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Molecular Physics
An International Journal at the Interface Between Chemistry and Physics
Volume 102, 2004 - Issue 13
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Original Articles

Singlet–triplet transitions in three-atomic molecules studied by time-dependent MCSCF and density functional theory

Pages 1391-1406 | Received 08 Dec 2003, Accepted 15 Dec 2003, Published online: 22 Aug 2006
 

Abstract

Singlet–triplet transition moments and phosphorescence lifetimes have been calculated for the three-atomic molecules HCN, O3, H2O, H2S, GeF2, GeCl2 and GeBr2 by time-dependent density functional theory (DFT) utilizing quadratic response functions in order to qualify DFT which recently has become available for studies of this kind [TUNELL, I., Rinkevivius, Z., VAHTRAS, O., SALEK, P., HELGAKER, T., and ÅGREN, H., 2003, J. chem. phys., 119, 11024]. Comparison with ab initio and experimental data indicates that DFT exhibit results of similar quality as explicitly correlated methods which indicates that it indeed is a viable approach for singlet–triplet transitions. O3 provides an intriguing example in that a systematic investigation of the singlet–triplet transition moment of its Wulf band indicates a clear advantage of the DFT technique despite the multiconfigurational character of the electronic structure of this molecule. The electronic spin–spin coupling and the hyperfine nuclear coupling constants have also been calculated in order to further characterize the triplet state in the spectra of the investigated systems.

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