Non-orthogonal localized orbitals and orthogonal atomic hybrids derived from Mulliken's population analysis

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Abstract

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.

Original languageEnglish
Pages (from-to)499-506
Number of pages8
JournalChemical Physics Letters
Volume242
Issue number4-5
DOIs
Publication statusPublished - Aug 25 1995

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Molecular orbitals
orbitals
Atoms
molecular orbitals
atoms
orthogonality
self consistent fields
Molecules
molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Physics and Astronomy(all)

Cite this

Non-orthogonal localized orbitals and orthogonal atomic hybrids derived from Mulliken's population analysis. / Mayer, I.

In: Chemical Physics Letters, Vol. 242, No. 4-5, 25.08.1995, p. 499-506.

Research output: Contribution to journalArticle

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