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Title: Nuclear Dynamics at Molecule–Metal Interfaces: A Pseudoparticle Perspective

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.
 [1] ;  [2]
  1. Univ. of California, San Diego, CA (United States). Dept. of Chemistry and Biochemistry
  2. Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Chemistry; Tel Aviv Univ., Tel Aviv (Israel). School of Chemistry
Publication Date:
Grant/Contract Number:
Published Article
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 6; Journal Issue: 24; Journal ID: ISSN 1948-7185
American Chemical Society
Research Org:
Univ. of California, San Diego, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Israel Science Foundation; US-Israel Binational Science Foundation
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ehrenfest dynamics; molecule−metal interface; surface-hopping formulation
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1436425