Saved in:
| Main Authors: | , , , , , |
|---|---|
| Format: | Preprint |
| Published: |
2025
|
| Subjects: | |
| Online Access: | https://arxiv.org/abs/2506.16807 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1866916802721742848 |
|---|---|
| author | Fu, Li Li, Yifan Sun, Menglin Yang, Xiaolong Jin, Bin Xu, Shenzhen |
| author_facet | Fu, Li Li, Yifan Sun, Menglin Yang, Xiaolong Jin, Bin Xu, Shenzhen |
| contents | Proton-coupled electron transfers (PCET) 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, 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 one order of magnitude impact on the computed rate constant, indicating an essential role of NQEs in electrochemistry. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2506_16807 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Electrochemistry-Enhanced Dynamic Paths Sampling Unveiling Nuclear Quantum Effects in Electrocatalysis Fu, Li Li, Yifan Sun, Menglin Yang, Xiaolong Jin, Bin Xu, Shenzhen Chemical Physics Proton-coupled electron transfers (PCET) 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, 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 one order of magnitude impact on the computed rate constant, indicating an essential role of NQEs in electrochemistry. |
| title | Electrochemistry-Enhanced Dynamic Paths Sampling Unveiling Nuclear Quantum Effects in Electrocatalysis |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2506.16807 |