Understanding chemistry with thesymmetry‐decomposed Voronoideformation density charge analysis

Abstract

The symmetry‐decomposed Voronoi deformation density (VDD) charge analysis is an insightful and robust computational tool to aid the understanding of chemical bonding throughout all fields of chemistry. This method quantifies the atomic charge flow associated with chemical‐bond formation and enables decomposition of this charge flow into contributions of (1) orbital interaction types, that is, Pauli repulsive or bonding orbital interactions; (2) per irreducible representation (irrep) of any point‐group symmetry of interacting closed‐shell molecular fragments; and now also (3) interacting open‐shell (i.e., radical) molecular fragments. The symmetry‐decomposed VDD charge analysis augments the symmetry‐decomposed energy decomposition analysis (EDA) so that the charge flow associated with Pauli repulsion and orbital interactions can be quantified both per atom and per irrep, for example, for σ, π, and δ electrons. This provides detailed insights into fundamental aspects of chemical bonding that are not accessible from EDA.

Multiple Bonding in AeN− (Ae=Ca, Sr, Ba)

“…[32] The NBO atomic partial charges and Wiberg bond orders (WBO) were computed using the natural bonding orbital (NBO7) program. [33] We also calculated atomic partial charges using the CM5, [34] Voronoi, [35] and Hirshfeld [36] methods and the Mayer bond orders. [37,38] The multireference calculations were done using the MOLPRO program package, [39] whereas all the other calculations mentioned above were performed by the Gaussian 16 package.…”