Nuclear Dynamics at Molecule–Metal Interfaces: A Pseudoparticle Perspective
Abstract
We discuss nuclear dynamics at molecule-metal interfaces including nonequilibrium molecular junctions. Starting from the many-body states (pseudoparticle) formulation of the molecule-metal system in the molecular vibronic basis, we introduce gradient expansion to reduce the adiabatic nuclear dynamics (that is, nuclear dynamics on a single molecular potential surface) into its semiclassical form while maintaining the effect of the nonadiabatic electronic transitions between different molecular charge states. Finally, this yields a set of equations for the nuclear dynamics in the presence of these nonadiabatic transitions, which reproduce the surface-hopping formulation in the limit of small metal-molecule coupling (where broadening of the molecular energy levels can be disregarded) and Ehrenfest dynamics (motion on the potential of mean force) when information on the different charging states is traced out.
- Authors:
-
- Department of Chemistry and Biochemistry, University of California at San Diego, La Jolla, California 92093, United States
- Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States, School of Chemistry, Tel Aviv University, Tel Aviv, 69978, Israel
- Publication Date:
- Research Org.:
- Univ. of California, San Diego, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Israel Science Foundation; US-Israel Binational Science Foundation
- OSTI Identifier:
- 1227076
- Alternate Identifier(s):
- OSTI ID: 1436425
- Grant/Contract Number:
- SC0006422
- Resource Type:
- Published Article
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Name: Journal of Physical Chemistry Letters Journal Volume: 6 Journal Issue: 24; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ehrenfest dynamics; molecule−metal interface; surface-hopping formulation
Citation Formats
Galperin, Michael, and Nitzan, Abraham. Nuclear Dynamics at Molecule–Metal Interfaces: A Pseudoparticle Perspective. United States: N. p., 2015.
Web. doi:10.1021/acs.jpclett.5b02331.
Galperin, Michael, & Nitzan, Abraham. Nuclear Dynamics at Molecule–Metal Interfaces: A Pseudoparticle Perspective. United States. https://doi.org/10.1021/acs.jpclett.5b02331
Galperin, Michael, and Nitzan, Abraham. Wed .
"Nuclear Dynamics at Molecule–Metal Interfaces: A Pseudoparticle Perspective". United States. https://doi.org/10.1021/acs.jpclett.5b02331.
@article{osti_1227076,
title = {Nuclear Dynamics at Molecule–Metal Interfaces: A Pseudoparticle Perspective},
author = {Galperin, Michael and Nitzan, Abraham},
abstractNote = {We discuss nuclear dynamics at molecule-metal interfaces including nonequilibrium molecular junctions. Starting from the many-body states (pseudoparticle) formulation of the molecule-metal system in the molecular vibronic basis, we introduce gradient expansion to reduce the adiabatic nuclear dynamics (that is, nuclear dynamics on a single molecular potential surface) into its semiclassical form while maintaining the effect of the nonadiabatic electronic transitions between different molecular charge states. Finally, this yields a set of equations for the nuclear dynamics in the presence of these nonadiabatic transitions, which reproduce the surface-hopping formulation in the limit of small metal-molecule coupling (where broadening of the molecular energy levels can be disregarded) and Ehrenfest dynamics (motion on the potential of mean force) when information on the different charging states is traced out.},
doi = {10.1021/acs.jpclett.5b02331},
journal = {Journal of Physical Chemistry Letters},
number = 24,
volume = 6,
place = {United States},
year = {Wed Nov 25 00:00:00 EST 2015},
month = {Wed Nov 25 00:00:00 EST 2015}
}
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https://doi.org/10.1021/acs.jpclett.5b02331
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