Journal of Physical Chemistry A, Vol.102, No.45, 8988-9000, 1998
Sharing analysis of the behavior of electrons in some simple molecules
The behavior of the electrons in the simple hydrides of the first row of eight elements, LiH, BeH2, BH3, CH4, NH3, H2O, and HF, together with H-2 and the complex He-2, is described at the one-electron level within the conceptual framework provided by the sharing index I(zeta; zeta'), which gives a quantitative measure of the sharing of an electron between the two points zeta and zeta', and the underlying sharing amplitude [zeta; zeta']. With the exception of Hel bond indices, self-sharing indices, delocalization indices, volume-point sharing indices, and sharing amplitudes are determined for the set of molecules from results of MP2/6-31++G** calculations. The calculations involving He-2 use a different basis set. The trends in all of these indices track the differences in the traditional electronegativities of the elements. The uniqueness of the carbon-hydrogen bond in methane among all the bonds described in this paper is associated with the equal participation of carbon and hydrogen in the sharing of an electron between the volumes associated with the atoms. The shapes of the sharing amplitudes can be described using much of the traditional language of bonding, such as hybrid orbitals and (partial) valence bond structures, in spite of the calculations including effects due to the correlation of electrons. The difference between covalent bonding and nonbonding (or weak antibonding) is illustrated by consideration of the complex He-2 formed between two closed shell atoms.