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Title: Surface hopping with a manifold of electronic states. III. Transients, broadening, and the Marcus picture

In a previous paper [Dou et al., J. Chem. Phys. 142, 084110 (2015)], we have introduced a surface hopping (SH) approach to deal with the Anderson-Holstein model. Here, we address some interesting aspects that have not been discussed previously, including transient phenomena and extensions to arbitrary impurity-bath couplings. In particular, in this paper we show that the SH approach captures phonon coherence beyond the secular approximation, and that SH rates agree with Marcus theory at steady state. Finally, we show that, in cases where the electronic tunneling rate depends on nuclear position, a straightforward use of Marcus theory rates yields a useful starting point for capturing level broadening. For a simple such model, we find I-V curves that exhibit negative differential resistance.
Authors:
;  [1] ;  [2]
  1. Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104 (United States)
  2. School of Chemistry, The Sackler Faculty of Science, Tel Aviv University, Tel Aviv 69978 (Israel)
Publication Date:
OSTI Identifier:
22490811
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 23; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; APPROXIMATIONS; COUPLINGS; IMPURITIES; PHONONS; SURFACES; TRANSIENTS; TUNNEL EFFECT; YIELDS