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American Institute of Physics, The Journal of Chemical Physics, 22(141), p. 224107

DOI: 10.1063/1.4903273

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Derivative discontinuity and exchange-correlation potential of meta-GGAs in density-functional theory

Journal article published in 2014 by F. G. Eich, Maria Hellgren ORCID
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

We investigate fundamental properties of meta-generalized-gradient approximations (meta-GGAs) to the exchange-correlation energy functional, which have an implicit density dependence via the Kohn-Sham kinetic-energy density. To this purpose, we construct the most simple meta-GGA by expressing the local exchange-correlation energy per particle as a function of a fictitious density, which is obtained by inverting the Thomas-Fermi kinetic-energy functional. This simple functional considerably improves the total energy of atoms as compared to the standard local density approximation. The corresponding exchange-correlation potentials are then determined exactly through a solution of the optimized effective potential equation. These potentials support an additional bound state and exhibit a derivative discontinuity at integer particle numbers. We further demonstrate that through the kinetic-energy density any meta-GGA incorporates a derivative discontinuity. However, we also find that for commonly used meta-GGAs the discontinuity is largely underestimated and in some cases even negative. ; Comment: 10 pages, 3 figures, 3 tables