Test of density-functional approximations in an exactly soluble model

Abstract

We consider an exactly soluble model consisting of two electrons attracted to a common center by harmonic-oscillator forces with mutual Coulomb repulsion between the electrons. The exact wave function and energy for the singlet ground state is obtained by separating the Schr\"odinger equation in center-of-mass and relative coordinates and numerically integrating the relative-coordinate eigenvalue equation. The exact Kohn-Sham (KS) orbital for the two equivalent electrons with opposite spins is constructed from the exact density, and the Kohn-Sham equation is inverted, yielding the exact exchange-correlation potential as a function of position.The exact correlation potential, as a function of position, is then obtained by subtracting the exact exchange potential from the exact exchange-correlation potential. The exact ground-state energy, exchange potential, correlation potential, KS single-particle energy eigenvalues ${\ensuremath{\epsilon}}_{\mathrm{KS}}$, exchange energy, and correlation energy are compared to the results given by density-functional theory employing the local-density approximation (LDA) plus correction terms and the exact KS orbitals for values of the harmonic-oscillator spring constant that vary over 4 orders of magnitude. We find that although total energies are accurately given by LDA plus correction terms, the values of ${\ensuremath{\epsilon}}_{\mathrm{KS}}$ are significantly in error. We show that this is mainly due to errors in the exchange potential.In addition we show analytically that in a singlet ground state of a two-electron system, the exact expectation value of the exchange potential equals the exact exchange energy, whereas the LDA expectation value of the exchange potential is only (2/3) the LDA exchange energy. Furthermore, we show that although the gradient expansion approximations for the exchange energy are significant improvements over the LDA, neither of these approximations significantly decreases the error in the LDA for the expectation value of the exchange potential. Both the correlation energy and the expectation value of the correlation potential in the LDA plus corrections are significantly in error when compared with the results of the exact calculation, the most accurate results being given by the LDA with self-interaction correction.