title: How to recover Marcus theory with fewest switches surface hopping: add just a touch of decoherence.
abstract: We present a slightly improved version of our augmented fewest switches surface hopping (A-FSSH) algorithm and apply it to the calculation of transition rates between diabatic electronic states within the spin-boson model. We compare A-FSSH rates with (i) Marcus rates from the golden rule, (ii) Tully-style FSSH rates, and (iii) FSSH rates using a simple, intuitive decoherence criterion. We show that unlike FSSH, A-FSSH recovers the correct scaling with diabatic coupling (quadratic in V) as well as the lack of dependence on harmonic frequency ω for small enough values of ω and large enough temperatures.
authors.affiliation: Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania 19104, USA.
authors.forename: Brian R
authors.initials: BR
authors.lastname: Landry
authors.forename: Joseph E
authors.initials: JE
authors.lastname: Subotnik