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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

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

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Author(s):
Braida, Benoit ; Galembeck, Sergio E. ; Hiberty, Philippe C.
Total Authors: 3
Document type: Journal article
Source: JOURNAL OF CHEMICAL THEORY AND COMPUTATION; v. 13, n. 7, p. 3228-3235, JUL 2017.
Web of Science Citations: 8
Abstract

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)

FAPESP's process: 08/02677-0 - Computational Study of the interaction between HIV-1 reverse transcriptase non-nucleoside inhibitors with amino acids of the inhibitory site
Grantee:Sergio Emanuel Galembeck
Support Opportunities: Regular Research Grants
FAPESP's process: 14/50265-3 - Distribution and metabolism of natural and synthetic xenobiotics: from the comprehension of reactional process to tissue imaging generation
Grantee:Norberto Peporine Lopes
Support Opportunities: BIOTA-FAPESP Program - Thematic Grants