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

Litman, Y., & Rossi, M. (2020). Multidimensional Hydrogen Tunneling in Supported Molecular Switches: The Role of Surface Interactions. Physical Review Letters, 125(21): 216001. doi:10.1103/PhysRevLett.125.216001.

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Item Permalink: https://hdl.handle.net/21.11116/0000-0007-323E-C Version Permalink: https://hdl.handle.net/21.11116/0000-000B-C16D-1
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Open Access. - 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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Details and convergence tests for electronic structure and ring polymer instanton calculations, analysis of instanton tunneling pathways, analysis of kinetic isotope effects on Cu(110) surface, analysis of the importance of vdW dispersion interaction, and description of the employed model to estimate transition temperatures.
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https://arxiv.org/abs/2005.13314 (Preprint)
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 Creators:
Litman, Y.1, 2, Author
Rossi, M.1, 3, Author           
Affiliations:
1Fritz Haber Institute of the Max Planck Society, ou_persistent22              
2Institute for Chemistry and Biochemistry, Freie Universität Berlin, ou_persistent22              
3Simulations from Ab Initio Approaches, Theory Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_3185035              

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 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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Language(s): eng - English
 Dates: 2020-05-152020-10-082020-11-172020-11-20
 Publication Status: Issued
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 Rev. Type: Peer
 Identifiers: arXiv: 2005.13314
DOI: 10.1103/PhysRevLett.125.216001
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Project name : The authors thank Stuart Althorpe, Aaron Kelly, and Matthias Koch for fruitful discussions and thank Takashi Kumagai and Jeremy Richardson for numerous discussions and a careful assessment of the manuscript. The authors acknowledge financing from the Max Planck Society and computer time from the Max Planck Computing and Data Facility (MPCDF) and the Swiss National Supercomputing Centre (CSCS) under Project ID No. s883.
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Title: Physical Review Letters
  Abbreviation : Phys. Rev. Lett.
Source Genre: Journal
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Publ. Info: Woodbury, N.Y. : American Physical Society
Pages: - Volume / Issue: 125 (21) Sequence Number: 216001 Start / End Page: - Identifier: ISSN: 0031-9007
CoNE: https://pure.mpg.de/cone/journals/resource/954925433406_1