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  Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory II: Benchmarks and Applications

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 II: Benchmarks and Applications. The Journal of Chemical Physics, 156(19): 194107. doi:10.1063/5.0088400.

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Supplementary material: a detailed description of the MCTDH simulations and convergence tests of the DFT and RPI(-EF) calculations. Also included are rate estimations for the asymmetric double well potential and the DFT energies, electronic friction values, and the projected density of states along the MEP for the H hopping reaction in Pd, Pt, Ag, Cu, and Al.
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https://arxiv.org/abs/2202.08681 (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: In Paper I [Litman et al., J. Chem. Phys. (in press) (2022)], we presented the ring-polymer instanton with explicit friction (RPI-EF) method and showed how it can be connected to the ab initio electronic friction formalism. This framework allows for the calculation of tunneling reaction rates that incorporate the quantum nature of the nuclei and certain types of non-adiabatic effects (NAEs) present in metals. In this paper, we analyze the performance of RPI-EF on model potentials and apply it to realistic systems. For a 1D double-well model, we benchmark the method against numerically exact results obtained from multi-layer multi-configuration time-dependent Hartree calculations. We demonstrate that RPI-EF is accurate for medium and high friction strengths and less accurate for extremely low friction values. We also show quantitatively how the inclusion of NAEs lowers the crossover temperature into the deep tunneling regime, reduces the tunneling rates, and, in certain regimes, steers the quantum dynamics by modifying the tunneling pathways. As a showcase of the efficiency of this method, we present a study of hydrogen and deuterium hopping between neighboring interstitial sites in selected bulk metals. The results show that multidimensional vibrational coupling and nuclear quantum effects have a larger impact than NAEs on the tunneling rates of diffusion in metals. Together with Paper I [Litman et al., J. Chem. Phys. (in press) (2022)], these results advance the calculations of dissipative tunneling rates from first principles.

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Language(s): eng - English
 Dates: 2022-02-162022-04-262022-05-172022-05-21
 Publication Status: Published in print
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 Rev. Type: Peer
 Identifiers: arXiv: 2202.08681
DOI: 10.1063/5.0088400
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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: 194107 Start / End Page: - Identifier: ISSN: 0021-9606
CoNE: https://pure.mpg.de/cone/journals/resource/954922836226