The influence of a Hamiltonian vibration vs a bath vibration on the 2D electronic spectra of a homodimer

Humphries, Ben, Green, Dale and Jones, Garth (2022) The influence of a Hamiltonian vibration vs a bath vibration on the 2D electronic spectra of a homodimer. The Journal of Chemical Physics, 156 (8). ISSN 0021-9606

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Abstract

We elucidate the influence of the system–bath boundary placement within an open quantum system, with emphasis on the two-dimensional electronic spectra, through the application of the hierarchical equations of motion formalism for an exciton system. We apply two different models, the Hamiltonian vibration model (HVM) and bath vibration model (BVM), to a monomer and a homodimer. In the HVM, we specifically include the vibronic states in the Hamiltonian capturing vibronic quenching, whereas in the BVM, all vibrational details are contained within the bath and described by an underdamped spectral density. The resultant spectra are analyzed in terms of energetic peak position and thermodynamic broadening precision in order to evaluate the efficacy of the two models. The HVM produces 2D spectra with accurate peak positional information, while the BVM is well suited to modeling dynamic peak broadening. For the monomer, both models produce equivalent spectra in the limit where additional damping associated with the underdamped vibration in the BVM approaches zero. This is supported by analytical results. However, for the homodimer, the BVM spectra are redshifted with respect to the HVM due to an absence of vibronic quenching in the BVM. The computational efficiency of the two models is also discussed in order to inform us of the most appropriate use of each method.

Item Type: Article
Additional Information: Funding Information: The research presented in this paper was carried out on the High Performance Computing Cluster supported by the Research and Specialist Computing Support service at the University of East Anglia. B.S.H. thanks the Faculty of Science, University of East Anglia, for studentship funding. G.A.J. and D.G. acknowledge support from the Engineering and Physical Sciences Research Council under Award No. EP/V00817X/1. Publisher Copyright: © 2022 Author(s).
Uncontrolled Keywords: physics and astronomy(all),physical and theoretical chemistry ,/dk/atira/pure/subjectarea/asjc/3100
Faculty \ School: Faculty of Science > School of Chemistry
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Depositing User: LivePure Connector
Date Deposited: 16 Mar 2022 09:30
Last Modified: 11 May 2022 00:44
URI: https://ueaeprints.uea.ac.uk/id/eprint/84077
DOI: 10.1063/5.0077404

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