A Catastrophe Theory Based Model for Optimal Control of Chemical Reactions by means of Oriented Electric Fields

Abstract

The e ect of oriented external electric elds (OEEF) on chemical reactivity has been studied theoretically and computationally in the last decades. A central goal in this research area is to predict the orientation and the smallest amplitude electric eld that renders a barrierles chemical process with the smallest possible strength. Recently, a model to nd the optimal electric eld has been proposed and described (J. M. Bo ll et. al., J. Chem. Theory Comput. 18, 935 (2022)). We here proof that this model is based on Catastrophe and Optimum Control Theories. Based on both theories a technical treatment of the model is given and applied to a two-dimensional generic example that provides insight into its nature and capability. Finally, the model is applied to determine the optimal OEEF for the trans-to-cis isomerization of a [3]cumulene derivative.