title: Bias-controlled selective excitation of vibrational modes in molecular junctions: a route towards mode-selective chemistry.
abstract: We show that individual vibrational modes in single-molecule junctions with asymmetric molecule-lead coupling can be selectively excited by applying an external bias voltage. Thereby, a non-statistical distribution of vibrational energy can be generated, that is, a mode with a higher frequency can be stronger excited than a mode with a lower frequency. This is of particular interest in the context of mode-selective chemistry, where one aims to break specific (not necessarily the weakest) chemical bond in a molecule. Such mode-selective vibrational excitation is demonstrated for two generic model systems representing asymmetric molecular junctions and/or scanning tunneling microscopy experiments. To this end, we employ two complementary theoretical approaches, a nonequilibrium Green's function approach and a master equation approach. The comparison of both methods reveals good agreement in describing resonant electron transport through a single-molecule contact, where differences between the approaches highlight the role of non-resonant transport processes, in particular co-tunneling and off-resonant electron-hole pair creation processes.
authors.affiliation: Schulich Faculty of Chemistry and the Lise Meitner Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel.
authors.forename: Roie
authors.initials: R
authors.lastname: Volkovich
authors.forename: Rainer
authors.initials: R
authors.lastname: Härtle
authors.forename: Michael
authors.initials: M
authors.lastname: Thoss
authors.forename: Uri
authors.initials: U
authors.lastname: Peskin