Discontinuity of the chemical potential in reduced-density-matrix-functional theory

Abstract

We present a novel method for calculating the fundamental gap. To this end, reduced-density-matrix-functional theory is generalized to fractional particle number. For each fixed particle number, $M$, the total energy is minimized with respect to the natural orbitals and their occupation numbers. This leads to a function, $E_{\mathrm{tot}}^M$, whose derivative with respect to the particle number has a discontinuity identical to the gap. In contrast to density functional theory, the energy minimum is generally not a stationary point of the total-energy functional. Numerical results, presented for alkali atoms, the LiH molecule, the periodic one-dimensional LiH chain, and solid Ne, are in excellent agreement with CI calculations and/or experimental data.