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We derive an explicit form for the electronic friction as felt by a molecule near a metal surface for the general case that molecule-metal couplings depend on nuclear coordinates. Our work generalizes a previous study by von Oppen et al. Beilstein J. Nanotechnol. 3, 144 (2012), where we now go beyond the Condon approximation (i.e., molecule-metal couplings are not held constant). Using a non-equilibrium Green’s function formalism in the adiabatic limit, we show that fluctuating metal-molecule couplings lead to new frictional damping terms and random forces, plus a correction to the potential of mean force. Numerical tests are performed and compared with a modified classical master equation; our results indicate that violating the Condon approximation can have a large effect on dynamics.
Dou et al. (Tue,) studied this question.