Studies in Nonequilibrium Rate Processes. III. The Vibrational Relaxation of a System of Anharmonic Oscillators

Abstract

The previous work on vibrational relaxation of a system of harmonic oscillators has been extended to a system of anharmonic (Morse) oscillators. Numerical solutions of the relevant relaxation equations have been obtained on the ILLIAC (University of Illinois electronic digital computer) for some particular cases of initial δ‐function and Boltzmann distributions. The results of these calculations show that the deviations of the fractional level population from the harmonic oscillator values are very small, being of the order of the anharmonicity in the case of relaxation of the initial Boltzmann distribution, and about five times the anharmonicity for the relaxation of the δ‐function distribution. A general analytical perturbation procedure for the solution of the relaxation equations has been outlined and analytical solutions for several special cases are discussed briefly.