Article
Assessment of the ΔSCF density functional theory approach for electronic excitations in organic dyes.
Journal of Chemical Physics
(2011)
Abstract
This paper assesses the accuracy of the ΔSCF method for computing low-lying HOMO→LUMO transitions in organic dye molecules. For a test set of vertical excitation energies of 16 chromophores, surprisingly similar accuracy is observed for time-dependent density functional theory and for ΔSCF density functional theory. In light of this performance, we reconsider the ad hoc ΔSCF prescription and demonstrate that it formally obtains the exact stationary density within the adiabatic approximation, partially justifying its use. The relative merits and future prospects of ΔSCF for simulating individual excited states are discussed.
Keywords
- Emission spectroscopy,
- Density functional theory,
- Adiabatic theorem
Disciplines
Publication Date
February 7, 2011
DOI
10.1063/1.3530801
Publisher Statement
© 2011 American Institute of Physics.
Citation Information
Tim Kowalczyk, Shane R Yost, Troy Van Voorhis (2011) Assessment of the ΔSCF density functional theory approach for electronic excitations in organic dyes. J. Chem. Phys. 134 (5), 054128.