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J Chem Phys. 2016 Nov 21;145(19):194107.

Vertical excitation energies from the adiabatic connection.

Author information

1
Department of Chemistry, Dalhousie University, 6274 Coburg Rd., P.O. Box 15000, Halifax, Nova Scotia B3H 4R2, Canada.

Abstract

Vertical single-particle excitations from closed-shell ground states are complicated by the fact that the singlet open-shell states are, even in the first approximation, two-determinantal. Thus two-electron integrals come into play and standard time-independent DFT (density-functional theory) does not apply. In this work, we use the "adiabatic connection" to analyse the role of the two-electron integrals, obtaining a time-independent DFT approach to excitation-energy calculations that is new and simple. A non-empirical modeling of the method works as well as the popular TD-B3LYP time-dependent approach to excited states, and can be made even simpler by introducing one reasonable semi-empirical parameter.

PMID:
27875864
DOI:
10.1063/1.4967813

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