The electrostatic potential as a descriptor for the protonation propensity in automated exploration of reaction mechanisms

Abstract

We discuss the possibility of exploiting local minima of the molecular electrostatic potential for locating protonation sites in molecules in a fully automated manner. We implement and apply this concept to exploring the mechanism of proton reduction catalyzed by a hydrogenase model complex [Orthaber et al., Dalton Trans., 2014, 43, 4537]. A large number of distinct structures arising already in the early stages of the hydrogen evolution mechanism demonstrates the need for reliable, automated algorithms for the thorough analysis of catalytic processes.