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Density Functional Theory of Polar Insulators

X. Gonze, Ph. Ghosez, R. W. Godby

cond-mat.mtrl-sciarXiv:cond-mat/9611234

Abstract

We examine the density-functional theory of macroscopic insulators, obtained in the large-cluster limit or under periodic boundary conditions. For polar crystals, we find that the two procedures are not equivalent. In a large-cluster case, the exact exchange-correlation potential acquires a homogeneous ``electric field'' which is absent from the usual local approximations, and the Kohn-Sham electronic system becomes metallic. With periodic boundary conditions, such a field is forbidden, and the polarization deduced from Kohn-Sham wavefunctions is incorrect even if the exact functional is used.

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