Journal of Physical Chemistry A, Vol.101, No.4, 541-548, 1997
Vibrational Mixing and Energy-Flow in Polyatomics - Quantitative Prediction Using Local Random-Matrix Theory
The theory of local random matrix models has provided a way for understanding many aspects of quantum ergodicity and energy flow in molecules. In this paper quantitative results are presented for a random matrix model that yields analytical expressions for the degree of vibrational mixing and flow rates in polyatomics in terms of a small number of parameters. The results of these generally applicable expressions are compared with large scale computation on energy flow in several organic molecules studied experimentally : formaldehyde, thiophosgene, and propyne. We show these systems are respectively below, at, and significantly above the quantum ergodicity transition. Effects of finite molecular size on the quantum ergodicity transition are also discussed.
Keywords:C-H STRETCH;ANHARMONIC INTERACTIONS;DOUBLE-RESONANCE;REDISTRIBUTION;MOLECULES;RELAXATION;SPECTROSCOPY;DYNAMICS;OVERTONE;SPECTRA