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Disentangling Multidimensional Nonequilibrium Dynamics of Adsorbates: CO Desorption from Cu(100)

Ken-ichi Inoue, Kazuya Watanabe, Toshiki Sugimoto, Yoshiyasu Matsumoto, and Tomokazu Yasuike
Phys. Rev. Lett. 117, 186101 – Published 26 October 2016
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Abstract

Hot carriers at metal surfaces can drive nonthermal reactions of adsorbates. Characterizing nonequilibrium statistics among various degrees of freedom in an ultrafast time scale is crucial to understand and develop hot carrier-driven chemistry. Here we demonstrate multidimensional vibrational dynamics of carbon monoxide (CO) on Cu(100) along hot-carrier induced desorption studied by using time-resolved vibrational sum-frequency generation with phase-sensitive detection. Instantaneous frequency and amplitude of the CO internal stretching mode are tracked with a subpicosecond time resolution that is shorter than the vibrational dephasing time. These experimental results in combination with numerical analysis based on Langevin simulations enable us to extract nonequilibrium distributions of external vibrational modes of desorbing molecules. Superstatistical distributions are generated with mode-dependent frictional couplings in a few hundred femtoseconds after hot-electron excitation, and energy flow from hot electrons and intermode anharmonic coupling play crucial roles in the subsequent evolution of the non-Boltzman distributions.

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  • Received 6 April 2016

DOI:https://doi.org/10.1103/PhysRevLett.117.186101

© 2016 American Physical Society

Physics Subject Headings (PhySH)

Condensed Matter, Materials & Applied PhysicsAtomic, Molecular & Optical

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The Calisthenics of Surface Femtochemistry

Published 26 October 2016

Application of a femtosecond spectroscopy technique to a copper surface has allowed the desorption of carbon monoxide molecules to be tracked with unprecedented detail.

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Authors & Affiliations

Ken-ichi Inoue*, Kazuya Watanabe, Toshiki Sugimoto, and Yoshiyasu Matsumoto

  • Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502, Japan

Tomokazu Yasuike

  • Department of Liberal Arts, The Open University of Japan, Chiba 261-8586, Japan

  • *Present address: RIKEN.
  • kw@kuchem.kyoto-u.ac.jp
  • yasuike@ouj.ac.jp Also at ESICB, Kyoto University.

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Issue

Vol. 117, Iss. 18 — 28 October 2016

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