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arXiv · 2002.06935

Relativistic short-range exchange energy functionals beyond the local-density approximation

Julien Paquier·Emmanuel Giner·Julien Toulouse
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Abstract

We develop relativistic short-range exchange energy functionals for four-component relativistic range-separated density-functional theory using a Dirac-Coulomb Hamiltonian in the no-pair approximation. We show how to improve the short-range local-density approximation exchange functional for large range-separation parameters by using the on-top exchange pair density as a new variable. We also develop a relativistic short-range generalized-gradient approximation exchange functional which further increases the accuracy for small range-separation parameters. Tests on the helium, beryllium, neon, and argon isoelectronic series up to high nuclear charges show that this latter functional gives exchange energies with a maximal relative percentage error of 3 %. The development of this exchange functional represents a step forward for the application of four-component relativistic range-separated density-functional theory to chemical compounds with heavy elements.

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Julien Paquier, Emmanuel Giner, Julien Toulouse. 2020-02-17. Relativistic short-range exchange energy functionals beyond the local-density approximation. https://doi.org/10.1063/5.0004926

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