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Meta-local density functionals: a new rung on Jacobs ladder

Authors: S. Lehtola, and M.A.L. Marques

Ref.: J. Chem. Theor. Comput. 17, 943-948 (2021)

Abstract: The homogeneous electron gas (HEG) is a key ingredient in the construction of most exchange-correlation functionals of density-functional theory. Often, the energy of the HEG is parameterized as a function of its spin density, leading to the local density approximation (LDA) for inhomogeneous systems. However, the connection between the electron density and kinetic energy density of the HEG can be used to generalize the LDA by evaluating it on a geometric average of the local spin density and the spin density of a HEG that has the local kinetic energy density of the inhomogeneous system. This leads to a new family of functionals that we term meta-local density approximations (meta-LDAs), which are still exact for the HEG, which are derived only from properties of the HEG, and which form a new rung of Jacobs ladder of density functionals [AIP Conf. Proc. 577, 1 (2001)]. The first functional of this ladder, the local-tau approximation (LTA) of Ernzerhof and Scuseria [J. Chem. Phys. 111, 911 (1999)] that corresponds to x=1 is unfortunately not stable enough to be used in self-consistent field calculations, because it leads to divergent potentials as we show in this work. However, a geometric averaging of the LDA and LTA densities with smaller values of x not only leads to numerical stability of the resulting functional, but also yields more accurate exchange energies in atomic calculations than the LDA, the LTA, or the tLDA functional ($x=1/4$) of Eich and Hellgren [J. Chem. Phys. 141, 224107 (2014)]. We choose x=0.50 as it gives the best total energy in self-consistent exchange-only calculations for the argon atom. Atomization energy benchmarks confirm that the choice x=0.50 also yields improved energetics in combination with correlation functionals in molecules, almost eliminating the well-known overbinding of the LDA and reducing its error by two thirds.

Citations: 0 (Google scholar)

DOI: 10.1021/acs.jctc.0c01147


	doi = {10.1021/acs.jctc.0c01147},
	url = {https://doi.org/10.1021%2Facs.jctc.0c01147},
	year = 2021,
	month = {jan},
	publisher = {American Chemical Society ({ACS})},
	volume = {17},
	number = {2},
	pages = {943--948},
	author = {Susi Lehtola and Miguel A. L. Marques},
	title = {Meta-Local Density Functionals: A New Rung on Jacob's Ladder},
	journal = {Journal of Chemical Theory and Computation}