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Occupation numbers in density-functional calculations
It is the intention of this paper to rigorously clarify the role of the
occupation numbers in the current practical applications of the density
functional formalism. In these calculations one has to decide how to distribute
a given, fixed number of electrons over a set of single-particle orbitals. The
conventional choice is to have orbitals below the Fermi level completely
occupied and the orbitals above the Fermi level empty. Although there is a
certain confusion in literature why this choice is superior to any others, the
general belief is that it can justified by treating the occupation numbers as
variational parameters and then applying Janak's theorem or similar reasoning.
We demonstrate that there is a serious flaw in those arguments,mainly the
kinetic energy and therefore the exchange-correlation potential are not
differentiable with respect to density for arbitrary occupation numbers. It is
rigorously shown that in the present context of the density functional
calculations there is no freedom to vary the occupation numbers. The occupation
numbers cannot be considered as variational parameters.Comment: 10 pages, Revtex, accepted for publication by Phys.Rev.