Ab Initio Computations in Atoms and Molecules

TLDR

The Roothaan–Hartree–Fock method has been detailed for atomic systems. This paper reviews the current state of ab initio computations for atomic and molecular wave functions, highlights IBM Research work, and proposes extensions of the self‑consistent field technique to macromolecules. The authors provide a systematic tabulation of atomic Hartree–Fock functions and discuss techniques for computing many‑center two‑electron matrix elements using Slater or Gaussian basis sets, while also suggesting extensions of the self‑consistent field method to macromolecules. The tabulated Hartree–Fock functions and matrix‑element techniques are made available in an extended supplement; the two basis‑set approaches are found to be comparable in efficiency, though the proposed macromolecular extensions remain untested.

Abstract

The present status of ab initio computations for atomic and molecular wave functions is analyzed in this paper, with special emphasis on the work done at the IBM Research Laboratory, San Jose. The Roothaan-Hartree-Fock method has been described in detail for atomic systems. A systematic tabulation of atomic Hartree-Fock functions has been made available in an extended supplement to this paper.† Techniques for computing many-center, two-electron matrix elements have been discussed for Slater or Gaussian basis sets. It is concluded that the two possibilities are comparable in efficiency. We have advanced a few suggestions for the extension of the self-consistent field technique to macromolecules. The validity of the suggestions have not been tested.