title: Surface hopping with a manifold of electronic states. III. Transients, broadening, and the Marcus picture.
abstract: 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.affiliation: Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA.
authors.forename: Wenjie
authors.initials: W
authors.lastname: Dou
authors.affiliation: School of Chemistry, The Sackler Faculty of Science, Tel Aviv University, Tel Aviv 69978, Israel.
authors.forename: Abraham
authors.initials: A
authors.lastname: Nitzan
authors.affiliation: Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA.
authors.forename: Joseph E
authors.initials: JE
authors.lastname: Subotnik