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Title: Hot-electron effects during reactive scattering of H 2 from Ag(111): the interplay between mode-specific electronic friction and the potential energy landscape

Abstract

The breakdown of the Born–Oppenheimer approximation gives rise to nonadiabatic effects in gas-surface reactions at metal surfaces. However, for a given reaction, it remains unclear which factors quantitatively determine whether these effects measurably contribute to surface reactivity in catalysis and photo/electrochemistry. Here, we systematically investigate hot electron effects during H 2 scattering from Ag(111) using electronic friction theory. We combine first-principles calculations of tensorial friction by time-dependent perturbation theory based on density functional theory and an analytical neural network representation, to overcome the limitations of existing approximations and explicitly simulate mode-specific nonadiabatic energy loss during molecular dynamics. Despite sizable hot-electron-induced energy loss, no measurable nonadiabatic effects can be found for H 2 scattering on Ag(111). This is in stark contrast to previous reports for vibrationally excited H 2 scattering on Cu(111). By detailed analysis of the two systems, we attribute this discrepancy to a subtle interplay between the magnitude of electronic friction along intramolecular vibration and the shape of the potential energy landscape that controls the molecular velocity at impact. On the basis of this characterization, we offer guidance for the search of highly nonadiabatic surface reactions.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Hefei National Laboratory for Physical Science at the Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei, China
  2. Department of Chemistry and Centre for Scientific Computing, University of Warwick, Coventry, UK, Department of Chemistry
  3. Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, USA
Publication Date:
Research Org.:
Yale Univ., New Haven, CT (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1482134
Alternate Identifier(s):
OSTI ID: 1609606
Grant/Contract Number:  
FG02-05ER15677; CHE-1462109
Resource Type:
Journal Article: Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 10 Journal Issue: 4; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry

Citation Formats

Zhang, Yaolong, Maurer, Reinhard J., Guo, Hua, and Jiang, Bin. Hot-electron effects during reactive scattering of H2 from Ag(111): the interplay between mode-specific electronic friction and the potential energy landscape. United Kingdom: N. p., 2019. Web. doi:10.1039/C8SC03955K.
Zhang, Yaolong, Maurer, Reinhard J., Guo, Hua, & Jiang, Bin. Hot-electron effects during reactive scattering of H2 from Ag(111): the interplay between mode-specific electronic friction and the potential energy landscape. United Kingdom. doi:10.1039/C8SC03955K.
Zhang, Yaolong, Maurer, Reinhard J., Guo, Hua, and Jiang, Bin. Wed . "Hot-electron effects during reactive scattering of H2 from Ag(111): the interplay between mode-specific electronic friction and the potential energy landscape". United Kingdom. doi:10.1039/C8SC03955K.
@article{osti_1482134,
title = {Hot-electron effects during reactive scattering of H2 from Ag(111): the interplay between mode-specific electronic friction and the potential energy landscape},
author = {Zhang, Yaolong and Maurer, Reinhard J. and Guo, Hua and Jiang, Bin},
abstractNote = {The breakdown of the Born–Oppenheimer approximation gives rise to nonadiabatic effects in gas-surface reactions at metal surfaces. However, for a given reaction, it remains unclear which factors quantitatively determine whether these effects measurably contribute to surface reactivity in catalysis and photo/electrochemistry. Here, we systematically investigate hot electron effects during H2 scattering from Ag(111) using electronic friction theory. We combine first-principles calculations of tensorial friction by time-dependent perturbation theory based on density functional theory and an analytical neural network representation, to overcome the limitations of existing approximations and explicitly simulate mode-specific nonadiabatic energy loss during molecular dynamics. Despite sizable hot-electron-induced energy loss, no measurable nonadiabatic effects can be found for H2 scattering on Ag(111). This is in stark contrast to previous reports for vibrationally excited H2 scattering on Cu(111). By detailed analysis of the two systems, we attribute this discrepancy to a subtle interplay between the magnitude of electronic friction along intramolecular vibration and the shape of the potential energy landscape that controls the molecular velocity at impact. On the basis of this characterization, we offer guidance for the search of highly nonadiabatic surface reactions.},
doi = {10.1039/C8SC03955K},
journal = {Chemical Science},
issn = {2041-6520},
number = 4,
volume = 10,
place = {United Kingdom},
year = {2019},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1039/C8SC03955K

Citation Metrics:
Cited by: 8 works
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