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Ab initio tensorial electronic friction for molecules on metal surfaces : nonadiabatic vibrational relaxation
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Maurer, Reinhard J., Askerka, Mikhail, Batista, Victor S. and Tully, John C. (2016) Ab initio tensorial electronic friction for molecules on metal surfaces : nonadiabatic vibrational relaxation. Physical Review B (Condensed Matter and Materials Physics), 94 . 115432. doi:10.1103/PhysRevB.94.115432 ISSN 1098-0121.
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Official URL: https://doi.org/10.1103/PhysRevB.94.115432
Abstract
Molecular adsorbates on metal surfaces exchange energy with substrate phonons and low-lying electron-hole pair excitations. In the limit of weak coupling, electron-hole pair excitations can be seen as exerting frictional forces on adsorbates that enhance energy transfer and facilitate vibrational relaxation or hot-electron-mediated chemistry. We have recently reported on the relevance of tensorial properties of electronic friction [M. Askerka et al., Phys. Rev. Lett. 116, 217601 (2016)] in dynamics at surfaces. Here we present the underlying implementation of tensorial electronic friction based on Kohn-Sham density functional theory for condensed phase and cluster systems. Using local atomic-orbital basis sets, we calculate nonadiabatic coupling matrix elements and evaluate the full electronic friction tensor in the Markov limit. Our approach is numerically stable and robust, as shown by a detailed convergence analysis. We furthermore benchmark the accuracy of our approach by calculation of vibrational relaxation rates and lifetimes for a number of diatomic molecules at metal surfaces. We find friction-induced mode-coupling between neighboring CO adsorbates on Cu(100) in a c(2×2) overlayer to be important for understanding experimental findings.
Item Type: | Journal Article | |||||||||
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Subjects: | Q Science > QD Chemistry | |||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | |||||||||
Library of Congress Subject Headings (LCSH): | Energy transfer, Exciton theory, Metals -- Surfaces, Density functionals, Molecular relaxation | |||||||||
Journal or Publication Title: | Physical Review B (Condensed Matter and Materials Physics) | |||||||||
Publisher: | American Physical Society | |||||||||
ISSN: | 1098-0121 | |||||||||
Official Date: | 23 September 2016 | |||||||||
Dates: |
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Volume: | 94 | |||||||||
Article Number: | 115432 | |||||||||
DOI: | 10.1103/PhysRevB.94.115432 | |||||||||
Status: | Peer Reviewed | |||||||||
Publication Status: | Published | |||||||||
Access rights to Published version: | Restricted or Subscription Access | |||||||||
Date of first compliant deposit: | 7 December 2017 | |||||||||
Date of first compliant Open Access: | 7 December 2017 | |||||||||
RIOXX Funder/Project Grant: |
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