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Updated: May 21, 2026

Dissolution Dynamic Nuclear Polarization Instrumentation for Real-time Enzymatic Reaction Rate Measurements by NMR
Published on: February 23, 2016
Electrochemistry-Enhanced Dynamic Path Sampling for Reaction Rate Calculations Considering Nuclear Quantum Effects
Li Fu1, Jiayue Han2, Yifan Li3
1School of Materials Science and Engineering, Peking University, Beijing 100871, People's Republic of China.
Abstract:
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.
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