Wavefunctions for large electronic systems

Abstract: Wavefunctions for large electron numbers suffer from an exponential growth of the Hilbert space which is required for their description. In fact, as pointed out by W. Kohn, for electron numbers $N > N_0$ where $N_0 \approx 10^3$ they become meaningless (exponential wall problem). Nevertheless, despite of the enormous successes of density functional theory, one would also like to develop electronic structure calculations for large systems based on wavefunctions. This is possible if one defines the latter in Liouville space with a cumulant metric rather than in Hilbert space. The cluster expansion of the free energy of a classical monoatomic gas makes it plausible that cumulants are a proper tool for electronic structure calculations.