, Volume 48, Issue 2, pp 127-141

Fourier representation method for electronic structures of linear polymers

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Abstract

The Fourier representation method described in the previous paper of this series is used to make electronic structure calculations for a linear chain of equally spaced hydrogen atoms. The electronic wavefunction is assumed to be a determinant of doubly-occupied crystal orbitals of modulated-plane-wave type, built from one 1s Slater-type orbital of screening parameter ζ centered on each atom. The energy is calculated from the electrostatic zero-order Hamiltonian with exact evaluation of all Coulomb and exchange contributions, and is optimized with respect to the lattice spacing and ζ value. Good agreement with work by others is noted, indicating a near-equivalence of modulated-plane-wave and tight-binding wavefunctions for this half-filled-valence-band system. The linear chain is calculated to be far more stable than cubic three-dimensional hydrogen crystals. This fact sheds light on the unusually large calculated nearest-neighbor distances in the cubic crystals, and is related to a suggestion that under certain conditions the most stable structure for solid atomic hydrogen may be of lower symmetry than cubic.

The previous paper of this series: Harris, F. E.: J. Chem. Phys.56, 4422 (1972) [1].
Chargé de Recherches du F.N.R.S. (Fonds National Belge de la Recherche Scientifique).