Exact and Model Exchange-Correlation Potentials for Open-Shell Systems.

The conventional approaches to the inverse density functional theory problem typically assume nondegeneracy of the Kohn-Sham (KS) eigenvalues, greatly hindering their use in open-shell systems. We present a generalization of the inverse density functional theory problem that can seamlessly admit degenerate KS eigenvalues. Additionally, we allow for fractional occupancy of the Kohn-Sham orbitals to also handle noninteracting ensemble-v-representable densities, as opposed to just noninteracting pure-v-representable densities. We present the exact exchange-correlation (XC) potentials for six open-shell systems─four atoms (Li, C, N, and O) and two molecules (CN and CH 2 )─using accurate ground-state densities from configuration interaction calculations. We compare these exact XC potentials with model XC potentials obtained using nonlocal (B3LYP, SCAN0) and local/semilocal (SCAN, PBE, PW92) XC functionals. Although the relative errors in the densities obtained from these DFT functionals are of O (10 -3 to 10 -2 ), the relative errors in the model XC potentials remain substantially large─ O (10 -1 to 10 0 ).