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Article: A resonance Raman spectroscopic and CASSCF investigation of the Franck-Condon region structural dynamics and conical intersections of thiophene

TitleA resonance Raman spectroscopic and CASSCF investigation of the Franck-Condon region structural dynamics and conical intersections of thiophene
Authors
KeywordsAbsorption band
Antisymmetries
CAS-SCF
Complete active space self-consistent fields
Computational results
Issue Date2010
PublisherAmerican Institute of Physics. The Journal's web site is located at http://jcp.aip.org/jcp/staff.jsp
Citation
Journal Of Chemical Physics, 2010, v. 133 n. 13 How to Cite?
AbstractResonance Raman spectra were acquired for thiophene in cyclohexane solution with 239.5 and 266 nm excitation wavelengths that were in resonance with ∼240 nm first intense absorption band. The spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion mostly along the reaction coordinates of six totally symmetry modes and three nontotally symmetry modes. The appearance of the nontotally symmetry modes, the CS antisymmetry stretch +C-C=C bend mode v 21 (B 2) at 754 cm-1 and the H 7 C 3 C 4 H 8 twist 9 (A 2) at 906 cm -1, suggests the existence of two different types of vibronic-couplings or curve-crossings among the excited states in the Franck-Condon region. The electronic transition energies, the excited state structures, and the conical intersection points 1B 1/ 1A 1 and 1B 2 / 1A 1 between 2 1A 1 and 1 1B 2 or 1 1B 1 potential energy surfaces of thiophene were determined by using complete active space self-consistent field theory computations. These computational results were correlated with the Franck-Condon region structural dynamics of thiophene. The ring opening photodissociation reaction pathway through cleavage of one of the C-S bonds and via the conical intersection point 1B/ 1A 1 was revealed to be the predominant ultrafast reaction channel for thiophene in the lowest singlet excited state potential energy hypersurface, while the internal conversion pathway via the conical intersection point 1B 2 / 1A 1 was found to be the minor decay channel in the lowest singlet excited state potential energy hypersurface. © 2010 American Institute of Physics.
Persistent Identifierhttp://hdl.handle.net/10722/138988
ISSN
2015 Impact Factor: 2.894
2015 SCImago Journal Rankings: 0.959
ISI Accession Number ID
Funding AgencyGrant Number
National Basic Research Program of China2007CB815203
NSFC21033002
20573097
20703038
NSFZJR405465
Research Grants Council (RGC) of Hong KongHKU 7039/07P
Croucher Foundation
University of Hong Kong
Funding Information:

This work was supported by grants from the National Basic Research Program of China (Grant No. 2007CB815203), NSFC (Grant Nos. 21033002, 20573097, and 20703038), NSFZJ (Grant No. R405465) to X. M., and from the Research Grants Council (RGC) of Hong Kong (HKU 7039/07P) to D. L. P. D. L. P. thanks the Croucher Foundation for the award of a Croucher Foundation Senior Research Fellowship (2006-2007) and the University of Hong Kong for an Outstanding Researcher Award (2006). X.Z. wishes to acknowledge the referees for their contributions in making this a better paper.

References

 

DC FieldValueLanguage
dc.contributor.authorWu, XFen_HK
dc.contributor.authorZheng, Xen_HK
dc.contributor.authorWang, HGen_HK
dc.contributor.authorZhao, YYen_HK
dc.contributor.authorGuan, Xen_HK
dc.contributor.authorPhillips, DLen_HK
dc.contributor.authorChen, Xen_HK
dc.contributor.authorFang, Wen_HK
dc.date.accessioned2011-09-23T05:43:44Z-
dc.date.available2011-09-23T05:43:44Z-
dc.date.issued2010en_HK
dc.identifier.citationJournal Of Chemical Physics, 2010, v. 133 n. 13en_HK
dc.identifier.issn0021-9606en_HK
dc.identifier.urihttp://hdl.handle.net/10722/138988-
dc.description.abstractResonance Raman spectra were acquired for thiophene in cyclohexane solution with 239.5 and 266 nm excitation wavelengths that were in resonance with ∼240 nm first intense absorption band. The spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion mostly along the reaction coordinates of six totally symmetry modes and three nontotally symmetry modes. The appearance of the nontotally symmetry modes, the CS antisymmetry stretch +C-C=C bend mode v 21 (B 2) at 754 cm-1 and the H 7 C 3 C 4 H 8 twist 9 (A 2) at 906 cm -1, suggests the existence of two different types of vibronic-couplings or curve-crossings among the excited states in the Franck-Condon region. The electronic transition energies, the excited state structures, and the conical intersection points 1B 1/ 1A 1 and 1B 2 / 1A 1 between 2 1A 1 and 1 1B 2 or 1 1B 1 potential energy surfaces of thiophene were determined by using complete active space self-consistent field theory computations. These computational results were correlated with the Franck-Condon region structural dynamics of thiophene. The ring opening photodissociation reaction pathway through cleavage of one of the C-S bonds and via the conical intersection point 1B/ 1A 1 was revealed to be the predominant ultrafast reaction channel for thiophene in the lowest singlet excited state potential energy hypersurface, while the internal conversion pathway via the conical intersection point 1B 2 / 1A 1 was found to be the minor decay channel in the lowest singlet excited state potential energy hypersurface. © 2010 American Institute of Physics.en_HK
dc.languageengen_US
dc.publisherAmerican Institute of Physics. The Journal's web site is located at http://jcp.aip.org/jcp/staff.jspen_HK
dc.relation.ispartofJournal of Chemical Physicsen_HK
dc.rightsJournal of Chemical Physics. Copyright © American Institute of Physics.-
dc.rightsCopyright (2010) American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in (Journal of Chemical Physics, 2010, v. 133 n. 13, article no. 134507) and may be found at (http://jcp.aip.org/resource/1/jcpsa6/v133/i13/p134507_s1).-
dc.rightsCreative Commons: Attribution 3.0 Hong Kong License-
dc.subjectAbsorption band-
dc.subjectAntisymmetries-
dc.subjectCAS-SCF-
dc.subjectComplete active space self-consistent fields-
dc.subjectComputational results-
dc.titleA resonance Raman spectroscopic and CASSCF investigation of the Franck-Condon region structural dynamics and conical intersections of thiopheneen_HK
dc.typeArticleen_HK
dc.identifier.emailPhillips, DL:phillips@hku.hken_HK
dc.identifier.authorityPhillips, DL=rp00770en_HK
dc.description.naturepublished_or_final_version-
dc.identifier.doi10.1063/1.3480361en_HK
dc.identifier.pmid20942546-
dc.identifier.scopuseid_2-s2.0-79955688490en_HK
dc.identifier.hkuros194568en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-79955688490&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume133en_HK
dc.identifier.issue13en_HK
dc.identifier.isiWOS:000282699800033-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridWu, XF=37862503800en_HK
dc.identifier.scopusauthoridZheng, X=7404090253en_HK
dc.identifier.scopusauthoridWang, HG=7501744689en_HK
dc.identifier.scopusauthoridZhao, YY=36792254900en_HK
dc.identifier.scopusauthoridGuan, X=8313149700en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK
dc.identifier.scopusauthoridChen, X=35781706600en_HK
dc.identifier.scopusauthoridFang, W=7202236871en_HK

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