Jump to main content
Jump to site search


Improved population operators for multi-state nonadiabatic dynamics with the mixed quantum-classical mapping approach

Author affiliations

Abstract

The mapping approach addresses the mismatch between the continuous nuclear phase space and discrete electronic states by creating an extended, fully continuous phase space using a set of harmonic oscillators to encode the populations and coherences of the electronic states. Existing quasiclassical dynamics methods based on mapping, such as the linearised semiclassical initial value representation (LSC-IVR) and Poisson bracket mapping equation (PBME) approaches, have been shown to fail in predicting the correct relaxation of electronic-state populations following an initial excitation. Here we generalise our recently published modification to the standard quasiclassical approximation for simulating quantum correlation functions. We show that the electronic-state population operator in any system can be exactly rewritten as a sum of a traceless operator and the identity operator. We show that by treating the latter at a quantum level instead of using the mapping approach, the accuracy of traditional quasiclassical dynamics methods can be drastically improved, without changes to their underlying equations of motion. We demonstrate this approach for the seven-state Frenkel-exciton model of the Fenna–Matthews–Olson light harvesting complex, showing that our modification significantly improves the accuracy of traditional mapping approaches when compared to numerically exact quantum results.

Graphical abstract: Improved population operators for multi-state nonadiabatic dynamics with the mixed quantum-classical mapping approach

Back to tab navigation

Publication details

The article was received on 25 Apr 2019, accepted on 04 Jun 2019 and first published on 24 Sep 2019


Article type: Paper
DOI: 10.1039/C9FD00050J
Faraday Discuss., 2020, Advance Article
  • Open access: Creative Commons BY license
  •   Request permissions

    Improved population operators for multi-state nonadiabatic dynamics with the mixed quantum-classical mapping approach

    M. A. C. Saller, A. Kelly and J. O. Richardson, Faraday Discuss., 2020, Advance Article , DOI: 10.1039/C9FD00050J

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements