Convexity and translational invariance constraint on the exchange-correlation functional

TL;DR

This paper investigates the properties of the exchange-correlation functional in density functional theory, deriving a convexity and translational invariance constraint, and shows that common approximations like LDA violate this inequality in the low-density limit.

Contribution

It introduces a new inequality constraint based on convexity and translational invariance for the exchange-correlation functional in the low-density limit.

Findings

Derived a convexity and translational invariance constraint.

Showed that the local-density approximation violates this inequality.

Provided insights into the properties of exchange-correlation functionals.

Abstract

Knowledge of the properties of the exchange-correlation functional in the form $\frac 1\lambda v_{xc}([\rho _\lambda ],\frac{{\bf r}}\lambda )$, where $\rho _\lambda ({\bf r})=$ $\lambda ^3\rho (\lambda {\bf r}),$ is important when expressing the exchange-correlation energy as a line integral $% E_{xc}[\rho ]=\int_0^1d\lambda \int d{\bf r}\frac 1\lambda v_{xc}([\rho _\lambda ],\frac{{\bf r}}\lambda )\left[ 3\rho ({\bf r})+{\bf r.\nabla }\rho ({\bf r})\right] $ (van Leeuwen and Baerends, Phys. Rev. A {\bf 51}, 170 (1995)). With this in mind, it is shown that in the low density limit $% \lim_{\lambda \rightarrow 0}\int \rho ({\bf r})\nabla ^2\frac 1\lambda v_{xc}([\rho _\lambda ],\frac{{\bf r}}\lambda )\ d^3r\leq 4\pi \int \rho (% {\bf r})^2d^3r.$ This inequality is violated in the local-density approximation.