Notes on Density Functional Theory

Rocco Martinazzo
E-mail: rocco.martinazzo@unimi.it

Contents

1 Introduction 1

2 Density Functional Theory 7

3 The Kohn-Sham approach 11

1 Introduction

We consider here a system with N electrons subjected to some external poten-

tial. The Hamiltonian of this system takes the following general form:

H = T + Vee + Vext

where

N
X p2i
T =
i=1
2me

is the kinetic energy operator,

1 X e2
Vee =
4π0 rij
i,j≥i

(rij = kri − rj k) is the potential term arising from the electron-electron (repul-
sive) interaction and

N
X
Vext = v(ri )
i=1

is the external eld acting (in the same way) on each electron of the system.
In the molecular Hamiltonian the external potential takes the form

M
1 X Zα e2
v(r) = −
4π0 α=1 kRα − rk

1
where the sum runs over nuclear labels and Rα specify the position of the nuclei.
The electronic system Hamiltonian is completely specied once N and v are
given. We may emphasize this fact by writing

H ≡ HvN

Electrons, like any other sets of identical particles, are indistinguishable from
each other and this implies that for any state Ψ
2 2
|Ψ(x1 , x2 , ..., xN )| = |Ψ(x2 , x1 , ..., xN )| = ...

holds. Here, xi = ri σi is a 4-dimensional vector specifying the position and the

spin of the i-th electron, i.e. the normalization condition
Z
2
|Ψ(x1 , x2 , ..., xN )| dN Γ = 1

dN Γ = d3 r1 d3 r2 ...d3 rN
R R P
means σ1 ,σ2 ,...,σN (σi takes only two values speci-
fying, e.g., the projection of the electron spin along a given axis). Since electrons
are fermions,

Ψ(x1 , x2 ..xi ..xj ..xN ) = −Ψ(x1 , x2 ..xj ..xi ..xN )

The wave function Ψ describes a particular state of the N -electron system.

In coordinate representation it is a very complicated, complex-valued function
depending on 4N variables which allows us to determine any system property
(for the given state). Indeed, for any observable A we have:
Z
hAi = hΨ| A |Ψi = Ψ∗ (x1 ...xN )AΨ(x1 ...xN )dN Γ

where A is the quantum-mechanical operator corresponding to the observable

A. Here, since electrons are equal to each other in any respect, for A to be
experimentally relevant it must be a symmetric function of the electron coor-
dinates.
Usually we are interested in one-, two- or few electrons properties. One-
electron operators are of the form

N
X
A= ai
i=1

where ai acts on the i-th electron only. Two-electron operators are of the form

N
X
A= aij
i,j≥i

Thus, for example, in our general Hamiltonian T and Vext are one-electron
operators and Vee is a two electron operator. m-electron operators are dened
in a analogous way.
We now show that in order to compute 1-, 2- or few electron properties Ψ
is much more than we need. Let's rst consider a one-electron operator and its
expectation value

2
 N Z
X
hAi = Ψ∗ (x1 x2 ...xi ...xN )ai Ψ(x1 x2 ...xi ...xN )dN Γ
i=1

Z
=N Ψ∗ (x1 x2 ...xi ...xN )a1 Ψ(x1 x2 ...xi ...xN )dN Γ

where the second line follows from the symmetry properties of the wave function.
Now

∗ N
R
RΨ (x1 x2 ...xi ...xN )a1∗Ψ(x
0
1 x2 ...xi ...x
 N )d NΓ=
a1 [Ψ(x1 x2 ...xN )Ψ (x1 x2 ...xN )] x0 =x d Γ

1 1

where x01 = x1 has to be replaced after a acted on the quantity between brackets.
Then 
N a1 [Ψ(x1 x2 ...xN )Ψ∗ (x01 x2 ...xN )]x0 =x dx1 dN −1 Γ
R
 1 1
= a1 γ(x1 |x01 )x0 =x dx1
R
1 1

where
Z
γ(x1 |x01 ) = N dN −1 Γ Ψ(x1 x2 ...xN )Ψ∗ (x01 x2 ...xN )

γ(x0 x) dened in this way is known as rst-order reduced density matrix. Note
that

X Z
2
n(r) = γ(rσ|rσ) = N dN −1 Γ |Ψ(xx2 ...xN )|
σ

is the electron density, correctly normalized to the number of particles:

Z
d3 rn(r) = N

γ is an extended density wich allows us to compute any one-electron property.

With the same token if A is a two-electron operator we have

X N (N − 1)
hAi = hΨ| aij |Ψi =
2
i,j≥i
Z 
a12 γ (2) (x1 x2 | x01 x02 )

dx1 dx2
0x1 =x1 ;x02 =x2

where

N (N − 1)
γ (2) (x1 x2 | x01 x02 ) =
Z 2
dN −2 Γ Ψ(x1 , x2 , ..., xN )Ψ∗ (x01 , x02 , ..., xN )

3
is the second-order reduced density matrix. In general, for an m-electron
operator A(m) ,
D E Z
A(m) = a12..m γ (m) (x1 x2 ..xm |x01 x02 ..x0m )|x0i =xi dx1 ..dxm

where
 
N
γ (m) (x1 ..., xm |x01 ..., x0m ) =
m
Z
dN −m Γ Ψ(x1 ...xm , xm+1 ..., xN )Ψ∗ (x01 ..., x0m , xm+1 ..., xN )

th
is the  m -order reduced density matrix. Note, that once an m-th order re-
duced density matrix is known, any density matrix of order n<m can easily
be obtained by properly integrating the known density matrix,

γ (m−1) (x1 ..xm−1 |x01 ..x0m−1 ) = N −m+1

m
(m) 0 0
R
dxm γ (x1 ..xm−1 xm |x1 ..xm−1 xm )
Since we are only interested in 1-, 2-, or few electron properties, the above
arguments suggest that we might replace the complicated function Ψ with some
sympler function. In particular, our general hamiltonian contains only 1- and
2- electron operators: if we were able to compute γ (2) than we could solve any
electronic problem, with as many electron as we like! This is the essence of the
density matrix theory of the electronic problem. Unfortunately, such a theory
has enormous diculties and cannot be used at present for all but a few model
problems. The reason is that is not yet clear how to select a general function
ρ(x1 x2 |x0 1 x0 2 ) in such a way that it represents a second order density matrix of
some electron system.
However, a powerful theory based on the simpler electronic density n(r)
turns out to be possible. As we shall see in the following it has the only prob-
lem that, in practice, it cannot be considered as truly ab initio. This Density
Functional Theory (DFT) is possible because of a number of facts.

1. We are usually interested in stationary states, that is we replace the Time-

Dependent Schrodinger Equation with the equation for stationary states

HΨ = EΨ
This is because we are only interested in situations in which all electrons
are bound to a given charged (stationary) core. Note that for such states

d hΨ| A |Ψi
=0
dt
for any (stationary, i.e. not explicitly time dependent) observable A.
2. We are usually interested in the ground-state Ψ0 , i.e. the state of minimum
energy. This is so because in molecules electronic energy levels are well-
separated in energy, and at normal temperature only the ground-state is
populated. Actually, this condition cannot be satised in metallic systems
where excited electronic states with vanishing small excitation energy can
be accessed even at very low temperatures ( electron-hole excitations).

4
Stationarity allows us to use the variational principle

 
hΨ|H|Ψi
δ =0
hΨ|Ψi

or simply

hδΨ|H|Ψi = 0

if the additional norm-conserving condition hδΨ|Ψi = 0 is enforced. In addition,

the ground state has the minimum energy property

E(Φ) = hΦ|H|Φi ≥ E0 = hΨ0 |H|Ψ0 i

which holds for any trial, normalized wavefunction Φ.

Note: Functionals and functional derivatives. The map

H→R
hΦ|H|Φi
Φ → E(Φ) =
hΦ|Φi
is called energy functional and the results

E(Φ) ≥ E0

is called wave function variational principle. In general, given a space of

functions E a map
E → R( or also C)
Φ → F [Φ]
is called a functional. Thus, for example,

Z
n(r 1 )n(r 2 )
EH [n] = d3 r 1 d3 r 2
kr 1 − r 2 k
Z
5
TT F [n] = A d3 rn 3 (r)

δF
are functionals of the electronic density. The functional derivative
δn is
dened by the equation
Z
δF
δF = d3 r (r)δn(r)
δn
δF
where δF = F [n + δn] − F [n]. In other words,
δn is a function of r
(and, in general, also a functional of n for any r ) which, once multiplied
by δn and integrated over r, gives the variation of F. More formally, let
us consider the following ordinary function of λ

F [n + λδn]

5
 where n and δn are two functions of the domain
1 E. The variation of
F is dened with the help of the standard derivative with respect to λ,
according to 
d 
δF [n, δn] = F [n + λδn]
dλ λ=0
This variation, or also dierential is, in general, a functional of both n
and δn. If it is linear in δn, that is

δF [n, δn] = ∆[n]δn

where ∆[n] is a linear operator from E to R(C), then we usually write

Z
δF
∆[n]Φ = d3 r (r)Φ(r)
δn
δF
and
δn , the previously dened functional derivative, is the integral rep-
resentation of the operator ∆[n]. Thus, for example,

Z
5
TT F [n] = A d3 rn 3 (r)
Z
5 2
δTT F [n, δn] = A d3 r n 3 (r)δn(r)
3
δTT F 2
i.e.:
δn (r) = A 53 n 3 (r). With the second (formally more correct) de-
nition Z
d  5
δTT F [n, δn] = A
dr(n + λδn)  = 3
dλ λ=0
Z  Z
5 2 5 2
= A d3 r (n + λδn) 3 (r)δn = A d3 r n 3 (r)δn(r)

3 λ=0 3
For EH we have
Z
δn(r 1 )n(r 2 ) + n(r 1 )δn(r 2 )
δEH [n, δn] = d3 r 1 d3 r 2 =
kr 1 − r 2 k

Z Z 
n(r 2 )
= d3 r 1 d3 r 2 δn(r 1 )
kr 1 − r 2 k
Z Z 
3 3 n(r 1 )
+ d r2 d r1 δn(r 2 ) =
kr 1 − r 2 k
Z
δEH
= d3 r (r)δn(r)
δn
δEH
R 3 0 n(r0 )
with
δn (r) = 2 d r kr−r 0 k .

1 If E is not linear one has to consider the curves n(λ) such that n(0) = n and n0 (0) = δn.

6
Since we are only interested in the ground-state Ψ of our N -electron system we
may write

v, N → ΨN
v → X = X [v, N ]

where the ΨN
v is a functional of v (and a function of N) and X is any ground-
state property of the system. The above relationship means that once N is xed
any ground-state property is a functional of v,

v → X = X [v]

The above relation holds thanks to the chain of relationships

v → Ψ [v]

Ψ → X [Ψ]

The only assumption we need is that the ground-state is non degenerate, in such
a way that the potential uniquely determines the ground-state function (apart
from an irrelevant phase factor).

2 Density Functional Theory

The beauty and power of the so-called Density Functional Theory relies on
two very simple theorems, known as Hohenberg-Kohn theorems, whose results
can be summarized as follow. In studying ground-state electronic properties
one can replace the ground-state electronic wave function Ψ(x1 , ..., xN ) with the
simple electron density n(r). In other words one can use the electron density as
fundamental variable: the ground-state wave function (and therefore any ground-
state property) is a functional of the electron density, Ψ = Ψ [n].
These properties follow from two very simple theorems:

Theorem I The density n uniquely determines v, that is v = v [n] or, in other

words, for each electron density n there exists one and only one potential
v (mathematically, ∀n ∃! v ) such that n is its ground-state density.

Proof. We use the reductio ad absurdum procedure rst used by Hohenberg

and Kohn. Suppose there exist two potentials v1 , v2 whose ground-state
density is n, i.e
v1 → Hv1 → Ψ1 → n
v2 → Hv2 → Ψ2 → n
Let's consider
Hv1 = T + Vee + V1ext = U + V1ext
Hv2 = T + Vee + V2ext = U + V2ext
where
N N
(i) (i)
X X
V1ext = v1 V2ext = v2
i=1 i=1

7
 Here U is the internal energy operator, U = T + Vee , a universal opera-
tor (in the sense that it is the same for any N -electron system). We have
(E(Φ) ≥ E0 )
Z
hΨ2 |Hv1 |Ψ2 i = hΨ2 |U |Ψ2 i + drv1 (r)n(r) >
Z
> hΨ1 |Hv1 |Ψ1 i ≡ hΨ1 |U |Ψ1 i + drv1 (r)n(r)

i.e.
hΨ2 |U |Ψ2 i > hΨ1 |U |Ψ1 i
With the same token, from

hΨ1 |Hv2 |Ψ1 i > hΨ2 |Hv2 |Ψ2 i

it follows
hΨ1 |U |Ψ1 i > hΨ2 |U |Ψ2 i

Note that we have implicitly assumed that Ψ is uniquely determined by v,

which is only possible if the ground-state is not degenerate (as it almost always
happens). Furthermore, il v1 and v2 give accidentaly the same Ψ (e.g. because
v1 = v2 + c) in any case Ψ is still uniquely given by n.
Note. To be precise, n is a function with the following properties,

n(r) ≥ 0
Z
d3 rn(r) = N

n ← Ψv ← v
Here the last condition means that n must be an electronic density deriv-
able from a ground state wavefunction Ψv for some external potential v.
This kind of densities are called v-representable.

The above theorem makes use of (i ) the non-degenerate nature of the ground-
state, and (ii ) the possibility to identify the class of  v -representable densities.
We will relax these two assumptions with a second, more general formulation.
Before doing this, however, let us state the second Hohenberg-Kohn theorem,
which proves to be extremely useful for the application of the theory.

Theorem II For any given external potential v a density variational principle

can be formulated, i.e. there exist a functional, called  energy functional 
Ev [n] such that
E [n] ≥ E0v
where E0 is the ground-state energy. The equality sign holds if and only
if n is the ground-state density.

Proof. Let us consider v xed. Then for any Φ giving the density n we may
write Z
hΦ|Hv |Φi = hΦ|U |Φi + d3 rv(r)n(r)

8
 Thanks to theorem I we can now focus on

Φ = Ψ [n]

where Ψ is the ground-state wavefunction for some unspecied potential

v0 uniquely determined by n. Then the quantity

Ev [n] = hΨ[n]|Hv |Ψ[n]i

is a functional of the electron density and we know that

Ev [n] ≥ E0v

the equality being satised by the ground-state density n of our problem

only (since in that case v0 = v is our xed external potential).

Please note that we have used again the v -representability property. Note also
that
Z
Ev [n] = U [n] + d3 rv(r)n(r)

and this functional can be minimized subjected to the constraint

Z
N= d3 rn(r)

This means
 Z 
3
δ Ev [n] − µ d rn (r) − N =0

that is
Z Z
3
δU [n] + d rv(r)δn(r) − µ d3 rδn(r) = 0

(where µ is the Langrange multiplier related to the above normalization con-

δU
R 3


traint) or also δU = δn (r)δn(r)d r

δU
(r) + v(r) = µ
δn
In principle, knowing U we should solve this equation for n(n = nµ ) Rand µ has
to be adjusted in order to satisfy the normalization constraint, i.e. nµ d 3 r =
N. In practice, U is an unknown functional and this means that it must be
ab-initio ,
approximated in some way. This explains why the theory is not
though it comes fromrst-principles .
Note: Lagrange multipliers and constrained minimization . Suppose
we have a function f = f (x1 , x2 ) to be minimized. In the absence of
constraints we use

∂f ∂f ∂f ∂f
df = dx1 + dx2 = 0 ⇒ = =0
∂x1 ∂x2 ∂x1 ∂x2

9
 since dx1 , dx2 are arbitrary (i.e. one can take for example dx2 = 0). If
the function f has to be minimized with the constraint

g(x1 , x2 ) = 0

we can no longer consider dx1 and dx2 arbitrary. Rather, we have

∂g ∂g
dg = dx1 + dx2 = 0
∂x1 ∂x2

This means that the vector dx = (dx1 dx2 )t must be orthogonal to the
∂g ∂g t
vector g= ( ∂x1 ∂x2
) , i.e., g · dx = 0. The stationary condition then reads

df = f · dx = 0 ∀dx ∈ g⊥

Here g⊥ is the orthogonal complement of g, that is the (linear) space

∂f ∂f t
of vectors orthogonal to g, and f = ( ∂x1 ∂x2 ) is the gradient vector. It
follows
f ∈ dx⊥ = g⊥⊥ = V {g}
where V {g} is the space spanned by g, V = {u such that u = λg, with λ ∈ R(C)},
or also
f − λg = 0
This equation has to be solved in conjuction with the constraint g(x) = 0,
which determines the value of the parameter λ, the so-called Lagrange
multiplier. Note that the above equation is equivalent to the constraint-
free stationarity condition

d(f − λg) = 0

of the Lagrange function Lλ = f − λg . Analogous relations hold for

functions of more than two variables, in the presence of a number of con-
straints.

Before considering the problem of how determining U (at least approximately)

let us consider an alternative derivation of Theorems I and II. This is due to
Levy and has the merit of removing some restrictions. From the wave function
variational principle we have

E0v = min hΨ|Hv |Ψi

Ψ

where minimization is over all possible normalized states. We can separate the
minimization in two steps by grouping wavefunctions which give the same
density
min ≡ min min
Ψ n Ψ→n

where Ψ→n means a Ψ n. Now, let us

which gives the density consider
Z
min hΨ|Hv |Ψi = min hΨ|U |Ψi + d3 rn(r)v(r)
Ψ→n Ψ→n

This is a well-dened functional of n,

10
 Z
Ev [n] = min hΨ|U |Ψi + d3 rn(r)v(r)
Ψ→n

We also have

E0v = min Ev [n]

n

which means that Ev [n] is minimum when n is the ground-state density. It

follows the following stationary condition

δU
(r) + v(r) = µ
δn
R
where µ is the Lagrange multiplier arising from the constraint dxn(x) = N .
This equation tells us that v is uniquely determined by n, or by one of the
ground-state densities if the ground-state is degenerate. We therefore have re-
moved the constraint of a non degenerate ground-state. We also note that
minimization of Ev is performed over all n which come from a wavefunction: it
is no longer necessary that Ψ is a ground-state wavefunction for some potential.
Densities satisfying
n(r) ≥ 0
Z
d3 rn(r) = n

n←Ψ
are called N −representable, a condition weaker than the v−representability.
N -representability is satised by any reasonable density. Specicaly, it can
be shown that n is N -representable if and only if
2

Z Z
1 2

n(r) ≥ 0 n(r)d3 r = n ∇n 2 d3 r < ∞

3 The Kohn-Sham approach

The energy density functional,

Z
Ev [n] = min hΨ|U |Ψi + d3 rn(r)v(r) =
Ψ→n

Z
= U [n] + d3 rn(r)v(r)

is quite hard to approximate because of the presence of the term

U [n] = min hΨ|T + Vee |Ψi

Ψ→n

which includes both kinetic and electronic repulsion terms. Let us then consider
a dierent form of this term.
2 See Parr&Yang, Density Functional Theory of Atoms and Molecules, p. 55

11
 Consider an alternative world, which we call the Kohn-Sham world, where
electrons do not interact with each other. In this world

UKS [n] ≡ TKS [n] = min hΨ|T |Ψi

Ψ→n

where the minimum has to be searched among those independent N-electron

wavefunctions that gives the density n, i.e. Slater determinants

1 
ΨKS = √ φKS KS KS 

1 φ1 ...φN
N

X 2
n(r) = φKS
i,σ (r)

i,σ

For any density n there exist a potential vKS (r) in which n is the ground-state
density
δTKS
(r) + vKS (r) = µ
δn
and such potential determines also the orbitals

p2
 
+ vKS (r) φKS KS
i,σ = i φi,σ
2me
If the above stationary condition in the Kohn-Sham world has to be equivalent
to

δU
(r) + v(r) = µ
δn
0
(we absorb any possible deerence between µ and µ in v(r)) we have to put

δU δTKS
vKS (r) = (r) − (r) + v(r)
δn δn
In this expression, U comes as the sum of a kinetic functional, the trivial part
of the electron-electron interaction functional (the Hartree functional) and an
0
exchange-correlation functional Exc
0
U [n] = T [n] + vH [n] + Eex [n]

and thus, absorbing the (reasonably small) dierence T [n] − TKS [n] into the
working exchange and correlation functional

Exc [n] := U [n] − TKS [n] − vH [n]

we arrive at

δvH δExc
vKS (r) = v(r) + (r) + (r)
δn δn
Therefore, one can solve the Kohn-Sham equation for the Kohn-Sham orbitals
{φKS
i,σ }

p2
 
δvH δExc
+ v(r) + (r) + (r) φKS KS
i,σ (r) = i φi,σ (r)
2me δn δn

12
and the ground-state density
X 2
n(r) = φKS
i (r)

i,σ

until self-consistency is reached, i.e. until the Kohn-Sham density n above

matches the density n0 used to build up the Kohn-Sham Hamiltonian
Once done, the total, ground-state energy is given by
Z
Ev = TKS [n̄] + vH [n̄] + Exc [n̄] + d3 rn̄(r)v(r) ≡
X Z
Θ(µ − i ) hψi |T |ψi i + vH [n] + Exc [n] + d3 rn(r)v(r)
i

where n is the self-consistent solution of the Kohn-Sham equation and


1 x≥0
Θ(x) =
0 x<0

This is the popular Kohn-Sham method: the only problem left is now to ap-
proximate Exc [n].
Note that from a computational point of view the method is almost equiv-
alent to the Hartree-Fock method. This, however, does not means that the
ground-state wavefunction is a Slater determinant! The latter is the ground-
state wave function of a ctitious independent electron problem with potential
vKS . Orbitals appear in the theory only as a tool to represent the ground-state
density, and to write down an exact expression for the kinetic energy functional.

Example We show here how to devise approximate functionals, focusing on

the exchange part of the exchange-correlation functional. If we consider
a uniform electron gas in the Hartree-Fock approximation the exchange
energy (per unit volume) can be easily computed for any value of the
density n, HF HF
ex = ex (n), and thus an approximate exchange functional
could be written as Z
Eex = d3 rHF
ex (n(r))

This is the Local Density Approximation to the exchange functional, also

known as Slater exchange (J.C. Slater, Phys. Rev. B, 81 (1951) 385).
The calculation is straightforward if we remember that in Hartree-Fock
theory the exchange operator takes the form

γ(x|x0 )
J(x|x0 ) =
||r − r 0 ||
where the rst-order density matrix reads as
X
γ(x|x0 ) = φv (x)φ∗v (x0 )
v

For a uniform electron gas (writing x = (r, σ))

1
φv (x) ≡ φk,σ0 (x) = √ eikr δσσ0
V

13
 where the set of k−vectors span the Fermi sphere
Z
X 2 8
N =2 1= d3 k = πk 2
∆k k≤kF 3∆k F
k

∆k = (2π)3 /V being the volume of k -space occupied by each k -vector.

That is
3
3π 2 n = kF3
is the relation linking the Fermi momentum to the electron gas density n.
It follows
Z
0
X
α 0 1 0
γαα (r|r ) = φα
k (r)φk (r ) = d3 keik(r−r )
∆kV k≤kF
k

i.e., after a straightforward integration,

3n sin(ξF ) − ξF cos(ξF )
γαα (r|r 0 ) ≡ f (ξF ) =
2 ξF3

where ξF = kF ∆r with ∆r = ||r−r 0 ||. Notice that f → n/2 as ∆r → 0, as

it should be since f in such limit represents the density of the α electrons
(similarly for the β species). Thus,

f (kF ∆r)
Jαα (r|r 0 ) = Jββ (r|r 0 ) =
∆r
Now, the exchange energy is given by

1X X
Eex = − hν|J|νi ≡ − hk|Jαα |ki
2 ν
k

where for each k

Z
1
hk|Jαα |ki = d3 r 1 d3 r 2 Jαα (r 1 |r 2 )eik(r2 −r1 )
V
f (kF ||r 2 − r 1 ||)
Z
1
≡ d3 r 1 d3 r 2 eik(r2 −r1 )
V ||r 2 − r 1 ||

The integral can be simplied by introducing the relative and the center
of mass coordinates (a transformation with unit Jacobian),

r = r2 − r1
r1 + r2
R=
2
3 With the same token one can obtain the energy (per unit volume) of the free-electron gas,
i.e. the quantity which denes the Thomas-Fermi functional.

X ~2 k 2 2 ~2
Z
V ~2
E=2 = d3 kk2 ≡ 2m
5
kF
k
2m e ∆k 2me k≤kF 10π e

Thus √
E 3 3 9π 4/3 ~2 5/3
T F [n] = = n
V 10me

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 namely
Z
f (kF r)
hk|Jαα |ki = d3 reikr
r
Summing over k we obtain

f (kF r)2
Z Z Z
X 1 f (kF r)
Eex = − hk|Jαα |ki = − d3 r d3 keikr = −V d3 r
∆k r k≤kF r
k

and thus, introducing ξ = kF r,

V 9n2 [sin(ξ) − ξcos(ξ)]2

Z
Eex = − d3 ξ
kF2 4 ξ7

i.e.
Eex
= = −C 0 kF4 = −Cn4/3
V
where C is a (positive) numerical coecient .
4

4 Note that the integral above is well dened, since for ξ→0 we have sinξ − ξcosξ → ξ 3 /3.

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