Electrochemistry-Enhanced Dynamic Path Sampling for Reaction Rate Calculations Considering Nuclear Quantum Effects
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.
Fields of Study & Subjects
CO2 Reduction Techniques and Catalysts
Metal-Catalyzed Oxygenation Mechanisms
Metalloenzymes and iron-sulfur proteins
Publication details
- Journal / source
- Journal of Chemical Theory and Computation
- Publisher
- American Chemical Society (ACS)
- Volume
- 22
- Issue
- 11
- Pages
- 5411–5419
- Publication date
- 20 May 2026
- Language
- EN