Localization-Delocalization Matrices and Electron Density-Weighted Adjacency/Connectivity Matrices: A Bridge Between the Quantum Theory of Atoms in Molecules and Chemical Graph Theory

Abstract

Chemical graph theory (CGT) starts by defining matrices that represent the molecular graph then proceed to extract numbering-independent matrix invariants to be used as molecular descriptors in empirical quantitative structure to activity (or property) relationships (QSAR/QSPR). Two proposed matrix representations of molecular structure are presented in this chapter as alternatives to simple connectivity molecular graphs. Firstly, it is proposed to use a more “nuanced” connectivity matrix by weighing the “ones” entered in a CGT molecular graph matrix by the bond critical point electron densities associated with each bond path to yield what we term the “electron density-weighted adjacency/connectivity matrices (EDWAM/EDWCM)”. In a second approach, it is proposed to use the localization and delocalization indices of the quantum theory of atoms in molecules (QTAIM) to construct a richer representation of the molecular graph, a “fuzzy” graph, whereby an edge exists between any two atoms (measured by the delocalization index between them) whether they share a bond path or not. Such a fuzzy graph is represented by what we term “electron localization-delocalization matrix (LDM)”. We show that the LDM representations of a series of molecules provide a powerful tool for robust QSAR/QSPR modeling.