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Exact density-functional theory as parallel ensemble variational hierarchies: from Lieb's formulation to Kohn-Sham theory

2026/03/24 by Nan Sheng
#physics.chem-ph #math-ph #math.MP

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Abstract

Exact density-functional theory is recast here as two parallel exact ensemble variational hierarchies: an interacting hierarchy rooted in Lieb's ensemble formulation and a noninteracting hierarchy rooted in exact noninteracting ensemble theory. In optimization terms, N-representability is primal feasibility, Legendre-Fenchel duality equates the primal and dual values, v-representability is dual attainment, and the Hohenberg-Kohn theorem gives uniqueness, modulo constants, of an attained local potential. The Kohn-Sham construction couples the interacting density-space optimality condition to a compatible noninteracting dual realization on their common N-representable density domain. State-class restrictions yield the Levy-Lieb and single-determinant branches, while fractional particle number and fractional occupations lead naturally to piecewise linearity, one-sided chemical potentials, Janak-type relations, and the derivative discontinuity. This organization locates the exactness of Kohn-Sham theory in the preservation of the interacting density-space optimization together with its compatible noninteracting realization, without implying a general many-body spectral interpretation of Kohn-Sham eigenvalues.

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