Fundamental Drivers of Electrochemical Barriers
We find that ion creation and destruction dominate the behavior of electrochemical reaction barriers, through grand-canonical electronic structure calculations of proton deposition on transition metal surfaces. We show that barriers respond to potential in a nonlinear manner and trace this to the co...
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| Published in: | Physical review letters Vol. 131; no. 23; p. 238003 |
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| Main Authors: | , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
United States
08-12-2023
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| Online Access: | Get full text |
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| Summary: | We find that ion creation and destruction dominate the behavior of electrochemical reaction barriers, through grand-canonical electronic structure calculations of proton deposition on transition metal surfaces. We show that barriers respond to potential in a nonlinear manner and trace this to the continuous degree of electron transfer as an ion is created or destroyed. This explains both Marcus-like curvature and Hammond-like shifts. Across materials, we find the barrier energy to be driven primarily by the charge presented on the surface, which, in turn, is dictated by the native work function, a fundamentally different driving force than in nonelectrochemical systems. |
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| Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| ISSN: | 0031-9007 1079-7114 |
| DOI: | 10.1103/PhysRevLett.131.238003 |