Abstract
A new computer realization of the LCAO Hartree—Fock crystal orbital method using contracted Gaussian orbitals is reported. All integrals over the atomic orbitals are calculated explicitly within a finite interaction range. No approximation with respect to exchange is used. The spin-unrestricted Hartree—Fock-type crystal orbital formalism has been programmed, too. Both programs are limited to quasi one-dimensional systems at present, provide nevertheless a useful tool for the theoretical investigation of the electronic structure of simple polymers and one-dimensional models of solids. Basic information on both programs is documented.
Some numerical aspects, especially the convergency properties of the methods with respect to the number of grid points in the Brillouin zone, the shape of the Fermi surface in the special case of partly filled bands, the starting density matrices in the self-consistent field iteration procedure and the size of the finite interaction range taken into account are discussed. The specific problem of the starting density matrices in the unrestricted HF case are also dealt with. Finally comparison is made with semi-empirical calculations.
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This work was partly performed at the Structural Chemistry Department, B. Kidric Chemical Institute, University of Ljubljana, and supported by the Kidric Fund (Yugoslavia).
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Kertész, M. On the AB initio crystal orbital method. Acta Physica 41, 107–123 (1976). https://doi.org/10.1007/BF03157511
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DOI: https://doi.org/10.1007/BF03157511