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  Recovering Marcus Theory Rates and Beyond without the Need for Decoherence Corrections: The Mapping Approach to Surface Hopping

Lawrence, J. E., Mannouch, J., & Richardson, a. J. O. (2024). Recovering Marcus Theory Rates and Beyond without the Need for Decoherence Corrections: The Mapping Approach to Surface Hopping. The Journal of Physical Chemistry Letters, 15(3), 707-716. doi:10.1021/acs.jpclett.3c03197.

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Item Permalink: https://hdl.handle.net/21.11116/0000-000E-59F0-F Version Permalink: https://hdl.handle.net/21.11116/0000-000E-59F4-B
Genre: Journal Article

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Supporting Information: Additional methodological details and figures illustrating the equivalence of different dividing surfaces, the MASH flux-correlation formalism, rates as a function of Δ for asymmetric systems, rates as a function of Δ for an overdamped system, behavior of FSSH Marcus turnover with decoherence, results for a system with a large reorganization energy, and equivalence of MASH and MASH+decoherence results in the prediction of Δ2 behavior
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https://doi.org/10.1021/acs.jpclett.3c03197 (Publisher version)
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https://arxiv.org/abs/2311.08802 (Preprint)
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 Creators:
Lawrence, J. E.1, Author
Mannouch, J.2, 3, Author           
Richardson, and Jeremy O.1, Author
Affiliations:
1Department of Chemistry and Applied Biosciences, ETH Zurich, ou_persistent22              
2Hamburg Center for Ultrafast Imaging, Universität Hamburg, ou_persistent22              
3Theory Group, Theory Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_2266715              

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 Abstract: It is well-known that fewest-switches surface hopping (FSSH) fails to correctly capture the quadratic scaling of rate constants with diabatic coupling in the weak-coupling limit, as expected from Fermi’s golden rule and Marcus theory. To address this deficiency, the most widely used approach is to introduce a “decoherence correction”, which removes the inconsistency between the wave function coefficients and the active state. Here we investigate the behavior of a new nonadiabatic trajectory method, called the mapping approach to surface hopping (MASH), on systems that exhibit an incoherent rate behavior. Unlike FSSH, MASH hops between active surfaces deterministically and can never have an inconsistency between the wave function coefficients and the active state. We show that MASH not only can describe rates for intermediate and strong diabatic coupling but also can accurately reproduce the results of Marcus theory in the golden-rule limit, without the need for a decoherence correction. MASH is therefore a significant improvement over FSSH in the simulation of nonadiabatic reactions.

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Language(s): eng - English
 Dates: 2023-12-222023-11-142024-01-052024-01-12
 Publication Status: Published online
 Pages: 10
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.jpclett.3c03197
arXiv: 2311.08802
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Project name : J.E.L. was supported by an ETH Zurich Postdoctoral Fellowship, and J.R.M. was supported by the Cluster of Excellence “CUI: Advanced Imaging of Matter” of the Deutsche Forschungsgemeinschaft (DFG)EXC 2056 (Project 390715994).
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Title: The Journal of Physical Chemistry Letters
  Abbreviation : J. Phys. Chem. Lett.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 15 (3) Sequence Number: - Start / End Page: 707 - 716 Identifier: ISSN: 1948-7185
CoNE: https://pure.mpg.de/cone/journals/resource/1948-7185