Algorithmic Explorations of Unimolecular and Bimolecular Reaction Spaces

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.