Molecular symmetry and closed‐shell SCF calculations. I

Michel Dupuis, Harry F. King

Research output: Contribution to journalArticle

164 Citations (Scopus)

Abstract

For efficient integral evaluation, orbital basis functions are grouped into shells and integrals into blocks in the recently developed SCF program Hondo. This shell structure is ideally suited to the scheme of Dacre and Elder for using point group symmetry. An entire block of two‐electron integrals is eliminated if it is symmetrically equivalent to another block with a higher index (four label). Using the “petite list” of blocks of integrals, a skeleton Fock matrix is formed from which the true Fock matrix is generated by “symmetrization.” We prove two theorems which provide a clear and rigorous justification for this version of the Dacre–Elder procedure. We compare SCF calculations on the phosphorus molecule using Td symmetry with those using various subgroups of Td. The number of integrals computed is found to be approximately inversely proportional to the order of the group. Integral evaluation time and SCF iteration time are each linear functions of the number of integrals. The computer spends a negligible amount of time in executing symmetry‐related code, and the human effort involved is little more than picking the appropriate Schönflies symbol for the molecule.

Original languageEnglish
Pages (from-to)613-625
Number of pages13
JournalInternational Journal of Quantum Chemistry
Volume11
Issue number4
DOIs
Publication statusPublished - 1977

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self consistent fields
Point groups
Molecules
Crystal symmetry
symmetry
Phosphorus
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evaluation
matrices
subgroups
musculoskeletal system
lists
iteration
phosphorus
molecules
theorems
orbitals

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

Molecular symmetry and closed‐shell SCF calculations. I. / Dupuis, Michel; King, Harry F.

In: International Journal of Quantum Chemistry, Vol. 11, No. 4, 1977, p. 613-625.

Research output: Contribution to journalArticle

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