Spin-flip time dependent density functional theory applied to excited states with single, double, or mixed electron excitation character
2010 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 133, no 11, 114104- p.Article in journal (Refereed) Published
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.
Place, publisher, year, edition, pages
2010. Vol. 133, no 11, 114104- p.
ab initio calculations, density functional theory, electron correlations, exchange interactions (electron), excited states, polymers
IdentifiersURN: urn:nbn:se:kth:diva-27122DOI: 10.1063/1.3479401ISI: 000282047500008ScopusID: 2-s2.0-77956969124OAI: oai:DiVA.org:kth-27122DiVA: diva2:375528
QC 201012082010-12-082010-12-062010-12-08Bibliographically approved