Simultaneously improving reaction coverage and computational cost in automated reaction prediction tasks.

Abstract

Automated reaction prediction has the potential to elucidate complex reaction networks for applications ranging from combustion to materials degradation, but computational cost and inconsistent reaction coverage are still obstacles to exploring deep reaction networks. Here we show that cost can be reduced and reaction coverage can be increased simultaneously by relatively straightforward modifications of the reaction enumeration, geometry initialization and transition state convergence algorithms that are common to many prediction methodologies. These components are implemented in the context of yet another reaction program (YARP), our reaction prediction package with which we report reaction discovery benchmarks for organic single-step reactions, thermal degradation of a γ-ketohydroperoxide, and competing ring-closures in a large organic molecule. Compared with recent benchmarks, YARP (re)discovers both established and unreported reaction pathways and products while simultaneously reducing the cost of reaction characterization by nearly 100-fold and increasing convergence of transition states. This combination of ultra-low cost and high reaction coverage creates opportunities to explore the reactivity of larger systems and more complex reaction networks for applications such as chemical degradation, where computational cost is a bottleneck.