Dynamic Electric Field Complicates Chemical Reactions in Solutions

Abstract

Chemical reactions can be strongly influenced by an external electric field (EEF), but because the EEF is often time-dependent and in case it does not adapt quickly enough to the reaction progress, especially during fast barrier crossing processes, dynamic effects could be important. Here we find that electrostatic interactions can reduce the height of the reaction barrier for a Claissen rearrangement reaction and accelerate the key motions for bonding. Meanwhile, strong electrostatic interactions can modify the barrier into an effective potential well, confining the system into the barrier until solvents adjust themselves to provide an appropriate EEF for charge redistribution. In this case, the otherwise concerted mechanism becomes a stepwise one. Consequently, the motion of solvents modulates the reaction dynamics and leads to heterogeneous reaction paths, even in a seemingly homogeneous aqueous solution. In addition, an excessive stabilization of transition state retards the barrier crossing process, making the thermodynamically favorable pathway less favored dynamically.