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Titolo:
Fluorofluoroxydioxirane and other CF2O3 isomers
Autore:
Song, J; Khait, YG; Hoffmann, MR;
Indirizzi:
Univ N Dakota, Dept Chem, Grand Forks, ND 58202 USA Univ N Dakota Grand Forks ND USA 58202 pt Chem, Grand Forks, ND 58202 USA
Titolo Testata:
JOURNAL OF PHYSICAL CHEMISTRY A
fascicolo: 4, volume: 105, anno: 2001,
pagine: 779 - 790
SICI:
1089-5639(20010201)105:4<779:FAOCI>2.0.ZU;2-P
Fonte:
ISI
Lingua:
ENG
Soggetto:
QUADRATIC CONFIGURATION-INTERACTION; CARBONYL OXIDE; ELECTRONIC-STRUCTURE; FLUOROFORMYL HYPOFLUORITE; VIBRATIONAL-SPECTRA; TRIPLE EXCITATIONS; ENERGY GRADIENTS; AB-INITIO; DIFLUORODIOXIRANE; DIOXIRANES;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
52
Recensione:
Indirizzi per estratti:
Indirizzo: Hoffmann, MR Univ N Dakota, Dept Chem, Grand Forks, ND 58202 USA Univ N Dakota Grand Forks ND USA 58202 d Forks, ND 58202 USA
Citazione:
J. Song et al., "Fluorofluoroxydioxirane and other CF2O3 isomers", J PHYS CH A, 105(4), 2001, pp. 779-790

Abstract

Seven structural isomers, and relevant transition states, on the lowest-energy spin-singlet potential energy surface of CF2O3 are characterized usingcorrelated ab initio electronic structure methods. On the basis of preliminary comparative calculations, second-order Moller-Plesset perturbation theory with a correlation-consistent polarized valence double-zeta one-electron basis set (MP2/cc-pVDZ) was chosen with which to describe equilibrium structures and harmonic vibrational frequencies of all relevant rotamers. Accurate energy differences were determined using the coupled cluster method, with perturbative inclusion of triple excitations, and a valence triple-zetabasis (CCSD(T)/cc-pVTZ). The lowest energy isomer is predicted to be the molozonide of difluorocarbene, whose adiabatic decay is prevented by a sizable barrier. Plausible mechanisms for the isomerization of the titled compound to the low-energy fluoroformyl peroxyhypofluorite and nearly isenergeticcarbonyl hypofluorite are suggested. An analogous reaction path may be of importance to the isomerization of difluorodioxirane (CF2O2) and is included in the study.

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Documento generato il 31/03/20 alle ore 18:41:06