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

N. Helbig1,2, N. N. Lathiotakis1, M. Albrecht3 and E. K. U. Gross1

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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, EtotM, 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.


PACS

71.10.-w Theories and models of many-electron systems

31.10.+z Theory of electronic structure, electronic transitions, and chemical binding

31.15.E- Density-functional theory

Subjects

Atomic and molecular physics

Computational physics

Condensed matter: electrical, magnetic and optical

Dates

Issue 6 (March 2007)

Received 10 October 2006, in final form 2 February 2007

Published 2 March 2007



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