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A broadened classical master equation approach for nonadiabatic dynamics at metal surfaces: Beyond the weak
Wenjie Dou1, Joseph E Subotnik1
1Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA.
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.
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