Maximal orbital analysis of molecular wavefunctions

Michel Dupuis, Meghana Nallapu

Research output: Contribution to journalArticlepeer-review


We describe a new way to decompose one-electron orbitals of a molecule into atom-centered or fragment-centered orbitals by an approach that we call “maximal orbital analysis” (MOA). The MOA analysis is based on the corresponding orbital transformation (COT) that has the unique mathematical property of maximizing any sub-trace of the overlap matrix, in Hilbert metric sense, between two sets of nonorthogonal orbitals. Here, one set comprises the molecule orbitals (Hartree–Fock, Kohn–Sham, complete-active-space, or any set of orthonormal molecular orbitals), the other set comprises the basis functions associated with an atom or a group of atoms. We show in prototypical molecular systems such as a water dimer, metal carbonyl complexes, and a mixed-valent transition metal complex, that the MOA orbitals capture very well key aspects of wavefunctions and the ensuing chemical concepts that govern electronic interactions in molecules.

Original languageEnglish
Pages (from-to)39-50
Number of pages12
JournalJournal of Computational Chemistry
Issue number1
Publication statusPublished - Jan 5 2019


  • corresponding orbital transformation
  • decomposition
  • fragment orbitals
  • molecular wavefunction

ASJC Scopus subject areas

  • Chemistry(all)
  • Computational Mathematics

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