# Universality of the Hohenberg-Kohn functional

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In a recent article H. L. Neal presents a pedagogical approach to density-functional theory in the formulation of Kohn and Sham, which is still largely ignored in undergraduate teaching despite its enormous significance in many branches of physics, by discussing the application to one-dimensional two-particle systems. In this context Neal derives an analytic expression for the Hohenberg-Kohn functional $`F[\rho ]`$, given by Eq. (30) of the original paper, that he suggests is exact for all systems with the harmonic interaction $`u(x_1,x_2)=k(x_1x_2)^2/2`$. The purpose of this comment is to refute this claim for arbitrary external potentials and to point out that the functional used in Ref.  really constitutes an approximation in the same spirit as the local-density approximation.

Exploiting the universality of the Hohenberg-Kohn functional, Neal calculates

$$F=Ev(x)\rho (x)𝑑x$$
(1)   
for an analytically solvable model of two coupled harmonic oscillators. He then rewrites the total energy $`E`$ and the external potential $`v`$ on the right-hand side in terms of the density $`\rho `$, using exact relations that are only valid at the ground state of the particular model, however. This substitution hence replaces the explicit dependence on the external potential by a system-specific energy surface and fails to produce a universal functional. In particular, the minimum of the total energy obtained in this way in general differs from the true ground state. This subtle point is best seen if the resulting functional $`F[\rho ]`$ is directly inserted into the variational expression

$$\frac{\delta }{\delta \rho (x)}\left(F[\rho ]+\left(v(x)\mu \right)\rho (x)𝑑x\right)=0$$
(2)   
that determines the ground-state density for arbitrary external potentials. The Lagrange multiplier $`\mu `$ enforces the proper normalization. In the notation of Ref. , which also provides $`\delta F[\rho ]/\delta \rho (x)`$ \[Eq. (31)\], one thus obtains

$$\rho (x)=\rho _0\mathrm{exp}\left(\frac{4\omega (v(x)v(0))}{\mathrm{}\omega _0(\omega _0+\omega )}\right)$$
(3)   
and hence recovers the specific relation between $`v`$ and $`\rho `$ that was previously employed to construct the functional $`F[\rho ]`$ in the first place. By design, this expression is exact for the coupled harmonic oscillators. For all other external potentials, however, Eq. (3) constitutes an approximation to the ground-state density that does not coincide with the minimum of the true total-energy surface.

The Kohn-Sham formalism requires $`F[\rho ]`$ as an auxiliary quantity to define

$$F_r[\rho ]=F[\rho ]T_r[\rho ],$$
(4)   
where $`T_r[\rho ]`$ denotes the kinetic energy of the noninteracting reference system. In the usual terminology, $`F_r[\rho ]`$ contains the Hartree and the exchange-correlation part of the total energy, its derivative $`\delta F_r[\rho ]/\delta \rho (x)`$ contributes to the effective potential that appears in the single-particle Kohn-Sham equations. It follows from the above argument that this term is not treated exactly in Ref. , because the Hohenberg-Kohn functional as well as $`T_r[\rho ]`$ are constructed for a particular system and hence are not free from an implicit dependence on the harmonic-oscillator potential. The Hartree and exchange-correlation potential is thus modelled by that of two coupled harmonic oscillators. In this sense the approach is analogous in spirit to the local-density approximation widely used in atomic and solid-state physics, which similarly replaces the exact exchange-correlation energy by that of a homogeneous electron gas with the same local density.

Much as the local-density approximation is successful for weakly inhomogeneous systems, so Neal’s effective potential may be applied to one-dimensional two-particle systems with the harmonic interaction in general confining potentials. Indeed, Ref.  presents meaningful results for several potential wells with different shapes. For a quantitative analysis we carefully reexamine the examples discussed in the original paper. We diagonalize the Hamiltonians using a basis of noninteracting harmonic-oscillator eigenfunctions. In this way all matrix elements can be calculated either analytically or by a numerically exact Gauss-Hermite quadrature. The results for case 2: $`v(x)=\alpha |x|`$ and case 3: $`v(x)=\alpha \mathrm{exp}(\beta x^2)`$, converged with respect to the number of basis functions, are more accurate and hence differ from those quoted in Ref. . We have set $`\alpha =1.0`$, $`\beta =0.1`$ and $`k=1.0`$. In Table I we contrast the exact total energy $`E`$ with the Kohn-Sham solution $`E_{\mathrm{KS}}`$. Although small, the deviation is genuine. For comparison we also quote the estimate $`E_{\mathrm{var}}`$ from a two-parameter variational wave function given in Ref. . The two approximate schemes yield similar small errors if the quantum well resembles a harmonic potential near the origin (case 3), otherwise the variational wave function is less appropriate and the effective potential gives better agreement with the exact solution (case 2).

In summary, although not exact, Neal’s scheme yields good approximate results for confined two-particle systems with the harmonic interaction in one dimension. Furthermore, the procedure closely follows the spirit of the widely used local-density approximation and is hence of additional pedagogical value. We hope that it will find recognition and contribute towards making density-functional theory more accessible to students.