Electronic friction near metal surfaces: a case where molecule-metal couplings depend on nuclear coordinates

Abstract

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 Journal of Nanotechnology, 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.

33 pages, 5 figures

References in corpus (7)

• Molecular Transport Junctions: Vibrational Effects
• Real-time path integral approach to nonequilibrium many-body quantum system
• Current-induced nonequilibrium vibrations in single-molecule devices
• Current-induced atomic dynamics, instabilities, and Raman signals: Quasi-classical Langevin equation approach
• Scattering theory of adiabatic reaction forces due to out-of-equilibrium quantum environments
• Vibrational cooling and thermoelectric response of nanoelectromechanical systems
• Spectrum of electronic excitations due to the adsorption of atoms on metal surfaces

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