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Density functional theory replaces the interacting many-electron ground state wavefunction by its spatial density $n(\mathbf{r})$. For fixed interaction and a nondegenerate ground state, the Hohenberg-Kohn theorem fixes the external potential up to an additive constant. If two distinct potentials gave the same density, their strict variational energy inequalities would sum to the contradiction $E_0+E_0^{\prime }<E_0+E_0^{\prime }$.

The density functional variational principle minimizesover admissible densities of the correct particle number. The universal $F$ contains the kinetic and interaction energies. This is exact in principle; an explicit useful functional is the practical difficulty.^[ref]

The Kohn-Sham equations introduce noninteracting orbitals with the same density and decompose $F=T_s+E_H+E_{\mathrm{xc}}$. With $n={\sum }_i{f}_i|{\varphi }_i{|}^2$,The exchange-correlation functional includes exchange, correlation and the interacting kinetic-energy correction relative to $T_s$. Guess a density, construct the potentials, solve and occupy orbitals, then mix and iterate to self-consistent field convergence. The local density approximation uses $E_{\mathrm{xc}}^{\mathrm{LDA}}=\int n{ϵ}_{\mathrm{xc}}^{\mathrm{uniform}}(n)d^{3}r$; a generalized gradient approximation also depends on density gradients.

Kohn–Sham orbital energies are not generally excitation energies, and their sum double counts interactions. The Kohn-Sham energy double-counting correction iswith ion–ion energy added for a total crystal energy. Approximate functionals can miss self-interaction cancellation, band gaps and strong correlation; convergence alone does not prove the global ground state.^[ref]

For fixed electron-electron interaction and electron number, a nondegenerate ground-state electron density determines the external potential up to an additive constant, and hence determines the Hamiltonian and ground-state observables.

Suppose two potentials $v,v^{\prime }$ differing by more than a constant have different ground states $\Psi ,{\Psi }^{\prime }$ but the same density $\rho$. Strict Rayleigh-Ritz variational principle inequalities giveAdding produces the contradiction $E+E^{\prime }<E+E^{\prime }$. This proves the first Hohenberg-Kohn theorem under the stated nondegeneracy assumptions. A constant potential shift changes energy by $N$ times that constant without changing the density.^[ref]

A theoretical condensed matter physicist who, with Walter Kohn, established a foundation of density functional theory in 1964. Their variational principle expresses the ground-state energy of interacting electrons through the electron density, making a three-dimensional quantity central to a many-particle problem.^[ref]

His 1967 work also ruled out the relevant finite-temperature long-range order in one- and two-dimensional bosonic and fermionic systems under the theorem's assumptions. This helps explain why dimensionality matters when discussing Bose-Einstein condensation.^[ref]

Walter Kohn and Pierre Hohenberg established a foundation for density functional theory: under their ground-state assumptions, the electron density determines the external scalar potential up to an additive constant. They formulated the ground-state energy as a universal density functional plus the external-potential contribution, with a variational principle selecting the physical density. This replaces the full many-electron wave function as the basic variable by a function of only three spatial coordinates. The theorem establishes the framework, rather than providing an explicit exact functional for practical computation.^[ref]