Grand Canonical Quantum Mechanics with Applications to Mechanisms and Rates for Electrocatalysis

We outline the recently developed Grand Canonical Potential Kinetics (GCP-K) method to implement Grand Canonical Quantum Mechanics for predicting electrochemical reactions as a function of applied potential rather than with fixed numbers of electrons as in traditional Quantum Mechanics (QM) calculations. We describe here the recent validation of GCP-K for The Co/TiO2 single atom catalyst for the Oxygen Evolution Reaction (OER) on a single crystal nanoparticle where a single surface facet was present. The basal plane of transition metal dichalcogenides (TMDs) in the 1 T’ phase of WSe₂ and WTe₂, which leads to high-performance for the hydrogen evolution reaction (HER). We find that GCP-K predicts accurate TOF and currents as a function of applied potential and accurate Tafel slopes for both the Co/TiO2 OER and the chalcogenide HER systems for which we can be confident of the surface structure. Thus we expect that these methods will be useful in the more common situation for which there is much less certainty about the surface structure under experimental conditions.