Chen, L, Borrelli, R, Shalashilin, DV orcid.org/0000-0001-6104-1277 et al. (2 more authors) (2021) Simulation of Time- and Frequency-Resolved Four-Wave-Mixing Signals at Finite Temperatures: A Thermo-Field Dynamics Approach. Journal of Chemical Theory and Computation. ISSN 1549-9618
Abstract
We propose a new approach to simulate four-wave-mixing signals of molecular systems at finite temperatures by combining the multiconfigurational Ehrenfest method with the thermo-field dynamics theory. In our approach, the four-time correlation functions at finite temperatures are mapped onto those at zero temperature in an enlarged Hilbert space with twice the vibrational degrees of freedom. As an illustration, we have simulated three multidimensional spectroscopic signals, time- and frequency-resolved fluorescence spectra, transient-absorption pump–probe spectra, and electronic two-dimensional (2D) spectra at finite temperatures, for a conical intersection-mediated singlet fission model of a rubrene crystal. It is shown that a detailed dynamical picture of the singlet fission process can be extracted from the three spectroscopic signals. An increasing temperature leads to lower intensities of the signals and broadened vibrational peaks, which can be attributed to faster singlet–triplet population transfer and stronger bath-induced electronic dephasing at higher temperatures.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2021 American Chemical Society. This is an author produced version of an article, published in Published online. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Physical Chemistry (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 28 Jun 2021 13:58 |
Last Modified: | 09 Jun 2022 00:38 |
Status: | Published online |
Publisher: | American Chemical Society (ACS) |
Identification Number: | 10.1021/acs.jctc.1c00259 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:175611 |