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Multidimensional Hydrogen Tunneling in Supported Molecular Switches: The Role of Surface Interactions

Yair Litman*

Mariana Rossi†

  • Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin, Germany and Institute for Chemistry and Biochemistry, Freie Universität Berlin, Arnimallee 22, 14195 Berlin, Germany

  • Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin, Germany and MPI for the Structure and Dynamics of Matter, Luruper Chaussee 149, 22761 Hamburg, Germany

  • *litman@fhi-berlin.mpg.de
  • †mariana.rossi@mpsd.mpg.de
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Phys. Rev. Lett. 125, 216001 – Published 17 November, 2020

DOI: https://doi.org/10.1103/PhysRevLett.125.216001

Abstract

The nuclear tunneling crossover temperature (Tc) of hydrogen transfer reactions in supported molecular-switch architectures can lie close to room temperature. This calls for the inclusion of nuclear quantum effects (NQEs) in the calculation of reaction rates even at high temperatures. However, computations of NQEs relying on standard parametrized dimensionality-reduced models quickly become inadequate in these environments. In this Letter, we study the paradigmatic molecular switch based on porphycene molecules adsorbed on metallic surfaces with full-dimensional calculations that combine density-functional theory for the electrons with the semiclassical ring-polymer instanton approximation for the nuclei. We show that the double intramolecular hydrogen transfer (DHT) rate can be enhanced by orders of magnitude due to surface fluctuations in the deep-tunneling regime. We also explain the origin of an Arrhenius temperature dependence of the rate below Tc and why this dependence differs at different surfaces. We propose a simple model to rationalize the temperature dependence of DHT rates spanning diverse fcc [110] surfaces.

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Phys. Rev. Lett. 125, 216001– Published 17 November, 2020
  • Received 15 May 2020
  • Accepted 8 October 2020
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Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article’s title, journal citation, and DOI. Open access publication funded by the Max Planck Society.

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