Pauling resonant structures in real space through electron number probability distributions.

Abstract

A general hierarchical framework for coarse-grained electron probability distributions, derived from exhaustive partitions of physical space, is introduced. When space is divided into atomic regions, these distributions are argued to offer a foundation for an orbital-invariant description of resonant structures. The study further demonstrates that total molecular energy and its constituent components can be decomposed into individual structure contributions, extending the interacting quantum atoms approach (J. Chem. Theory Comput. 2005, 1, 1096). These concepts are applied to the hydrogen molecule, yielding a complete statistical and energetic decomposition into covalent and ionic contributions.

Mechanism

By partitioning physical space into atomic regions and analyzing electron number probability distributions, the molecular energy of the hydrogen molecule was decomposed into covalent and ionic structural contributions within an orbital-invariant framework.