Statistical dynamics and kinetics of unimolecular processes

Abstract

The statistical theory of arbitrary unimolecular reactions is developed with an ergodic theoretic basis. In the process, unimolecular kinetics is derived from dynamics, in terms of well-defined mixing and time-scale assumptions. The statistical theory is then taken beyond kinetics via the new ‘‘generalized flux renewal model’’ which incorporates ‘‘nonstatistical effects’’ due to nonzero relaxation time and direct components. Effects of direct component delays and nonzero relaxation times are examined closely. In particular, an estimate of the longest reaction time scale accounting for these effects is provided.