Generalized gradient approximation correlation energy functionals based on the uniform electron gas with gap model

Abstract

We studied uniform electron gas with a gap model in the context of density functional theory. On the basis of this analysis, we constructed two local gap models that are used in generalized gradient approximation (GGA) correlation functionals that satisfy numerous exact constraints for correlation energy. The first one, named GAPc, fulfills the full second-order correlation gradient expansion at any density regime and is very accurate for jellium surfaces, comparable to state-of-the-art GGAs for atomic systems and molecular systems, and is well compatible with known semilocal exchanges. The second functional, named GAPloc, satisfies the same exact conditions, except that the second-order gradient expansion is sacrificed for a better behavior under the Thomas-Fermi scaling and a more realistic correlation energy density of the helium atom. The GAPloc functional displays a high accuracy for atomic correlation energies, still preserving a reasonable behavior for jellium surfaces. Moreover, it shows a higher compatibility with the Hartree-Fock exchange than other semilocal correlation functionals. This feature is explained in terms of the real-space analysis of the GAPloc correlation energy. © 2014 American Chemical Society.