Springer, Journal of Mathematical Chemistry, 10(51), p. 2687-2698, 2013
DOI: 10.1007/s10910-013-0230-z
Full text: Download
The criterion of maximum overlap with the canonical free-atom orbitals is used to construct a minimal set of molecule-intrinsic orthogonal atomic orbitals that resemble the most their promolecular origins. Partial atomic charges derived from population analysis within representation of such molecule-adopted atomic orbitals are examined on example of first-row hydrides and compared with charges from other methods. The maximum overlap criterion is also utilized to approximate the exact free-atom orbitals obtained from ab initio calculations in any arbitrary basis set and the influence of the resulting fitted canonical atomic orbitals on properties of molecule- adopted atomic orbitals is briefly discussed.