A valence bond description of the prefulvene extended conical intersection seam of benzene
dc.contributor.author
dc.date.accessioned
2015-11-11T08:04:18Z
dc.date.available
2015-11-11T08:04:18Z
dc.date.issued
2012
dc.identifier.issn
1549-9618
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dc.description.abstract
The permutational isomers of the prefulvene-like minimum energy conical intersection lie on an extended conical intersection seam, where they are connected by higher symmetry structures. Here, we present a VB analysis of the electronic states involved along this extended seam. The VB method produces a spin-exchange density (ie. a bonding pattern) that provides the basis to assign resonance structures to the states. The results show that in the high symmetry region of the seam, the character of the states is dominated by the positive and negative combination of the Kekulé structures, (A+B) and (A-B). The low energy parts of the seam, comprised of lower symmetry conical intersection structures, are stabilized by mixing with the Dewar resonance structures. This feature is responsible for the stability of the benzvalene-like conical intersections. The validity of the VB model is confirmed by calculating the branching space vectors at this level of theory, which are in good agreement with the CASSCF calculated vectors. The VB analysis has also allowed us to complete our picture of the global seam, since it has provided the clue to locate a conical intersection saddle point that interconverts two minima of the prefulvene conical intersection where the carbon bent out of the plane is inverted and rotated by 60°. This saddle point has a benzvalene-like geometry, in agreement with the VB picture
dc.description.sponsorship
We thank Q. Li for help with the CASSCF computations. This work has been supported by grants CTQ2011-26573 from the Spanish Ministerio de Economia y Competividad, SGR0528 from the Catalan Agencia de Gestio d'Ajuts Universitaris i de Recerca (AGAUR), UNGI08-4E-003 from the Spanish Ministerio de Ciencia e Innovacion and the FEDER fund (European Fund for Regional Development), and the Xarxa de Referencia en Quimica Teorica i Computacional de Catalunya from AGAUR. M.A.R. acknowledges a travel grant from AGAUR (2010PIV00086)
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation
info:eu-repo/grantAgreement/MICINN//CTQ2011-26573/ES/MODELIZACION QUIMICO CUANTICA DE FOTOQUIMICA Y TRANSFERENCIA ELECTRONICA: SISTEMAS GRANDES, EFECTOS COLECTIVOS Y CONTROL OPTICO/
info:eu-repo/grantAgreement/MEC//UNGI08-4E-003/ES/Clúster de PCs para cálculo intensivo en química cuántica/
AGAUR/2009-2014/2009 SGR-528
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Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ct300625u
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© Journal of Chemical Theory and Computation, 2012, vol. 8, núm. 12, p. 4922-4930
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Articles publicats (D-Q)
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Tots els drets reservats
dc.subject
dc.title
A valence bond description of the prefulvene extended conical intersection seam of benzene
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/embargoedAccess
dc.embargo.terms
Cap
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
017093
dc.contributor.funder
dc.relation.ProjectAcronym
dc.identifier.eissn
1549-9626