title: Modelling charge transfer reactions with the frozen density embedding formalism.
abstract: The frozen density embedding (FDE) subsystem formulation of density-functional theory is a useful tool for studying charge transfer reactions. In this work charge-localized, diabatic states are generated directly with FDE and used to calculate electronic couplings of hole transfer reactions in two π-stacked nucleobase dimers of B-DNA: 5'-GG-3' and 5'-GT-3'. The calculations rely on two assumptions: the two-state model, and a small differential overlap between donor and acceptor subsystem densities. The resulting electronic couplings agree well with benchmark values for those exchange-correlation functionals that contain a high percentage of exact exchange. Instead, when semilocal GGA functionals are used the electronic couplings are grossly overestimated.
authors.affiliation: Gorlaeus Laboratories, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands. m.pavanello@chem.leidenuniv.nl
authors.forename: Michele
authors.initials: M
authors.lastname: Pavanello
authors.forename: Johannes
authors.initials: J
authors.lastname: Neugebauer
mesh_terms: D000465:Algorithms; D020029:Base Pairing; D059371:DNA, B-Form / Q000737:chemistry*; D019281:Dimerization; D004579:Electron Transport; D008958:Models, Molecular; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry
chemical_list: D059371:DNA, B-Form; D012997:Solvents