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Updated: Jul 5, 2025

High-Throughput Analysis of Optical Mapping Data Using ElectroMap
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Recovering Marcus Theory Rates and Beyond without the Need for Decoherence Corrections: The Mapping Approach to

Joseph E Lawrence1, Jonathan R Mannouch2, Jeremy O Richardson1

  • 1Department of Chemistry and Applied Biosciences, ETH Zurich, 8093 Zurich, Switzerland.

The Journal of Physical Chemistry Letters
|January 12, 2024
PubMed
Summary

The new mapping approach to surface hopping (MASH) accurately simulates nonadiabatic reactions, overcoming limitations of fewest-switches surface hopping (FSSH) without needing decoherence corrections.

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Area of Science:

  • Quantum chemistry
  • Chemical dynamics
  • Computational modeling

Background:

  • Fewest-switches surface hopping (FSSH) inaccurately models rate constants in the weak-coupling limit.
  • Existing decoherence corrections for FSSH address wave function inconsistencies but are not ideal.
  • Accurate simulation of nonadiabatic reactions is crucial for understanding chemical processes.

Purpose of the Study:

  • To investigate the performance of the mapping approach to surface hopping (MASH) for nonadiabatic reaction simulations.
  • To evaluate MASH's ability to capture rate constant behavior across different coupling regimes.
  • To determine if MASH can reproduce established theoretical limits without artificial corrections.

Main Methods:

  • Developed and applied the mapping approach to surface hopping (MASH) simulation technique.
  • Tested MASH on systems exhibiting incoherent rate behavior.
  • Compared MASH results against Marcus theory and Fermi's golden rule predictions.

Main Results:

  • MASH deterministically hops between surfaces, avoiding wave function inconsistencies inherent in FSSH.
  • MASH accurately describes rates for intermediate and strong diabatic coupling.
  • MASH successfully reproduces Marcus theory results in the golden-rule limit without decoherence correction.

Conclusions:

  • MASH offers a significant improvement over FSSH for simulating nonadiabatic reactions.
  • The method correctly captures rate constant scaling without artificial adjustments.
  • MASH provides a more robust and accurate approach to modeling complex chemical dynamics.