Electrochemistry-Enhanced Dynamic Path Sampling for Reaction Rate Calculations Considering Nuclear Quantum Effects.

Proton-coupled electron transfers (PCETs) are elementary steps in electrocatalysis. However, accurate calculations of PCET rates remain challenging, especially considering nuclear quantum effects (NQEs) under a constant potential condition. Statistical sampling of reaction paths is an ideal approach for rate calculations; however, it is always limited by the rare-event issue. Here, we develop an electrochemistry-driven quantum dynamics approach enabling realistic enhanced paths sampling under constant potentials without defined reaction coordinates. We apply the method in modeling the Volmer step of the hydrogen evolution reaction and demonstrate that the NQEs exhibit more than 1 order of magnitude impact on the computed rate constant, indicating an essential role of NQEs in electrochemistry.