Search results for "anharmonicity"
showing 10 items of 118 documents
Theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis-, and trans-1,2-difluoroethylenes.
2014
A theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis- and trans-1,2-difluoroethylenes is reported. The results obtained using density functional theory (DFT) combined with large basis sets and gauge-independent atomic orbital calculations were critically compared with experiment and conventional, higher level correlated electronic structure methods. Accurate structural, vibrational, and NMR parameters of difluoroethylenes were obtained using several density functionals combined with dedicated basis sets. B3LYP/6-311++G(3df,2pd) optimized structures of difluoroethylenes closely reproduced experimental geometries and earlier reported b…
Vibrational spectra and force constants of symmetric tops
1983
The infrared spectrum of H3SiI in the 800–1050 cm-1 region has been recorded with a resolution of 0·04 cm-1 and rotationally analysed. Features related to the Fermi resonance between v 5 and v 3 + v 6 and to the Coriolis x, y resonance between v 2 and v 5 have been explained, and a set of vibration-rotation parameters for the three bands has been determined by least-squares calculations, σ(J, K) = 9·4 × 10-3 cm-1. The Fermi resonance matrix element |W 356| is found to be 3·7859(7) cm-1 and the vibrational frequencies are v 2 0 = 904·551(1), v 5 0 = 941·0746(8) and (v 3 + v 6)0 = 953·688(3) cm-1. The anharmonicity constant, x 36 = -1·745(9) cm-1, has been determined. Comparison is made with …
Harmonic oscillator model for the atom-surface Casimir-Polder interaction energy
2012
In this paper we consider a quantum harmonic oscillator interacting with the electromagnetic radiation field in the presence of a boundary condition preserving the continuous spectrum of the field, such as an infinite perfectly conducting plate. Using an appropriate Bogoliubov-type transformation we can diagonalize exactly the Hamiltonian of our system in the continuum limit and obtain non-perturbative expressions for its ground-state energy. From the expressions found, the atom-wall Casimir-Polder interaction energy can be obtained, and well-know lowest-order results are recovered as a limiting case. Use and advantage of this method for dealing with other systems where perturbation theory …
Investigations of methyl lactate in the presence of reverse micelles by vibrational spectroscopy and circular dichroism
2012
Abstract The FT-IR and vibrational circular dichroism (VCD) spectra of ( S )- and -( R )-methyl lactate have been recorded for neat samples and at various concentrations in CCl 4 and DMSO solutions. These spectra are used to analyse the FT-IR and VCD spectra of methyl lactates in presence of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) in CCl 4 , where the surfactant molecules are known to form reverse micelles. Some tendency of methyl lactate to interact with AOT micellar aggregates is observed, but not as well defined as previously observed for dimethyl tartrate in analogous circumstances. Besides, near infrared (NIR) absorption and VCD data have been obtained for most of the above system…
Oscillations of a highly discrete breather with a critical regime
2000
We analyze carefully the essential features of the dynamics of a stationary discrete breather in the ultimate degree of energy localization in a nonlinear Klein-Gordon lattice with an on-site double-well potential. We demonstrate the existence of three different regimes of oscillatory motion in the breather dynamics, which are closely related to the motion of the central particle in an effective potential having two nondegenerate wells. In given parameter regions, we observe an untrapped regime, in which the central particle executes large-amplitude oscillations from one to the other side of the potential barrier. In other parameter regions, we find the trapped regime, in which the central …
Study of High-Temperature Behaviour of ZnO by Ab Initio Molecular Dynamics Simulations and X-ray Absorption Spectroscopy
2021
Wurtzite-type zinc oxide (w-ZnO) is a widely used material with a pronounced structural anisotropy along the c axis, which affects its lattice dynamics and represents a difficulty for its accurate description using classical models of interatomic interactions. In this study, ab initio molecular dynamics (AIMD) was employed to simulate a bulk w-ZnO phase in the NpT ensemble in the high-temperature range from 300 K to 1200 K. The results of the simulations were validated by comparison with the experimental Zn K-edge extended X-ray absorption fine structure (EXAFS) spectra and known diffraction data. AIMD NpT simulations reproduced well the thermal expansion of the lattice, and the pronounced …
Anharmonicity deformation and curvature in supersymmetric potentials
1994
An algebraic description of the class of 1D supersymmetric shape invariant potentials is investigated in terms of the shape-invariant-potential (SIP) deformed algebra, the generators of which act both on the dynamical variable and on the parameters of the potentials. The phase space geometry associated with SIP's is studied by means of a coherent state (SIP-CS) path integral and the ray metric of the SIP-CS manifold. The anharmonicity of SIP's results in a inhomogeneous phase space manifold with one Killing vector and with a modified symplectic Kahler structure, and it induces a non constant curvature into the generalized phase space. Analogous results from the phase space geometry of someq…
Rigid versus Flexible Protein Matrix: Light-Harvesting Complex II Exhibits a Temperature-Dependent Phonon Spectral Density
2018
Dynamics-function correlations are usually inferred when molecular mobility and protein function are simultaneously impaired at characteristic temperatures or hydration levels. In this sense, excitation energy transfer in the photosynthetic light-harvesting complex II (LHC II) is an untypical example because it remains fully functional even at cryogenic temperatures relying mainly on interactions of electronic states with protein vibrations. Here, we study the vibrational and conformational protein dynamics of monomeric and trimeric LHC II from spinach using inelastic neutron scattering (INS) in the temperature range of 20-305 K. INS spectra of trimeric LHC II reveal a distinct vibrational …
Extrapolation of water and formaldehyde harmonic and anharmonic frequencies to the B3LYP/CBS limit using polarization consistent basis sets
2010
The harmonic and anharmonic frequencies of fundamental vibrations in formaldehyde and water were successfully estimated using the B3LYP Kohn-Sham limit. The results obtained with polarization- and correlation-consistent basis sets were fitted with a two-parameter formula. Anharmonic corrections were obtained by a second order perturbation treatment (PT2). We compared the performance of the PT2 scheme on the two title molecules using SCF, MP2 and DFT (BLYP, B3LYP, PBE and B3PW91 functionals) methods combined with polarization consistent pc-n (n = 0, 1, 2, 3, 4) basis sets, Dunning’s basis sets (aug)-cc-pVXZ where X = D, T, Q, 5, 6 and Pople’s basis sets up to 6-311++G(3df,2pd). The influence…
Raman study of the phase transitions sequence in pure WO3 at high temperature and in HxWO3 with variable hydrogen content
1999
Abstract An extensive investigation of the temperature dependence of Raman spectra has been carried out on WO 3 powders from room temperature to 800°C. In particular the orthorhombic-to-tetragonal phase transition occurring at about 740°C has been studied for the first time. The Raman active mode at 710 cm −1 of the orthorhombic phase disappears from the spectrum at temperature below the phase transition point and the Raman activity in the tetragonal phase results very low. A comparative study of hydrogenated tungsten bronzes H x WO 3 ( x ≤0.23), where the same transition sequence is driven by an increase of the proton concentration from x =0 to 0.23, reveals similar behaviour of the high f…