Enthalpies of formation for organosulfur compounds: Atomization energy and hypohomodesmotic reaction schemes via ab initio composite methods

Abstract

Hypohomodesmotic reaction schemes, as described by Wheeler et al. [J. Am. Chem. Soc. 131 (2009) 2547] for the determination of enthalpies of formation (ΔHf,298) for hydrocarbons, have been extended to include sulfur. The impact of hypohomodesmotic schemes, in comparison to the atomization energy approach, upon the determination of enthalpies of formation for organosulfur compounds has been assessed. The gas phase ΔHf,298 of 43 organosulfur compounds have been calculated using the correlation consistent Composite Approach (ccCA), Gaussian-3 (G3), and Gaussian-4 (G4) methodologies using proposed hypohomodesmotic reaction mechanisms and an atomization energy approach. Effects of method and basis set combinations for these schemes have also been assessed.