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

Physical Chemistry Chemical Physics, vol. 22, pp. 25892–25903

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.

Authors 2

1. Leonard Reuter Aachen Institute of Physical Chemistry

   RWTH Aachen University

   Affiliation as printed

   52074 Aachen

   Germany

   Institute of Physical Chemistry

   RWTH Aachen University

   Institute of Physical Chemistry, RWTH Aachen University, Landoltweg 2, 52074 Aachen, Germany

2. Arne Lüchow corresponding Aachen Institute of Physical Chemistry

   RWTH Aachen University

   Affiliation as printed

   52074 Aachen

   Germany

   Institute of Physical Chemistry

   RWTH Aachen University

   Institute of Physical Chemistry, RWTH Aachen University, Landoltweg 2, 52074 Aachen, Germany