The importance of dynamic effects in chemical reactions in condensed phase

Abstract

Energy transfer and spatial diffusion are two significant sub-processes in chemical reaction. Traditional rate theory is based on two assumptions: (1) energy transfer is faster than chemical reaction so that specific energy transfer channel is not important. (2) The solvents can respond to the change of solute quickly resulting in equilibrium solvation. Then once system cross the barrier, it will enter the product basin. But when energy transfer is fast enough to distribute the energy into all degrees of freedom according to certain ratio, the specific energy transfer pathways should be considered. Our previous studies have found that the polar functional groups play the major role in the intermolecular energy transfer process. And the energy accumulation and dissipation are completed by the motion with specific frequency. Furthermore, the major energy transfer channel is different in different solutions. Moreover, the length of transition path is very short, leading to the existence of different transient solvation configurations with distinctly different strengths of interaction between solutes and solvents. Consequently, the motion of solvents modulates the reaction dynamics and results in heterogeneous reaction paths. Therefore, the dynamic effects are vital for understanding and controlling the chemical reaction.