A dataset of homolytic C-Cl bond dissociation energies obtained by means of W1w theory

We herein report a dataset of 28 homolytic C-Cl bond dissociation energies (BDEs) (to be known as the CCl28 dataset), obtained using the benchmark-quality W1w thermochemical protocol. This set contains chlorinated organic molecules that consist of either sp3-, sp2- or sp-hybridized C-Cl bonds. The species in this set have C-Cl BDEs (at 298 K) that differ by as much as 168.4 kJ mol-1, with allyl chloride having the lowest BDE (291.7 kJ mol-1) and 1-chloroprop-1-yne having the largest (460.1 kJ mol-1). Given the benchmark quality of the CCl28 dataset, it may serve as a useful reference for assessing the performance of more approximate quantum chemical methods, such as density functional theory (DFT) and double-hybrid DFT methods.