dc.creator | Takahata, Y | |
dc.creator | Marques, AD | |
dc.creator | Custodio, R | |
dc.date | 2009 | |
dc.date | DEC 30 | |
dc.date | 2014-11-14T09:44:41Z | |
dc.date | 2015-11-26T17:14:16Z | |
dc.date | 2014-11-14T09:44:41Z | |
dc.date | 2015-11-26T17:14:16Z | |
dc.date.accessioned | 2018-03-29T00:02:36Z | |
dc.date.available | 2018-03-29T00:02:36Z | |
dc.identifier | Journal Of Molecular Structure-theochem. Elsevier Science Bv, v. 916, n. 41699, n. 119, n. 124, 2009. | |
dc.identifier | 0166-1280 | |
dc.identifier | WOS:000272259400017 | |
dc.identifier | 10.1016/j.theochem.2009.09.015 | |
dc.identifier | http://www.repositorio.unicamp.br/jspui/handle/REPOSIP/74673 | |
dc.identifier | http://www.repositorio.unicamp.br/handle/REPOSIP/74673 | |
dc.identifier | http://repositorio.unicamp.br/jspui/handle/REPOSIP/74673 | |
dc.identifier.uri | http://repositorioslatinoamericanos.uchile.cl/handle/2250/1281772 | |
dc.description | Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) | |
dc.description | It 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.description | 916 | |
dc.description | 41699 | |
dc.description | 119 | |
dc.description | 124 | |
dc.description | Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) | |
dc.description | Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) | |
dc.description | CNPq [304751/2006-5, 302440/2005-4] | |
dc.description | CNPq [553292/2005-6] | |
dc.language | en | |
dc.publisher | Elsevier Science Bv | |
dc.publisher | Amsterdam | |
dc.publisher | Holanda | |
dc.relation | Journal Of Molecular Structure-theochem | |
dc.relation | Theochem-J. Mol. Struct. | |
dc.rights | fechado | |
dc.rights | http://www.elsevier.com/about/open-access/open-access-policies/article-posting-policy | |
dc.source | Web of Science | |
dc.subject | Substituent effect | |
dc.subject | CEBE | |
dc.subject | n-Hexanes | |
dc.subject | n-Hexatrienes | |
dc.subject | Resonance effect | |
dc.subject | Sigma Constants | |
dc.subject | Accurate | |
dc.subject | Shifts | |
dc.subject | Spectroscopy | |
dc.subject | Ionization | |
dc.subject | Reactivity | |
dc.title | Substituent effect in n-hexanes and n-hexatrienes based on core-electron binding energies calculated with density-functional theory | |
dc.type | Artículos de revistas | |