Algorithmic Explorations of Unimolecular and Bimolecular Reaction Spaces.

Abstract

Algorithmic reaction exploration based on transition state searches has already made inroads into many niche applications, but its potential as a general-purpose tool is still largely unrealized. Computational cost and the absence of benchmark problems involving larger molecules remain obstacles to further progress. Here an ultra-low cost exploration algorithm is implemented and used to explore the reactivity of unimolecular and bimolecular reactants, comprising a total of 581 reactions involving 51 distinct reactants. The algorithm discovers all established reaction pathways, where such comparisons are possible, while also revealing a much richer reactivity landscape, including lower barrier reaction pathways and a strong dependence of reaction conformation in the apparent barriers of the reported reactions. The diversity of these benchmarks illustrate that reaction exploration algorithms are approaching general-purpose capability.