Ab initio and density functional theory study of the enthalpies of formation of F2SOx and FClSOx (x=1, 2).

MARIA EUGENIA TUCCERI; BADENES, M. P.; COBOS, C. J.

Journal of Fluorine Chemistry

Año: 2002 vol. 116 p. 135 - 141

0022-1139

Enthalpies of formation of F2SO, F2SO2, FClSO and FClSO2 molecules have been determined using ab initio molecular orbital theory and density functional theory (DFT) calculations. Different DFT approaches and levels of the Gaussian-3 and the complete basis set (CBS) ab initio model chemistries have been employed to calculate enthalpies of formation from both total atomization energies and isodesmic reaction schemes. The best values at 298 K for F2SO, F2SO2, FClSO and FClSO2 as derived from an average of G3, G3B3, CBS-Q and CBS-QB3 isodesmic energies are −140.6, −181.1, −92.6 and −132.3 kcal mol−1, respectively. The results obtained suggest that the accumulated small component errors found in the DFT-based methods are significantly reduced at the ab initio levels employed. Structural properties, harmonic vibrational frequencies, mode assignations and infrared intensities derived from B3LYP and mPW1PW91 functional with the 6-311+G(3df) basis set are presented.