Search results for "Anharmonicity"
showing 10 items of 118 documents
Spectral broadening of the Soret band in myoglobin: an interpretation by the full spectrum of low-frequency modes from a normal modes analysis.
2005
In this work the temperature dependence of the Soret band line shape in carbon-monoxy myoglobin is re-analyzed by using both the full correlator approach in the time domain and the frequency domain approach. The new analyses exploit the full density of vibrational states of carbon-monoxy myoglobin available from normal modes analysis, and avoid the artificial division of the entire set of vibrational modes coupled to the Soret transition into "high-frequency" and "low-frequency" subsets; the frequency domain analysis, however, makes use of the so-called short-times approximation, while the time domain one avoids it. Time domain and frequency domain analyses give very similar results, thus s…
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…
Comparison of full-configuration interaction and coupled-cluster harmonic and fundamental frequencies for BH and HF
2001
The harmonic and fundamental frequencies are calculated for the potential-energy curves of BH and HF using the full-configuration interaction model and two hierarchies of coupled-cluster wavefunction models. The anharmonic contributions are also obtained using second-order vibrational perturbation theory. A consistent and systematic improvement is seen for both the harmonic and anharmonic contributions when increasing the level of the correlation treatment. The changes are largest for the harmonic contributions. This is also the case when including valence or diffuse functions in the basis set. Second-order perturbation theory gives a good approximation to the anharmonic contribution and in…
Scaling property of variational perturbation expansion for a general anharmonic oscillator with xp-potential
1995
We prove a powerful scaling property for the extremality condition in the recently developed variational perturbation theory which converts divergent perturbation expansions into exponentially fast convergent ones. The proof is given for the energy eigenvalues of an anharmonic oscillator with an arbitrary $x^p$-potential. The scaling property greatly increases the accuracy of the results.
Phase transition systematics in BiVO4 by means of high-pressure–high-temperature Raman experiments
2018
We report here high-pressure--high-temperature Raman experiments performed on ${\text{BiVO}}_{4}$. We characterized the fergusonite and scheelite phases (powder and single crystal samples) and the zircon polymorph (nanopowder). The experimental results are supported by ab initio calculations, which, in addition, provide the vibrational patterns. The temperature and pressure behavior of the fergusonite lattice modes reflects the distortions associated with the ferroelastic instability. The linear coefficients of the zircon phase are in sharp contrast to the behavior observed in the fergusonite phase. The boundary of the fergusonite-to-scheelite second-order phase transition is given by ${T}_…
Ab InitioCalculations and High-Resolution Spectroscopy of the Bending Pentad of SiH2D2in the 10–16 μm Region
1998
Abstract The SiH 2 D 2 asymmetric top has nine vibrational modes, five of them forming a pentad strongly perturbed by Coriolis interactions. High-level ab initio calculations of SiH 2 D 2 have been performed which yield numerous spectroscopic parameters related to the harmonic and anharmonic force fields. The bending pentad comprising ν 4 (A 1 ), ν 7 (B 1 ), ν 5 (A 2 ), ν 9 (B 2 ), and ν 3 (A 1 ) has been studied by high-resolution Fourier transform spectroscopy; the region 600–1050 cm −1 has been investigated with a resolution of ca. 4 × 10 −3 cm −1 . Raman BOXCARS spectroscopy has been used for the infrared inactive ν 5 band. The Raman apparatus function was 0.0054 cm −1 . Assignments of …
Expressions of Effective Hamiltonian Parameters of XY4 Molecules in the Tetrahedral Formalism
1998
We have derived expressions of second-order effective Hamiltonian parameters of XY4 molecules in the tetrahedral formalism (1992, J. P. Champion et al., "Spectroscopy of the Earth's Atmosphere and Interstellar Medium: Spherical Top Spectra," Academic Press, San Diego). They are written as a function of the force constants of the potential expanded in terms of the dimensionless normal coordinates. These expressions can be used in the isolated band scheme as well as in the polyad one. The ambiguity of the effective Hamiltonian parameters is treated. Relations between the parameters for q2 and q4 terms and Hecht's anharmonicity constants (1960, K. T. Hecht, J. Mol. Spectrosc. 5, 355-389) in th…
Vibrational Energy Levels via Finite-Basis Calculations Using a Quasi-Analytic Form of the Kinetic Energy
2015
A variational method for the calculation of low-lying vibrational energy levels of molecules with small amplitude vibrations is presented. The approach is based on the Watson Hamiltonian in rectilinear normal coordinates and characterized by a quasi-analytic integration over the kinetic energy operator (KEO). The KEO beyond the harmonic approximation is represented by a Taylor series in terms of the rectilinear normal coordinates around the equilibrium configuration. This formulation of the KEO enables its extension to arbitrary order until numerical convergence is reached for those states describing small amplitude motions and suitably represented with a rectilinear system of coordinates. …
The empirical equilibrium structure of diacetylene
2008
High-level quantum-chemical calculations are reported at the MP2 and CCSD(T) levels of theory for the equilibrium structure and the harmonic and anharmonic force fields of diacetylene, HCCCCH. The calculations were performed employing Dunning's hierarchy of correlation-consistent basis sets cc-pVXZ, cc-pCVXZ, and cc-pwCVXZ, as well as the ANO2 basis set of Almloef and Taylor. An empirical equilibrium structure based on experimental rotational constants for thirteen isotopic species of diacetylene and computed zero-point vibrational corrections is determined (r_e^emp: rC-H=1.0615 A, rCtripleC=1.2085 A, rC-C = 1.3727 A) and in good agreement with the best theoretical structure (CCSD(T)/cc-pCV…
Coriolis interaction parameters of the (2100; F2) bands of SiH4 and GeH4. A test of local mode models
1995
Abstract The high-resolution spectra of the (2100; F 2 , N ), N = 1 and 2, bands of SiH 4 and GeH 4 have been recorded and preliminary analyzed. The Coriolis interaction parameter 2 Bζ 3 is obtained; it provides a test of three widely used models: the harmonically coupled anharmonic oscillators model with two different kinds of variables, and the normal mode model with Darling-Dennison resonance included.