The Bond Energy of the Carbon Skeleton in Polyaromatic Halohydrocarbon Molecules

We have investigated the thermochemical stability of the carbon skeleton in polycyclic aromatic (halo) hydrocarbons using a systematic collection of molecules (the PAHH343 set). With high-level quantum chemistry methods such as W1X-2, we have obtained chemically accurate (i. e.,±~5 kJmol^-1 ) “normalized carbon skeleton” bond energies. They are calculated by removing the C H and C X (X=F, Cl) bond energies from the total atomization energy, and then normalizing on a per-carbon basis. For species with isomeric halogen-substitution pattern, the energetic variation is generally small, though larger difference can also be seen due to structural distortion from steric repulsion. The skeleton energy becomes smaller with an increasing number of halogen atoms due to the withdrawal of electron density from the bonding orbitals, mainly through the σ-bonds. We have further assessed the performance of some low-cost quantum chemistry methods for the PAHH343 set. The deviations from reference values are largely systematic, and can thus be compensated for, yielding errors that are on average below 10 kJmol^-1. This provides the prospect for the study of an even wider range of PAHH and related systems.