Markovian Kassel theory

Abstract

The possibility of extending Kassel's theory to allow for Markovian fluctuations in the critical oscillator energy is examined using a simple model based on pairwise interaction of normal modes. The results of this are numerically not very different from those of ordinary Kassel theory; nevertheless rate parameters can be calculated which include the effects of intramolecular relaxation and non-random collisional excitation, quantities uninterpreted in the simple theory. The model investigated shows that the condition of detailed balance places such stringent requirements on allowable transition probabilities for the critical oscillator as to make it extremely difficult to extend the notion of a “collisional” type intramolecular energy transfer much beyond the original Kassel terms.