CH4, an ab initio story of an archetypal species

Abstract

The methane molecule is an archetypal species in the whole of chemistry for its ability to form four bonds that result in a myriad of compounds of chemical and biological importance. The hybrid orbitals involved in the bonding have been scrutinized for too many decades but only lately under the ab initio microscope. In this study, we detail the formation routes CH n + (4 − n) H → CH4 ( n = 0, 1, and 2) both diabatically and adiabatically with the help of established computational techniques. The evolution of the Mulliken populations, of the non-adiabatic matrix coupling elements, and of the Kotani spin functions along the dissociation paths and finally the shape of the diabatic curves unambiguously point to a parental C atom of an excited 2 s12 p3 electronic configuration.