Anatomy of bond formation. Bond length dependence of the extent of electron sharing in chemical bonds from the analysis of domain-averaged Fermi holes

Abstract

We demonstrate that domain-average Fermi hole (DAFH) analysis, which has previously been used at the Hartree–Fock level, remains useful after the proper introduction of electron correlation. We perform a systematic investigation of the variation of the picture of bonding with increasing bond length in simple diatomic molecules such as N₂ and LiH. Alongside values of a shared-electron distribution index (SEDI), this analysis provides further insight into the geometry dependence of the extent of electron sharing in polar and non-polar systems. We also use DAFH analysis, with correlated wave functions, to evaluate the (potential) multicentre bonding in the electron-deficient and electron-rich molecules CH₂Li₂ and CH₂N₂, respectively.