Application of a general self-consistency scheme in the linear combination of atomic orbitals formalism to the electronic and structural properties of Si and W

Abstract

We present a general self-consistency procedure formulated in momentum space for electronic structure and total-energy calculations of crystalline solids. It is shown that both the charge density and the change in the Hamiltonian matrix elements in each iteration can be calculated in a straight-forward fashion once a set of overlap matrices is computed. The present formulation has the merit of bringing the self-consistency problem for different basis sets to the same footing. The scheme is used to extend a first-principles pseudopotential linear combination of Gaussian orbitals method to full point-by-point self-consistency, without refitting of potentials. It is shown that the set of overlap matrices can be calculated very efficiently if we exploit the translational and space-group symmetries of the system under consideration. This scheme has been applied to study the structural and electronic properties of Si and W, prototypical systems of very different bonding properties. The results agree well with experiment and other calculations. The fully self-consistent results are compared with those obtained by a variational procedure [J. R. Chelikowsky and S. G. Louie, Phys. Rev. B 29, 3470 (1984)]. We find that the structural properties for bulk Si and W (both systems have no interatomic charge transfer) can be treated accurately by the variational procedure. However, full self-consistency is needed for an accurate description of the band energies.