A broadened classical master equation approach for nonadiabatic dynamics at metal surfaces: Beyond the weak molecule-metal coupling limit

Wenjie Dou; Joseph E Subotnik

doi:10.1063/1.4939734

A broadened classical master equation approach for nonadiabatic dynamics at metal surfaces: Beyond the weak molecule-metal coupling limit

J Chem Phys. 2016 Jan 14;144(2):024116. doi: 10.1063/1.4939734.

Authors

Wenjie Dou¹, Joseph E Subotnik¹

Affiliation

¹ Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA.

PMID: 26772563
DOI: 10.1063/1.4939734

Abstract

A broadened classical master equation (BCME) is proposed for modeling nonadiabatic dynamics for molecules near metal surfaces over a wide range of parameter values and with arbitrary initial conditions. Compared with a standard classical master equation-which is valid in the limit of weak molecule-metal couplings-this BCME should be valid for both weak and strong molecule-metal couplings. (The BCME can be mapped to a Fokker-Planck equation that captures level broadening correctly.) Finally, our BCME can be solved with a simple surface hopping algorithm; numerical tests of equilibrium and dynamical observables look very promising.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.