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  Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory I: Theory

Litman, Y., Pós, E. S., Box, C. L., Martinazzo, R., Maurer, R. J., & Rossi, M. (2022). Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory I: Theory. The Journal of Chemical Physics, 156(19): 194106. doi:10.1063/5.0088399.

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5.0088399.pdf (Publisher version), 6MB
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https://doi.org/10.1063/5.0088399 (Publisher version)
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https://arxiv.org/abs/2202.08668 (Preprint)
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 Creators:
Litman, Y.1, Author              
Pós, E. S.1, Author              
Box, C. L.2, Author
Martinazzo, R.3, Author
Maurer, R. J.2, Author
Rossi, M.1, Author              
Affiliations:
1Simulations from Ab Initio Approaches, Theory Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_3185035              
2Department of Chemistry, University of Warwick, ou_persistent22              
3Department of Chemistry, Università degli Studi di Milano, ou_persistent22              

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 Abstract: Reactions involving adsorbates on metallic surfaces and impurities in bulk metals are ubiquitous in a wide range of technological applications. The theoretical modelling of such reactions presents a formidable challenge for theory because nuclear quantum effects (NQEs) can play a prominent role and the coupling of the atomic motion with the electrons in the metal gives rise to important non-adiabatic effects (NAEs) that alter atomic dynamics. In this work, we derive a theoretical framework that captures both NQEs and NAEs and, due to its high efficiency, can be applied to first-principles calculations of reaction rates in high-dimensional realistic systems. More specifically, we develop a method that we coin ring polymer instanton with explicit friction (RPI-EF), starting from the ring-polymer instanton formalism applied to a system-bath model. We derive general equations that incorporate the spatial and frequency dependence of the friction tensor, and then combine this method with the ab initio electronic friction formalism for the calculation of thermal reaction rates. We show that the connection between RPI-EF and the form of the electronic friction tensor presented in this work does not require any further approximations, and it is expected to be valid as long as the approximations of both underlying theories remain valid.

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Language(s): eng - English
 Dates: 2022-02-162022-04-262022-05-162022-05-21
 Publication Status: Published in print
 Pages: -
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: arXiv: 2202.08668
DOI: 10.1063/5.0088399
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Title: The Journal of Chemical Physics
  Abbreviation : J. Chem. Phys.
Source Genre: Journal
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Publ. Info: Woodbury, N.Y. : American Institute of Physics
Pages: - Volume / Issue: 156 (19) Sequence Number: 194106 Start / End Page: - Identifier: ISSN: 0021-9606
CoNE: https://pure.mpg.de/cone/journals/resource/954922836226