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

¹  Institut für Theoretische Physik, Freie Universität Berlin - Arnimallee 14, D-14195 Berlin, Germany
²  Fritz-Haber-Institut der Max-Planck-Gesellschaft - Faradayweg 4-6, 14195 Berlin, Germany
³  Theoretical Chemistry FB 08, University of Siegen - 57068 Siegen - Germany

Received: 10 October 2006
Accepted: 2 February 2007

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, , 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.