Freixas, VM, Tretiak, S, Makhov, DV et al. (2 more authors) (2020) Vibronic Quantum Beating between Electronic Excited States in a Heterodimer. The Journal of Physical Chemistry B. ISSN 1520-6106
Abstract
Energy transfer in multichromophoric molecules can be affected by coherences that are induced by the electronic and vibrational couplings between chromophore units. Coherent electron-vibrational dynamics can persist at the subpicosecond time scale even at room temperature. Furthermore, wave-like localized-delocalized motions of the electronic wave function can be modulated by vibrations that actively participate in the intermolecular energy transfer process. Herein, nonadiabatic excited state molecular dynamics simulations have been performed on a rigid synthetic heterodimer that has been proposed as a simplified model for investigating the role and mechanism of coherent energy transfer in multichromophoric systems. Both surface hopping (SH) and Ehrenfest approaches (EHR) have been considered. After photoexcitation of the system at room temperature, EHR simulations reveal an ultrafast beating of electronic populations between the two lowest electronic states. These oscillations are not observed at low temperature and have vibrational origins. Furthermore, they cannot be reproduced using SH approach. This periodic behavior of electronic populations induces oscillations in the spatial localization of the electronic transition density between monomers. Vibrations whose frequencies are near-resonant with energy difference between the two lowest electronic excited states are in the range of the electronic population beating, and they are the ones that contribute the most to the coherent dynamics of these electronic transitions.
Metadata
Item Type: | Article |
---|---|
Authors/Creators: |
|
Copyright, Publisher and Additional Information: | © 2020 American Chemical Society. This is an author produced version of an article published in Journal of Physical Chemistry B . Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
|
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: | 11 May 2020 15:34 |
Last Modified: | 30 Apr 2021 00:38 |
Status: | Published online |
Publisher: | American Chemical Society |
Identification Number: | 10.1021/acs.jpcb.0c01685 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:160540 |