New techniques for the study of non-equilibrium effects in non-first-order systems

Abstract

We demonstrate that the phenomenological rate constants for a second-order system far from equilibrium may be calculated by eigenanalysis of a linearized master equation. We also calculate some of these rate constants by a simple iterative method. The results are in good agreement with numerical integration of the non-linear master equation. Furthermore the eigenanalysis provides additional insights into the mechanism of non-equilibrium effects.