Spin-flip time dependent density functional theory applied to excited states with single, double, or mixed electron excitation character.
We analyze the ability of spin-flip time dependent density functional theory (TD-DFT) to uniformly describe excited states of single, double, and mixed excitation character in closed-shell molecular systems, using the polyene oligomers as a primary test case. The results of comparison between conventional and spin-flip TD-DFT and with correlated ab initio methods indicate that spin-flip TD-DFT provides a more consistent description of the ordering and relative positions of the excited states than conventional TD-DFT provided a suitable exchange-correlation functional is used in the calculations. It is found that spin-flip TD-DFT provides a physically appealing picture of excitation processes which involve one or two electrons, as it captures their most important features and facilitates a more uniform description of excited states with different character. This makes spin-flip TD-DFT a promising approach for general modeling of excited states and spectra of medium and large size molecules, which exhibit low-lying excited states with strong double excitation character.
Rinkevicius
Zilvinas
Z
Theoretical Chemistry, School of Biotechnology, Royal Institute of Technology, SE-106 91 Stockholm, Sweden. rinkevic@theochem.kth.se
Vahtras
Olav
O
Agren
Hans
H
D002070:Butadienes / Q000737:chemistry; D004583:Electrons; D011108:Polymers / Q000737:chemistry; D011789:Quantum Theory; D013997:Time Factors
D002070:Butadienes; D011108:Polymers