An Introduction to Density Functional Theory

Ricksy
(Dated: December 29, 2021)
In this paper I cover the theoretical background of density functional theory including the first
and second Hohenberg-Kohn theorems and the approach to solving it via the Kohn-Sham equations.

I. INTRODUCTION III. FIRST THEOREM OF HOHENBERG-KOHN

A many-body system such as a solid that consists
of electrons and nuclei can be modelled using the fol-
lowing Schrödinger equation after applying the Born-
Oppenheimer approximation 1
X ℏ2 ∇2i 1 1 X −e2 1 X −e2 ZA
Ĥ = − + +
2mi 2 4π0 |ri − rj | 4π0 |RA − ri |
i i̸=j
A wavefunction solution to this equation has complexity
that increases with the number of bodies involved making
it highly challenging to solve problems involving large
numbers of interacting particles [1]. Density functional
theory transforms the problem from one involving wave-
functions to one involving charge densities. Mathemati-
cally this is an exact transformation without information
loss and we can get an equivalent of the Scrhödinger equa-
tion involving densities instead of wavefunctions. But in
reality we do not know what the transformation ”looks
like”. One approach for dealing with this problem involves
a set of equations called the Kohn-Sham equations. In
this paper I will describe the basics of the theory and the
Kohn-Sham approach.
II. ELECTRON DENSITY
The electron density for a system is the number of
electrons per unit volume. For a single electron it is
simply
n(r) = |Ψ(r)| 2
For N electrons
Z
n(r) = Ψ⋆ (r, r2 , . . . , rN )Ψ ⋆ (r, r2 , . . . , rN )dr2 . . . drN
Each ground state wavefunction must be associated
with a single external potential Vext otherwise it would
solve the Schrodinger equation for two different systems.
This is because the wavefunction contains all the infor-
mation about a system and if it describes two systems
then they must both be the same and thus have the same
external potential.
At first sight the density appears to be a less complex
A,i
object. No matter how many electrons are involved it
(1)
is always a function from R3 to R. However it turns
out [? ] that there is a bijection from the ground state
wavefunctions for a given external potential and densities.
We will prove this for a system with non-degenerate
ground states. Consider the set of wavefunctions that
solve the Schrodinger equation for at least one external
potential.
Let Ψ1 = ̸ Ψ2 be the ground state wavefunctions for
two different systems with hamiltonians H1 = T + W +
V1 , H2 T +W +V2 . Assume however that the corresponding
densities are equal ρ1 = ρ2 = ρ. By the variational
principle we know that for any wavefunction Ψ2
Egs,1 = ⟨Ψ1 |H1 |Ψ1 ⟩⟨Ψ2 |H1 |Ψ2 ⟩
= ⟨Ψ2 |H2 − V2 +RV1 |Ψ2 ⟩
3
= ⟨Ψ2 |H2 |Ψ
R 2 ⟩ + ρ(r) [v1 (r) − v23(r)] d r
= Egs,2 + ρ1 (r) [v1 (r) − v2 (r)] d r
where the inequality is strict since the ground states
(2) are degenerate.
Switching around Ψ1 and Ψ2 above we get
Z
Egs,2 Egs,1 + ρ2 (r) [v2 (r) − v1 (r)] d3 r
Adding the two inequalities together and using the
(3) assumption that ρ1 = ρ2 we get

Egs,1 + Egs,2 Egs,1 + Egs,2

1 I believe this topic is covered in the last chapter of the course
notes so I am not going into detail here but I will update it based which is a contradiction proving that the densities can-
on what much is covered not be equal.
 2

IV. SECOND THEOREM OF they experience a potential such that the resulting ground
HOHENBERG-KOHN state charge density is identical to that of the interacting
system.
The first theorem shows that the charge density is They satisfy the following Schrödinger equations
a fundamental variable of the problem rather than one
that is derived from the wavefunction. It is possible to 1
− ∇2 ϕi (r) + Vs (r)ϕi (r) = ϵi ϕi (r)
formulate the equivalent of the Schr´’odinger equation 2
using densities. and the associated density is
Since we have shown that each n(r) corresponds to a
single Ψ and Vext , the expected value of any operator N
 which using wavefunctions has an equivalent density
X
|ϕi (r)|2
functional representation i=1

The kinetic energy for this system is defined as

A[n] = ⟨Ψ|Â|Ψ⟩ (4)
Ts [n] = min ⟨Φ|T̂ |Φ⟩ (9)
We have seen in equation [?] that we can write this Φ→n
explicitly for ⟨Ψ|V̂ext |Ψ⟩. Let us now write a functional The Kohn-Sham wavefunction of density n(r) is the
for the other two operators in the Hamiltonian (equation wavefunction which yields n(r) and has lowest kinetic
[?]) energy.
The expectation of the Hamiltonian can be expressed
in terms of n(r) as follows
F [n] = ⟨Ψ|T̂ + V̂ee |Ψ⟩ (5)
Z
The functional is well-defined in principle but we do E = ⟨T̂s + V̂s ⟩ = ⟨T̂s ⟩ + ⟨V̂s ⟩ = Ts [n] + vs n(r)d3 r
not know what it actually looks like. This is called the
universal density functional. (10)
From the first theorem we know that for any charge From this we get the following functional differential
density n(r) there is a unique external potential for which equation
the charge density is ground state charge density. The
charge density also corresponds to ground state wave δTs
function of the many-body Hamiltonian that comes about + vs (r) = µ (11)
from this external potential. δn(r)
Combining equations [?] and [?] we can write out an It can be shown that the Slater determinant is the exact
energy functional in terms of the density solution for a system of non-interacting electrons.
Ts [n] accounts for a part of F [n]. Another part comes
 Z  from
E[n] = F [n] + n(r)vext (r)d3 r (6)
n(r)n(r′ ) 3 3 ′
Z Z
1
U [n] = d rd r (12)
The charge density that minimises E[n] will be the 2 |r − r′ |
ground state charge density which can be seen from the whose functional derivative is
variational principle.
′
There is some Vext for which n′ corresponds but here we δU 1
Z
n(r)n(r′ )
fix Vext and only look at the ground state wave function vH (r) = = d3 r
Ψ′ corresponding to some density n′ and denoting the δn 2 |r − r′ |
ground state wavefunction as Ψ0 Written in terms of equations [?] and [?] we can write
[?] as

E[n′ ] = ⟨Ψ′ |T̂ + V̂ee + V̂ext |P si′ ⟩ (7)

F [n] = Ts [n] + U [n] + EXC [n] (13)
≥ ⟨Ψ0 |T̂ + V̂ee + V̂ext |Ψ0 ⟩ = E0 (8)
where the term EXC [n] is called the exchange correla-
tion energy.
V. KOHN-SHAM EQUATIONS We can write down an equation for this analogous to
equations [?] and [?]
Now we use these three equations get an expression for
The previous two theorems do not provide a practical
the Kohn-Sham potential
approach to find the density. We now consider a system
similar to our original systems but one in which the elec-
trons which do not interact with each other. However vs (r) = vXC (r) + vH (r) + v(r) (14)
 3

VI. DISCUSSION relation functional. This can be estimated using methods

such as local density approximation [2].
At this point there is only one term that is not explicitly
expressed in terms of densities namely the exchange cor-

[1] W. Kohn, “Nobel Lecture.” Nobel Foundation, 1999. index.htm. MIT OpenCourseWare.
https://www.nobelprize.org/uploads/2018/06/ [3] P. Manninen, Lecture Notes for 554017 Advanced
kohn-lecture.pdf. Quantum Chemistry. University of Helsinki, 2012.
[2] G. Ceder and N. Marzari, “3.320 Atomistic Computer http://www.chem.helsinki.fi/~manninen/aqc2012/
Modeling of Materials (SMA 5107),” 2005. lecture_notes.pdf.
https://ocw.mit.edu/courses/ [4] K. Burke, The ABC of DFT. University of California,
materials-science-and-engineering/ Irvine, 2007. https://dft.uci.edu/doc/g1.pdf.
3-320-atomistic-computer-modeling-of-materials-sma-5107-spring-2005/