The heats of formation of haloacetylenes are evaluated using the recent W1
and W2 ab initio computational thermochemistry methods. These calculations
involve CCSD and CCSD(T) coupled cluster methods, basis sets of up to spdfgh
quality, extrapolations to the one-particle basis set limit, and contributions
of inner-shell correlation, scalar relativistic effects, and (where relevant)
first-order spin-orbit coupling. The heats of formation determined using W2
theory are: \hof(HCCH) = 54.48 kcal/mol, \hof(HCCF) = 25.15 kcal/mol,
\hof(FCCF) = 1.38 kcal/mol, \hof(HCCCl) = 54.83 kcal/mol, \hof(ClCCCl) = 56.21
kcal/mol, and \hof(FCCCl) = 28.47 kcal/mol. Enthalpies of hydrogenation and
destabilization energies relative to acetylene were obtained at the W1 level of
theory. So doing we find the following destabilization order for acetylenes:
FCCF > ClCCF > HCCF > ClCCCl > HCCCl > HCCH. By a combination of W1
theory and isodesmic reactions, we show that the generally accepted heat of
formation of 1,2-dichloroethane should be revised to -31.8±0.6 kcal/mol, in
excellent agreement with a very recent critically evaluated review. The
performance of compound thermochemistry schemes such as G2, G3, G3X and CBS-QB3
theories has been analyzed.Comment: Mol. Phys., in press (E. R. Davidson issue