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dc.contributor.authorAndrzejak, Marcinen_US
dc.contributor.authorWitek, Henryk A.en_US
dc.date.accessioned2014-12-08T15:11:40Z-
dc.date.available2014-12-08T15:11:40Z-
dc.date.issued2011-05-01en_US
dc.identifier.issn1432-881Xen_US
dc.identifier.urihttp://dx.doi.org/10.1007/s00214-011-0916-xen_US
dc.identifier.urihttp://hdl.handle.net/11536/8954-
dc.description.abstractA systematic multi-reference perturbation theory investigation of the excitation energies and oscillator strengths for the lowest excited states of 2,2'-bithiophene unequivocally shows that its optical spectrum is produced by two (1) B (u) states separated from each other by approximately 1 eV. This picture is confirmed by additional calculations with alternative quantum chemical methods. Our findings are in strong contrast with the previous CASPT2 results of Rubio et al. [J Chem Phys 102:3580 (1995) and Chem Phys Chem 4:1308 (2003)], who predicted that the two lowest (1) B (u) states are quasi-degenerate. The methodological reasons responsible for the previous seemingly erroneous assignment of the optical spectrum of bithiophene are identified and explained in terms of unusually large coupling between the (1) B (u) states introduced by dynamical correlation effects. A general discussion of applicable computational techniques is offered aiming at avoiding similar problems for other molecular systems.en_US
dc.language.isoen_USen_US
dc.subjectExcited statesen_US
dc.subjectBithiopheneen_US
dc.subjectCASSCFen_US
dc.subjectCASPT2en_US
dc.subjectVertical excitation energiesen_US
dc.subjectAbsorption spectrumen_US
dc.titleThe elusive excited states of bithiophene: a CASPT2 detective storyen_US
dc.typeArticleen_US
dc.identifier.doi10.1007/s00214-011-0916-xen_US
dc.identifier.journalTHEORETICAL CHEMISTRY ACCOUNTSen_US
dc.citation.volume129en_US
dc.citation.issue2en_US
dc.citation.spage161en_US
dc.citation.epage172en_US
dc.contributor.department應用化學系zh_TW
dc.contributor.department應用化學系分子科學碩博班zh_TW
dc.contributor.departmentDepartment of Applied Chemistryen_US
dc.contributor.departmentInstitute of Molecular scienceen_US
dc.identifier.wosnumberWOS:000289898800004-
dc.citation.woscount8-
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