Abstract
Covalent bond dissociation is examined by three geminal-based theories. One approach (antisymmetrised product of strongly orthogonal geminals) assumes purely singlet geminals, while two others operate with mixtures of singlets and triplets (cf. restricted-unrestricted strongly orthogonal singlet-type geminals, hereafter RUSSG). The RUSSG is the wavefunction in the second method. It is spin contaminated. The spin contamination of RUSSG is projected out in a spin-purification step in the third method. Description of local (i.e. atomic) spin by geminal-based theories is examined. Prototype systems showing the deficiency of singlet coupling are taken as test cases. We find that the local spin of equilibrium structures is correctly described by purely singlet geminals. Triplet geminals are shown to be essential for the description of local spin when dissociating multiple bonds, or switching between two Lewis structures of the same molecule.
| Original language | English |
|---|---|
| Pages (from-to) | 249-259 |
| Number of pages | 11 |
| Journal | Molecular Physics |
| Volume | 113 |
| Issue number | 3-4 |
| DOIs | |
| Publication status | Published - febr. 16 2015 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Condensed Matter Physics
- Biophysics
- Molecular Biology
Cite this
Local spin from strongly orthogonal geminal wavefunctions. / Jeszenszki, Péter; Rassolov, Vitaly; Surján, P.; Szabados, A.
In: Molecular Physics, Vol. 113, No. 3-4, 16.02.2015, p. 249-259.Research output: Article
}
TY - JOUR
T1 - Local spin from strongly orthogonal geminal wavefunctions
AU - Jeszenszki, Péter
AU - Rassolov, Vitaly
AU - Surján, P.
AU - Szabados, A.
PY - 2015/2/16
Y1 - 2015/2/16
N2 - Covalent bond dissociation is examined by three geminal-based theories. One approach (antisymmetrised product of strongly orthogonal geminals) assumes purely singlet geminals, while two others operate with mixtures of singlets and triplets (cf. restricted-unrestricted strongly orthogonal singlet-type geminals, hereafter RUSSG). The RUSSG is the wavefunction in the second method. It is spin contaminated. The spin contamination of RUSSG is projected out in a spin-purification step in the third method. Description of local (i.e. atomic) spin by geminal-based theories is examined. Prototype systems showing the deficiency of singlet coupling are taken as test cases. We find that the local spin of equilibrium structures is correctly described by purely singlet geminals. Triplet geminals are shown to be essential for the description of local spin when dissociating multiple bonds, or switching between two Lewis structures of the same molecule.
AB - Covalent bond dissociation is examined by three geminal-based theories. One approach (antisymmetrised product of strongly orthogonal geminals) assumes purely singlet geminals, while two others operate with mixtures of singlets and triplets (cf. restricted-unrestricted strongly orthogonal singlet-type geminals, hereafter RUSSG). The RUSSG is the wavefunction in the second method. It is spin contaminated. The spin contamination of RUSSG is projected out in a spin-purification step in the third method. Description of local (i.e. atomic) spin by geminal-based theories is examined. Prototype systems showing the deficiency of singlet coupling are taken as test cases. We find that the local spin of equilibrium structures is correctly described by purely singlet geminals. Triplet geminals are shown to be essential for the description of local spin when dissociating multiple bonds, or switching between two Lewis structures of the same molecule.
KW - geminal
KW - local spin
KW - singlet coupling
KW - spin unrestricted
KW - strong orthogonality
UR - http://www.scopus.com/inward/record.url?scp=84921895309&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84921895309&partnerID=8YFLogxK
U2 - 10.1080/00268976.2014.936919
DO - 10.1080/00268976.2014.936919
M3 - Article
AN - SCOPUS:84921895309
VL - 113
SP - 249
EP - 259
JO - Molecular Physics
JF - Molecular Physics
SN - 0026-8976
IS - 3-4
ER -