Caprasecca, StefanoCurutchet Barat, Carles E.Mennucci, Benedetta2021-03-252021-03-252013-06-201932-7447https://hdl.handle.net/2445/175735We 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.9 p.application/pdfeng(c) American Chemical Society , 2013Transferència d'energiaPorfirinesQuímica quànticaComplexitat computacionalEnergy transferPorphyrinsQuantum chemistryComputational complexityinfo:eu-repo/semantics/article6248682021-03-25info:eu-repo/semantics/openAccess