Vibrational energy relaxation in liquids

A theory of vibrational relaxation of polyatomic molecules in liquids is presented which expresses the rate of decay of a vibrational state in terms of atomic force autocorrelation functions. These force correlation functions can be estimated from hydrodynamics or from an independent binary collision model. The results of calculations on small molecules dissolved in inert, cryogenic solvents are discussed, including the dependence of the rates on the details of the intramolecular potential surface.