Decoding the Chemical Bond—On the Connection between Probability Density Analysis, QTAIM, and VB Theory

Classification of bonds is essential for understanding and predicting the reactivity of chemical compounds. This classification mainly manifests in the bond order and the contribution of different Lewis resonance structures. Here, we outline a first principles approach to obtain these orders and contributions for arbitrary wave functions in a manner that is both, related to the quantum theory of atoms in molecules and consistent with valence bond theory insight: the Lewis structures arise naturally as attractors of the all-electron probability density |Ψ|². Doing so, we introduce valence bond weight definitions that do not collapse in the basis set limit.