Wavefunctions for large electronic systems

2017/05/23 by Peter Fulde, Fulde, Peter
Chemical Engineering · Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Advanced Physical and Chemical Molecular Interactions #Catalysis and Oxidation Reactions #Chemical Physics (physics.chem-ph) #FOS: Physical sciences

paper · pdf · doi:10.48550/arxiv.1705.08144

openalex publication_date 2017/05/23 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28

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 > N₀ where N₀ ≈ 10³ 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.

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