Thermal Rates and High-Temperature Tunneling from Surface Reaction Dynamics and First-Principles
Studying dynamics of the dissociative adsorption and recombinative desorption of hydrogen on copper surfaces has shaped our atomic-scale understanding of surface chemistry, yet experimentally determining the thermal rates for these processes, which dictate the outcome of catalytic reactions, has been impossible so far. In this work, we determine the thermal rate constants for dissociative adsorption and recombinative desorption of hydrogen on Cu(111) between 200 and 1000 K using data from reaction dynamics experiments. Contrary to current understanding, our findings demonstrate the predominant role of quantum tunneling, even at temperatures as high as 400 K. We also provide precise values for the reaction barrier (0.619 ± 0.020 eV) and adsorption energy (0.348 ± 0.026 eV) for H<sub>2</sub> on Cu(111). Remarkably, the thermal rate constants are in excellent agreement with a first-principles quantum rate theory based on a new implementation of ring polymer molecular dynamics for reactions on surfaces, paving the way to discovering better catalysts using reliable and efficient computational methods.
Authors
- Daniel J. Auerbach (ORCID: https://orcid.org/0000-0001-9494-3066)
- Igor Rahinov (ORCID: https://orcid.org/0000-0002-9187-4875)
- Alec M. Wodtke (ORCID: https://orcid.org/0000-0002-6509-2183)
- Alexander Kandratsenka
- Nils Hertl (ORCID: https://orcid.org/0000-0002-6298-3597)
- Oihana Galparsoro (ORCID: https://orcid.org/0000-0003-4964-1696)
- Hua Guo (ORCID: https://orcid.org/0000-0001-9901-053X)
- Dmitriy Borodin (ORCID: https://orcid.org/0000-0002-2195-0721)
- Theofanis N. Kitsopoulos (ORCID: https://orcid.org/0000-0001-6228-1002)
- Florian Nitz (ORCID: https://orcid.org/0009-0000-1976-6039)
- Liang Zhang (ORCID: https://orcid.org/0000-0002-3446-3172)
Institutions
- Ewha Womans University (KR)
- Open University of Israel (IL)
- University of the Basque Country (ES)
- University of New Mexico (US)
- University of Warwick (GB)
- Max Planck Institute for Dynamics and Self-Organization (DE)
- Institute for Basic Science (KR)
- Center for Quantum Nanoscience (KR)
- Max Planck Institute for Multidisciplinary Sciences (DE)
- University of Southern Mississippi (US)
- Donostia International Physics Center (ES)
- University of Göttingen (DE)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2024-11-08
- DOI
- https://doi.org/10.1021/jacs.4c09017
- Citations
- 14
- Primary Topic
- Quantum, superfluid, helium dynamics
- Type
- article
- Field-Weighted Citation Impact
- 4.73
Funders
- National Science Foundation
- Alexander von Humboldt-Stiftung
- UK Research and Innovation
- Ministerio de Ciencia, Innovación y Universidades
- Open University of Israel
- European Commission
- Deutsche Forschungsgemeinschaft
- Eusko Jaurlaritza
- Euskal Herriko Unibertsitatea
- Israel Science Foundation
- Max-Planck-Gesellschaft
- Institute for Basic Science
- Agencia Estatal de Investigación
- Division of Chemistry
- H2020 European Research Council