Quantum Monte Carlo investigations of density functional theory of the strongly inhomogeneous electron gas

Abstract

We use a variational quantum Monte Carlo realization of the adiabatic connection technique to calculate the most relevant quantities in Hohenberg-Kohn-Sham density functional theory for several strongly inhomogeneous electron-gas systems. Results for the coupling-constant dependence of the exchange-correlation energy, the pair-correlation function, the exchange-correlation hole, and the exchange and correlation energy densities are presented. Comparisons are made with the interaction strength interpolation ~ISI! approximation, the local density approximation ~LDA!, the gradient expansion approximation ~GEA!, the generalized gradient approximation ~GGA!, and the weighted density approximation ~WDA!. The coupling-constant dependence of the exchange-correlation energy is accurately described by an ISI model that incorporates information on the strong-interaction limit. Unlike either the LDA or GEA, the WDA is successful in describing the nonlocal structure of the exchange-correlation hole. The LDA errors in the exchange-correlation energy density show a remarkable correlation with the Laplacian of the density. The GGA worsens the error in the integrated exchange-correlation energy as the inhomogeneity of the systems increases. This failure is shared by current meta-GGA functionals and is shown to be caused by the inability of these functionals to describe the LDA overestimation ~in absolute value! of the exchange energy density around density maxima. It is suggested that this effect could be taken into account by including Laplacian terms in semilocal density functionals.