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

Abstract

Abstract 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 sp 3 -, sp 2 - 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.