title: Performance of Frozen Density Embedding for Modeling Hole Transfer Reactions.
abstract: We have carried out a thorough benchmark of the frozen density-embedding (FDE) method for calculating hole transfer couplings. We have considered 10 exchange-correlation functionals, 3 nonadditive kinetic energy functionals, and 3 basis sets. Overall, we conclude that with a 7% mean relative unsigned error, the PBE and PW91 functionals coupled with the PW91k nonadditive kinetic energy functional and a TZP basis set constitute the most stable and accurate levels of theory for hole transfer coupling calculations. The FDE-ET method is found to be an excellent tool for computing diabatic couplings for hole transfer reactions.
authors.affiliation: Department of Chemistry, Rutgers University, Newark, New Jersey 07102, United States.
authors.forename: Pablo
authors.initials: P
authors.lastname: Ramos
authors.affiliation: Department of Chemistry, Rutgers University, Newark, New Jersey 07102, United States.
authors.forename: Markos
authors.initials: M
authors.lastname: Papadakis
authors.affiliation: Department of Chemistry, Rutgers University, Newark, New Jersey 07102, United States.
authors.forename: Michele
authors.initials: M
authors.lastname: Pavanello