Vibrational distribution functions and relaxation rate in anharmonic-oscillator systems

Analytical expressions were derived for the vibrational distribution function in a system of anharmonic oscillators under conditions where the supply of vibrational energy considerably exceeded the equilibrium value. Distribution was found by considering the effect of vibrational-vibrational and vibrational-translational energy exchange, as well as spontaneous radiative transitions. Analytical expressions were also obtained for the relaxation rate of vibrational energy. It was shown that where there is a strong deviation from equilibrium this rate can significantly exceed the corresponding value for a model of harmonic oscillators and is determined by the probability of vibrational-vibrational exchange in the molecules.