Analytical second derivatives in ab initio Hartree-Fock crystal orbital theory of polymers

So Hirata, Suehiro Iwata

Research output: Contribution to journalArticle

Abstract

In the framework of ab initio Hartree-Fock crystal orbital theory of polymers, the formulas for the analytical second derivatives of energy with respect to in-phase (k = 0) nuclear coordinates are derived. The coupled perturbed Hartree-Fock (CPHF) equation is iteratively solved by using the direct (recomputation of two-electron integrals) atomic-orbital-based algorithm. Frequencies of the Brillouin zone center (k = 0) vibrations of all-trans polyethylene are calculated by using the STO-3G, 3-21G and 6-31G* basis sets. The dependence of the frequencies on the number of neighbors included in the lattice summations, on the number of momentum sampling points in the first Brillouin zone, and on the convergence criterion for the CPHF solutions is examined. In our implementation, the use of analytical second derivatives is more efficient than the use of the finite differences of analytical first derivatives.

Original languageEnglish (US)
Pages (from-to)121-134
Number of pages14
JournalJournal of Molecular Structure: THEOCHEM
Volume451
Issue number1-2
DOIs
StatePublished - Sep 28 1998

Keywords

  • Ab initio Hartree-Fock crystal orbital theory
  • All-trans polyethylene
  • Analytical second derivative method
  • Harmonic vibrational frequencies

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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