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Ozone and Other 1,3-Dipoles: Toward a Quantitative Measure of Diradical Character

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Autor(es):
Braida, Benoit ; Galembeck, Sergio E. ; Hiberty, Philippe C.
Número total de Autores: 3
Tipo de documento: Artigo Científico
Fonte: JOURNAL OF CHEMICAL THEORY AND COMPUTATION; v. 13, n. 7, p. 3228-3235, JUL 2017.
Citações Web of Science: 0
Resumo

Ozone and its sulfur-substituted isomers are studied by means of the Breathing Orbital Valence Bond ab initio method, with the objective of estimating their controversial diradical characters. The calculated weights of the various VB structures and their individual diabatic energies are found to be consistent with each other. All 1,3 dipoles can be described in terms of three major. VB structures, one diradical and two zwitterionic ones, out of the six structures, forming a complete basis. Ozone has a rather large diradical character, estimated to 44%-49%. SOO and SOS are even more diradicalar, whereas SSO and especially OSO are better described as closed-shell zwitterions. Moreover, the description of 1,3-dipoles, in terms of the three major structures, yields VB weights in full agreement with simple chemical wisdom, i.e., a diradical weight of 33% when the three structures are quasi-degenerate, and a smaller (larger) value when the diradical structure is higher (lower) in energy than the zwitterionic ones. Therefore, the VB-calculated weight of the diradical structure of a molecule qualifies itself as a quantitative measure of diradical character, and not only as an indicator of tendencies. Other definitions of the diradical character, based on molecular orbital/configuration interaction methods, are discussed. (AU)

Processo FAPESP: 14/50265-3 - Metabolismo e distribuição de xenobióticos naturais e sintéticos: da compreensão dos processos reacionais à geração de imagens teciduais
Beneficiário:Norberto Peporine Lopes
Linha de fomento: Auxílio à Pesquisa - Programa BIOTA - Temático
Processo FAPESP: 08/02677-0 - Estudo computacional da interação entre inibidores não nucleosídeos da transcriptase reversa do vírus HIV-1 com aminoácidos do sítio inibitório
Beneficiário:Sergio Emanuel Galembeck
Linha de fomento: Auxílio à Pesquisa - Regular