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Type: Artigo de periódico
Title: Substituent effect in n-hexanes and n-hexatrienes based on core-electron binding energies calculated with density-functional theory
Author: Takahata, Y
Marques, AD
Custodio, R
Abstract: 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.
Subject: Substituent effect
Resonance effect
Country: Holanda
Editor: Elsevier Science Bv
Rights: fechado
Identifier DOI: 10.1016/j.theochem.2009.09.015
Date Issue: 2009
Appears in Collections:Artigos e Materiais de Revistas Científicas - Unicamp

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