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Phys Rev Lett. 2008 Apr 11;100(14):146401. Epub 2008 Apr 7.

Localization and delocalization errors in density functional theory and implications for band-gap prediction.

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Department of Chemistry, Duke University, Durham, North Carolina 27708, USA.


The band-gap problem and other systematic failures of approximate exchange-correlation functionals are explained from an analysis of total energy for fractional charges. The deviation from the correct intrinsic linear behavior in finite systems leads to delocalization and localization errors in large and bulk systems. Functionals whose energy is convex for fractional charges such as the local density approximation display an incorrect apparent linearity in the bulk limit, due to the delocalization error. Concave functionals also have an incorrect apparent linearity in the bulk calculation, due to the localization error and imposed symmetry. This resolves an apparent paradox and identifies the physical nature of the error to be addressed to obtain accurate band gaps from density functional theory.

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