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American Institute of Physics, The Journal of Chemical Physics, 7(144), p. 074109, 2016

DOI: 10.1063/1.4941848

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Molecular electronic states near metal surfaces at equilibrium using potential of mean force and numerical renormalization group methods: Hysteresis revisited

Journal article published in 2016 by Wenjie Dou ORCID, Abraham Nitzan ORCID, Joseph E. Subotnik
This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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Abstract

We investigate equilibrium observables for molecules near metals by employing a potential of mean force (PMF) that takes level broadening into account. Through comparison with exact data, we demonstrate that this PMF approach performs quite well, even for cases where molecule-electrode couplings depend on nuclear position. As an application, we reexamine the possibility of hysteresis effects within the Anderson-Holstein model (i.e., an impurity coupled both to a metal surface and a nuclear oscillator). As compared against the standard mean field approach by Galperin et al. [Nano Lett. 5, 125 (2005)], our PMF approach agrees much better with exact results for average electronic populations both at zero and finite temperature; we find, however, that mean field theory can be very useful for predicting the onset of dynamical instabilities, metastable states, and hysteresis.