A Comparison of Exact and Model Exchange-Correlation Potentials for Molecules.

Abstract

Accurate exchange-correlation (XC) potentials for three-dimensional systems─via solution of the inverse density functional theory (DFT) problem─are now available to test the quality of DFT approximations. Herein, the exact XC potential for seven molecules─dihydrogen at four different bond-lengths, lithium hydride, water, and ortho-benzyne─are computed from full configuration interaction reference densities. These are compared to model XC potentials from nonlocal (B3LYP, HSE06, SCAN0, and M08-HX) and semilocal/local (SCAN, PBE, and PW92) XC functionals. Whereas for most systems, relative errors in the ground-state densities are , the model XC potentials have much higher errors of . Among the model XC functionals, SCAN0 offers the best agreement with the exact XC potential, underlining the significance of satisfying exact conditions as well as including nonlocal effects in XC functionals. This work indicates that tests against the exact XC potential will provide a promising new direction for building more accurate XC functionals for DFT.