A microscopic statistical mechanical theory of the vibrational energy
relaxation of a diatomic solute in an atomic solvent is presented. The
diatomic is treated as a breathing Lennard-Jones sphere. The relaxati
on rate is obtained from the Fourier transform of the force-force time
-correlation function. The latter is expanded in powers of time (up to
t(4)), and expressions for the expansion coefficients are derived usi
ng equilibrium statistical mechanics. These coefficients are used to d
etermine the parameters of an analytic ansatz for this correlation fun
ction, which can be evaluated at all times (and thus can be Fourier tr
ansformed). The resulting theory for the time-correlation function is
compared to numerical results from a molecular dynamics simulation. Th
eoretical results for the vibrational relaxation rate are compared to
experiments on I-2 in Xe over a wide range of densities and temperatur
es. (C) 1996 American Institute of Physics.