High Accuracy Quantum Chemical and Thermochemical Network Data for the Heats of Formation of Fluorinated and Chlorinated Methanes and Ethanes

Reliable heats of
formation are reported for numerous fluorinated
and chlorinated methane and ethane derivatives by means of an accurate
thermochemical protocol, which involves explicitly correlated coupled-cluster
calculations augmented with anharmonic, scalar relativistic, and diagonal
Born–Oppenheimer corrections. The theoretical results, along
with additional experimental data, are further enhanced with the help
of the thermochemical network approach. For 28 species, out of 50,
this study presents the best estimates, and discrepancies with previous
reports are also highlighted. Furthermore, the effects of the less
accurate theoretical data on the results yielded by thermochemical
networks are discussed.