Density-gradient-free variable in exchange-correlation functionals for detecting inhomogeneities in the electron density

Abstract

An alternative type of approximation for the exchange and correlation functional in density functional theory is proposed. This approximation depends on a variable $u$ that is able to detect inhomogeneities in the electron density $\rho$ without using derivatives of $\rho$. Instead, $u$ depends on the orbital energies which can also be used to measure how a system differs from the homogeneous electron gas. Starting from the functional of Perdew, Burke, and Ernzerhof (PBE) [Phys. Rev. Lett. 77, 3865 (1996)], a functional depending on $u$ is constructed. Tests on the lattice constant, bulk modulus, and cohesive energy of solids show that this $u$-dependent PBE-like functional is on average as accurate as the original PBE or its solid-state version PBEsol. Since $u$ carries more nonlocality than the reduced density gradient $s$ used in functionals of the generalized gradient approximation (GGA) like PBE and $\alpha$ used in meta-GGAs, it will be certainly useful for the future development of more accurate exchange-correlation functionals.