Vibrational relaxation and line widths in liquids dephasing by intermolecular forces

A theory of vibrational relaxation in liquids is presented in which the vibrations are loosely coupled to a bath or lattice of molecular translations and rotations by intermolecular forces. Using the second-order perturbation expressions familiar from magnetic resonance the secular contribution to the line width is calculated. Different coupling paths are considered and expressions given for the line widths in a liquid mixture in terms of number densities and diffusion coefficients valid when reorientation is slow and translation diffusional.     

Vibrational relaxation study in 4-chloroacetophenone

Vibrational relaxation process has been emerged as a useful tool in probing the nature of solute solvent interactions in liquid phase. The Laser Raman techniques have been used to study the vibrational and rotational frequencies of molecules, which provide detailed information about the dynamic processes involved in liquids. Raman spectra of C=O stretching mode of 4-chloroacetophenone dissolved in acetonitrile and chlorobenzene have been recorded as a function of solvent concentration ranging from 10% to 90% concentration at room temperature. The 4-chloroacetophenone is a molecule having wide application in manufacture of drugs, perfumes and cosmetics. This study may provide useful information about the vibrational relaxation mechanisms in liquid solutions at molecular level. The Laser Raman components were determined and the spectra were analyzed at different solvent concentrations. The theoretical models have been tested and compare with the experimental results.     

Multipoles and rotational relaxation in liquids

The role of multipolar interactions in quenching free rotation in condensed phases is discussed, with particular attention paid to the HCl-SF₆ system. The magnitude of these interactions is shown to be closely correlated with the dielectric loss of the solvent, and to be sufficient to explain at least partially the variations of linewidth in the HCl rotational spectrum.     

Vibrational energy transfer between molecules dissolved in cryogenic liquids

Results from recent papers on vibrational energy transfer in cryogenic liquids are discussed. An overview of the significance of these results is given especially with respect to failures of the Isolated Binary Collision hypothesis for both near-resonant and non-resonant energy transfer. Preliminary results obtained for energy exchange between CO isotopes are reported and a new explanation is suggested for the solvation effects of liquid N₂/Ar mixtures on the non-resonant deactivation of N₂(v=1).     

Non-markovian properties of dielectric relaxation in liquids

Statistical molecular memory is investigated in dielectric relaxation in a liquid medium. A new method of closing the infinite chain of kinetic equations for the time correlation function is proposed, and used to obtain an equation permitting the calculation of the smallest-order memory functions. The spectrum of the non-Markovian parameter obtained indicates that dielectric relaxation in liquid CH₃I is a significantly non-Markovian process.Kazan' State Pedagogical Institute. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 27–31, October, 1995.     

Spin — lattice relaxation in chlorofluorocarbon liquids

We have used the spin — echo method to measure spin — lattice relaxation times in liquid chlorofluorocarbons over a wide range of temperatures, frequencies, and molecular weights. Analysis of the experimental data shows that to determine the kinetic parameters of viscous liquids it is necessary to use the theory of nuclear magnetic relaxation by translational diffusion. We describe a method for the computer calculation of these parameters and discuss the results.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 46–51, March, 1976.     

Vibrational relaxation processes and molecular form factors

A theory that relates collision matrix elements for vibrational/rotational transfer processes between molecular systems to molecular form factors is presented.     

Acoustic relaxation spectrometers for liquids.

In this tutorial article methods of acoustic relaxation measurements of liquids are reviewed. The present performance of various techniques is described and desirable trends in future developments are shown. An account is given on standards in the optical monitoring of acoustic waves (Brillouin scattering), on time domain (jump) techniques, as well as on frequency domain (continuous and pulse modulated ultrasonic wave) methods. The merits and limitations of the different techniques of measurement, covering the frequency range from 10 kHz up to nearly 10 GHz now, corresponding with relaxation times between about 0.1 ms and 100 ps, are discussed. Efforts to further enhance the experimental accuracy and to reduce the required sample volume are indicated.     

Vibrational relaxation of a molecule in a dense medium

In this paper we consider some features of vibrational relaxation of a guest molecule in a host matrix. The model system involves a harmonic molecule interacting with a harmonic medium. The molecule-medium coupling was handled by the rotating wave approximation considering linear terms in the intramolecular displacements and high terms in the medium displacements. Three specific models for the molecule-medium coupling were considered, which involve single phonon decay, vibron-phonon decay and multiphonon decay. Within the framework of the random phase approximation the Heisenberg equations of motion for the system could be expressed in terms of a unified scheme which is valid for both single phonon and multiphonon processes. Explicit solutions were derived utilizing the Wigner-Weisskopf approximation. This generalized formalism was applied for the study of the time evolution of the distribution, the cooling and the heating processes of the oscillator by a thermal field and for the coupling between vibrational relaxation and infra-red emission.     

Minimal model for Beta relaxation in viscous liquids

Contrasts between beta relaxation in equilibrium viscous liquids and glasses are rationalized in terms of a double-well potential model with structure-dependent asymmetry, assuming structure is described by a single order parameter. The model is tested for tripropylene glycol where it accounts for the hysteresis of the dielectric beta loss peak frequency and magnitude during cooling and reheating through the glass transition.