Chapter 3

Fermions and bosons

We now turn to the quantum statistical description of many-particle systems.

The indistinguishability of microparticles leads to a number of far-reaching
consequences for the behavior of particle ensembles. Among them are the
symmetry properties of the wave function. As we will see there exist only two
different symmetries leading to either Bose or Fermi-Dirac statistics.
Consider a single nonrelativistic quantum particle described by the hamil-
tonian ĥ. The stationary eigenvalue problem is given by the Schrödinger equa-
tion
ĥ|φi i = ǫi |φi i, i = 1, 2, . . . (3.1)
where the eigenvalues of the hamiltonian are ordered, ǫ1 < ǫ2 < ǫ3 . . . . The
associated single-particle orbitals φi form a complete orthonormal set of states
in the single-particle Hilbert space1

hφi |φj i = δi,j ,

∞
X
|φi ihφi | = 1. (3.2)
i=1

3.1 Spin statistics theorem

We now consider the quantum mechanical state |Ψi of N identical particles
which is characterized by a set of N quantum numbers j1 , j2 , ..., jN , meaning
that particle i is in single-particle state |φji i. The states |Ψi are elements of the
N -particle Hilbert space which we define as the direct product of single-particle
1
The eigenvalues are assumed non-degenerate. Also, the extension to the case of a con-
tinuous basis is straightforward.

87
88 CHAPTER 3. FERMIONS AND BOSONS

Figure 3.1: Example of the occupation of single-particle orbitals by 3 particles.

Exchange of identical particles (right) cannot change the measurable physical
properties, such as the occupation probability.

Hilbert spaces, HN = H1 ⊗ H1 ⊗ H1 ⊗ . . . (N factors), and are eigenstates of

the total hamiltonian Ĥ,
Ĥ|Ψ{j} i = E{j} |Ψ{j} i, {j} = {j1 , j2 , . . . } (3.3)
The explicit structure of the N −particle states is not important now and will
be discussed later2 .
Since the particles are assumed indistinguishable it is clear that all physical
observables cannot depend upon which of the particles occupies which single
particle state, as long as all occupied orbitals, i.e. the set j, remain unchainged.
In other words, exchanging two particles k and l (exchanging their orbitals,
jk ↔ jl ) in the state |Ψi may not change the probability density, cf. Fig. 3.1.
The mathematical formulation of this statement is based on the permutation
operator Pkl with the action
Pkl |Ψ{j} i = Pkl |Ψj1 ,...,jk ,...jl ,...,jN i =
= |Ψj1 ,...,jl ,...jk ,...,jN i ≡ |Ψ′{j} i, ∀k, l = 1, . . . N, (3.4)
where we have to require
hΨ′{j} |Ψ′{j} i = hΨ{j} |Ψ{j} i. (3.5)

Indistinguishability of particles requires Pkl Ĥ = Ĥ and [Pkl , Ĥ] = 0, i.e. Pkl

and Ĥ have common eigenstates. This means Pkl obeys the eigenvalue problem
Pkl |Ψ{j} i = λkl |Ψ{j} i = |Ψ′{j} i. (3.6)
2
In this section we assume that the particles do not interact with each other. The
generalization to interacting particles will be discussed in Sec. 3.2.5.
3.2. N -PARTICLE WAVE FUNCTIONS 89

Obviously, Pkl† = Pkl , so the eigenvalue λkl is real. Then, from Eqs. (3.5) and
(3.6) immediately follows

λ2kl = λ2 = 1, ∀k, l = 1, . . . N, (3.7)

with the two possible solutions: λ = 1 and λ = −1. From Eq. (3.6) it follows
that, for λ = 1, the wave function |Ψi is symmetric under particle exchange
whereas, for λ = −1, it changes sign (i.e., it is “anti-symmetric”).
This result was obtained for an arbitrary pair of particles and we may
expect that it is straightforwardly extended to systems with more than two
particles. Experience shows that, in nature, there exist only two classes of
microparticles – one which has a totally symmetric wave function with re-
spect to exchange of any particle pair whereas, for the other, the wave func-
tion is antisymmetric. The first case describes particles with Bose-Einstein
statistics (“bosons”) and the second, particles obeying Fermi-Dirac statistics
(“fermions”)3 .
The one-to-one correspondence of (anti-)symmetric states with bosons (fer-
mions) is the content of the spin-statistics theorem. It was first proven by Fierz
[Fie39] and Pauli [Pau40] within relativistic quantum field theory. Require-
ments include 1.) Lorentz invariance and relativistic causality, 2.) positivity
of the energies of all particles and 3.) positive definiteness of the norm of all
states.

3.2 Symmetric and antisymmetric N -particle

wave functions
We now explicitly construct the N -particle wave function of a system of many
fermions or bosons. For two particles occupying the orbitals |φj1 i and |φj2 i,
respectively, there are two possible wave functions: |Ψj1 ,j2 i and |Ψj2 ,j1 i which
follow from one another by applying the permutation operator P12 . Since both
wave functions represent the same physical state it is reasonable to eliminate
this ambiguity by constructing a new wave function as a suitable linear com-
bination of the two,

|Ψj1 ,j2 i± = C12 {|Ψj1 ,j2 i + A12 P12 |Ψj1 ,j2 i} , (3.8)

with an arbitrary complex coefficient A12 . Using the eigenvalue property of

the permutation operator, Eq. (3.6), we require that this wave function has
3
Fictitious systems with mixed statistics have been investigated by various authors, e.g.
[MG64, MG65] and obey “parastatistics”. For a text book discussion, see Ref. [Sch], p. 6.
90 CHAPTER 3. FERMIONS AND BOSONS

the proper symmetry,

P12 |Ψj1 ,j2 i± = ±|Ψj1 ,j2 i± . (3.9)

The explicit form of the coefficients in Eq. (3.8) is obtained by acting on

this equation with the permutation operator and equating this to ±|Ψj1 ,j2 i± ,
2
according to Eq. (3.9), and using P12 = 1̂,

P12 |Ψj1 ,j2 i± = C12 |Ψj2 ,j1 i + A12 P12

2

|Ψj1 ,j2 i =
= C12 {±A12 |Ψj2 ,j1 i ± |Ψj1 ,j2 i} ,

the requirement A12 = λ, whereas normalization of |Ψj1 ,j2 i±

which leads to √
yields C12 = 1/ 2. The final result is

1
|Ψj1 ,j2 i± = √ {|Ψj1 ,j2 i ± P12 |Ψj1 ,j2 i} ≡ Λ±
12 |Ψj1 ,j2 i (3.10)
2

where,
1
Λ±12 = √ {1 ± P12 }, (3.11)
2
denotes the (anti-)symmetrization operator of two particles which is a linear
combination of the identity operator and the pair permutation operator.
The extension of this result to 3 fermions or bosons is straightforward. For
3 particles (1, 2, 3) there exist 6 = 3! permutations: three pair permutations,
(2, 1, 3), (3, 2, 1), (1, 3, 2), that are obtained by acting with the permuation op-
erators P12 , P13 , P23 , respectively on the initial configuration. Further, there
are two permutations involving all three particles, i.e. (3, 1, 2), (2, 3, 1), which
are obtained by applying the operators P13 P12 and P23 P12 , respectively. Thus,
the three-particle (anti-)symmetrization operator has the form
1
Λ±
123 = √ {1 ± P12 ± P13 ± P23 + P13 P12 + P23 P12 }, (3.12)
3!
where we took into account the necessary sign change in the case of fermions
resulting for any pair permutation.
This result is generalized to N particles where there exists a total of N !
permutations, according to4

|Ψ{j} i± = Λ±
1...N |Ψ{j} i,
(3.13)
4
This result applies only to fermions. For bosons the prefactor has to be corrected, cf.
Eq. (3.25).
3.2. N -PARTICLE WAVE FUNCTIONS 91

with the definition of the (anti-)symmetrization operator of N particles,

1 X
Λ±
1...N = √ sign(P )P̂ (3.14)
N ! P ǫSN

where the sum is over all possible permutations P̂ which are elements of the
permutation group SN . Each permutation P has the parity, sign(P ) = (±1)Np ,
which is equal to the number Np of successive pair permuations into which P̂
can be decomposed (cf. the example N = 3 above). Below we will construct
the (anti-)symmetric state |Ψ{j} i± explicitly. But before this we consider an
alternative and very efficient notation which is based on the occupation number
formalism.
The properties of the (anti-)symmetrization operators Λ± 1...N are analyzed
in Problem 1, see Sec. 3.8.

3.2.1 Occupation number representation

The original N -particle state |Ψ{j} i contained clear information about which
particle occupies which state. Of course this is unphysical, as it is in conflict
with the indistinguishability of particles. With the construction of the sym-
metric or anti-symmetric N -particle state |Ψ{j} i± this information about the
identity of particles is eliminated, an the only information which remained is
how many particles np occupy single-particle orbital |φp i. We thus may use a
different notation for the state |Ψ{j} i± in terms of the occupation numbers np
of the single-particle orbitals,

|Ψ{j} i± = |n1 n2 . . . i ≡ |{n}i, np = 0, 1, 2, . . . , p = 1, 2, . . . (3.15)

Here {n} denotes the total set of occupation numbers of all single-particle
orbitals. Since this is the complete information about the N -particle system
these states form a complete system which is orthonormal by construction of
the (anti-)symmetrization operators,

h{n}|{n′ }i = δ{n},{n′ } = δn1 ,n′1 δn2 ,n′2 . . .

X
|{n}ih{n}| = 1. (3.16)
{n}

The nice feature of this representation is that it is equally applicable to

fermions and bosons. The only difference between the two lies in the possible
values of the occupation numbers, as we will see in the next two sections.
92 CHAPTER 3. FERMIONS AND BOSONS

3.2.2 Fock space

In Sec. 3.1 we have introduced the N -particle Hilbert space HN . In the fol-
lowing we will need either totally symmetric or totally anti-symmetric states
+ −
which form the sub-spaces HN and HN of the Hilbert space. Furthermore,
below we will develop the formalism of second quantization by defining cre-
ation and annihilation operators acting on symmetric or anti-symmetric states.
Obviously, the action of these operators will give rise to a state with N + 1
or N − 1 particles. Thus, we have to introduce, in addition, a more gen-
eral space containing states with different particle numbers: We define the
symmetric (anti-symmetric) Fock space F ± as the direct sum of symmetric
±
(anti-symmetric) Hilbert spaces HN with particle numbers N = 0, 1, 2, . . . ,

F + = H0 ∪ H1+ ∪ H2+ ∪ . . . ,
F − = H0 ∪ H1− ∪ H2− ∪ . . . . (3.17)

Here, we included the vacuum state |0i = |0, 0, . . . i which is the state without
particles which belongs to both Fock spaces.

3.2.3 Many-fermion wave function

Let us return to the case of two particles, Eq. (3.10), and consider the case
j1 = j2 . Due to the minus sign in front of P12 , we immediately conclude that
|Ψj1 ,j1 i− ≡ 0. This state is not normalizable and thus cannot be physically
realized. In other words, two fermions cannot occupy the same single-particle
orbital – this is the Pauli principle which has far-reaching consequences for the
behavior of fermions.
We now construct the explicit form of the anti-symmetric wave function.
This is particularly simple if the particles are non-interacting. Then, the total
hamiltonian is additive5 ,
XN
Ĥ = ĥi , (3.18)
i=1

and all hamiltonians commute, [ĥi , ĥj ] = 0, for all i and j. Then all par-
ticles have common eigenstates, and the total wave function (prior to anti-
symmetrization) has the form of a product

|Ψ{j} i = |Ψj1 ,j2 ,...jN i = |φj1 (1)i|φj2 (2)i . . . |φjN (N )i

5
This is an example of an observable of single-particle type which will be discussed more
in detail in Sec. 3.3.1.
3.2. N -PARTICLE WAVE FUNCTIONS 93

where the argument of the orbitals denotes the number (index) of the particle
that occupies this orbital. As we have just seen, for fermions, all orbitals have
to be different. Now, the anti-symmetrization of this state can be performed
immediately, by applying the operator Λ− 1...N given by Eq. (3.14). For two
particles, we obtain
1
|Ψj1 ,j2 i− = √ {|φj1 (1)i|φj2 (2)i − |φj1 (2)i|φj2 (1)i} =
2!
= |0, 0, . . . , 1, . . . , 1, . . . i. (3.19)
In the last line, we used the occupation number representation, which has
everywhere zeroes (unoccupied orbitals) except for the two orbitals with num-
bers j1 and j2 . Obviously, the combination of orbitals in the first line can be
written as a determinant which allows for a compact notation of the general
wave function of N fermions as a Slater determinant,
 
 |φj1 (1)i |φj1 (2)i ... |φj1 (N )i 
 
− 1  |φj2 (1)i |φj2 (2)i ... |φj2 (N )i 
|Ψj1 ,j2 ,...jN i = √  =
N!  ... ... ... ... 
 ... ... ... ... 
= |0, 0, . . . , 1, . . . , 1, . . . , 1, . . . , 1, . . . i. (3.20)
In the last line, the 1’s are at the positions of the occupied orbitals. This
becomes obvious if the system is in the ground state, then the N energetically
lowest orbitals are occupied, j1 = 1, j2 = 2, . . . jN = N , and the state has
the simple notation |1, 1, . . . 1, 0, 0 . . . i with N subsequent 1’s. Obviously, the
anti-symmetric wave function is normalized to one.
As discussed in Sec. 3.2.1, the (anti-)symmetric states form an orthonormal
basis in Fock space. For fermions, the restriction of the occupation numbers
leads to a slight modification of the completeness relation which we, therefore,
repeat:
h{n}|{n′ }i = δn1 ,n′1 δn2 ,n′2 . . . ,
1 X
X 1
. . . |{n}ih{n}| = 1. (3.21)
n1 =0 n2 =0

3.2.4 Many-boson wave function

The case of bosons is analyzed analogously. Considering again the two-particle
case
1
|Ψj1 ,j2 i+ = √ {|φj1 (1)i|φj2 (2)i + |φj1 (2)i|φj2 (1)i} =
2!
= |0, 0, . . . , 1, . . . , 1, . . . i, (3.22)
94 CHAPTER 3. FERMIONS AND BOSONS

the main difference to the fermions is the plus sign. Thus, this wave function
is not represented by a determinant, but this combination of products with
positive sign is called a permanent.
The plus sign in the wave function (3.22) has the immediate consequence
that the situation j1 = j2 now leads to a physical state, i.e., for bosons, there
is no restriction on the occupation numbers, except for their normalization
∞
X
np = N, np = 0, 1, 2, . . . N, ∀p. (3.23)
p=1

Thus, the two single-particle orbitals |φj1 i and |φj2 i occuring in Eq. (3.22) can
accomodate an arbitrary number of bosons. If, for example, the two particles
are both in the state |φj i, the symmetric wave function becomes
|Ψj,j i+ = |0, 0, . . . , 2, . . . i =
1 
= C(nj ) √ |φj (1)i|φj (2)i + |φj (2)i|φj (1)i , (3.24)
2!
where the coefficient C(nj ) is introduced to assure the normalization condition
+
hΨj,j |Ψj,j i+ = 1. Since the two terms in (3.24) are identical √ the normalization
gives 1 = 4|C(nj )|2 /2, i.e. we obtain C(nj = 2) = 1/ 2. Repeating this
analysis for a state with an arbitrary occupation number nj , there will be nj !
√
identical terms, and we obtain the general result C(nj ) = 1/ P nj . Finally, if
there are several states with occupation numbers n1 , n2 , . . . with ∞ p=1 np = N ,
−1/2
the normalization constant becomes C(n1 , n2 , ...) = (n1 ! n2 ! . . . ) . Thus, for
+
the case of bosons action of the symmetrization operator Λ1...N , Eq. (3.14), on
the state |Ψj1 ,j2 ,...jN i will not yield a normalized state. A normalized symmetric
state is obtained by the following prescription,
1
|Ψj1 ,j2 ,...jN i+ = √ Λ+ |Ψj1 ,j2 ,...jN i (3.25)
n1 !n2 !... 1...N

1 X
Λ+
1...N = √ P̂ . (3.26)
N ! P ǫSN

Hence the symmetric state contains the prefactor (N !n1 !n2 !...)−1/2 in front of
the permanent.
An example of the wave function of N bosons is
k
X
+
|Ψj1 ,j2 ,...jN i = |n1 n2 . . . nk , 0, 0, . . . i, np = N, (3.27)
p=1
3.2. N -PARTICLE WAVE FUNCTIONS 95

where np 6= 0, for all p ≤ k, whereas all orbitals with the number p > k are
empty. In particular, the energetically lowest state of N non-interacting bosons
(ground state) is the state where all particles occupy the lowest orbital |φ1 i,
i.e. |Ψj1 ,j2 ,...jN i+
GS = |N 0 . . . 0i. This effect of a macroscopic population which
is possible only for particles with Bose statistics is called Bose-Einstein con-
densation. Note, however, that in the case of interaction between the particles,
a permanent constructed from the free single-particle orbitals will not be an
eigenstate of the system. In that case, in a Bose condensate a finite fraction of
particles will occupy excited orbitals (“condensate depletion”). The construc-
tion of the N-particle state for interacting bosons and fermions is subject of
the next section.

3.2.5 Interacting bosons and fermions

So far we have assumed that there is no interaction between the particles and
the total hamiltonian is a sum of single-particle hamiltonians. In the case of
interactions,
X N
Ĥ = ĥi + Ĥint , (3.28)
i=1

and the N -particle wave function will, in general, deviate from a product of
single-particle orbitals. Moreover, there is no reason why interacting particles
should occupy single-particle orbitals |φp i of a non-interacting system.
The solution to this problem is based on the fact that the (anti-)symmetric
states, |Ψ{j} i± = |{n}i, form a complete orthonormal set in the N -particle
Hilbert space, cf. Eq. (3.16). This means, any symmetric or antisymmetric
state can be represented as a superposition of N -particle permanents or deter-
minants, respectively,
X
±
|Ψ{j} i± = C{n} |{n}i (3.29)
{n}, N =const

The effect of the interaction between the particles on the ground state wave
function is to “add” contributions from determinants (permanents) involving
higher lying orbitals to the ideal wave function, i.e. the interacting ground
state includes contributions from (non-interacting) excited states. For weak
interaction, we may expect that energetically low-lying orbitals will give the
dominating contribution to the wave function. For example, for two fermions,
the dominating states in the expansion (3.29) will be |1, 1, 0, . . . i, |1, 0, 1, . . . i,
|1, 0, 0, 1 . . . i, |0, 1, 1, , 0 . . . i and so on. The computation of the ground state of
an interacting many-particle system is thus transformed into the computation
96 CHAPTER 3. FERMIONS AND BOSONS

±
of the expansion coefficients C{n} . This is the basis of the exact diagonalization
method or configuration interaction (CI). It is obvious that, if we would have
obtained the eigenfunctions of the interacting hamiltonian, it would be repre-
sented by a diagonal matrix in this basis whith the eigenvalues populating the
diagonal.6

This approach of computing the N -particle state via a superposition of

permanents or determinants can be extended beyond the ground state prop-
erties. Indeed, extensions to thermodynamic equilibrium (mixed ensemble
where the superpositions carry weights proportional to Boltzmann factors,
e.g. [SBF+ 11]) and also nonequilibrium versions of CI (time-dependent CI,
TDCI) that use pure states are meanwhile well established. In the latter,
±
the coefficients become time-dependent, C{n} (t), whereas the orbitals remain
fixed. We will consider the extension of the occupation number formalism to
the thermodynamic properties of interacting bosons and fermions in Chapter 4.
Further, nonequilibrium many-particle systems will be considered in Chapter 7
where we will develop an alternative approach based on nonequilibrium Green
functions.

The main problem of CI-type methods is the exponential scaling with the
number of particles which dramatically limits the class of solvable problems.
Therefore, in recent years a large variety of approximate methods has been
developed. Here we mention multiconfiguration (MC) approaches such as
MC Hartree or MC Hartree-Fock which exist also in time-dependent variants
(MCTDH and MCTDHF), e.g. [MMC90] and are now frequently applied to
interacting Bose and Fermi systems. In this method not only the coefficients
C ± (t) are optimized but also the orbitals are adapted in a time-dependent
fashion. The main advantage is the reduction of the basis size, as sompared to
CI. A recent time-dependent application to the photoionization of helium can
be found in Ref. [HB11]. Another very general approach consists in subdivid-
ing the N -particle state in various classes with different properties. This has
been termed “Generalized Active Space” (or restricted active space) approach
and is very promising due to its generality [HB12, HB13]. An overview on first
results is given in Ref. [HHB14].

6
This N -particle state can be constructed from interacting single-particle orbitals as
well. These are called “natural orbitals” and are the eigenvalues of the reduced one-particle
density matrix. For a discussion see [SvL13].
3.3. SECOND QUANTIZATION FOR BOSONS 97

3.3 Second quantization for bosons

We have seen in Chapter 1 for the example of the harmonic oscillator that an
elegant approach to quantum many-particle systems is given by the method
of second quantization. Using properly defined creation and annihilation op-
erators, the hamiltonian of various N -particle systems was diagonalized. The
examples studied in Chapter 1 did not explicitly include an interaction con-
tribution to the hamiltonian – a simplification which will now be dropped.
We will now consider the full hamiltonian (3.28) and transform it into second
quantization representation. While this hamiltonian will, in general, not be
diagonal, nevertheless the use of creation and annihilation operators yields a
quite efficient approach to the many-particle problem.

3.3.1 Creation and annihilation operators for bosons

We now introduce the creation operator â†i acting on states from the symmetric
Fock space F + , cf. Sec. 3.2.2. It has the property to increase the occupation
number ni of single-particle orbital |φi i by one. In analogy to the harmonic
oscillator, Sec. 2.3 we use the following definition
√
â†i |n1 n2 . . . ni . . . i = ni + 1 |n1 n2 . . . ni + 1 . . . i (3.30)

While in case of coupled harmonic oscillators this operator created an ad-

ditional excitation in oscillator “i”, now its action leads to a state with an
additional particle in orbital “i”. The associated annihilation operator âi of
orbital |φi i is now constructed as the hermitean adjoint (we use this as its def-
inition) of â†i , i.e. [â†i ]† = âi , and its action can be deduced from the definition
(3.30),
X
âi |n1 n2 . . . ni . . . i = |{n′ }ih{n′ }|âi |n1 n2 . . . ni . . . i
{n′ }
X
= |{n′ }ihn1 n2 . . . ni . . . |â†i |n′1 . . . n′i . . . i∗ =
{n′ }
Xp
i ′
= n′i + 1 δ{n},{n ′ } δni ,n′ +1 |{n }i =
i
{n′ }
√
= ni |n1 n2 . . . ni − 1 . . . i, (3.31)

yielding the same explicit definition that is familiar from the harmonic os-
cillator7 : the adjoint of â†i is indeed an annihilation operator reducing the
7
See our results for coupled harmonic oscillators in section 2.3.2.
98 CHAPTER 3. FERMIONS AND BOSONS

occupation of orbital |φi i by one. In the third line of Eq. (3.31) we introduced
the modified Kronecker symbol in which the occupation number of orbital i is
missing,

i
δ{n},{n ′} = δn1 ,n′1 . . . δni−1 ,n′i−1 δni+1 ,n′i+1 . . . . (3.32)
ik
δ{n},{n ′} = δn1 ,n′1 . . . δni−1 ,n′i−1 δni+1 ,n′i+1 . . . .δnk−1 ,n′k−1 δnk+1 ,n′k+1 . . . . (3.33)

In the second line, this definition is extended to two missing orbitals.

We now need to verify the proper bosonic commutation relations, which
are given by the
Theorem: The creation and annihilation operators defined by Eqs. (3.30,
3.31) obey the relations

[âi , âk ] = [â†i , â†k ] = 0, ∀i, k, (3.34)

h i
âi , â†k = δi,k . (3.35)

Proof of relation (3.35):

Consider first the case i 6= k and evaluate the commutator acting on an arbi-
trary state
h i √
âi , â†k |{n}i = âi nk + 1| . . . ni , . . . nk + 1 . . . i
√
− â†k ni | . . . ni − 1, . . . nk . . . i = 0

Consider now the case i = k: Then

h i
âk , â†k |{n}i = (nk + 1)|{n}i − nk |{n}i = |{n}i,

which proves the statement since no restrictions with respect to i and k were
made. Analogously one proves the relations (3.34), see problem 18 . We now
consider the second quantization representation of important operators.

Construction of the N -particle state

As for the harmonic oscillator or any quantized field, an arbitrary many-
particle state can be constructed from the vacuum state by repeatedly applying
8
From this property we may also conclude that the ladder operators of the harmonic
oscillator have bosonic nature, i.e. the elementary excitations of the oscillator (oscillation
quanta or phonons) are bosons.
3.3. SECOND QUANTIZATION FOR BOSONS 99

the creation operator(s). For example, single and two-particle states with the
proper normalization are obtained via

|1i = ↠|0i,

|0, 0 . . . 1, 0, . . . i = â†i |0i,
1  † 2
|0, 0 . . . 2, 0, . . . i = √ âi |0i,
2!
|0, 0 . . . 1, 0, . . . 1, 0, . . . i = â†i â†j |0i, i 6= j,

where, in the second (third) line, the 1 (2) stands on position i, whereas in
the last line the 1’s are at positions i and j. This is readily generalized to an
arbitrary symmetric N -particle state according to9 .

1  n 1  n 2
|n1 , n2 , . . . i = √ â†1 â†2 . . . |0i (3.36)
n1 !n2 ! . . .

Particle number operators

The operator
n̂i = â†i âi (3.37)

is the occupation number operator for orbital i because, for ni ≥ 1,

√
â†i âi |{n}i = â†i ni |n1 . . . ni − 1 . . . i = ni |{n}i,

whereas, for ni = 0, â†i âi |{n}i = 0. Thus, the symmetric state |{n}i is an
eigenstate of n̂i with the eigenvalue coinciding with the occupation number
ni of this state. In other words: all n̂i have common eigenfunctions with the
hamiltonian and commute, [n̂i , H] = 0.
The total particle number operator is defined as
∞
X ∞
X
N̂ = n̂i = â†i âi , (3.38)
i=1 i=1

because
P∞ its action yields the total number of particles in the system: N̂ |{n}i =
n
i=1 i |{n}i = N |{n}i. Thus, also N̂ commutes with the hamiltonian and
has the same eigenfunctions.
9
The origin of the prefactors was discussed in Sec. 3.2.4 and is also analogous to the case
of the harmonic oscillator Sec. 2.3.
100 CHAPTER 3. FERMIONS AND BOSONS

Single-particle operators
Consider now a general single-particle operator10 defined as
N
X
B̂1 = b̂α , (3.39)
α=1

where b̂α acts only on the variables associated with particle with number “α”.
We will now transform this operator into second quantization representation.
To this end we define the matrix element with respect to the single-particle
orbitals
bij = hi|b̂|ji, (3.40)
and the generalized projection operator11
N
X
Π̂ij = |iiα hj|α , (3.41)
α=1

where |iiα denotes the orbital i occupied by particle α.

Theorem: The second quantization representation of a single-particle opera-

tor is given by
∞
X ∞
X
B̂1 = bij Π̂ij = bij â†i âj (3.42)
i,j=1 i,j=1

Proof:
We first expand b̂, for an arbitrary particle α into a basis of single-particle
orbitals |ii = |φi i,
∞
X ∞
X
b̂ = |iihi|b̂|jihj| = bij |iihj|,
i,j=1 i,j=1

where we used the definition (3.40) of the matrix element. With this result we
can transform the total operator (3.39), using the definition (3.41),
N X
X ∞ ∞
X
B̂1 = bij |iiα hj|α = bij Π̂ij , (3.43)
α=1 i,j=1 i,j=1

10
Examples are the total momentum, total kinetic energy, angular momentum or potential
energy of the system.
11
For i = j this definition contains the standard projection operator on state |ii, i.e. |iihi|,
whereas for i 6= j this operator projects onto a transition, i.e. transfers an arbitrary particle
from state |ji to state |ii.
3.3. SECOND QUANTIZATION FOR BOSONS 101

We now express Π̂ij in terms of creation and annihilation operators by an-

alyzing its action on a symmetric state (3.25), taking into account that Π̂ij
commutes with the symmetrization operator Λ+ 12
1...N , Eq. (3.26) ,

N
1 X
Π̂ij |{n}i = √ Λ+ |iiα hj|α · |j1 i|j2 i . . . |jN i. (3.44)
n1 !n2 ! . . . 1...N α=1

The product state is constructed from all orbitals including the orbitals |ii and
|ji. Among the N factors there are, in general, ni factors |ii and nj factors
|ji. Let us consider two cases.
1), j 6= i: Since the single-particle orbitals form an orthonormal basis, hj|ji =
1, multiplication with hj|α reduces the number of occurences of orbital j in the
product state by one, whereas multiplication with |iiα increases the number of
orbitals i by one. The occurence of nj such orbitals (occupied by nj particles)
in the product state gives rise to an overall factor of nj because nj terms of
the sum will yield a non-vanishing contribution.
Finally, we compare this result to the properly symmetrized state which
follows from |{n}i by increasing ni by one and decreasing nj by one will be
denoted by

{n}ij = |n1 , n2 . . . ni + 1 . . . nj − 1 . . . i
 

1
=p Λ+
1...N · |j1 i|j2 i . . . |jN i. (3.45)
n1 ! . . . (ni + 1)! . . . (nj − 1)! . . .

It contains the same particle number N as the state |{n}i but, due to the differ-
√ √
ent orbital occupations, the prefactor in front of Λ+1...N differs by n j / n i + 1,
compared to the one in Eq. (3.44) which we, therefore, can rewrite as
√
ni + 1 
{n}ij

Π̂ij |{n}i = nj √
nj
= â†i âj |{n}i. (3.46)

2), j = i: The same derivation now leads again to a number nj of factors,

whereas the square roots in Eq. (3.46) compensate, and we obtain

Π̂jj |{n}i = nj |{n}i

= â†j âj |{n}i. (3.47)
12
From the definition (3.41) it is obvious that Π̂ij is totally symmetric in all particle
indices.
102 CHAPTER 3. FERMIONS AND BOSONS

Thus, the results (3.46) and (3.47) can be combined to the operator identity

N
X
|iiα hj|α = â†i âj (3.48)
α=1

which, together with the definition (3.45), proves the theorem13 .

For the special case that the orbitals are eigenfunctions of an operator,
b̂α |φi i = bi |φi i—such as the single-particle hamiltonian, the corresponding
matrix is diagonal, bij = bi δij , and the representation (3.42) simplifies to
∞
X ∞
X
B̂1 = bi â†i âi = bi n̂i , (3.49)
i=1 i=1

where bi are the eigenvalues of b̂. Equation (3.49) naturally generalizes the
familiar spectral representation of quantum mechanical operators to the case
of many-body systems with arbitrary variable particle number.

Two-particle operators
A two-particle operator is of the form
N
1 X
B̂2 = b̂α,β , (3.50)
2! α6=β=1

where b̂α,β acts only on particles α and β. An example is the operator of

the pair interaction, b̂α,β → w(|rα − rβ |). We introduce again matrix elements,
now with respect to two-particle states composed as products of single-particle
orbitals, which belong to the two-particle Hilbert space H2 = H1 ⊗ H1 ,

bijkl = hij|b̂|kli, (3.51)

Theorem: The second quantization representation of a two-particle operator

is given by
∞
1 X
B̂2 = bijkl â†i â†j âl âk (3.52)
2! i,j,k,l=1

Proof:
We expand b̂ for an arbitrary pair α, β into a basis of two-particle orbitals
13
See problem 2.
3.3. SECOND QUANTIZATION FOR BOSONS 103

|iji = |φi i|φj i,

∞
X ∞
X
b̂ = |ijihij|b̂|klihkl| = |ijihkl| bijkl ,
i,j,k,l=1 i,j,k,l=1

leading to the following result for the total two-particle operator,

∞ N
1 X X
B̂2 = bijkl |iiα |jiβ hk|α hl|β . (3.53)
2! i,j,k,l=1 α6=β=1

The second sum is readily transformed, using the property (3.48) of the sigle-
particle states. We first extend the summation over the particles to include
α = β,
N
X N
X N
X N
X
|iiα |jiβ hk|α hl|β = |iiα hk|α |jiβ hl|β − δk,j |iiα hl|α
α6=β=1 α=1 β=1 α=1

= â†i âk â†j âl − δk,j â†i âl

n o
= â†i â†j âk + δk,j âl − δk,j â†i âl
= â†i â†j âk âl .
In the third line we have used the commutation relation (3.35). After ex-
changing the order of the two annihilators (they commute) and inserting this
expression into Eq. (3.53), we obtain the final result (3.52)14 .

General many-particle operators

The above results are directly extended to more general operators involving K
particles out of N
N
1 X
B̂K = b̂α ,...α , (3.54)
K! α 6=α 6=...α =1 1 K
1 2 K

and which have the second quantization representation

∞
1 X
B̂K = bj1 ...jk m1 ...mk â†j1 . . . â†jk âmk . . . .âm1 (3.55)
K! j
1 ...jk m1 ...mk =1

14
Note that the order of the creation operators and of the annihilators, respectively, is
arbitrary. In Eq. (3.52) we have chosen an ascending order of the creators (same order as the
indices of the matrix element) and a descending order of the annihilators, since this leads
to an expression which is the same for Bose and Fermi statistics, cf. Sec. 3.4.1.
104 CHAPTER 3. FERMIONS AND BOSONS

where we used the general matrix elements with respect to k-particle product
states, bj1 ...jk m1 ...mk = hj1 . . . jk |b̂|m1 . . . mk i. Note again the inverse ordering of
the annihilation operators. Obviously, the result (3.55) includes the previous
examples of single and two-particle operators as special cases.

3.4 Second quantization for fermions

We now turn to particles with half-integer spin, i.e. fermions, which are de-
scribed by anti-symmetric wave functions and obey the Pauli principle, cf.
Sec. 3.2.3.

3.4.1 Creation and annihilation operators for fermions

As for bosons we wish to introduce creation and annihilation operators that
should again allow to construct any many-body state out of the vacuum state
according to [cf. Eq. (3.36)]
 n 1  n 2
|n1 , n2 , . . . i = Λ−
1...N |i1 . . . iN i = â†1 â†2 . . . |0i. ni = 0, 1, (3.56)

Due to the Pauli principle we expect that there will be no additional prefactors
resulting from multiple occupations of orbitals, as in the case of bosons15 . So
far we do not know how these operators look like explicitly. Their definition
has to make sure that the N -particle states have the correct anti-symmetry
and that application of any creator more than once will return zero.
To solve this problem, consider the example of two fermions which can
occupy the orbitals k or l. The two-particle state has the symmetry |kli =
−|lki, upon particle exchange. The anti-symmetrized state is constructed of
the product state of particle 1 in state k and particle 2 in state l and has the
properties
† † † †
Λ− −
1...N |kli = âl âk |0i = |11i = −Λ1...N |lki = −âk âl |0i, (3.57)

i.e., it changes sign upon exchange of the particles (third equality). This
indicates that the state depends on the order in which the orbitals are filled,
i.e., on the order of action of the two creation operators. One possible choice
is used in the above equation and immediately implies that

â†k â†l + â†l â†k = [â†k , â†l ]+ = 0, ∀k, l, (3.58)

15
The prefactors are always equal to unity because 1! = 1
3.4. SECOND QUANTIZATION FOR FERMIONS 105

Figure 3.2: Illustration of the phase factor α in the fermionic creation and
annihiliation operators. The single-particle orbitals are assumed to be in a
definite order (e.g. with respect to the energy eigenvalues). The position of
the particle that is added to (removed from) orbital φk is characterized by the
number αk of particles occupying orbitals to the left, i.e. with energies smaller
than ǫk .

16
where we have introduced the
2 anti-commutator . In the special case, k = l,
we immediately obtain â†k = 0, for an arbitrary state, in agreement with
the Pauli principle. Calculating the hermitean adjoint of Eq. (3.58) we obtain
that the anti-commutator of two annihilators vanishes as well,

[âk , âl ]+ = 0, ∀k, l. (3.59)

We expect that this property holds for any two orbitals k, l and for any N -
particle state that involves these orbitals.
Now we can introduce an explicit definition of the fermionic creation oper-
ator which has all these properties. The operator creating a fermion in orbital
k of a general many-body state is defined as17

X
â†k | . . . , nk , . . . i = (1 − nk )(−1)αk | . . . , nk + 1, . . . i, αk = nl (3.60)
l<k

where the prefactor explicitly enforces the Pauli principle, and the sign factor
takes into account the position of the orbital k in the many-fermion state and
the number of fermions standing “to the left” of the “newly created” particle,
cf. Fig. 3.2. In other words, with αk pair exchanges (anti-commutations) the
particle would move from the leftmost place to the position (e.g. according
to an ordering with respect to the orbital energies Ek ) of orbital k in the N -
particle state. We now derive the annihilation operator by inserting a complete

16
This was introduced by P. Jordan and E. Wigner in 1927.
17
There can be other conventions which differ from ours by the choice of the exponent αk
which, however, is irrelevant for physical observables.
106 CHAPTER 3. FERMIONS AND BOSONS

set of anti-symmetric states and using (3.60)

X
âk | . . . , nk , . . . i = |{n′ }ih{n′ }|âk | . . . , nk , . . . i =
{n′ }
X
= |{n′ }ih{n}|â†k |{n′ }i∗
{n′ }
X ′
= k
(1 − n′k )(−1)αk δ{n ′
′ },{n} δnk ,n′ +1 |{n }i
k
{n′ }

= (2 − nk )(−1)αk | . . . , nk − 1, . . . i
≡ nk (−1)αk | . . . , nk − 1, . . . i

where, in the third line, we used definition (3.32). Also, αk′ = αk because the
sum involves only occupation numbers that are not altered. Note that the
factor 2 − nk = 1, for nk = 1. However, for nk = 0 the present result is not
correct, as it should return zero. To this end, in the last line we have added
the factor nk that takes care of this case. At the same time this factor does not
alter the result for nk = 1. Thus, the factor 2 − nk can be skipped entirely, and
we obtain the expression for the fermionic annihilation operator of a particle
in orbital k

âk | . . . , nk , . . . i = nk (−1)αk | . . . , nk − 1, . . . i (3.61)

Using the definitions (3.60) and (3.61) one readily proves the anti-commutation
relations given by the
Theorem: The creation and annihilation operators defined by Eqs. (3.60) and
(3.61) obey the relations

[âi , âk ]+ = [â†i , â†k ]+ = 0, ∀i, k, (3.62)

h i
âi , â†k = δi,k . (3.63)
+

Proof of relation (3.62):

Consider, the case of two annihilators and the action on an arbitrary anti-
symmetric state

[âi , âk ]+ |{n}i = (âi âk + âk âi ) |{n}i, (3.64)

and consider first case i = k. Inserting the definition (3.61), we obtain

(âk )2 |{n}i ∼ nk âk |n1 . . . nk − 1 . . . i = 0,

3.4. SECOND QUANTIZATION FOR FERMIONS 107

and thus the anti-commutator vanishes as well. Consider now the case18 i < k:
P
âi âk |{n}i = âi nk (−1) l<k nl |n1 . . . nk − 1 . . . i =
P P
= ni nk (−1) l<k nl (−1) l<i nl |n1 . . . ni − 1 . . . nk − 1 . . . i.
Now we compute the result of the action of the exchanged operator pair
P
âk âi |{n}i = âk ni (−1) l<i nl |n1 . . . ni − 1 . . . i =
P P
= ni nk (−1) l<i nl (−1) l<k nl −1 |n1 . . . ni − 1 . . . nk − 1 . . . i,
The only difference compared to the first result is in the additional −1 in the
second exponent. It arises because, upon action of âk after âi , the number of
particles to the left of k is already reduced by one. Thus, the two expressions
differ just by a minus sign, which proves vanishing of the anti-commutator.

The proof of relation (3.63) proceeds analogously and is subject of Problem 3,

cf. Sec. 3.8.
Thus we have proved all anti-commutation relations for the fermionic op-
erators and confirmed that the definitions (3.60) and (3.61) obey all properties
required for fermionic field operators. We can now proceed to use thes oper-
ators to bring arbitrary quantum-mechanical operators into second quantized
form in terms of fermionic orbitals.

Particle number operators

As in the case of bosons, the operator
n̂i = â†i âi (3.65)
is the occupation number operator for orbital i because, for ni = 0, 1,
â†i âi |{n}i = â†i (−1)αi |n1 . . . ni − 1 . . . i = ni [1 − (ni − 1)]|{n}i,
where the prefactor equals ni , for ni = 1 and zero otherwise. Thus, the anti-
symmetric state |{n}i is an eigenstate of n̂i with the eigenvalue coinciding with
the occupation number ni of this state19 .
The total particle number operator is defined as
X∞ X∞
N̂ = n̂i = â†i âi , (3.66)
i=1 i=1
P∞
because its action yields the total particle number: N̂ |{n}i = i=1 ni |{n}i =
N |{n}i.
18
This covers the general case of i 6= k, since i and k are arbitrary.
19
This result, together with the anti-commutation relations for the operators a and a†
proves the consistency of the definitions (3.60) and (3.61).
108 CHAPTER 3. FERMIONS AND BOSONS

Single-particle operators
Consider now again a single-particle operator
N
X
B̂1 = b̂α , (3.67)
α=1

and let us find its second quantization representation.

Theorem: The second quantization representation of a single-particle opera-
tor is given by
X∞
B̂1 = bij â†i âj (3.68)
i,j=1

Proof:
As for bosons, cf. Eq. (3.43), we have
N X
X ∞ ∞
X
B̂1 = bij |iiα hj|α = bij Π̂ij , (3.69)
α=1 i,j=1 i,j=1

where Π̂ij was defined by (3.41), and it remains to show that Π̂ij = â†i âj , for
fermions as well. To this end we consider action of Π̂ij on an anti-symmetric
state, taking into accont that Π̂ij commutes with the anti-symmetrization op-
erator Λ−1...N , Eq. (3.14),

N
1 XX
Π̂ij |{n}i = √ sign(π)|iiα hj|α · |j1 iπ(1) |j2 iπ(2) . . . |jN iπ(N ) . (3.70)
N ! α=1 πǫSN

If the product state does not contain the orbital |ji expression (3.70) vanishes,
due to the orthogonality of the orbitals. Otherwise, let jk = j. Then hj|jk i = 1,
and the orbital |jk i will be replaced by |ii, unless the state |ii is already present,
then we again obtain zero due to the Pauli principle, i.e.

Π̂ij |{n}i ∼ (1 − ni )nj {n}ij ,

 
(3.71)

where we used the notation (3.45). What remains is to figure out the sign
change due to the removal of a particle from the i-th orbital and creation of
one in the k-th orbital. To this end we first P
“move” the (empty) orbital |ji
past all orbitals to the left occupied by αj = p<j np particles, requiring just
αj pair permutations P and sign changes. Next we move the “new” particle to
orbital “i” past αi = p<i np particles occupying the orbitals with an energy
3.4. SECOND QUANTIZATION FOR FERMIONS 109

lower then Ei leading to αi pair exchanges and sign changes20 . Taking into
account the definitions (3.60) and (3.61) we obtain21

Π̂ij |{n}i = (−1)αi +αj (1 − ni )nj {n}ij = â†i âj |{n}i

 
(3.72)

which, together with the equation (3.69), proves the theorem. Thus, the second
quantization representation of single-particle operators is the same for bosons
and fermions.

Two-particle operators
As for bosons, we now derive the second quantization representation of a two-
particle operator B̂2 .
Theorem: The second quantization representation of a two-particle operator
is given by
∞
1 X
B̂2 = bijkl â†i â†j âl âk (3.73)
2! i,j,k,l=1

Proof:
As for bosons, we expand B̂ into a basis of two-particle orbitals |iji = |φi i|φj i,
∞ N
1 X X
B̂2 = bijkl |iiα |jiβ hk|α hl|β , (3.74)
2! i,j,k,l=1 α6=β=1

and transform the second sum

N
X N
X N
X N
X
|iiα |jiβ hk|α hl|β = |iiα hk|α |jiβ hl|β − δk,j |iiα hl|α
α6=β=1 α=1 β=1 α=1

= − δk,j â†i âl

â†i âk â†j âl
n o
= â†i −â†j âk + δk,j âl − δk,j â†i âl
= −â†i â†j âk âl .
20
Note that, if i > j, the occupation numbers occuring in αi have changed by one compared
to those in αj .
21
One readily verifies that this result applies also to the case j = i. Then the prefactor is
just [1 − (nj − 1)]nj = nj , and αi = αj , resulting in a plus sign

Π̂jj |{n}i = nj |{n}i = â†j âj |{n}i.

110 CHAPTER 3. FERMIONS AND BOSONS

In the third line we have used the anti-commutation relation (3.63). After
exchanging the order of the two annihilators, which now leads to a sign change,
and inserting this expression into Eq. (3.74), we obtain the final result (3.73).

General many-particle operators

The above results are directly extended to a general K-particle operator, K ≤

N , which was defined in Eq. (3.54). Its second quantization representation is
found to be
∞
1 X
B̂K = bj1 ...jk m1 ...mk â†j1 . . . â†jk âmk . . . .âm1 (3.75)
K! j
1 ...jk m1 ...mk =1

where we used the general matrix elements with respect to k-particle product
states, bj1 ...jk m1 ...mk = hj1 . . . jk |b̂|m1 . . . mk i. Note again the inverse ordering
of the annihilation operators which exactly agrees with the expression for a
bosonic system. Obviously, the result (3.75) includes the previous examples of
single and two-particle operators as special cases.

3.4.2 Matrix elements in Fock space

We now further extend the analysis of the anti-symmetric Fock space. A con-
venient orthonormal basis for a system of N fermions are the anti-symmetric
states |{n}i, cf. Eq. (3.21). Then operators are completely defined by their
action on these states and by their matrix elements. For fermions the occupa-
tion number representation can be cast into a simple spinor formulation which
we consider next.

Spinor representation of single-particle states

The fact that the fermionic occupation numbers have only two possible values
is very similar to the two spin projections of spin 1/2 particles and allows
for a very intuitive description in terms of spinors. Thus, an empty or singly
occupied orbital can be written as a column
 
1
|0i → − empty state, (3.76)
0
 
0
|1i → − occupied state, (3.77)
1
3.4. SECOND QUANTIZATION FOR FERMIONS 111

and, analogously for the “bra”-states,

h0| → 1 0 − empty state, (3.78)


h1| → 0 1 − occupied state, (3.79)
where the two form an orthonormal basis with h0|0i = h1|1i = 1 and h0|1i = 0.

Spinor representation of operators

In the spinor representation each second quantization operator becomes a 2×2
matrix,
 
A00 A01
 → , (3.80)
A10 A11
where Aαβ = hα|Â|βi and α, β = 0, 1.
The particle number operator has the following action
 
1
n̂ = 0, (3.81)
0
   
0 0
n̂ = 1 , (3.82)
1 1
and is, therefore, given by a diagonal matrix in this spinor representation with
its eigenvalues on the diagonal,22
 
′ ′ 0 0
n̂ → hn|n̂|n i = n 1̂ = , (3.83)
0 1
and one readily confirms that this is consistent with the action of the operator
given by Eqs. (3.81) and (3.82).

Spinor representation of â and â†

Using the definitions (3.60) and (3.61) we readily obtain the matrix elements
of the creation and annihilation operator. We again consider the matrices with
respect to single-particle states |φk i and take into account that, for fermions,
nk is either 0 or 1. As a result, we obtain
 
D   E
 † ′ 0 0
nk âk  nk = = δnk ,1 δnk ,n′k +1 ≡ A†k , (3.84)
1 0
 
′ 0 1
hnk |âk | nk i = = δnk ,0 δnk ,n′k −1 ≡ Ak , (3.85)
0 0
22
The first [second] row corresponds to the case hn| = h0| [hn| = h1|], whereas the first
[second] column corresponds to |ni = |0i [|ni = |1i].
112 CHAPTER 3. FERMIONS AND BOSONS

where the matrix of âk is the transposed of that of â†k and we introduced the
short-hand notation Ak for the matrix δnk ,0 δn′k ,1 in the space of single-particle
orbitals |φk i 23 .

Matrix elements of â and ↠in Fock space

It is now easy to extend this to matrix elements with respect to anti-symmetric

N -particle states. These matrices will have the same structure as (3.84) and
(3.85), with respect to orbital k, and be diagonal with respect to all other
orbitals. In addition, there will be a sign factor depending on the position of
orbital k in the N -particle state, cf. definitions (3.60) and (3.61),

D   E
{n} â†k  {n′ } = (−1)αk δ{n},{n
k †
′ } Ak (3.86)
 

where the original prefactor 1 − n′k has been transformed into an additional
Kronecker delta for nk . The matrix of the annihilation operator is

h{n} |âk | {n′ }i = (−1)αk δ{n},{n

k
′ } Ak (3.87)

Matrix elements of one-particle operators in Fock space

To compute the matrix elements of one-particle operators, Eq. (3.43), we need

the matrix of the projector Π̂kl . Using the results (3.87) for the annihiliator

23
We summarize the main properties of the matrices Ak and A†k which are a consequence
of the properties of â†k and âk and can be verified by direct matrix multiplication:
 2
1. A2k = A†k = 0.

 
0 0
2. A†k Ak = = nk 1̂k , – a diagonal matrix with the eigenvalues of n̂k on the
0 1
diagonal, cf. Eq. (3.83).
 
1 0
3. Ak A†k = = (1 − nk )1̂k = 1 − A†k Ak , i.e. A†k and Ak anti-commute.
0 0

4. For different single-particle spaces, k 6= l, [A†k , Al ]+ = [A†k , A†l ]+ = [Ak , Al ]+ = 0.

3.4. SECOND QUANTIZATION FOR FERMIONS 113

and (3.86) for the creator successively we obtain, for the case k 6= l,
D   E XD   E
{n} â†l âk  {n′ } = {n} â†l  {n̄} h{n̄} |âk | {n′ }i =
   
{n̄}
X
α′k
= (−1) (−1)ᾱl δn̄k ,0 δ{n̄},{n
k l
′ } δn̄k ,n′ −1 δnl ,1 δ{n̄},{n} δn̄l +1,nl
k
{n̄}
X
α′k
kl
= (−1) δnl ,1 δ{n},{n ′} (−1)ᾱl δn̄k ,0 δn̄k ,nk δn̄l ,n′l δn̄k ,n′k −1 δn̄l +1,nl
n̄,n̄k
†
X X
= kl
(−1)αk′ l δ{n},{n ′ } Al Ak , αk ′ l = n′m + nm , (3.88)
m<k m<l

which is a diagonal matrix in all orbitals except k and l whereas, with respect
to orbital k, it has the structure of the matrix (3.86) and, for orbital l, the form
of matrix (3.87). Note that the occupation numbers entering the exponent αk′ l
are restricted by the Kronecker symbols. For the case k = l we recover the
matrix of the particle number operator which is completely diagonal24
D   E
{n} â†k âk  {n′ } = h{n} |n̂k | {n′ }i = nk δ{n},{n′ } . (3.89)
 

With the results (3.88) and (3.89) we readily obtain the matrix represen-
tation of a single-particle operator, defined by Eq. (3.67),

D   E X∞ D   E
{n} B̂1  {n′ } = blk {n} â†l âk  {n′ } (3.90)
   
k,l=1

First, for a diagonal operator B diag , blk = bk δkl , the result is simply

D   E ∞
X N
X
{n} B̂1diag  {n′ } = δ{n},{n′ } bk nk = δ{n},{n′ } bnk . (3.91)
 
k=1 k=1

where, in the last equality, we have simplified the summation by including only
the occupied orbitals which have the numbers n1 , n2 . . . nN .

24
ThisPresult is contained in expression (3.88). Indeed, in the special case k = l we obtain
αk′ l → m<k (n′m + nm ), δ{n},{n
kl k
′ } → δ{n},{n′ } and the matrix product in k-orbital space

yields A†k Ak → nk δnk ,n′k [cf. property 2 in footnote 23] which combines to the results (3.89).
114 CHAPTER 3. FERMIONS AND BOSONS

For the general case of a non-diagonal operator it follows from (3.90)25

( N
D   E X
{n} B̂1  {n′ } = δ{n},{n′ } bn k n k +
 
k=1
N
)
X nk nl
+ (−1)k+l+γkl bnl nk δ{n},{n †
′ } Anl Ank , . (3.92)
k6=l=1

where γkl = 1, for k < l, and 0, otherwise.

Matrix elements of two-particle operators in Fock space

To compute the matrix elements of two-particle operators, Eq. (3.73), we need
the matrix elements of four-operator products, which we transform, using the
anti-commutation relations (3.63) according to
â†i â†j âl âk = −â†i âl â†j âk + δjl â†i âk . (3.93)
Next, transform the matrix element of the first term on the right,
D   E XD   ED   E
 † †  ′  †   †  ′
{n} âi âl âj âk  {n } = {n} âi âl  {n̄} {n̄} âj âk  {n } =
{n̄}
X jk
= il
(−1)αil̄ δ{n},{n̄} δni ,1 δn̄i ,0 δnl ,0 δn̄l ,1 × (−1)αj̄k′ δ{n̄},{n ′ } δn̄j ,1 δn′ ,0 δn̄k ,0 δn′ ,1 ,
j k
{n̄}

where αj̄k′ = p<j n̄p + p<k n′ etc. Performing the summation, with the help
P P

of the Kronecker deltas we obtain the final result26

D   E
 † †  ′ iljk † †
{n} âi âl âj âk  {n } = (−1)αilj′ k′ δ{n},{n ′ } Ai Al Aj Ak (3.94)
X X X X
with αilj ′ k′ = np + np + n′p + n′p .
p<i p<l p<j p<k

25
The non-diagonal matrix elements are transformed to summation over occupied orbitals
as
∞ D   E N
{n} â†l âk  {n′ } =
X X
bnl nk {n} â†nl ânk  {n′ } ,

  
blk
 
k6=l=1 k6=l=1

where it remains to carry out the action oft the two operators. Note that the sign of the
result is different for nl < nk and nl > nk .
26
We first rewrite
X X
il
δ{n},{n̄ δ jk
p } {n̄p },{n′ }
= iljk
δ{n},{n ′ } δnj ,n̄j δnk ,n̄k δn̄i ,n′ δn̄l ,n′ ,
i l
{n̄p } n̄i n̄l n̄j n̄k

Taking into account the other

P Kronecker deltas we can combine pairs and perform the
remaining four summations, n̄i δn̄i ,n′i δn̄i ,0 = δn′i ,0 and so on.
3.4. SECOND QUANTIZATION FOR FERMIONS 115

This is a general result which also contains the cases of equal index pairs.
Then, proceeding as in footnote 24, we obtain the results for the special cases.
jk †
i=l: (−1)αj′ k′ δ{n},{n ′ } ni Aj Ak

†
j=k: (−1)αil δ{n},{n
il
′ } nj Ai Al

†
ik
l=j: (−1)αik′ δ{n},{n ′ } (1 − nl )Ai Ak

i=l, j=k: δ{n},{n′ } ni nj

lj †
k=i: (−1)αlj′ δ{n},{n ′ } ni Al Aj + (−1) δ{n},{n′ } δij A†i Al
αil il

3.4.3 Fock Matrix of the binary interaction

Of particular importance is the occupation number matrix representation of
the interaction potential. This is an example of a two-particle quantity the
properties of which we discussed in section 3.4.2. But for this special case, we
can make further progress27 . Starting point is the pair interaction
N
1 X
V̂ = ŵ(α, β), (3.95)
2 α6=β=1

with the second quantization representation (3.73)

1X
V̂ = wijkl â†i â†j âl âk , (3.96)
2 ijkl

where the matrix elements are defined as

Z
wijkl = d3 xd3 y φ∗i (x)φ∗j (y)w(x, y)φk (x)φl (y), (3.97)

and have the following symmetries

wijkl = = wjilk , (3.98)

∗
wijkl = wklij , (3.99)

where property (3.99) follows from the symmetry of the potential w(x, y) =
w(y, x). This allows us to eliminate double counting of pairs from the sum in
27
M. Heimsoth contributed to this section.
116 CHAPTER 3. FERMIONS AND BOSONS

Eq. (3.96)28
∞
X ∞
X
V̂ = −
wijkl â†j â†i âk âl , (3.100)
1≤i<j 1≤k<l
−
wijkl = wijkl − wijlk , (3.101)

where we introduced an antisymmetrized potential w− . Note the change of

the order of the creation and annihilation operator pairs in Eq. (3.100).
We now compute the matrix of (3.100) with fully antisymmetric vectors
|{n}i and |{n′ }i
∞
X ∞
X
′
h{n}|V̂ |{n }i = −
wijkl h{n}|â†j â†i âk âl |{n′ }i. (3.102)
1≤i<j 1≤k<l

Each of the two vectors contains N particles (the interaction does not change
the particle number), i.e. exactly N occupied orbitals which are all different.
So the sums over i, j and k, l, in fact, run over two (possibly different) sets of N
orbitals with the numbers (m1 , m2 . . . mN ) and (m′1 , m′2 . . . m′N ), respectively,29

h{n}|V̂ |{n′ }i → h{m}|V̂ |{m′ }i =

XN XN
− † † ′
= wm ′
i mj m m
′ h{m}|âm âm âm′ âm′ |{m }i. (3.103)
j i k l
k l
1≤i<j 1≤k<l

Using the definitions of the creation and annihilation operators, Eqs. (3.60),
28
We summarize the main steps: First, using the anti-commutation relations of the anni-
hilators and perfoming an index change, we transform (the contribution k = l vanishes),
X X X
−
wijkl âl âk = (wijkl − wijlk )âl âk = wijkl âl âk .
kl k<l k<l

Extending this to the sum over i, j and using the symmetry properties (3.98), we obtain

(wijkl − wijlk )â†i â†j âl âk = (wijkl − wjikl − wijlk + wjilk )â†i â†j âl âk =
X X

ij,k<l i<j,k<l

â†i â†j âl âk = 2 â†j â†i âk âl

X X
− −
= 2 wijkl wijkl
i<j,k<l i<j,k<l

29
by |{m}i = |{m}i(|{n}i) we will denote the subset of N occupied orbitals contained
in the state |{n}i. For example, a three-particle state |{n}i = |1, 0, 0, 1, 1i transforms into
|m1 m2 m3 i where the mi point to the original orbitals with numbers m1 = 1, m2 = 4, m3 = 5.
Note that the matrix h{n}|V̂ |{n′ }i is diagonal in all orbitals missing simultaneously in h{m}|
and |{m′ }i.
3.4. SECOND QUANTIZATION FOR FERMIONS 117

(3.61), and taking advantage of the operator order in (3.103)30 , the operators
can be evaluated, with the result
N
X N
X
′ −
h{m}|V̂ |{m }i = (−1)i+j+k+l wm ′
i mj m m
′
′ h{m}|mi ,mj |{m }im′ ,m′ ,
k l
k l
1≤i<j 1≤k<l
(3.104)
where the notation |{m′ }im′k ,m′l means that the single-particle orbitals with
number m′k and m′l are missing in the state |{m′ }i which now is a state of
N − 2 particles, and similarly for h{m}|mi ,mj . The scalar product of the two
anti-symmetric N −2-particle states in (3.104) is non-zero only if the two states
contain N − 2 identical orbitals. To simplify the analysis, in Eq. (3.104) we
have moved the missing orbitals to positions one and two in the states thereby
accumulating the total sign factor contained in this expression. Thus, the
remaining orbitals are not only identical but they also have identical numbers,
i.e. m3 = m′3 , m4 = m′4 , . . . .
Finally, expression (3.104) will be only non-zero if the missing orbitals fall
in one of three cases31 :
1. The two states are identical, {n} ≡ {n′ } and, consequently {m} ≡ {m′ }.
Then Eq. (3.104) yields
N
X
h{n}|V̂ |{n′ }i = δ{n},{n′ } −
wm i mj mi mj
. (3.105)
1≤i<j

2. The two states are identical except for one orbital: the orbital mp with
number p is present in state h{m}| but is missing in state |{m′ }i which,
instead, contains an orbital mr with number r missing in h{m}|. Then
the scalar product of the two N − 2 particle states is nonzero only if both
these states are annihilated and Eq. (3.104) yields32
N −1
mp m′r
X
′ † −
h{n}|V̂ |{n }i = δ{n},{n ′ } Amp Am′r (−1)p+r · Θ(p, r, i) wm i mp mi mr
′

1≤i,i6=p,r
(3.106)
Here Θ(p, r, i) = −1, if either mp < mi or m′r
< mi , otherwise Θ(p, r, i) =
1. This case describes single-particle excitations where |{n′ }i = |{n}rp i.
30
Since i < j and k < l, the signs produced by the first and second operators are inde-
pendent of each other.
31
Thereby we return to the full vectors (including the empty orbitals) and restore the
delta functions.
32
To obtain the correct sign we move the orbitals p and r to the last place in the product
in state h{n}| and in |{n′ }i, respectively and count the number of transpositions (difference).
118 CHAPTER 3. FERMIONS AND BOSONS

3. The two states are identical except for two orbitals with the numbers mp
and mq in h{m}| and m′r and m′s in |{m′ }i, respectively. Without loss of
generality we can use mp < mq and m′r < m′s . Then Eq. (3.104) yields
m m m′ m′s −
h{n}|V̂ |{n′ }i = δ{n},{n
p q r
A†mp Am′r A†mq Am′s (−1)p+q+r+s wm
′} p mq mr ms
′ ′

(3.107)
This case describes two-particle excitations where |{n′ }i = |{n}rspq i.

These results are known as Slater-Condon rules and were obtained by those
two authors in 1929 and 1930 [Sla29, Con30] and are of prime importance for
wave function based many-body methods such as configuration interaction
(CI) and Multiconfiguration Hartree-Fock (MCHF) and their time-dependent
extensions, e.g. [HHB14]. Similarly this representation is used in configura-
tion path integral Monte Carlo simulations of strongly correlated fermions,
e.g. [SBF+ 11] and references therein.

3.5 Coordinate representation of second quan-

tization operators. Field operators
So far we have considered the creation and annihilation operators in an arbi-
trary basis of single-particle states. The coordinate and momentum represen-
tations are of particular importance and will be considered in the following.
As before, an advantage of the present second quantization approach is that
these considerations are entirely analogous for fermions and bosons and can
be performed at once for both, the only difference being the details of the
commutation (anticommutation) rules of the respective creation and annihila-
tion operators. Here we start with the coordinate representation whereas the
momentum representation will be introduced below, in Sec. 3.6.

3.5.1 Definition of field operators

We now introduce operators that create or annihilate a particle at a given
space point rather than in given orbital φi (r). To this end we consider the
superposition in terms of the functions φi (r) where the coefficients are the
creation and annihilation operators,
∞
X
ψ̂(x) = φi (x)âi , (3.108)
i=1
X∞
ψ̂ † (x) = φ∗i (x)â†i . (3.109)
i=1
3.5. FIELD OPERATORS 119

Figure 3.3: Illustration of the relation of the field operators to the second
quantization operators defined on a general basis {φi (x)}. The field operator
ψ̂ † (x) creates a particle at space point x (in spin state |σi) to which all single-
particle orbitals φi contribute. The orbitals are vertically shifted for clarity.

Here x = (r, σ), i.e. φi (x) is an eigenstate of the operator r̂, and the φi (x)
form a complete orthonormal set. Obviously, these operators have the desired
property to create (annihilate) a particle at space point r in spin state σ. From
the (anti-)symmetrization properties of the operators a and a† we immediately
obtain
h i
ψ̂(x), ψ̂(x′ ) = 0, (3.110)
h i∓
ψˆ† (x), ψˆ† (x′ ) = 0, (3.111)
∓
h i
ψ̂(x), ψˆ† (x′ ) = δ(x − x′ ). (3.112)
∓

These relations are straightforwardly proven by direct insertion of the def-

initions (3.108) and (3.109). We demonstrate this for the last expression.

h i ∞
X h i
† ′
ψ̂(x), ψ̂ (x ) = φi (x)φ∗j (x′ ) âi , â†j =
∓ ∓
i,j=1
X ∞
= φi (x)φ∗i (x′ ) = δ(x − x′ ) = δ(r − r′ )δσ,σ′ ,
i=1

where, in the last line, we used the representation of the delta function in
terms of a complete set of functions.
120 CHAPTER 3. FERMIONS AND BOSONS

3.5.2 Representation of operators

We now transform operators into second quantization representation using the
field operators, taking advantage of the identical expressions for bosons and
fermions.

Single-particle operators

The general second-quantization representation was given by [cf. Secs. 3.3,

3.4]
X∞
B̂1 = hi|b̂|jia†i aj . (3.113)
i,j=1

We now transform the matrix element to coordinate representation:

Z
hi|b̂|ji = dxdx′ φ∗i (x)hx|b̂|x′ iφj (x′ ), (3.114)

and obtain for the operator, taking into account the definitions (3.108) and
(3.109),

∞ Z
X
B̂1 = dxdx′ a†i φ∗i (x)hx|b̂|x′ iφj (x′ )aj =
i,j=1
Z
= dxdx′ ψ̂ † (x)hx|b̂|x′ iψ̂(x′ ). (3.115)

For the important case that the matrix is diagonal, hx|b̂|x′ i = b̂(x)δ(x − x′ ),
the final expression simplifies to
Z
B̂1 = dx ψ̂ † (x)b̂(x)ψ̂(x) (3.116)

Consider a few important examples. The first is again the density operator.
In first quantization the operator of the particle density for N particles follows
from quantizing the classical result for point particles,

N
X
n̂(x) = δ(x − xα ), (3.117)
α=1
3.5. FIELD OPERATORS 121

and the expectation value in a certain N -particle state Ψ(x1 , x2 , . . . xN ) is33

N
X
hn̂i(x) = h Ψ| δ(x − xα )|Ψ i
α=1
Z
= N d2d3 . . . dN |Ψ(1, 2, . . . N )|2 = n(r, σ), (3.118)

which is the single-particle spin density of a (in general correlated) N -particle

system. The second quantization representation of the density operator follows
from our above result (3.116) by replacing b̂ → δ(x − x′ ), i.e.
Z
n̂(x) = dx′ ψ̂ † (x′ )δ(x − x′ )ψ̂(x′ ) = ψ̂ † (x)ψ̂(x), (3.119)

and the operator of the total density is the sum (integral) over all coordinate-
spin states Z Z
N̂ = dx n̂(x) = dx ψ̂ † (x)ψ̂(x), (3.120)

naturally extending the previous results for a discrete basis to continuous

states.
The second example is the kinetic energy operator which is also diagonal
and has the second-quantized representation
 
1 2
Z
†
T̂ = dx ψ̂ (x) − ∇ ψ̂(x). (3.121)
2

The third example is the second quantization representation of the single-

particle potential v(r) given by
Z
V̂ = dx ψ̂ † (x)v(r)ψ̂(x). (3.122)

Two-particle operators
In similar manner we obtain the field operator representation of a general
two-particle operator
∞
1 X
B̂2 = hij|b̂|klia†i a†j al ak . (3.123)
2 i,j,k,l=1

33
This is the example of an (anti-)symmetrized pure state which is easily extended to
mixed states.
122 CHAPTER 3. FERMIONS AND BOSONS

We now transform the matrix element to coordinate representation:

Z
hij|b̂|kli = dx1 dx2 dx3 dx4 φ∗i (x1 )φ∗j (x2 )hx1 x2 |b̂|x3 x4 iφl (x3 )φk (x4 ), (3.124)

and, assuming that the matrix is diagonal,

hx1 x2 |b̂|x3 x4 i = b̂(x1 , x2 )δ(x1 − x3 )δ(x2 − x4 ), we obtain, after inserting this
result into (3.123),
∞
1 X
Z
B̂2 = dx1 dx2 a†i φ∗i (x1 )a†j φ∗j (x2 )b̂(x1 , x2 )φl (x1 )al φk (x2 )ak .
2 i,j,k,l=1

Using again the defintion of the field operators the final result for a diagonal
two-particle operator in coordinate representation is
1
Z
B̂2 = dx1 dx2 ψ̂ † (x1 )ψ̂ † (x2 )b̂(x1 , x2 )ψ̂(x2 )ψ̂(x1 ) (3.125)
2
Note again the inverse ordering of the destruction operators which makes this
result universally applicable to fermions and bosons. The most important
example of this representation is the operator of the two-particle interaction,
Ŵ , which is obtained by replacing b̂(x1 , x2 ) → w(x1 − x2 ).

3.6 Momentum representation of second quan-

tization operators
We now consider the momentum representation of the creation and annihila-
tion operators. This is useful for translationally invariant systems such as the
electron gas or the jellium model, since the eigenfunctions of the momentum
operator,
1
hx|φk,s i = φk,s (x) = 1/2 eik·r δs,σ , x = (r, σ), (3.126)
V
are eigenfunctions of the translation operator. Here we use periodic boundary
conditions to represent an infinite system by a finite box of length L and volume
V = L3 , so the wave numbers have discrete values kx = 2πnx /L, . . . kz =
2πnz /L with nx , ny , nz being integer numbers. The eigenfunctions (3.126)
form a complete orthonormal set, where the orthonormality condition reads
1
Z X
′
hφk,s |φk′ ,s′ i = d3 r ei(k −k)r δs,σ δs′ ,σ = δk,k′ δs,s′ , (3.127)
V V σ

where we took into account that the integral over the finite volume V equals
zero for k 6= k′ and V otherwise.
3.6. MOMENTUM REPRESENTATION 123

3.6.1 Creation and annihilation operators

in momentum space
The creation and annihilation operators on the Fock space of N -particle states
constructed from the orbitals (3.126) are obtained by inverting the definition of
the field operators (3.108) written with respect to the momentum-spin states
(3.126)
X
ψ̂(x) = φk′ ,σ′ (x)ak′ ,σ′ .
k′ σ ′

Multiplication by φ∗k,σ (x) and integrating over x yields, with the help of con-
dition (3.127),
1
Z Z
ak,σ = dx φ∗k′ σ′ ψ̂(x) = 1/2 d3 r e−ik·r ψ̂(r, σ), (3.128)
V V

and, similarly for the creation operator,

1
Z
†
ak,σ = d3 r eik·r ψ̂ † (r, σ). (3.129)
V 1/2 V
Relations (3.128) and (3.129) are nothing but the Fourier transforms of the
field operators. These operators obey the same (anti-)commutation relations as
the field operators, which is a consequence of the linear superpositions (3.128),
(3.129), cf. the proof of Eq. (3.112).

3.6.2 Representation of operators

We again construct the second quantization representation of the relevant op-
erators, now in terms of creation and annihilation operators in momentum
space.

Single-particle operators
For a single-particle operator we have, according to our general result, Eq.
(3.69), and denoting x = (r, s), x′ = (r′ , s′ ),
XX †
B̂1 = akσ hkσ|b̂|k′ σ ′ i ak′ σ′
kσ k′ σ ′
XXZ
= dx dx′ a†kσ hkσ|xihx|b̂|x′ ihx′ |k′ σ ′ i ak′ σ′
kσ k′ σ ′
1 XX
Z
dx dx′ a†kσ e−ikr hx|b̂|x′ ieik r ak′ σ′ δσ,s δσ′ ,s′ , (3.130)
′ ′
=
V kσ k′ σ′
124 CHAPTER 3. FERMIONS AND BOSONS

where, in the last line, we inserted complete sets of momentum eigenstates

(3.126). If the momentum matrix elements of the operator b̂ are known, the
first line can be used directly. Otherwise, the matrix element is obtained from
the the known coordinate space result in the last line.
For an operator that commutes with the momentum operator and, thus,
is given by a diagonal matrix one integration (and spin summation) can be
performed. We demonstrate this for the example of the kinetic energy operator.
2 ∇2
Then hx|b̂|x′ i → − ~2m δ(x − x′ ), and we obtain, using the property (3.127),
2 ′2
1 XX −ikr ~ k
Z
3 † ′
T̂ = d r akσ e eik r ak′ σ
V kσ k′ V 2m
X ~2 k 2 †
= a akσ . (3.131)
kσ
2m kσ

In similar fashion we obtain for the single-particle potential, upon replacing

hx|b̂|x′ i → v(r)δ(x − x′ ),
1
XX † Z
′
V̂ = akσ ak σ′ d3 r e−ikr v(r) eik r
kσ k′
V V
XX
= ṽk−k′ a†kσ ak′ σ , (3.132)
kσ k′

where we Rintroduced the Fourier transform of the single-particle potential,

ṽq = V −1 d3 r v(r)e−iqr . Finally, the operator of the single-particle density
becomes, in momentum space by Fourier transformation,
X X1Z
n̂q = n̂qσ = d3 r ψσ† (r)ψσ (r) e−iqr
σ σ
V V

1 X † 1
Z
′
= ak′ σ akσ d3 r ei(k−k )r e−iqr
V σkk′ V V
1X †
= a akσ . (3.133)
V σk k−q,σ

This shows that the Fourier component of the density operator, n̂q , describes
a density fluctuation corresponding to a transition of a particle from state
|φkσ i to state |φk−q,σ i, for arbitrary k. With this result we may rewrite the
single-particle potential (3.132) as
X
V̂ = V ṽq n̂−q . (3.134)
q
3.6. MOMENTUM REPRESENTATION 125

Two-particle operators
We now turn to two-particle operators. Rewriting the general result (3.73) for
a spin-momentum basis, we obtain
1 X X †
B̂2 = ak1 σ1 a†k2 σ2 hk1 σ1 k2 σ2 |b̂|k′1 σ1′ k′2 σ2′ i ak′2 σ2′ ak′1 σ1′ (3.135)
2! k σ k σ ′ ′ ′ ′
1 1 2 2 k 1 σ1 k 2 σ 2

We now apply this result to the interaction potential where the matrix element
in momentum representation was computed before, hk1 σ1 k2 σ2 |ŵ|k′1 σ1′ k′2 σ2′ i =
w̃(k1 − k′1 )δk1 +k2 −k′1 −k′2 δσ1 ,σ1′ δσ2 ,σ2′ , and w̃ denotes the Fourier transform of the
pair interaction, and the interaction does not change the spin of the involved
particles, see problem 6, Sec. 3.8. Inserting this into Eq. (3.135) and intro-
ducing the momentum transfer q = k′1 − k1 = k2 − k′2 , we obtain
1 X X
Ŵ = w̃(q)a†k1 σ1 a†k2 σ2 ak2 −q,σ2 ak1 +q,σ1 , (3.136)
2! k k q σ σ
1 2 1 2

In similar manner other two-particle quantities are computed. With this

result we can write down the second quantization representation in spin-
momentum space of a generic hamiltonian that contains kinetic energy, an
external potential and a pair interaction contribution. From the expressions
(3.131, 3.132, 3.136) we obtain
X ~2 k 2 † X
Ĥ = akσ akσ + ṽk−k′ a†kσ ak′ σ
kσ
2m kk′ σ
1 X X
+ w̃(q)a†k1 σ1 a†k2 σ2 ak2 −q,σ2 ak1 +q,σ1 . (3.137)
2! k k q σ σ
1 2 1 2

This result is a central starting point for many investigations in condensed

matter physics, quantum plasmas or nuclear matter.

3.6.3 The uniform electron gas (jellium)

An important special case where the momentum representation is advanta-
geous is the uniform electron gas (UEG) or jellium. The system is spatially
homogeneous, so the momentum is conserved. The hamiltonian of this system
follows from the result (3.137) by omitting the external potential,
X ~2 k 2 † ξM
Ĥ = akσ akσ + N
kσ
2m 2
1 X X
+ w̃(q)a†k1 σ1 a†k2 σ2 ak2 −q,σ2 ak1 +q,σ1 . (3.138)
2! k k q σ σ
1 2 1 2
126 CHAPTER 3. FERMIONS AND BOSONS

The thermodynamic properties of the UEG will be discussed in Sec. 4.3.3.

Application to relativistic quantum systems

The momentum representation is conveniently extended to relativistic many-
particle systems. In fact, since the Dirac equation of a free particle has plane
wave solutions, we may use the same single-particle orbitals as in the non-
relativistic case. With this, the matrix elements of the single-particle potential
and of the interaction potential remain unchanged (if magnetic corrections to
the interaction are neglected). The only change is in the kinetic energy con-
tribution, due√ to the relativistic modification of the single-particle dispersion,
2 k2
ǫk = ~2m → ~2 k 2 c2 + m2 c4 , where m is the rest mass. In the ultra-relativistic
limit, ǫk = ~ck. Otherwise the hamiltonian (3.137) remains valid.
Of course, this is true only as long as pair creation processes are negligible.
Otherwise we would need√to extend the description by introducing the negative
energy branch ǫk− = − ~2 k 2 c2 + m2 c4 and the corresponding second set of
plane wave states. In all matrix elements we would need to include a second
index (+, −) referring to the energy band.

3.7 Discussion and outlook

After investigating the basic properties of the method of second quantization
we now turn to more advanced topics. One of them is the extension of the
analysis to systems at a finite temperature, i.e. in a mixed ensemble. This
will be the subject of Chapter 4. After this we turn to the time evolution of
the field operators following an external perturbation. This will be studied in
detail for the case of single-time observables, in Chapter 5. A second route to
nonequilibrium dynamics is to use field operator products that depend on two
times which leads to the theory of nonequilibrium Green functions which we
discuss in Chapter 7.

3.8 Problems to Chapter 3

1. Express Λ± ±
123 via Λ12 , cf. Eqs. (3.11) and (3.12).

2. Generalize the previous result to find a decomposition of Λ±

1...N into lower
order operators.

3. Prove the bosonic commutation relations (3.34).

3.8. PROBLEMS TO CHAPTER 3 127

4. Prove the anti-commuation relation (3.63) between fermionic creation

and annhiliation operators.

5. Discuss what happened to the sum over α in the derivation of Eq. (3.48).

6. Compute the momentum matrix element of the pair interaction.