Abstract
Multistate density functional theory (MSDFT) is presented to estimate the effective transfer integral associated with electron and hole transfer reactions. In this approach, the charge-localized diabatic states are defined by block localization of Kohn-Sham orbitals, which constrain the electron density for each diabatic state in orbital space. This differs from the procedure used in constrained density functional theory that partitions the density within specific spatial regions. For a series of model systems, the computed transfer integrals are consistent with experimental data and show the expected exponential attenuation with the donor-acceptor separation. The present method can be used to model charge transfer reactions including processes involving coupled electron and proton transfer. © 2016 American Chemical Society.