Yang, X, Keane, T., Delor, M. et al. (3 more authors) (2017) Identifying electron transfer coordinates in Donor-Bridge-Acceptor systems using mode projection analysis. Nature Communications.
Abstract
We report upon an analysis of the vibrational modes that couple and drive the state-to-state electronic transfer branching ratios in a model donor-bridge-acceptor system consisting of a phenothiazine-based donor linked to a naphthalene-monoimide acceptor via a platinum-acetylide bridging unit. Our analysis is based upon an iterative Lanczos search algorithm that finds superpositions of vibronic modes that optimize the electron/nuclear coupling using input from excited-state quantum chemical methods. Our results indicate that the electron transfer reaction coordinates between a triplet charge transfer state and lower lying chargeseparated and localised excitonic states are dominated by asymmetric and symmetric modes of the acetylene groups on either side of the central atom in this system. In particular, we find that while a nearly symmetric mode couples both the charge-separation and charge-recombination transitions more or less equally, the coupling along an asymmetric mode is far greater suggesting that IR excitation of the acetylene modes preferentially enhances charge recombination transition relative to charge-separation.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © The Author(s) 2017. This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 23 Feb 2017 15:58 |
Last Modified: | 02 Mar 2017 16:01 |
Published Version: | http://doi.org/10.1038/ncomms14554 |
Status: | Published |
Publisher: | Nature Publishing Group |
Refereed: | Yes |
Identification Number: | 10.1038/ncomms14554 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:112708 |