Electronic spectroscopy of thiones

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dc.check.embargoformatNot applicableen
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dc.contributor.advisorBrint, Paulen
dc.contributor.authorDoherty, William G.
dc.date.accessioned2014-07-28T11:46:36Z
dc.date.available2014-07-28T11:46:36Z
dc.date.issued2003
dc.date.submitted2003
dc.description.abstractThe phosphorescence excitation spectra of two thiones, 4-H-1-xanthione (XT) and 4-H-1-pyrane-4-thione (PT), cooled in a supersonic jet were investigated. The vibronic lineshape of the T1z origin of PT measured by cavity ring-down spectroscopy is considered and the excited state rotational constants are calculated. For XT the 3A2(nπ* ) → X1A1 phosphorescence excitation spectrum was investigated in the region 14900-17600 cm-1. The structure observed is shown to be due to the T1← S0 absorption and an assignment in terms of the vibronic structure of the band is proposed. A previous assignment of the S1 ← S0 origin is considered and the transition involved is shown to be most probably due to the absorption of a vibronic tiplet state T1z,v7. An alternative but tentative assignment of the S1,0 ←S0,0 transition is suggested. In the case of PT the phosphorescence excitation spectrum was investigated in the region of the 1A2(ππ*) ← X1A1 absorption band between 27300 and 28800 cm-1. The spectrum exhibits complex features which are typical for the strong vibronic coupling case of two adjacent electronic states. The observed intermediate level structure was attributed to the coupling with a lower lying dark electronic state 1B1(nπ*2), whose origin was estimated to be ~ 825 - 1025 cm-1 below the origin of 1A2(ππ*)0. Consequences of the vibronic coupling on the decay dynamics of 1A2(ππ*) as well as tentative assignments of vibronic transitions 1A2(ππ*)v ← X1A1 are also discussed. In the T1z ← S0 cavity ring-down absorption spectrum of PT, the vibronic lineshape of the T1z origin is analysed. As the T1z line is separated from the T1x,1y lines by a large zero-field splitting it is possible to use an Asyrot-like program to calculate the vibrational-rotational parameters determining the lineshape. It is shown that PT is non-planar in the first excited triplet state and the lineshape is composed of a mixture of A-type and C-type bandshapes. The non-planarity of PT is discussed.en
dc.description.statusNot peer revieweden
dc.description.versionAccepted Version
dc.format.mimetypeapplication/pdfen
dc.identifier.citationDoherty, W. G. 2003. Electronic spectroscopy of thiones. PhD Thesis, University College Cork.en
dc.identifier.urihttps://hdl.handle.net/10468/1601
dc.language.isoenen
dc.publisherUniversity College Corken
dc.relation.urihttp://library.ucc.ie/record=b1360019~S0
dc.rights© 2003, William G. Dohertyen
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/3.0/en
dc.subjectThionesen
dc.subjectPhosphorescence excitation spectraen
dc.subject.lcshSpectrum analysisen
dc.thesis.opt-outfalse
dc.titleElectronic spectroscopy of thionesen
dc.typeDoctoral thesisen
dc.type.qualificationlevelDoctoralen
dc.type.qualificationnamePhD (Science)en
ucc.workflow.supervisorcora@ucc.ie
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