Substituent effect in n-hexanes and n-hexatrienes based on core-electron binding energies calculated with density-functional theory

dc.creatorTakahata, Y
dc.creatorMarques, AD
dc.creatorCustodio, R
dc.date2009
dc.dateDEC 30
dc.date2014-11-14T09:44:41Z
dc.date2015-11-26T17:14:16Z
dc.date2014-11-14T09:44:41Z
dc.date2015-11-26T17:14:16Z
dc.date.accessioned2018-03-29T00:02:36Z
dc.date.available2018-03-29T00:02:36Z
dc.identifierJournal Of Molecular Structure-theochem. Elsevier Science Bv, v. 916, n. 41699, n. 119, n. 124, 2009.
dc.identifier0166-1280
dc.identifierWOS:000272259400017
dc.identifier10.1016/j.theochem.2009.09.015
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/74673
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/74673
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/74673
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1281772
dc.descriptionConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
dc.descriptionIt was shown that core-electron binding energy (CEBE) is a very convenient quantity to monitor substituent effect at each carbon atom in a substituted n-hexane (1-X-hexane), a chain sigma-system, and a substituted n-hexatriene (1-X-hexatriene), a chain pi-system. The core-electron binding energy was calculated using the density-functional theory with a scheme: Delta E(KS)(PW86-PW91)/TZP + C(ret)//HF/6-31G* The calculated CEBE(i) of ith orbital is equal to the sum of the ionization energy (-epsilon(i)) due to the Koopmans' theorem and relaxation energy (R). The variation of the ionization energy (-epsilon(i)) parallels closely to that of CEBE(i). The relaxation energy curve does not follow the CEBE curve. The behavior of CEBE in a molecule M depends almost exclusively upon the electronic structure of its neutral parent molecule M, and not upon its core-ionized cation M(+). The substituent effect in the sigma-system is considered as inductive effect. The substituent effect in the pi-system consists of inductive and resonant/pi-electron effects. Assuming that the inductive effect of the pi-system, 1-X-hexatriene, can be approximated by that of the sigma-systems, 1-X-hexane, resonant effect of the pi-system was estimated. (C) 2009 Elsevier B.V. All rights reserved.
dc.description916
dc.description41699
dc.description119
dc.description124
dc.descriptionConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
dc.descriptionConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
dc.descriptionCNPq [304751/2006-5, 302440/2005-4]
dc.descriptionCNPq [553292/2005-6]
dc.languageen
dc.publisherElsevier Science Bv
dc.publisherAmsterdam
dc.publisherHolanda
dc.relationJournal Of Molecular Structure-theochem
dc.relationTheochem-J. Mol. Struct.
dc.rightsfechado
dc.rightshttp://www.elsevier.com/about/open-access/open-access-policies/article-posting-policy
dc.sourceWeb of Science
dc.subjectSubstituent effect
dc.subjectCEBE
dc.subjectn-Hexanes
dc.subjectn-Hexatrienes
dc.subjectResonance effect
dc.subjectSigma Constants
dc.subjectAccurate
dc.subjectShifts
dc.subjectSpectroscopy
dc.subjectIonization
dc.subjectReactivity
dc.titleSubstituent effect in n-hexanes and n-hexatrienes based on core-electron binding energies calculated with density-functional theory
dc.typeArtículos de revistas


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