Inclusion of Long-range Exchange in TD-DFT: Towards a Quantitative Charge-transfer Model
American Chemical Society Meeting
American Chemical Society (ACS)
San Francisco, CA
September 10-14, 2006
Date of Presentation
Recently, the poor behavior of TD-DFT as regards charge-transfer (CT) excited states has been discussed in the literature. Building on a scheme proposed by Tawada et. al. [J. Chem. Phys. 120 8425 (2004)], we have developed an add-on exchange kernel for use with any functional. It has the property of preserving the ground-state functional while producing the correct electrostatics on the excited state surface, fully self-consistently. Introduction of a system-dependent parameter into the model allows quantitative agreement of asymptotic CT and ionization energies by construction. The value of this parameter may often be estimated from properties of the ground state, with the unmodified functional. We will present the results of recent tests and applications of this functional modification.
Dutoi, A. D.,
Inclusion of Long-range Exchange in TD-DFT: Towards a Quantitative Charge-transfer Model.
Paper presented at American Chemical Society Meeting in San Francisco, CA.