Vibrational energy relaxation of polyatomic solutes in simple liquids and supercritical fluids

被引:76
作者
Egorov, SA [1 ]
Skinner, JL
机构
[1] Univ Wisconsin, Inst Theoret Chem, Madison, WI 53706 USA
[2] Univ Wisconsin, Dept Chem, Madison, WI 53706 USA
关键词
D O I
10.1063/1.480654
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A microscopic statistical mechanical theory of vibrational energy relaxation rates for polyatomic solutes in simple solvents is presented. The theory is based on a model of a spherical solute present at infinite dilution in a fluid of spherical solvent particles, and the solute-solvent interaction potential depends on the vibrational coordinates of the solute. The theory is applied to study the experimentally observed anomalous density and temperature dependence of vibrational relaxation rates in supercritical fluids in the vicinity of the critical point. A quantitative comparison of the theory with experiment is presented, and the agreement is satisfactory. (C) 2000 American Institute of Physics. [S0021-9606(99)51347-0].
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页码:275 / 281
页数:7
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