Origin of Hydrocarbons Stability from a Computational Perspective: A Case Study of Ortho-Xylene Isomers

It is shown herein that intuitive and text-book steric-clash based interpretation of the higher energy in-in xylene isomer (as arising solely from the repulsive CH....HC contact) with respect to the corresponding global-minimum out-out configuration (where the clashing C-H bonds are tilted out) is misleading. It is demonstrated that the two hydrogen atoms engaged in the CH...HC contact in in-in are involved in attractive interaction so they cannot explain the lower stability of this isomer. We have proven, based on the arsenal of modern bonding descriptors (EDDB, HOMA, NICS, FALDI, ETS-NOCV, DAFH, FAMSEC, IQA), that in order to understand the relative stability of in-in versus out-out xylenes isomers one must consider the changes in the electronic structure encompassing the entire molecules as arising from the cooperative action of hyperconjugation, aromaticity and unintuitive London dispersion plus charge delocalization based intra-molecular CH.....HC interactions.