Locating Transition States by Variational Reaction Path Optimization with an Energy-Derivative-Free Objective Function

Abstract

Locating transition states is essential for understanding molecular reactions. We propose a double-ended transition state search method by revisiting a variational reaction path optimization method known as the MaxFlux method. Although its original purpose is to add temperature effects to reaction paths, we conversely let the temperature approach zero to obtain an asymptotically exact minimum energy path and its corresponding transition state in variational formalism with an energy-derivative-free objective function. Using several numerical techniques to directly optimize the objective function, the present method reliably finds transition states with low computational cost. In particular, only three force evaluations per iteration are sufficient. This is confirmed on a variety of molecular reactions where the nudged elastic band method often fails. The present method is implemented in Python using the Atomic Simulation Environment and is available on GitHub.