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http://hdl.handle.net/2445/175735
Title: | Dissecting the nature of exciton interactions in ethyne-linked tetraarylporphyrin arrays |
Author: | Caprasecca, Stefano Curutchet Barat, Carles E. Mennucci, Benedetta |
Keywords: | Transferència d'energia Porfirines Química quàntica Complexitat computacional Energy transfer Porphyrins Quantum chemistry Computational complexity |
Issue Date: | 20-Jun-2013 |
Publisher: | American Chemical Society |
Abstract: | We investigate how electronic energy transfer in a series of three ethyne-linked Zinc- and free base-tetraarylporphyrin dimers is tuned by the type of linker and by substitution on the porphyrin rings. We use TD-DFT combined with a recently developed fully polarizable QM/MM/PCM method. This allows us to dissect the bridge-mediated contributions to energy transfer in terms of superexchange (through-bond) interactions and Coulomb (through space) terms mediated by the polarizability of the bridge. We explore the effects of the substituents and of the bridge-chromophore mutual orientation on these contributions. We find that bridge-mediated superexchange contributions largely boost energy transfer between the porphyrin units. When the effect of the solvent is also considered through PCM, we find good agreement with the through-bond versus through-space contributions determined experimentally, thus indicating the need to properly include both solvent and bridge effects in the study of energy transfer in bridged molecular dyads. |
Note: | Versió postprint del document publicat a: http://dx.doi.org/10.1021/jp4020433 |
It is part of: | Journal of Physical Chemistry C, 2013, vol. 117, num. 24, p. 12423-12431 |
URI: | http://hdl.handle.net/2445/175735 |
ISSN: | 1932-7447 |
Appears in Collections: | Articles publicats en revistes (Farmàcia, Tecnologia Farmacèutica i Fisicoquímica) |
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