title: A Subsystem TDDFT Approach for Solvent Screening Effects on Excitation Energy Transfer Couplings.
abstract: We present a QM/QM approach for the calculation of solvent screening effects on excitation-energy transfer (EET) couplings. The method employs a subsystem time-dependent density-functional theory formalism [J. Chem. Phys. 2007, 126, 134116] and explicitly includes solvent excited states to account for the environmental response. It is investigated how the efficiency of these calculations can be enhanced in order to treat systems with very large solvation shells while fully including the environmental response. In particular, we introduce a criterion to select solvent excited states according to their approximate contribution weight to the environmental polarization. As a model system, we investigate the perylene diimide dimer in a water cluster in comparison to a recent polarizable QM/MM method for EET couplings in the condensed phase [J. Chem. Theory Comput. 2009, 5, 1838]. A good overall agreement in the description of the solvent screening is found. Deviations can be observed for the effect of the closest water molecules, whereas the screening introduced by outer solvation shells is very similar in both methods. Our results can thus be helpful to determine at which distance from a chromophore environmental response effects may safely be approximated by classical models.
authors.affiliation: Gorlaeus Laboratories, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands, Department of Chemistry, 80 St. George Street, Institute for Optical Sciences and Centre for Quantum Information and Quantum Control, University of Toronto, Toronto, Ontario M5S 3H6 Canada, Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus Montilivi 17071 Girona, Catalonia, Spain, and Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via Risorgimento 35, 56126 Pisa, Italy.
authors.forename: Johannes
authors.initials: J
authors.lastname: Neugebauer
authors.affiliation: Gorlaeus Laboratories, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands, Department of Chemistry, 80 St. George Street, Institute for Optical Sciences and Centre for Quantum Information and Quantum Control, University of Toronto, Toronto, Ontario M5S 3H6 Canada, Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus Montilivi 17071 Girona, Catalonia, Spain, and Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via Risorgimento 35, 56126 Pisa, Italy.
authors.forename: Carles
authors.initials: C
authors.lastname: Curutchet
authors.affiliation: Gorlaeus Laboratories, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands, Department of Chemistry, 80 St. George Street, Institute for Optical Sciences and Centre for Quantum Information and Quantum Control, University of Toronto, Toronto, Ontario M5S 3H6 Canada, Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus Montilivi 17071 Girona, Catalonia, Spain, and Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via Risorgimento 35, 56126 Pisa, Italy.
authors.forename: Aurora
authors.initials: A
authors.lastname: Muñoz-Losa
authors.affiliation: Gorlaeus Laboratories, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands, Department of Chemistry, 80 St. George Street, Institute for Optical Sciences and Centre for Quantum Information and Quantum Control, University of Toronto, Toronto, Ontario M5S 3H6 Canada, Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus Montilivi 17071 Girona, Catalonia, Spain, and Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via Risorgimento 35, 56126 Pisa, Italy.
authors.forename: Benedetta
authors.initials: B
authors.lastname: Mennucci