Resonance energy transfer: When a dipole fails

Andrews, D.L. and Leeder, J.M. (2009) Resonance energy transfer: When a dipole fails. The Journal of Chemical Physics, 130 (18). ISSN 0021-9606

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The Coulombic coupling of electric dipole (E1) transition moments is the most commonly studied and widely operative mechanism for energy migration in multichromophore systems. However a significant number of exceptions exist, in which donor decay and/or acceptor excitation processes are E1-forbidden. The alternative transfer mechanisms that can apply in such cases include roles for higher multipole transitions, exciton- or phonon-assisted interactions, and non-Coulombic interactions based on electron exchange. A quantum electrodynamical formulation provides a rigorous basis to assess the first of these, specifically addressing the relative significance of higher multipole contributions to the process of energy transfer in donor-acceptor systems where electric dipole transitions are precluded by symmetry. Working within the near-zone limit, where donor-acceptor separations are small in comparison to the chromophore scale, the analysis highlights the contributions of both electric quadrupole-electric quadrupole (E2-E2) coupling and the seldom considered second-order electric dipole-electric dipole (El -El) coupling. For both forms of interaction, experimentally meaningful rate equations are secured by the use of orientational averaging, and the mechanisms are analyzed with reference to systems in which E1-forbidden transitions are commonly reported. © 2009 American Institute of Physics.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
UEA Research Groups: Faculty of Science > Research Groups > Physical and Analytical Chemistry (former - to 2017)
Faculty of Science > Research Groups > Chemistry of Light and Energy
Faculty of Science > Research Groups > Centre for Photonics and Quantum Science
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Depositing User: Rachel Smith
Date Deposited: 27 Oct 2010 10:16
Last Modified: 09 Feb 2023 13:34
DOI: 10.1063/1.3131168

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