The heats of formation of the haloacetylenes XCCY [X, Y = H, F, Cl]: basis set limit ab initio results and thermochemical analysis

Abstract

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: δH₁ ²⁹⁸(HCCH) = 54.48 kcal mol⁻¹, δH_f ²⁹⁸(HCCH) = 25.15 kcal mol, δH_f ²⁹⁸(FCCF) = 1.38 kcal mol⁻¹, δH_f ²⁹⁸(HCCC1) = 54.83 kcal mol⁻¹, δH_f ²⁹⁸(CICCC1) = 56.21 kcal mol⁻¹, and δH_f ²⁹⁸(FCCC1) = 28.47 kcal mo1⁻¹. Enthalpies of hydrogenation and destabilization energies relative to acetylene were obtained at the WI level of theory. So doing we find the following destabilization order for acetylenes: FCCF > ClCCF > HCCF > ClCCCl > HCCCI > HCCH. By a combination of WI 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⁻¹, 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 analysed.