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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 a priori 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.
Fu et al. (Wed,) studied this question.
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