Non-orthogonal localized orbitals and orthogonal atomic hybrids derived from Mulliken's population analysis
✍ Scribed by I. Mayer
- Publisher
- Elsevier Science
- Year
- 1995
- Tongue
- English
- Weight
- 570 KB
- Volume
- 242
- Category
- Article
- ISSN
- 0009-2614
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✦ Synopsis
The construction of non-orthogonal localized molecular orbitals (Wannier functions of extended systems) with maximal degree of localization according to the Magnasco-Perico localization criterion derived from Mulliken's population analysis is discussed and several forms of the equations giving these orbitals are presented. A partial orthogonality property of these orbitals permits an easy determination of the effective orthogonal atomic orbitals characterizing the actual state of the atom in the molecule; this helps to find connections between large-scale ab initio SCF calculations and traditional atomic orbital concepts. Calculations indicate full agreement with the traditional AO picture: for all 'ordinary' compounds one gets as many molecular orbitals appreciably localized on the given atom as are contained in the classical 'minimal basis' for that atom.