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On the connection between probability density analysis, QTAIM, and VB theory†
Leonard Reuter,Arne Lüchow
Physical Chemistry Chemical Physics Pub Date : 11/02/2020 00:00:00 , DOI:10.1039/D0CP02209H
Abstract

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 a valence bond weight definition that does not collapse in the basis set limit.

Graphical abstract: On the connection between probability density analysis, QTAIM, and VB theory
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