Articles you may be interested inA study of molecular vibrational relaxation mechanism in condensed phase based upon mixed quantumclassical molecular dynamics. I. A test of IBC model for the relaxation of a nonpolar solute in nonpolar solvent at high density Solvent dependence of the deuteron quadrupole coupling constant of CDCl3 determined by 2H spinlattice relaxation and Raman line shape studies Vibrational and reorientational correlation functions and correlation times for the VI band of CDCl 3 in the pure liquid and in solutions in carbon tetrachloride. n -hexane. and carbon disulfide have been obtained using spontaneous Raman scattering. and reorientational correlation times have been obtained from deuterium spin relaxation measurements. The concentration dependence of the reorientational correlation times in the CDCl 3 /CS 2 and CDCl/ n -hexane solutions closely paralleled the solution viscosity. while in CDCl/CCI 4 mixtures. the correlation time exhibited little concentration dependence. These features reflect differences in the anisotropy of the intermolecular potential experienced by the CDCl 3 molecules in these solutions. The reorientational correlation functions for the pure liquid exhibited time dependences different from that of the extended rotational diffusion models and a stochastic second-order memory function model. The temperature dependence of the vibrational relaxation times and vibrational second moments of VI in CDCl 3 liquid is not consistent with Kubo-type dephasing models. The vibrational relaxation data indicate that collisional dephasing (Fischer-Lauberau model) is the probable mechanism of relaxation. but do not rule out contributions from energy relaxation via independent binary collisions. In CDCl 3 1CS 2 mixtures. the band frequency and the bandwidth exhibit concentration dependence in accord with microscopic concentration fluctuations in the solution.4280
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