Computational methods for the determination of electrocatalytic mechanisms

In order to elucidate detailed mechanisms of reactions on electrode surfaces and identify compn.-activity relationships, we have employed quantum mechanics-based atomistic models including transition states, solvation and controlledelectrochem. potential simulations. We have lately detd. mechanisms for the redn. of protons on various sites on MoS_2 and for water oxidn. on IrO_2 facets. Using such reactions and benchmarking studies as illustrations, we will discuss the consequences of tech. choices required by these simulations: e.g. d. functionals, continuum solvation models, explicit solvation, the chem. potential of electrons and protons relative to vacuum.