Interpretation of vibrational IR spectrum of uracil using anharmonic calculation of frequencies and intensities in second-order perturbation theory

The anharmonic frequencies of fundamental vibrations, overtones, and combination vibrations, as well as the intensities of absorption bands in the IR spectrum of uracil, are calculated. The anharmonic quartic force field and the third-order dipole moment surface calculated by the DFT quantum-mechanical method (B3LYP/6-31+G(d,p)) are taken as the initial parameters. The anharmonic frequencies and intensities of vibrations are determined using the second-order perturbation theory in the form of contact transformations. Multiple Fermi resonances and polyads are determined by the diagonalization of a small interaction matrix of vibrations of different types (fundamental, combination, and overtone frequencies). The total experimental IR spectrum of matrix-isolated uracil is interpreted. It is shown that the used method of calculating anharmonic frequencies and intensities can form a basis for anharmonic calculations of vibrations of moderate molecules.     

Theoretical Interpretation of the Vibrational Spectra of Carboxylic-Acid Dimers in the High-Frequency Range

An anharmonic band shift in the vibrational spectra of carboxylic-acid dimers is estimated on the basis of ab initio quantum calculations of anharmonic force constants. The implementation of ab initio quantum calculations taking into account the anharmonic nature of vibrations is connected with the choice of the atomic basis in the framework of a specific quantum method. All these factors together with the exclusion principle for bands in the infrared and Raman scattering spectra allow identification of the position of the bands of valence vibrations of CH bonds in the range of 2500–3500 cm^–1. The results of model calculations give reason to assert that the fundamental vibrations of the carboxylic fragment are the characteristic frequency and vibrational mode and, for OH bonds, also the characteristic intensity. Small doublet splitting and the exclusion principle for frequencies allow identification of the valence vibrations of CH bonds.     

Energy of the frequency-elastic effect in solids

A decrease in the frequency of skeletal vibrations (frequency-elastic effect) has been measured using Raman spectroscopy, and the stretching of backbone interatomic bonds in polyethylene molecules under elastic tensile loading of oriented polyethylene fibers has been measured using X-ray diffraction. It has been found that there are differences in the sign and magnitude of the changes in the zero-point energy and the work of the external force. The energy of the frequency-elastic effect has been explained in terms of the influence exerted by the initial (before loading) anharmonic stretching of backbone bonds and the force of anharmonic pressure, with the separation of the anharmonic (potential) component of the zero-point energy of the solid. A change in the frequency of vibrations corresponds to a change in the harmonic component of the zero-point energy. The loading with an external force causes a redistribution of the zero-point energy components. An energy analysis of the loaded quantum anharmonic oscillator has confirmed the conclusion regarding the mechanism of energy transfer and revealed that, under loading, there is a redistribution of the average values of the kinetic and potential components of the internal energy of the oscillator.     

On the line shape of EELS-spectra

The influence of anharmonic coupling between vibrations of an adsorbate parallel and perpendicular to the surface on electron energy loss spectra is investigated. Although in most cases vibrations parallel to the surface are not directly observable in EELS, this anharmonic coupling can be the origin of satellites in the loss spectra.     

A Nekhoroshev-type theorem for Hamiltonian systems with infinitely many degrees of freedom

We study the propagation of lattice vibrations in models of disordered, classical anharmonic crystals. Using classical perturbation theory with an optimally chosen remainder term (i.e. a Nekhoroshev-type scheme), we are able to show that vibrations corresponding to localized initial conditions do essentially not propagate through the crystal up to times larger than any inverse power of the strength of the anharmonic couplings.     

Anharmonic <Emphasis Type="Italic">T</Emphasis> ⊗ ɛ Jahn-Teller coupling in LiCaAlF<Subscript>6</Subscript>: Cr<Superscript>3+</Superscript>

For an octahedral system, we analyzed the coupling between the triple degenerate electronic states of a transition metal ion and the double degenerate vibration of the ligands of the host matrix. The vibrations of the ligands of the lattice are described by new anharmonic coherent states of the Morse potential. For the linear coupling between electronic states and anharmonic vibrations, we built the matrix elements from the interaction Hamiltonian and corresponding energy levels.     

Thickness-shear vibrations in round variable-thickness piezoelectric crystal plates

A computer algorithm proposed for the numerical solution of the problem of natural vibrations of axisymmetric variable-thickness piezoelectric elements can determine the complete spectrum of thickness-shear vibrations of a given class of piezoelectric elements and their displacements distribution. Examples are given of the calculation of the spectrum of piezoelectric elements with the corresponding vibration topograms and the temperature—frequency characteristics and anharmonic vibrations.Mytishchi Scientific-Research Institute of Radio-Measuring Instruments. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 37, No. 12, pp. 1519–1531, December, 1994.     

Anharmonicity of lattice vibrations induced by charged nickel impurities in II–VI semiconductors

The lattice vibrations induced by nickel impurities with a negative charge relative to the lattice in ZnSe: Ni, ZnO: Ni, ZnS: Ni, and CdS: Ni semiconductors are investigated using very sensitive field-induced vibronic spectroscopy. This technique is based on the interaction of lattice vibrations with impurity excitons and the effect of an ac electric field on these excitons. The phonon replicas of the zero-phonon line (ZPL) of impurity excitons (including intense peaks of combination replicas up to the eighth order) in the experimental spectra of the system under investigation are observed for the first time. These spectra make it possible to analyze the interaction between different vibrations. The experimental results are interpreted in terms of model calculations of the vibrations in a lattice with a charged impurity center and vibrations in a monoatomic chain with a strong anharmonicity. It is demonstrated that charged impurity centers initiate new lattice vibrations, namely, extrinsic anharmonic modes with a considerable third-or fourth-order anharmonicity.     

Direct observation of anharmonic coupling in the time domain with femtosecond stimulated Raman scattering

Off-resonant impulsive Raman excitation is used to initiate nonstationary nuclear motion in low-frequency vibrational modes of deuterio-chloroform. Femtosecond time-resolved stimulated Raman probing of the high-frequency C-D stretch reveals additional vibrational sidebands that arise as a result of anharmonic coupling between the impulsively excited low-frequency and the probed high-frequency vibrations. These experiments illustrate the detailed molecular information on anharmonic and reactive surfaces available from multidimensional femtosecond stimulated Raman techniques.     

Boson factorization approximation for anharmonic nuclear vibrations

A new approach is proposed for treating anharmonic nuclear vibrations, based on a kind of Hartree factorization applied to the Hamiltonian in a boson representation. The method is illustrated with the exactly solvable model of Lipkin, Meshkov and Glick.     

The study of anharmonic properties and s-p-d hybridization in barium at extreme environment

Theory of pseudopotential has been used in the present study to carry out computation of various thermodynamic parameters of barium. The role of anharmonic effect due to vibrations of lattice ions has been accounted by coupling local pseudopotential with mean field potential which has been computed using second-order perturbation theory. Contribution due to thermally excited electrons has been accounted by Mermin functional. The excellent agreement of presently computed pressure with experimental result has also been observed at which body centered cubic to hexagonal close packed structure phase transition occurs. Such success leads to conclude that the s-p-d hybridization and anharmonic effects are included properly in the presently used conjunction scheme with additional advantage of its computational simplicity.     

Diagram technique in an improved nonsymmetrized self-consistent field method

The free energy of a strongly anharmonic crystal is expanded in powers of a small parameter which is the ratio between the mean amplitude of thermal atom vibrations and the interatomic spacing, where the main contribution of the principal anharmonic terms is included in the zeroth approximation (the nonsymmetrized self-consistent field approximation). A diagram representation is used to calculate the corrections. As an illustration of the method, the corrections to the free energy of a strongly anharmonic monatomic linear chain are obtained.Translated from Izvestiya Vysshlkh Uchebnykh Zavedenii, Fizika, No. 6, pp. 67–72, June, 1984.     

Low-temperature anharmonic vibrations in the cuprates: a bipolaron model

Il Nuovo Cimento D - Starting from the recent experiments that have revealed large-amplitude anharmonic vibrations in the cuprates, the possibility of formation of bipolarons has been investigated....     

Ionoluminescence in the presence of ionizing radiation

An increase in the ionoluminescence intensity from a ZnS-CdS:Ag sample by a factor of more than 20 upon additional electronic excitation by UV light has been found. The effect decreases in magnitude with an increase in the energy of bombarding H₂⁺ ions and peaks at an energy below 175 eV. This effect manifests itself in samples having a system of shallow electron traps and is due to the relaxation of highly excited anharmonic atomic vibrations, caused by the ion impact, through the electronic channel. A mechanism is proposed and computed for the phenomenon revealed.     

Application of the algebraic approach to molecular thermodynamics and quantum deformations

An algebraic model based on Lie-algebraic techniques is applied to vibrational molecular thermodynamics. The model uses the isomorphism between the SU(2) algebra and the one-dimensional Morse oscillator. A vibrational high-temperature partition function and the related thermodynamic properties are derived in terms of the parameters of the model. The anharmonic vibrations are described as anharmonic q-bosons using a first-order expansion of a quantum deformation. It is shown, that this quantum deformation is related to the shape of the Morse potential.     

Molecular motion under the influence of a coherent infrared-laser field

The quantum dynamics of molecular vibrations under the influence of coherent infrared-laser multiphoton excitation is irregular, in most cases, on the time scale of experimental interest. This irregularity arises from the anharmonic nature of the molecular force fields and is already present in one dimensional anharmonic oscillators. We analyse the onset of the irregularity in the model of a Morse oscillator and discuss the role of statistical or “chaotic” behaviour of the time dependent probability density. We further discuss the role of direct multiphoton excitation in these multilevel systems and compare the results with exact solutions for the harmonic oscillator.     

Influence of interactions of excited vibrations on the molecular parameters

The interaction of vibrations is studied by the algebraic method of perturbation theory. Formulas are derived that take into account the influence of interactions on the anharmonic spectroscopic parameters of excited vibrations with compound frequencies. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 27–32, March, 2008.     

高压下FCC相金属氢结构稳定性和非谐效应的理论研究

利用第一性原理分子动力学方法研究金属氢体系的非简谐效应, 给出金属氢的声子谱, 讨论金属氢声子谱的温度效应。计算得到氢的同位素氕、氘和氚的FCC相在非零温下的声子谱, 不同温度下的声子谱对比发现零温下3.6 TPa为热力学稳定的临界压强点, 而有限温度下(100 K)临界压强点降到2.8 TPa, 非简谐效应显著地改变了体系的结构稳定性和声子振动性质。     

Localization in disordered,nonlinear dynamical systems

We study localization and wave trapping in disordered, nonlinear dynamical systems. For some models of classical, disordered anharmonic crystal lattices, we prove that, with large probability, there are quasiperiodic lattice vibrations of finite total energy which lie on some infinite-dimensional, compact invariant tori in phase space. Such vibrations remain localized, for all times, and there is no transport of energy through the lattice. Our general concepts and techniques extend to other systems, such as disordered, nonlinear Schrödinger equations, or randomly coupled rotors.