An Automated Variable E-Field DFT Application (A.V.E.D.A.) for Evaluation of Optimally Oriented Electric Fields on Chemical Reactivity

Recent theoretical and experimental work at molecular junctions has provided a strong conceptualization for the effects of oriented electric fields (OEFs) on organic reactions. Depending upon the axis of application, OEFs can increase (or decrease) reaction rate or distinguish between enantiomeric pathways. Despite the conceptual elegance of OEFs, which may be applied externally or induced locally, as tools for catalyzing organic reactions, implementation in synthetically relevant systems has been hampered by inefficiencies in evaluating reaction sensitivity to field effects. Herein we describe the development of the Automated Variable Electric-Field DFT Application (A.V.E.D.A.) for streamlined evaluation of a reaction’s susceptibility to OEFs. This open-source software was designed to be accessible for novice users of computational or programming tools. Following initiation by a single command (and with no subsequent intervention) the Linux workflow manages a series of density functional theory (DFT) calculations and mathematical manipulations to optimize ground-state and transition-state geometries in oriented, electric fields of increasing magnitude. The resulting field-perturbed geometries, molecular and reaction dipole moments, and net effective activation energies are compiled for user interpretation. Ten representative pericyclic reactions that showcase the development and evaluation of A.V.E.D.A. are described.