Abstract: The activated complex as a transition state in chemical kinetics processes is actually at a kind of non-equilibrium steady state. In this paper, the non-equilibrium statistical problems concerning with the non-equilibrium behavior of the activated complex was commented at the level of phenomenological theory. By analyzing the effects on the reaction rate from the dissipation-fluctuations in the activated complexation process, we further proposed a revised formulation for TST in which the non-equilibrium effects of the activated complexation process were involved. As a result, a basic relationship between reaction rate and non-equilibrium dissipation function, instead of equilibrium constant, of the activated complexation, was established. Finally, the statistical “drift” of the reaction rate constant induced by what influence the dissipation-fluctuations in the activated complexation process was also discussed briefly.

Key words: Transition-state theory(TST), Phenomenological theory of non-equilibrium statistical mechanics, Non-equilibrium steady-state, Activated complexation dissipation function, Dissipation-fluctuation