Multistate Density Functional Theory for Effective
Diabatic Electronic Coupling
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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