calculated on the basis of a crystalline 1/1 approximant by the recurrence method. To describe the interaction of atoms in a quasicrystal, the semiempirical EAM model was used. It is shown that the calculated spectra are in satisfactory agreement with the experimental neutron inelastic scattering data.
Durig, James R; Klaassen, Joshua J; Sawant, Dattatray K; Deodhar, Bhushan S; Panikar, Savitha S; Gurusinghe, Ranil M; Darkhalil, Ikhlas D; Tubergen, Michael J
2015-02-01
The infrared and Raman spectra (3200-50 cm(-1)) of the gas, liquid or solution, and solid have been recorded of isocyanocyclopentane, c-C5H9NC. FT-microwave studies have also been carried out and 23 transitions were recorded for the envelope-axial (Ax) conformer. Variable temperature (-65 to -100 °C) studies of the infrared spectra (3200-400 cm(-1)) dissolved in liquid xenon have been carried out. From these data, both the Ax and envelope-equatorial (Eq) conformers have been identified and their relative stabilities obtained. The enthalpy difference has been determined to be 102±10 cm(-1) (1.21±0.11 kJ mol(-1)) with the Ax conformer the more stable form. The percentage of the Eq conformer is estimated to be 38±1% at ambient temperature. The conformational stabilities have been predicted from ab initio calculations by utilizing several different basis sets up to aug-cc-pVTZ from both MP2(full) and density functional theory calculations by the B3LYP method. Vibrational assignments have been made for the observed bands for both conformers with initial predictions by MP2(full)/6-31G(d) ab initio calculations to obtain harmonic force constants, wavenumbers, infrared intensities, Raman activities and depolarization ratios for both conformers. The structural parameter values for the Ax form are; for the heavy atom distances (Å): C?N = 1.176 (3); C?-N=1.432 (3); C?-C?,C?'=1.534 (3); C?-C?,C?'=1.542 (3); C?-C?'=1.554 (3) and angles (°):?C?-N?C=177.8 (5); ?C?C?-N=110.4 (5);
Sawant, Dattatray K; Klaassen, Joshua J; Gounev, Todor K; Durig, James R
2015-12-01
The infrared and Raman spectra (3100-50cm(-1)) of the gas, liquid or solution, and solid have been recorded of cyanocyclopentane, c-C5H9CN. Variable temperature (-60 to -100°C) studies of the infrared spectra (3100-400cm(-1)) of the sample dissolved in liquid xenon have been carried out. From these data, both the envelope-equatorial (Eq) and Ax conformers have been identified and their relative stabilities obtained. The enthalpy difference has been determined to be 55±12cm(-1) (0.66±0.14kJ/mol) with the Eq conformer the more stable form. The percentage of the Ax conformer is estimated to be 45±1% at ambient temperature. The conformational stabilities have been predicted from ab initio calculations by utilizing several different basis sets up to aug-cc-pVTZ from both MP2(full) and density functional theory calculations by the B3LYP method. Vibrational assignments have been made for the observed bands for both conformers with initial predictions by MP2(full)/6-31G(d) ab initio calculations to obtain harmonic force constants, wavenumbers, infrared intensities, Raman activities and depolarization ratios for both conformers. The r0 structural parameter values for the Eq[Ax] form are; for the heavy atom distances (Å): CN=1.160 [1.160] (3); C?-C=1.463 [1.463] (3); C?-C?, C?'=1.543 [1.545] (3); C?-C?, C?'=1.540 [1.541] (3); C?-C?'=1.552 [1.553] (3) and angles (°): ?C?-CN=179.0 [178.9] (5); ?C?C?-C=113.1 [110.1] (5); ?C?C?C?'=103.0 [102.1] (5); ?C?C?C?=104.1 [104.8] (5); ?C?C?C?'=106.3 [106.0] (5). The results are discussed and compared to the corresponding properties of some related molecules. PMID:26151436
Hiremath, C S; Sundius, Tom
2009-12-01
FT-IR (4000-400 cm(-1)) and FT-Raman (3500-50 cm(-1)) spectral measurements of solid samples of 2-bromo-5-fluorobenzaldehyde (BFB) have been done. Ab initio (RHF/6-311G*) and DFT (B3LY/6-311G* and B3PW91/6-311G*) calculations have been performed giving energies, optimized structures, harmonic vibrational frequencies, depolarization ratios, infrared intensities, Raman activities and atomic displacements. Furthermore force field calculations have been performed by normal coordinate analysis. Force field calculations showed that several normal modes are mixed in terms of the internal coordinates. A complete assignment of the observed spectra, based on spectral correlations, electronic structure and normal coordinate analysis, has been proposed. Optimization leads to C(S) symmetry with O-trans and O-cis isomers, with respect to aldehydic oxygen and bromine, with O-trans-isomer as the low energy stable form. The energy difference between the two isomers is 2.95084 kcal/mol. The results of the calculations have been used to simulate IR and Raman spectra for BFB that showed excellent agreement with the observed spectra. The SQM method, which implies multiple scaling of the ab initio and DFT force fields has been shown superior to the uniform scaling approach. PMID:19864179
NASA Astrophysics Data System (ADS)
Hiremath, C. S.; Sundius, Tom
2009-12-01
FT-IR (4000-400 cm -1) and FT-Raman (3500-50 cm -1) spectral measurements of solid samples of 2-bromo-5-fluorobenzaldehyde (BFB) have been done. Ab initio (RHF/6-311G*) and DFT (B3LY/6-311G* and B3PW91/6-311G*) calculations have been performed giving energies, optimized structures, harmonic vibrational frequencies, depolarization ratios, infrared intensities, Raman activities and atomic displacements. Furthermore force field calculations have been performed by normal coordinate analysis. Force field calculations showed that several normal modes are mixed in terms of the internal coordinates. A complete assignment of the observed spectra, based on spectral correlations, electronic structure and normal coordinate analysis, has been proposed. Optimization leads to C S symmetry with O- trans and O- cis isomers, with respect to aldehydic oxygen and bromine, with O- trans-isomer as the low energy stable form. The energy difference between the two isomers is 2.95084 kcal/mol. The results of the calculations have been used to simulate IR and Raman spectra for BFB that showed excellent agreement with the observed spectra. The SQM method, which implies multiple scaling of the ab initio and DFT force fields has been shown superior to the uniform scaling approach.
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.
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. PMID:21237700
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.
Vibrational spectra, theoretical calculations, and structure of 4-silaspiro(3,3)heptane.
Ocola, Esther J; Medders, Cross; Cooke, Joel M; Laane, Jaan
2014-09-15
Theoretical computations have been carried out for 4-silaspiro(3,3)heptane (SSH) in order to calculate its structure and vibrational spectra. SSH was found to have two puckered four-membered rings with dihedral angles of 34.2° and a tilt angle of 9.4° between the two rings. The puckering and tilting reduce the D2d symmetry to C2. Nonetheless, the vibrational assignments can be done quite well on the basis of D2d symmetry. This is confirmed by the fact that all but the lowest E vibrations show insignificant splitting into A and B modes of C2 symmetry. However, the observed splittings of the lowest frequency modes do confirm the lower conformational symmetry. The calculated infrared and Raman spectra were compared to the experimental spectra collected for the vapor, liquid, and solid states, and the agreement is excellent. PMID:24810025
NASA Astrophysics Data System (ADS)
Roldán, María L.; Ledesma, Ana E.; Raschi, Ana B.; Castillo, María V.; Romano, Elida; Brandán, Silvia A.
2013-06-01
A new study on the structural and vibrational properties of the aminoethylphosphonic acid was performed in aqueous solution phase by using the self-consistent reaction field (SCRF) method. We have studied and characterized it by infrared and Raman spectroscopies in solid and aqueous solution phases. The Density Functional Theory (DFT) method with Pople's basis set show that three stable zwitterions for the title molecule have been theoretically determined in aqueous solution and that probably they are present in it medium. Here, the solvent effects were studied by means of the self-consistent reaction field (SCRF) method with the polarized continuum model (PCM). The harmonic vibrational frequencies for the optimized geometries of the three zwitterions were calculated at the B3LYP/6-31G? level of the theory. A complete assignment of the IR and Raman spectra of the compound in aqueous solution was performed combining the DFT calculations with Pulay's Scaled Quantum Mechanics Force Field (SQMFF) methodology in order to fit the theoretical frequency values to the experimental ones. Moreover, Natural Bond Orbital (NBO) and topological properties calculations were performed to analyze the energies and geometrical parameters of its three zwitterions in aqueous medium as well as the magnitude of the intramolecular interactions. The bond orders, atomic charges, solvation energies, dipole moments, molecular electrostatic potentials and force constants parameters calculated for zwitterions in aqueous solution, may be used to gain chemical and vibrational insights into related compounds.
Boyarinov, V. F.; Davidenko, V. D.; Polismakov, A. A.; Tsibulsky, V. F. [Russian Research Center Kurchatov Inst., Nuclear Reactor Inst., 123182, Moscow (Russian Federation)
2006-07-01
Development of the SUHAM-U code for burnup calculations of VVER-1000 fuel assemblies with uranium and MOX fuel is described. Developed SUHAM-U code has capacity to calculate burnup in each fuel or poison zone of each cell of VVER-1000 fuel assembly. In so doing Surface Harmonics Method is used for calculation of the detail neutron spectra in fuel assembly at separated burnup values. Verification of SUHAM-U code by burnup calculations of VVER-1000 fuel assemblies with uranium and MOX fuel has been carried out. Comparisons were carried out with calculations by UNK and RECOL codes. UNK code uses the first collisions probabilities method for solution of the neutron transport equation and RECOL code uses Monte-Carlo method with point-wise continues energy presentation of cross-sections. The main conclusion of all comparisons is the SUHAM-U code calculates the fuel burnup of VVER-1000 fuel assemblies with uranium and MOX fuel with enough high accuracy. Time expenditures are adduced. (authors)
ERIC Educational Resources Information Center
Cutchins, M. A.
1982-01-01
Presents programmable calculator solutions to selected problems, including area moments of inertia and principal values, the 2-D principal stress problem, C.G. and pitch inertia computations, 3-D eigenvalue problems, 3 DOF vibrations, and a complex flutter determinant. (SK)
McGaughey, Alan
Predicting alloy vibrational mode properties using lattice dynamics calculations, molecular-defect scattering. The mode properties are then used to predict thermal conductivity under the VC approximation. For the Lennard-Jones alloys, where high-frequency modes make a significant contribution to thermal conductivity
Density functional theory based calculations of the vibrational properties of chlorophyll-a
Hastings, Gary
Density functional theory based calculations of the vibrational properties of chlorophyll-a Ruili in revised form 8 March 2007; accepted 13 March 2007 Available online 23 March 2007 Abstract Chlorophyll organisms, such as plants algae and cyanobacteria. To study the chlorophyll-a species at the heart
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 (?0) and related properties (?, ?0, ??) 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
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 (?0) and related properties (?, ?0, ??) of MBBH are also calculated. All theoretical calculations were performed on the basis of B3LYP/6-311++G(d,p) level of theory.
NASA Astrophysics Data System (ADS)
Guggenberger, Johannes; Müller, Gerhard
Low frequent vibrations may cause from disturbing up to damaging effects. There is no precise distinction between structure-borne sound and vibrations. However - depending on the frequency range - measurements and predictions require different techniques. In a wide frequency range, the generation, transmission and propagation of vibrations can be investigated similar to structure-borne sound (see Chap. 9).
Frédéric Bouyer; Gérard Picard; Jean-Jacques Legendre
1995-01-01
Quantum chemical calculations are used to study AlCly?xFx3?y (y = 5 or 6, x = 0,…,y) species that can occur in aluminum electrorefining melts. These theoretical studies are included in a wider research program concerning the chemical instabilities in the bulk of molten salts during the refinement process. Stabilization energies, equilibrium geometries and vibrational frequencies of the complexes are calculated
Water vapor line width and shift calculations with accurate vibration–rotation wave functions
A. D. Bykov; N. N. Lavrentieva; T. P. Mishina; L. N. Sinitsa; R. J. Barber; R. N. Tolchenov; J. Tennyson
2008-01-01
Calculations of H216O rotation–vibration line broadening and shifting due to N2 pressure effects are performed using a semi-empirical approach. The calculations are based on impact theory modified by introducing additional parameters to extend the use of empirical data. These model parameters are determined by fitting the broadening and shifting coefficients to experimental data. The method is further developed by using
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.
Byung-Taek Kim; Byun-Il Kwon; Seung-Chan Park
1999-01-01
The harmonics in electromagnetic force are a source of mechanical vibration and audible noise in an asynchronous traction motor. This paper describes an approach to reduce the force harmonics by changing the rotor slot number. Both the radial and tangential forces acting on the stator teeth are calculated by Maxwell stress tensor and their time harmonics are examined by the
Molecular structure and vibrational spectra of dithionite ion by ab initio calculations
NASA Astrophysics Data System (ADS)
Leszczynski, Jerzy; Zerner, Michael C.
1989-07-01
The structure of the dithionite ion, S 2O 42-, is examined using quantum chemical calculations. These studies strongly suggest that only the C 2h (trans) isomer is stable in solution. The C 2v (cis) form reported in Na 2S 2O 4·2H 2O is stabilized by crystal forces. The calculated vibrational spectrum of the C 2h form is in excellent agreement with that observed in aqueous solution. Taking into account the negative frequency calculated for the C 2v structure yields a calculated spectrum in good agreement with that observed for the crystal.
Theoretical calculation and vibrational spectral analysis of L-arginine trifluoroacetate
NASA Astrophysics Data System (ADS)
Sun, Z. H.; Zhang, L.; Xu, D.; Wang, X. Q.; Liu, X. J.; Zhang, G. H.
2008-11-01
Fourier transform infrared and Raman spectra of the nonlinear optical crystal, L-arginine trifluoroacetate ( L-arginine·CF 3COOH, abbreviated as LATF) have been calculated by the first-principles calculation and investigated in experiment. The calculated results are slightly different from those experimental values because of the distinction resulted from the intermolecular hydrogen bonds. The role of this type of intermolecular interaction on the crystal vibrational spectra and nonlinear optical properties has been discussed. The absorption-edge on the IR side has been estimated by the theoretical approach on basis of the calculated infrared spectrum, which will be meaningful for further research on NLO crystal.
Tuning natural modes of vibration by prestress in the design of a harmonic gong.
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
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 (?) and the first order hyper polarizability (?) 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. PMID:24556133
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 (?) and the first order hyper polarizability (?) 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.
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.
Fast vibrational self-consistent field calculations through a reduced mode-mode coupling scheme.
Benoit, David M
2004-01-01
We present a new methodology to perform fast correlation-corrected vibrational self-consistent field (CC-VSCF) calculations using ab initio potential energy points calculated on the fly. Our method is based on the replacement of all-electron basis sets with a pseudo-potential basis for heavy atoms, and on an efficient reduction of the number of pair-coupling elements used in the CC-VSCF procedure. The method is applied to several test systems: H2O, NH3, and CH4, where it proves to be efficient, providing a speedup factor of 2 compared to a standard CC-VSCF calculation. We also apply our technique to the simulation of the vibrational spectrum of ethane and show that very accurate results can be obtained with a substantial speedup for this system. PMID:15267890
Vibration-rotation variational calculations: Precise results on HCN up to 25 000 cm-1
NASA Astrophysics Data System (ADS)
Carter, Stuart; Mills, Ian M.; Handy, Nicholas C.
Variation calculations of the vibration-rotation energy levels of many isotopomers of HCN are reported, for J=0, 1, and 2, extending up to approximately 8 quanta of each of the stretching vibrations and 14 quanta of the bending mode. The force field, which is represented as a polynomial expansion in Morse coordinates for the bond stretches and even powers of the angle bend, has been refined by least squares to fit simultaneously all observed data on the ? and ? state vibrational energies, and the ? state rotational constants, for both HCN and DCN. The observed vibrational energies are fitted to roughly ±0.5 cm-1, and the rotational constants to roughly ±0.0001 cm-1. The force field has been used to predict the vibration rotation spectra of many isotopomers of HCN up to 25 000 cm-1. The results are consistent with the axis-switching assignments of some weak overtone bands reported recently by Jonas, Yang, and Wodtke, and they also fit and provide the assignment for recent observations by Romanini and Lehmann of very weak absorption bands above 20 000 cm-1.
NASA Technical Reports Server (NTRS)
Hornick, R. J.
1973-01-01
Man's reactions to vibration are emphasized rather than his reactions to the vibrational characteristics of vehicles. Vibrational effects studies include: performance effects reflected in tracking proficiency, reaction time, visual impairment, and other measures related to man's ability to control a system; physiological reactions; biodynamic responses; subjective reactions; and human tolerance limits. Technological refinements in shaker systems and improved experimental designs are used to validate the data.
OJ287: Post-Newtonian Calculation in Harmonic Coordinate and Pulsar Timing Residual Confirmation
NASA Astrophysics Data System (ADS)
Cheng, Bin; Zhang, Yang
2015-07-01
We calculate and discuss the motion of the binary black hole OJ287 based on Post-Newtonian approximation in a harmonic coordinate. With gravitational waveform obtained, theoretical timing residual of PSR B1855+09 induced by gravitational radiation of OJ287 is presented and compared with observed data, further shows that hypothesis referring to OJ287 as a binary BH system might be proper. The energy flux of gravitational radiation from binary is also provided, from which we find that the flux changes sign successively: ?N > 0, ?1PN < 0, ?2PN > 0, in agreement with the relative signs of forces of each PN order, revealed in the previous work. Supported by National Natural Science Foundation of China under Grant Nos. 11275187, 11421303, and the Strategic Priority Research Program “The Emergence of Cosmological Structures” of the Chinese Academy of Sciences under Grant No. XDB09000000
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.
Rodriguez-Gallardo, M.; Arias, J. M.; Gomez-Camacho, J.; Moro, A. M.; Johnson, R. C.; Tostevin, J. A.; Thompson, I. J.
2008-06-15
The scattering of a weakly bound three-body system by a target is discussed. A transformed harmonic oscillator basis is used to provide an appropriate discrete and finite basis for treating the continuum part of the spectrum of the projectile. The continuum-discretized coupled-channels framework is used for the scattering calculations. The formalism is applied to different reactions, {sup 6}He+{sup 12}C at 229.8 MeV, {sup 6}He+{sup 64}Zn at 10 and 13.6 MeV, and {sup 6}He+{sup 208}Pb at 22 MeV, induced by the Borromean nucleus {sup 6}He. Both the Coulomb and nuclear interactions with a target are taken into account.
Absolute free-energy calculations of liquids using a harmonic reference state.
Tyka, Michael D; Sessions, Richard B; Clarke, Anthony R
2007-08-16
Absolute free-energy methods provide a potential solution to the overlap problem in free-energy calculations. In this paper, we report an extension of the previously published confinement method (J. Phys. Chem. B 2006, 110, 17212-20) to fluid simulations. Absolute free energies of liquid argon and liquid water are obtained accurately and compared with results from thermodynamic integration. The method works by transforming the liquid state into a harmonic, solid reference state. This is achieved using a special restraint potential that allows molecules to change their restraint position during the simulation, which circumvents the need for the molecules to sample the full extent of their translational freedom. The absolute free energy of the completely restrained reference state is obtained from a normal mode calculation. Because of the generic reference state used, the method is applicable to nonhomogeneous, diffusive systems and could provide an alternative method in situations in which solute annihilation fails due to the size of the solute. Potential applications include calculation of solvation energies of large molecules and free energies of peptide conformational changes in explicit solvent. PMID:17655215
Infrared and ultraviolet cutoffs in variational calculations with a harmonic oscillator basis
Sidney A Coon
2013-03-26
I abstract from a recent publication [1] the motivations for, analysis in and conclusions of a study of the ultraviolet and infrared momentum regulators induced by the necessary truncation of the model spaces formed by a variational trial wave function. This trial function is built systematically from a complete set of many-body basis states based upon three-dimensional harmonic oscillator (HO) functions. Each model space is defined by a truncation of the expansion characterized by a counting number (N) and by the intrinsic scale ($\\hbar\\omega$) of the HO basis. Extending both the uv cutoff to infinity and the ir cutoff to zero is prescribed for a converged calculation. In [1] we established practical procedures which utilize these regulators to obtain the extrapolated result from sequences of calculations with model spaces. Finally, I update this subject by mentioning recent work on our extrapolation prescriptions which have appeared since the submission of [1]. The numerical example chosen for this contribution consists of calculations of the ground state energy of the triton with the "bare" and "soft" Idaho N3LO nucleon-nucleon (NN) interaction.
Shin, Hee Won; Ocola, Esther J.; Laane, Jaan, E-mail: laane@mail.chem.tamu.edu [Department of Chemistry, Texas A and M University, College Station, Texas 77843-3255 (United States)] [Department of Chemistry, Texas A and M University, College Station, Texas 77843-3255 (United States); Kim, Sunghwan [National Center for Biotechnology Information, National Library of Medicine, National Institutes of Health, Department of Health and Human Services, 8600 Rockville Pike, Bethesda, Maryland 20894 (United States)] [National Center for Biotechnology Information, National Library of Medicine, National Institutes of Health, Department of Health and Human Services, 8600 Rockville Pike, Bethesda, Maryland 20894 (United States)
2014-01-21
The fluorescence excitation spectra of jet-cooled benzocyclobutane have been recorded and together with its ultraviolet absorption spectra have been used to assign the vibrational frequencies for this molecule in its S{sub 1}(?,?{sup *}) electronic excited state. Theoretical calculations at the CASSCF(6,6)/aug-cc-pVTZ level of theory were carried out to compute the structure of the molecule in its excited state. The calculated structure was compared to that of the molecule in its electronic ground state as well as to the structures of related molecules in their S{sub 0} and S{sub 1}(?,?{sup *}) electronic states. In each case the decreased ? bonding in the electronic excited states results in longer carbon-carbon bonds in the benzene ring. The skeletal vibrational frequencies in the electronic excited state were readily assigned and these were compared to the ground state and to the frequencies of five similar molecules. The vibrational levels in both S{sub 0} and S{sub 1}(?,?{sup *}) states were remarkably harmonic in contrast to the other bicyclic molecules. The decreases in the frequencies of the out-of-plane skeletal modes reflect the increased floppiness of these bicyclic molecules in their S{sub 1}(?,?{sup *}) excited state.
Shin, Hee Won; Ocola, Esther J.; Kim, Sunghwan; Laane, Jaan
2014-01-01
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 S1(?,?*) 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 S0 and S1(?,?*) electronic states. In each case the decreased ? bonding in the electronic excited states results in longer carbon-carbon bonds in the benzene ring. The skeletal vibrational frequencies in the electronic excited state were readily assigned and these were compared to the ground state and to the frequencies of five similar molecules. The vibrational levels in both S0 and S1(?,?*) 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 S1(?,?*) excited state. PMID:25669377
NASA Astrophysics Data System (ADS)
Bürger, H.; Kuna, R.; Ma, S.; Breidung, J.; Thiel, W.
1994-07-01
Fourier transform infrared spectra of KrF2, XeF2, and monoisotopic 136XeF2 have been recorded in the ?3 and ?1+?3 ranges with an effective resolution of 0.003-0.007 cm-1. About 10 000 rovibrational lines belonging to cold bands and to hot bands with ?1, ?2, 2?2, and ?3 as lower levels have been assigned and fitted. The high-resolution results from this work and from two previous studies provide a rather complete set of precise spectroscopic constants and accurate ground-state and equilibrium geometries for both molecules. In the case of 84KrF2, r0=188.2821(9) pm supersedes previous incorrect r0 values, and re=187.6930(23) pm represents the first determination of the Kr-F equilibrium distance. Ab initio calculations employing effective core potentials and polarized double-zeta basis sets have been carried out at the following levels: self-consistent-field (SCF) theory, the Møller-Plesset second order perturbation theory (MP2), and coupled cluster theory with single and double excitations (CCSD) and a perturbational treatment of triple excitations (CCSD(T)). Pronounced correlation effects are found, especially for KrF2. The agreement between the correlated theoretical and the experimental results is generally quite good. A theoretical analysis clarifies the origin of the positive ?2 vibration-rotation coupling constants which have been observed for the bending vibrations in both molecules. Reliable harmonic and anharmonic force fields are presented for KrF2 and XeF2.
Park, G Barratt
2014-10-01
Franck-Condon vibrational overlap integrals for the A? Au1-X? 1?g+ transition in acetylene have been calculated in full dimension in the harmonic normal mode basis. The calculation uses the method of generating functions first developed for polyatomic Franck-Condon factors by Sharp and Rosenstock [J. Chem. Phys. 41(11), 3453-3463 (1964)], and previously applied to acetylene by Watson [J. Mol. Spectrosc. 207(2), 276-284 (2001)] in a reduced-dimension calculation. Because the transition involves a large change in the equilibrium geometry of the electronic states, two different types of corrections to the coordinate transformation are considered to first order: corrections for axis-switching between the Cartesian molecular frames and corrections for the curvilinear nature of the normal modes at large amplitude. The angular factor in the wavefunction for the out-of-plane component of the trans bending mode, ?4(?), is treated as a rotation, which results in an Eckart constraint on the polar coordinates of the bending modes. To simplify the calculation, the other degenerate bending mode, ?5(?), is integrated in the Cartesian basis and later transformed to the constrained polar coordinate basis, restoring the conventional v and l quantum numbers. An updated A?-state harmonic force field obtained recently in the R. W. Field research group is evaluated. The results for transitions involving the gerade vibrational modes are in qualitative agreement with experiment. Calculated results for transitions involving ungerade modes are presented in Paper II of this series [G. B. Park, J. H. Baraban, and R. W. Field, "Full dimensional Franck-Condon factors for the acetylene A? Au1-X? 1?g+ transition. II. Vibrational overlap factors for levels involving excitation in ungerade modes," J. Chem. Phys. 141, 134305 (2014)]. PMID:25296803
NASA Astrophysics Data System (ADS)
Park, G. Barratt
2014-10-01
Franck-Condon vibrational overlap integrals for the tilde{A} {^1A_u}—{tilde{X}} {^1? _g^+} transition in acetylene have been calculated in full dimension in the harmonic normal mode basis. The calculation uses the method of generating functions first developed for polyatomic Franck-Condon factors by Sharp and Rosenstock [J. Chem. Phys. 41(11), 3453-3463 (1964)], and previously applied to acetylene by Watson [J. Mol. Spectrosc. 207(2), 276-284 (2001)] in a reduced-dimension calculation. Because the transition involves a large change in the equilibrium geometry of the electronic states, two different types of corrections to the coordinate transformation are considered to first order: corrections for axis-switching between the Cartesian molecular frames and corrections for the curvilinear nature of the normal modes at large amplitude. The angular factor in the wavefunction for the out-of-plane component of the trans bending mode, ? _4^' ' }, is treated as a rotation, which results in an Eckart constraint on the polar coordinates of the bending modes. To simplify the calculation, the other degenerate bending mode, ? _5^' ' }, is integrated in the Cartesian basis and later transformed to the constrained polar coordinate basis, restoring the conventional v and l quantum numbers. An updated tilde{A}-state harmonic force field obtained recently in the R. W. Field research group is evaluated. The results for transitions involving the gerade vibrational modes are in qualitative agreement with experiment. Calculated results for transitions involving ungerade modes are presented in Paper II of this series [G. B. Park, J. H. Baraban, and R. W. Field, "Full dimensional Franck-Condon factors for the acetylene tilde{A} {^1A_u}—{tilde{X}} {^1? _g^+} transition. II. Vibrational overlap factors for levels involving excitation in ungerade modes," J. Chem. Phys. 141, 134305 (2014)].
NASA Astrophysics Data System (ADS)
Lü, Jing-Tao; Christensen, Rasmus B.; Foti, Giuseppe; Frederiksen, Thomas; Gunst, Tue; Brandbyge, Mads
2014-02-01
We extend the simple and efficient lowest order expansion (LOE) for inelastic electron tunneling spectroscopy (IETS) to include variations in the electronic structure on the scale of the vibration energies. This enables first-principles calculations of IETS line shapes for molecular junctions close to resonances and band edges. We demonstrate how this is relevant for the interpretation of experimental IETS using both a simple model and first-principles simulations.
Nagabalasubramanian, P B; Periandy, S; Karabacak, Mehmet; Govindarajan, M
2015-06-15
The solid phase FT-IR and FT-Raman spectra of 4-vinylcyclohexene (abbreviated as 4-VCH) have been recorded in the region 4000-100cm(-1). The optimized molecular geometry and vibrational frequencies of the fundamental modes of 4-VCH have been precisely assigned and analyzed with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) method at 6-311++G(d,p) level basis set. The theoretical frequencies were properly scaled and compared with experimentally obtained FT-IR and FT-Raman spectra. Also, the effect due the substitution of vinyl group on the ring vibrational frequencies was analyzed and a detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated total energy distribution (TED). The time dependent DFT (TD-DFT) method was employed to predict its electronic properties, such as electronic transitions by UV-Visible analysis, HOMO and LUMO energies, molecular electrostatic potential (MEP) and various global reactivity and selectivity descriptors (chemical hardness, chemical potential, softness, electrophilicity index). Stability of the molecule arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Atomic charges obtained by Mulliken population analysis and NBO analysis are compared. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures are also calculated. PMID:25795608
NASA Astrophysics Data System (ADS)
Nagabalasubramanian, P. B.; Periandy, S.; Karabacak, Mehmet; Govindarajan, M.
2015-06-01
The solid phase FT-IR and FT-Raman spectra of 4-vinylcyclohexene (abbreviated as 4-VCH) have been recorded in the region 4000-100 cm-1. The optimized molecular geometry and vibrational frequencies of the fundamental modes of 4-VCH have been precisely assigned and analyzed with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) method at 6-311++G(d,p) level basis set. The theoretical frequencies were properly scaled and compared with experimentally obtained FT-IR and FT-Raman spectra. Also, the effect due the substitution of vinyl group on the ring vibrational frequencies was analyzed and a detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated total energy distribution (TED). The time dependent DFT (TD-DFT) method was employed to predict its electronic properties, such as electronic transitions by UV-Visible analysis, HOMO and LUMO energies, molecular electrostatic potential (MEP) and various global reactivity and selectivity descriptors (chemical hardness, chemical potential, softness, electrophilicity index). Stability of the molecule arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Atomic charges obtained by Mulliken population analysis and NBO analysis are compared. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures are also calculated.
A hybrid one-step inversion method for shear modulus imaging using time-harmonic vibrations
NASA Astrophysics Data System (ADS)
Lee, Tae Hwi; Ahn, Chi Young; In Kwon, Oh; Seo, Jin Keun
2010-08-01
We propose a hybrid inversion method for imaging the shear modulus ? in tissue-like subjects using internal measurement of the displacement u induced by an external low-frequency mechanical vibrations made on the boundary of the subject. The proposed method is designed to provide high-resolution imaging in a heterogeneous subject, with no need for an iterative procedure, and deal with the intrinsically noisy displacement data. We recover the shear modulus ? by decomposing it into two components: one is for capturing the main feature of ? using a relatively noise-insensitive inversion method, and the other is to correct the residual caused by the quantity ?? × ?u. Numerical simulations show that the proposed method significantly improves reconstructions without requiring boundary conditions.
NASA Astrophysics Data System (ADS)
Arivazhagan, M.; Jeyavijayan, S.; Geethapriya, J.
2013-03-01
The FTIR and FT-Raman spectra of 5-nitro-2-furaldehyde oxime (NFAO) have been recorded in the regions 4000-400 cm-1 and 3500-50 cm-1, respectively. The total energies of different conformations have been obtained from DFT (B3LYP) with 6-311++G(d,p) basis set calculations. The computational results identify the most stable conformer of NFAO as the C1 form. Utilizing the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. The optimum molecular geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities, were calculated by density functional theory (DFT/B3LYP) method with 6-31+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. A detailed interpretation of the infrared and Raman spectra of NFAO is also reported based on total energy distribution (TED). Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. Besides, molecular electrostatic potential (MEP), HOMO and LUMO analysis, and several thermodynamic properties were performed by the DFT method. Mulliken's net charges have been calculated and compared with the natural atomic charges. Ultraviolet-visible spectrum of the title molecule has also been calculated using TD-DFT method.
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 ?, and hyperpolarizability ? using the above mentioned basis sets. The molecular properties such as ionization potential, electronegativity, chemical potential, electrophilicity have been deduced from HOMO-LUMO analysis employing the same basis sets. A detailed interpretation of the infrared and Raman spectra of title molecules were reported. UV spectrum was measured in different solvent. The energy and oscillator strength are calculated by Time Dependant Density Functional Theory (TD-DFT) results. The calculated HOMO and LUMO energies also confirm that charge transfer occurs within the molecule. The complete assignments were performed on the basis of the potential energy distribution (PED) of vibrational modes, calculated with scaled quantum mechanics (SQM) method. Finally the theoretical FT-IR, FT-Raman, and UV spectra of the title molecules have also been constructed.
Karabacak, M; Cinar, Z; Kurt, M; Sudha, S; Sundaraganesan, N
2012-01-01
The solid phase FTIR and FT-Raman spectra of 4-butyl benzoic acid (4-BBA) have been recorded in the regions 400-4000 and 50-4000cm(-1), respectively. The spectra were interpreted in terms of fundamentals modes, combination and overtone bands. The structure of the molecule was optimized and the structural characteristics were determined by density functional theory (DFT) using B3LYP method with 6-311++G(d,p) as basis set. The vibrational frequencies were calculated for monomer and dimer by DFT method and were compared with the experimental frequencies, which yield good agreement between observed and calculated frequencies. The infrared and Raman spectra were also predicted from the calculated intensities. (13)C and (1)H NMR spectra were recorded and (13)C and (1)H nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. UV-visible spectrum of the compound was recorded in the region 200-400nm and the electronic properties HOMO and LUMO energies were measured by time-dependent TD-DFT approach. The geometric parameters, energies, harmonic vibrational frequencies, IR intensities, Raman intensities, chemical shifts and absorption wavelengths were compared with the available experimental data of the molecule. PMID:22024454
NASA Astrophysics Data System (ADS)
Karabacak, M.; Cinar, Z.; Kurt, M.; Sudha, S.; Sundaraganesan, N.
2012-01-01
The solid phase FTIR and FT-Raman spectra of 4-butyl benzoic acid (4-BBA) have been recorded in the regions 400-4000 and 50-4000 cm -1, respectively. The spectra were interpreted in terms of fundamentals modes, combination and overtone bands. The structure of the molecule was optimized and the structural characteristics were determined by density functional theory (DFT) using B3LYP method with 6-311++G(d,p) as basis set. The vibrational frequencies were calculated for monomer and dimer by DFT method and were compared with the experimental frequencies, which yield good agreement between observed and calculated frequencies. The infrared and Raman spectra were also predicted from the calculated intensities. 13C and 1H NMR spectra were recorded and 13C and 1H nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. UV-visible spectrum of the compound was recorded in the region 200-400 nm and the electronic properties HOMO and LUMO energies were measured by time-dependent TD-DFT approach. The geometric parameters, energies, harmonic vibrational frequencies, IR intensities, Raman intensities, chemical shifts and absorption wavelengths were compared with the available experimental data of the molecule.
Fiuza, S M; Silva, T M; Marques, M P M; de Carvalho, L A E Batista; Amado, A M
2015-10-01
The present work provides sets of correction factors to adjust the calculated vibrational frequencies of a series of ?,?-diamines hydrochloride salts to account for the intermolecular interactions with the counterion. The study was performed using different theory levels for predicting the vibrational data of isolated dicationic ?,?-diamines and their hydrochloride forms, with and without the explicit account of the interactions with the chloride counterions. Different sets of correction factors were determined for each theory level considering the four smallest elements for the ?,?-diamines series, while their transferability and reliability was evaluated considering the larger elements of the series. The theory level simplification was also evaluated and was found to neither compromise the vibrational frequencies estimates nor the magnitude and accuracy of the pre-defined scaling factors. This suggests that transferability of the correction factors is possible not only for different diamines but also between different levels of theory with the averaged group correction factor, ? g (a) , being the best choice to account for the effects of the N-H?·?·?·?Cl interactions. The possibility of simplifying the theory level without compromising efficiency and accuracy is additionally of utmost importance. This computational approach can constitute a valuable tool in the future for studying the hydrochloride forms of larger and more complex diamine systems. Graphical Abstract A computational approach that may constitute a valuable tool for studying the hydrochloride forms of large and complex diamine systems. Correction factors to adjust the vibrational frequencies calculated for isolated dicationic primary diamines for the effects of the interactions with chloride counterions, without their explicit account in the calculations, are presented and evaluated for eficiency. PMID:26386957
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.
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.
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.
Arjunan, V; Rani, T; Santhanam, R; Mohan, S
2012-10-01
The FT-IR and FT-Raman spectra of H bond inner conformer of 2,3-epoxypropanol have been recorded in the regions 3700-400 and 3700-100 cm(-1), respectively. The spectra were interpreted in terms of fundamentals modes, combination and overtone bands. The normal coordinate analysis was carried out to confirm the precision of the assignments. The structure of the conformers H bond inner and H bond outer1 were optimised and the structural characteristics were determined by density functional theory (DFT) using B3LYP and MP2 methods with 6-31G** and 6-311++G** basis sets. The vibrational frequencies were calculated in all these methods and were compared with the experimental frequencies which yield good agreement between observed and calculated frequencies. The electronic properties HOMO and LUMO energies were measured by time-dependent TD-DFT approach. PMID:22652541
NASA Astrophysics Data System (ADS)
Arjunan, V.; Rani, T.; Santhanam, R.; Mohan, S.
2012-10-01
The FT-IR and FT-Raman spectra of H bond inner conformer of 2,3-epoxypropanol have been recorded in the regions 3700-400 and 3700-100 cm-1, respectively. The spectra were interpreted in terms of fundamentals modes, combination and overtone bands. The normal coordinate analysis was carried out to confirm the precision of the assignments. The structure of the conformers H bond inner and H bond outer1 were optimised and the structural characteristics were determined by density functional theory (DFT) using B3LYP and MP2 methods with 6-31G?? and 6-311++G?? basis sets. The vibrational frequencies were calculated in all these methods and were compared with the experimental frequencies which yield good agreement between observed and calculated frequencies. The electronic properties HOMO and LUMO energies were measured by time-dependent TD-DFT approach.
NASA Astrophysics Data System (ADS)
Moghanian, Hassan; Mobinikhaledi, Akbar; Monjezi, Roya
2013-11-01
In this work, 8-formyl-7-hydroxy-4-methylcoumarin has been synthesized and characterized by elemental analysis, FT-IR, FT Raman, 1H NMR, 13C NMR and UV-vis spectra. The molecular geometry, harmonic vibrational frequencies and gauge including atomic orbital (GIAO) 1H and 13C chemical shift values of the title compound in the ground state have been calculated by using Hartree-Fock (HF) and density functional methods (B3LYP) with 6-311++G(d,p) as basis set. The vibrational assignments of wave numbers were interpreted in terms of potential energy distribution (PED) analysis and the scaled B3LYP/6-311++G(d,p) results show the good agreement with the experimental values. The UV spectra of investigated compound were recorded in the region of 230-500 nm in chloroform solution. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) in gas and CHCl3 theoretically and results were compared with experimental observations. The molecular stability arising from hyperconjugative interactions and charge delocalization have been analyzed using natural bond orbital (NBO) analysis. In addition, Frontier Molecular Orbitals (FMO), Molecular Electrostatic Potential (MEP) and thermodynamic properties of the studied compound such as heat capacity (C), entropy (S) and enthalpy changes (H) at different temperatures have been calculated.
NASA Astrophysics Data System (ADS)
Robles, Norma L.; Cutin, Edgardo H.; Mews, Rüdiger; Della Védova, Carlos O.
2010-08-01
The vibrational spectra of pentafluoroethyliminosulfur difluoride, CF 3CF 2N dbnd SF 2, were recorded in the gas phase with IR spectroscopy and in the liquid state with Raman spectroscopy. Quantum chemical calculations at the B3LYP (6-311+G(d) and 6-311+G(2df) basis sets) and MP2 levels of theory (6-31+G(d) and 6-311G(d) basis sets) were performed. According to all calculations the lowest energy conformer possesses C1 symmetry with syn orientation of the SF 2 group relative to the C sbnd N bond and near- trans orientation of the CF 3 group relative to the N dbnd S bond ( syn- trans). Calculations predict the hypothetical presence of a second stable conformer with anti-orientation of the SF 2 group ( anti- trans) which, however, possesses considerably higher energy and is therefore not observed in the analysis of the experimental spectra. The vibrational spectra were assigned for a single conformer in agreement with these calculations.
Jingrong Huang; James J. Valentini; James T. Muckerman
1995-01-01
We apply the adiabatic switching (AS) method to determine the polyatomic classical motions that correspond to selected vibrational quantum states on multidimensional, anharmonic potential energy surfaces, and use these semiclassically quantized motions as initial conditions for quasiclassical trajectory (QCT) calculations of state-to-state reaction dynamics. Specifically, we calculate the classical motion corresponding to the quantum mechanical zero-point vibration of deuterated methane,
NASA Technical Reports Server (NTRS)
Gregurick, Susan K.; Chaban, Galina M.; Gerber, R. Benny; Kwak, Dochou (Technical Monitor)
2001-01-01
The second-order Moller-Plesset ab initio electronic structure method is used to compute points for the anharmonic mode-coupled potential energy surface of N-methylacetamide (NMA) in the trans(sub ct) configuration, including all degrees of freedom. The vibrational states and the spectroscopy are directly computed from this potential surface using the Correlation Corrected Vibrational Self-Consistent Field (CC-VSCF) method. The results are compared with CC-VSCF calculations using both the standard and improved empirical Amber-like force fields and available low temperature experimental matrix data. Analysis of our calculated spectroscopic results show that: (1) The excellent agreement between the ab initio CC-VSCF calculated frequencies and the experimental data suggest that the computed anharmonic potentials for N-methylacetamide are of a very high quality; (2) For most transitions, the vibrational frequencies obtained from the ab initio CC-VSCF method are superior to those obtained using the empirical CC-VSCF methods, when compared with experimental data. However, the improved empirical force field yields better agreement with the experimental frequencies as compared with a standard AMBER-type force field; (3) The empirical force field in particular overestimates anharmonic couplings for the amide-2 mode, the methyl asymmetric bending modes, the out-of-plane methyl bending modes, and the methyl distortions; (4) Disagreement between the ab initio and empirical anharmonic couplings is greater than the disagreement between the frequencies, and thus the anharmonic part of the empirical potential seems to be less accurate than the harmonic contribution;and (5) Both the empirical and ab initio CC-VSCF calculations predict a negligible anharmonic coupling between the amide-1 and other internal modes. The implication of this is that the intramolecular energy flow between the amide-1 and the other internal modes may be smaller than anticipated. These results may have important implications for the anharmonic force fields of peptides, for which N-methylacetamide is a model.
Burton, Benjamin P.
First Principles Phase Diagram Calculations for the System NaCl-KCl: the role of excess vibrational phase diagram calculations were performed for the system NaCl-KCl. Planewave pseudopotential the agreement between calculated and experimental phase diagrams: experimentally, the consolute point is {XC = 0
Benoit, David M
2008-12-21
We introduce a new reduced-coupling technique to accelerate direct calculations of a selected number of vibrational frequencies in large molecular systems. Our method combines the advantages of the single-to-all correlation-corrected vibrational self-consistent field (STA-CC-VSCF) approach [D. M. Benoit, J. Chem. Phys. 125, 244110 (2006)] with those of the fast-CC-VSCF technique [D. M. Benoit, J. Chem. Phys. 120, 562 (2004)] and allows the ab initio calculation of only the relevant parts of the required potential energy surface (PES). We demonstrate, using a set of five aliphatic alcohol molecules, that the new fast-STA-CC-VSCF method is accurate and leads to very substantial time gains for the computations of the PES. We then use the fast-STA-CC-VSCF method to accelerate the computation of the OH-stretch and NH-stretch frequencies of the two lowest-energy conformers of noradrenaline, namely, AG1a and GG1a. Our new approach enables us to run the calculation 89 times faster than the standard CC-VSCF technique and makes it possible to use a high-level MP2/TZP description of the PES. We demonstrate that the influence of the strong mode-mode couplings is crucial for a realistic description of the particular OH-stretch vibrational signature of each conformer. Finally, of the two possible low-energy conformers, we identify AG1a as the one most likely to have been observed in the experiments of Snoek et al. [Mol. Phys. 101, 1239 (2003)]. PMID:19102529
NASA Astrophysics Data System (ADS)
Kirillov, Andrey S.
The calculated quenching rate constants of the c1, A'3, A3 states of O2 by molecules in [Kirillov, 2014, Chem. Phys. Lett., v.592, p.103] are applied in the simulation of vibrational populations of the Herzberg states in the nightglow of upper atmosphere of Venus and Mars where carbon dioxide is the main gas and in the mixture of molecular oxygen with CO2, CO, N2 gases for laboratory conditions. The results of the simulation show very important role of electronic-vibrational (EV) energy transfer processes in the redistribution of electronic excitation energy on vibrational levels of the states. The main aim of the simulation is an attempt to explain the high intensities of the Herzberg II band system observed in laboratory experiments with high CO2 concentrations [Lawrence et al., 1977, Science, v.195, p.573; Slanger, 1978, J. Chem. Phys., v.69, p.4779] and registered with spacecraft spectrometers in the nightglow of the Venus atmosphere [Krasnopolsky et al., 1977, Cosmic Res., v.14, p.687; Gerard et al., 2013, Icarus, v.223, p.602].
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(+).
NSDL National Science Digital Library
William C. Robertson, Ph.D.
2003-01-01
Harmonic convergence refers to a day back in 1987 where there was a particular planetary alignment. New Agers went crazy over the event, and if you want to get a taste of what it was like, enter harmonic convergence into your favorite Internet search engine and sit back and enjoy. This chapter adds to the previous discussion of resonance by expanding the list of vibrating things to metal rods and columns of air.
Calculation of low-frequency vibrational modes of biologically important isomers
NASA Astrophysics Data System (ADS)
Jones, Inke; Rainsford, Tamath J.; Fischer, Bernd M.; Abbott, Derek
2007-12-01
In this paper we compare the value of different molecular modeling techniques for the prediction of vibrational modes, especially in the mid- and far-infrared region. There is a wide range of different levels of theory available for molecular modelling - the choice depending on the kind of system to be investigated. For our calculations we use different theoretical approaches such as Hartree-Fock and Density functional theory. We also compare the performances of two available electronic structure programs-Gamess-US and Gaussian03. As examples, we use two different retinoids - all-trans retinal and all-trans retinoic acid - derivatives of Vitamin A.
The variational method for the calculation of RO-vibrational energy levels
NASA Astrophysics Data System (ADS)
Carter, S.; Handy, N. C.
1986-12-01
In this paper the current status of the variational method for the determination of the rotational-vibrational energy levels of polyatomic systems is reviewed. Special attention is made for the derivation of the kinetic energy operator in various coordinate systems, and several forms are given. Similarly, analytic forms which are in current use for the potentials are given. The calculation of the Hamiltonian matrix elements (expansion functions, numerical integration grid points and weights) is described in detail, and a description of our programs for this problem is given in section 6.
Lowest vibrational states of {sup 4}He{sup 3}He{sup +}: Non-Born-Oppenheimer calculations
Stanke, Monika; Bubin, Sergiy [Department of Chemistry, University of Arizona, Tucson, Arizona 85721 (United States); Kedziera, Dariusz [Department of Chemistry, Nicholaus Copernicus University, ul. Gagarina 7, PL 87-100 Torun (Poland); Molski, Marcin [Department of Theoretical Chemistry, Faculty of Chemistry, Adam Mickiewicz University, ul. Grunwaldzka 6, Poznan, PL 60-780 (Poland); Adamowicz, Ludwik [Department of Chemistry, University of Arizona, Tucson, Arizona 85721 (United States); Department of Physics, University of Arizona, Tucson, Arizona 85721 (United States)
2007-11-15
Very accurate quantum mechanical calculations of the first five vibrational states of the {sup 4}He{sup 3}He{sup +} molecular ion are reported. The calculations have been performed explicitly including the coupling of the electronic and nuclear motions [i.e., without assuming the Born-Oppenheimer (BO) approximation]. The nonrelativistic non-BO wave functions were used to calculate the {alpha}{sup 2} relativistic mass velocity, Darwin, and spin-spin interaction corrections. For the lowest vibrational transition, whose experimental energy is established with high precision, the calculated and the experimental results differ by only 0.16 cm{sup -1}.
NASA Astrophysics Data System (ADS)
Arivazhagan, M.; Manivel, S.; Jeyavijayan, S.; Meenakshi, R.
2015-01-01
The FTIR and FT-Raman spectra of 2-ethylimidazole (2EIDZ) have been recorded in the region 4000-400 cm-1 and 3500-50 cm-1, respectively. Utilizing the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. The optimized molecular geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities, were calculated by ab initio Hartree-Fock (HF) and density functional theory (DFT/B3LYP) methods with 6-311++G(d,p) basis set. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. A detailed interpretation of the infrared and Raman spectra of 2EIDZ is also reported based on total energy distribution (TED). The values of the total dipole moment (?) and the first-order hyperpolarizability (?) of the compound were computed. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. Besides, HOMO and LUMO analysis, Mulliken's charge analysis and several thermodynamic properties have been calculated.
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.
NASA Astrophysics Data System (ADS)
Castillo, María V.; Pergomet, Jorgelina L.; Carnavale, Gustavo A.; Davies, Lilian; Zinczuk, Juan; Brandán, Silvia A.
2015-01-01
In this study 3,3?,4,4?-tetrachloroazobenzene (TCAB) was prepared and then characterized by infrared, Raman, multidimensional nuclear magnetic resonance (NMR) and ultraviolet-visible spectroscopies. The density functional theory (DFT) together with the 6-31G* and 6-311++G** basis sets were used to study the structures and vibrational properties of the two cis and trans isomers of TCAB. The harmonic vibrational wavenumbers for the optimized geometries were calculated at the same theory levels. A complete assignment of all the observed bands in the vibrational spectra of TCAB was performed combining the DFT calculations with the scaled quantum mechanical force field (SQMFF) methodology. The molecular electrostatic potentials, atomic charges, bond orders and frontier orbitals for the two isomers of TCAB were compared and analyzed. The comparison of the theoretical ultraviolet-visible spectrum with the corresponding experimental demonstrates a good concordance while the calculated 1H and 13C chemicals shifts are in good conformity with the corresponding experimental NMR spectra of TCAB in solution. The np®p* transitions for both forms were studied by natural bond orbital (NBO) while the topological properties were calculated by employing Bader's Atoms in the Molecules (AIM) theory. This study shows that the cis and trans isomers exhibit different structural and vibrational properties and absorption bands.
Castillo, María V; Pergomet, Jorgelina L; Carnavale, Gustavo A; Davies, Lilian; Zinczuk, Juan; Brandán, Silvia A
2015-01-01
In this study 3,3',4,4'-tetrachloroazobenzene (TCAB) was prepared and then characterized by infrared, Raman, multidimensional nuclear magnetic resonance (NMR) and ultraviolet-visible spectroscopies. The density functional theory (DFT) together with the 6-31G(*) and 6-311++G(**) basis sets were used to study the structures and vibrational properties of the two cis and trans isomers of TCAB. The harmonic vibrational wavenumbers for the optimized geometries were calculated at the same theory levels. A complete assignment of all the observed bands in the vibrational spectra of TCAB was performed combining the DFT calculations with the scaled quantum mechanical force field (SQMFF) methodology. The molecular electrostatic potentials, atomic charges, bond orders and frontier orbitals for the two isomers of TCAB were compared and analyzed. The comparison of the theoretical ultraviolet-visible spectrum with the corresponding experimental demonstrates a good concordance while the calculated (1)H and (13)C chemicals shifts are in good conformity with the corresponding experimental NMR spectra of TCAB in solution. The npp(*) transitions for both forms were studied by natural bond orbital (NBO) while the topological properties were calculated by employing Bader's Atoms in the Molecules (AIM) theory. This study shows that the cis and trans isomers exhibit different structural and vibrational properties and absorption bands. PMID:25106816
Vibrational spectra of light and heavy water with application to neutron cross section calculations
Damian, J. I. Marquez; Granada, J. R. [Neutron Physics Department and Instituto Balseiro, Centro Atomico Bariloche, CNEA (Argentina); Malaspina, D. C. [Department of Biomedical Engineering and Chemistry of Life Processes Institute, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208 (United States)
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.
The excitation scheme: A new method for calculation of vibrational circular dichroism spectra
NASA Astrophysics Data System (ADS)
Bou?, P.; McCann, J.; Wieser, H.
1998-06-01
An alternate procedure for calculating vibrational circular dichroism is proposed. The method eliminates the need to solve the magnetically perturbed SCF equations which leads to an overall decrease in computer time. Instead, an expansion over electronic excited states is partially used to estimate the molecular response to the magnetic field and nuclear displacements. A rigid orbital approximation is used for the electronic states. The rotational strengths obtained in this manner are compared to original experimental data for camphor and ?-pinene, and previous calculations on propylene oxide and oxirane. In all cases good agreement of simulated spectral intensities with experiment is observed. Although extensive approximations had to be adopted in the current implementation, the excitation scheme yields results superior to those obtained by the classical MFP or VCT formulations of VCD for camphor and ?-pinene, whereas MFP/GIAO theory performs better in the case of oxirane.
Vibrational spectra of light and heavy water with application to neutron cross section calculations
NASA Astrophysics Data System (ADS)
Damian, J. I. Marquez; Malaspina, D. C.; Granada, J. R.
2013-07-01
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.
Farantos, Stavros C.
The vibrational energies of ozone up to the dissociation threshold: Dynamics calculations present an ab initio potential energy surface for the ground electronic state of ozone. It is global, i. All bound states of nonrotating ozone up to more than 99% of the dissociation energy are calculated
Calculations of N 2 triplet states vibrational populations and band emissions in venusian dayglow
NASA Astrophysics Data System (ADS)
Bhardwaj, Anil; Jain, Sonal Kumar
2012-02-01
A model for N 2 triplet states band emissions in the venusian dayglow has been developed for low and high solar activity conditions. Steady state photoelectron fluxes and volume excitation rates for N 2 triplet states have been calculated using the Analytical Yield Spectra (AYS) technique. Model calculated photoelectron flux is in good agreement with Pioneer Venus Orbiter-observed electron flux. Since inter-state cascading is important for the triplet states of N 2, populations of different levels of N 2 triplet states are calculated under statistical equilibrium considering direct electron impact excitation, and cascading and quenching effects. Densities of all vibrational levels of each triplet state are calculated in the model. Height-integrated overhead intensities of N 2 triplet band emissions are calculated, the values for Vegard-Kaplan (A3?u+-X1?g+), First Positive (B3?g-A3?u+), Second Positive ( C3? u - B3? g), and Wu-Benesch ( W3? u - B3? g) bands of N 2, are 1.9 (3.2), 3 (6), 0.4 (0.8), and 0.5 (1.1) kR, respectively, for solar minimum (maximum) conditions. The intensities of the three strong Vegard-Kaplan bands (0, 5), (0, 6), and (0, 7) are 94 (160), 120 (204), and 114 (194) R, respectively, for solar minimum (maximum) conditions. Limb profiles are calculated for VK (0, 4), (0, 5), (0, 6) and (0, 7) bands. The calculated intensities on Venus are about a factor 10 higher than those on Mars. The present study provides a motivation for a search of N 2 triplet band emissions in the dayglow of Venus.
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.
DFT calculation of vibrational frequencies of clusters in GaAs and the Raman spectra.
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. PMID:22634223
NASA Astrophysics Data System (ADS)
Drolshagen, Gerhard; Toennies, J. Peter
1983-09-01
Pure vibrational excitation cross sections for a large number of ion (atom)—diatom collision systems are calculated using the breathing-sphere approximation. A realistic spherical potential adapted from the SCF potential calculated and fitted by Lester for Li + + H 2 is used for all systems. The effect of the collision energy from threshold up to the equivalent of 30 vibrational quanta and the effect of the masses of the incoming atom (1-133 amu) and target molecule (2-160 amu) on the integral inelastic cross sections is studied systematically. In another set of calculations the effect of 10% variations of various potential parameters on the excitation cross sections is examined and discussed in terms of potential range effects and vibrational coupling. Vibrationally inelastic differential cross sections for the system Li - + H 2 are calculated at total energies of 1.47, 2.0 and 3.65 eV and for Li + + Br 2 at 0.074, 0.080, and 0.321 eV. Finally the energy dependence of integral cross sections is compared with the predictions of the Schwartz—Slawsky—Herzfeld (SSH) theory. Despite different potentials the qualitative agreement is good except for vibrational excitation of heavy molecules by light atoms. The energy dependence of integral inelastic cross sections and rate constants for this case are derived from the sudden approximation.
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.
An efficient wave based approach for the time-harmonic vibration analysis of 3D plate assemblies
NASA Astrophysics Data System (ADS)
Vergote, Karel; Vanmaele, Caroline; Vandepitte, Dirk; Desmet, Wim
2013-04-01
For the analysis of the vibrational behaviour of mechanical structures the Finite Element Method (FEM) and the Statistical Energy Analysis (SEA) are most commonly used. The use of the FEM is limited to low frequency applications, since finer meshes are required at higher frequencies to preserve the same accuracy, hence increasing the computational load. The use of SEA is mostly limited to high frequency applications, due to its underlying assumptions. This paper discusses the principles of the Wave Based Method (WBM) for the steady-state dynamic analysis of thin, flat plates coupled at an arbitrary angle, including both out-of-plane and in-plane plate behaviour. Two numerical examples illustrate the beneficial convergence rate of the WBM and show the importance that in-plane displacements can have in the simulation of non-coplanar plate assemblies. As a result of its higher efficiency, the WBM is able to relax the existing frequency limit of the FEM and in this way can reduce the mid-frequency gap which exists between the low and the high frequency techniques. Furthermore, it can be used to provide more accurate input parameters for SEA-calculations in order to lower the frequency range of SEA.
NASA Astrophysics Data System (ADS)
Robbins, Timothy J.; Wang, Yongmei; Yao, Qi-Zheng; Wang, Zhao-Hui; Cheng, Jingcai; Li, Ying-Sing
2013-09-01
For centuries Danggui Longhui Wan has been used to treat chronic ailments, such as myelocytic leukemia. In the 1960s, the active ingredient in Danggui Longhui Wan was isolated and identified as indirubin. Indirubin has shown potent inhibition of cyclin-dependent kinase through binding to the ATP-binding site. However, indirubin shows poor solubility and low absorption, hence many derivatives have been developed to enhance these properties. One such derivative is 5?-chloro-1-isopropyl-7-azaindirubin-3?-oxime (CIADO), investigated in the current work. Infrared and Raman spectra were collected and compared with predicted spectra using density functional theory. Based on theoretical calculations, the most stable form of CIADO isomer is found to be cis (Z) and trans (E) with respect to the ring system linkage and the 3?-oxime functional group respectively. Also observed were two distinct internal rotational minima for the 1-isoprooyl group separated by a large energy barrier. The presence of two distinct isopropyl conformations observed in our calculations was confirmed with temperature-dependent IR experiments. Assignment of experimental vibrational modes was carried out based on functional group displacement observed in the calculations.
DFT Ab initio Calculation of Vibrational Frequencies in AsSe glass
NASA Astrophysics Data System (ADS)
Shrivastava, Keshav; Kassim, Hasan; Nazrul Rosli, Ahmad
2008-03-01
By using DFT double zeta wave functions, we calculated the structure, bond length (picometer, pm), frequencies(intensities)[degeneracy] for various clusters of arsenic selenide. Our results are as follows. (i) AsSe(diatomic) bond length 216pm, 244.0(1/cm). (ii) As2Se(linear) bond length 228.5 pm, frequencies 27.6(1.9) and 387.6(4.3). (iii) As2Se(triangular) As-Se 243.4 pm, As-As 223.3 pm, frequencies 237.3(2.4) and 332.4(0.05)(1/cm). (iv) As3Se (triangular) bond length 238.4 pm, frequencies 107.5 and 296(weak)(1/cm). (v) As4Se (square) bond length 250.2 pm, 58.5(0.04), 241.3(5.9)(1/cm). (vi) AsSe3 (triangular), bond length 231.2 pm, 75.9(0.003), 103.5(1.26)[2], 350.9(33.2)[2]. From this study we identify that linear As-Se-As for which the calculated frequency is 27.6(1/cm) is in agreement with the data of Nemanich, Phys. Rev. B 16, 1655(1977), J. C. Phillips et al Phys. Rev B 21, 5724(1980). We have successfully calculated several vibrational frequencies accurately which agree with the Raman data. *V. R. Devi et al J. Non-Cryst. Solids 351, 489(2005);353,111(2007)
NASA Astrophysics Data System (ADS)
Klaassen, Joshua J.; Groner, Peter; Durig, James R.
2013-06-01
The FT-microwave spectrum of cyclobutylcarboxylic acid chloride, c-C_{4}H_{7}C(O)Cl, has been recorded and 153 transitions for the ^{35}Cl and ^{37}Cl isotopologues have been assigned for the gauche-equatorial conformation. The ground state rotational constants were determined from these assignments with following values for ^{35}Cl [^{37}Cl]: A = 4349.84294(48) [4322.0555(56)], B = 1414.80319(36) [1384.50581(105)], C = 1148.24114(18) [1126.35465(101)]. From the determined microwave rotational constants and ab initio MP2(full)/6-311+G(d,p) predicted structural values, adjusted r_{0} parameters are reported. Variable temperature (-70 to -100^{o}C) infrared spectra (4000 to 400 cm^{-1}) were recorded in liquid xenon and gauche-equatorial conformer is the most stable form with an enthalpy differences of 91 ± 9 cm^{-1} (1.09 ± 0.05 kJ/mol) with gauche-axial and 173 ± 17 cm^{-1} (2.07 ± 0.04 kJ/mol) with the trans-equatorial conformer. The relative amounts present at an ambient temperature are 54% gauche-equatorial, 35 ± 1% gauche-axial and 12 ± 1% trans-equatorial. The conformational stabilities have been predicted from ab initio calculations utilizing several different basis sets up to aug-cc-pVTZ from both MP2(full) and density functional theory calculations by the B3LYP method. Vibrational assignments have been provided for the observed bands for all three conformers which are supported by ab initio calculations to predict harmonic force constants, vibrational wavenumbers, infrared intensities, Raman activities and depolarization ratios. The results are discussed and compared to the corresponding properties of some related molecules.
Price, Rachel Elizabeth
2011-01-01
Recent works have discussed "chaotic" or "Type-II" riser motion and suggested that it is a general feature of VIV riser response. Chaotic riser response contains broad-banded harmonics and a combination of standing and ...
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.
Anitha, R; Gunasekaran, M; Kumar, S Suresh; Athimoolam, S; Sridhar, B
2015-11-01
The common house hold pharmaceutical drug, paracetamol (PAR), has been synthesized from 4-chloroaniline as a first ever report. After the synthesis, good quality single crystals were obtained for slow evaporation technique under the room temperature. The crystal and molecular structures were re-determined by the single crystal X-ray diffraction. The vibrational spectral measurements were carried out using FT-IR and FT-Raman spectroscopy in the range of 4000-400cm(-1). The single crystal X-ray studies shows that the drug crystallized in the monoclinic system polymorph (Form-I). The crystal packing is dominated by NH?O and OH?O classical hydrogen bonds. The ac diagonal of the unit cell features two chain C(7) and C(9) motifs running in the opposite directions. These two chain motifs are cross-linked to each other to form a ring R4(4)(22) motif and a chain C2(2)(6) motif which is running along the a-axis of the unit cell. Along with the classical hydrogen bonds, the methyl group forms a weak CH?O interactions in the crystal packing. It offers the support for molecular assembly especially in the hydrophilic regions. Further, the strength of the hydrogen bonds are studied the shifting of vibrational bands. Geometrical optimizations of the drug molecule were done by the Density Functional Theory (DFT) using the B3LYP function and Hartree-Fock (HF) level with 6-311++G(d,p) basis set. The optimized molecular geometry and computed vibrational spectra are compared with experimental results which show significant agreement. The factor group analysis of the molecule was carried out by the various molecular symmetry, site and factor group species using the standard correlation method. The Natural Bond Orbital (NBO) analysis was carried out to interpret hyperconjugative interaction and intramolecular charge transfer (ICT). The chemical softness, chemical hardness, electro-negativity, chemical potential and electrophilicity index of the molecule were found out first time by HOMO-LUMO plot. The frontier orbitals shows lower band gap values signify the possible biological/pharmaceutical activity of the molecule. The thermodynamical properties are also obtained from the calculated frequencies of the optimized structures. PMID:26072380
NASA Astrophysics Data System (ADS)
Durig, James R.; Panikar, Savitha; Zhou, Xiaohua; El Defrawy, Ahmed M.
2008-03-01
From analysis of the infrared and Raman spectra along with support from the ab initio predictions it is concluded that there is only one stable conformer of dimethylaminodifluorophosphine, (CH 3) 2NPF 2, in the gaseous and liquid phases which has a planar PNC 2 moiety with Cs symmetry. The adjusted r0 structural parameters have been obtained by combining the MP2(full)/6-311 + G(d) predicted values with the previous reported rotational constants for four isotopomers obtained from previously reported microwave studies. The difference in the two NC distances is 0.002 Å whereas, these two parameters were previously assumed to have the same values from the microwave and electron diffraction studies but a reported difference of 0.025 Å from the structural parameters of the crystal. The adjusted r0 heavy atom distances and angles are: r(PF) = 1.593(3); r(NP) = 1.654(3); r(NC i) = 1.455(3); r(NC o) = 1.453(3) Å; ?FPF = 93.5(5); ?NPF = 100.8(5); ?CNC = 116.0(5); ?C iNP = 124.1(5); ?C oNP = 120.0°. The planar bonding around the nitrogen atom is consistent with the previously reported structural information from the microwave study but differs from the slightly pyramidal bonding obtained in the electron diffraction investigation. To support the vibrational assignment MP2(full) ab initio calculations with the 6-31G(d) basis set were carried out to predict the fundamental vibrational frequencies, infrared intensities, Raman activities, depolarization values, infrared band contours, and centrifugal distortion constants. Vibrational assignments are given for (CH 3) 2NPF 2 and (CD 3) 2NPF 2 and comparisons are made with the predicted intensities, frequencies and centrifugal distortion constants. Frequencies of some of the lattice modes are reported from both the infrared and Raman spectra with suggested assignments based on the factor group symmetry of the crystal of D2h16 (Pnma) with four molecules per primitive cell. These results are compared to the corresponding quantities of some similar molecules.
Al-Saadi, Abdulaziz A. H.
2009-05-15
,3-cyclopentenopyridine (pyrindan). Ab initio results showed that -crotonolactone is rigidly planar in the electronic ground state and has a nearly harmonic ring-puckering potential function. The calculated vibrational levels were shown to be in very good agreement...
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.
Harmonic synchronization of nonlinear oscillators
I. Schmideg
1971-01-01
The locking range of a harmonic synchronized oscillator is calculated, and it is shown to be proportional to the relative harmonic amplitude produced by the nonlinearity. For completeness a simple method is given for calculating the harmonic output produced.
NASA Astrophysics Data System (ADS)
Choi, Jun-Ho; Cheon, Sangheon; Cho, Minhaeng
2010-02-01
Determining absolute configuration of chiral molecule can be achieved by using vibrational optical activity (VOA) measurement methods, such as vibrational circular dichroism and Raman optical activity (ROA). Recently, vibrationally resonant sum frequency generation and difference frequency generation utilizing circularly polarized beams were theoretically studied and shown that they can be alternative and complementary VOA measurement techniques [S. Cheon and M. Cho, Phys. Rev. A 71, 013808 (2005); J. Phys. Chem. A 113, 2438 (2009)]. Even for randomly oriented chiral molecules in solutions, the sum- and difference-frequency-generation signals induced by linearly polarized incident beams with mutually perpendicular polarization directions can be nonzero and are determined by the optical activity hyperpolarizability given by a product of antisymmetric Raman tensor and vibrational transition dipole. If one of the beams involved in the three-wave-mixing processes is circularly polarized and if the difference signal is measured, not only the same optical activity hyperpolarizability but also that including electric quadrupole-ROA tensor are required to determine the signals. Here, we carried out quantum chemistry calculations to obtain these quantities for a representative chiral molecule, (S)-methyl lactate, and numerically simulated the corresponding spectra. It is shown that the circular polarization three-wave-mixing signal intensities are quantitatively similar to those of the linear polarization three-wave-mixing signals, respectively, and that they are sensitive to the absolute configuration of chiral molecule. The calculation results thus suggest that these two novel techniques will be of use in studying molecular chirality even in time domain, once polarization-modulated ultrashort pulses are used to carry out circular polarization three-wave-mixing experiments.
Seongeun Yang; Minhaeng Cho
2009-01-01
The vibrational absorption (IR) and vibrational circular dichroism (VCD) spectra of alanine dipeptide analog in water are directly calculated by Fourier transforming the time correlation functions of the electric and magnetic dipole moments, which are calculated using the dynamic partial charges and trajectory of the peptide generated from the quantum mechanical\\/molecular mechanical molecular dynamics simulations. The alanine dipeptide analog is
NASA Astrophysics Data System (ADS)
Marchewka, M. K.; Drozd, M.; Janczak, J.
2011-08-01
The N-(4-nitrophenyl)-?-alanine in crystalline form directly by the addition of 4-nitroaniline to the acrylic acid in aqueous solution has been obtained. The title ?-alanine derivative crystallizes in the P2 1/ c space group of monoclinic system with four molecules per unit cell. The X-ray geometry of ?-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 ?-alanine derivative weakly interact via N-H⋯O hydrogen bonds between the H atom of ?-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.
Yu, Hua-Gen; Ndengue, Steve; Li, Jun; Dawes, Richard; Guo, Hua
2015-08-28
Accurate vibrational energy levels of the simplest Criegee intermediate (CH2OO) were determined on a recently developed ab initio based nine-dimensional potential energy surface using three quantum mechanical methods. The first is the iterative Lanczos method using a conventional basis expansion with an exact Hamiltonian. The second and more efficient method is the multi-configurational time-dependent Hartree (MCTDH) method in which the potential energy surface is refit to conform to the sums-of-products requirement of MCTDH. Finally, the energy levels were computed with a vibrational self-consistent field/virtual configuration interaction method in MULTIMODE. The low-lying levels obtained from the three methods are found to be within a few wave numbers of each other, although some larger discrepancies exist at higher levels. The calculated vibrational levels are very well represented by an anharmonic effective Hamiltonian. PMID:26328847
Calculated vibrational populations of O2 Herzberg states in the mixture of CO2, CO, N2, O2 gases
NASA Astrophysics Data System (ADS)
Kirillov, A. S.
2014-05-01
Calculated in (Kirillov, 2014) constants are applied for simulations of vibrational populations of Herzberg states in mixtures of O2 with CO2, CO, N2 gases for laboratory conditions. Results show very important role of electronic-vibrational processes in redistribution of electronic excitation energy among vibrational levels. It is shown that the interaction between O2(A?3?u) and O2 causes effective production O2(c1?u-,v = 0) observed in laboratory conditions. The inclusion of the interaction between O2(A?3?u) and CO2 molecules may explain high intensities of Herzberg II system observed in laboratory experiments with high CO2 concentrations and registered in the nightglow of Venusian atmosphere.
NASA Astrophysics Data System (ADS)
Krishnakumar, V.; Mathammal, R.; Muthunatesan, S.
2008-06-01
This work deals with the vibrational spectroscopy of 1-naphthyl acetic acid. The molecular vibrations of 1-naphthyl acetic acid (NAA) is investigated in polycrystalline sample, at room temperature, by Fourier transform infrared (FT-IR) and FT-Raman spectroscopy. In parallel, ab initio and various density functional (DFT) methods were used to determine the geometrical, energetic and vibrational characteristics of NAA. On the basis of B3LYP/6-311 + G** method and basis set combinations, a normal mode analysis was performed to assign the various fundamental frequencies according to the total energy distribution (TED). Simulation of infrared and Raman spectra, utilizing the results of these calculations led to excellent overall agreement with observed spectral patterns by refinement of scale factors.
NASA Astrophysics Data System (ADS)
Arjunan, V.; Balamourougane, P. S.; Saravanan, I.; Mohan, S.
2009-10-01
The Fourier transform infrared (FTIR) and FT-Raman spectra of 2-nitro-m-xylene (2NMX), 4-nitro-m-xylene (4NMX) and 5-nitro-m-xylene (5NMX) have been recorded in the range 4000-400 and 4000-100 cm -1, respectively. The experimental vibrational frequency was compared with that obtained theoretically by ab initio HF and DFT-B3LYP gradient calculations employing the standard 6-31G(d,p) basis set for the optimised geometries of the compounds. The complete vibrational assignment, analysis and correlation of the fundamental modes of the compounds were carried out using the experimental FTIR and FT-Raman data, and ab initio and DFT quantum chemical studies. The geometrical parameters and the wavenumbers of normal modes of vibration obtained from the HF and DFT methods are in good agreement with the experimental values. The potential energy distribution of the fundamental modes was calculated with ab initio force fields utilising Wilson's FG matrix method. The influence of bulky methyl groups on the nitro group fundamental modes and on the ring skeletal vibrations are investigated.
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.
Homayoon, Zahra; Bowman, Joel M
2014-10-28
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 (15)NO3 are also presented and these are also in good agreement with experiment. PMID:25362265
Calculation of vibrational frequencies through a variational reduced-coupling approach
NASA Astrophysics Data System (ADS)
Scribano, Yohann; Benoit, David M.
2007-10-01
In this study, we present a new method to perform accurate and efficient vibrational configuration interaction computations for large molecular systems. We use the vibrational self-consistent field (VSCF) method to compute an initial description of the vibrational wave function of the system, combined with the single-to-all approach to compute a sparse potential energy surface at the chosen ab initio level of theory. A Davidson scheme is then used to diagonalize the Hamiltonian matrix built on the VSCF virtual basis. Our method is applied to the computation of the OH-stretch frequency of formic acid and benzoic acid to demonstrate the efficiency and accuracy of this new technique.
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 in aqueous solution could be detected by Raman spectroscopy. The hydrogen bonds between carbonate in heavy water are stronger than the ones in normal water. In sodium and potassium carbonate solutions no contact ion pairs could be detected even up to the saturated solutions. However, solvent separated ion pairs were inferred in concentrated solutions in accordance with recent dielectric relaxation spectroscopy (DRS) measurements. Quantitative Raman measurements of the hydrolysis of carbonate in aqueous K(2)CO(3) solutions were carried out and the hydrolysis degree a was determined as a function of concentration at 22 degrees C. The second dissociation constant, pK(2), of the carbonic acid was determined to be equal to 10.38 at 22 degrees C. PMID:16542564
Prabhu, T; Periandy, S; Ramalingam, S
2011-12-01
Fourier-transform Raman and infrared spectra of 2-nitroanisole are recorded (4000-100 cm(-1)) and interpreted by comparison with respective theoretical spectra calculated using HF and DFT method. The geometrical parameters with C(S) symmetry, harmonic vibrational frequencies, infrared and Raman scattering intensities are determined using HF/6-311++G (d, p), B3LYP/6-311+G (d, p), B3LYP/6-311++G (d, p) and B3PW91/6-311++G (d, p) level of theories. A detailed vibrational spectral analysis has been carried out and assignments of the observed fundamental bands have been proposed on the basis of peak positions and relative intensities. The results of the calculations have been used to simulate IR and Raman spectra for the molecule that showed good agreement with the observed spectra. The SQM method, which implies multiple scaling of the DFT force fields has been shown superior to the uniform scaling approach. The vibrational frequencies and the infrared intensities of the C-H modes involved in back-donation and conjugation are also investigated. PMID:21963192
NASA Astrophysics Data System (ADS)
Prabhu, T.; Periandy, S.; Ramalingam, S.
2011-12-01
Fourier-transform Raman and infrared spectra of 2-nitroanisole are recorded (4000-100 cm -1) and interpreted by comparison with respective theoretical spectra calculated using HF and DFT method. The geometrical parameters with CS symmetry, harmonic vibrational frequencies, infrared and Raman scattering intensities are determined using HF/6-311++G (d, p), B3LYP/6-311+G (d, p), B3LYP/6-311++G (d, p) and B3PW91/6-311++G (d, p) level of theories. A detailed vibrational spectral analysis has been carried out and assignments of the observed fundamental bands have been proposed on the basis of peak positions and relative intensities. The results of the calculations have been used to simulate IR and Raman spectra for the molecule that showed good agreement with the observed spectra. The SQM method, which implies multiple scaling of the DFT force fields has been shown superior to the uniform scaling approach. The vibrational frequencies and the infrared intensities of the C-H modes involved in back-donation and conjugation are also investigated.
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).
NASA Astrophysics Data System (ADS)
Durig, J. R.; Wang, A. Y.; Little, T. S.; Brletic, P. A.
1990-07-01
The far-infrared spectrum of gaseous 2-chloropropenoyl fluoride, CH2 CClCFO, has been recorded at a resolution of 0.10 cm-1 in the region of 350-35 cm-1. The fundamental asymmetric torsional frequencies of the more stable s-trans (two double bonds oriented trans to one another) and the high energy s-cis conformations have been observed at 67.80 and 49.96 cm-1, respectively, each with several excited states falling to lower frequencies. From these data the asymmetric torsional potential function governing the internal rotation about the C-C bond has been determined. The potential coefficients are V1 =-125±1, V2 =1586±6, V3 =375±2, V4 =-36±2, and V5 =-65±1 cm-1. The s-trans to s-cis and s-cis to s-trans barriers have been determined to be 1755 and 1570 cm-1, respectively, with an energy difference between the conformations of 185±9 cm-1 (529±26 cal/mol). From studies of the Raman spectrum at variable temperatures, the conformational enthalpy difference has been determined to be 176±40 cm-1 (503±114 cal/mol) and 625±51 cm-1 (1787±146 cal/mol) for the gas and liquid, respectively. A complete assignment of the vibrational fundamentals observed from the infrared spectra (3500-50 cm-1) of the gas and solid and the Raman spectra (3200-10 cm-1) of all three physical states is proposed. All of these data are compared to the corresponding quantities obtained from ab initio Hartree-Fock gradient calculations employing both the 3-21G* and 6-31G* basis sets. Additionally, complete equilibrium geometries have been determined for both rotamers. The results are discussed and compared with the corresponding quantities obtained for some similar molecules.
Vibrational spectrum of p-fluoroanisole in the first excited state (S 1) and ab initio calculations
NASA Astrophysics Data System (ADS)
Xiao, Daoqing; Yu, Dan; Xu, Xiling; Yu, Zijun; Du, Yikui; Gao, Zhen; Zhu, Qihe; Zhang, Cunhao
2008-06-01
The vibronic structure of p-fluoroanisole in the first excited state (S 1) has been investigated with mass selected resonance-enhanced two photon ionization spectroscopy. The band origin of S 1 ? S 0 transition of p-fluoroanisole is measured to be 35149 cm -1, which is red-shifted by 1234 cm -1 with respect to that of anisole. Combining with the ab initio calculations, the measured frequencies 397, 487, 559, 840 and 1150 cm -1 in the S 1 state are assigned as the in-plane ring vibrational mode 9 b, 6 a, 6 b, 1 and 9 a, respectively. The optimized molecular geometries and vibrational frequencies of p-fluoroanisole in the ground state (S 0) and cation ground state (D 0) are also achieved from DFT calculations.
NASA Astrophysics Data System (ADS)
Yu, Hua-Gen
2002-08-01
A full dimensional variational algorithm to calculate vibrational energies of penta-atomic molecules is presented. The quantum mechanical Hamiltonian of the system for J=0 is derived in a set of orthogonal polyspherical coordinates in the body-fixed frame without any dynamical approximation. The vibrational Hamiltonian has been obtained in an explicitly Hermitian form. Variational calculations are performed in a direct product discrete variable representation basis set. The sine functions are used for the radial coordinates, whereas the Legendre polynomials are employed for the polar angles. For the azimuthal angles, the symmetrically adapted Fourier-Chebyshev basis functions are utilized. The eigenvalue problem is solved by a Lanczos iterative diagonalization algorithm. The preliminary application to methane is given. A comparison with previous results is made.
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.
NASA Astrophysics Data System (ADS)
Leadenham, S.; Erturk, A.
2014-11-01
Over the past few years, nonlinear oscillators have been given growing attention due to their ability to enhance the performance of energy harvesting devices by increasing the frequency bandwidth. Duffing oscillators are a type of nonlinear oscillator characterized by a symmetric hardening or softening cubic restoring force. In order to realize the cubic nonlinearity in a cantilever at reasonable excitation levels, often an external magnetic field or mechanical load is imposed, since the inherent geometric nonlinearity would otherwise require impractically high excitation levels to be pronounced. As an alternative to magnetoelastic structures and other complex forms of symmetric Duffing oscillators, an M-shaped nonlinear bent beam with clamped end conditions is presented and investigated for bandwidth enhancement under base excitation. The proposed M-shaped oscillator made of spring steel is very easy to fabricate as it does not require extra discrete components to assemble, and furthermore, its asymmetric nonlinear behavior can be pronounced yielding broadband behavior under low excitation levels. For a prototype configuration, linear and nonlinear system parameters extracted from experiments are used to develop a lumped-parameter mathematical model. Quadratic damping is included in the model to account for nonlinear dissipative effects. A multi-term harmonic balance solution is obtained to study the effects of higher harmonics and a constant term. A single-term closed-form frequency response equation is also extracted and compared with the multi-term harmonic balance solution. It is observed that the single-term solution overestimates the frequency of upper saddle-node bifurcation point and underestimates the response magnitude in the large response branch. Multi-term solutions can be as accurate as time-domain solutions, with the advantage of significantly reduced computation time. Overall, substantial bandwidth enhancement with increasing base excitation is validated experimentally, analytically, and numerically. As compared to the 3 dB bandwidth of the corresponding linear system with the same linear damping ratio, the M-shaped oscillator offers 3200, 5600, and 8900 percent bandwidth enhancement at the root-mean-square base excitation levels of 0.03g, 0.05g, and 0.07g, respectively. The M-shaped configuration can easily be exploited in piezoelectric and electromagnetic energy harvesting as well as their hybrid combinations due to the existence of both large strain and kinetic energy regions. A demonstrative case study is given for electromagnetic energy harvesting, revealing the importance of higher harmonics and the need for multi-term harmonic balance analysis for predicting the electrical power output accurately.
M. E. Zandler; E. C. Behrman; M. B. Arrasmith; J. R. Myers; T. V. Smith
1996-01-01
We have performed semiempirical molecular orbital calculations, using the Austin Model 1# (AM1) and Parametric Method 3# (PM3) Hamiltonians of the program mopac for the geometric, electronic, and vibrational structure of (ZnO)n (where n = 1–16), spheroids, and (MX)12 analogs, where M = Be, Mg, Zn, Cd, Hg, Pb, Sn, Ge, Si, C when X = O, S and where
S. W. Ong; B. X. B. Lee; H. C. Kang
2011-01-01
We have performed Car-Parrinello molecular dynamics (CPMD) calculations of the hydrogen-bonded NH3-HCl dimer. Our main aim is to establish how ionic-orbital coupling in CPMD affects the vibrational dynamics in hydrogen-bonded systems by characterizing the dependence of the calculated vibrational frequencies upon the orbital mass in the adiabatic limit of Car-Parrinello calculations. We use the example of the NH3-HCl dimer because
S. W. Ong; B. X. B. Lee; H. C. Kang
2011-01-01
We have performed Car-Parrinello molecular dynamics (CPMD) calculations of the hydrogen-bonded NH3–HCl dimer. Our main aim is to establish how ionic-orbital coupling in CPMD affects the vibrational dynamics in hydrogen-bonded systems by characterizing the dependence of the calculated vibrational frequencies upon the orbital mass in the adiabatic limit of Car-Parrinello calculations. We use the example of the NH3–HCl dimer because
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
NASA Astrophysics Data System (ADS)
Kannan, V.; Thirupugalmani, K.; Brahadeeswaran, S.
2013-10-01
Single crystals of N-Succinopyridine (NSP) have been grown from water using solution growth method by isothermal solvent evaporation technique. The solid state Fourier Transform Infrared (FTIR) spectrum of the grown crystal shows a broad absorption extending from 3450 down to 400 cm-1, due to H-bond vibrations and other characteristic vibrations. Fourier Transform Raman (FT-Raman) spectrum of NSP single crystal shows Raman intensities ranging from 3100 to 100 cm-1 due the characteristics vibrations of functional groups present in NSP. The proton and carbon positions of NSP have been described by 1H and 13C NMR spectrum respectively. Ab initio quantum chemical calculations on NSP have been performed by density functional theory (DFT) calculations using B3LYP method with 6-311++G(d,p) basis set. The predicted first hyperpolarizability is found to be 1.29 times greater than that of urea and suggests that the title compound could be an attractive material for nonlinear optical applications. The calculated HOMO-LUMO energies show that charge transfers occur within the molecule and other related molecular properties. Molecular properties such as Mulliken population analysis, thermodynamic functions and perturbation theory energy analysis have also been reported. Electrostatic potential map (ESP) of NSP obtained by electron density isosurface provided the information about the size, shape, charge density distribution and site of chemical reactivity of the title molecule. The molecular stability and bond strength have been investigated through the Natural Bond Orbital (NBO) analysis.
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 ?, polarizability ?, anisotropy of polarizability ??, and molecular first hyperpolarizability ? 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 (?), chemical potential (?), electrophilicity value (?), 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.
Appalakondaiah, S.; Vaitheeswaran, G., E-mail: gvaithee@gmail.com [Advanced Centre of Research in High Energy Materials (ACRHEM), University of Hyderabad, Prof. C. R. Rao Road, Gachibowli, Hyderabad 500 046, Andhra Pradesh (India); Lebègue, S. [Laboratoire de Cristallographie, Résonance Magnétique et Modélisations (CRM2, UMR CNRS 7036), Institut Jean Barriol, Université de Lorraine, BP 239, Boulevard des Aiguillettes, 54506 Vandoeuvre-lès-Nancy (France)] [Laboratoire de Cristallographie, Résonance Magnétique et Modélisations (CRM2, UMR CNRS 7036), Institut Jean Barriol, Université de Lorraine, BP 239, Boulevard des Aiguillettes, 54506 Vandoeuvre-lès-Nancy (France)
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.
NASA Astrophysics Data System (ADS)
Kisiel, A.; Brown, D. A.
2009-12-01
We present the formalism for calculating the femtoscopic correlation function directly in spherical harmonics. The numerator and denominator are stored as a set of one-dimensional histograms representing the spherical harmonic decompositions of each. We present the formalism to calculate the correlation function from them directly, without going to any three-dimensional histogram. We discuss the practical implementation of the method and we provide an example of its use. We also discuss the stability of the method in the presence of angular holes in the underlying data (e.g., from experimental acceptance).
Elastic and vibrational properties of Mg2Si1-xSnx alloy from first principles calculations
NASA Astrophysics Data System (ADS)
Peng, H.; Wang, C. L.; Li, J. C.; Wang, H. C.; Sun, Y.; Zheng, Q.
2012-05-01
The structural, elastic and phonon properties of Mg2Si1-xSnx alloy are investigated by performing density functional theory and density functional perturbation theory calculations. The calculated lattice parameter increases with the increase of Sn content obeying Vegard's Law that is in good agreement with available experimental data. Shear modulus, Young's modulus and sound velocities are determined from the obtained elastic constants. Phonon dispersion curves show a pronounced softening with increasing of Sn content. The softening mechanism has been discussed based upon the element mass and bond strength. Besides, phonon contribution to the Helmholtz free energy, the entropy and the constant-volume heat capacity are calculated within the harmonic approximation based on the calculated phonon density of states. Results show Mg2Si1-xSnx is thermodynamically more stable with higher Sn content.
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.
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
High Harmonic Electron-Bernstein Wave Mode Conversion Calculations for NSTX
M. D. Carter; E. F. Jaeger; G. Taylor
2004-01-01
Electron Bernstein waves (EBW) can locally heat electrons in over-dense plasmas. Ray tracing can be used to follow EBW inside the mode-conversion layer (MCL), but it breaks down where the launched waves pass through the MCL. Full wave calculations can accurately determine the power that is mode-converted to EBW for ray initialization, and the OPTIPOL code finds the optimum polarization
for collision energies between 0.1 and 15 000 cm-1 based on the three-dimensional potential energy surface, 094308 (2005); 10.1063/1.2032948 Vibrationally inelastic collisions in H + + CO system: Comparing quantumQuantum scattering calculations for ro-vibrational de-excitation of CO by hydrogen atoms Lei Song
NASA Astrophysics Data System (ADS)
Ramalingam, S.; Jayaprakash, A.; Mohan, S.; Karabacak, M.
2011-11-01
FT-IR and FT-Raman (4000-100 cm -1) spectral measurements of 3-methyl-1,2-butadiene (3M12B) have been attempted in the present work. Ab-initio HF and DFT (LSDA/B3LYP/B3PW91) calculations have been performed giving energies, optimized structures, harmonic vibrational frequencies, IR intensities and Raman activities. Complete vibrational assignments on the observed spectra are made with vibrational frequencies obtained by HF and DFT (LSDA/B3LYP/B3PW91) at 6-31G(d,p) and 6-311G(d,p) basis sets. The results of the calculations have been used to simulate IR and Raman spectra for the molecule that showed good agreement with the observed spectra. The potential energy distribution (PED) corresponding to each of the observed frequencies are calculated which confirms the reliability and precision of the assignment and analysis of the vibrational fundamentals modes. The oscillation of vibrational frequencies of butadiene due to the couple of methyl group is also discussed. A study on the electronic properties such as HOMO and LUMO energies, were performed by time-dependent DFT (TD-DFT) approach. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. The thermodynamic properties of the title compound at different temperatures reveal the correlations between standard heat capacities ( C) standard entropies ( S), and standard enthalpy changes ( H).
Ramalingam, S; Jayaprakash, A; Mohan, S; Karabacak, M
2011-11-01
FT-IR and FT-Raman (4000-100 cm(-1)) spectral measurements of 3-methyl-1,2-butadiene (3M12B) have been attempted in the present work. Ab-initio HF and DFT (LSDA/B3LYP/B3PW91) calculations have been performed giving energies, optimized structures, harmonic vibrational frequencies, IR intensities and Raman activities. Complete vibrational assignments on the observed spectra are made with vibrational frequencies obtained by HF and DFT (LSDA/B3LYP/B3PW91) at 6-31G(d,p) and 6-311G(d,p) basis sets. The results of the calculations have been used to simulate IR and Raman spectra for the molecule that showed good agreement with the observed spectra. The potential energy distribution (PED) corresponding to each of the observed frequencies are calculated which confirms the reliability and precision of the assignment and analysis of the vibrational fundamentals modes. The oscillation of vibrational frequencies of butadiene due to the couple of methyl group is also discussed. A study on the electronic properties such as HOMO and LUMO energies, were performed by time-dependent DFT (TD-DFT) approach. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. The thermodynamic properties of the title compound at different temperatures reveal the correlations between standard heat capacities (C) standard entropies (S), and standard enthalpy changes (H). PMID:21813316
NASA Astrophysics Data System (ADS)
Ferber, Steven Dwight
2005-11-01
The Vibrational Circular Dichroism (VCD) of Nucleic Acids is a sensitive function of their conformation. DeVoe's classically derived polarizability theory allows the calculation of polymer absorption and circular dichroism spectra in any frequency range. Following the approach of Tinoco and Cech as modified by Moore and Self, calculations were done in the infrared (IR) region with theoretically derived monomer input parameters. Presented herein are calculated absorption and CD spectra for nucleic acid oligomers and polymers. These calculations improve upon earlier attempts, which utilized frequencies, intensities and normal modes from empirical analysis of the nitrogenous base of the monomers. These more complete input polarizability parameters include all contributions to specific vibrational normal modes for the entire nucleotide structure. They are derived from density functional theory (DFT) vibrational analysis on quasi-nucleotide monomers using the GAUSSIAN '98/'03 program. The normal modes are "integrated" for the first time into single virtual (DeVoe) oscillators by incorporating "fixed partial charges" in the manner of Schellman. The results include the complete set of monomer normal modes. All of these modes may be analyzed, in a manner similar to those demonstrated here (for the 1500-1800 cm-1 region). A model is utilized for the polymer/oligomer monomers which maintains the actual electrostatic charge on the adjacent protonated phosphoryl groups (hydrogen phosphate, a mono-anion). This deters the optimization from "collapsing" into a hydrogen-bonded "ball" and thereby maintains the extended (polymer-like) conformation. As well, the precise C2 "endo" conformation of the sugar ring is maintained in the DNA monomers. The analogous C3 "endo" conformation is also maintained for the RNA monomers, which are constrained by massive "anchors" at the phosphates. The complete IR absorbance spectra (0-4,000 cm-1) are calculated directly in Gaussian. Calculated VCD and Absorbance Spectra for the eight standard Ribonucleic and Deoxy-ribonucleic acid homo-polymers in the nitrogenous base absorbing region 1550-1750 cm-1 are presented. These spectra match measured spectra at least as well as spectra calculated from empirical parameters. These results demonstrate that the purely theoretical calculation, an example given herein, should serve to provide more transferable, universal parameters for the polarizability treatment of the optical properties of oligomers and polymers.
Temperature-dependent vibrational spectroscopic study and DFT calculations of the sorbic acid
NASA Astrophysics Data System (ADS)
Saraiva, G. D.; Nogueira, C. E. S.; Freire, P. T. C.; de Sousa, F. F.; da Silva, J. H.; Teixeira, A. M. R.; Mendes Filho, J.
2015-02-01
This work reports a temperature-dependent vibrational spectroscopic study of the sorbic acid (C6H8O2), as well as the mode assignment at ambient conditions, based on the density functional theory. Temperature-dependent vibrational properties have been performed in polycrystalline sorbic acid through both Raman and infrared spectroscopy in the 20-300 K and 80-300 K temperature ranges, respectively. These studies present the occurrence of some modifications in the Raman spectra that could be interpreted as a low temperature phase transition undergone by sorbic acid from the monoclinic phase to an unknown phase with conformational change of the molecules in the unit cell.
Thore, A. Dahlqvist, M. E-mail: bjoal@ifm.liu.se Alling, B. E-mail: bjoal@ifm.liu.se Rosén, J. E-mail: bjoal@ifm.liu.se
2014-09-14
In this paper, we report the by first-principles predicted properties of the recently discovered magnetic MAX phase Mn?GaC. The electronic band structure and vibrational dispersion relation, as well as the electronic and vibrational density of states, have been calculated. The band structure close to the Fermi level indicates anisotropy with respect to electrical conductivity, while the distribution of the electronic and vibrational states for both Mn and Ga depend on the chosen relative orientation of the Mn spins across the Ga sheets in the Mn–Ga–Mn trilayers. In addition, the elastic properties have been calculated, and from the five elastic constants, the Voigt bulk modulus is determined to be 157?GPa, the Voigt shear modulus 93?GPa, and the Young's modulus 233?GPa. Furthermore, Mn?GaC is found relatively elastically isotropic, with a compression anisotropy factor of 0.97, and shear anisotropy factors of 0.9 and 1, respectively. The Poisson's ratio is 0.25. Evaluated elastic properties are compared to theoretical and experimental results for M?AC phases where M?=?Ti, V, Cr, Zr, Nb, Ta, and A?=?Al, S, Ge, In, Sn.
NASA Astrophysics Data System (ADS)
Carter, Stuart; Meyer, Wilfried
1990-12-01
A full variational procedure is presented which is particularly suited to the calculation of vibrational (J=0) energy levels of triatomic potentials with large amplitude motions and also allows for high permutational symmetries. Starting from simple basis functions reflecting the structure of the kinetic energy operator, an optimized basis set is derived by a step-wise contraction scheme. The method is applied to H+3 and Na+3 (D3h) and to model potentials for H2O+ (C2v) and HLiH- (D?h). The results for H+3 are shown to be superior to all previous calculations, in particular for those energy levels that lie above 20 000 cm-1. A new ab initio potential is presented for Na+3, for which converged energy levels are calculated up to 3500 cm-1. For H2O+ and HLiH-, the calculated energy levels agree with those obtained from a variational procedure in internal valence coordinates.
Mielke, Steven L; Truhlar, Donald G
2015-01-28
We present an improved version of our "path-by-path" enhanced same path extrapolation scheme for Feynman path integral (FPI) calculations that permits rapid convergence with discretization errors ranging from O(P(-6)) to O(P(-12)), where P is the number of path discretization points. We also present two extensions of our importance sampling and stratified sampling schemes for calculating vibrational-rotational partition functions by the FPI method. The first is the use of importance functions for dihedral angles between sets of generalized Jacobi coordinate vectors. The second is an extension of our stratification scheme to allow some strata to be defined based only on coordinate information while other strata are defined based on both the geometry and the energy of the centroid of the Feynman path. These enhanced methods are applied to calculate converged partition functions by FPI methods, and these results are compared to ones obtained earlier by vibrational configuration interaction (VCI) calculations, both calculations being for the Jordan-Gilbert potential energy surface. The earlier VCI calculations are found to agree well (within ?1.5%) with the new benchmarks. The FPI partition functions presented here are estimated to be converged to within a 2? statistical uncertainty of between 0.04% and 0.07% for the given potential energy surface for temperatures in the range 300-3000 K and are the most accurately converged partition functions for a given potential energy surface for any molecule with five or more atoms. We also tabulate free energies, enthalpies, entropies, and heat capacities. PMID:25637967
NASA Astrophysics Data System (ADS)
Mielke, Steven L.; Truhlar, Donald G.
2015-01-01
We present an improved version of our "path-by-path" enhanced same path extrapolation scheme for Feynman path integral (FPI) calculations that permits rapid convergence with discretization errors ranging from O(P-6) to O(P-12), where P is the number of path discretization points. We also present two extensions of our importance sampling and stratified sampling schemes for calculating vibrational-rotational partition functions by the FPI method. The first is the use of importance functions for dihedral angles between sets of generalized Jacobi coordinate vectors. The second is an extension of our stratification scheme to allow some strata to be defined based only on coordinate information while other strata are defined based on both the geometry and the energy of the centroid of the Feynman path. These enhanced methods are applied to calculate converged partition functions by FPI methods, and these results are compared to ones obtained earlier by vibrational configuration interaction (VCI) calculations, both calculations being for the Jordan-Gilbert potential energy surface. The earlier VCI calculations are found to agree well (within ˜1.5%) with the new benchmarks. The FPI partition functions presented here are estimated to be converged to within a 2? statistical uncertainty of between 0.04% and 0.07% for the given potential energy surface for temperatures in the range 300-3000 K and are the most accurately converged partition functions for a given potential energy surface for any molecule with five or more atoms. We also tabulate free energies, enthalpies, entropies, and heat capacities.
NASA Astrophysics Data System (ADS)
Tremblay, Jean Christophe
2013-06-01
A model for treating excitation and relaxation of adsorbates at metallic surfaces induced by non-adiabatic coupling is developed. The derivation is based on the concept of resonant electron transfer, where the adsorbate serves as a molecular bridge for the inelastic transition between an electron source and a sink. In this picture, energy relaxation and scanning tunneling microscopy (STM) at metallic surfaces are treated on an equal footing as a quasi-thermal process. The model goes beyond the local harmonic approximation and allows for an unbiased description of floppy systems with multiple potential wells. Further, the limitation of the product ansatz for the vibronic wave function to include the position-dependence of the non-adiabatic couplings is avoided by explicitly enforcing detailed balance. The theory is applied to the excitation of hydrogen on palladium, which has multiple local potential minima connected by low energy barriers. The main aspects investigated are the lifetimes of adsorbate vibrations in different adsorption sites, as well as the dependence of the excitation, response, and transfer rates on an applied potential bias. The excitation and relaxation simulations reveal intricate population dynamics that depart significantly from the simplistic tunneling model in a truncated harmonic potential. In particular, the population decay from an initially occupied local minimum induced by the contact with an STM tip is found to be better described by a double exponential. The two rates are interpreted as a response to the system perturbation and a transfer rate following the perturbation. The transfer rate is found to obey a power law, as was the case in previous experimental and theoretical work.
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
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.
Kim, B.T.; Kwon, B.I.; Park, S.C.
1999-09-01
The harmonics in electromagnetic force are source of the mechanical vibration and the audible noise in an asynchronous traction motor. This paper describes an approach to reduce the force harmonics by changing the rotor slot number. Both the radial and tangential forces acting on the stator teeth are calculated by Maxwell stress tenser and their time harmonics are examined by the discrete Fourier decomposition. As a result, the optimal slot number of the rotor to reduce or eliminate the specific force harmonics is determined.
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.
High-order-harmonic generation from H2+ molecular ions near plasmon-enhanced laser fields
NASA Astrophysics Data System (ADS)
Yavuz, I.; Tikman, Y.; Altun, Z.
2015-08-01
Simulations of plasmon-enhanced high-order-harmonic generation are performed for a H2+ molecular cation near the metallic nanostructures. We employ the numerical solution of the time-dependent Schrödinger equation in reduced coordinates. We assume that the main axis of H2+ is aligned perfectly with the polarization direction of the plasmon-enhanced field. We perform systematic calculations on plasmon-enhanced harmonic generation based on an infinite-mass approximation, i.e., pausing nuclear vibrations. Our simulations show that molecular high-order-harmonic generation from plasmon-enhanced laser fields is possible. We observe the dispersion of a plateau of harmonics when the laser field is plasmon enhanced. We find that the maximum kinetic energy of the returning electron follows 4 Up . We also find that when nuclear vibrations are enabled, the efficiency of the harmonics is greatly enhanced relative to that of static nuclei. However, the maximum kinetic energy 4 Up is largely maintained.
Petrenko, T.; George, S.D.; Aliaga-Alcalde, N.; Bill, E.; Mienert, B.; Xiao, Y.; Guo, Y.; Sturhahn, W.; Cramer, S.P.; Wieghardt, K.; Neese, F.; /Bonn U., LTC /SLAC, SSRL /Max Planck Inst., Mulheim /UC, Davis /Argonne /LBL, Berkeley
2007-10-19
The characterization of high-valent iron species is of interest due to their relevance to biological reaction mechanisms. Recently, we have synthesized and characterized an [Fe(V)-nitrido-cyclam-acetato]+ complex, which has been characterized by M{umlt o}ssbauer, magnetic susceptibility data, and XAS spectroscopies combined with DFT calculations. The results of this study indicated that the [Fe(V)-nitrido-cyclam-acetato]+ complex is an unusual d3 system with a nearly orbitally degenerate S = 1/2 ground state. Although the calculations predicted fairly different Fe-N stretching frequencies for the S = 1/2 and the competing S = 3/2 ground states, a direct experimental determination of this important fingerprint quantity was missing. Here we apply synchrotron-based nuclear resonance vibrational scattering (NRVS) to characterize the Fe-N stretching frequency of an Fe(V)-nitrido complex and its Fe(III)-azide precursor. The NRVS data show a new isolated band at 864 cm-1 in the Fe(V)-nitrido complex that is absent in the precursor. The NRVS spectra are fit and simulated using a DFT approach, and the new feature is unambiguously assigned to a Fe(V)-N stretch. The calculated Fe-N stretching frequency is too high by {approx}75 cm-1. Anharmonic contributions to the Fe-N stretching frequency have been evaluated and have been found to be small (-5.5 cm-1). The NRVS data provided a unique opportunity to obtain this vibrational information, which had eluded characterization by more traditional vibrational spectroscopies.
Petrenko, T.; George, S. D.; Aliaga-Alcalde, N.; Bill, E.; Mienert, B.; Xiao, Y.; Guo, Y.; Sturhahn, W.; Cramer, S.P.; Wieghardt, K.; Neese, F.; X-Ray Science Division; Institut of Physikalische und Theoretische Chemie; SSRL; Standford Univ.; Max-Planck Institut fur Bioanogranische Chemie; Univ. of California at Davis; LBNL
2007-01-01
The characterization of high-valent iron species is of interest due to their relevance to biological reaction mechanisms. Recently, we have synthesized and characterized an [Fe(V)-nitrido-cyclam-acetato]{sup +} complex, which has been characterized by M{umlt o}ssbauer, magnetic susceptibility data, and XAS spectroscopies combined with DFT calculations . The results of this study indicated that the [Fe(V)-nitrido-cyclam-acetato]+ complex is an unusual d{sup 3} system with a nearly orbitally degenerate S = 1/2 ground state. Although the calculations predicted fairly different Fe-N stretching frequencies for the S = 1/2 and the competing S = 3/2 ground states, a direct experimental determination of this important fingerprint quantity was missing. Here we apply synchrotron-based nuclear resonance vibrational scattering (NRVS) to characterize the Fe-N stretching frequency of an Fe(V)-nitrido complex and its Fe(III)-azide precursor. The NRVS data show a new isolated band at 864 cm{sup -1} in the Fe(V)-nitrido complex that is absent in the precursor. The NRVS spectra are fit and simulated using a DFT approach, and the new feature is unambiguously assigned to a Fe(V)-N stretch. The calculated Fe-N stretching frequency is too high by {approx}75 cm{sup -1}. Anharmonic contributions to the Fe-N stretching frequency have been evaluated and have been found to be small (-5.5 cm{sup -1}). The NRVS data provided a unique opportunity to obtain this vibrational information, which had eluded characterization by more traditional vibrational spectroscopies.
Calculation of rotational-vibrational preionization in H2 by multichannel quantum defect theory
NASA Astrophysics Data System (ADS)
Jungen, Ch.; Dill, Dan
1980-10-01
Multichannel quantum defect theory is adapted to treat simultaneous rotational and vibrational preionization in H2. The strongly preionized spectrum between the N+=0 and N+=2 rotational thresholds of photoionization of H2X1?g+(J?=0, v?=0) to produce H2+X2?g+(N+, v+=0) is computed as example and good agreement is obtained with the photoionization data of Dehmer and Chupka.
Vibrationally excited states of HC 5N: millimeter-wave spectroscopy and coupled cluster calculations
C. Degli Esposti; L. Bizzocchi; P. Botschwina; K. M. T. Yamada; G. Winnewisser; S. Thorwirth; P. Förster
2005-01-01
The rotational spectrum of HC5N has been investigated in the millimeter-wave region, from 60 to 290GHz, for 15 vibrationally excited states which lie approximately between 500 and 860cm?1, namely (v6v7v8v9v10v11)=(000005), (000006), (000007), (000008), (000020), (000030), (001000), (010000), (100000), (000021), (000101), (001001), (010001), (000110), and (001010). Gas-phase copyrolysis of pyridine and phosphorus trichloride or, alternatively, a dc discharge in a gaseous
Yu, Hua-Gen
2015-01-28
We report a rigorous full dimensional quantum dynamics algorithm, the multi-layer Lanczos method, for computing vibrational energies and dipole transition intensities of polyatomic molecules without any dynamics approximation. The multi-layer Lanczos method is developed by using a few advanced techniques including the guided spectral transform Lanczos method, multi-layer Lanczos iteration approach, recursive residue generation method, and dipole-wavefunction contraction. The quantum molecular Hamiltonian at the total angular momentum J = 0 is represented in a set of orthogonal polyspherical coordinates so that the large amplitude motions of vibrations are naturally described. In particular, the algorithm is general and problem-independent. An applicationmore »is illustrated by calculating the infrared vibrational dipole transition spectrum of CH? based on the ab initio T8 potential energy surface of Schwenke and Partridge and the low-order truncated ab initio dipole moment surfaces of Yurchenko and co-workers. A comparison with experiments is made. The algorithm is also applicable for Raman polarizability active spectra.« less
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 [Spectrochimica Acta, Part A 57, 887 (2001)] and the low-order truncated ab initio dipole moment surfaces of Yurchenko et al. [J. Mol. Spectrosc. 291, 69 (2013)]. A comparison with experiments is made. The algorithm is also applicable for Raman polarizability active spectra. PMID:25637968
Singh, Swapnil; Singh, Harshita; Srivastava, Anubha; Tandon, Poonam; Sinha, Kirti; Bharti, Purnima; Kumar, Sudhir; Kumar, Padam; Maurya, Rakesh
2014-11-11
In the present work, a detailed conformational study of cladrin (3-(3,4-dimethoxy phenyl)-7-hydroxychromen-4-one) has been done by using spectroscopic techniques (FT-IR/FT-Raman/UV-Vis/NMR) and quantum chemical calculations. The optimized geometry, wavenumber and intensity of the vibrational bands of the cladrin in ground state were calculated by density functional theory (DFT) employing 6-311++G(d,p) basis sets. The study has been focused on the two most stable conformers that are selected after the full geometry optimization of the molecule. A detailed assignment of the FT-IR and FT-Raman spectra has been done for both the conformers along with potential energy distribution for each vibrational mode. The observed and scaled wavenumber of most of the bands has been found to be in good agreement. The UV-Vis spectrum has been recorded and compared with calculated spectrum. In addition, 1H and 13C nuclear magnetic resonance spectra have been also recorded and compared with the calculated data that shows the inter or intramolecular hydrogen bonding. The electronic properties such as HOMO-LUMO energies were calculated by using time-dependent density functional theory. Molecular electrostatic potential has been plotted to elucidate the reactive part of the molecule. Natural bond orbital analysis was performed to investigate the molecular stability. Non linear optical property of the molecule have been studied by calculating the electric dipole moment (?) and the first hyperpolarizability (?) that results in the nonlinearity of the molecule. PMID:24892542
Elleuch, S; Feki, H; Abid, Y
2007-11-01
The conformational stability and vibrational modes of the N-diethylendiamine organic cation (N-DD(2+)) were studied by experimental (Raman) spectroscopy combined with theoretical calculations. Various ab initio theories were used: Hartree-Fock (HF) theory, Möller-Plesset second-order perturbation (MP2) theory and density functional theory (DFT). Three stable conformers of N-DD(2+), trans-trans, gauche-gauche and gauche-trans were calculated. A comparison between the computed structural parameters of the conformers at both levels of theory and the X-ray data was made. It is demonstrated that the N-DD(2+) cation adopts more probably the gauche-gauche conformation at room temperature. In order to make a more detailed interpretation of the low temperature phase transition of N-DDHP, the Raman spectra of N-DDHP were recorded at room and low temperature in the 200-3400 cm(-1) region. The vibrational frequencies of the different conformers of N-DD(2+) were also calculated using the DFT/B3LYP (6-31G(d)) level of theory. By comparison between the experimental and theoretical results, the conformational dynamic of the N-DD(2+) organic cation was confirmed. It is shown that the N-DD(2+) cation configuration changes from gauche-gauche conformer to gauche-trans conformer when decreasing the temperature. PMID:17317286
NASA Astrophysics Data System (ADS)
Lebedieva, Tetiana; Gubanov, Victor; Dovbeshko, Galyna; Pidhirnyi, Denys
2015-07-01
Different notations of graphene irreducible representations and optical modes could be found in the literature. The goals of this paper are to identify the correspondence between available notations, to calculate the optical modes of graphene in different points of the Brillouin zone, and to compare them with experimental data obtained by Raman and coherent anti-Stokes Raman scattering (CARS) spectroscopy. The mechanism of the resonance enhancement of vibration modes of the molecules adsorbed on graphene in CARS experiments is proposed. The possibility of appearance of the discrete breathing modes is discussed.
NASA Astrophysics Data System (ADS)
Xie, Congwei; Zeng, Qingfeng; Dong, Dong; Gao, Shuang; Cai, Yongqing; Oganov, Artem R.
2014-05-01
First-principles calculations have been conducted to study the structural, dielectric, and vibrational properties of ferroelectric and paraelectric BaAl2O4. High-frequency and static dielectric constants, and phonon frequencies at the Brillouin zone center are reported. Both BaAl2O4 polymorphs are promising infrared-transparent materials due to their low electronic dielectric constants. The ferroelectric and paraelectric BaAl2O4 have much smaller permittivity compared to the classical ferroelectric materials. From an atomic nanostructure standpoint, the abnormally low permittivity of BaAl2O4 polymorphs is mainly related to low coordination numbers of Ba (9) and Al (4).
NASA Astrophysics Data System (ADS)
Ucun, Fatih; Sa?lam, Adnan; Güçlü, Vesile
2007-06-01
The molecular structures, vibrational frequencies and corresponding vibrational assignments of xanthine and its methyl derivatives (caffeine and theobromine) have been calculated using ab initio Hartree-Fock (HF) and density functional theory (B3LYP) methods with 6-31G(d, p) basis set level. The calculations were utilized to the CS symmetries of the molecules. The obtained vibrational frequencies and optimised geometric parameters (bond lengths and bond angles) were seen to be well agreement with the experimental data. The used scale factors which have been obtained the ratio of the frequency values of the strongest peaks in the calculated and experimental spectra seem to cause the gained vibrations well corresponding to the experimental ones. Theoretical infrared intensities and Raman activities are also reported.
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.
NASA Astrophysics Data System (ADS)
Kavitha, E.; Sundaraganesan, N.; Sebastian, S.; Kurt, M.
2010-10-01
In this work, we report anharmonic vibrational frequencies, molecular structure, NBO and HOMO, LUMO analysis of naphthalene acetic acid (NAA). The optimized geometric bond lengths and bond angles obtained by computation show good agreement with experimental X-ray data. The computed dimer parameters also show good agreement with experimental data. Anharmonic frequencies of NAA were determined and analyzed by DFT level of theory utilizing 6-311+G(d,p) basis set. Good agreement between the calculated and experimental spectra was obtained. Stability of the molecule arising from hyperconjugative interactions and charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The results show that charge in electron density (ED) in the ?* and ?* antibonding orbitals and E2 energies. This confirms the occurrence of ICT (Intermolecular Charge Transfer) within the molecule. The calculated HOMO and LUMO energies also show that charge transfer occurs within the molecule.
NASA Astrophysics Data System (ADS)
Tuyterev, Vladimir
2010-06-01
It has become increasingly common to use accurate potential energy surfaces and dipole moment surfaces for predictions and assignment of high-resolution vibration-rotation molecular spectra. These surfaces are obtained either from high-level ab initio electronic structure calculations or from a direct fit to experimental spectroscopic data. The talk will continue a discussion of some recent advances in the domain of the "potentiology". The role of basis extrapolations, of the Born-Oppenheimer breakdown corrections , in particular for very highly excited vibration states will be considered. As effective polyad Hamiltonians and band transition moment operators are still widely used for data reductions in high-resolutions molecular spectroscopy, experimental spectra analyses invoke a need for accurate methods of building physically meaningful effective models from ab initio surfaces. This involves predictions for various spectroscopic constants, including vibration dependence of rotational and centrifugal distortion and resonance coupling parameters. Topics planned for discussion include: high-order Contact Transformations of rovibrational Hamiltonians and of the dipole moment for small polyatomic molecules; convergence issues; the role of the anharmonicity in a potential energy function and of resonance couplings on the normal mode mixing and on vib-rot assignments with application to high energy vibration levels of SO_2 and to ozone near the dissociation limit; intensity anomalies in H_2S / HDS / D_2S spectra, relation of the shape of ab initio dipole moment surfaces with a "mystery" of nearly vanishing symmetry allowed bands. A full account for symmetry properties requires efficient theoretical tools for transformations of molecular Hamiltonians such as irreducible tensor formalism, applications using phosphine and methane potentials will be discussed. Both potential functions and effective polyad Hamiltonians allow studying changes in quasi-classical vibration periodic orbits and in of the nodal structure of wavefunctions with mass variations. An investigation of the consequences of symmetry breaking by isotopic substitution, in the classical and quantum dynamics is particularly instructive. This helps understanding the fingerprints of bifurcations effects in the quantum states of isotopologues and their assignment. The work of our research team with collaborators in these areas will be described.
Singh, Harshita; Singh, Swapnil; Srivastava, Anubha; Tandon, Poonam; Bharti, Purnima; Kumar, Sudhir; Maurya, Rakesh
2014-01-01
Daidzein (C15H10O4) is a type of isoflavone. It was isolated from Butea monosperma that belongs to the Fabaceae family. Soybeans and soy products are the abundant source of daidzein. It is the subject of investigation for many reasons, as it has got wide applications, such as anti-tumor, anti-estrogen, weak pro-estrogen and anti-cancer activities. In the present study, a complete vibrational assignment is provided for the observed IR and Raman spectra of daidzein. Electronic properties have been analyzed using TD-DFT method for both gaseous and solvent phase. The optimized geometry, total energy, potential energy surface and vibrational wavenumbers of daidzein have been determined using density functional theory (DFT/B3LYP) method with 6-311++G(d,p) basis set and a good correlation was found between observed and calculated values. The double well potential energy curve of the molecule about three bonds, has been plotted, as obtained from DFT/6-31G basis. The HOMO-LUMO energy gap of possible conformers has been calculated for comparing their chemical activity. Global reactivity descriptors have been calculated for predicting the chemical reactivity and the stability of chemical systems. Electrostatic potential surface has been plotted for predicting the structure activity relationship. NBO analysis has also been performed to study the stability of the molecule. NLO study reveals the nonlinear properties of the molecule. 1H and 13C NMR spectra have also been studied. Finally, the calculated results were used to simulate infrared and Raman spectra of the title compound which showed a good agreement with the observed spectra. PMID:24211623
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.
Aragó, Juan; Ponce Ortiz, Rocío; Nieto-Ortega, Belén; Hernández, Víctor; Casado, Juan; Facchetti, Antonio; Marks, Tobin J; Viruela, Pedro M; Ortí, Enrique; López Navarrete, Juan T
2012-01-16
This work investigates the evolution of the molecular, vibrational, and optical properties within a family of carbonyl-functionalized quaterthiophenes: 5,5'''-diheptanoyl-2,2':5',2'':5'',2'''-quaterthiophene (1), 5,5'''-diperfluorohexylcarbonyl-2,2':5',2'':5'',2'''-quaterthiophene (2), and 2,7-[bis(5-perfluorohexylcarbonylthien-2-yl)]-4H-cyclopenta[2,1-b:3,4-b']-dithiophene-4-one (3). The analysis is performed by Raman and UV/Vis absorption/excitation/fluorescence spectroscopy in combination with density functional calculations. Theoretical calculations show that substitution with carbonyl groups and perfluorohexyl chains induces progressive quinoidization of the ?-conjugated backbone in comparison to the carbonyl-free compound 5,5'''-dimethyl-2,2':5',2'':5'',2'''-quaterthiophene (DM-4T) used as reference. Raman spectra are dominated by a strong Raman line which mainly corresponds to a combination of C-C/C=C stretching vibrations spreading over the whole thiophene core. This band undergoes a remarkable downshift as a consequence of the structural changes induced by the electron-withdrawing groups on the ?-conjugated backbone. The band splitting on incorporation of a central carbonyl bridge evidences the formation of two structural domains in the molecule. The excitation and fluorescence spectra recorded at low temperature show well-resolved vibronic structures associated with the most intense collective C-C/C=C stretching mode. Optical absorption and fluorescence bands exhibit remarkable bathochromic dispersion on carbonyl functionalization, indicative of extension of ? conjugation. TDDFT calculations enable a detailed description of the trends observed in the absorption spectra. Resonance Raman spectra reflect the structural changes predicted for the S(0)?S(1) electronic transition and evidence the cross-conjugated character that the central carbonyl group confers on 3. PMID:22135109
NASA Astrophysics Data System (ADS)
Li, Bin; Bian, Wensheng
2008-07-01
Full-dimensional quantum calculations of vibrational states of C2H2 and C2D2 are performed in the high-energy region (above 20400cm-1 relative to the acetylene minimum). The theoretical scheme is a combination of several methods. To exploit the full parity and permutation symmetry, the CC-HH diatom-diatom Jacobi coordinates are chosen; phase space optimization in combination with physical considerations is used to obtain an efficient radial discrete variable representation, whereas a basis contraction scheme is applied for angular coordinates. The preconditioned inexact spectral transform method combined with an efficient preconditioner is employed to compute eigenstates within a desired spectral window. The computation is efficient. More definite assignments on vinylidene states than previous studies are acquired using the normal mode projection; in particular, a consistent analysis of the ?1 (symmetric CH stretch) state is provided. The computed vinylidene vibrational energy levels are in general good agreement with experiment, and several vinylidene states are reported for the first time.
Sun, Shou-Tian; Jiang, Ling; Liu, J W; Heine, Nadja; Yacovitch, Tara I; Wende, Torsten; Asmis, Knut R; Neumark, Daniel M; Liu, Zhi-Feng
2015-09-30
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[double bond, length as m-dash]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. PMID:26105043
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
Vorob`ev, Yu.S.; Kanilo, S.P.; Shepel, A.I.; Sapelkina, Z.V. [Institute of Problems of Machine Building, Kharkov (Russian Federation)
1994-09-01
We examine the application of the static condensation method in reducing the dimension of the resolving equations in calculating the natural frequencies and modes of turbine blades of complex geometric configuration on the basis of three-dimensional finite element models. We show the influence of the number of active nodes on the calculation accuracy and time for examples of the solution of test and real problems.
NASA Astrophysics Data System (ADS)
Titov, S. V.; Tovbin, Yu. K.
2014-12-01
Four main functions of a Lennard-Jones defect argon crystal with an FCC lattice are considered in the context of the lattice gas model: Helmholtz free energy, entropy, internal energy, and heat capacity at a constant volume (allowing for normal vibrations of a solid). Properties of the defect crystal are calculated from the distribution function of the frequencies of an ideal crystal, and corrections to it that reflect local atomic vibrations around vacancies, in the context of the Lifshits linear approximation according to vacancy density. To find the free energy of a defect-free ideal crystal, frequencies of normal vibrations of the crystal are calculated with allowance for the interactions of the four nearest neighbors. The nonlocality of the chemical potentials of the atoms of a solid is discussed, and the influence of contributions from various segments of the vibrational spectrum to the values of thermodynamic functions is investigated. It is shown that ignoring the acoustic or antiphase segments of the spectrum when calculating the free energy leads to increasing of its deviation from the one calculated using the full vibrational spectrum with an increase in temperature. It is concluded that the nonequilibrium state of the defect crystal can lead to negative values of heat capacity at a constant volume.
NASA Astrophysics Data System (ADS)
Wu, Di
2010-12-01
Free-energy perturbation calculation is frequently used to calculate free-energy differences because it is easy to implement and the computation is fast. However, the calculation is subject to large inaccuracies in some circumstances due to the insufficient sampling of the relevant tails of the energy-difference distributions. Here we expand this knowledge of insufficient sampling into a two-dimensional (2D) energy space using a model of harmonic oscillators. We show analytically the relation between the energies of the sampling system and those of the desired target energy spaces, which provide the basis to understand the difficulties in free-energy perturbation calculations. We clarify the reasons of the inaccurate calculation in the different harmonic cases that stem from the spatial separations of the reference and the target energy pairs located in the two-dimensional energy space. The potential-energy space introduced into this 2D energy-space model provides additional clues to improve the sampling efficiency. Based on this understanding, we propose two ways to calculate the free-energy differences using the two schemes of the distribution method. We show that the distribution method implemented in the appropriate energy space—the energy-difference space and the potential-energy space, respectively—can improve the calculation of free energies in different circumstances. This analysis implies that the sampling can be improved if it is directed toward the appropriate region in the potential-energy space, which is easily implemented in various types of free-energy calculations. To test this, we calculate the free-energy surface of alanine dipeptide in gas phase and in aqueous phase, respectively. We demonstrate that the free-energy surface calculation is improved when the biased sampling of the potential energy is integrated into the sampling scheme.
Lee, Christopher M; Mohamed, Naseer M A; Watts, Heath D; Kubicki, James D; Kim, Seong H
2013-06-01
Sum-frequency-generation (SFG) vibration spectroscopy selectively detects noncentrosymmetric vibrational modes in crystalline cellulose inside intact lignocellulose. However, SFG peak assignment in biomass samples is challenging due to the complexity of the SFG processes and the lack of reference SFG spectra from the two crystal forms synthesized in nature, cellulose I? and I?. This paper compares SFG spectra of laterally aligned cellulose I? and I? crystals with vibration frequencies calculated from density functional theory with dispersion corrections (DFT-D2). Two possible hydrogen-bond networks A and B ( Nishiyama et al. Biomacromolecules 2008 , 9 , 3133 ) were investigated for both polymorphs. From DFT-D2 calculations the energetically favorable structures for cellulose I? and I? had CH2OH groups in tg conformations and network A hydrogen bonding. The calculated frequencies of C-H stretch modes agreed reasonably well with the peak positions observed with SFG and were localized vibrations; thus, peak assignments to specific alkyl groups were proposed. DFT-D2 calculations underestimated the distances between hydrogen-bonded oxygen atoms compared to the experimentally determined values; therefore, the OH stretching calculated frequencies were ~100 cm(-1) lower than observed. The SFG peak assignments through comparison with DFT-D2 calculations will guide the SFG analysis of the crystalline cellulose structure in plant cell walls and lignocellulose biomass. PMID:23738844
Vibrational spectroscopic study and structure calculation for model compounds and polyurethanes
Wang, Q.
1992-01-01
Vibrational spectroscopy has been applied to the study of a small ring molecule, three model urethane compounds and Poly[4,4[prime]-bis(6-hydroxyhexyloxy)biphenyl-co-2,4-toluenediisocyanate] (2,4-TDI polyurethane) systems. The computer program POLYGRAF was used to estimate the stability of some conformers of the three model compounds. Grazing angle microscopy was used to study the surface structure of thin films of polyurethane. The synthesis, far infrared spectra, temperature dependent mid-infrared spectra and the Fourier transform Raman spectra are reported for polycrystalline samples of three model urethanes, 1,3-phenyl di(methyl carbamate) (1,3-PDI based urethane), 2,6-toluene di(methyl carbamate) (2,6-TDI based urethane), and 2,4-toluene di(methyl carbamate) (2,4-TDI based urethane). Geometry optimization is reported for phenyl methyl carbamate by ab initio and molecular mechanics methods, and of the three model urethanes by molecular mechanics methods using the Dreiding I force field. The results suggest that in isotropic surroundings only a very small number of the many possible conformers of the urethane groups in these molecules contribute appreciably to the structure. The intermolecular interaction, morphology and microstructure of 2,4-TDI polyurethane are studied. A molecular interpretation of hydrogen bonding behavior is given. The temperature dependence of infrared spectra of the 2,4-TDI polyurethane films are reported together with some kinetic data. A very thin film was prepared to study the surface behavior of 2,4-TDI polyurethane. An infrared spectrum was obtained by grazing angle reflection-absorption. The results suggest that 2,4-TDI polyurethane has a layered structure and that most of the NH groups and carbonyl groups are free on the surface. The infrared spectra of 1,4-cyclohexadiene and 1,4-cyclohexadiene-3,3,6,6-d4 were recorded in the gas phase at room temperature.
On complex resonance vibration systems calculation S.B. Karavashkin and O.N. Karavashkina
of this new method, as well as on many other subjects of mathematical physics and related themes. You and celestial mechanics, to Hamiltonian dynamics, theoretical and mathematical physics'' [2, p.173]. Some of the calculation and experimental curves. And the main, this method gives exact solutions, and this is non
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.
NASA Astrophysics Data System (ADS)
Ben hassen, C.; Boujelbene, M.; Bahri, M.; Zouari, N.; Mhiri, T.
2014-09-01
The present paper undertakes the study of a new hybrid compound [2-CH3C6H4NH3]2SeO4 characterized by the X-ray diffraction, IR, DFT calculation, TG-DTA, DSC and electrical conductivity. This new organic-inorganic hybrid compound crystallizes in the monoclinic system with P21/c space group and the following parameters a = 14.821 (5) Å; b = 16.245 (5) Å; c = 6.713 (5) Å; ß = 102.844 (5)°, Z = 4 and V = 1575.8 (14) Å3. The atomic arrangement can be described as isolated tetrahedral SeO42- connected with the organic groups by means of Nsbnd H⋯O hydrogen bonds to form infinite sinusoidal chains in the c-direction. BHHLYP/6-311g** method was used to determine the harmonic frequencies for two optimized cluster structures. The calculated modes were animated using the Molden graphical package to give tentative assignments of the observed IR spectra. Thermal analysis of the title compound does not indicate the occurrence of a phase transition in the temperature range of 300-650 K. Dielectric study of this compound has been measured, in order to determine the conductivity. The conductivity relaxation parameters associated with some H+ conduction have been determined from an analysis of the M?/M?max spectrum measured in a wide temperature range.
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.
NASA Astrophysics Data System (ADS)
Mezei, J. Zs; Backodissa-Kiminou, R. D.; Tudorache, D. E.; Morel, V.; Chakrabarti, K.; Motapon, O.; Dulieu, O.; Robert, J.; Tchang-Brillet, W.-Ü. L.; Bultel, A.; Urbain, X.; Tennyson, J.; Hassouni, K.; Schneider, I. F.
2015-06-01
The latest molecular data—potential energy curves and Rydberg/valence interactions—characterizing the super-excited electronic states of CO are reviewed, in order to provide inputs for the study of their fragmentation dynamics. Starting from this input, the main paths and mechanisms for CO+ dissociative recombination are analyzed; its cross sections are computed using a method based on multichannel quantum defect theory. Convoluted cross sections, giving both isotropic and anisotropic Maxwellian rate coefficients, are compared with merged-beam and storage-ring experimental results. The calculated cross sections underestimate the measured ones by a factor of two, but display a very similar resonant shape. These facts confirm the quality of our approach for the dynamics, and call for more accurate and more extensive molecular structure calculations.
Vibrational study and semiempirical calculation for the hexaazacyclophane copper(II) complex
M. M Campos-Vallette; R. E Clavijo C; F Mendizabal; G Diaz F; J Costamagna; J Canales; J Vargas
1997-01-01
The FTIR and Raman spectra of the hexaazacyclophane Cu(II) complex were recorded, and analyzed from a normal coordinate treatment by using an extended number of internal coordinates. The CuN force constant equal to 1.0 mdyn Å?1 represents satisfactorily the CuN bonding. Bond orders and total charge density for the metal free macrocycle and the complex were calculated within the molecular
NASA Astrophysics Data System (ADS)
Fu, Chong-Long
We have used a self-consistent pseudopotential method within local-density-functional theory to calculate the equilibrium ground state properties of transition metals Mo, Nb, and Zr. From our calculations, we obtain equilibrium lattice constants, cohesive energies, and bulk moduli which are in excellent agreement with the experiments. First principles frozen phonon calculations are then performed for the longitudinal (2/3,2/3,2/3) phonon in Mo, Nb, and bcc Zr as well as the H-point phonon in Mo and Nb. These calculations involve the precise evaluation of the total crystalline energy as a function of lattice displacement and yield phonon frequencies to within a few percent of the experimental values. Anharmonic terms are obtained with little additional effort and are found to be very important for causing the tendency toward the (omega) -phase instability in bcc Zr. These calculations allow a detailed analysis of the mechanisms causing phonon anomalies. They also provide first principle benchmarks at a few wavevectors where phenomenological models can be tested or their parameters determined. The validity of the adiabatic approximation is investigated for the Mo H-point phonon. Non-adiabatic effects are found to be small, while effects caused by the many-body renormalization of electronic states near the Fermi energy are found to be of the same order of magnitude as the discrepancy between experiment and the frozen phonon results. The microscopic interactions responsible for the vast frequency differences of the longitudinal (2/3,2/3,2/3) phonon in Mo, Nb, and Zr are analyzed by making use of the Hellmann-Feynman theorem. The stiffening of this mode as the electron per atom ratio increases from Nb to Mo is shown to arise from a development of directional bonding. The precipitous dip in this mode for the high temperature bcc phase of Zr is related to the d-electron screening, and the. tendency for this mode to go soft and cause a transformation to the (omega)-phase is also associated with details of the electronic structure. ('1)DOE Report IS-T-1065. This work was performed under Contract No. W-7405-Eng-82 with the U.S. Department of Energy.
NASA Astrophysics Data System (ADS)
Atalay, Y.; Ucun, F.; Avc?, D.; Ba?o?lu, A.
2006-06-01
The vibrational frequencies and molecular geometry of (R)- and (rac)-4-phenly-1,3-oxazolidin-2-one (4-POO) in the ground state have been calculated using the Hartree-Fock and density functional method (B3LYP) with 6-31G(d) basis set. The optimized geometric bond lengths are described better by HF while bond angles are reproduced more accurately by DFT (B3LYP). Comparison of the observed fundamental vibrational frequencies of (R)-POO and (rac)-4-POO and calculated results by density functional B3LYP and Hartree-Fock methods indicate that B3LYP is superior to the scaled Hartree-Fock approach for molecular vibrational problems.
NASA Astrophysics Data System (ADS)
Takeuchi, Hiroshi; Ito, Masaki; Egawa, Toru
2007-09-01
We have investigated the molecular structure and conformation of diethylmethylamine, C(4)H 3C(2)H 2N(1)[CH 3]C(3)H 2C(5)H 3, by gas electron diffraction and vibrational spectroscopy with the aid of theoretical calculations. Diffraction data are consistent with a conformational mixture of 35(14)% tt + 27(14)% g +t + 20(17)% g -t + 18(23)% g +g + where the numbers in parentheses denote three times the standard errors (3 ?). Normal-coordinate analysis based on B3LYP/6-311+G ?? calculations supports the existence of the four conformers. The dihedral angle ?1(C4C2N1C3) (= - ?2(C5C3N1C2)) of the tt conformer was 170(4)° whereas the ?1 and ?2 values of the other conformers were fixed at the B3LYP/6-311++G(2df,p) values: 72.4° and -163.3° for the g +t, -66.0° and -158.2° for the g -t, and 60.3° and 63.5° for the g +g +. Average values of the structural parameters ( rg/Å and ? ?/°) with 3 ? are: < r(N-C)> = 1.462(2), < r(C-C)> = 1.523(3), < r(C-H)> = 1.113(2), = 111.6(5), = 114.5(5), = 110.6(5).
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.
A split-frequency harmonic balance method for nonlinear oscillators with multi-harmonic forcing
NASA Astrophysics Data System (ADS)
Dunne, J. F.; Hayward, P.
2006-08-01
A new harmonic balance method (HBM) is presented for accurately computing the periodic responses of a nonlinear sdof oscillator with multi-harmonic forcing and non-expansible nonlinearities. The presence of multi-harmonic forcing requires a large number of solution harmonics with a substantial increase in computational demand for either the conventional or the incremental HBM. In this method, the oscillator equation-error is first defined in terms of two functions (originally proposed for obtaining free-vibration periods in: R.E. Mickens, Iteration procedure for determining approximate solutions to nonlinear oscillator equations, Journal of Sound and Vibration 116 (1987) 185-187; and more recently: R.E. Mickens, A Generalised iteration procedure for calculating approximations to periodic solutions of "truly nonlinear oscillations", Journal of Sound and Vibration 287 (2005) 1045-1051). A Fourier series solution is assumed, in which the total number of harmonics is fixed by the chosen discrete-time interval—this series is split into two partial sums nominally associated with either low-frequency or high-frequency harmonics. By exploiting a convergence property of the equation-error functions, the total solution is obtained in a new iterative scheme in which the low-frequency components are computed via a conventional HBM using a small number of algebraic equations, whereas the high frequency components are obtained in a separate step by updating. By gradually increasing the number of harmonics in the low-frequency group, the equation-error can be progressively reduced. Efficient use is made of FFT-based algebraic equation generation which allows an important class of non-expansible nonlinearities to be handled. The proposed method is tested on a Duffing-type oscillator, and an oscillator with a non-expansible 7th power stiffness term, where in both cases up to 24 component multi-harmonic forcing is applied. As a comparison, a conventional HBM is also used on the Duffing model in which the algebraic equations are generated in symbolic form to totally avoid errors from entering the formulation through complicated expansion of the cubic stiffness term (as in: I. Senjanovi?, Harmonic analysis of nonlinear oscillations of cubic dynamical systems, Journal of Ship Research 38 (3) (1994) 225-238; and in: A. Raghothama, S. Narayanan, Periodic response and chaos in nonlinear systems with parametric excitation and time delay, Nonlinear dynamics 27 (2002) 341-365). The paper shows that in obtaining period-1 solutions, the computational accuracy and efficiency of the proposed method is very good.
Elrod, Matthew J.
Fully coupled six-dimensional calculations of the water dimer vibration-rotation-tunneling states February 1997 A novel and efficient pseudospectral method for performing fully coupled six- dimensional 4D IPS of (HCl)2, but upon extending this approach to the six-dimensional 6D case of two
Dust Crystal Vibrational Frequencies Calculated with an Approximated Nonlinear Screening Potential
NASA Astrophysics Data System (ADS)
Cereceda, Carlo; Puerta, Julio; Martin, Pablo
2000-10-01
The oscillations of Coulomb quasi lattices involving high charged dust grains have already been described by a simple but well suited model. In this model, the interaction between particles is assumed to be the Debye screening potential, which is a good approximation for r << Debye length. Using a nonlinear screening potential of no-point charges we determine the frequencies of the vertical modes of oscillation of the upper and lower dust grain chains. The use of this screening potential is more realistic than that of Debye or dressed potentials. An analysis of these frequencies as a function of the various dust crystal parameters is carried out and compared with the values obtained using previous models. In the limit of very small grain to grain distance we recover the frequencies calculated with the Debye potential. However, for the range of dust grain distances such as those in the experiments, for each chain, a lower frequency is found using the approximated non linear potential
NASA Astrophysics Data System (ADS)
Berger, C. E.; Anderson, E. R.; Drut, J. E.
2015-05-01
We determine the ground-state energy and Tan's contact of attractively interacting few-fermion systems in a one-dimensional harmonic trap, for a range of couplings and particle numbers. Complementing those results, we show the corresponding density profiles. The calculations were performed with a lattice Monte Carlo approach based on a nonuniform discretization of space, defined via Gauss-Hermite quadrature points and weights. This particular coordinate basis is natural for systems in harmonic traps, and can be generalized to traps of other shapes. In all cases, it yields a position-dependent coupling and a corresponding nonuniform Hubbard-Stratonovich transformation. The resulting path integral is performed with hybrid Monte Carlo as a proof of principle for calculations at finite temperature and in higher dimensions. We present results for N =4 ,...,20 particles (although the method can be extended beyond that) to cover the range from few- to many-particle systems. This method is exact up to statistical and systematic uncertainties, which we account for—and thus also represents an ab initio calculation of this system, providing a benchmark for other methods and a prediction for ultracold-atom experiments.
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.
NASA Astrophysics Data System (ADS)
Sekkal, Majda; Legrand, Pierre; Vergoten, Gérard; Dauchez, Manuel
1992-07-01
The infrared spectra of ?- and ?- D-galactose were recorded, both in the mid-IR range (4000-500 cm -1) and in the far-IR (500-50 cm -1). The Raman spectra were also obtained. These spectra constitute the basis of a crystalline-state force field established for these two molecules through a normal coordinate analysis. A modified Urey—Bradley—Shimanouchi force field was combined with an intermolecular potential energy function which includes van der Waals interactions, electrostatic terms and an explicit hydrogen bond function. The force constants were varied, so as to obtain an agreement between the observed vibrational frequencies and the calculated ones of ?- D-galactose. The force field obtained was then applied to ?- D-galactose O- d5 and ?- D-galactose, in order to test its transferability. The computed potential energy distribution was found to be compatible with previous assignments for D-glucose, particularly for the modes involving C6 and C?OH groups. For ?- D-galactose the same force field was used with changing the force constants due to the C1 and C6 groups.
NASA Astrophysics Data System (ADS)
Gróf, M.; Polovková, J.; Gatial, A.; Milata, V.; ?ernuchová, P.; Prónayová, N.; Mat?jka, P.
2007-05-01
The isomers and conformers of two push-pull hydrazines: 3- N, N-dimethylhydrazino-2-acetyl propenenitrile [(H 3C) 2N sbnd NH sbnd CH dbnd C(CN)(COCH 3)] (DMHAP) and 3- N, N-dimethylhydrazino-2-methylsulfonyl propenenitrile [(H 3C) 2N sbnd NH sbnd CH dbnd C(CN)(SO 2CH 3)] (DMHSP) have been studied experimentally by NMR and vibrational spectroscopy and theoretically by the ab initio calculations at MP2 level in 6-31G** basis set. The IR and Raman spectra of both compounds as a solid and solute in various solvents have been recorded. The NMR spectra were obtained in chloroform and DMSO at room temperature. Both compounds have been prepared by the same way. NMR spectra revealed that DMHAP was prepared as a pure Z-isomer whereas in the case of DMHSP a pure E-isomer was obtained. Due to the low barrier for both compounds practically free isomerisation process occurred in the solutions but in opposite directions. Whereas DMHAP exists in the solid state and in the less polar solvent as Z-isomer, in more polar solvents the appearance of next two conformers of E-isomer was observed. On the contrary DMHSP exists in the solid state and in the more polar solvent as E-isomer only but in less polar solvent the presence of Z-isomer was observed as well. Conformational possibilities of both studied compounds are given by the rotation of dimethylhydrazino group with its anti- or syn-orientation towards the olefinic double bond. Moreover, by the rotation of the acetyl group with Z- and E-orientation of carbonyl bond towards olefinic double bond can occur in DMHAP. Vibrational and NMR spectra revealed the existence of single conformer with intramolecular hydrogen bond for Z-isomer in less polar solvent and next two conformers for E-isomer of DMHAP with Z-orientation of acetyl group and anti and syn orientation of dimethylhydrazine group in more polar solvents. For E-isomer of DMHSP two conformers with anti or syn orientations of dimethylhydrazino group have been also confirmed by NMR spectra in more polar solvents. Additionally the third DMHSP conformer with anti orientation of dimethylhydrazino group originating from Z-isomer was detected in less polar solvents. These experimental findings have been supported by ab initio calculations with solvent effect inclusion.
Ab initio structures and vibrational analysis of the isoprene conformers
NASA Astrophysics Data System (ADS)
Bock, Ch. W.; Panchenko, Yu. N.; Krasnoshchiokov, S. V.; Aroca, R.
1987-09-01
Complete gradient optimizations of the structures and the calculation of the harmonic force fields of the s- trans( anti) and gauche conformers of isoprene (2-methylbuta-1,3-diene) are reported at the RHF/6-31G level. The dihedral angle of the gauche conformer is found to be 41.0° from the planar s- cis( syn) form. The force fields obtained are refined using scale factors transferred from analogous calculations for trans-butadiene-1,3 and ethane. The direct vibrational problems are solved for both conformers of isoprene. A complete assignment of the experimental vibrational frequencies is given.
Rodríguez Ortega, P G; Montejo, M; Márquez, F; López González, J J
2015-07-01
A thorough DFT and MM study of the conformational landscape, molecular and electronic structures of (-)-S-anabasine is reported aimed to reveal the mechanism controlling its conformational preference. Although the conformational flexibility and diversity of this system is quite extensive, only two structures are populated both in gas-phase and solution (CCl4 and DMSO). NBO-aided electronic structure analyses performed for the eight conformers representing minima in the potential energy surface of (-)-S-anabasine indicate that both steric and electrostatic factors are determinant in the conformational distribution of the sample in gas phase. Nonetheless, hyperconjugative effects are the key force tipping the balance in the conformational equilibrium between the two main rotamers. Increasing the polarity of the medium (using the IEF-PCM formalism) barely affect the conformational energy profile, although a slight increase in the theoretical population of those structures more affected by electrostatic interactions is predicted. The validity of the theoretical models and calculated conformers populations are endorsed by the accurate reproduction of the IR and VCD spectra (recorded in pure liquid and in CCl4 solution) of the sample (that have been firstly recorded and assigned in the present work) which are consistent with the occurrence of a 2:1 conformational ratio. PMID:26059478
NASA Astrophysics Data System (ADS)
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.
NASA Astrophysics Data System (ADS)
Diao, Chuan-Ling; Wang, Chun-Hai; Luo, Neng-Neng; Qi, Ze-Ming; Shao, Tao; Wang, Yu-Yin; Lu, Jing; Wang, Quan-Chao; Kuang, Xiao-Jun; Fang, Liang; Shi, Feng; Jing, Xi-Ping
2014-03-01
1:2 B-site cation ordered Ba(Mg1/3Nb2/3)O3 ceramic was synthesized using conventional solid-state reaction at 1600 °C for 12 h. The structure parameters were obtained through Rietveld refinement of X-ray diffraction data. The Raman peak frequencies were obtained by Lorenz fitting on Raman spectrum. Four-parameter semiquantum model was used to fit the infrared (IR) reflectivity spectrum, and the fitted parameters were used to calculate the dielectric permittivity ? and dielectric loss tan?. A total of 9 active Raman and 16 active IR modes were obtained using first-principle calculations based on density functional theory with local density approximation. All of the vibrational modes were assigned and represented by linear combinations of the symmetry coordinates deduced using group theory analysis. The Raman mode with the highest frequency A1g(4) (789 cm-1) can be described as the breathing vibration of NbO6. The IR modes Eu(1) (149 cm-1) and A2u(2) (212 cm-1), which can be described as the twisting vibrations of Ba-MgO6/Ba-NbO6 on the a-b plane and the stretching vibrations of Ba-MgO6/Ba-NbO6 along the c direction, respectively, are the dominant contributing modes to ? and tan?. The dielectric property parameters obtained using IR spectrum fittings, first-principal calculations, and microwave measurements were compared.
Miliordos, Evangelos; Apra, Edoardo; Xantheas, Sotiris S.
2013-09-21
We report the first optimum geometries and harmonic vibrational frequencies for the ring pentamer and several water hexamer (prism, cage, cyclic and two book) at the CCSD(T)/aug-cc-pVDZ level of theory. All five hexamer isomer minima previously reported by MP2 are also minima on the CCSD(T) potential energy surface (PES). In addition, all CCSD(T) minimum energy structures for the n=2-6 cluster isomers are quite close to the ones previously obtained by MP2 on the respective PESs, as confirmed by a modified Procrustes analysis that quantifies the difference between any two cluster geometries. The CCSD(T) results confirm the cooperative effect of the homodromic ring networks (systematic contraction of the nearest-neighbor (nn) intermolecular separations with cluster size) previously reported by MP2, albeit with O-O distances shorter by ~0.02 Å, indicating that MP2 overcorrects this effect. The harmonic frequencies at the minimum geometries were obtained by the double differentiation of the CCSD(T) energy using an efficient scheme based on internal coordinates that reduces the number of required single point energy evaluations by ~15% when compared to the corresponding double differentiation using Cartesian coordinates. Negligible differences between MP2 and CCSD(T) are found for the librational modes, while uniform increases of ~15 and ~25 cm-1 are observed for the bending and “free” OH harmonic frequencies. The largest differences between MP2 and CCSD(T) are observed for the harmonic hydrogen bonded frequencies. The CCSD(T) red shifts from the monomer frequencies (??) are smaller than the MP2 ones, due to the fact that the former produces shorter elongations (?R) of the respective hydrogen bonded OH lengths from the monomer value with respect to the latter. Both the MP2 and CCSD(T) results for the hydrogen bonded frequencies were found to closely follow the relation - ?? = s ? ?R, with a rate of s = 20.3 cm-1 / 0.001 Å. The CCSD(T) harmonic frequencies, when corrected using the MP2 anharmonicities obtained from second order vibrational perturbation theory (VPT2), produce anharmonicCCSD(T) estimates that are within < 60 cm-1 from the measured infrared (IR) active bands of the n=2-6 clusters and furthermore trace the observed red shifts with respect to the monomer (??) quite accurately. The energetic order between the various hexamer isomers on the PES (prism has the lowest energy) previously reported at MP2 was found to be preserved at the CCSD(T) level, whereas the inclusion of anharmonic corrections further stabilizes the cage among the hexamer isomers.
Vibrational spectroscopic studies and DFT calculations on NaCH3CO2(aq) and CH3COOH(aq).
Rudolph, Wolfram W; Fischer, Dieter; Irmer, Gert
2014-02-28
Aqueous solutions of sodium acetate, NaCH3CO2, and acetic acid, CH3COOH, were studied using Raman and infrared spectroscopy. The spectra were recorded over a large concentration range, in the terahertz region and up to 4000 cm(-1). In the isotropic Raman spectrum in R-format, a polarized band at 189 cm(-1) was assigned to the ?1Na-O stretch of the hydrated Na(+)-ion and a shoulder at 245 cm(-1) to the restricted translation band, ?sO-H···O* of the hydrated acetate ion, CH3CO2(-)(aq). The CH3CO2(-)(aq) and the hydrated acetic acid, CH3COOH(aq), possess pseudo Cs symmetry. Geometrical parameters for the species in the gas phase and for CH3CO2(-)(aq) and CH3COOH(aq) are reported. Characteristic bands for CH3CO2(-)(aq) and CH3COOH(aq) were assigned under the guidance of the DFT vibrational frequency calculations and discussed in detail. In aqueous NaCH3CO2 solutions, at high concentrations, no contact ion pairs could be detected, but instead solvent separated ion pairs were found. In LiCH3CO2(aq), however, contact ion pairs are formed which is indicated by the appearance of a shoulder at 939 cm(-1) and the shift of the symmetric stretching mode of the -CO2(-) group to higher wavenumbers. PMID:24346353
Chakraborty, Indrani; Shirodkar, Sharmila N; Gohil, Smita; Waghmare, Umesh V; Ayyub, Pushan
2014-01-15
We report the optical, electronic, vibrational and mechanical properties of a stable, anisotropic, hexagonal (4H) form of silver. First principles calculations based on density functional theory were used to simulate the phonon dispersion curves and electronic band structure of 4H-Ag. The phonon dispersion data at 0 K do not contain unstable phonon modes, thereby confirming that it is a locally stable structure. The Fermi surface of the 4H phase differs in a subtle way from that of the cubic phase. Experimental measurements indicate that, when compared to the commonly known face-centered cubic (3C) form of silver, the 4H-Ag form shows a 130-fold higher, strongly anisotropic, in-plane resistivity and a much lower optical reflectance with a pronounced surface plasmon contribution that imparts a distinctive golden hue to the material. Unlike common silver, the lower symmetry of the 4H-Ag structure allows it to be Raman active. Mechanically, 4H-Ag is harder, more brittle and less malleable. Overall, this novel, poorly metallic, anisotropic, darker and harder crystallographic modification of silver bears little resemblance to its conventional counterpart. PMID:24305516
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.
NASA Astrophysics Data System (ADS)
Sanson, A.; Pokrovski, G. S.; Giarola, M.; Mariotto, G.
2015-01-01
The vibrational dynamics of germanium dioxide in the rutile structure has been investigated by using polarized micro-Raman scattering spectroscopy coupled with first-principles calculations. Raman spectra were carried out in backscattering geometry at room temperature from micro-crystalline samples either unoriented or oriented by means of a micromanipulator, which enabled successful detection and identification of all the Raman active modes expected on the basis of the group theory. In particular, the Eg mode, incorrectly assigned or not detected in the literature, has been definitively observed by us and unambiguously identified at 525 \\text{cm}-1 under excitation by certain laser lines, thus revealing an unusual resonance phenomenon. First-principles calculations within the framework of the density functional theory allow quantifying both wave number and intensity of the Raman vibrational spectra. The excellent agreement between calculated and experimental data corroborates the reliability of our findings.
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.
X. Y. Liu; M. S. Jin
1992-01-01
The nonsingularity BEM is used to obtain a numerical solution for calculating the natural frequencies and vibration response of plates subjected to arbitrarily distributed harmonic disturbing forces and elastically supported on a nonhomogeneous foundation. The method has certain advantages over FEM and FD which include good precision, less computation time, less unknowns, and suitability for a microcomputer. The adaptability of
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.
NASA Astrophysics Data System (ADS)
Reynard, B.; Caracas, R.
2007-12-01
D/H partitioning between water and minerals are often not well constrained from equilibrium experiments, except for simple hydroxides such as brucite. Vibrational models and experiments can be used to constrain more accurately isotopic fractionation factors, provided they are first calibrated and tested on relatively simple systems such as MgO-SiO2-H2O (MSH) starting with brucite Mg(OH)2, then going towards increasing complexity in minerals like talc Mg3Si4O10(OH)2 and antigorite Mg48Si34O85(OH)62. We present here first results from combining Raman and IR spectroscopic and ab initio calculations on brucite. Raman measurements were carried out on significantly isotopically doped phases, with several intermediate compositions between end-members. Various mode behaviors are observed, with low frequency modes shifting smoothly in frequency with increasing isotopic substitution while high frequency modes present a two-mode behavior. The good agreement between predicted and observed frequencies allows to identify the modes corresponding to those associated to OH-OD vibrations. Ab initio calculations can thus be used as a guide for deciphering the more complex vibrational spectra such as those obtained on antigorite; and will help constructing reliable vibrational models of D/H partitioning.
NASA Astrophysics Data System (ADS)
Searle, G. F. C.
2014-05-01
1. Elementary theory of harmonic motion; 2. Experimental work in harmonic motion; Experiment 1. Determination of g by a simple pendulum; Experiment 2. Harmonic motion of a body suspended by a spring; Experiment 3. Harmonic motion of a rigid body suspended by a torsion wire; Experiment 4. Study of a system with variable moment of inertia; Experiment 5. Dynamical determination of ratio of couple to twist for a torsion wire; Experiment 6. Comparison of the moments of inertia of two bodies; Experiment 7. Experiment with a pair of inertia bars; Experiment 8. Determination of the moment of inertia of a rigid pendulum; Experiment 9. Experiment on a pendulum with variable moment of inertia; Experiment 10. Determination of g by a rigid pendulum; Experiment 11. Pendulum on a yielding support; Experiment 12. Determination of the radius of curvature of a concave mirror by the oscillations of a sphere rolling in it; Experiment 13. Determination of g by the oscillations of a rod rolling on a cylinder; Experiment 14. Study of a vibrating system with two degrees of freedom; Note 1. On the vibration of a body suspended from a light spring; Note 2. Periodic time of a pendulum vibrating through a finite arc; Note 3. Periodic time for finite motion; Note 4. Periodic times of a pendulum with two degrees of freedom.
Knaanie, Roie; Šebek, Ji?í; 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
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.
Nogueira, C E S; Caselli, P E S; Freire, P T C; Teixeira, A M R; Oliveira, I M M; Bento, R R F; Faria, J L B; Gusmão, G O M; Silva, L E
2015-10-01
In this work we present a study of the vibrational spectra of 4,5,6,8,9-pentachloropyrimido-[1,2-a][1,8]naphthyridin-10-one, C11H2Cl5N3O, a substance belonging to the important pharmacological class of 1,8-naphthyridine derivatives. The Fourier transform infrared and the Fourier transform Raman spectra of the crystal were recorded at room temperature in the regions 400-4000 and 50-4000cm(-1), respectively. Vibrational wavenumbers were predicted using Density Functional Theory calculations with the B3LYP functional on 6-31G(d,p) and 6-311++G(d,p) basis sets. The descriptions of the normal modes were made after calculating the potential energy distribution. Additionally, potential reaction sites were evaluated through Mulliken population and Frontier Orbital analysis. PMID:25965513
A. J. C. Varandas; J. M. C. Marques
1994-01-01
A method for calculating quasiclassical trajectories on potential energy surfaces defined using a sequence of model quadratic surfaces (QCT\\/GH) is suggested, and tested for atom–diatom collisions against the traditional quasiclassical trajectory approach. A simple model is also suggested to constrain the classical energy of a bound vibrational mode to be greater than a specified amount, namely, its zero-point energy value.
Mark W. Coffey
2008-12-09
We evaluate binomial series with harmonic number coefficients, providing recursion relations, integral representations, and several examples. The results are of interest to analytic number theory, the analysis of algorithms, and calculations of theoretical physics, as well as other applications.
Premkumar, S; Jawahar, A; Mathavan, T; Kumara Dhas, M; Milton Franklin Benial, A
2015-03-01
The vibrational spectra of 2-amino-7-bromo-5-oxo-[1]benzopyrano [2,3-b]pyridine-3 carbonitrile were recorded using fourier transform-infrared and fourier transform-Raman spectrometer. The optimized structural parameters, vibrational frequencies, Mulliken atomic charge distribution, frontier molecular orbitals, thermodynamic properties, temperature dependence of thermodynamic parameters, first order hyperpolarizability and natural bond orbital calculations of the molecule were performed using the Gaussian 09 program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using the VEDA 4.0 program. The calculated first order hyperpolarizability of ABOBPC molecule was obtained as 6.908×10(-30) issue, which was 10.5 times greater than urea. The nonlinear optical activity of the molecule was also confirmed by the frontier molecular orbitals and natural bond orbital analysis. The frontier molecular orbitals analysis shows that the lower energy gap of the molecule, which leads to the higher value of first order hyperpolarizability. The natural bond orbital analysis indicates that the nonlinear optical activity of the molecule arises due to the ???(?) transitions. The Mulliken atomic charge distribution confirms the presence of intramolecular charge transfer within the molecule. The reactive site of the molecule was predicted from the molecular electrostatic potential contour map. The values of thermo dynamic parameters were increasing with increasing temperature. PMID:25498822
NASA Astrophysics Data System (ADS)
Premkumar, S.; Jawahar, A.; Mathavan, T.; Kumara Dhas, M.; Milton Franklin Benial, A.
2015-03-01
The vibrational spectra of 2-amino-7-bromo-5-oxo-[1]benzopyrano [2,3-b]pyridine-3 carbonitrile were recorded using fourier transform-infrared and fourier transform-Raman spectrometer. The optimized structural parameters, vibrational frequencies, Mulliken atomic charge distribution, frontier molecular orbitals, thermodynamic properties, temperature dependence of thermodynamic parameters, first order hyperpolarizability and natural bond orbital calculations of the molecule were performed using the Gaussian 09 program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using the VEDA 4.0 program. The calculated first order hyperpolarizability of ABOBPC molecule was obtained as 6.908 × 10-30 issue, which was 10.5 times greater than urea. The nonlinear optical activity of the molecule was also confirmed by the frontier molecular orbitals and natural bond orbital analysis. The frontier molecular orbitals analysis shows that the lower energy gap of the molecule, which leads to the higher value of first order hyperpolarizability. The natural bond orbital analysis indicates that the nonlinear optical activity of the molecule arises due to the ? ? ?? transitions. The Mulliken atomic charge distribution confirms the presence of intramolecular charge transfer within the molecule. The reactive site of the molecule was predicted from the molecular electrostatic potential contour map. The values of thermo dynamic parameters were increasing with increasing temperature.
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. PMID:19850513
NASA Astrophysics Data System (ADS)
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.
Suvitha, A; Periandy, S; Boomadevi, S; Govindarajan, M
2014-01-01
In this work, the vibrational spectral analysis is carried out by using Raman and infrared spectroscopy in the range 100-4000 cm(-1)and 50-4000 cm(-1), respectively, for pycolinaldehyde oxime (PAO) (C6H6N2O) molecule. The vibrational frequencies have been calculated and scaled values are compared with experimental FT-IR and FT-Raman spectra. The structure optimizations and normal coordinate force field calculations are based on HF and B3LYP methods with 6-311++G(d,p) basis set. The results of the calculation shows excellent agreement between experimental and calculated frequencies in B3LYP/6-311++G(d,p) basis set. The optimized geometric parameters are compared with experimental values of PAO. The non linear optical properties, NBO analysis, thermodynamics properties and mulliken charges of the title molecule are also calculated and interpreted. A study on the electronic properties, such as HOMO and LUMO energies, are performed by time-dependent DFT (TD-DFT) approach. Besides, frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) are performed. The effects due to the substitutions of CH=NOH ring are investigated. The (1)H and (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule are calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. PMID:23994677
NASA Astrophysics Data System (ADS)
Suvitha, A.; Periandy, S.; Boomadevi, S.; Govindarajan, M.
2014-01-01
In this work, the vibrational spectral analysis is carried out by using Raman and infrared spectroscopy in the range 100-4000 cm-1and 50-4000 cm-1, respectively, for pycolinaldehyde oxime (PAO) (C6H6N2O) molecule. The vibrational frequencies have been calculated and scaled values are compared with experimental FT-IR and FT-Raman spectra. The structure optimizations and normal coordinate force field calculations are based on HF and B3LYP methods with 6-311++G(d,p) basis set. The results of the calculation shows excellent agreement between experimental and calculated frequencies in B3LYP/6-311++G(d,p) basis set. The optimized geometric parameters are compared with experimental values of PAO. The non linear optical properties, NBO analysis, thermodynamics properties and mulliken charges of the title molecule are also calculated and interpreted. A study on the electronic properties, such as HOMO and LUMO energies, are performed by time-dependent DFT (TD-DFT) approach. Besides, frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) are performed. The effects due to the substitutions of CHdbnd NOH ring are investigated. The 1H and 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule are calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results.
NASA Astrophysics Data System (ADS)
Krishna Kumar, V.; Suganya, S.; Mathammal, R.
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. 13C and 1H 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.
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.
NASA Astrophysics Data System (ADS)
Mahadevan, D.; Periandy, S.; Ramalingam, S.
2011-09-01
The FT-IR and FT-Raman vibrational spectra of 1,3-dichlorobenzene (1,3-DCB) have been recorded using Bruker IFS 66 V Spectrometer in the range 4000-100 cm -1. A detailed vibrational spectral analysis has been carried out and assignments of the observed fundamental bands have been proposed on the basis of peak positions and relative intensities. The optimized molecular geometry, vibrational frequencies, atomic charges, dipole moment, rotational constants and several thermodynamic parameters in the ground state were calculated using ab initio Hartree-Fock (HF) and DFT (B3LYP) methods with 6-31++G (d, p) and 6-311++G (d, p) basis sets. With the help of different scaling factors, the observed vibrational wave numbers in FT-IR and FT-Raman spectra were analyzed and assigned to different normal modes of the molecule. Most of the modes have wave numbers in the expected range. The inductive effect of Chlorine atoms in the benzene molecule has also been investigated.
Mahadevan, D; Periandy, S; Ramalingam, S
2011-09-01
The FT-IR and FT-Raman vibrational spectra of 1,3-dichlorobenzene (1,3-DCB) have been recorded using Bruker IFS 66 V Spectrometer in the range 4000-100 cm(-1). A detailed vibrational spectral analysis has been carried out and assignments of the observed fundamental bands have been proposed on the basis of peak positions and relative intensities. The optimized molecular geometry, vibrational frequencies, atomic charges, dipole moment, rotational constants and several thermodynamic parameters in the ground state were calculated using ab initio Hartree-Fock (HF) and DFT (B3LYP) methods with 6-31++G (d, p) and 6-311++G (d, p) basis sets. With the help of different scaling factors, the observed vibrational wave numbers in FT-IR and FT-Raman spectra were analyzed and assigned to different normal modes of the molecule. Most of the modes have wave numbers in the expected range. The inductive effect of Chlorine atoms in the benzene molecule has also been investigated. PMID:21561799
Non-linear vibrations of doubly curved shallow shells
M. Amabili
2005-01-01
Large amplitude (geometrically non-linear) vibrations of doubly curved shallow shells with rectangular base, simply supported at the four edges and subjected to harmonic excitation normal to the surface in the spectral neighbourhood of the fundamental mode are investigated. Two different non-linear strain–displacement relationships, from the Donnell's and Novozhilov's shell theories, are used to calculate the elastic strain energy. In-plane inertia
delta-pairing forces and collective pairing vibrations
Kamila Sieja; Andrzej Baran; Krzysztof Pomorski
2003-11-04
The collective pairing hamiltonian is obtained in the framework of the generator coordinate method in the gaussian overlap approximation with a slightly modified BCS function used as a generator function. The collective variable alpha, measuring the monopole moment of the pairing field, and the gauge transformation angle phi are chosen as generator coordinates. The vibrational ground states are calculated by diagonalisation of the collective pairing hamiltonian in the harmonic oscillator basis.
Miliordos, Evangelos; Aprà, Edoardo; Xantheas, Sotiris S
2013-09-21
We report the first optimum geometries and harmonic vibrational frequencies for the ring pentamer and several water hexamer (prism, cage, cyclic and two book) at the coupled-cluster including single, double, and full perturbative triple excitations (CCSD(T))/aug-cc-pVDZ level of theory. All five examined hexamer isomer minima previously reported by Møller-Plesset perturbation theory (MP2) are also minima on the CCSD(T) potential energy surface (PES). In addition, all CCSD(T) minimum energy structures for the n = 2-6 cluster isomers are quite close to the ones previously obtained by MP2 on the respective PESs, as confirmed by a modified Procrustes analysis that quantifies the difference between any two cluster geometries. The CCSD(T) results confirm the cooperative effect of the homodromic ring networks (systematic contraction of the nearest-neighbor (nn) intermolecular separations with cluster size) previously reported by MP2, albeit with O-O distances shorter by ~0.02 Å, indicating that MP2 overcorrects this effect. The harmonic frequencies at the minimum geometries were obtained by the double differentiation of the CCSD(T) energy using an efficient scheme based on internal coordinates that reduces the number of required single point energy evaluations by ~15% when compared to the corresponding double differentiation using Cartesian coordinates. Negligible differences between MP2 and CCSD(T) frequencies are found for the librational modes, while uniform increases of ~15 and ~25 cm(-1) are observed for the bending and "free" OH harmonic frequencies. The largest differences between CCSD(T) and MP2 are observed for the harmonic hydrogen bonded frequencies, for which the former produces larger absolute values than the latter. Their CCSD(T) redshifts from the monomer values (??) are smaller than the MP2 ones, due to the fact that CCSD(T) produces shorter elongations (?R) of the respective hydrogen bonded OH lengths from the monomer value with respect to MP2. Both the MP2 and CCSD(T) results for the hydrogen bonded frequencies were found to closely follow the relation -?? = s · ?R, with a rate of s = 20.2 cm(-1)/0.001 Å for hydrogen bonded frequencies with IR intensities >400 km/mol. The CCSD(T) harmonic frequencies, when corrected using the MP2 anharmonicities obtained from second order vibrational perturbation theory, produce anharmonic CCSD(T) estimates that are within <60 cm(-1) from the measured infrared (IR) active bands of the n = 2-6 clusters. Furthermore, the CCSD(T) harmonic redshifts (with respect to the monomer) trace the measured ones quite accurately. The energetic order between the various hexamer isomers on the PES (prism has the lowest energy) previously reported at MP2 was found to be preserved at the CCSD(T) level, whereas the inclusion of anharmonic corrections further stabilizes the cage among the hexamer isomers. PMID:24070285
NASA Astrophysics Data System (ADS)
Miliordos, Evangelos; Aprà, Edoardo; Xantheas, Sotiris S.
2013-09-01
We report the first optimum geometries and harmonic vibrational frequencies for the ring pentamer and several water hexamer (prism, cage, cyclic and two book) at the coupled-cluster including single, double, and full perturbative triple excitations (CCSD(T))/aug-cc-pVDZ level of theory. All five examined hexamer isomer minima previously reported by Møller-Plesset perturbation theory (MP2) are also minima on the CCSD(T) potential energy surface (PES). In addition, all CCSD(T) minimum energy structures for the n = 2-6 cluster isomers are quite close to the ones previously obtained by MP2 on the respective PESs, as confirmed by a modified Procrustes analysis that quantifies the difference between any two cluster geometries. The CCSD(T) results confirm the cooperative effect of the homodromic ring networks (systematic contraction of the nearest-neighbor (nn) intermolecular separations with cluster size) previously reported by MP2, albeit with O-O distances shorter by ˜0.02 Å, indicating that MP2 overcorrects this effect. The harmonic frequencies at the minimum geometries were obtained by the double differentiation of the CCSD(T) energy using an efficient scheme based on internal coordinates that reduces the number of required single point energy evaluations by ˜15% when compared to the corresponding double differentiation using Cartesian coordinates. Negligible differences between MP2 and CCSD(T) frequencies are found for the librational modes, while uniform increases of ˜15 and ˜25 cm-1 are observed for the bending and "free" OH harmonic frequencies. The largest differences between CCSD(T) and MP2 are observed for the harmonic hydrogen bonded frequencies, for which the former produces larger absolute values than the latter. Their CCSD(T) redshifts from the monomer values (??) are smaller than the MP2 ones, due to the fact that CCSD(T) produces shorter elongations (?R) of the respective hydrogen bonded OH lengths from the monomer value with respect to MP2. Both the MP2 and CCSD(T) results for the hydrogen bonded frequencies were found to closely follow the relation -?? = s . ?R, with a rate of s = 20.2 cm-1/0.001 Å for hydrogen bonded frequencies with IR intensities >400 km/mol. The CCSD(T) harmonic frequencies, when corrected using the MP2 anharmonicities obtained from second order vibrational perturbation theory, produce anharmonic CCSD(T) estimates that are within <60 cm-1 from the measured infrared (IR) active bands of the n = 2-6 clusters. Furthermore, the CCSD(T) harmonic redshifts (with respect to the monomer) trace the measured ones quite accurately. The energetic order between the various hexamer isomers on the PES (prism has the lowest energy) previously reported at MP2 was found to be preserved at the CCSD(T) level, whereas the inclusion of anharmonic corrections further stabilizes the cage among the hexamer isomers.
NASA Astrophysics Data System (ADS)
Ishida, Yukio; Inoue, Tsuyoshi; Kagawa, Taishi; Ueda, Motohiko
In the rotating machinery, such as automobile engines, the driving torque changes periodically and torsional vibrations occur. In this study, the dynamic characteristics of centrifugal pendulum vibration absorbers which are used to suppress torsional vibrations are investigated both theoretically and experimentally. In the theoretical analysis, the nonlinear characteristics are taken into consideration under the assumption that the pendulums vibrate with large amplitude. It is clarified that, although the centrifugal pendulum has remarkable effects on suppressing harmonic vibration, it induces large amplitude harmonic vibrations, the second and third order superharmonic resonances, and unstable vibrations of harmonic type under some condition,. Moreover, this paper proposes various methods to suppress these secondarily induced vibrations, and show that it is possible to suppress torsional vibrations to the substantially zero amplitude-level in the whole rotational speed range.
NASA Astrophysics Data System (ADS)
Cassam-Chenaï, P.; Rousseau, G.; Ilmane, A.; Bouret, Y.; Rey, M.
2015-07-01
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.
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
Structural and vibrational study of maprotiline
NASA Astrophysics Data System (ADS)
Yavuz, A. E.; Haman Bayar?, S.; Kazanc?, N.
2009-04-01
Maprotiline ( N-methyl-9,10-ethanoanthracene-9(10H)-propanamine) is a tetra cyclic antidepressant. It is a highly selective inhibitor of norepinephrine reuptake. The solid and solution in CCl 4 and methanol infrared spectra of maprotiline were recorded. The fully optimized equilibrium structure of maprotiline was obtained from DFT calculations by using the B3LYP functional in combination with 6-31G and 6-311G(d,p) basis sets. The results of harmonic and anharmonic frequency calculations on maprotiline were presented. The vibrational spectra were interpreted, with the aid of normal coordinate analysis based on a scaled quantum mechanical (SQM) force field. Vibrational assignment of all the fundamentals was made using the total energy distribution (TED). The possible interaction between maprotiline and neurotransmitter serotonin (5-HT) were investigated.
NASA Astrophysics Data System (ADS)
Kaindl, Reinhard; Sohr, Gerhard; Huppertz, Hubert
2013-12-01
The two oxoborates ?-ZnB4O7 and ?-CaB4O7 were synthesized and investigated by FTIR- and Raman spectroscopy and ab initio quantum chemical calculations. Maximum and mean deviations between experimentally determined bands and calculated modes ranged between 15-36 cm-1 and 5-7 cm-1, respectively, allowing band assignments to vibrational modes in most cases. The complex network structures with tetrahedral BO4 and planar OB3 groups are mirrored by the spectra and numerous vibrational modes, not assignable by standard borates classification schemes. It was confirmed that OB3 units, despite similar force constants and geometry, do not absorb in the same range as BO3 units. Bands in the high wavenumber range are rather caused by B-O-(Zn/Ca), O-B-O, B-O-B, and B-O stretching and bending vibrations. The experimental observation of inactive or Raman-active modes in the absorption spectra indicates defects or structural distortions in both compounds.
Vibrational relaxation of ClO2 in water
NASA Astrophysics Data System (ADS)
Poulsen, J. Aa.; Thomsen, C. L.; Keiding, S. R.; Thøgersen, J.
1998-05-01
Photodissociation of ClO2 in aqueous solution at 400 nm results in the formation of ClO+O and Cl+O2. ClO and O geminately recombine to ClO2 in the electronic ground state (2B1), formed with an initial vibrational energy of ?2.5 eV. In this paper the vibrational relaxation of ClO2(2B1) in aqueous solution is studied by femtosecond transient absorption spectroscopy in the spectral range 234 to 1024 nm. The measured transient absorption of the vibrationally relaxing ClO2 molecules is compared with the transient absorption calculated for relaxation in the asymmetric stretch as well as the symmetric stretch and bending modes. The calculations of the absorption spectra pertaining to the asymmetric stretch are based on a harmonic potential derived from the experimentally determined fundamental vibrational energy, whereas that of the symmetrical vibrations are based on ab initio potentials. An excellent agreement is obtained by assuming that the vibrational relaxation predominantly occurs in the asymmetric stretch with a 9.5 ps relaxation time. A weak spectral feature in the ultraviolet part of the spectrum is assigned to vibrational relaxation in the symmetric stretch and bending modes, indicating a coupling between the asymmetric and symmetric modes.
Mary, Y Sheena; Raju, K; Panicker, C Yohannan; Al-Saadi, Abdulaziz A; Thiemann, Thies
2014-10-15
The conformational behavior and structural stability of (2E)-3-(3-chlorophenyl)prop-2-enoic anhydride were investigated by using density functional theory. The optimized molecular structure, vibrational wavenumbers, corresponding vibrational assignments of (2E)-3-(3-chlorophenyl)prop-2-enoic anhydride have been investigated experimentally and theoretically. The HOMO and LUMO analysis are used to determine the charge transfer within the molecule. The stability of the molecule arising from hyperconjugative interaction and charge delocalization has been analyzed using NBO analysis. The calculated first hyperpolarizability of the title compound is 15.8×10(-30)esu, and is 121.54 times that of the standard NLO material urea and the title compound is an attractive object for future studies of nonlinear optical properties. MEP was performed by the DFT method and the predicted infrared intensities and Raman activities have also been reported. PMID:24840488
NASA Astrophysics Data System (ADS)
Raoult, M.; Jungen, Ch.
1981-03-01
Multichannel quantum defect theory has been used to calculate the effect of vibrational preionization on the total and partial oscillator strength distributions and photoelectron angular distribution in H2 for excitation between 790 and 760 Å. The total oscillator-strength distribution obtained agrees well with the high-resolution photoionization data of Dehmer and Chupka. The partial oscillator strength resonance profiles are predicted to have different shapes in different vibrational ionization channels, while their widths change little with channel. The preionization resonances are also predicted to affect the angular distribution asymmetry parameters b over a broader range than they affect the oscillator strength distribution. The gross features of the preionization resonances are discussed in terms of approximate solutions of the MQD equations.
Kandasamy, M; Velraj, G; Kalaichelvan, S; Mariappan, G
2015-01-01
In this work, we reported a combined experimental and theoretical study on molecular structure, vibrational spectra and natural bond orbital (NBO) analysis of 1,5-dimethoxynaphthalene. The optimized molecular structure, atomic charges, vibrational frequencies and natural bond orbital analysis of 1,5-dimethoxynaphthalene have been studied by performing DFT/B3LYP/6-31G(d,p) level of theory. The FTIR, FT-Raman spectra were recorded in the region of 4000-400 cm(-1) and 3500-50 cm(-1) respectively. The scaled wavenumbers are compared with the experimental values. The difference between the observed and scaled wavenumber values of the most fundamentals is very small. The formation of hydrogen bond was investigated in terms of the charge density by the NBO analysis. Natural Population Analysis (NPA) was used for charge determination in the title molecule. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis were investigated using theoretical calculations. PMID:25014641
NASA Astrophysics Data System (ADS)
Bowman, Joel M.; Gazdy, Bela; Bentley, Joseph A.; Lee, Timothy J.; Dateo, Christopher E.
1993-07-01
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.
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.
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.
Mary, Y Sheena; Panicker, C Yohannan; Thiemann, Thies; Al-Azani, Mariam; Al-Saadi, Abdulaziz A; Van Alsenoy, C; Raju, K; War, Javeed Ahmad; Srivastava, S K
2015-12-01
FT-IR and FT-Raman spectra of bis[(E)-anthranyl-9-acrylic]anhydride were recorded and analyzed. The conformational behavior is also investigated. The vibrational wave numbers were calculated using density functional theory (DFT) quantum chemical calculations. The data obtained from wave number calculations are used to assign vibrational bands obtained in Infrared and Raman spectra. Potential energy distribution was done using GAR2PED program. The geometrical parameters are compared with related structures. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using Natural Bonding Orbital (NBO) analysis. The Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) analysis are used to determine the charge transfer within the molecule. Molecular Electrostatic Potential (MEP) was performed by the DFT method. The calculated first hyperpolarizability of the title compound is comparable with the reported values of similar derivatives and is 4.23 times that of the standard nonlinear optical (NLO) material urea and the title compound and its derivatives are an attractive object for future studies of nonlinear optical properties. To evaluate the in silico antitumor activity of the title compound molecular docking studies were carried out against protein Bcl-xL. The (1)H-NMR spectrum is also reported. PMID:26143327
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 (?) of about 0.35 cm(-1). Introducing three semiempirical scaling parameters, two affecting the BO PES and one controlling nonadiabatic effects, reduces ? below 0.1 cm(-1). Introducing one further rotational nonadiabatic parameter gives ? 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. PMID:23517285
NASA Astrophysics Data System (ADS)
Petrenko, Taras; Neese, Frank
2012-12-01
In this work, an improved method for the efficient automatic simulation of optical band shapes and resonance Raman (rR) intensities within the "independent mode displaced harmonic oscillator" is described. Despite the relative simplicity of this model, it is able to account for the intensity distribution in absorption (ABS), fluorescence, and rR spectra corresponding to strongly dipole allowed electronic transitions with high accuracy. In order to include temperature-induced effects, we propose a simple extension of the time dependent wavepacket formalism developed by Heller which enables one to derive analytical expressions for the intensities of hot bands in ABS and rR spectra from the dependence of the wavepacket evolution on its initial coordinate. We have also greatly optimized the computational procedures for numerical integration of complicated oscillating integrals. This is important for efficient simulations of higher-order rR spectra and excitation profiles, as well as for the fitting of experimental spectra of large molecules. In particular, the multimode damping mechanism is taken into account for efficient reduction of the upper time limit in the numerical integration. Excited state energy gradient as well as excited state geometry optimization calculations are employed in order to determine excited state dimensionless normal coordinate displacements. The gradient techniques are highly cost-effective provided that analytical excited state derivatives with respect to nuclear displacements are available. Through comparison with experimental spectra of some representative molecules, we illustrate that the gradient techniques can even outperform the geometry optimization method if the harmonic approximation becomes inadequate.
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.
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.
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.
VIBRATIONS OF SHELLS CONTACTING FLUID: ASYMPTOTIC ANALYSIS
Levitin, Michael
VIBRATIONS OF SHELLS CONTACTING FLUID: ASYMPTOTIC ANALYSIS M. LEVITIN Department of Mathematics ABSTRACT We consider free and forced harmonic vibrations of a thin elastic shell filled with or immersed of free vibrations, and of the solu- tions of non-homogeneous problems, using the relative shell thickness
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…
Lukose, Jilu; Yohannan Panicker, C; Nayak, Prakash S; Narayana, B; Sarojini, B K; Van Alsenoy, C; Al-Saadi, Abdulaziz A
2015-01-25
The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 2-phenyl-N-(pyrazin-2-yl)acetamide have been investigated experimentally and theoretically using Gaussian09 software package. The title compound was optimized by using the HF/6-31G(6D,7F) and B3LYP/6-31G(6D,7F) calculations. The geometrical parameters are in agreement with the XRD data. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. Gauge-including atomic orbital (1)H-NMR chemical shifts calculations were carried out and compared with experimental data. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. Molecular electrostatic potential was performed by the DFT method. First hyperpolarizability is calculated in order to find its role in non linear optics. From the XRD data, in the crystal, molecules are held together by strong C-H?O and N-H?O intermolecular interactions. PMID:25124846
Harmonic force field for nitro compounds.
Bellido, Edson P; Seminario, Jorge M
2012-06-01
Molecular simulations leading to sensors for the detection of explosive compounds require force field parameters that can reproduce the mechanical and vibrational properties of energetic materials. We developed precise harmonic force fields for alanine polypeptides and glycine oligopeptides using the FUERZA procedure that uses the Hessian tensor (obtained from ab initio calculations) to calculate precise parameters. In this work, we used the same procedure to calculate generalized force field parameters of several nitro compounds. We found a linear relationship between force constant and bond distance. The average angle in the nitro compounds was 116°, excluding the 90° angle of the carbon atoms in the octanitrocubane. The calculated parameters permitted the accurate molecular modeling of nitro compounds containing many functional groups. Results were acceptable when compared with others obtained using methods that are specific for one type of molecule, and much better than others obtained using methods that are too general (these ignore the chemical effects of surrounding atoms on the bonding and therefore the bond strength, which affects the mechanical and vibrational properties of the whole molecule). PMID:22119786
NASA Astrophysics Data System (ADS)
Marchewka, M. K.; Drozd, M.
2012-12-01
Crystalline complexes between ethylenediammonium dication and terephthalate, chloroacetate, phosphite, selenite and sulfamate anions were obtained by slow evaporation from water solution method. Room temperature powder infrared and Raman measurements were carried out. For ethylenediammonium terephthalate theoretical calculations of structure were performed by two ways: ab-initio HF and semiempirical PM3. In this case the PM3 method gave more accurate structure (closer to X-ray results). The additional PM3 calculations of vibrational spectra were performed. On the basis theoretical approach and earlier vibrational studies of similar compounds the vibrational assignments for observed bands have been proposed. All compounds were checked for second harmonic generation (SHG).
McGuire, John Andrew
2004-11-24
The high temporal resolution and broad bandwidth of a femtosecond laser system are exploited in a pair of nonlinear optical studies of surfaces. The dephasing dynamics of resonances associated with the adatom dangling bonds of the Si(111)7 x 7 surface are explored by transient second-harmonic hole burning, a process that can be described as a fourth-order nonlinear optical process. Spectral holes produced by a 100 fs pump pulse at about 800 nm are probed by the second harmonic signal of a 100 fs pulse tunable around 800 nm. The measured spectral holes yield homogeneous dephasing times of a few tens of femtoseconds. Fits with a Lorentzian spectral hole centered at zero probe detuning show a linear dependence of the hole width on pump fluence, which suggests that charge carrier-carrier scattering dominates the dephasing dynamics at the measured excitation densities. Extrapolation of the deduced homogeneous dephasing times to zero excitation density yields an intrinsic dephasing time of {approx} 70 fs. The presence of a secondary spectral hole indicates that scattering of the surface electrons with surface optical phonons at 570 cm{sup -1} occurs within the first 200 fs after excitation. The broad bandwidth of femtosecond IR pulses is used to perform IR-visible sum frequency vibrational spectroscopy. By implementing a Fourier-transform technique, we demonstrate the ability to obtain sub-laser-bandwidth spectral resolution. FT-SFG yields a greater signal when implemented with a stretched visible pulse than with a femtosecond visible pulse. However, when compared with multichannel spectroscopy using a femtosecond IR pulse but a narrowband visible pulse, Fourier-transform SFG is found to have an inferior signal-to-noise ratio. A mathematical analysis of the signal-to-noise ratio illustrates the constraints on the Fourier-transform approach.
Morzyk-Ociepa, Barbara; Dysz, Karolina; Turowska-Tyrk, Ilona; Michalska, Danuta
2015-02-01
3-Chloro-7-azaindole (3Cl7AI) is the carrier ligand in a new anticancer platinum(II) agent cis-[PtCl2(3Cl7AI)2]. In this work 3Cl7AI has been studied by a single crystal X-ray diffraction, infrared and Raman spectroscopy and density functional calculations. The compound crystallizes in the monoclinic system, space group P21/n, with a=12.3438(3), b=3.85964(11), c=14.4698(4)Å, ?=100.739(2)°, V=677.31(3)Å(3) and Z=4. In the crystal, a pair of 3Cl7AI molecules forms a centrosymmetric dimer linked by the moderately strong dual N-H?N hydrogen bonds. The nitrogen atom in the pyrrole ring acts as the proton donor, while the nitrogen atom in the pyridine ring is the proton acceptor. The FT-IR and FT-Raman spectra (3500-60 cm(-1)) have been recorded. The theoretical studies on the molecular structures and vibrational spectra of the monomeric and dimeric forms of 3Cl7AI and its N-deuterated derivative were performed using the B3LYP method with 6-311++G(d,p) basis set. The theoretically predicted Raman spectrum for the dimer shows very good agreement with experiment. Detailed vibrational assignments for the two isotopomers have been made on the basis of the calculated potential energy distributions (PEDs). The dual N-H?N hydrogen bonds in 3Cl7AI dimer are characterized by a very broad and complicated structure of the absorption band between 3300 and 2500 cm(-1), which is caused by multiple Fermi resonances between the N-H stretching vibration and various combinations bands. PMID:25315872
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.
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. PMID:16043056
A finite element method for nonlinear forced vibrations of beams
NASA Technical Reports Server (NTRS)
Mei, C.; Decha-Umphai, K.
1984-01-01
Techniques for defining a finite element model (FEM) for analysis of nonlinear vibrations in beam structures subjected to harmonic excitation are presented. The resulting model covers longitudinal deformation and inertial effects. The nonlinear oscillations of a beam element under forced excitation are modeled by a harmonic force matrix based on first order approximations of the Jacobian elliptic forcing function. Harmonic force and nonlinear stiffness matrices are derived and the nonlinear forced responses of beams are calculated under various boundary conditions. The results of FEM computations for simply-supported and clamped beams show that midplane stretching caused by large deflections increases the nonlinearity. Axially-restrained beams experience only hardening nonlinearity, while axially-free beams have reduced nonlinearity in deformation and inertia and an increase in linearity due to large deflection.
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) ?-octahydrocyclotetramethylene-tetranitramine (?-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.
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. PMID:25561302
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.
NASA Astrophysics Data System (ADS)
Tasinato, Nicola; Regini, Giorgia; Stoppa, Paolo; Charmet, Andrea Pietropolli; Gambi, Alberto
2012-06-01
Difluoromethane (CH2F2, HFC-32) is a molecule used in refrigerant mixtures as a replacement of the more environmentally hazardous, ozone depleting, chlorofluorocarbons. On the other hand, presenting strong vibration-rotation bands in the 9 ?m atmospheric window, it is a greenhouse gas which contributes to global warming. In the present work, the vibrational and ro-vibrational properties of CH2F2, providing basic data for its atmospheric modeling, are studied in detail by coupling medium resolution Fourier transform infrared spectroscopy to high-level electronic structure ab initio calculations. Experimentally a full quantum assignment and accurate integrated absorption cross sections are obtained up to 5000 cm-1. Ab initio calculations are carried out by using CCSD(T) theory and large basis sets of either the correlation consistent or atomic natural orbital hierarchies. By using vibrational perturbation theory to second order a complete set of vibrational and ro-vibrational parameters is derived from the ab initio quartic anharmonic force fields, which well compares with the spectroscopic constants retrieved experimentally. An excellent agreement between theory and experiment is achieved for vibrational energy levels and integrated absorption cross sections: transition frequencies up to four quanta of vibrational excitation are reproduced with a root mean square deviation (RMSD) of 7 cm-1 while intensities are predicted within few km mol-1 from the experiment. Basis set performances and core correlation effects are discussed throughout the paper. Particular attention is focused in the understanding of the anharmonic couplings which rule the vibrational dynamics of the |?1?, |2?8?, |2?2? three levels interacting system. The reliability of the potential energy and dipole moment surfaces in reproducing the vibrational eigenvalues and intensities as well as in modeling the vibrational and ro-vibrational mixings over the whole 400-5000 cm-1 region is also demonstrated by spectacular spectral simulations carried out by using the ro-vibrational Hamiltonian constants, and the relevant coupling terms, obtained from the perturbation treatment of the ab initio anharmonic force field. The present results suggest CH2F2 as a prototype molecule to test ab initio calculations and theoretical models.
Power system harmonics estimation and monitoring
Beides, H.M.; Heydt, G.T. )
1992-01-01
In this paper dynamic state estimation of power system harmonics is used to estimate the system bus voltage magnitudes and phase angles at different harmonic levels. These estimated variables are used to calculate harmonic factors and indices that are used to obtain the harmonic profile of the system. The term power system harmonic monitoring'' is proposed to collectively refer to the calculation of total harmonic distortion, distortion index, telephone influence factor, C-message ides, and the KVT and KIT factors. The IEEE 30 bus system, with the three six-pulse rectifier loads, is used as an illustrative example.
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.
Arjunan, V; Kalaivani, M; Marchewka, M K; Mohan, S
2013-04-15
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 OH···O and NH···O hydrogen bonds shows notable vibrational effects. PMID:23416913
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.
NASA Astrophysics Data System (ADS)
Mishra, Alok; Srivastava, Sunil Kumar; Swati, D.
2013-09-01
The structure-activity relationship of the anticoagulant drug warfarin were studied by studying two enantiomeric forms (S-form and R-form) of warfarin and its protonated as well as deprotonated structures in aqueous media using density functional theory (DFT). Theoretically computed Raman and IR spectra of all the computed structures were compared and their specific vibrational spectroscopic signatures were discussed. The percentage contributions of individual normal modes of warfarin, which provides direct evidence of the different molecular activity due to change in relative atomic position of atoms in molecule, were investigated through potential energy distribution (PED). The optimized energy and molecular electrostatic potential (MEP) maps show that the S-form of the drug molecules warfarin is energetically more stable than R-form and provides higher docking opportunity for the molecular binding with the receptors in the bio-systems.
Makowska-Janusik, Malgorzata; Kajzar, Francois; Miniewicz, Andrzej; Mydlova, Lucia; Rau, Ileana
2015-02-26
Results of first principle quantum chemical calculations of electronic and vibrational properties of the push-pull 3-(1,1-dicyanoethenyl)-1-phenyl-4,5-dihydro-1H-pyrazole (DCNP) molecule are reported and discussed. The structure of DCNP was optimized with HF/6-311G methodology and found to be planar. On the basis of obtained geometry, infrared absorption and Raman spectra were computed within the HF/6-311++G** formalism. They allow to conclude that the changes of molecule dipole moment and variation of its polarizability appear at the same vibrational mode and affect the optical properties of the DCNP. Four different methodologies: time-dependent HF and time-dependent DFT method with B3LYP, LC-BLYP, and CAM-B3LYP potentials were used to compute the optical absorption spectra of DCNP. Influence of solvent on molecular electronic structure was studied within the C-PCM model. It predicts the DFT/B3LYP methodology as the best one to compute the NLO properties of the DCNP. The computed HOMO and LUMO orbitals show evidence that the ground state of the molecule is located at its aromatic part. The discussion of charge transfer during the excitation process for the transition S0-S1 was performed. The charge transfer parameter calculated in vacuum and in solvent gives the evidence that the solvent environment weakly enhance the molecular charge transfer. It confirms the tendency of an occurrence of the intermolecular charge transfer in DCNP which is crucial for its hyperpolarizability magnitude. It was proved that the second-order susceptibility corresponding to SHG may be calculated for host-guest polymer/DCNP composite using the simple oriented gas model and the rigorous local field approach should not necessarily be applied. PMID:25648877
Technology Transfer Automated Retrieval System (TEKTRAN)
The structures and energies of glucose and glucose monohydrates have been calculated at the B3LYP/6-311++G** level of theory. Both the alpha and beta anomers were studied, with all possible combinations of hydroxymethyl rotamer (gg, gt, or tg) and hydroxyl orientation (clockwise or counter-clockwis...
NASA Astrophysics Data System (ADS)
Durig, James R.; Zhou, Sarah Xiaohua; Zheng, Chao; Durig, Douglas T.
2010-05-01
Variable temperature (-55 to -155 °C) studies of the infrared spectra (400-3500 cm -1) of ethylisocyanate, CH 3CH 2NCO, dissolved in liquid xenon and krypton have been recorded. Additionally the infrared spectra of the gas and solid have been re-investigated. These spectroscopic data indicate two conformers in the fluid states which are the cis and trans forms with a large proportion of molecules in the gas phase at ambient temperature in the excited states of the NCO torsional mode which has a very low barrier to conformational interchange. Variable temperature (-110 to -155 °C) studies of krypton solutions were carried out and by using two conformer pairs, an enthalpy difference of 100 ± 4 cm -1 (1.20 ± 0.05 kJ/mol) was obtained with the cis conformer the more stable form. To aid in the analyses of the vibrational and rotational spectra, ab initio calculations have been carried out by the perturbation method to the second order (MP2) with full electron correlation using a variety of basis sets up to 6-311+G(2df,2pd) and cc-PVQZ. With the basis sets 6-311+G(2d,2p) and larger, the barrier at the cis position ranged from a low value of 11 cm -1 to a high value of 31 cm -1 with a value of 19 cm -1 from the largest basis set of cc-PVQZ. Thus, the gauche well is probably so shallow that it does not contain a bound vibrational state. This results in the cis conformer as the most stable form which is consistent with the experimental rotational and vibrational data. The predicted energy difference from these calculations between the cis conformer and the transitional-state skew form is ˜100 cm -1 which is consistent with the assigned microwave lines for four excited states of the NCO torsion. Density functional theory calculation by the B3LYP method with many of the same basis sets provided little information. By utilizing the previously reported microwave rotational constants with the structural parameters predicted by the ab initio MP2(full)/6-311+G(d,p) calculations, adjusted r0 structural parameters have been obtained for the cis form. The determined heavy atom parameters are: r(C dbnd N) = 1.211(5), r(C dbnd O) = 1.167(5), r(C sbnd N) = 1.448(5), r(C sbnd C) = 1.516(5) Å for the distances and angles of ?CCN = 112.6(5), ?CNC = 137.5(5), ?NCO = 172.9(5)°. The centrifugal distortion constants, dipole moments, conformational stability, vibrational frequencies, infrared intensities and Raman activities have been predicted from ab initio calculations and compared to experimental quantities when available. These results are compared to the corresponding quantities of some similar molecules.
NASA Astrophysics Data System (ADS)
Cárdenas, A. E.; Coalson, R. D.
1999-06-01
A Gaussian wave packet/path integral (GWD/PI) method is used to compute final internal state distributions for a molecule photodesorbing from the surface of a zero-temperature crystal with internal vibrations in the situation where nonadiabatic coupling between two excited state potential surfaces is significant. The internal state distributions of the desorbed molecule are influenced by vast numbers of internal vibrational state transitions in the crystal which are not resolved in the calculation (or in experiment). A correlation function technique, introduced previously for the case of direct photodissociation on a single excited potential surface, is generalized to systems where two or more excited potential surfaces are nonadiabatically coupled. The accuracy of the method is successfully tested on a two-dimensional model for which numerically exact results can be computed. The method is then applied to a collinear model of a diatomic molecule photodesorbing from a chain of atoms coupled by Hooke's law springs. While exact results cannot be obtained in this case, sum rule checks suggest that the results of the GWD/PI are of acceptable accuracy (fractional error of several percent). It is found that for the class of problems under study, which feature nonadiabatic coupling that decays to zero along the photodesorption coordinate, only a few paths through the electronic state space have significant weight. This suggests that the method can be utilized to treat more complicated problems.
Vibrational overtone stretching transitions in sarin
NASA Astrophysics Data System (ADS)
Petryk, Michael W. P.
2006-10-01
The CH stretching overtone transitions of the nerve agent sarin (O-isopropyl methylphosphonofluoridate) are of interest to the standoff detection of chemical warfare agents, as many of these transitions occur near regions where small, efficient, portable diode lasers (originally developed for use in the telecommunications industry) operate. However, the interpretation of experimental vibrational overtone spectra is often difficult, and the computational simulation of overtone transitions in a molecule is challenging. Presented herein are the simulated CH overtone stretching transitions in sarin. Spectral regions are simulated from overtone transition energies and intensities, both of which are calculated within the harmonically coupled anharmonic oscillator (HCAO) model. Data for HCAO calculations are obtained from ab initio calculations, without any recourse to experimental data.
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.
Al-Abdullah, Ebtehal S; Sebastian, Sr S H Roseline; Al-Wabli, Reem I; El-Emam, Ali A; Panicker, C Yohannan; Van Alsenoy, Christian
2014-12-10
The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 5-(Adamantan-1-yl)-3-[(4-fluoroanilino)methyl]-2,3-dihydro-1,3,4-oxadiazole-2-thione are investigated experimentally and theoretically using Gaussian09 software package. Potential energy distribution of normal modes vibrations was done using GAR2PED program. The HOMO and LUMO analysis are used to determine the charge transfer within the molecule. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The calculated geometrical parameters are in agreement with the XRD data. The calculated first hyperpolarizability is high and the title compound is an attractive candidate for further studies in non-linear optical applications. To estimate the chemical reactivity of the molecule, the molecular electrostatic potential is calculated for the optimized geometry of the molecule. PMID:24992920
NASA Astrophysics Data System (ADS)
Al-Abdullah, Ebtehal S.; Roseline, Sebastian S. H., Sr.; Al-Wabli, Reem I.; El-Emam, Ali A.; Panicker, C. Yohannan; Van Alsenoy, Christian
2014-12-01
The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 5-(Adamantan-1-yl)-3-[(4-fluoroanilino)methyl]-2,3-dihydro-1,3,4-oxadiazole-2-thione are investigated experimentally and theoretically using Gaussian09 software package. Potential energy distribution of normal modes vibrations was done using GAR2PED program. The HOMO and LUMO analysis are used to determine the charge transfer within the molecule. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The calculated geometrical parameters are in agreement with the XRD data. The calculated first hyperpolarizability is high and the title compound is an attractive candidate for further studies in non-linear optical applications. To estimate the chemical reactivity of the molecule, the molecular electrostatic potential is calculated for the optimized geometry of the molecule.
Vibration Analysis of AN Induction Motor
NASA Astrophysics Data System (ADS)
WANG, C.; LAI, J. C. S.
1999-07-01
With the advent of power electronics, variable speed induction motors are finding increasing use in industries because of their low cost and potential savings in energy consumption. However, the acoustic noise emitted by the motor increases due to switching harmonics introduced by the electronic inverters. Consequently, the vibro-acoustic behaviour of the motor structure has attracted more attention. In this paper, considerations given to modelling the vibration behaviour of a 2·2 kW induction motor are discussed. By comparing the calculated natural frequencies and the mode shapes with the results obtained from experimental modal testing, the effects of the teeth of the stator, windings, outer casing, slots, end-shields and support on the overall vibration behaviour are analyzed. The results show that when modelling the vibration behaviour of a motor structure, the laminated stator should be treated as an orthotropic structure, and the teeth of the stator could be neglected. As the outer casing, end-shields and the support all affect the vibration properties of the whole structure, these substructures should be incorporated in the model to improve the accuracy.
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.
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.
NASA Astrophysics Data System (ADS)
Mohamed, Tarek A.; Hassan, Ali M.; Soliman, Usama A.; Zoghaib, Wajdi M.; Husband, John; Hassan, Saber M.
2011-09-01
The Raman and infrared spectra of solid methyl-5-amino-4-cyano-3-(methylthio)-1H-pyrazole-1-carbodithioate (MAMPC, C 7H 8N 4S 3) were measured in the spectral range of 3700-100 cm -1 and 4000-200 cm -1 with a resolution of 4 and 0.5 cm -1, respectively. Room temperature 13C NMR and 1H NMR spectra from room temperature down to -60 °C were also recorded. As a result of internal rotation around C-N and/or C-S bonds, eighteen rotational isomers are suggested for the MAMPC molecule (Cs symmetry). DFT/B3LYP and MP2 calculations were carried out up to 6-311++G(d,p) basis sets to include polarization and diffusion functions. The results favor conformer 1 in the solid (experimentally) and gaseous (theoretically) phases. For conformer 1, the two -CH 3 groups are directed towards the nitrogen atoms (pyrazole ring) and C dbnd S, while the -NH 2 group retains sp 2 hybridization and C-C tbnd N bond is quasi linear. To support NMR spectral assignments, chemical shifts ( ?) were predicted at the B3LYP/6-311+G(2d,p) level using the method of Gauge-Invariant Atomic Orbital (GIAO) method. Moreover, the solvent effect was included via the Polarizable Continuum Model (PCM). Additionally, both infrared and Raman spectra were predicted using B3LYP/6-31G(d) calculations. The recorded vibrational, 1H and 13C NMR spectral data favors conformer 1 in both the solid phase and in solution. Aided by normal coordinate analysis and potential energy distributions, confident vibrational assignments for observed bands have been proposed. Moreover, the CH 3 barriers to internal rotations were investigated. The results are discussed herein are compared with similar molecules whenever appropriate.
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 (13)C NMR and (1)H 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. PMID:25498815
Durig, James R; Pan, Chunhua; Guirgis, Gamil A
2003-03-15
The infrared (3100-40 cm(-1)) and Raman (3100-20 cm(-1)) spectra of gaseous and solid n-propylsilane, CH(3)CH(2)CH(2)SiH(3) and the Si-d(3) isotopomer, CH(3)CH(2)CH(2)SiD(3), have been recorded. Additionally, the Raman spectra of the liquids have been recorded and qualitative depolarization values obtained. Both the anti and gauche conformers have been identified in the fluid phases but only the anti conformer remains in the solid. Variable temperature (-105 to -150 degrees C) studies of the infrared spectra of n-propylsilane dissolved in liquid krypton have been recorded and the enthalpy difference has been determined to be 220+/-22 cm(-1) (2.63+/-0.26 kJ mol(-1)) with the anti conformer the more stable form. A similar value of 234+/-23 cm(-1) (2.80+/-0.28 kJ mol(-1)) was obtained for deltaH for the Si-d(3) isotopomer. At ambient temperature it is estimated that there is 30+/-2% of the gauche conformer present. The potential function governing the conformation interchange has been estimated from the far infrared spectral data, the enthalpy difference, and the dihedral angle of the gauche conformer, which is compared to the one predicted from ab initio MP2/6-31G(d) calculations. The barriers to conformational interchange are: 942, 970 and 716 cm(-1) for the anti to gauche, gauche to gauche, and gauche to anti conformers, respectively. Relatively complete vibrational assignments are proposed for both the n-propylsilane-d(0) and Si-d(3) molecules based on the relative infrared and Raman spectral intensities, infrared band contours, depolarization ratios, and normal coordinate calculations. The geometrical parameters, harmonic force constants, vibrational frequencies, infrared intensities, Raman activities and depolarization ratios, and energy differences have been obtained for the anti and gauche conformers from ab initio MP2/6-31G(d) calculations. Structural parameters and energy differences have also been obtained utilizing the larger 6-311 + G(d,p) and 6-311 + G(2d,2p) basis sets. From the isolated Si-H stretching frequency from the Si-d(2) isotopomer the r(0) distances of 1.484 and 1.485 A have been determined for the SiH(s) and SiH(a) bonds, respectively, for the anti conformer, and 1.486 A for the SiH bond for the gauche conformer. Utilizing previously reported microwave rotational constants for the anti conformer and the determined SiH distances along with ab initio predicted parameters 'adjusted r(0)' parameters have been obtained for the anti conformer. The results are discussed and compared to those obtained for some similar molecules. PMID:12633715
Vibrational infrared spectra of biuret and its thioanalogs. An ab initio SCF/3-21G study
NASA Astrophysics Data System (ADS)
Sullivan, Richard H.; Kwiatkowski, Józef S.; Leszczy?ski, Jerzy; Jabalameli, Ali
1993-05-01
The results of ab initio SCF/3-21G * calculations are reported for vibrational IR spectra (harmonic wavenumbers, absolute intensities) of biuret, thiobiuret, dithiobiuret and their model systems, formamide and thioformamide. The predicted vibrational spectra of both biurets and model systems compare well with the available experimental data, and the observed shifts of the IR wavenumbers upon deuteration of the molecules are correctly predicted by the calculations. The positions and relative intensities of characteristic IR bands of formamide and thioformamide correlate well with the corresponding data for the biurets.
NASA Astrophysics Data System (ADS)
Karakaya, Mustafa; Kürekçi, Mehmet; Eskiyurt, Buse; Sert, Yusuf; Ç?rak, Ça?r?
2015-01-01
In present study, the experimental and theoretical harmonic vibrational frequencies of gliclazide molecule have been investigated. The experimental FT-IR (400-4000 cm-1) and Laser-Raman spectra (100-4000 cm-1) of the molecule in the solid phase were recorded. Theoretical vibrational frequencies and geometric parameters (bond lengths and bond angles) have been calculated using ab initio Hartree Fock (HF), density functional theory (B3LYP hybrid function) methods with 6-311++G(d,p) and 6-31G(d,p) basis sets by Gaussian 09W program. The assignments of the vibrational frequencies were performed by potential energy distribution (PED) analysis by using VEDA 4 program. Theoretical optimized geometric parameters and vibrational frequencies have been compared with the corresponding experimental data, and they have been shown to be in a good agreement with each other. Also, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies have been found.
NASA Astrophysics Data System (ADS)
Kouach-Alix, I.; Vergoten, G.
1994-07-01
Combining the modified Urey—Bradley—Shimanouchi intramolecular potential energy function with an appropriate intermolecular energy function, normal coordinate calculations have been performed for N-acetyl-?- D-glucosamine in the crystalline state. The infrared spectra in the mid range (4000-500 cm -1) and the Raman spectra in 3500-20 cm -1 range were recorded. The overall agreement between the observed and calculated frequencies led to an average error of the order of 3.5 cm -1. The computed potential energy distribution was found to be compatible with previous assignments of D-glucose and D-galactose for the pyranose ring and for N-methylacetamide for the acetamido group. The set of force constants used for N-acetyl-?- D-glucosamine was approximately the same as that obtained for the glucose and N-methylacetamide respectively for the pyranose ring and the acetamido group, a difference existing only for the atoms involved in the anomeric and hydroxy groups.
NASA Astrophysics Data System (ADS)
Ledesma, A. E.; Contreras, C.; Svoboda, J.; Vektariane, A.; Brandán, S. A.
2010-04-01
A theoretical structural and experimental vibrational study for the benzothieno [3,2- b] furan and thieno [3,2- b] benzofuran compounds is presented. The density functional theory (DFT) has been used to study its structures and vibrational properties. The geometries were fully optimised at the B3LYP/6-31G? and B3LYP/6-311++G?? levels of theory and the harmonic vibrational frequencies were evaluated at the same levels. The calculated harmonic vibrational frequencies for the compound are consistent with the experimental IR spectrum in chloroform solution. These calculations gave us precise knowledge of the normal modes of vibration of these compounds. A complete assignment of all the observed bands in the infrared and Raman spectra for both benzothieno [3,2- b] furans compound was performed. The nature of the different rings bonds in both compounds was quantitatively investigated by means of Natural Bond Orbital (NBO) analysis. The topological properties of electronic charge density are analysed by employing Bader's Atoms in the Molecules theory (AIM).
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.
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.
NASA Astrophysics Data System (ADS)
Sarma, Manabendra; Singh, Raman K.; Mishra, Manoj K.
2007-12-01
Vibrational excitation cross-sections ?n?m(E) in resonant e-N2, e-CO and e-H2 scattering are calculated from transition matrix elements Tn?m(E) obtained using Fourier transform of the cross correlation function where ?m(R,t); e-iHA-(R)t/??m(R). Time evolution under the influence of the resonance anionic Hamiltonian HA-(A- = N2-/CO/H2-) is effected using Lanczos and fast Fourier transforms and the target (A) vibrational eigenfunctions ?m(R) and ?n(R) are calculated using Fourier grid Hamiltonian method applied to PE curve of the neutral target. The resulting vibrational excitation cross-section profiles provide reasonable agreement with experimental results and the cross correlation functions offer an unequivocal differentiation between the boomerang and impulse models.
Nonperturbative vibrational energy relaxation effects on vibrational line shapes
Cao, Jianshu
approach to vibrational phase and energy relaxation is based on perturbation theory and Fermi's golden rule quantum dynamics of solutes in a condensed phase is proposed to calculate linear and nonlinear vibrational between population relaxations of different vibrational states. These predictions cannot be reproduced
Method and apparatus for vibrating a substrate during material formation
Bailey, Jeffrey A. (Richland, WA) [Richland, WA; Roger, Johnson N. (Richland, WA) [Richland, WA; John, Munley T. (Benton City, WA) [Benton City, WA; Walter, Park R. (Benton City, WA) [Benton City, WA
2008-10-21
A method and apparatus for affecting the properties of a material include vibrating the material during its formation (i.e., "surface sifting"). The method includes the steps of providing a material formation device and applying a plurality of vibrations to the material during formation, which vibrations are oscillations having dissimilar, non-harmonic frequencies and at least two different directions. The apparatus includes a plurality of vibration sources that impart vibrations to the material.
NASA Astrophysics Data System (ADS)
Belmonte, D.; Ottonello, G.; Zuccolini, M. Vetuschi
2013-02-01
We present the results of a computational investigation of the structure-energy and vibrational properties of alumina under various aggregation states (crystalline, glassy, and liquid) with ab initio procedures. IV-fold, V-fold, and VI-fold oxygen-coordinated aluminum monomeric forms in a dielectric continuum with dielectric constant ? = 4.575 were investigated through DFT/B3LYP gas-phase calculations coupled with a Polarized Continuum Model approach and those of the periodical structure D63d (R-3c) which leads to the ?-Al2O3 polymorph of alumina, when subjected to symmetry operations, were investigated with the same functional within the LCAO approximation and in the framework of Bloch's theorem. Based on the computed energies and vibrational features, an aggregate of the D63d positively charged cluster [Al12O11]14+ contoured by [AlO4]5- units in an approximate 1:3 proportion to achieve neutrality satisfactorily reproduce the heat capacity of the liquid within experimental uncertainty. The glass is seen as a wrong accretionary form induced by fast cooling rates and subjected to steric forces that locally modify the coordination state of the central atom. Cessation of rotational and translational movements, only partly counterbalanced by acoustic sine-wave-dispersed and excess phonons, gives rise to the huge heat-capacity gap observed at the glass transition (˜5.3R). When cooling rates are sufficiently slow, the accretion around the D63d seeds follows the structural constraints and the heat capacity of ?-alumina is almost perfectly reproduced by the 27 Einstein oscillators coupled with the 3 acoustic terms and the anharmonic corrections.
Lewandowska, Kornelia; Jeli?ska, Anna; Zalewski, Przemys?aw; Oszczapowicz, Irena; Sikora, Adam; Kozak, Maciej
2015-01-01
FT-IR and Raman scattering spectra of cefuroxime axetil were proposed for identification studies of its crystalline and amorphous forms. An analysis of experimental spectra was supported by quantum-chemical calculations performed with the use of B3LYP functional and 6-31G(d,p) as a basis set. The geometric structure of a cefuroxime axetil molecule, HOMO and LUMO orbitals, and molecular electrostatic potential were also determined by using DFT (density functional theory). The benefits of applying FT-IR and Raman scattering spectroscopy for characterization of drug subjected to degradation were discussed. PMID:25654137
NASA Astrophysics Data System (ADS)
M?czka, M.; Zierkiewicz, W.; Michalska, D.; Hanuza, J.
2014-07-01
Experimental Raman and IR spectra of multiferroic [(CH3)2NH2][Ni(HCOO)3] were recorded at room temperature. The three-parameter hybrid B3LYP density functional method has been used with the 6-31G(d, p) basis set to derive the equilibrium geometry, atomic spin densities, vibrational wavenumbers, infrared intensities and Raman scattering activities. Based on these calculations, the assignment of the observed bands to the respective internal and lattice modes is proposed. The performed calculations revealed that the ?(NH2) stretching, ?(NH2) rocking and ?(CH3) torsional modes are very sensitive to formation of the hydrogen bond between the DMA+ cation and Ni-formate framework. Therefore, these modes are suitable probes for strength of hydrogen bonds in this family of metal-formate frameworks and study of their temperature dependence may provide significant information on a role of the hydrogen bonds in mechanism of the ferroelectric phase transition occurring in these compounds at low temperatures.
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.
Thermal weights for semiclassical vibrational response functions.
Moberg, Daniel R; Alemi, Mallory; Loring, Roger F
2015-08-28
Semiclassical approximations to response functions can allow the calculation of linear and nonlinear spectroscopic observables from classical dynamics. Evaluating a canonical response function requires the related tasks of determining thermal weights for initial states and computing the dynamics of these states. A class of approximations for vibrational response functions employs classical trajectories at quantized values of action variables and represents the effects of the radiation-matter interaction by discontinuous transitions. Here, we evaluate choices for a thermal weight function which are consistent with this dynamical approximation. Weight functions associated with different semiclassical approximations are compared, and two forms are constructed which yield the correct linear response function for a harmonic potential at any temperature and are also correct for anharmonic potentials in the classical mechanical limit of high temperature. Approximations to the vibrational linear response function with quantized classical trajectories and proposed thermal weight functions are assessed for ensembles of one-dimensional anharmonic oscillators. This approach is shown to perform well for an anharmonic potential that is not locally harmonic over a temperature range encompassing the quantum limit of a two-level system and the limit of classical dynamics. PMID:26328812
Thermal weights for semiclassical vibrational response functions
NASA Astrophysics Data System (ADS)
Moberg, Daniel R.; Alemi, Mallory; Loring, Roger F.
2015-08-01
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.
Powell, B J; Baruah, T; Bernstein, N; Brake, K; McKenzie, Ross H; Meredith, P; Pederson, M R
2004-05-01
We report first-principles density-functional calculations for hydroquinone (HQ), indolequinone (IQ), and semiquinone (SQ). These molecules are believed to be the basic building blocks of the eumelanins, a class of biomacromolecules with important biological functions (including photoprotection) and with the potential for certain bioengineering applications. We have used the difference of self-consistent fields method to study the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, Delta(HL). We show that Delta(HL) is similar in IQ and SQ, but approximately twice as large in HQ. This may have important implications for our understanding of the observed broadband optical absorption of the eumelanins. The possibility of using this difference in Delta(HL) to molecularly engineer the electronic properties of eumelanins is discussed. We calculate the infrared and Raman spectra of the three redox forms from first principles. Each of the molecules have significantly different infrared and Raman signatures, and so these spectra could be used in situ to nondestructively identify the monomeric content of macromolecules. It is hoped that this may be a helpful analytical tool in determining the structure of eumelanin macromolecules and hence in helping to determine the structure-property-function relationships that control the behavior of the eumelanins. PMID:15267788
NASA Astrophysics Data System (ADS)
Powell, B. J.; Baruah, T.; Bernstein, N.; Brake, K.; McKenzie, Ross H.; Meredith, P.; Pederson, M. R.
2004-05-01
We report first-principles density-functional calculations for hydroquinone (HQ), indolequinone (IQ), and semiquinone (SQ). These molecules are believed to be the basic building blocks of the eumelanins, a class of biomacromolecules with important biological functions (including photoprotection) and with the potential for certain bioengineering applications. We have used the difference of self-consistent fields method to study the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, ?HL. We show that ?HL is similar in IQ and SQ, but approximately twice as large in HQ. This may have important implications for our understanding of the observed broadband optical absorption of the eumelanins. The possibility of using this difference in ?HL to molecularly engineer the electronic properties of eumelanins is discussed. We calculate the infrared and Raman spectra of the three redox forms from first principles. Each of the molecules have significantly different infrared and Raman signatures, and so these spectra could be used in situ to nondestructively identify the monomeric content of macromolecules. It is hoped that this may be a helpful analytical tool in determining the structure of eumelanin macromolecules and hence in helping to determine the structure-property-function relationships that control the behavior of the eumelanins.
NASA Astrophysics Data System (ADS)
Ramírez-Solís, A.; Jolibois, Franck; Maron, Laurent
2011-06-01
Born-Oppenheimer DFT molecular dynamics (BO-DFT-MD) simulations were performed on the three lowest energy isomers of S2O2. After a careful calibration of the electronic structure method, the calculations were done using the B3PW91/aug-cc-pVTZ method. The dynamic vibrational spectra are reported and the lowest vibrational modes are identified, which correlate well with ab initio static predictions. The non-harmonic effects are non-negligible for the studied isomers. The largest non-harmonic contributions (up to 22%) were found for the third and fourth modes of the cis-OSSO C2v isomer. The relative vibrational peak intensities provide valuable information for the identification of this as yet undetected stable species.
Vibrational Heat Transport in Molecular Junctions
Segal, Dvira
2015-01-01
We review studies of vibrational energy transfer in a molecular junction geometry, consisting of a molecule bridging two heat reservoirs, solids or large chemical compounds. This setup is of interest for applications in molecular electronics, thermoelectrics, and nanophononics, and for addressing basic questions in the theory of classical and quantum transport. Calculations show that system size, disorder, structure, dimensionality, internal anharmonicities, contact interaction, and quantum coherent effects, are factors that interplay to determine the predominant mechanism (ballistic/diffusive), effectiveness (poor/good) and functionality (linear/nonlinear) of thermal conduction at the nanoscale. We review recent experiments and relevant calculations of quantum heat transfer in molecular junctions. We recount the Landauer approach, appropriate for the study of elastic (harmonic) phononic transport, and outline techniques which incorporate molecular anharmonicities. Theoretical methods are described along with...
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.
Large scale exact quantum dynamics calculations: Ten thousand quantum states of acetonitrile
NASA Astrophysics Data System (ADS)
Halverson, Thomas; Poirier, Bill
2015-03-01
'Exact' quantum dynamics (EQD) calculations of the vibrational spectrum of acetonitrile (CH3CN) are performed, using two different methods: (1) phase-space-truncated momentum-symmetrized Gaussian basis and (2) correlated truncated harmonic oscillator basis. In both cases, a simple classical phase space picture is used to optimize the selection of individual basis functions-leading to drastic reductions in basis size, in comparison with existing methods. Massive parallelization is also employed. Together, these tools-implemented into a single, easy-to-use computer code-enable a calculation of tens of thousands of vibrational states of CH3CN to an accuracy of 0.001-10 cm-1.
Chiral vibrations in the A=135 region
Daniel Almehed; Friedrich Doenau; Stefan Frauendorf
2011-01-31
Chiral vibrations are studied with the RPA plus self-consistent tilted axis cranking formalism in the A=135 region. In this method chiral vibrations appear as a precursor to the static chiral regime. The properties of the RPA phonons are discussed and compared to experimental data. We discuss the limits the chiral region and the transition to the non harmonic regime.
Joni C. Gray; Donald G. Truhlar; Laura Clemens; James W. Duff; Frank M. Chapman; Glenn O. Morrell; Edward F. Hayes
1978-01-01
Quantum mechanical calculations are compared to quasiclassical trajectory forward (QCT) calculations for the collinear, endoergic reaction H2(n1)+I?H+HI for two different potential energy surfaces, a rotated-Morse-curve (RMC) surface and the semiempirical valence-bond surface of Raff etal. Vibrationally state-selected reaction probabilities and rate constants and Arrhenius parameters are presented. Thermally averaged rate constants and their Arrhenius parameters are also given. For one
Brauer, Brina; Dubnikova, Faina; Zeiri, Yehuda; Kosloff, Ronnie; Gerber, R Benny
2008-12-15
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. PMID:18554978
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.
Optimized Structure and Vibrational Properties by Error Affected Potential Energy Surfaces
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
B. I. Swanson; T. H. Arnold; Y. Yamaguchi
1979-01-01
A semiempirical method combining SCF-MO calculations and limited vibrational data has been employed to evaluate the completely general quadratic potential fields of fluoroform, methyl acetylene, and acetonitrile. MOCIC (molecular orbital constraint using interaction coordinates) potential fields are presented for gas phase molecules of intermediate size. Here general harmonic force fields or excellent approximations utilizing extensive experimental data are available as
A vibrational spectroscopy study on anserine and its aqueous solutions.
Akkaya, Y; Balci, K; Goren, Y; Akyuz, S; Stricker, M C; Stover, D D; Ritzhaupt, G; Collier, W B
2015-10-01
In this study based on vibrational spectroscopic measurements and Density Functional Theory (DFT), we aimed for a reliable interpretation of the IR and Raman spectra recorded for anserine in the solid phase and water (H2O) and heavy water (D2O) solutions. Initial DFT calculations at the B3LYP/6-31G(d) searched possible conformers of the anserine zwitterion using a systematic conformational search. The corresponding equilibrium geometrical parameters and vibrational spectral data were determined for each of the stable conformers (in water) by the geometry optimization and hessian calculations performed at the same level of theory using the polarized continuum model (PCM). The same calculations were repeated to determine the most energetically preferred dimer structure for the molecule and the associated geometry, force field and vibrational spectral data. The harmonic force constants obtained from these calculations were scaled by the Scaled Quantum Mechanical Force Field (SQM) method and then used in the calculation of the refined wavenumbers, potential energy distributions, IR and Raman intensities. These refined theoretical data, which confirm the zwitterion structure for anserine in the solid phase or aqueous solvents, revealed the remarkable effects of intermolecular hydrogen bonding on the structural properties and observed IR and Raman spectra of this molecule. PMID:25997178
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.
Vibration of String and Wave Propagation
Mikio Tohyama
\\u000a Strings are naturally musical sound instruments as are acoustic pipes. This is because free vibration of one-dimensionally\\u000a extending media such as a string can be composed of a fundamental and its harmonics, which are important for musical sound\\u000a and with scales. Scientific studies on the resonance of string vibrations date from Pythagoras, and Galileo mentioned eigenfrequencies\\u000a of free vibration of
NASA Astrophysics Data System (ADS)
Krishnakumar, V.; Prabavathi, N.
2010-09-01
This work deals with the vibrational spectroscopy of 6,7-dimethoxy-1,4-dihydro-1,3-quinoxalinedione by means of quantum chemical calculations. The mid and far FT-IR and FT-Raman spectra are recorded in the condensed State. The fundamental vibrational frequencies and intensity of vibrational bands are evaluated using density functional theory (DFT) with the standard B3LYP/6-31G* method and basis set combination and is scaled using various scale factors which yields a good agreement between observed and calculated frequencies. The vibrational spectrum is interpreted with the aid of normal coordinate analysis based on scaled density functional force field. The results of the calculations are applied to simulate infrared and Raman spectra of the title compounds, which showed excellent agreement with the observed spectra. The infrared unscaled frequencies and intensities are used to disentangle the role played by back-donation in the title compound. For this purpose five other molecules are considered as references: ethane, dimethyl ether, anisole, p-nitro-anisole, and p-hydroxyanisole, in which back-donation has already been ascertained also experimentally. From the study of infrared intensities it is shown that no back-donation of electrons from the oxygen lone pairs takes place, independently of the conformation of the methoxy-group.
NASA Astrophysics Data System (ADS)
Nenghabi, Emmanuel N.; Myles, Charles W.
2008-11-01
We have performed density-functional calculations of the vibrational and thermal properties of some of the type-I semiconductor clathrate “alloys” Ba8Ga16SixGe30-x and Sr8Ga16SixGe30-x as a function of Si composition x . We find that the guest-atoms Ba and Sr produce localized vibrational modes lying below 80cm-1 , which tend to reduce the acoustic bandwidth of the host material. Our results also predict an upshift in the flat optic modes of the host framework as the Si content of the lattice increases and that the guest-atom-associated Einstein temperature in these materials varies with x . Our calculated isotropic atomic displacement parameters as functions of temperature for the guest Ba and Sr atoms in these clathrates predict that Sr has a larger isotropic displacement parameter than Ba, thus suggesting that Sr should be more efficient than Ba in suppressing the thermal conductivity. We have also calculated the temperature dependences of the vibrational contributions to the specific heat, the entropy, and the Helmholtz free energy in these materials. We find that the heat capacities of these clathrates increase smoothly with temperature and approach the Dulong-Petit value at around room temperature. As expected, we also find that in these materials, there is also a slight x dependence of the heat capacity, free energy, and vibrational entropy.
The Effect of Anharmonicity on Diatomic Vibration; A Spreadsheet Simulation
NSDL National Science Digital Library
Instructors and students can use this spreadsheet to quickly and easily observe how the shape of a one-dimensional vibrational potential energy curve and its associated vibrational quantum energy levels depend on the anharmonicity. This illustrates the connection between the harmonic (approximation) and anharmonic descriptions of molecular vibrations.
Vibrational corrections to properties at arbitrary reference geometry
NASA Astrophysics Data System (ADS)
Ingamells, Victoria E.; Papadopoulos, Manthos G.; Sadlej, Andrzej J.
2000-01-01
We demonstrate how vibrational contributions to any (static) electric property may be computed with respect to an arbitrary reference geometry which, at a given level of electronic structure theory, need not correspond to the associated minimum energy geometry. Within the harmonic approximation, it is shown that the formulas for the vibrational contributions can be extended to include a second-order corrective term, which is a function of the energy gradient and the (nuclear) first derivatives of the property in question. Taking the BH molecule as a test case, we illustrate that the order of magnitude of the correction increases with order of property (i.e., ??10-2???101-102), and that this value is equivalent to the difference in (pure) electronic contributions evaluated with respect to the optimum and nonoptimum geometries. Furthermore, we show that for a diatomic, vibrational [zero-point vibrational average (ZPVA) and pure] contributions computed at a nonoptimum geometry may be readily corrected to give the optimum geometry values. Thus we provide a route for obtaining total (electronic+vibrational) properties associated with a minimum energy geometry, using information calculated at a nonoptimum geometry.
NASA Technical Reports Server (NTRS)
Grigoryey, N. V.; Fedorovich, M. A.
1973-01-01
The vibroacoustical characteristics of different types of electric motors are discussed. It is shown that the basic source of low frequency vibrations is rotor unbalance. A flexible damping support, with an antivibrator, is used to obtain the vibroacoustical effect of reduction in the basic harmonic of the electric motor. A model of the electric motor and the damping apparatus is presented. Mathematical models are developed to show the relationships of the parameters. The basic purpose in using a calculation model id the simultaneous replacement of the exciting force created by the rotor unbalance and its inertial rigidity characteristics by a limiting kinematic disturbance.
Nový, Jakub; Böhm, Stanislav; Králová, Jarmila; Král, Vladimír; Urbanová, Marie
2008-02-01
Variations in the structure of d(GGGA)(5) oligonucleotide in the presence of Li(+), Na(+), and K(+) ions and its temperature stability were studied using electronic and vibrational circular dichroism, IR absorption, and ab initio calculations with the Becke 3-Lee-Yang-Parr functional at the 6-31G** level. The samples were characterized by nondenaturing gel electrophoresis. Oligonucleotide d(GGGA)(5) in the presence of Li(+) forms a nonplanar single tetramer, with angles of 102 degrees and 171 degrees between neighboring guanine bases. This tetramer changes its geometry at temperatures >50 degrees C, but does not form a quadruplex structure. In the presence of Na(+), the d(GGGA)(5) structure was optimized to almost planar tetramers with an angle of 177 degrees between neighboring guanines. The spectral results suggest that it stacks into a quadruplex helical structure. This quadruplex structure decayed to a single tetramer at temperatures >60 degrees C. The Hartree-Fock energies imply that d(GGGA)(5) prefers to form complexes with Na(+) rather than Li(+). The d(GGGA)(5) structure in the presence of monovalent ions is stabilized against thermal denaturation in the order Li(+) < Na(+) < K(+). PMID:17960602
NASA Astrophysics Data System (ADS)
Witek, Henryk A.; Irle, Stephan; Zheng, Guishan; de Jong, Wibe A.; Morokuma, Keiji
2006-12-01
The self-consistent charge density-functional tight-binding (SCC-DFTB) method is employed for studying various molecular properties of small fullerenes: C28, C60, and C70. The computed bond distances, vibrational infrared and Raman spectra, vibrational densities of states, and electronic densities of states are compared with experiment (where available) and density-functional theory (DFT) calculations using various basis sets. The presented DFT benchmark calculations using the correlation-consistent polarized valence triple zeta basis set are at present the most extensive calculations on harmonic frequencies of these species. Possible limitations of the SCC-DFTB method for the prediction of molecular vibrational and optical properties are discussed. The presented results suggest that SCC-DFTB is a computationally feasible and reliable method for predicting vibrational and electronic properties of such carbon nanostructures comparable in accuracy with small to medium size basis set DFT calculations at the computational cost of standard semiempirical methods.
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.
Harmonic generation at high intensities
Schafer, K.J.; Krause, J.L.; Kulander, K.C.
1993-06-01
Atomic electrons subject to intense laser fields can absorb many photons, leading either to multiphoton ionization or the emission of a single, energetic photon which can be a high multiple of the laser frequency. The latter process, high-order harmonic generation, has been observed experimentally using a range of laser wavelengths and intensities over the past several years. Harmonic generation spectra have a generic form: a steep decline for the low order harmonics, followed by a plateau extending to high harmonic order, and finally an abrupt cutoff beyond which no harmonics are discernible. During the plateau the harmonic production is a very weak function of the process order. Harmonic generation is a promising source of coherent, tunable radiation in the XUV to soft X-ray range which could have a variety of scientific and possibly technological applications. Its conversion from an interesting multiphoton phenomenon to a useful laboratory radiation source requires a complete understanding of both its microscopic and macroscopic aspects. We present some recent results on the response of single atoms at intensities relevant to the short pulse experiments. The calculations employ time-dependent methods, which we briefly review in the next section. Following that we discuss the behavior of the harmonics as a function of laser intensity. Two features are notable: the slow scaling of the harmonic intensities with laser intensity, and the rapid variation in the phase of the individual harmonics with respect to harmonic order. We then give a simple empirical formula that predicts the extent of the plateau for a given ionization potential, wavelength and intensity.
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.
NASA Astrophysics Data System (ADS)
Jung, Joon O.; Gerber, R. Benny
1996-12-01
The vibrational ground state and the fundamental excited states of (Ar)13 were studied by vibrational self-consistent field (VSCF) calculations. These calculations treat the interaction between different modes through a mean potential approximation, and incorporate anharmonicity in full. The good accuracy of VSCF for such systems was demonstrated by test calculations for (Ar)3 and other clusters. The study of (Ar)13 focused on the properties of the wave functions and the excitation energies, on the role of the coupling between the modes and on the deviation from the harmonic approximation. It was found that SCF excitation energies for the fundamental transitions differ from the harmonic values by about 25% for the softest modes, and by about 10% for the stiffest modes. Coupling between the modes, treated by SCF, was found to be much more important than the intrinsic anharmonicity of the individual modes. For the ground state, the harmonic wave function compares well with VSCF, but for the fundamental excited states appreciable differences were found. The results for a potential field expanded to fourth-order polynomial in the normal mode displacements are found to be valid, almost indentical with those for a more elaborate sixth-order polynomial expansion. The fundamental excitation frequencies computed using the Aziz-Slaman Ar-Ar pair potential are very similar, with some quantitative deviations, to the values obtained with a Lennard-Jones potential. The differences are larger for certain specific modes, and very small for the others. These calculations demonstrate the computational power of VSCF as a tool for quantum-mechanical calculations for large clusters, at the level of specific wave functions.
Structure and vibrational analysis of methyl 3-amino-2-butenoate
NASA Astrophysics Data System (ADS)
Berenji, Ali Reza; Tayyari, Sayyed Faramarz; Rahimizadeh, Mohammad; Eshghi, Hossein; Vakili, Mohammad; Shiri, Ali
2013-02-01
The molecular structure and vibrational spectra of methyl 3-(amino)-2-butenoate (MAB) and its deuterated analogous, D3MAB, were investigated using density functional theory (DFT) calculations. The geometrical parameters and harmonic vibrational wavenumbers of MAB and D3MAB were obtained at the B3LYP/6-311++G(d,p) level. The calculated vibrational wavenumbers were compared with the corresponding experimental results. The assignment of the IR and Raman spectra of MAB and D3MAB was facilitated by calculating the anharmonic wavenumbers at the B3LYP/6-311G(d,p) level as well as recording and calculating the MAB spectra in CCl4 solution. The assigned normal modes were compared with a similar molecule, 4-amino-3-penten-2-one (APO). The theoretical results were in good agreement with the experimental data. All theoretical and experimental results indicate that substitution of a methyl group with a methoxy group considerably weakens the intramolecular hydrogen bond and reduces the ?-electron delocalization in the chelated ring system. The IR spectra also indicate that in the solid state, MAB is not only engaged in an intramolecular hydrogen bond, but also forms an intermolecular hydrogen bond. However, the intermolecular hydrogen bond will be removed in dilute CCl4 solution.
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.
Molecular structure, vibrational spectroscopy, NBO and HOMO, LUMO studies of o-methoxybenzonitrile
NASA Astrophysics Data System (ADS)
Elanthiraiyan, M.; Jayasudha, B.; Arivazhagan, M.
2015-01-01
In the present study, the FT-IR and FT-Raman spectra of o-methoxybenzonitrile (O-MBN) have been recorded in the region 4000-400 cm-1 and 3500-50 cm-1, respectively. The fundamental modes of vibrational frequencies of O-MBN are assigned. Theoretical information on the optimized geometry, harmonic vibrational frequencies, infrared and Raman intensities were obtained by means of ab initio Hartree-Fock (HF) and density functional theory (DFT) gradient calculations with complete relaxation in the potential energy surface using 6-311++G(d,p) basis set. The vibrational frequencies which were determined experimentally from the spectral data are compared with those obtained theoretically from ab initio and DFT calculations. A close agreement was achieved between the observed and calculated frequencies by refinement of the scale factors. The infrared and Raman spectra were also predicted from the calculated intensities. Thermodynamic properties like entropy, heat capacity, zero point energy, have been calculated for the molecule. The predicted first hyperpolarizability also shows that the molecule might have a reasonably good non-linear optical (NLO) behavior. The calculated HOMO-LUMO energy gap reveals that charge transfer occurs within the molecule. Stability of the molecule arising from hyper conjugative interactions, charge delocalization have been analyzed using natural bond orbitals (NBO) analysis. Unambiguous vibrational assignment of all the fundamentals was made using the total energy distribution (TED).
Non-equilibrium Casimir force between vibrating plates.
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
VIBRATION CONTROL OF SHALLOW SHELL STRUCTURES USING A SHELL-TYPE DYNAMIC VIBRATION ABSORBER
T. Aida; T. Aso; K. Nakamoto; K. Kawazoe
1998-01-01
In this study, a new shell-type dynamic vibration absorber is presented for suppressing several modes of vibration of the shallow shell (main shell) under harmonic load. It consists of a shallow shell (the dynamic absorbing shell), under the same boundary condition and with the same shape as those of the main shell, with connecting springs and dampers in the vertical
Bennett, Charles L. (Livermore, CA)
2009-10-20
A high efficiency harmonic engine based on a resonantly reciprocating piston expander that extracts work from heat and pressurizes working fluid in a reciprocating piston compressor. The engine preferably includes harmonic oscillator valves capable of oscillating at a resonant frequency for controlling the flow of working fluid into and out of the expander, and also preferably includes a shunt line connecting an expansion chamber of the expander to a buffer chamber of the expander for minimizing pressure variations in the fluidic circuit of the engine. The engine is especially designed to operate with very high temperature input to the expander and very low temperature input to the compressor, to produce very high thermal conversion efficiency.
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.
Singh, R; Yadav, R A
2014-09-15
Raman and FTIR spectra of solid 2,4-Dithiouracil (DTU) at room temperature have been recorded. DFT calculations were carried out to compute the optimized molecular geometries, GAPT charges and fundamental vibrational frequencies along with their corresponding IR intensities, Raman activities and depolarization ratios of the Raman bands for the neutral DTU molecule and its cation (DTU+) and anion (DTU-) using the Gaussian-03 software. Addition of one electron leads to increase in the atomic charges on the sites N1 and N3 and decrease in the atomic charges on the sites S8 and S10. Due to ionization of DTU molecule, the charge at the site C6 decreases in the cationic and anionic radicals of DTU as compared to its neutral species. As a result of anionic radicalization, the C5C6 bond length increases and loses its double bond character while the C4C5 bond length decreases. In the case of the DTU+ ion the IR and Raman band corresponding to the out-of-phase coupled NH stretching mode is strongest amongst the three species. The anionic DTU radical is found to be the most stable. The two NH out-of-plane bending modes are found to originate due to out-of-phase and in-phase coupling of the two NH bonds in the anion and cation contrary to the case of the neutral DTU molecule in which the out-of-plane bending motions of the two NH bonds are not coupled. PMID:24785092
Harmonic Fluids Changxi Zheng Doug L. James
Columbia University
fluid solvers with particle-based models for bubble creation, vibration, advec- tion, and radiation for automatic procedural synthesis of synchronized harmonic bubble-based sounds from 3D fluid ani- mations of bubble os- cillators. We weight each oscillator by its bubble-to-ear acoustic transfer function, which
The Quantum Harmonic Oscillator C. David Sherrill
Sherrill, David
in chemistry as a model for the vibrational motion in a diatomic molecule. Polyatomic molecules can be modeled by coupled harmonic oscillators. The atoms are viewed as point masses which are connected by bonds which act) which is a second-order differential equation describing the displacement x from the rest length l0
Pirozhnaya, L.N.; Zubkova, O.B.
1986-05-01
In the valence-optical scheme approximation, vibrational frequencies and absorption band intensities have been calculated for the molecules n-C/sub 4/F/sub 10/ (I) and n-C/sub 6/F/sub 14/ (II) in various conformations. A comparison of the calculated and observed spectra shows that I in the gas and liquid phases contains molecules in the T and G forms, and II in the conformations TTT, TTG, TGT, and TGT'. The crystalline phase of both compounds consists of molecules in the extended form. The most informative region for determination of rotational isomers for the perfluoroparaffins is the 720-1150 cm/sup -1/ frequency region in the IR spectrum, corresponding to the frequency phase branch of symmetric stretching vibrations of CF/sub 2/ in the spectrum of polytetrafluoroethylene.
Spectroscopic analysis and DFT calculations of a food additive Carmoisine
NASA Astrophysics Data System (ADS)
Snehalatha, M.; Ravikumar, C.; Hubert Joe, I.; Sekar, N.; Jayakumar, V. S.
2009-04-01
FT-IR and Raman techniques were employed for the vibrational characterization of the food additive Carmoisine (E122). The equilibrium geometry, various bonding features, and harmonic vibrational wavenumbers have been investigated with the help of density functional theory (DFT) calculations. A good correlation was found between the computed and experimental wavenumbers. Azo stretching wavenumbers have been lowered due to conjugation and ?-electron delocalization. Predicted electronic absorption spectra from TD-DFT calculation have been analysed comparing with the UV-vis spectrum. The first hyperpolarizability of the molecule is calculated. Intramolecular charge transfer (ICT) responsible for the optical nonlinearity of the dye molecule has been discussed theoretically and experimentally. Stability of the molecule arising from hyperconjugative interactions, charge delocalization and C-H⋯O, improper, blue shifted hydrogen bonds have been analysed using natural bond orbital (NBO) analysis.
NASA Astrophysics Data System (ADS)
Hofmeister, Anne M.
1991-09-01
The bulk modulus KT can be related to structural parameters and to the sum of the squares of the vibrational frequencies. ?vi2, for N-atom crystals of cubic symmetry or for any symmetry that contains only one nearest-neighbor distance. Required assumptions are the existence of (1) electrostatic forces exclusively between atoms at equivalent positions in the primitive unit cell, (2) pair-wise central repulsive potentials between all other atoms, and (3) rigid ions. Including pressure in the derivation requires a more stringent version of point 2, namely, (4) that the structure scales isotropically upon compression. This leads to structurally independent formulas for the pressure derivatives of bulk modulus at 1 atm: the only variables are KT and sums involving vi2 and the first or second pressurderivative of vi, i.e., the mode Grüneisen parameters. Implicit in all equations is the independence of the sums on wave vector. Thus, knowledge of zone center phonons (mostly infrared and Raman bands) is sufficient to calculate elastic properties. Investigating these relationships for 45 minerals with 10 different structures shows that KT(0) is predicted within 7% of experiment for 21 solids, all of which should lack strong interactions between atoms at equivalent sites in the Bravais unit cell (i.e., rutile, corundum, ilmenite, and spinel structures). The accuracy of the model strongly depends on the accuracy of the sum ?vi2. Agreement for B1, B2, fluorite, and wurtzite structures is moderate to poor, as expected, because these structures place like atoms as second nearest neighbors and can thus violate assumption 1. For rocksalt, agreement varies, depends on the size of the cation, not on the polarizability (i.e. the ionic rigidity) as inferred earlier. Calculated KT for the garnets is 1.367 time experimental KT, instead of unity, which is related to the structure not scaling perfectly with pressure. Agreement is variable (3-20%) for the perovskite structure with large discrepancies associated with ill-constrained sums. However, for all structures, the relative size of KT is predicted, so that the theory can be used for systematics for all minerals with the proper symmetry, reguardless of whether the assumptions are satisified. For all of the above mentioned structures, K'o and K?o are predicted within the experimental uncertainties from the available spectroscopic measurements of 13 solids for K'o and 6 solids for K?o at pressure. Based on this, the good agreement for ilmenite, which does not meet the symmetry requirements, and the structural independence of the formulas, the relations involving K'o and K?o are inferred to hold for structures more complex than cubic or AXBY.
Active vibration control in Duffing mechanical systems using dynamic vibration absorbers
NASA Astrophysics Data System (ADS)
Beltrán-Carbajal, F.; Silva-Navarro, G.
2014-07-01
This paper deals with the multi-frequency harmonic vibration suppression problem in forced Duffing mechanical systems using passive and active linear mass-spring-damper dynamic vibration absorbers. An active vibration absorption scheme is proposed to extend the vibrating energy dissipation capability of a passive dynamic vibration absorber for multiple excitation frequencies and, simultaneously, to perform reference position trajectory tracking tasks planned for the nonlinear primary system. A differential flatness-based disturbance estimation scheme is also described to estimate the unknown multiple time-varying frequency disturbance signal affecting the differentially flat nonlinear vibrating mechanical system dynamics. Some numerical simulation results are provided to show the efficient performance of the proposed active vibration absorption scheme and the fast estimation of the vibration disturbance signal.
Converged vibrational energy levels and quantum mechanical vibrational partition function of ethane
Truhlar, Donald G
Converged vibrational energy levels and quantum mechanical vibrational partition function of ethane function of ethane is calculated in the temperature range of 200600 K using well-converged energy levels25 In this article, we report converged vibrational levels and converged quantum mechanical vibrational partition
NASA Astrophysics Data System (ADS)
Aruldhas, D.; Jayakumar, V. S.; Joe, I. Hubert
2008-11-01
The FT-Raman and IR spectra of chlorothalonil have been recorded and analyzed. Optimized molecular structures and normal modes of vibrations of chlorothalonil have been obtained from the B3LYP/6-31G (d) basis set. All observed harmonic Raman bands of chlorothalonil have been assigned in the frameworks of the calculations. From the parameters of the fitted peaks, the integrated intensities, with respect to normal coordinates of the Raman active fundamentals are determined. NBO analysis reveals that in chlorothalonil, the resonance energy associated with the ?* C2-C3 derealization is 468.41 kcal mol-1. The calculated first hyperpolarizability of chlorothalonil is 9 times that of urea.
Superradiance of Harmonic Oscillators
Delanty, Michael; Twamley, Jason
2011-01-01
Superradiance, the enhanced collective emission of light from a coherent ensemble of quantum systems, has been typically studied in atomic ensembles. In this work we study the enhanced emission of energy from coherent ensembles of harmonic oscillators. We show that it should be possible to observe harmonic oscillator superradiance in a variety of physical platforms such as waveguide arrays in integrated photonics and resonator arrays in circuit QED. We find general conditions specifying when emission is superradiant and subradiant and find that superradiant, subradiant and dark states take the form of multimode squeezed coherent states and highly entangled multimode Fock states. The intensity, two-mode correlations and fraction of quanta trapped in the system after decay are calculated for a range of initial states including multimode Fock, squeezed, coherent and thermal states. In order to explore these effects, the Law and Eberly protocol [C. K. Law and J. H. Eberly, Phys. Rev. Lett. 76, 1055 (1996)] is gen...
NASA Astrophysics Data System (ADS)
Vijayalakshmi, S.; Kalyanaraman, S.; Ravindran, T. R.
2014-02-01
Second harmonic generation (SHG) in Bis (Cinnamic acid): Hexamine cocrystal was extensively analyzed through charge transfer (CT). The CT interactions through hydrogen bonding were well established with the aid of vibrational analysis and Natural Bond Orbital (NBO) analysis. The retentivity of coplanar nature of the cinnamic acid in the cocrystal was confirmed through UV-Visible spectroscopy and supported by Raman studies. Structural analysis indicated the quinoidal character of the given material presenting a high SHG efficiency. The first order hyperpolarizability value was calculated theoretically by density functional theory (DFT) and Hartree-Fock (HF) methods in support for the large value of SHG.
Diao, Chuan-Ling [College of Physics and Electronics, Shandong Normal University, Jinan 250014 (China); State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); Wang, Chun-Hai; Lu, Jing [State Key Laboratory for Artificial Microstructure and Mesoscopic Physics, School of Physics, Peking University, Beijing 100871 (China); Luo, Neng-Neng; Jing, Xi-Ping, E-mail: sf751106@sina.com.cn, E-mail: xpjing@pku.edu.cn [State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); Qi, Ze-Ming; Shao, Tao; Wang, Yu-Yin [National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029 (China); Wang, Quan-Chao; Kuang, Xiao-Jun; Fang, Liang [MOE Key Laboratory of New Processing Technology for Nonferrous Metals and Materials, College of Materials Science and Engineering, Guilin University of Technology, Guilin 541004 (China); Shi, Feng, E-mail: sf751106@sina.com.cn, E-mail: xpjing@pku.edu.cn [College of Physics and Electronics, Shandong Normal University, Jinan 250014 (China)
2014-03-21
1:2 B-site cation ordered Ba(Mg{sub 1/3}Nb{sub 2/3})O{sub 3} ceramic was synthesized using conventional solid-state reaction at 1600?°C for 12?h. The structure parameters were obtained through Rietveld refinement of X-ray diffraction data. The Raman peak frequencies were obtained by Lorenz fitting on Raman spectrum. Four-parameter semiquantum model was used to fit the infrared (IR) reflectivity spectrum, and the fitted parameters were used to calculate the dielectric permittivity ? and dielectric loss tan?. A total of 9 active Raman and 16 active IR modes were obtained using first-principle calculations based on density functional theory with local density approximation. All of the vibrational modes were assigned and represented by linear combinations of the symmetry coordinates deduced using group theory analysis. The Raman mode with the highest frequency A{sub 1g}{sup (4)} (789?cm{sup ?1}) can be described as the breathing vibration of NbO{sub 6}. The IR modes E{sub u}{sup (1)} (149?cm{sup ?1}) and A{sub 2u}{sup (2)} (212?cm{sup ?1}), which can be described as the twisting vibrations of Ba–MgO{sub 6}/Ba–NbO{sub 6} on the a–b plane and the stretching vibrations of Ba–MgO{sub 6}/Ba–NbO{sub 6} along the c direction, respectively, are the dominant contributing modes to ? and tan?. The dielectric property parameters obtained using IR spectrum fittings, first-principal calculations, and microwave measurements were compared.
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.
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 ?* and ?* 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.
Harmonic motion microwave Doppler imaging: a simulation study using a simple breast model.
Top, Can Bari?; 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. PMID:24108714
Vibrational spectroscopy of resveratrol
NASA Astrophysics Data System (ADS)
Billes, Ferenc; Mohammed-Ziegler, Ildikó; Mikosch, Hans; Tyihák, Ern?
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.
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.
Vibrational contributions to the stability of point defects in bcc iron: A first-principles study
NASA Astrophysics Data System (ADS)
Lucas, G.; Schäublin, R.
2009-09-01
The purpose of this study is to investigate the modes of vibration of the self-interstitial atoms and the vacancy in bcc iron and to estimate how the vibrational properties can affect the stability of these defects. The phonon density of states of the vacancy and the self-interstitials have been calculated within the quasi harmonic approximation using density functional theory calculations. It was observed that self-interstitial atoms have several localized high frequency modes of vibration related to the stretching of the dumbbell bond, but also soft modes favoring their migration. From the phonon density of states, the vibrational contributions to the free energy have been estimated for finite temperatures. Results are compared to previous work performed by others using empirical potentials. We found a rather large formation entropy for the vacancy, SVf = 4.08 kB. Our results show that the vibrational entropy can have a significant influence on the formation of the point defects even at moderate temperature. Possible consequences on the mobility of these defects are also discussed.
Reaction dynamics on surfaces in the harmonic approximation
NASA Astrophysics Data System (ADS)
Sumithra, K.; Sebastian, K. L.
1991-07-01
We suggest a method for calculating the rates of reactions involving adsorbates on the surfaces of a semi-infinite solid. The method makes use of multidimensional quantum transition-state theory to obtain an expression for the rate. Using the harmonic approximation, one can take into account all vibrational degrees of freedom of the solid. The final expression for the rate is expressed in terms of a few matrix elements of the Green function for the perfect solid (one in which there are no adsorbates). As there exist efficient methods for evaluation of the required matrix elements, it is possible to apply the procedure to various processes like desorption, diffusion and recombination on the surfaces.
Experimental Study of Non-Linear Vibrations in a Loudspeaker Cone
NASA Astrophysics Data System (ADS)
ZHANG, Z. L.; TAO, Q. T.
2001-11-01
An experimental study of non-linear vibrations in a loudspeaker cone was made. The sub-harmonic, super sub-harmonic and beat between them are observed. Our experimental results show that non-linear vibrations in a thin shell are related to bending resonance.
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.
Nonlinear harmonic generation by diurnal tides
NASA Astrophysics Data System (ADS)
Wunsch, Scott
2015-09-01
Recent observations from the South China Sea have demonstrated that semi-diurnal tides sometimes generate a double-frequency harmonic. Similar harmonic generation has been found in laboratory experiments and numerical simulations of internal wave beams refracting into a pycnocline. Here, a weakly nonlinear theory of internal wave refraction is applied to oceanic internal tides in an idealized stratification profile. The steady state harmonic amplitude is calculated as a function of the tidal frequency and the pycnocline characteristics. The results indicate that harmonic generation by nonlinear refraction of semi-diurnal tides is consistent with the South China Sea observations.
Biswanath Rath
2015-05-19
For the first time in the literature of Quantum Physics, we present complex energy eigenvalues of non-Hermitian Harmonic Oscillator $H=\\frac{(p+iLx)}^{2}}{2} + W^{2} \\frac{x^{2}}{2}$ with real wave function having positive frequency of vibration $(w)$ under some selective choice of $L$ and $W$ .Interestingly for the same values of $L$ and $W$, if the frequency of vibration $w$ in the real wave function is (some how) related as $w=L\\pmW$ or $w=W-L$ then the same oscillator can reflect either pure positive or negative energy eigenvalues.The real energy levels are in conformity with the perturbative calculation. PACS :03.65.Db;11.39.Er. Key words: Positive frequency, real wave function, complex energy, real positive energy,negative energy.
NASA Astrophysics Data System (ADS)
Prasath, M.; Muthu, S.; Arun Balaji, R.
2013-09-01
The FT-IR and FT-Raman spectrum of 7-chloro-2-methylamino-5-phenyl-3H-1, 4-benzodiazepine-4-oxide (7CMP4BO) has been recorded in the region 4000-400 and 4000-100 cm-1 respectively. The optimized geometry, Thermodynamic properties, NBO, Molecular Electrostatic Potentials, PES, frequency and intensity of the vibrational bands of 7CMP4BO were obtained by the ab initio HF and density functional theory (DFT), B3LYP/6-31G (d,p) basis set. The molecule orbital contributions were studied by using the total (TDOS), partial (PDOS), and overlap population (OPDOS) density of states. The harmonic vibrational frequencies were calculated and the scaled values have been compared with experimental 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 linear polarizability (?) and the first order hyperpolarizability (?) values of the investigated molecule have been computed using DFT quantum mechanical calculations. The observed and the calculated frequencies are found to be in good agreement. The experimental spectra also coincide satisfactorily with those of theoretically calculated values.
Chun, Hye Jin
2014-12-08
and their derivatives. In each case the agreement between observed and calculated infrared and Raman spectra was very good. Theoretical computations have also been used to calculate the potential energy surfaces (PES) for four cyclic silanes. The calculated ring...
VIBRATIONALLY EXCITED C{sub 6}H
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.
Quantum jumps and classical harmonics
William A. Fedak; Jeffrey J. Prentis
2002-01-01
We present an introduction to quantum mechanics based on the formal correspondence between the atomic properties of quantum jumps and the classical harmonics of the electron's periodic motion. By adding a simple quantum condition to the classical Fourier analysis, we readily find the energies of the stationary states, calculate the transition probabilities between the states, and construct the line spectrum
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. PMID:15473771
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.
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.
Vibrations of a discreetly fastened cylindrical shell
NASA Astrophysics Data System (ADS)
Antufev, B. A.
1993-10-01
Small harmonic vibrations of a thin elastic ring cylindrical shell are considered. The shell is of a constant thickness and is fastened at the ends and at N points of its lateral surface. Two approaches are offered to solve the problem of the shell, vibrating with additional supports. In some cases, a simplified dynamic model can be used, based on the division of the deformed state of the cylinder into the general and local states. An example has been given.
Jelliarko Palgunadi; Kim Hoon Sik
2010-01-01
The vibrational infrared spectra of 1-methyl-3-methylimidazolium dimethylphosphate [MMIM][Me2PO4] have been studied using the ab initio density functional theory (DFT) method. The purpose of this study is to analyze and compare experimental and computed infrared spectra of the ionic liquid. Four DFT functionals with dispersion correction scheme, i.e., the dispersion-corrected B3LYP (B3LYP-D), PW91, PBE0, and M052X, were employed in order to
Mary, Y Sheena; Varghese, Hema Tresa; Panicker, C Yohannan; Thiemann, Thies; Al-Saadi, Abdulaziz A; Popoola, Saheed A; Van Alsenoy, C; Al Jasem, Yosef
2015-11-01
FT-IR and FT-Raman spectra of ethyl 3-(E)-(anthracen-9-yl)prop-2-enoate were recorded and analyzed. The conformational behavior of the molecule was also investigated. The vibrational wavenumbers were calculated using DFT quantum chemical calculations. The data obtained from the wavenumber calculations were used to assign vibrational bands obtained experimentally. The geometrical parameters are in agreement with XRD data. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The HOMO and LUMO analysis were used to determine the charge transfer within the molecule and quantum chemical parameters related to the title compound. From the MEP analysis, it is clear that the negative electrostatic potential regions are mainly localized over the carbonyl groups and anthracene ring and are possible sites for electrophilic attack and the positive regions are localized at all the hydrogen atoms as possible sites for nucleophilic attack. NLO and NMR studies are also reported. Molecular docking studies suggest that the title compound might exhibit inhibitory activity against IDE and may act as an insulysin inhibitor. Conformational analysis is also reported. PMID:26079511
Vibrational and Thermophysical Properties of PETN from First Principles
NASA Astrophysics Data System (ADS)
Gonzalez, Joseph; Landerville, Aaron; Oleynik, Ivan
2015-06-01
Thermophysical properties are urgently sought as input for meso- and continuum-scale modeling of energetic materials (EMs). However, empirical data in this regard are often limited to specific pressures and temperatures. Such modeling of EMs can be greatly improved by inclusion of thermophysical properties over a wide range of pressures and temperatures, provided such data could be reliably obtained from theory. We demonstrate such a capability by calculating the equation of state, heat capacities, coefficients of thermal expansion, and Gruneissen parameters for pentaerythritol tetranitrate (PETN) using first-principles density functional theory, which includes proper description of van der Waals interactions and zero-point and thermal free energy contributions to pressure, the latter being calculated using the quasi-harmonic approximation. Further, we investigate the evolution of the vibration spectrum of PETN as a function of pressure.
Intermolecular charge transfer and vibrational analysis of hydrogen bonding in acetazolamide
NASA Astrophysics Data System (ADS)
Chaturvedi, Deepika; Gupta, Vineet; Tandon, Poonam; Sharma, Anamika; Baraldi, C.; Gamberini, M. C.
2012-12-01
In the present work the structural and spectral characteristics of acetazolamide have been studied by methods of infrared, Raman spectroscopy and quantum chemistry. Electrostatic potential surface, optimized geometry, harmonic vibrational frequencies, infrared intensities and activities of Raman scattering were calculated by density functional theory (DFT) employing B3LYP with complete relaxation in the potential energy surface using 6-311++G(d,p) basis set. Based on these results, we have discussed the correlation between the vibrational modes and the structure of the dimers of acetazolamide. The calculated vibrational spectra of three dimers of acetazolamide have been compared with observed spectra, and the assignment of observed bands was carried out using potential energy distribution. The observed spectra agree well with the values computed from the DFT. A comparison of observed and calculated vibrational spectra clearly shows the effect of hydrogen bonding. The frequency shifts observed for the different dimers are in accord with the hydrogen bonding in acetazolamide. Natural bond orbital (NBO) analyses reflect the charge transfer interaction in the individual hydrogen bond units and the stability of different dimers of acetazolamide.
PREFACE: Vibrations at surfaces Vibrations at surfaces
NASA Astrophysics Data System (ADS)
Rahman, Talat S.
2011-12-01
This special issue is dedicated to the phenomenon of vibrations at surfaces—a topic that was indispensible a couple of decades ago, since it was one of the few phenomena capable of revealing the nature of binding at solid surfaces. For clean surfaces, the frequencies of modes with characteristic displacement patterns revealed how surface geometry, as well as the nature of binding between atoms in the surface layers, could be different from that in the bulk solid. Dispersion of the surface phonons provided further measures of interatomic interactions. For chemisorbed molecules on surfaces, frequencies and dispersion of the vibrational modes were also critical for determining adsorption sites. In other words, vibrations at surfaces served as a reliable means of extracting information about surface structure, chemisorption and overlayer formation. Experimental techniques, such as electron energy loss spectroscopy and helium-atom-surface scattering, coupled with infra-red spectroscopy, were continually refined and their resolutions enhanced to capture subtleties in the dynamics of atoms and molecules at surfaces. Theoretical methods, whether based on empirical and semi-empirical interatomic potential or on ab initio electronic structure calculations, helped decipher experimental observations and provide deeper insights into the nature of the bond between atoms and molecules in regions of reduced symmetry, as encountered on solid surfaces. Vibrations at surfaces were thus an integral part of the set of phenomena that characterized surface science. Dedicated workshops and conferences were held to explore the variety of interesting and puzzling features revealed in experimental and theoretical investigations of surface vibrational modes and their dispersion. One such conference, Vibrations at Surfaces, first organized by Harald Ibach in Juelich in 1980, continues to this day. The 13th International Conference on Vibrations at Surfaces was held at the University of Central Florida, Orlando, in March 2010. Several speakers at this meeting were invited to contribute to the special section in this issue. As is clear from the articles in this special section, the phenomenon of vibrations at surfaces continues to be a dynamic field of investigation. In fact, there is a resurgence of effort because the insights provided by surface dynamics are still fundamental to the development of an understanding of the microscopic factors that control surface structure formation, diffusion, reaction and structural stability. Examination of dynamics at surfaces thus complements and supplements the wealth of information that is obtained from real-space techniques such as scanning tunneling microscopy. Vibrational dynamics is, of course, not limited to surfaces. Surfaces are important since they provide immediate deviation from the bulk. They display how lack of symmetry can lead to new structures, new local atomic environments and new types of dynamical modes. Nanoparticles, large molecules and nanostructures of all types, in all kinds of local environments, provide further examples of regions of reduced symmetry and coordination, and hence display characteristic vibrational modes. Given the tremendous advance in the synthesis of a variety of nanostructures whose functionalization would pave the way for nanotechnology, there is even greater need to engage in experimental and theoretical techniques that help extract their vibrational dynamics. Such knowledge would enable a more complete understanding and characterization of these nanoscale systems than would otherwise be the case. The papers presented here provide excellent examples of the kind of information that is revealed by vibrations at surfaces. Vibrations at surface contents Poisoning and non-poisoning oxygen on Cu(410)L Vattuone, V Venugopal, T Kravchuk, M Smerieri, L Savio and M Rocca Modifying protein adsorption by layers of glutathione pre-adsorbed on Au(111)Anne Vallée, Vincent Humblot, Christophe Méthivier, Paul Dumas and Claire-Marie Pradier Relating temperature dependence of atom
Arslan, Hakan; Demircan, Aydin; Göktürk, Ersen
2008-01-01
The IR spectra of 5-chloro-10-oxa-3-thia-tricyclo[5.2.1.0(1,5)]dec-8-ene-3,3-dioxide (COTDO) has been recorded in the region 4000-525cm(-1). The optimized molecular geometry, frequency and intensity of the vibrational bands of COTDO in the ground state has been calculated using the Hartree-Fock and density functional using Becke's three-parameter hybrid method with the Lee, Yang, and Parr correlation functional methods with 6-31G(d,p) and 6-311G(d,p) basis sets. The harmonic vibrational frequencies were calculated and the scaled values have been compared with experimental IR spectra. The calculated geometrical parameters and harmonic vibrations are predicted in a very good agreement with the experimental data. The theoretical vibrational spectra of the title compound were interpreted by means of potential energy distributions (PEDs) using VEDA 4 program. With the help of this modern technique we were able to complete the assignment of the vibrational spectra of the title compound. PMID:17475544
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.
Vertical vibration and shape oscillation of acoustically levitated water drops
Geng, D. L.; Xie, W. J.; Yan, N.; Wei, B., E-mail: bbwei@nwpu.edu.cn [Department of Applied Physics, Northwestern Polytechnical University, Xi'an 710072 (China)
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.
Vibration analysis of composite laminate plate excited by piezoelectric actuators.
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
NASA Astrophysics Data System (ADS)
Dai, Zuyang; Sun, Wei; Wang, Jia; Mo, Yuxiang
2015-08-01
The spin-vibronic energy levels of the cyanoacetylene cation have been measured using the one-photon zero-kinetic energy (ZEKE) photoelectron spectroscopic method. All three degenerate vibrational modes showing vibronic coupling, i.e., Renner-Teller (RT) effect, have been observed. All the splitting spin-vibronic energy levels of the fundamental H—C?C bending vibration (v5) have been determined. The spin-vibronic energy levels of the degenerate vibrational modes have also been calculated using a diabatic model in which the harmonic terms as well as all the second-order vibronic coupling terms are used. The theoretical predictions are in good agreement with the experimental data and are used to assign the ZEKE spectrum. It is found that the RT effects for the H—(CC)—CN bending (v7) and the C—C?N bending (v6) vibrations are weak, whereas they are strong for the H—C?C bending (v5) vibration. The cross-mode RT couplings between any of the two degenerate vibrations are strong. The spin-orbit resolved fundamental vibrational energy levels of the C?N stretching (v2) and C—H stretching (v1) vibrations have also been observed. The spin-orbit energy splitting of the ground state has been determined for the first time as 43 ± 2 cm-1, and the ionization energy of HCCCN is found to be 93 903.5 ± 2 cm-1.
NASA Astrophysics Data System (ADS)
Pang, Min; Yang, Pan; Shen, Wei; Li, Ming; He, Rongxing
2015-05-01
Based on the density functional theory and its time-dependent extension, the properties of the ground and the first excited states of phenanthrene were calculated. In harmonic and anharmonic approximations, the well-resolved absorption and emission spectra of phenanthrene were simulated using the Franck-Condon approximation combined with the Herzberg-Teller and Duschinsky effects, and the results reproduced the experimental spectra very well. The mirror symmetry breakdown between absorption and emission spectra is induced mainly from the Herzberg-Teller effect and Duschinsky mode mixing. Moreover, most of the vibrational modes were tentatively assigned and compared with the experiment.
Structure, vibrational spectrum, and energetics of the CH5(+) ion - A theoretical investigation
NASA Technical Reports Server (NTRS)
Komornicki, Andrew; Dixon, David A.
1987-01-01
Analytic derivative techniques are utilized to determine molecular geometries, vibration spectra, molecular force field, proton affinity, and energetics of clustering of protonated methane. It is observed that the geometries are gradient optimized, while the harmonic force fields and IR intensities are also determined analytically at the SCF level. It is determined that the frequency of the torsional model for rotation of the H2 about the pseudothreefold axis of the CH3(+) group is extremely low, and the proton affinity of CH4 is calculated as 129.0 kcal/mol.
Anharmonic vibrator description of collective nuclei
Casten, R.F.; Zamfir, N.V. ||
1995-07-01
It is shown that a simple anharmonic vibrator model can account for the properties of yrast states in collective nuclei, as well as the quasi-band states built on the {gamma}-vibration or on the O{sub 2}{sup +} state. This description extends from nearly harmonic vibrator nuclei to pure rotor nuclei and encompasses both energies and B(E2) values. It survives both ``horizontal`` and ``vertical`` perspectives on the data of nuclear physics and offers a challenge to microscopic theories of nuclear structure.
Vibration by relativistic effects
Enrique Oradaz Romay
2005-12-27
Relativity, time reversal invariance in mechanics and principle of causality can be in the bases of a type of vibration of the extensive objects. It is because, the detailed analysis of the relativistic movement of an extensive body entail that all the objects must have inherent a vibratory movement to their own size. Such effect does not happen when it works with point particles thus is not stranger who happens unnoticed in the traditional studies. Also we can find relation between the form of vibration of the extensive objects and the energy that calculates by quantum considerations.
NASA Astrophysics Data System (ADS)
Torrico-Vallejos, Sonia; Erben, Mauricio F.; Piro, Oscar E.; Castellano, Eduardo E.; Della Védova, Carlos O.
2010-06-01
Structural and conformational properties of 1H-Isoindole-1,3(2H)-dione, 2-[(methoxycarbonyl)thio] ( S-phthalimido O-methyl thiocarbonate) are analyzed using a combined approach including X-ray diffraction, vibrational spectra and theoretical calculation methods. The vibrational properties have been studied by infrared and Raman spectroscopies along with quantum chemical calculations (B3LYP and B3PW91 functional in connection with the 6-311++G ** and aug-cc-pVDZ basis sets). The crystal structure was determined by X-ray diffraction methods. The substance crystallizes in the monoclinic P2 1/c space group with a = 6.795(1), b = 5.109(1), c = 30.011(3) Å, ? = 90.310(3)° and Z = 4 molecules per unit cell. The conformation adopted by the N sbnd S sbnd C dbnd O group is syn (C dbnd O double bond in synperiplanar orientation with respect to the N sbnd S single bond). The experimental molecular structure is well reproduced by the MP2/aug-cc-pVDZ method.
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 ? 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.
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. The effect of various design parameters on the output torque and torque ripple are discussed. Design parameters include winding patterns, magnetization direction, magnet arc length, number of segments in poles and magnet pole shaping. New designs of trapezoidal BEMF motors are proposed to reduce the electromagnetic torque ripple. Magnet stepping and magnet edge shaping with reduced arc length, significantly reduce torque ripple, with minimal sacrifice of the maximum output torque. Acoustic noise of electromagnetic origin is investigated using a magnetic frame which emulates a DC motor. The driving electromagnetic force is calculated using finite element analysis and the resulting vibration and acoustic noise is measured. Acoustic noise of purely electromagnetic origin was also tested with a DC brushless motor to confirm the results of the magnetic frame. The mechanism of noise generation in a DC motor is a quasi-static response of a stator not only at the fundamental frequency but also at higher harmonic frequencies of alternating switched DC, which is a current characteristic of a DC motor. Noise generation is significantly aggravated when some of those harmonics are close to the resonant frequencies of the stator. Therefore, acoustic noise is highly dependent upon the excitation current shape, as higher harmonics may match with resonant frequencies of the stator.
Vibrational genetic algorithm as a new concept in airfoil design
Abdurrahman Hacio?lu; ?brahim Özkol
2002-01-01
We introduce the Vibration concept for real coded Genetic Algorithm and its implementation to inverse airfoil design, which decreases the number of CFD calculations. This concept assures efficient diversity in the population and consequently gives faster solution. We used the Vibration concept as vibrational mutation and vibrational crossover. For the mutational manner, a sinusoidal wave with random amplitude is introduced
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.
Superradiance of Harmonic Oscillators
Michael Delanty; Stojan Rebic; Jason Twamley
2011-07-25
Superradiance, the enhanced collective emission of light from a coherent ensemble of quantum systems, has been typically studied in atomic ensembles. In this work we study the enhanced emission of energy from coherent ensembles of harmonic oscillators. We show that it should be possible to observe harmonic oscillator superradiance in a variety of physical platforms such as waveguide arrays in integrated photonics and resonator arrays in circuit QED. We find general conditions specifying when emission is superradiant and subradiant and find that superradiant, subradiant and dark states take the form of multimode squeezed coherent states and highly entangled multimode Fock states. The intensity, two-mode correlations and fraction of quanta trapped in the system after decay are calculated for a range of initial states including multimode Fock, squeezed, coherent and thermal states. In order to explore these effects, the Law and Eberly protocol [C. K. Law and J. H. Eberly, Phys. Rev. Lett. 76, 1055 (1996)] is generalized to prepare highly entangled multimode Fock states in circuit QED.
Monitoring molecular dynamics using coherent electrons from high harmonic generation
Wagner, Nicholas L.; Wüest, Andrea; Christov, Ivan P.; Popmintchev, Tenio; Zhou, Xibin; Murnane, Margaret M.; Kapteyn, Henry C.
2006-01-01
We report a previously undescribed spectroscopic probe that makes use of electrons rescattered during the process of high-order harmonic generation. We excite coherent vibrations in SF6 using impulsive stimulated Raman scattering with a short laser pulse. A second, more intense laser pulse generates high-order harmonics of the fundamental laser, at wavelengths of ?20–50 nm. The high-order harmonic yield is observed to oscillate, at frequencies corresponding to all of the Raman-active modes of SF6, with an asymmetric mode most visible. The data also show evidence of relaxation dynamics after impulsive excitation of the molecule. Theoretical modeling indicates that the high harmonic yield should be modulated by both Raman and infrared-active vibrational modes. Our results indicate that high harmonic generation is a very sensitive probe of vibrational dynamics and may yield more information simultaneously than conventional ultrafast spectroscopic techniques. Because the de Broglie wavelength of the recolliding electron is on the order of interatomic distances, i.e., ?1.5 Å, small changes in the shape of the molecule lead to large changes in the high harmonic yield. This work therefore demonstrates a previously undescribed spectroscopic technique for probing ultrafast internal dynamics in molecules and, in particular, on the chemically important ground-state potential surface. PMID:16895984
Agarwalla, Bijay Kumar; Segal, Dvira
2015-01-01
We study the statistical properties of charge and energy transport in electron conducting junctions with electron-phonon interactions, specifically, the thermoelectric efficiency and its fluctuations. The system comprises donor and acceptor electronic states, representing a two-site molecule or a double quantum dot system. Electron transfer between metals through the two molecular sites is coupled to a particular vibrational mode which is taken to be either harmonic or anharmonic- a truncated (two-state) spectrum. Considering these models we derive the cumulant generating function in steady state for charge and energy transfer, correct to second-order in the electron-phonon interaction, but exact to all orders in the metal-molecule coupling strength. This is achieved by using the non-equilibrium Green's function approach (harmonic mode) and a kinetic quantum master equation method (anharmonic mode). From the cumulant generating function we calculate the charge current and its noise and the large deviation fun...
Vibrational and thermodynamic properties of ?-, ?-, ?-, and 6, 6, 12-graphyne structures.
Perkgöz, Nihan Kosku; Sevik, Cem
2014-05-01
Electronic, vibrational, and thermodynamic properties of different graphyne structures, namely ?-, ?-, ?-, and 6, 6, 12-graphyne, are investigated through first principles-based quasi-harmonic approximation by using phonon dispersions predicted from density-functional perturbation theory. Similar to graphene, graphyne was shown to exhibit a structure with extraordinary electronic features, mechanical hardness, thermal resistance, and very high conductivity from different calculation methods. Hence, characterizing its phonon dispersions and vibrational and thermodynamic properties in a systematic way is of great importance for both understanding its fundamental molecular properties and also figuring out its phase stability issues at different temperatures. Thus, in this research work, thermodynamic stability of different graphyne allotropes is assessed by investigating vibrational properties, lattice thermal expansion coefficients, and Gibbs free energy. According to our results, although the imaginary vibrational frequencies exist for ?-graphyne, there is no such a negative behavior for ?-, ?-, and 6, 6, 12-graphyne structures. In general, the Grüneisen parameters and linear thermal expansion coefficients of these structures are calculated to be rather more negative when compared to those of the graphene structure. In addition, the predicted difference between the binding energies per atom for the structures of graphene and graphyne points out that graphyne networks have relatively lower phase stability in comparison with the graphene structures. PMID:24737253
Vibrational and thermodynamic properties of ?-, ?-, ?-, and 6, 6, 12-graphyne structures
NASA Astrophysics Data System (ADS)
Kosku Perkgöz, Nihan; Sevik, Cem
2014-05-01
Electronic, vibrational, and thermodynamic properties of different graphyne structures, namely ?-, ?-, ?-, and 6,6,12-graphyne, are investigated through first principles-based quasi-harmonic approximation by using phonon dispersions predicted from density-functional perturbation theory. Similar to graphene, graphyne was shown to exhibit a structure with extraordinary electronic features, mechanical hardness, thermal resistance, and very high conductivity from different calculation methods. Hence, characterizing its phonon dispersions and vibrational and thermodynamic properties in a systematic way is of great importance for both understanding its fundamental molecular properties and also figuring out its phase stability issues at different temperatures. Thus, in this research work, thermodynamic stability of different graphyne allotropes is assessed by investigating vibrational properties, lattice thermal expansion coefficients, and Gibbs free energy. According to our results, although the imaginary vibrational frequencies exist for ?-graphyne, there is no such a negative behavior for ?-, ?-, and 6,6,12-graphyne structures. In general, the Grüneisen parameters and linear thermal expansion coefficients of these structures are calculated to be rather more negative when compared to those of the graphene structure. In addition, the predicted difference between the binding energies per atom for the structures of graphene and graphyne points out that graphyne networks have relatively lower phase stability in comparison with the graphene structures.
First principles study on the molecular structure and vibrational spectra of ketoprofen
NASA Astrophysics Data System (ADS)
Liu, Lekun; Gao, Hongwei
2012-11-01
The aim of this work was to compare the performance of different DFT methods at different basis sets in predicting geometry and vibration spectrum of ketoprofen. The molecular geometry and vibrational frequencies of ketoprofen have been calculated using five different density function theory (DFT) methods, including LSDA, B3LYP, mPW1PW91, B3PW91 and HCTH, with various basis sets, including 6-311G, 6-311+G, 6-311++G, 6-311+G (d, p) and 6-311++G (2d, 2p). The results indicate that mPW1PW91/6-311++G (2d, 2p) level is clearly superior to all the remaining density functional methods in predicting the bond lengths and bond angles of ketoprofen. Mean absolute deviations between the calculated harmonic and observed fundamental vibration frequencies for each method shows that LSDA/6-311G method is the best to predict vibrational spectra of ketoprofen comparing other DFT methods.
Asymmetric Gaussian harmonic steering in second-harmonic generation
NASA Astrophysics Data System (ADS)
Olsen, M. K.
2013-11-01
Intracavity second-harmonic generation is one of the simplest of the quantum optical processes and is well within the expertise of most optical laboratories. It is well understood and characterized, both theoretically and experimentally. We show that it can be a source of continuous-variable asymmetric Gaussian harmonic steering with fields which have a coherent excitation, hence combining the important effects of harmonic entanglement and asymmetric steering in one easily controllable device, adjustable by the simple means of tuning the cavity loss rates at the fundamental and harmonic frequencies. We find that whether quantum steering is available via the standard measurements of the Einstein-Podolsky-Rosen correlations can depend on which quadrature measurements are inferred from output spectral measurements of the fundamental and the harmonic. Altering the ratios of the cavity loss rates can be used to tune the regions where symmetric steering is available, with the results becoming asymmetric over all frequencies as the cavity damping at the fundamental frequency becomes significantly greater than at the harmonic. This asymmetry and its functional dependence on frequency is a potential new tool for experimental quantum information science, with possible utility for quantum key distribution. Although we show the effect here for Gaussian measurements of the quadratures, and cannot rule out a return of the steering symmetry for some class of non-Gaussian measurements, we note here that the system obeys Gaussian statistics in the operating regime investigated and Gaussian inference is at least as accurate as any other method for calculating the necessary correlations. Perhaps most importantly, this system is simpler than any other methods we are aware of which have been used or proposed to create asymmetric steering.
NASA Astrophysics Data System (ADS)
Gupta, Amita; Singh, Ranvir; Ahmad, Amir; Kumar, Mahesh
2003-10-01
Today, vibration sensors with low and medium sensitivities are in great demand. Their applications include robotics, navigation, machine vibration monitoring, isolation of precision equipment & activation of safety systems e.g. airbags in automobiles. Vibration sensors have been developed at SSPL, using silicon micromachining to sense vibrations in a system in the 30 - 200 Hz frequency band. The sensing element in the silicon vibration sensor is a seismic mass suspended by thin silicon hinges mounted on a metallized glass plate forming a parallel plate capacitor. The movement of the seismic mass along the vertical axis is monitored to sense vibrations. This is obtained by measuring the change in capacitance. The movable plate of the parallel plate capacitor is formed by a block connected to a surrounding frame by four cantilever beams located on sides or corners of the seismic mass. This element is fabricated by silicon micromachining. Several sensors in the chip sizes 1.6 cm x 1.6 cm, 1 cm x 1 cm and 0.7 cm x 0.7 cm have been fabricated. Work done on these sensors, techniques used in processing and silicon to glass bonding are presented in the paper. Performance evaluation of these sensors is also discussed.
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)
NASA Astrophysics Data System (ADS)
Brandán, S. A.; Márquez López, F.; Montejo, M.; López González, J. J.; Ben Altabef, A.
2010-05-01
Theoretical calculations on the molecular geometry and the vibrational spectrum of 4-hydroxybenzoic acid were carried out by the Density Functional Theory (DFT/B3LYP) method. In addition, IR and Raman spectra of the 4-hydroxybenzoic acid in solid phase were newly recorded using them in conjunction the experimental and theoretical data (including SQM calculations), a vibrational analysis of this molecular specie was accomplished and a reassignment of the normal modes corresponding to some spectral bands was proposed. The geometries of monomers and dimers in gas phase were optimized using the DFT B3LYP method with the 6-31G*, D95** and 6-311++G** basis sets. Also, both the vibrational spectra recorded and the results of the theoretical calculations show the presence of one stable conformer for the 4-hydroxybenzoic acid cyclic dimer. The B3LYP/6-31G* method was used to study the structure for cyclic dimer of 4-hydroxybenzoic acid and for a complete assignment our results were compared with results of the cyclic dimer of benzoic acid. A scaled quantum mechanical analysis was carried out to yield the best set of harmonic force constants. The formation of the hydrogen bond was investigated in terms of the charge density by the AIM program and by the NBO calculations.
Brandán, S A; Márquez López, F; Montejo, M; López González, J J; Ben Altabef, A
2010-05-01
Theoretical calculations on the molecular geometry and the vibrational spectrum of 4-hydroxybenzoic acid were carried out by the Density Functional Theory (DFT/B3LYP) method. In addition, IR and Raman spectra of the 4-hydroxybenzoic acid in solid phase were newly recorded using them in conjunction the experimental and theoretical data (including SQM calculations), a vibrational analysis of this molecular specie was accomplished and a reassignment of the normal modes corresponding to some spectral bands was proposed. The geometries of monomers and dimers in gas phase were optimized using the DFT B3LYP method with the 6-31G*, D95** and 6-311++G** basis sets. Also, both the vibrational spectra recorded and the results of the theoretical calculations show the presence of one stable conformer for the 4-hydroxybenzoic acid cyclic dimer. The B3LYP/6-31G* method was used to study the structure for cyclic dimer of 4-hydroxybenzoic acid and for a complete assignment our results were compared with results of the cyclic dimer of benzoic acid. A scaled quantum mechanical analysis was carried out to yield the best set of harmonic force constants. The formation of the hydrogen bond was investigated in terms of the charge density by the AIM program and by the NBO calculations. PMID:20223703
NASA Astrophysics Data System (ADS)
Kumru, M.; Bardakci, T.; Sari, L.
2009-06-01
We have discussed the applicability limits of HF, MP2 and DFT-B3LYP methods on 4-amino-1-methylbenzene in our previous work [1]. We have found the DFT-B3LYP method very promising for vibrational spectral analyses. In this study, we extend DFT calculations with different basis sets for more appropriateness to exprimental results. The optimized molecular structures, vibrational frequencies and coresponding vibrational assigments of 4-amino-1-methylbenzene have been obtained from the DFT-B3LYP, DFT-B3PW91 and DFT-PBEPBE methods implementing the 6-311G+** and aug-ccPVQZ basis sets. Scale factors, which bring computational frequencies in closer agreement with the experimental data, have been calculated for predominant vibrational motions of the normal modes at each level considered. All observed harmonic IR and Raman bands of 4-amino-1-methylbenzene have been assigned in the frameworks of the calculations. The comparison of calculations with FT-IR and FT-Raman spectra of 4-amino-1-methylbenzene have been carried out. We are planing to extend this work to the transition metal complexes in the form of MX2L2 [M: Transition metals e.g. Mn(II), Co(II) and Ni(II) . . . ; X : Halogens e.g Cl, Br, I, L: 4-amino-1-methylbenzene] 1. A. Altun, K. Golcuk, M. Kumru, "Structure and vibrational spectra of p-methylaniline: Hartree-Fock, MP2 and density functional theory studies", JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM 637: 155-169 OCT 3 2003
Harmonization of Biodiesel Specifications
Alleman, T. L.
2008-02-01
Worldwide biodiesel production has grown dramatically over the last several years. Biodiesel standards vary across countries and regions, and there is a call for harmonization. For harmonization to become a reality, standards have to be adapted to cover all feedstocks. Additionally, all feedstocks cannot meet all specifications, so harmonization will require standards to either tighten or relax. For harmonization to succeed, the biodiesel market must be expanded with the alignment of test methods and specification limits, not contracted.
First-principles study of the phonon vibrational spectra and thermal properties of hexagonal MoS2
NASA Astrophysics Data System (ADS)
Yuan, Jiaonan; Lv, Zhenlong; Lu, Qing; Cheng, Yan; Chen, Xiangrong; Cai, Lingcang
2015-02-01
The phonon spectra and thermal properties of the hexagonal MoS2 are investigated by using first-principles calculations within the density functional theory (DFT). Finite displacement method is used to calculate the phonon vibrational spectra and phonon density of states. The vibrational modes at the Gamma point are analyzed by using group theory. The temperature and pressure dependence of its thermal quantities such as the thermal expansion, the heat capacity at constant volume, the Gibbs energy and entropy are obtained based on the quasi-harmonic approximation (QHA). Our results show that both the thermal expansion coefficient ? and the heat capacity CV increase with T3 at low temperatures and gradually turn almost linear as the temperature increases. It is found that the entropy is sensitive to the temperature while the Gibbs free energy is more sensitive to the pressure change.
Marc Welker; Gerold Steinebrunner; Jan Solca; Hanspeter Huber
1996-01-01
A four-dimensional potential energy surface for the carbon dioxide dimer composed from rigid monomers is determined. 226 energy points were calculated ab initio with a large basis set on the MP2 level including full counterpoise correction. An analytical site-site potential is fitted to these points. The stationary points of the analytical surface are determined, harmonic vibrational frequencies and second virial
NASA Technical Reports Server (NTRS)
Messaro. Semma; Harrison, Phillip
2010-01-01
Ares I Zonal Random vibration environments due to acoustic impingement and combustion processes are develop for liftoff, ascent and reentry. Random Vibration test criteria for Ares I Upper Stage pyrotechnic components are developed by enveloping the applicable zonal environments where each component is located. Random vibration tests will be conducted to assure that these components will survive and function appropriately after exposure to the expected vibration environments. Methodology: Random Vibration test criteria for Ares I Upper Stage pyrotechnic components were desired that would envelope all the applicable environments where each component was located. Applicable Ares I Vehicle drawings and design information needed to be assessed to determine the location(s) for each component on the Ares I Upper Stage. Design and test criteria needed to be developed by plotting and enveloping the applicable environments using Microsoft Excel Spreadsheet Software and documenting them in a report Using Microsoft Word Processing Software. Conclusion: Random vibration liftoff, ascent, and green run design & test criteria for the Upper Stage Pyrotechnic Components were developed by using Microsoft Excel to envelope zonal environments applicable to each component. Results were transferred from Excel into a report using Microsoft Word. After the report is reviewed and edited by my mentor it will be submitted for publication as an attachment to a memorandum. Pyrotechnic component designers will extract criteria from my report for incorporation into the design and test specifications for components. Eventually the hardware will be tested to the environments I developed to assure that the components will survive and function appropriately after exposure to the expected vibration environments.
NASA Astrophysics Data System (ADS)
Yagi, Kiyoshi; Hirao, Kimihiko; Taketsugu, Tetsuya; Schmidt, Michael W.; Gordon, Mark S.
2004-07-01
For polyatomic molecules, n-mode coupling representations of the quartic force field (nMR-QFF) are presented, which include terms up to n normal coordinate couplings in a fourth-order polynomial potential energy function. The computational scheme to evaluate third-and fourth-order derivatives by finite differentiations of the energy is fully described. The code to generate the nMR-QFF has been implemented into GAMESS program package and interfaced with the vibrational self-consistent field (VSCF) and correlation corrected VSCF (cc-VSCF) methods. As a demonstration, fundamental frequencies have been calculated by the cc-VSCF method based on 2MR-QFF for formaldehyde, ethylene, methanol, propyne, and benzene. The applications show that 2MR-QFF is a highly accurate potential energy function, with errors of 1.0-1.9% relative to the experimental value in fundamental frequencies. This approach will help quantitative evaluations of vibrational energies of a general molecule with a reasonable computational cost.
Nuclear momentum distribution in solid and liquid HF from ab initio calculation.
Krzystyniak, M
2010-10-14
A calculation of nuclear momentum distribution of liquid and solid hydrogen fluoride was performed. In both systems, density functional theory generalized gradient approximation functional of Perdew, Burke, and Ernzerhof was used for the calculation: for liquid hydrogen fluoride, using an atom centered basis set for an isolated molecule with optimized geometry, and for solid hydrogen fluoride using plane-wave basis sets on optimized orthorhombic crystal cell. For liquid hydrogen fluoride, a semiclassical approach was adopted with the vibrational contribution to momentum distribution obtained from the density functional theory calculation and translational and rotational contributions calculated classically. Nuclear momentum distribution in the solid hydrogen fluoride was calculated entirely quantum mechanically using phonon dispersion and vibrational density of states calculated in the framework of plane-wave density functional theory. Theoretical results were contrasted with recently obtained results of Compton (deep inelastic) neutron scattering on liquid and solid hydrogen fluoride. In case of liquid hydrogen fluoride, almost a perfect agreement between theory and experiment was achieved within the harmonic Born-Oppenheimer approximation. For the solid system under investigation, the harmonic approximation leads to small (4%) overestimation of the square root of the second moment indicating that neutron Compton scattering technique is sensitive to proton delocalization due to hydrogen bonding in solid hydrogen fluoride. PMID:20950015
Semiclassical approaches to below-threshold harmonics
Hostetter, James A.; Tate, Jennifer L. [Department of Physics and Astronomy, Louisiana State University, Baton Rouge, Louisiana 70803-4001 (United States); Schafer, Kenneth J.; Gaarde, Mette B. [Department of Physics and Astronomy, Louisiana State University, Baton Rouge, Louisiana 70803-4001 (United States); PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, California 94025 (United States)
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.
Matanovic, Ivana; Atanassov, Plamen; Kiefer, Boris; Garzon, Fernando; Henson, Neil J.
2014-10-05
The structural equilibrium parameters, the adsorption energies, and the vibrational frequencies of the nitrogen molecule and the hydrogen atom adsorbed on the (111) surface of rhodium have been investigated using different generalized-gradient approximation (GGA), nonlocal correlation, meta-GGA, and hybrid functionals, namely, Perdew, Burke, and Ernzerhof (PBE), Revised-RPBE, vdW-DF, Tao, Perdew, Staroverov, and Scuseria functional (TPSS), and Heyd, Scuseria, and Ernzerhof (HSE06) functional in the plane wave formalism. Among the five tested functionals, nonlocal vdW-DF and meta-GGA TPSS functionals are most successful in describing energetics of dinitrogen physisorption to the Rh(111) surface, while the PBE functional provides the correct chemisorption energy for the hydrogen atom. It was also found that TPSS functional produces the best vibrational spectra of the nitrogen molecule and the hydrogen atom on rhodium within the harmonic formalism with the error of 22.62 and 21.1% for the NAN stretching and RhAH stretching frequency. Thus, TPSS functional was proposed as a method of choice for obtaining vibrational spectra of low weight adsorbates on metallic surfaces within the harmonic approximation. At the anharmonic level, by decoupling the RhAH and NAN stretching modes from the bulk phonons and by solving one- and two-dimensional Schr€odinger equation associated with the RhAH, RhAN, and NAN potential energy we calculated the anharmonic correction for NAN and RhAH stretching modes as 231 cm21 and 277 cm21 at PBE level. Anharmonic vibrational frequencies calculated with the use of the hybrid HSE06 function are in best agreement with available experiments.
NASA Astrophysics Data System (ADS)
Ingamells, Victoria E.; Papadopoulos, Manthos G.; Handy, Nicholas C.; Willetts, Andrew
1998-08-01
Electronic, vibrational and rotational contributions to the dipole moment ? , polarizability ? , and first and second hyperpolarizabilities, ? and ? , are presented for the boron hydride molecule; static and dynamic rovibrational properties are reported for the first time. The electronic contributions are computed ab initio by finite differencing the electronic energy computed at the Hartree-Fock level of theory, and using various sophisticated correlated methods. Specifically these are Mo/ller-Plesset perturbation theory at second order, and fourth order (including single, double, triple and quadruple substitutions), and the Brueckner variant of the coupled-cluster method including triple excitations; density functional theory with the B3LYP functional is used for comparison. Vibrational (and rotational) contributions to the properties are calculated at the Hartree-Fock level of theory; for the vibrational properties, electron correlation is partially included using second order Mo/ller-Plesset theory. Basis set and electron correlation effects on both electronic and vibrational contributions are assessed and discussed. The dependence of the vibrational properties on the mechanical and electrical anharmonicity is examined, and the two methods used in its computation — a finite difference approach and a perturbation theoretic method — are compared and contrasted. A brief analysis of the frequency dependence of vibrational contributions to ?(-??;?1) , ?(-??;?1,?2) in the electro-optic Pockels and second harmonic generation effects, and ?(-??;?1,?2,?3) in the electro-optic Kerr and electric-field-induced second harmonic generation effects, is presented. The electronic results are compared with literature values believed to the best currently available; agreement is shown to be acceptable.
Photothermal Study of Free and Forced Elastic Vibrations of Microcantilevers
NASA Astrophysics Data System (ADS)
Todorovic, D. M.; Cretin, B.; Vairac, P.; Song, Y.; Rabasovic, M. D.; Markushev, D. D.
2015-06-01
Dynamic free (spontaneous) and forced (optically excited) elastic vibration spectra of a cantilever (CL) were studied. The amplitude and phase elastic displacements of silicon CLs were measured as a function of the modulation frequency with and without optical excitation. Typically, four obvious peaks can be observed in the elastic vibration spectrum. The first peak represents the forced vibrations at the same frequency as the modulation of laser excitation, while two other peaks are the third and fifth harmonics. One small peak is the first natural resonance of the CL (free vibrations, spontaneous vibrations). The amplitude of elastic vibrations without optical excitation changes with frequency, and it is possible to distinguish two frequency regions. In the high frequency range above 10 kHz, the amplitude elastic vibration spectra are not a function of the frequency which is typically for white noise. The white noise level, which corresponds to the thermomechanical noise, was found. The forced vibrations are precisely studied by modulated optical excitation where the frequency is varied from 3 kHz to 45 kHz and by measuring the response with a lock-in-amplifier (measuring the amplitude and phase of the elastic vibrations). The optically excited elastic vibrations are the consequence of thermal and electronic elastic effects in the silicon CL. The mechanical response of the optically excited CL was modeled with good approximation by a damped harmonic oscillator. The experimental amplitude and phase spectra were fitted with theoretical curves, and the quality factor near the natural (resonance) frequency was obtained.
Vibrational spectroscopy of Methyl benzoate.
Maiti, Kiran Sankar
2015-08-14
Methyl benzoate is studied as a model compound for the development of new IR pulse schemes with possible applicability to biomolecules. Anharmonic vibrational modes of Methyl benzoate are calculated on different level (MP2, SCS, CCSD(T) with varying basis sets) ab initio PESs using the vibrational self-consistent field (VSCF) method and its correlation corrected extensions. Dual level schemes, combining different quantum chemical methods for diagonal and coupling potentials, are systematically studied and applied successfully to reduce the computational cost. Isotopic substitution of ?-hydrogen by deuterium is studied to obtain a better understanding of the molecular vibrational coupling topology. PMID:26050760
Rahman, Talat S
2011-11-15
This special issue is dedicated to the phenomenon of vibrations at surfaces-a topic that was indispensible a couple of decades ago, since it was one of the few phenomena capable of revealing the nature of binding at solid surfaces. For clean surfaces, the frequencies of modes with characteristic displacement patterns revealed how surface geometry, as well as the nature of binding between atoms in the surface layers, could be different from that in the bulk solid. Dispersion of the surface phonons provided further measures of interatomic interactions. For chemisorbed molecules on surfaces, frequencies and dispersion of the vibrational modes were also critical for determining adsorption sites. In other words, vibrations at surfaces served as a reliable means of extracting information about surface structure, chemisorption and overlayer formation. Experimental techniques, such as electron energy loss spectroscopy and helium-atom-surface scattering, coupled with infra-red spectroscopy, were continually refined and their resolutions enhanced to capture subtleties in the dynamics of atoms and molecules at surfaces. Theoretical methods, whether based on empirical and semi-empirical interatomic potential or on ab initio electronic structure calculations, helped decipher experimental observations and provide deeper insights into the nature of the bond between atoms and molecules in regions of reduced symmetry, as encountered on solid surfaces. Vibrations at surfaces were thus an integral part of the set of phenomena that characterized surface science. Dedicated workshops and conferences were held to explore the variety of interesting and puzzling features revealed in experimental and theoretical investigations of surface vibrational modes and their dispersion. One such conference, Vibrations at Surfaces, first organized by Harald Ibach in Juelich in 1980, continues to this day. The 13th International Conference on Vibrations at Surfaces was held at the University of Central Florida, Orlando, in March 2010. Several speakers at this meeting were invited to contribute to the special section in this issue. As is clear from the articles in this special section, the phenomenon of vibrations at surfaces continues to be a dynamic field of investigation. In fact, there is a resurgence of effort because the insights provided by surface dynamics are still fundamental to the development of an understanding of the microscopic factors that control surface structure formation, diffusion, reaction and structural stability. Examination of dynamics at surfaces thus complements and supplements the wealth of information that is obtained from real-space techniques such as scanning tunneling microscopy. Vibrational dynamics is, of course, not limited to surfaces. Surfaces are important since they provide immediate deviation from the bulk. They display how lack of symmetry can lead to new structures, new local atomic environments and new types of dynamical modes. Nanoparticles, large molecules and nanostructures of all types, in all kinds of local environments, provide further examples of regions of reduced symmetry and coordination, and hence display characteristic vibrational modes. Given the tremendous advance in the synthesis of a variety of nanostructures whose functionalization would pave the way for nanotechnology, there is even greater need to engage in experimental and theoretical techniques that help extract their vibrational dynamics. Such knowledge would enable a more complete understanding and characterization of these nanoscale systems than would otherwise be the case. The papers presented here provide excellent examples of the kind of information that is revealed by vibrations at surfaces. Vibrations at surface contents Poisoning and non-poisoning oxygen on Cu(410)L Vattuone, V Venugopal, T Kravchuk, M Smerieri, L Savio and M Rocca Modifying protein adsorption by layers of glutathione pre-adsorbed on Au(111)Anne Vallée, Vincent Humblot, Christophe Méthivier, Paul Dumas and Claire-Marie Pradier Relating temperature dependence of atom sc
Balachandran, V; Karpagam, V; Revathi, B; Kavimani, M; Santhi, G
2015-01-25
The FT-IR and FT-Raman spectra of 3-tert-butyl-4-hydroxyanisole (TBHA) molecule have been recorded in the region 4000-400 cm(-1) and 3500-100 cm(-1), respectively. Optimized geometrical structure, harmonic vibrational frequencies has been computed by B3LYP level using 6-31G (d,p) and 6-311+G (d,p) basis sets. The observed FT-IR and FT-Raman vibrational frequencies are analyzed and compared with theoretically predicted vibrational frequencies. The geometries and normal modes of vibration obtained from DFT method are in good agreement with the experimental data. The Mulliken charges, the natural bonding orbital (NBO) analysis, the first-order hyperpolarizability of the investigated molecule were computed using DFT calculations. Besides, charge transfer occurring in the molecule between HOMO and LUMO energies, frontier energy gap, molecular electrostatic potential (MEP) were calculated and analyzed. The isotropic chemical shift computed by (1)H and (13)C nuclear magnetic resonance (NMR) chemical shifts of the TBHA calculated using the gauge invariant atomic orbital (GIAO) method also shows good agreement with experimental observations. PMID:25173520
Vibration suppression of advanced space cryocoolers: an overview
NASA Astrophysics Data System (ADS)
Ross, Ronald G., Jr.
2003-07-01
Mechanical cryocoolers represent a significant enabling technology for precision space instruments by providing cryogenic temperatures for sensitive infrared, gamma-ray, and x-ray detectors. However, the vibration generated by the cryocooler's refrigeration compressor has long been identified as a critical integration issue. The key sensitivity is the extent to which the cooler's vibration harmonics excite spacecraft resonances and prevent on-board sensors from achieving their operational goals with respect to resolution and pointing accuracy. To reduce the cryocooler's vibration signature to acceptable levels, a variety of active vibration suppression technologies have been developed and implemented over the past 15 years. At this point, nearly all space cryocoolers have active vibration suppression systems built into their drive electronics that reduce the peak unbalanced forces to less than 1% of their original levels. Typical systems of today individually control the vibration in each of the cryocoolers lowest drive harmonics, with some controlling as many as 16 harmonics. A second vibration issue associated with cryocoolers is surviving launch. Here the same pistons and coldfingers that generate vibration during operation are often the most critical elements in terms of surviving high input acceleration levels. Since electrical power is generally not available during launch, passive vibration suppression technologies have been developed. Common vibration damping techniques include electrodynamic braking via shorted motor coils and the use of particle dampers on sensitive cryogenic elements. This paper provides an overview of the vibration characteristics of typical linear-drive space cryocoolers, outlines their history of development, and presents typical performance of the various active and passive vibration suppression systems being used.
Dai, Zuyang; Sun, Wei; Wang, Jia; Mo, Yuxiang
2015-08-01
The spin-vibronic energy levels of the cyanoacetylene cation have been measured using the one-photon zero-kinetic energy (ZEKE) photoelectron spectroscopic method. All three degenerate vibrational modes showing vibronic coupling, i.e., Renner-Teller (RT) effect, have been observed. All the splitting spin-vibronic energy levels of the fundamental H-C?C bending vibration (v5) have been determined. The spin-vibronic energy levels of the degenerate vibrational modes have also been calculated using a diabatic model in which the harmonic terms as well as all the second-order vibronic coupling terms are used. The theoretical predictions are in good agreement with the experimental data and are used to assign the ZEKE spectrum. It is found that the RT effects for the H-(CC)-CN bending (v7) and the C-C?N bending (v6) vibrations are weak, whereas they are strong for the H-C?C bending (v5) vibration. The cross-mode RT couplings between any of the two degenerate vibrations are strong. The spin-orbit resolved fundamental vibrational energy levels of the C?N stretching (v2) and C-H stretching (v1) vibrations have also been observed. The spin-orbit energy splitting of the ground state has been determined for the first time as 43 ± 2 cm(-1), and the ionization energy of HCCCN is found to be 93 903.5 ± 2 cm(-1). PMID:26254647
Breaking the symmetry of a circular system of coupled harmonic oscillators
J. N. Boyd; R. G. Hudepohl; P. N. Raychowdhury
2002-01-01
First we compute the natural frequencies of vibration of four identical particles cou- pled by ideal, massless harmonic springs. The four particles are constrained to move on a fixed circle. The initial computations are simplified by a transformation to sym- metry coordinates. Then the symmetry of the vibrating system is broken by changing the mass of a single particle by
NASA Astrophysics Data System (ADS)
Sun, Yu-Xi; Hao, Qing-Li; Yu, Zong-Xue; Jiang, Wen-Jun; Lu, Lu-De; Wang, Xin
2009-09-01
This work deals with the IR and Raman spectroscopy of 4-(2-furanylmethyleneamino) antipyrine (FAP), 4-benzylideneaminoantipyrine (BAP) and 4-cinnamilideneaminoantipyrine (CAP) by means of experimental and quantum chemical calculations. The equilibrium geometries, harmonic frequencies, infrared intensities and Raman scattering activities were calculated by density functional B3LYP method with the 6-31G(d) basis set. The comparisons between the calculated and experimental results covering molecular structures, assignments of fundamental vibrational modes and thermodynamic properties were investigated. The optimized molecular geometries have been compared with the experimental data obtained from XRD data, which indicates that the theoretical results agree well with the corresponding experimental values. For the three compounds, comparisons and assignments of the vibrational frequencies indicate that the calculated frequencies are close to the experimental data, and the IR spectra are comparable with some slight differences, whereas the Raman spectra are different clearly and the strongest Raman scattering actives are relative tightly to the molecular conjugative moieties linked through their Schiff base imines. The thermodynamic properties (heat capacities, entropies and enthalpy changes) and their correlations with temperatures were also obtained from the harmonic frequencies of the optimized strucutres.
NASA Astrophysics Data System (ADS)
Issaoui, Noureddine; Ghalla, Houcine; Muthu, S.; Flakus, H. T.; Oujia, Brahim
2015-02-01
In this work, the molecular structure, harmonic vibrational frequencies, UV, NBO and AIM of 3-thiophenecarboxilic acid (abbreviated as 3-TCA) monomer and dimer has been investigated. The FT-IR and FT-Raman spectra were recorded. The ground-state molecular geometry and vibrational frequencies have been calculated by using the Hartree-Fock (HF) and density functional theory (DFT)/B3LYP methods and 6-311++G(d,p) as a basis set. The fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with VEDA program. Comparison of the observed fundamental vibrational frequencies of 3-TCA with calculated results by HF and DFT methods indicates that B3LYP is better to HF method for molecular vibrational problems. The difference between the observed and scaled wavenumber values is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title compound have been constructed. A study on the Mulliken atomic charges, the electronic properties were performed by time-dependent DFT (TD-DFT) approach, frontier molecular orbitals (HOMO-LUMO), molecular electrostatic potential (MEP) and thermodynamic properties have been performed. The electric dipole moment (?) and the first hyperpolarizability (?) values of the investigated molecule have been also computed.
Vibrational spectra, NBO, HOMO-LUMO and conformational stability studies of 4-hydroxythiobenzamide
NASA Astrophysics Data System (ADS)
Sambathkumar, Kuppusamy
2015-08-01
In this work, the experimental and theoretical study on molecular structure, vibrational spectral analysis of 4-hydroxythiobenzamide (HTB) have been reported. The solid phase FTIR (4000-400 cm-1) and FT-Raman spectra (3500-50 cm-1) were recorded. The molecular geometry, harmonic vibrational frequencies and bonding features of HTB in the ground-state have been calculated by the density functional method (B3LYP) with 6-311+G(d,p) and 6-311++G(d,p) as basis sets. Utilizing the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. Stability of the molecule arising from hyperconjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The results show that the value of electron density (ED) in the ?? antibonding orbitals and E(2) energies confirms the occurrence of ICT (intra-molecular charge transfer) within the molecule. The UV spectrum was measured in ethanol solution. The energy and oscillator strength calculated by time-dependent density functional theory (TD-DFT) correlates with the experimental findings. The calculated molecular electrostatic potential (MESP), HOMO and LUMO energies show that charge transfer occurs within the molecule. Besides, the simulated infrared and Raman spectra of the title compound which show good agreement with observed spectra.
Vibrational spectra, NBO, HOMO-LUMO and conformational stability studies of 4-hydroxythiobenzamide.
Sambathkumar, Kuppusamy
2015-08-01
In this work, the experimental and theoretical study on molecular structure, vibrational spectral analysis of 4-hydroxythiobenzamide (HTB) have been reported. The solid phase FTIR (4000-400 cm(-1)) and FT-Raman spectra (3500-50 cm(-1)) were recorded. The molecular geometry, harmonic vibrational frequencies and bonding features of HTB in the ground-state have been calculated by the density functional method (B3LYP) with 6-311+G(d,p) and 6-311++G(d,p) as basis sets. Utilizing the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. Stability of the molecule arising from hyperconjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The results show that the value of electron density (ED) in the ?(?) antibonding orbitals and E((2)) energies confirms the occurrence of ICT (intra-molecular charge transfer) within the molecule. The UV spectrum was measured in ethanol solution. The energy and oscillator strength calculated by time-dependent density functional theory (TD-DFT) correlates with the experimental findings. The calculated molecular electrostatic potential (MESP), HOMO and LUMO energies show that charge transfer occurs within the molecule. Besides, the simulated infrared and Raman spectra of the title compound which show good agreement with observed spectra. PMID:25827766
Analysis of vibration effects on holographic data storage system
NASA Astrophysics Data System (ADS)
Ishii, Toshiki; Shimada, Ken-ichi; Hoshizawa, Taku; Takashima, Yuzuru
2015-09-01
It is crucial to understand the effects of random mechanical vibration on holographic data storage system, but such effects have not yet been formalized. Therefore, we developed a generalized formalization of vibration effects using a concept of time-averaged holography. Normalized intensity as a function of a statistical measure of vibration waveforms is simulated by simple harmonic oscillation, then normalized intensity is predicted well even for random vibration waveforms. Servo and mechanical systems will be designed solely by specifying the required signal level, which enables efficient product development.
Vibration characteristics of OH-58A helicopter main rotor transmission
NASA Technical Reports Server (NTRS)
Lewicki, David G.; Coy, John J.
1987-01-01
Experimental vibration tests covering a range of torque and speed conditions were performed on the OH-58A helicopter main rotor transmission at the NASA Lewis Research Center. Signals from accelerometers located on the transmission housing were analyzed by using Fourier spectra, power spectral density functions, and averaging techniques. Most peaks of the Fourier spectra occurred at the spiral bevel and planetary gear mesh harmonics. The highest level of vibration occurred at the spiral bevel meshing frequency. Transmission speed and vibration measurement location had a significant effect on measured vibration; transmission torque and measurement direction had a small effect.
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…
NASA Astrophysics Data System (ADS)
Arjunan, V.; Balamourougane, P. S.; Mythili, C. V.; Mohan, S.; Nandhakumar, V.
2011-12-01
The FT-IR (4000-400 cm -1) and FT-Raman (4000-100 cm -1) spectral measurements of 2-amino-6-fluorobenzothiazole (2A6FBT) and complete assignments of the observed spectra have been proposed. Ab initio and DFT calculations have been performed and the structural parameters of the compound are determined from the optimised geometry with 6-31G(d,p), 6-311++G(d,p) and cc-pVDZ basis sets and giving energies, harmonic vibrational frequencies, depolarisation ratios, IR intensities, Raman activities and atomic displacements. 1H and 13C NMR spectra were recorded and 1H and 13C nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. UV-Visible spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies, were measured by time-dependent DFT (TD-DFT) approach. The geometric parameters, energies, harmonic vibrational frequencies, IR intensities, Raman activities chemical shifts and absorption wavelengths were compared with the available experimental data of the molecule. The influences of fluoro and amino group on the skeletal modes and on the proton chemical shifts have been investigated.
NASA Astrophysics Data System (ADS)
Durig, James R.; Panikar, Savitha S.; Guirgis, Gamil A.; Gounev, Todor K.; Klæboe, Peter; Horn, Anne; Nielsen, Claus J.; Peebles, Rebecca A.; Peebles, Sean A.; Liberatore, Richard J.
2010-04-01
The infrared spectra (3100-40 cm -1) of gaseous and amorphous solid and Raman spectra (3200-20 cm -1) of the liquid at various temperatures for methylgermylcyclopropane, c-C 3H 5GeH 2CH 3, have been obtained. Additionally, variable temperature (-55 to -100 °C) studies of the infrared spectra of the sample dissolved in xenon have been recorded. From these spectral data, two conformers have been identified with one the cis (syn) form where the methyl group is over the three-membered ring and the other the gauche form. By utilizing six conformer pairs of the vibrational bands the enthalpy difference of the sample dissolved in xenon has been determined to be 43 ± 11 cm -1 (0.51 ± 0.13 kJ mol -1) with the gauche form the more stable conformer. It is estimated that there is approximately 30 ± 3% of the cis form present at ambient temperature. It was not possible to achieve crystallization of the compound by annealing it, and both conformers were present at all temperatures. The Ge-H distances of 1.531 and 1.533 Å for the gauche conformer have been determined from their stretching frequencies. By utilizing the microwave rotational constants of the gauche conformer for five isotopomers ( 70Ge, 72Ge, 73Ge, 74Ge, 76Ge) combined with the structural parameters predicted from the MP2(full)/6-311+G(d,p) calculations, the adjusted r0 structural parameters have been obtained. The heavy atom distances (Å) are: (GeC 2) = 1.925(5); (C 2C 4) = 1.517(3); (C 2C 5) = 1.519(3); (C 4C 5) = 1.502(3); (GeC 6) = 1.947(5) and the angles (°) are: ?CGeC = 110.6(5); ?GeC 2C 4 = 120.1(5); ?GeC 2C 5 = 119.2(5). For the cis form very small differences of 0.003 and 0.001 Å from those of the gauche form are predicted for the GeC bonds whereas the other distances are predicted to be the same or differ at the most by 0.002 Å. A complete vibrational assignment is given for both the conformers. To support the vibrational assignments, 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. Barriers to internal rotation have been predicted. The results are discussed and compared to the corresponding properties of some similar molecules.
Vibrational assignment and crystal structure of 3-amino-1-phenyl-2-buten-1-one
NASA Astrophysics Data System (ADS)
Tayyari, Sayyed Faramarz; Ghafari, Maliheh; Jamialahmadi, Mina; Chahkandi, Behzad; Patrick, Brian O.; Wang, Yan Alexander
2013-08-01
3-Amino-1-phenyl-2-buten-1-one (APBO) was synthesized by amination of benzoylacetone (BA) and its structure was studied by X-ray crystallographic method. The geometry of APBO was also optimized by means of density functional theory (DFT) and ab initio calculations and the results were compared with the X-ray crystallographic data. The vibrational fundamentals predicted within harmonic model, calculated at the B3LYP/6-311++G**, and by anharmonic model, calculated at the B3LYP/6-31G** level, display excellent agreement with the measured data. The proposed assignments are further confirmed by observing the deuterium isotopic shifts of different bands through predictions by the same theoretical method. The theoretical results obtained for APBO were compared with those of 4-amino-3-penten-2-one (APO).
Suresh, S; Gunasekaran, S; Srinivasan, S
2015-03-01
The solid phase FT-IR and FT-Raman spectra of 4-Hydroxy-2-methyl-N-(2-pyridinyl)-2H-1,2-benzothiazine-3-carboxamide-1,1-dioxide (Piroxicam) have been recorded in the region 4000-400 and 4000-100cm(-1) respectively. The molecular geometry, harmonic vibrational frequencies and bonding features of piroxicam in the ground state have been calculated by Hartree-Fock (HF) and density functional theory (DFT) methods using 6-311++G(d,p) basis set. The calculated harmonic vibrational frequencies are scaled and they are compared with experimental obtained by FT-IR and FT-Raman spectra. A detailed interpretation of the vibrational spectra of the title compound has been made on the basis of the calculated potential energy distribution (PED). The electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MESP) are also performed. The linear polarizability (?) and the first order hyper polarizability (?) values of the title compound have been computed. The molecular stability arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. PMID:25523048
Structure and vibrations of different charge Ge impurity in ?-quartz
Kislov, A. N., E-mail: a.n.kislov@urfu.ru; Mikhailovich, A. P., E-mail: a.n.kislov@urfu.ru; Zatsepin, A. F., E-mail: a.n.kislov@urfu.ru [Ural Federal University, 19 Mira St., Yekaterinburg, 620002 (Russian Federation)
2014-10-21
Atomic structure and localized vibrations of ??SiO{sub 2}:Ge are studied using computer modeling techniques. The simulation was carried out by the lattice dynamics calculation of the local density of vibrational states. Local structures parameters are calculated, localized symmetrized vibrations frequency caused by Ge impurity in different charge states are defined. The movements of atoms located near Ge impurity are analyzed and their contribution into localized vibrations of different type is evaluated.