Decoding real space bonding descriptors in valence bond language

Abstract

Real space bonding descriptors are orbital invariant indices that can be obtained independently of the theoretical framework used to compute a given wavefunction. Here we show how to use them to read in real space some widely used concepts in Valence Bond (VB) theory, such as ionic/covalent characters or covalent-ionic resonance energies. All of these are essential ingredients used when building VB chemical insight. Electron number distribution functions are employed to directly map ionic and covalent weights with real space delocalization indices. We show that covalency, understood as delocalization, emerges in position space from the fluctuation of electron populations. This is mapped in VB to covalent-ionic resonance. The reasons why this is not so in the standard language of non-orthogonal VB are examined. A simple real space ionic character index that maintains the essence of its VB equivalent is defined and examined in simple model systems. The conclusions of this work ease travelling among the sometimes conflicting molecular orbital, real space, and valence bond interpretations in chemical bonding theory.