Natural Bond Critical Point analysis: quantitative relationships between natural bond orbital-based and QTAIM-based...

We have developed a "Natural Bond Critical Point" (NBCP) module for the natural bond orbital (NBO) program that allows mutual analysis of NBO-based versus Bader-type quantum theory of atoms in molecules (QTAIM) topological descriptors of chemical bonding interactions. Conventional QTAIM bond path and bond critical point (BCP) descriptors deduced from total electron density ρ(r) can thereby be compared with analogous "natural" (NBCP) descriptors for idealized densities ρ(NAIM)(r) composed solely from NBO-based "natural atoms in molecules" (NAIM) at the terminal nuclei. Standard ρ(r(BCP)) and [nabla](2)ρ(r(BCP)) descriptors can also be decomposed into unique contributions from individual NBOs or other localized, semilocalized, or delocalized orbital components. These results allow one to recognize many relationships between QTAIM and NBO analyses, showing why close correlations are often found between NBO-based versus ρ(r(BCP))-based characterizations of chemical bonding interactions, despite strongly divergent conceptions of "the atom in the molecule."