An algorithm to find the optimal oriented external electrostatic field for annihilating a reaction barrier in a polarizable molecular system

Abstract

The use of oriented external electric fields (OEEFs) to promote and control chemical reactivity has motivated many theoretical and computational studies in the last decade to model the action of OEEFs on a molecular system and its effects on chemical pro- cesses. Given a reaction, a central goal in this research area is to predict the optimal OEEF (oOEEF) required to annihilate the reaction energy barrier with the smallest possible field strength. Here, we present a model rooted in catastrophe and optimum control theories that allows us to find the oOEEF for a given reaction valley in the potential energy surface (PES). In this model, the effective (or perturbed) PES of a polarizable molecular system is constructed by adding to the original, non-perturbed, PES a term accounting for the interaction of the OEEF with the intrinsic electric dipole and polarizability of the molecular system, so called the polarizable molecular electric dipole (PMED) model. We demonstrate that the oOEEF can be established by locating a point in the original PES with unique topological properties: the optimal barrier breakdown or bond-breaking point (oBBP). The essential feature of the oBBP structure is the fact that this point maintains its topological properties for all the applied OEEFs, also for the unperturbed PES, thus becoming much more relevant than the commonly used minima and transition state structures. The PMED model proposed here has been imple- mented in an open access package and is shown to successfully predict the oOEEF for two processes: an isomerization reaction of a cumulene derivative and the Huisgen cycloaddition reaction.