title: Electronic Couplings for Resonance Energy Transfer from CCSD Calculations: From Isolated to Solvated Systems.
abstract: Quantum mechanical (QM) calculations of electronic couplings provide great insights for the study of resonance energy transfer (RET). However, most of these calculations rely on approximate QM methods due to the computational limitations imposed by the size of typical donor-acceptor systems. In this work, we present a novel implementation that allows computing electronic couplings at the coupled cluster singles and doubles (CCSD) level of theory. Solvent effects are also taken into account through the polarizable continuum model (PCM). As a test case, we use a dimer of indole, a common model system for tryptophan, which is routinely used as an intrinsic fluorophore in Förster resonance energy transfer studies. We consider two bright π → π* states, one of which has charge transfer character. Lastly, the results are compared with those obtained by applying TD-DFT in combination with one of the most popular density functionals, B3LYP.
authors.affiliation: Department of Chemistry, University of Kansas , 1251 Wescoe Hall Drive, Lawrence, Kansas 66045, United States.
authors.forename: Marco
authors.initials: M
authors.lastname: Caricato
authors.affiliation: Departament de Fisicoquímica, Facultat de Farmàcia, Universitat de Barcelona , Av. Joan XXIII s/n, 08028 Barcelona, Spain.
authors.forename: Carles
authors.initials: C
authors.lastname: Curutchet
authors.affiliation: Dipartimento di Chimica e Chimica Industriale, University of Pisa , via G. Moruzzi 3, 56124 Pisa, Italy.
authors.forename: Benedetta
authors.initials: B
authors.lastname: Mennucci
authors.affiliation: Gaussian, Inc. , 340 Quinnipiac Street, Building 40, Wallingford, Connecticut 06492, United States.
authors.forename: Giovanni
authors.initials: G
authors.lastname: Scalmani