Journal article
Ab initio and DFT investigation of the structures and properties of chloromethyl and chlorofluoromethyl peroxyl radicals

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Publication Details
Author list: S. El-Taher
Publisher: Wiley: 12 months
Publication year: 2005
Journal: International Journal of Quantum Chemistry
Volume number: 102
Issue number: 2
Start page: 178
End page: 188
Number of pages: 11
ISSN: 0020-7608
Web of Science ID: 000227345700008
PubMed ID:
Scopus ID: 15944365196

Ab initio and Density Functional Theory (DFT) calculations were performed to determine the equilibrium geometries, charge distributions, spin density distributions, dipole moments, electron affinities (EAs), and C-O bond dissociation energies (BDEs) of (CH2ClO2CHCl2O2.)-C-., CCl3O2., CF2ClO2., CFCl2O2., and CHFClO2. peroxyl radicals. The C-H BDEs of the parent methanes were calculated using the same levels of theories. Both MP2(full) and B3LYP methods, using the 6-31G(d,p) basis set, were found to be capable of accurately predicting the geometries of peroxyl radicals. The B3LYP/6-31G(d,p) method was found to be comparable to high ab initio levels in predicting C-O BDEs of studied peroxyl radicals and C-H BDEs of the parent alkanes. The progressive chlorine substitution of hydrogen atoms in methyl peroxyl radicals results in an increase (decrease) of the spin density on the terminal (inner) oxygen, a decrease in dipole moments, and an increase in electron affinities. The substitution of fluorine by chlorine in the series CF3O2. - CCl3O2. was found to lengthen (destabilize) the C-O bonds. Both C-O BDEs and EAs of peroxyl radicals (RO2.) were found to correlate well with Taft sigma* substituent constants for the R groups. (C) 2004 Wiley Periodicals, Inc.

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ab initio, bond dissociation energy (BDE), DFT, electron affinity, peroxyl radicals

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Last updated on 2018-05-11 at 14:53