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Anales de la Asociación Química Argentina
Print version ISSN 0365-0375
Abstract
ERBEN, M. F. and DELLA VEDOVA, C. O.. O-O bond dissociation enthalpy in perfluoromethyl fluorocarbonyl peroxide, CF3OOC(O)F. A density functional quantum chemical analysis. An. Asoc. Quím. Argent. [online]. 2004, vol.92, n.1-3, pp.133-138. ISSN 0365-0375.
Density functional at the B3LYP levels of theory using the Pople's 6-311+G(3df) basis sets and the Dunning's aug-cc-pVTZ correlation consistent basis sets have been employed to determine the enthalpy of formation ΔHf0(298)) of CF3OOC(O)F at 298 K, using the isodesmic reaction CF3OOCF3 + FC(O)OOC(O)F → 2 CF3OOC(O)F. Thus, the B3LYP/6-311+G(3df) and B3LYP/aug-cc-pVTZ methods yield ΔHf0(298) values of -273.3 and -273.2 kcal mol-1, respectively. From the reported ΔHf0(298) for CF3O· and FC(O)O· radicals, bond energy dissociation (DO-O) values of 38.3 and 38.2 kcal mol-1 are deduced for CF3OOC(O)F, which are in agreement with the reported value for related peroxides. Also, calculations for the enthalpy change in the peroxide bond excision reaction were performed at the B3LYP and B3PW91 using several basis sets. The corresponding DO-O values obtained using these enthalpy changes are too low independently of both basis sets and method of calculation used for the calculation.