Abstract
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 language | English |
|---|---|
| Journal | Journal of Computational Chemistry |
| DOIs | |
| Publication status | Accepted/In press - Jan 1 2018 |
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Keywords
- corresponding orbital transformation
- decomposition
- fragment orbitals
- molecular wavefunction
ASJC Scopus subject areas
- Chemistry(all)
- Computational Mathematics
Cite this
Maximal orbital analysis of molecular wavefunctions. / Dupuis, Michel; Nallapu, Meghana.
In: Journal of Computational Chemistry, 01.01.2018.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Maximal orbital analysis of molecular wavefunctions
AU - Dupuis, Michel
AU - Nallapu, Meghana
PY - 2018/1/1
Y1 - 2018/1/1
N2 - 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.
AB - 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.
KW - corresponding orbital transformation
KW - decomposition
KW - fragment orbitals
KW - molecular wavefunction
UR - http://www.scopus.com/inward/record.url?scp=85053707767&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85053707767&partnerID=8YFLogxK
U2 - 10.1002/jcc.25385
DO - 10.1002/jcc.25385
M3 - Article
JO - Journal of Computational Chemistry
JF - Journal of Computational Chemistry
SN - 0192-8651
ER -