Spin-Mapping Methods for Simulating Ultrafast Nonadiabatic Dynamics

Authors

  • Johan E. Runeson Laboratory of Physical Chemistry, ETH Zurich, 8093 Zurich
  • Jonathan R. Mannouch Laboratory of Physical Chemistry, ETH Zurich, 8093 Zurich
  • Graziano Amati Laboratory of Physical Chemistry, ETH Zurich, 8093 Zurich
  • Marit R. Fiechter Laboratory of Physical Chemistry, ETH Zurich, 8093 Zurich
  • Jeremy O. Richardson Laboratory of Physical Chemistry, ETH Zurich, 8093 Zurich

DOI:

https://doi.org/10.2533/chimia.2022.582

Keywords:

Conical intersections, Light harvesting, Nonadiabatic dynamics, Nonlinear spectroscopy, Quantum-classical, Spin mapping, Strong field

Abstract

Many chemical reactions exhibit nonadiabatic effects as a consequence of coupling between electronic states and/or interaction with light. While a fully quantum description of nonadiabatic reactions is unfeasible for most realistic molecules, a more computationally tractable approach is to combine a classical description of the nuclei with a quantum description of the electronic states. Combining the formalisms of quantum and classical dynamics is however a difficult problem for which standard methods (such as Ehrenfest dynamics and surface hopping) may be insufficient. In this article, we review a new trajectory-based approach developed in our group that is able to describe nonadiabatic dynamics with a higher accuracy than previous approaches but for a similar level of computational effort. This method treats the electronic states with a phase-space representation for discrete-level systems, which in the two-level case is analogous to a spin-½. We point out the key features of the method and demonstrate its use in a variety of applications, including ultrafast transfer through conical intersections, damped coherent excitation under coupling to a strong light field, and nonlinear spectroscopy of light-harvesting complexes.

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Published

2022-06-29

How to Cite

[1]
J. E. Runeson, J. R. Mannouch, G. Amati, M. R. Fiechter, J. O. Richardson, Chimia 2022, 76, 582, DOI: 10.2533/chimia.2022.582.