Abstract
Symmetry methods employed in the ab initio polyatomic program HONDO are extended to the coupled perturbed Hartree–Fock (CPHF) formalism, a key step in the analytical computation of energy first derivatives for configuration interaction (CI) wavefunctions, and energy second derivatives for Hartree–Fock (HF) wavefunctions. One possible computational strategy is to construct Fock‐like matrices for each nuclear coordinate in which the one‐ and two‐electron integrals of the usual Fock matrix are replaced by the integral first derivatives. “Skeleton” matrices are constructed from the unique blocks of electron‐repulsion integral derivatives. The correct matrices are generated by applying a symmetrization operator. The analysis is valid for many wavefunctions, including closed‐ or open‐shell spin‐restricted and spin‐unrestricted HF wavefunctions. To illustrate the method, we compare the computer time required for setting up the coupled perturbed HF equations for eclipsed ethane using D3 h symmetry point group and various subgroups of D3 h. Computational times are roughly inversely proportional to the order of the point group.
| Original language | English |
|---|---|
| Pages (from-to) | 234-240 |
| Number of pages | 7 |
| Journal | Journal of Computational Chemistry |
| Volume | 4 |
| Issue number | 2 |
| DOIs | |
| Publication status | Published - 1983 |
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ASJC Scopus subject areas
- Chemistry(all)
- Computational Mathematics
Cite this
Molecular symmetry. IV. The coupled perturbed Hartree–Fock method. / Takada, Toshikazu; Dupuis, Michel; King, Harry F.
In: Journal of Computational Chemistry, Vol. 4, No. 2, 1983, p. 234-240.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Molecular symmetry. IV. The coupled perturbed Hartree–Fock method
AU - Takada, Toshikazu
AU - Dupuis, Michel
AU - King, Harry F.
PY - 1983
Y1 - 1983
N2 - Symmetry methods employed in the ab initio polyatomic program HONDO are extended to the coupled perturbed Hartree–Fock (CPHF) formalism, a key step in the analytical computation of energy first derivatives for configuration interaction (CI) wavefunctions, and energy second derivatives for Hartree–Fock (HF) wavefunctions. One possible computational strategy is to construct Fock‐like matrices for each nuclear coordinate in which the one‐ and two‐electron integrals of the usual Fock matrix are replaced by the integral first derivatives. “Skeleton” matrices are constructed from the unique blocks of electron‐repulsion integral derivatives. The correct matrices are generated by applying a symmetrization operator. The analysis is valid for many wavefunctions, including closed‐ or open‐shell spin‐restricted and spin‐unrestricted HF wavefunctions. To illustrate the method, we compare the computer time required for setting up the coupled perturbed HF equations for eclipsed ethane using D3 h symmetry point group and various subgroups of D3 h. Computational times are roughly inversely proportional to the order of the point group.
AB - Symmetry methods employed in the ab initio polyatomic program HONDO are extended to the coupled perturbed Hartree–Fock (CPHF) formalism, a key step in the analytical computation of energy first derivatives for configuration interaction (CI) wavefunctions, and energy second derivatives for Hartree–Fock (HF) wavefunctions. One possible computational strategy is to construct Fock‐like matrices for each nuclear coordinate in which the one‐ and two‐electron integrals of the usual Fock matrix are replaced by the integral first derivatives. “Skeleton” matrices are constructed from the unique blocks of electron‐repulsion integral derivatives. The correct matrices are generated by applying a symmetrization operator. The analysis is valid for many wavefunctions, including closed‐ or open‐shell spin‐restricted and spin‐unrestricted HF wavefunctions. To illustrate the method, we compare the computer time required for setting up the coupled perturbed HF equations for eclipsed ethane using D3 h symmetry point group and various subgroups of D3 h. Computational times are roughly inversely proportional to the order of the point group.
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U2 - 10.1002/jcc.540040214
DO - 10.1002/jcc.540040214
M3 - Article
AN - SCOPUS:84986469551
VL - 4
SP - 234
EP - 240
JO - Journal of Computational Chemistry
JF - Journal of Computational Chemistry
SN - 0192-8651
IS - 2
ER -