Bias-controlled selective excitation of vibrational modes in molecular junctions: a route towards mode-selective chemistry

Volkovich R, Härtle R, Thoss M, Peskin U (2011)

Publication Type: Journal article

Publication year: 2011

Journal

Physical Chemistry Chemical Physics Royal Society of Chemistry

Publisher: Royal Society of Chemistry

Book Volume: 13

Pages Range: 14333

URI: http://pubs.rsc.org/en/Content/ArticleLanding/2011/CP/C1CP21161G

DOI: 10.1039/C1CP21161G

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. © the Owner Societies 2011.

Authors with CRIS profile

Rainer Härtle Professur für Theoretische Physik mit dem Schwerpunkt Molekulare Materialien Michael Thoss Professur für Theoretische Physik mit dem Schwerpunkt Molekulare Materialien

Additional Organisation(s)

Exzellenz-Cluster Engineering of Advanced Materials

Involved external institutions

Technion - Israel Institute of Technology IL Israel (IL)

How to cite

APA:

Volkovich, R., Härtle, R., Thoss, M., & Peskin, U. (2011). Bias-controlled selective excitation of vibrational modes in molecular junctions: a route towards mode-selective chemistry. Physical Chemistry Chemical Physics, 13, 14333. https://doi.org/10.1039/C1CP21161G

MLA:

Volkovich, Roie, et al. "Bias-controlled selective excitation of vibrational modes in molecular junctions: a route towards mode-selective chemistry." Physical Chemistry Chemical Physics 13 (2011): 14333.

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