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Introduction to Quantum Field Theory


and Quantum Statistics

Michael Bonitz

Insitut für Theoretische Physik und Astrophysik


Kiel University

February 9, 2015

preliminary lecture notes, not for distribution


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Contents

1 Canonical Quantization 11
1.1 Minimal action principle . . . . . . . . . . . . . . . . . . . . . . 11
1.1.1 Classical mechanics of a point particle . . . . . . . . . . 16
1.1.2 Canonical momentum and Hamilton density of classical
fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.2 Conservation laws in classical field theory . . . . . . . . . . . . . 19
1.2.1 Translational invariance. Energy and momentum con-
servation . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.3 Field quantization . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1.4 Phonons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
1.4.1 Application of canonical field theory . . . . . . . . . . . 27
1.4.2 Expansion in terms of eigenfunctions . . . . . . . . . . . 28
1.4.3 Quantization of the displacement field . . . . . . . . . . 30
1.5 Photons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
1.5.1 Maxwell’s equations. Electromagnetic potentials. Field
tensor . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
1.5.2 Lagrange density of the free electromagnetic field . . . . 38
1.5.3 Normal mode expansion of the
electromagnetic field . . . . . . . . . . . . . . . . . . . . 42
1.5.4 Quantization of the electromagnetic field . . . . . . . . . 44
1.6 EMF Quantization in Matter . . . . . . . . . . . . . . . . . . . 48
1.6.1 Lagrangian of a classical relativistic particle . . . . . . . 48
1.6.2 Relativistic particle coupled to
the electromagnetic field . . . . . . . . . . . . . . . . . . 50
1.6.3 Lagrangian of charged particles in an EM field . . . . . . 51
1.6.4 Quantization of the electromagnetic field coupled to charges 54
1.6.5 Quantization of the EM field in a dielectric medium or
plasma . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
1.7 Quantization of the Schrödinger field . . . . . . . . . . . . . . . 58
1.8 Quantization of the Klein-Gordon field . . . . . . . . . . . . . . 58

3
4 CONTENTS

1.9 Coupled equations for the Schrödinger and Maxwell fields . . . . 58


1.10 Problems to Chapter 1 . . . . . . . . . . . . . . . . . . . . . . . 58

2 Second Quantization 59
2.1 Second quantization in phase space . . . . . . . . . . . . . . . . 59
2.1.1 Classical dynamics in terms of point particles . . . . . . 59
2.1.2 Point particles coupled via classical fields . . . . . . . . . 60
2.1.3 Classicle dynamics via particle and Maxwell fields . . . . 61
2.2 Quantum mechanics and first quantization . . . . . . . . . . . . 65
2.3 The ladder operators . . . . . . . . . . . . . . . . . . . . . . . . 66
2.3.1 One-dimensional harmonic oscillator . . . . . . . . . . . 67
2.3.2 Generalization to several uncoupled oscillators . . . . . . 70
2.4 Interacting Particles . . . . . . . . . . . . . . . . . . . . . . . . 71
2.4.1 One-dimensional chain and its normal modes . . . . . . . 71
2.4.2 Quantization of the 1d chain . . . . . . . . . . . . . . . . 75
2.4.3 Generalization to arbitrary interaction . . . . . . . . . . 77
2.4.4 Quantization of the N -particle system . . . . . . . . . . 80
2.5 Continuous systems . . . . . . . . . . . . . . . . . . . . . . . . . 81
2.5.1 Continuum limit of 1d chain . . . . . . . . . . . . . . . . 81
2.5.2 Equation of motion of the 1d string . . . . . . . . . . . . 82
2.6 Problems to chapter 2 . . . . . . . . . . . . . . . . . . . . . . . 85

3 Fermions and bosons 87


3.1 Spin statistics theorem . . . . . . . . . . . . . . . . . . . . . . . 87
3.2 N -particle wave functions . . . . . . . . . . . . . . . . . . . . . 89
3.2.1 Occupation number representation . . . . . . . . . . . . 91
3.2.2 Fock space . . . . . . . . . . . . . . . . . . . . . . . . . . 92
3.2.3 Many-fermion wave function . . . . . . . . . . . . . . . . 92
3.2.4 Many-boson wave function . . . . . . . . . . . . . . . . . 93
3.2.5 Interacting bosons and fermions . . . . . . . . . . . . . . 95
3.3 Second quantization for bosons . . . . . . . . . . . . . . . . . . 97
3.3.1 Creation and annihilation operators for bosons . . . . . . 97
3.4 Second quantization for fermions . . . . . . . . . . . . . . . . . 104
3.4.1 Creation and annihilation operators for fermions . . . . . 104
3.4.2 Matrix elements in Fock space . . . . . . . . . . . . . . . 110
3.4.3 Fock Matrix of the binary interaction . . . . . . . . . . . 115
3.5 Field operators . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
3.5.1 Definition of field operators . . . . . . . . . . . . . . . . 118
3.5.2 Representation of operators . . . . . . . . . . . . . . . . 119
3.6 Momentum representation . . . . . . . . . . . . . . . . . . . . . 122
CONTENTS 5

3.6.1 Creation and annihilation operators


in momentum space . . . . . . . . . . . . . . . . . . . . . 122
3.6.2 Representation of operators . . . . . . . . . . . . . . . . 123
3.7 Problems to Chapter 3 . . . . . . . . . . . . . . . . . . . . . . . 126

4 Bosons and fermions in equilibrium 127


4.1 Density operator . . . . . . . . . . . . . . . . . . . . . . . . . . 127
4.2 Path Integral Monte Carlo . . . . . . . . . . . . . . . . . . . . . 127
4.3 Configuration Path Integral . . . . . . . . . . . . . . . . . . . . 127
4.3.1 Canonical ensemble . . . . . . . . . . . . . . . . . . . . . 128
4.3.2 Evaluation of Correlation energy contributions . . . . . . 138
4.3.3 Electron gas at finite temperature . . . . . . . . . . . . . 138
4.4 Problems to Chapter 4 . . . . . . . . . . . . . . . . . . . . . . . 138

5 Dynamics of field operators 139


5.1 Equation of motion of the field operators . . . . . . . . . . . . . 139
5.2 General Operator Dynamics . . . . . . . . . . . . . . . . . . . . 143
5.3 Extension to time-dependent hamiltonians . . . . . . . . . . . . 144
5.4 Schrödinger dynamics of the field operators . . . . . . . . . . . . 145
5.5 Dynamics of the density matrix operator . . . . . . . . . . . . . 147
5.6 Fluctuations and correlations . . . . . . . . . . . . . . . . . . . 151
5.6.1 Fluctuations and correlations . . . . . . . . . . . . . . . 151
5.6.2 Stochastic Mean Field Approximation . . . . . . . . . . 154
5.6.3 Iterative Improvement of Stochastic Mean Field Approx-
imation . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
5.6.4 Ensemble average of the field operators . . . . . . . . . . 155
5.6.5 Field operators and reduced density matrices . . . . . . . 156
5.6.6 BBGKY-hierarchy . . . . . . . . . . . . . . . . . . . . . 159
5.7 Problems to Chapter 5 . . . . . . . . . . . . . . . . . . . . . . . 159

6 Hubbard model 161


6.1 One-dimensional Hubbard chain . . . . . . . . . . . . . . . . . . 161
6.2 Ensemble averages . . . . . . . . . . . . . . . . . . . . . . . . . 166

7 Nonequilibrium Green Functions 169


7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
7.2 Nonequilibrium Green functions . . . . . . . . . . . . . . . . . . 173
7.2.1 Keldysh Contour . . . . . . . . . . . . . . . . . . . . . . 173
7.2.2 One-Particle Nonequilibrium Green Function . . . . . . . 182
7.2.3 Matrix Representation of the Green Function . . . . . . 187
7.2.4 Langreth-Wilkins Rules . . . . . . . . . . . . . . . . . . 191
6 CONTENTS

7.2.5 Proporties of the Nonequilibrium Green function . . . . 195


7.3 Kadanoff-Baym-Ansatz . . . . . . . . . . . . . . . . . . . . . . . 202
7.4 Keldysh-Kadanoff-Baym Equations . . . . . . . . . . . . . . . . 210
7.4.1 Derivation of the Martin-Schwinger hierarchy . . . . . . 210
7.4.2 Selfenergy. Keldysh-Kadanoff-Baym equations . . . . . . 218
7.4.3 Equilibrium Limit. Dyson Equation . . . . . . . . . . . . 220
7.5 Many-Body Approximations . . . . . . . . . . . . . . . . . . . . 221
7.5.1 Requirements for a Conserving Scheme . . . . . . . . . . 222
7.5.2 Perturbation Expansions. Born approximation . . . . . . 223
7.5.3 Vertex function . . . . . . . . . . . . . . . . . . . . . . . 228
7.5.4 Bethe-Salpeter equation . . . . . . . . . . . . . . . . . . 232
7.5.5 Strong coupling. T-matrix selfenergy . . . . . . . . . . . 232
7.6 Single-time equations . . . . . . . . . . . . . . . . . . . . . . . . 234
7.6.1 The Reconstruction Problem for the One-Particle Green
Function . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
7.6.2 The Generalized Kadanoff-Baym Ansatz . . . . . . . . . 239

8 Matter in strong fields 243


8.1 Free particle in a time-dependent field . . . . . . . . . . . . . . 243
8.1.1 Classical approach . . . . . . . . . . . . . . . . . . . . . 243
8.1.2 Quantum-mechanical approach . . . . . . . . . . . . . . 245
8.1.3 Alternative analytical methods . . . . . . . . . . . . . . 252
8.1.4 Computational methods . . . . . . . . . . . . . . . . . . 253
8.2 Atoms in electromagnetic fields . . . . . . . . . . . . . . . . . . 253
8.2.1 Schrödinger equation for atom in EM field . . . . . . . . 253
8.2.2 Stationary electrical fields. Stark effect. . . . . . . . . . . 254
8.2.3 Ionization processes . . . . . . . . . . . . . . . . . . . . . 255
8.3 Excitation and ionization processes in strong fields . . . . . . . . 256
8.3.1 Classification of laser intensities . . . . . . . . . . . . . . 256
8.3.2 Multiphoton processes in weak fields (γ  1) . . . . . . . 256
8.3.3 Strong field effects, γ  1 . . . . . . . . . . . . . . . . . 258
8.3.4 Strong field approximation. Keldysh theory. . . . . . . . 258
8.4 Strong field phenomena . . . . . . . . . . . . . . . . . . . . . . . 260
8.4.1 Above threshold ionization . . . . . . . . . . . . . . . . . 260
8.4.2 Higher harmonics generation (HHG) . . . . . . . . . . . 260
8.5 Problems to Chapter 8 . . . . . . . . . . . . . . . . . . . . . . . 261

A Perturbation expansion for NEGF 263


A.1 Functional Derivative of a
Contour-Ordered Operator Product . . . . . . . . . . . . . . . . 263
CONTENTS 7

A.2 Selfenergy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265

A Solutions to problems 269


A.1 Problems from chapter 2 . . . . . . . . . . . . . . . . . . . . . . 269
A.2 Problems from chapter 3 . . . . . . . . . . . . . . . . . . . . . . 269
A.3 Problems from chapter 4 . . . . . . . . . . . . . . . . . . . . . . 271
A.4 Problems from chapter 5 . . . . . . . . . . . . . . . . . . . . . . 271
A.5 Problems from chapter 6 . . . . . . . . . . . . . . . . . . . . . . 272

Bibliography 293
Chapter 2

Introduction to second
quantization

2.1 Second quantization in phase space


2.1.1 Classical dynamics in terms of point particles
We consider systems of a large number N of identical particles which interact
via pair potentials V and may be subject to an external field U . The system
is described by the Hamilton function
N N
X p2i X X
H(p, q) = + U (ri ) + V (ri − rj ) (2.1)
i=1
2m i=1 1≤i<j≤N

where p and q are 3N -dimensional vectors of all particle momenta and coordi-
nates, p ≡ {p1 , p2 , . . . pN } and q ≡ {r1 , r2 , . . . rN }. Examples of the external
potentials can be the electrostatic potential of a capacitor, the potential of
an atomic nucleus or the potential an electron feels at a solid surface. The
interaction potentials can arise from gravitational fields, from the Coulomb
interaction of charged particles, the magnetic interaction of currents and so
on. From the hamiltonian (2.1) the equations of motion follow by applying
Hamilton’s equations1 ,
∂H pi
q̇i = = , (2.2)
∂pi m
∂H ∂U X ∂V
ṗi = − =− − , (2.3)
∂qi ∂qi j6=i
∂q i

1
Generalized equations of motion can, of course, also be obtained for non-Hamiltonian
(dissipative) systems

59
60 CHAPTER 2. SECOND QUANTIZATION

which is to be understood as two systems of 3N scalar equations for x1 , y1 , . . . zN


and px1 , py1 , . . . pzN where ∂/∂q ≡ {∂/∂r1 , . . . ∂/∂rN }, and the last equalities
are obtained by inserting the hamiltonian (2.1). The system (2.3) is nothing
but Newton’s equations containing the forces arising from the gradient of the
external potential and the gradient from all pair interactions involving the
given particle, i.e. for any particle i = 1 . . . N
∂U (r1 , . . . rN ) X ∂V (ri − rj )
ṗi = − − . (2.4)
∂ri j6=i
∂r i

Consider, as an example, a system of identical charged particles with charge


ei which may be subject to an external electrostatic potential φext and interact
ei ej
with each other via the Coulomb potential Vc = |ri −r j|
. Then Newton’s equa-
tion (2.4) for particle i contains, on the r.h.s., the gradients of the potential
U = ei φext and of the N − 1 Coulomb potentials involving all other particles.
∂ei φext (ri ) X ∂ ei ej
ṗi = − − , (2.5)
∂ri ∂r i |ri − rj |
j6=i

2.1.2 Point particles coupled via classical fields


An alternative way of writing Eq. (2.5) is to describe the particle interaction
not by all pair interactions but to compute the total electric field, E(r, t),
all particles produce in the whole space. The force particle “i” experiences
is then just the Lorentz force, ei E, which is minus the gradient of the total
electrostatic potential φ which is readily identified from the r.h.s. of Eq. (2.5)

∂φ(r, t)
ṗi = ei E(ri , t) = −ei , (2.6)
∂r r=ri
N
X ej
φ(r, t) = φext (r) + . (2.7)
j=1
|r − rj (t)|

In this case we explicitly know the form of the potential (2.7) but we can also
rewrite this in terms of the Poisson equation which is solved by the potential
(2.7)
N
X
∆φ(r, t) = −4π ej δ[r − rj (t)] = −4πρ(r, t). (2.8)
j=1

φ contains the external potential and the potentials induced by all particles at
a given space point r at time t. When computing the force on a given particle
2.1. SECOND QUANTIZATION IN PHASE SPACE 61

i the potential has to be taken at r = ri (t) and the contribution of particle “i”
to the sum over the particles in Eqs. (2.7, 2.8) has to be excluded (to avoid
selfinteraction). Also, on the r.h.s. we have introduced the charge density ρ of
the system of N point particles.
Considering the formal structure of Eq. (2.6) we notice that the Coulomb
forces between discrete particles have been completely eliminated in favor of a
space dependent function, the electric field. Obviously, this description is read-
ily generalized to the case of time-dependent external potentials and magnetic
fields which yields a coupled set of Newton’s and Maxwell’s equations,
 
1
ṗi = ei E(ri , t) + vi × B(ri , t) , (2.9)
c
1 ∂B(r, t)
divE(r, t) = 4πρ(r, t), ∇ × E(r, t) = − , (2.10)
c ∂t
4π 1 ∂E(r, t)
divB(r, t) = 0, ∇ × B(r, t) = j(r, t) + , (2.11)
c c ∂t
where we introduced P the current density j which, for a system of point particles
is given by j(r, t) = N j=1 ej vj (t)δ[r − rj (t)]. Charge and current density are
determined by the instantaneous phase space trajectories {q(t), p(t)} of all
particles.
The two sets of equations (2.6,2.8) and (2.9,2.10, 2.11) form closed sys-
tems coupling the dynamics of classical charged point particles and a classical
electromagnetic field. This coupling occurs, in the particle equation, via the
Lorentz force and, in the field equations, via charge and current density. The
classical description, therefore, requires knowledge of the N discrete particle
trajectories {q(t), p(t)} and of the two continuous vector fields E(r, t), B(r, t).
Using the electric and magnetic fields, we may rewrite the Hamilton func-
tion (2.1) corresponding to the full system (2.6, 2.10, 2.11)

N N
p2i
Z
X X 1
d3 r E2 (r, t) + B2 (r, t)

H= + U (ri ) + (2.12)
i=1
2m i=1 8π

where the integral contains the energy of the electromagnetic field familiar
from standard electrodynamics.

2.1.3 Classicle dynamics via particle and Maxwell fields


We have now found two alternative descriptions of the dynamics of interacting
point charges:
62 CHAPTER 2. SECOND QUANTIZATION

1. via the system (2.5), involving only discrete point particles, and

2. via the system (2.9, 2.10, 2.11) which gives a hybrid description in which
the particles are discrete but the fields (or the particle interaction) con-
tinuous.
One may ask if there is third form which contains only continuous field-type
quantities. This would require to represent also the particles by fields. This
is, indeed possible, as we show in this section.
In fact, the right hand sides of Maxwell’s equation already do contain (for-
mally) continuous quantities ρ and j representing the particles. However, they
contain (via the delta functions) only the particle coordinates. It is, therefore,
tempting to consider a symmetric with respect to q and p quantity – the mi-
croscopic phase space density which was introduced by Yuri Klimontovich in
the 1950s [Kli57]

N
X N
X
N (r, p, t) = δ[r − ri (t)]δ[p − pi (t)] ≡ δ[x − xi (t)] (2.13)
i=1 i=1

where we introduced the short notations x ≡ {r, p} and xi (t) ≡ {ri (t), pi (t)}.2
The function N is related to the particle density n(r, t) and it obeys a normal-
ization condition,
Z
d3 p N (r, p, t) = n(r, t), (2.14)
Z
d6 x N (r, p, t) = N (t). (2.15)

If there are no particle sources or sinks, N (t) =const, and there exists a local
conservation law dtd N = 0. From this we obtain the equation of motion of N :
N
dN (r, p, t) ∂N X ∂ ∂ri
= + δ[p − pi (t)] δ[r − ri (t)] +
dt ∂t i=1
∂r ∂t
N
X ∂ ∂pi
δ[r − ri (t)] δ[p − pi (t)] .
i=1
∂p ∂t

Using Newton’s equations (2.5) the time derivatives can be computed after
which the delta functions allow to replace ri → r and pi → p which can be
2
Note that for a vector y = {y1 , y2 , y3 }, δ[y] ≡ δ[y1 ]δ[y2 ]δ[y3 ], so N contains a product
of six scalar delta functions.
2.1. SECOND QUANTIZATION IN PHASE SPACE 63

taken out of the sum. As a result we obtain3


   
∂ ∂ 1 ∂
+ v + e E(r, t) + v × B(r, t) N (r, p, t) = 0. (2.16)
∂t ∂r c ∂p
Thus we have obtained a field description of the particles via the function N
and eliminated (formally) all discrete particle information. The field N also
replaces the charge and current density in Maxwell’s equations (2.10, 2.11) via
the relations [cf. Eq. (2.14)]
Z
ρ(r, t) = e d3 p N (r, p, t), (2.17)
Z
j(r, t) = e d3 p vN (r, p, t). (2.18)

A particularly simple form is obtained in the absence of a magnetic field,


in the case of particles interacting by Coulomb potentials, cf. Eqs. (2.6, 2.7)
above. Then, we may use the solution of Poisson’s equation, expressing ρ via
N
ρ(r0 , t)
Z
φ(r, t) = φext (r, t) + dr0
|r − r0 |
eN (r0 , p0 , t)
Z Z
= φext (r, t) + dr0 dp0 . (2.19)
|r − r0 |
With this expression the electrostatic field has been eliminated and the particle
dynamics (2.16) becomes a closed equation for N :
0 0
  Z  
∂ ∂ ∂ 6 0 eN (r , p , t) ∂
+v −e φext + d x N (r, p, t) = 0 (2.20)
∂t ∂r ∂r |r − r0 | ∂p

Using the phase space density, all observables of the system can be ex-
pressed in terms of fields. For example, the hamilton function now becomes
p2
Z Z
6
H = dx N (r, p, t) + d6 x U (r)N (r, p, t) +
2m
Z
1
d3 r E2 (r, t) + B2 (r, t) ,

+ (2.21)

We underline that this is an exact equation (as long as a classical descrip-
tion is valid) – no assumptions with respect to the interactions have been
3
To simplify the notation, in the following we consider a one-component system with
identical charges, e1 = . . . eN = e. An extension to multi-component systems is straightfor-
wardly done by introducing a separate function Na , for each component.
64 CHAPTER 2. SECOND QUANTIZATION

made. It is fully equivalent to Newton’s equations (2.6). The discrete nature


of the particles has now vanished – it is hidden in the highly singular phase
space field N . As Newton’s equation, Eq. (2.20) allows for an exact solution
of the particle dynamics, once the initial conditions are precisely known. This
may be the case for a few particles. In contrast, if our goal is to describe the
behavior of a macroscopic particle ensemble any particular initial condition,
and the resulting dynamics have to be regarded as random. However, we will
be interested in statistically reliable predictions so we need to average over a
certain statistical ensemble, e.g. over all possible initial conditions. An en-
semble average of N yields directly the single-particle phase space distribution
hN (r, p, t)i = f (r, p, t), and Eq. (2.20) turns into an equation for the distri-
bution function f , i.e. a kinetic equation. The use of the phase space density
N as starting point for derivation of a kinetic theory of gases and plasmas has
been successfully demonstrated by Klimontovich, for details see his text books
[Kli75, Kli80].

With Eqs. (2.16) and (2.20) we have realized the third picture of coupled
particle electromagnetic field dynamics – in terms of the particle field N and
the electric and magnetic fields. While we have concentrated on charged par-
ticles and Coulomb interaction, the approach may be equally applied to other
interactions, e.g. electrons interaction with lattice vibrations of a solid de-
scribed by the displacement field, see Sec. 2.5.1. Thus the basis for a classical
field theory has been achieved.

Of course, this picture is based on classical physics, i.e. on Newton’s equa-


tions for point particles and Maxwell’s equations for the electromagnetic field.
No quantum effects appear, neither in the description of the particles nor the
field. The classical picture has been questioned only at the end of the 19th
century where the experiments on black body radiation could not be correctly
explained by Maxwell’s theory of the electromagnetic field. The classical ex-
pression for the field energy of an electromagnetic wave which only depends on
the field amplitudes E0 , B0 and, therefore, is a continuous function, cf. hamil-
tonian (2.21), did not reproduce the measured spectral energy density. The
solution which was found by Max Planck indicated that the field energy cannot
depend on the field amplitudes alone. The energy exchange between electro-
magnetic field and matter is even entirely independent of E0 , B0 , instead it
depends on the frequency ω of the wave. Thus the total energy of an electro-
magnetic wave of frequency ω is an integer multiple of an elementary energy,
Wfield (ω) = N ~ω, where ~ is Planck’s constant, i.e. the energy is quantized.
2.2. QUANTUM MECHANICS AND FIRST QUANTIZATION 65

What Planck had discovered in 1900 was the quantization of the electro-
magnetic field 4 . This concept is very different from the quantum mechanical
description of the electron dynamics from which it is, therefore, clearly distin-
guished by the now common notion of “second quantization”. Interestingly,
however, the “first quantization” of the motion of microparticles was intro-
duced only a quarter century later when quantum mechanics was discovered.

2.2 Quantum mechanics and first quantization


Let us briefly recall the main ideas of quantum theory. The essence of quantum
mechanics or “first” quantization is to replace functions by operators, starting
from the coordinate and momentum,

r → r̂ = r,
~ ∂
p → p̂ = ,
i ∂r
where the last equalities refer to the coordinate representation. These opera-
tors are hermitean, r̂† = r̂ and p̂† = p̂, and do not commute

[x̂i , p̂j ] = i~δi,j , (2.22)

which means that coordinate and momentum (the same components) cannot
be measured simultaneously. The minimal uncertainty of such a simultaneous
measurement is given by the Heisenberg relation
~
∆x̂i ∆p̂i ≥ , (2.23)
2

where the standard deviation (“uncertainty”) of an operator  is definied as


s
 2 
∆ =  − hÂi , (2.24)

and the average is computed in a given state |ψi, i.e. hÂi = hψ|Â|ψi. The
general formulation of quantum mechanics describes an arbitrary quantum
system in terms of abstract states |ψi that belong to a Hilbert space (Dirac’s
4
Planck himself regarded the introduction of the energy quantum ~ω only as a formal
mathematical trick and did not question the validity of Maxwell’s field theory. Only half
a century later, when field quantization was systematically derived, the coexistence of the
concepts of energy quanta and electromagnetic waves became understandable, see Sec. 1.5
66 CHAPTER 2. SECOND QUANTIZATION

notation), and operators act on these state returning another Hilbert space
state, Â|ψi = |φi.
The central quantity of classical mechanics – the hamilton function – retains
its functional dependence on coordinate and momentum in quantum mechan-
ics as well (correspondence principle) but becomes an operator depending on
operators, H(r, p) → Ĥ(r̂, p̂). The classical equations of motion – Hamil-
ton’s equations or Newton’s equation (2.4) – are now replaced by a partial
differential equation for the Hamilton operator, the Schrödinger equation


i~ |ψ(t)i = Ĥ|ψ(t)i. (2.25)
∂t

Stationary properties are governed by the stationary Schrödinger equation that


follows from the ansatz5
i
|ψ(t)i = e− ~ Ĥt |ψi.
Ĥ|ψi = E|ψi, (2.26)

The latter is an eigenvalue equation for the Hamilton operator with the eigen-
functions |ψi and corresponding eigenvalues E. “First” quantization is evident
in the case of particle motion in a confining potential U (r), such as an oscil-
lator potential: classical bounded motion transforms, in quantum mechanics,
into a set of eigenstates |ψn i (that are localized as well) that exist only for a
sequence of discrete (quantized) energies En . This example is discussed more
in detail below.

2.3 The linear harmonic oscillator and the lad-


der operators
Let us now recall the simplest example of quantum mechanics: one particle in
a one-dimensional harmonic potential U (x) = m2 ω 2 x2 , i.e. in Eq. (2.1), N = 1
and the interaction potentials vanish. We will use this example to introduce
the basic idea of “second quantization”. In writing the potential U (x) we
switched to the coordinate representation where states |ψn i are represented by
functions of the coordinate, ψn (x). At the end we will return to the abstract
notation in terms of Dirac states.
5
Here we assume a time-independent hamiltonian.
2.3. THE LADDER OPERATORS 67

2.3.1 One-dimensional harmonic oscillator


The stationary properties of the harmonic oscillator follow from the stationary
Schrödinger equation (2.26) which now becomes, in coordinate representation
 2
mω 2 2


Ĥ(x̂, p̂)ψn (x) = + x̂ ψn (x) = En ψn (x), (2.27)
2m 2
d
where x̂ = x and p̂ = ~i dx . We may bring the Hamilton operator to a more
symmetric form by introducing the dimensionless coordinate ξ = x/x0 with
the length scale x0 = [~/mω]1/2 , whereas energies will be measured in units of
d
~ω. Then we can replace dx = x10 dξ
d
and obtain

∂2
 
Ĥ 1 2
= − 2 +ξ . (2.28)
~ω 2 ∂ξ

This quadratic form can be rewritten in terms of a product of two first order
operators a, a† , the “ladder operators”,
 
1 ∂
a = √ +ξ , (2.29)
2 ∂ξ
 
† 1 ∂
a = √ − +ξ . (2.30)
2 ∂ξ

Indeed, computing the product


   
† 1 ∂ 1 ∂
N̂ = a a = √ +ξ √ − +ξ (2.31)
2 ∂ξ 2 ∂ξ
∂2
 
1
= − 2 + ξ2 − 1 ,
2 ∂ξ

the hamiltonian (2.28) can be written as

Ĥ 1
= N̂ + . (2.32)
~ω 2

It is obvious from (2.32) that N̂ commutes with the hamiltonian,

[Ĥ, N̂ ] = 0, (2.33)

and thus the two have common eigenstates. This way we have transformed the
hamiltonian from a function of the two non-commuting hermitean operators
68 CHAPTER 2. SECOND QUANTIZATION

x̂ and p̂ into a function of the two operators a and a† which are also non-
commuting6 , but not hermitean, instead they are the hermitean conjugate of
each other,

[a, a† ] = 1, (2.34)
(a)† = a† , (2.35)

which is easily verified.


The advantage of the ladder operators is that they allow for a straight-
forward computation of the energy spectrum of Ĥ, using only the properties
(2.31) and (2.34), without need to solve the Schrödinger equation, i.e. avoid-
ing explicit computation of the eigenfunctions ψn (ξ) 7 . This allows us to re-
turn to a representation-independent notation for the eigenstates, ψn → |ni.
The Ponly thing we require is that these states are complete and orthonormal,
1 = n |nihn| and hn|n0 i = δn,n0 .
Now, acting with N̂ on an eigenstate, using Eq. (2.32), we obtain
 
† En 1
N̂ |ni = a a |ni = − |ni = n|ni, ∀n, (2.36)
~ω 2
En 1
n = − ,
~ω 2
where the last line relates the eigenvalues of N̂ and n̂ that correspond to the
common eigenstate |ni. Let us now introduce two new states that are created
by the action of the ladder operators,

a|ni = |ñi,
a† |ni = |n̄i,

where this action is easily computed. In fact, multiplying Eq. (2.36) from the
left by a, we obtain
 
† En 1
aa |ñi = − |ñi.
~ω 2
Using the commutation relation (2.34) this expression becomes
 
† En 3
a a |ñi = − |ñi = (n − 1)|ñi,
~ω 2
6
The appearance of the standard commutator indicates that these operators describe
bosonic excitations.
7
R We will use the previous notation ψ, which means that the normalization is
x0 dξ|ψ(ξ)|2 =1
2.3. THE LADDER OPERATORS 69

which means the state |ñi is an eigenstate of N̂ [and, therefore, of Ĥ] and has
an energy lower than |ni by ~ω whereas the eigenvalue of N̂ is ñ = n−1. Thus,
the action of the operator a is to switch from an eigen state with eigenvalue
n to one with eigenvalue n − 1. Obviously, this is impossible for the ground
state, i.e. when a acts on |0i, so we have to require

|0̃i = a|0i ≡ 0. (2.37)

When we use this result in Eq. (2.36) for n = 0, the l.h.s. is zero with the con-
sequence that the term in parantheses must vanish. This immediately leads to
the well-known result for the ground state energy: E0 = ~ω/2, corresponding
to the eigenvalue 0 of N̂ .
From this we now obtain the energy spectrum of the excited states: acting
with a† from the left on Eq. (2.36) and using the commutation relation (2.34),
we obtain
 
En 1
N̂ |n̄i = − + 1 |n̄i = n̄|n̄i.
~ω 2

Thus, n̄ is again an eigenstate of N̂ and Ĥ. Further, if the eigenstate |ni


has an energy En , cf. Eq. (2.36), then n̄ has an energy En + ~ω, whereas
the associated eigenvalue of N̂ is n̄ = n + 1. Starting from the ground state
and acting repeatedly with a† we construct the whole spectrum, En , and may
express all eigenfunctions via ψ0 :
 
1
En = ~ω n + , n = 0, 1, 2, . . . (2.38)
2
n
|ni = Cn a† |0i. (2.39)
1
Cn = √ , (2.40)
n!

where the normalization constant Cn will be verified from the properties of a†


below. The above result shows that the eigenvalue of the operator N̂ is just
the quantum number n of the eigenfunction |ni. In other words, since |ni is
obtained by applying a† to the ground state function n times or by “n-fold
excitation”, the operator N̂ is the number operator counting the number of
excitations (above the ground state). Therefore, if we are not interested in the
analytical details of the eigenstates we may use the operator N̂ to count the
number of excitations “contained” in the system. For this reason, the common
notion for the operator a (a† ) is “annihilation” (“creation”) operator of an
excitation. For an illustration, see Fig. 2.3.1.
70 CHAPTER 2. SECOND QUANTIZATION

Figure 2.1: Left: oscillator potential and energy spectrum. The action of the
operators a and a† is illustrated. Right: alternative interpretation: the op-
erators transform between “many-particle” states containing different number
of elementary excitations.

From the eigenvalue problem of N̂ , Eq. (2.36) we may also obtain the
explicit action of the two operators a and a† . Since the operator a transforms
a state into one with quantum number n lower by 1 we have

a|ni = n|n − 1i, n = 0, 1, 2, . . . (2.41)

where the prefactor may be understood as an ansatz8 . The correctness is


proven by deriving, from Eq. (2.41), the action of a† and then verifying that
we recover the eigenvalue problem of N̂ , Eq. (2.36). The action of the creation
operator is readily obtained using the property (2.35):
X X
a† |ni = |n̄ihn̄|a† |ni = |n̄i a[hn̄|] |ni
n̄ n̄
X √ √
= |n̄i n̄ hn̄ − 1 |ni = n + 1 |n + 1i. (2.42)

Inserting these explicit results for a and a† into Eq. (2.36), we immediately
verify the consistency of the choice (2.41). Obviously the oscillator eigenstates
|ni are no eigenstates of the creation and annihilation operators 9 .

A more detailed discussion is part of the problems, see Sec. 2.6.

2.3.2 Generalization to several uncoupled oscillators


The previous results are directly generalized to a three-dimensional harmonic
oscillator with frequencies ωi , i = 1, 2, 3, which is described by the hamiltonian
3
X
Ĥ = Ĥ(x̂i , p̂i ), (2.43)
i=1

which is the sum of three one-dimensional hamiltonians (2.27) with the po-
tential energy U (x1 , x2 , x3 ) = m2 (ω12 x21 + ω22 x22 + ω32 x23 ). Since [pi , xk ] ∼ δk,i
8
This expression is valid also for n = 0 where the prefactor assures that application of a
to the ground state does not lead to a contradiction.
9
A particular case are Glauber states (coherent states) that are a special superposition
of the oscillator states which are the eigenstate of the operator a.
2.4. INTERACTING PARTICLES 71

all three hamiltonians commute and have joint eigenfunction (product states).
The problem reduces to a superposition of three independent one-dimensional
oscillators. Thus we may introduce ladder operators for each component inde-
pendently as in the 1d case before,
 
1 ∂
ai = √ + ξi , (2.44)
2 ∂ξi
 
† 1 ∂
ai = √ − + ξi , [ai , a†k ] = δi,k . (2.45)
2 ∂ξ i

Thus the hamiltonian and its eigenfunctions and eigenvalues can be written as
3  
X † 1
Ĥ = ~ωi ai ai +
i=1
2
ai |0i = 0, i = 1, 2, 3
1
ψn1 ,n2 ,n3 = |n1 n2 n3 i = √ (a†1 )n1 (a†2 )n2 (a†3 )n3 |0i (2.46)
n1 !n2 !n3 !
3  
X 1
E = ~ωi ni + .
i=1
2

Here |0i ≡ |000i = |0i|0i|0i denotes the ground state and a general state
|n1 n2 n3 i = |n1 i|n2 i|n3 i contains ni elementary excitations in direction i, cre-
ated by ni times applying operator a†i to the ground state.
Finally, we may consider a more general situation of any number M of
coupled independent linear oscillators and generalize all results by replacing
the dimension 3 → M .

2.4 Generalization to interacting particles.


Normal modes
The previous examples of independent linear harmonic oscillators are of course
the simplest situations which, however, are of limited interest. In most prob-
lems of many-particle physics the interaction between the particles which was
neglected so far, is of crucial importance. We now discuss how to apply the
formalism of the creation and annihilation operators to interacting systems.

2.4.1 One-dimensional chain and its normal modes


We consider the simplest case of an interacting many-particle system: N iden-
tical classical particles arranged in a linear chain and interacting with their
72 CHAPTER 2. SECOND QUANTIZATION

Figure 2.2: Illustration of the one-dimensional chain with nearest neighbor


interaction. The chain is made infinite by connecting particle N + 1 with
particle 1 (periodic boundary conditions).

left and right neighbor via springs with constant k.10 , see Fig. 2.2.

This is the simplest model of interacting particles because each particle is


assumed to be fixed around a certain position xi in space around which it can
perform oscillations with the displacement qi and the associated momentum
pi .11 Then the hamiltonian (2.1) becomes
N  2
pj

X k 2
H(p, q) = + (qj − qj+1 ) . (2.47)
j=1
2m 2

Applying Hamilton’s equations we obtain the system of equations of motion


(2.4)
mq̈j = k (qj+1 − 2qj + qj−1 ) , j = 1...N (2.48)
which have to be supplemented with boundary and initial conditions. In the
following we consider a macroscopic system and will not be interested in ef-
fects of the left and right boundary. This can be achieved by using “peri-
odic” boundary conditions, i.e. periodically repeating the system according
to qj+N (t) = qj (t) for all j [for solutions for the case of a finite system, see
Problem 5, Sec. 2.6]. We start with looking for particular (real) solutions of
the following form12
qj (t) = ei(−ωt+jl) + c.c., (2.49)
which, inserted into the equation of motion, yield for any j

−mω 2 qj + qj∗ = k eil − 2 + e−il qj + qj∗ ,


  
(2.50)

resulting in the following relation between ω and k (dispersion relation)13 :


l k
ω 2 (l) = ω02 sin2 , ω02 = 4 . (2.51)
2 m
10
Here we follow the discussion of Huang [Hua98].
11
Such “lattice” models are very popular in theoretical physics because they allow to study
many-body effects in the most simple way. Examples include the Ising model, the Anderson
model or the Hubbard model of condensed matter physics.
12
In principle, we could use a prefactor qj0 = q 0 different from one, but by rescaling of
q it can always be eliminated. The key is that the amplitudes of all particles are strictly
coupled.
13
We use the relation 1 − cos x = 2 sin2 x2 .
2.4. INTERACTING PARTICLES 73

Figure 2.3: Dispersion of the normal modes, Eq. (2.51), of the 1d chain with
periodic boundary conditions.

Here ω0 is just the eigenfrequency of a spring with constant k, and the prefactor
2 arises from the fact that each particle interacts with two neighbors. While
the condition (2.51) is independent of the amplitudes qj0 , i.e. of the initial
conditions, we still need to account for the boundary (periodicity) condition.
Inserting it into the solution (2.49) gives the following condition for l, indepen-
dently of ω: l → ln = Nn 2π, where n = 0, ±1, ±2, · · · ± N2 . Thus there exists
a discrete spectrum of N frequencies of modes which can propagate along the
chain (we have to exclude n = 0 since this corresponds to a time-independent
trivial constant displacement),
k nπ N
ωn2 = 4 sin2 , n = ±1, ±2, · · · ± . (2.52)
m N 2
This spectrum is shown in Fig. 2.3. These N solutions are the complete set of
normal modes of the system (2.47), corresponding to its N degrees of freedom.
These are collective modes in which all particles participate, all oscillate with
the same frequency but with a well defined phase which depends on the particle
number. These normal modes are waves running along the chain with a phase
velocity14 cn ∼ ωn /ln .
Due to the completeness of the system of normal modes, we can expand
any excitation of particle j and the corresponding momentum pj (t) = mq̇j (t)
into a supersposition of normal mode contributions (n 6= 0)
N N
2 2
1 X n 1 X
qj (t) = √ Q0n ei(−ωn t+2π N j ) = √ e−iωn t Qn (j) (2.53)
N N N N
n=− 2
n=− 2
N N
2 2
1 X 0 i(−ωn t+2π Nn j ) 1 X −iωn t
pj (t) = √ Pn e =√ e Pn (j), (2.54)
N N N N
n=− 2
n=− 2

where Pn0 = −imωn Q0n . Note that the complex conjugate contribution to mode
n is contained in the sum (term −n). Also, qj (t) and pj (t) are real functions.
By computing the complex conjugate qj∗ and equating the result to qj we obtain
the conditions (Q0n )∗ = Q0−n and ω−n = −ω−n . Analogously we obtain for the
momenta (Pn0 )∗ = P−n 0
. To make the notation more compact we introduced
14
The actual phase velocity is ωn /kn , where the wave number kn = ln /a involves a length
scale a which does not appear in the present discrete model.
74 CHAPTER 2. SECOND QUANTIZATION

the N -dimensional complex vectors Q ~ n and P~n with the component j being
0 i2πnj/N
equal to Qn (j) = Qn e and Pn (j) = Pn0 ei2πnj/N . One readily proofs15
that these vectors form an orthogonal system by computing the scalar product
N
n+m
X
~ nQ
Q ~ m = Q0 Q0 ei2π N
j
= N Q0n Q0m δn,−m . (2.55)
n m
j=1

Using this property it is now straightforward to compute the hamilton


function in normal mode representation. Consider first the momentum contri-
bution,
N N
N 2 2
X 1 X X
p2j (t) = P~n P~m e−i(ωn +ωm )t , (2.56)
j=1
N N N
n=− 2
m=− 2

where the sum over j has been absorbed in the scalar product. Using now the
orthogonality condition (2.55) we immediately simplify

N
X X
p2j (t) = |Pn0 |2 . (2.57)
j=1 n

Analogously, we compute the potential energy


N N
N 2 2
kX 2 k X X
U = [qj (t) − qj+1 (t)] = e−i(ωn +ωm )t
2 j=1 2N N N
n=− 2
m=− 2
N
n n m m
X
Q0n Q0m ei2π N j − ei2π N (j+1) ei2π N j − ei2π N (j+1) .
 
×
j=1

The sum over j can again be simplified using the orthogonality condition (2.55),
which allows to replace m by −n,
N
1 X 0 0  i2π n j n m m
Qn Qm e N − ei2π N (j+1) ei2π N j − ei2π N (j+1) =

N j=1
n  m
= 1 − ei2π N 1 − ei2π N Q ~ nQ
~m =
ω2
 
2πn
= 2 1 − cos δn,−m Q0n Q0m = 4 n2 δn,−m |Q0n |2 ,
N ω0
15
See problem 5, Sec. 2.6.
2.4. INTERACTING PARTICLES 75

where we have used Eq. (2.51) and the relation 1 − cos x = 2 sin2 x2 . This yields
for the potential energy

k X mωn2
U=
2 n k

and for the total hamilton function


N
2  
X 1 0 2 m 2 02
H(P, Q) = |P | + ωn |Qn | . (2.58)
N
2m n 2
n=− 2

2.4.2 Quantization of the 1d chain


We now quantize the interacting system (2.47) by replacing coordinates and
momenta of all particles by operators

(qi , pi ) → (q̂i , p̂i ) , i = 1, . . . N,


† †
with q̂i = q̂j , p̂i = p̂i , [q̂i , p̂j ] = i~δij . (2.59)

The Hamilton function (2.47) now becomes an operator of the same functional
form (correspondence principle),
N  2
p̂j

X k 2
Ĥ(p̂, q̂) = + (q̂j − q̂j+1 ) ,
j=1
2m 2

and we still use the periodic boundary conditions q̂N +i = q̂i . The normal
modes of the classical system remain normal modes in the quantum case as
well, only the amplitudes Q0n and Pn0 become operators
N
2
1 X
q̂j (t) = √ e−iωn t Q̂n (j) (2.60)
N N
n=− 2
N
2
1 X −iωn t
pj (t) = √ e P̂n (j), (2.61)
N N
n=− 2

where Q̂n (j) = Q̂0n exp{i2πnj/N }, P̂n (j) = P̂n0 exp{i2πnj/N } and P̂n0 =
−imωn Q̂0n .
What remains is to impose the necessary restrictions on the operators Q̂0n
and P̂n0 such that they guarantee the properties (2.59). One readily verifies
76 CHAPTER 2. SECOND QUANTIZATION

that hermiticity of the operators is fulfilled if (Q̂0 )†n = Q̂0−n , (P̂ 0 )†n = P̂−n
0
and
ω−n = −ωn . Next, consider the commutator of q̂i and p̂j and use the normal
mode representations (2.60, 2.61),
1 X X 0 0 −i(ωn +ωm )t i 2π (kn+jm)
[q̂k , p̂j ] = [Q̂ , P̂ ]e e N . (2.62)
N n m n m

A sufficient condition for this expression to be equal i~δk,j is evidently [Q̂0n , P̂m0 ] =
i~δn,−m which is verified separately for the cases k = j and k 6= j. In other
words, the normal mode operators obey the commutation relation
h i
Q̂0n , (P̂m0 )† = i~δn,m , (2.63)

and the hamiltonian becomes, in normal mode representation,


N
2  
X 1 0 2 m 2 02
Ĥ(P̂ , Q̂) = |P̂ | + ωn |Q̂n | . (2.64)
N
2m n 2
n=− 2

This is a superposition of N independent linear harmonic oscillators with the


frequencies ωn given by Eq. (2.52). Applying the results for the superposition
of oscillators, Sec. 2.3.2, we readily can perform
p mωn the secondNquantization by
N
defining dimensionless coordinates, ξn = ~
Qn , n = − 2 , . . . 2 , n 6= 0,
and introducing the creation and annihilation operators,
 
1 ∂
an = √ + ξn , (2.65)
2 ∂ξn
 
1 ∂

an = √ − + ξn , [an , a†k ] = δn,k . (2.66)
2 ∂ξ n

Thus the hamiltonian and its eigenfunctions and eigenvalues can be written as
N
2  
X 1
Ĥ = ~ωn a†n an +
2
n=− N
2

N N
an |0i = 0, n=−
,...
2 2
1 

m1  mN
ψm1 ,...mN = |m1 . . . mN i = √ a− N . . . a†N |0i
m1 ! . . . mN ! 2 2

N
2  
X 1
E = ~ωn mn + .
N
2
n=− 2
2.4. INTERACTING PARTICLES 77

Here |0i ≡ |0 . . . 0i = |0i . . . |0i [N factors] denotes the ground state and a
general state |m−N/2 . . . mN/2 i = |m−N/2 i . . . |mN/2 i contains mn elementary
excitations of the normal mode n, created by mn times applying operator a†n
to the ground state.

Finally we notice that the commutation relation (2.63) is that of bosons.


This result was independent of whether the particles in the chain are fermions
or bosons. This is discussed in Problem 6, Sec. 2.6.

2.4.3 Generalization to arbitrary interaction


Of course, the simple 1d chain is a model with a limited range of applicability.
A real system of N interacting particles in 1d will be more difficult, at least by
three issues: first, the pair interaction potential V may have any form. Second,
the interaction, in general, involves not only nearest neighbors, and third, the
effect of the full 3d geometry may be relevant. We, therefore, now return to
the general 3d system of N classical particles (2.1) with the total potential
energy16
N
X X
Utot (q) = U (ri ) + V (ri − rj ), (2.67)
i=1 1≤i<j≤N

leading to Newton’s equations


mr̈i = − Utot (q), i = 1, . . . N. (2.68)
∂ri
Let us consider stationary solutions, where the time derivatives on the l.h.s.
vanish. The system will then be in a stationary state “s00 corresponding to
(0) (0) (0)
a minimum qs of Utot of depth Us = Utot (qs ) [the classical ground state
corresponds to the deepest minimum]. In the case of weak excitations from the
(0) (0)
minimum, q = qs + ξ, with |ξ| << qs , the potential energy can be expanded
in a Taylor series17

∂ 1
Utot (q) = Us(0) + Utot (q = qs(0) )ξ + ξ T H(s) ξ + ... (2.69)
∂q 2

where all first derivatives are zero, and we limit ourselves to the second order
(harmonic approximation). Here we introduced the 3N × 3N Hesse matrix
16
Here we follow the discussion of Ref. [HKL+ 09]
17 (0)
Recall that q, qs and ξ are 3N -dimensional vectors in configuration space.
78 CHAPTER 2. SECOND QUANTIZATION

(s) 2 (0)
Hij = ∂x∂i ∂xj Utot (q = qs ), where xi , xj = x1 , y1 , . . . zN , and ξ T is the trans-
posed vector (row) of ξ. Thus, for weak excitations, the potential energy
(0)
change ∆Utot = Utot (q) − Us is reduced to an expression which is quadratic
in the displacements ξ, i.e. we are dealing with a system of coupled harmonic
oscillators18
We can easily transform this to a system of uncoupled oscillators by di-
agonalizing the Hesse matrix which can be achieved by solving the eigenvalue
problem (we take the mass out for dimensional reasons)
λn mQn = HQn , n = 1, . . . 3N. (2.70)
Since H is real, symmetric and positive definite19 the eigenvalues √ are real
and positive corresponding to the normal mode frequencies ωn = λn . Fur-
thermore, as a result of the diagonalization, the 3N -dimensional eigenvectors
P3N a complete orthogonal system {Qn } with the scalar product Qn Qm ≡
form
i=1 Qn (i)Qm (i) ∼ δm,n which means that any excitation can be expanded
into a superposition of the eigenvectors (normal modes),
3N
X
q(t) = qs(0) + cn (t)Qn . (2.71)
n=1

The expansion coefficients cn (t) (scalar functions) are the normal coordinates.
Their equation of motion is readily obtained by inserting a Taylor expansion
of the gradient of Utot [analogous to (2.69)] into (2.68),
∂Utot
0 = mq̈ + = mq̈ + H · ξ, (2.72)
∂q
and, using Eq. (2.71) for q̈ and eliminating H with the help of (2.70),
3N
X
c̈n (t) + cn (t)ωn2 Qn .

0=m (2.73)
n=1

Due to the orthogonality of the Qn which are non-zero, the solution of this
equation implies that the terms in the parantheses vanish simultaneously for
every n, leading to an equation for a harmonic oscillator with the solution
cn (t) = An cos{ωn t + Bn }, n = 1, . . . 3N, (2.74)
18
Strictly speaking, from the 3N degrees of freedom, up to three [depending on the sym-
metry of U ] may correspond to rotations of the whole system (around one of the three
coordinate axes, these are center of mass excitations which do not change the particle dis-
tance), and the remaining are oscillations.
19 (0)
qs corresponds to a mininmum, so the local curvature of Utot is positive in all directions
2.4. INTERACTING PARTICLES 79

where the coefficients An and Bn depend on the initial conditions. Thus, the
normal coordinates behave as independent linear 1d harmonic oscillators.
In analogy to the coordinates, also the particle momenta, corresponding
to some excitation q(t), can be expanded in terms of normal modes by using
p(t) = mq̇(t). Using the result for cn (t), Eq. (2.74), we have the following
general expansion

3N
X 3N
X
q(t) − qs(0) = An cos{ωn t + Bn }Qn ≡ Qn (t) (2.75)
n=1 n=1
3N
X 3N
X
p(t) = An sin{ωn t + Bn }Pn ≡ Pn (t), (2.76)
n=1 n=1

where the momentum amplitude vector is Pn = −mωn Qn . Finally, we can


transform the Hamilton function into normal mode representation, using the
harmonic expansion (2.69) of the potential energy

N
p2 X p2
i 1X T (s)
H(p, q) = + Utot (q) = Us(0) + + ξ (i)Hij ξ(j). (2.77)
2m i=1
2m 2 i6=j

Eliminating the Hesse matrix with the help of (2.70) and inserting the expan-
sions (2.75) and (2.76) we obtain

3N X
3N  
X Pn (t)Pn0 (t)m 2
H(p, q) − Us(0) = + ωn δn,n0 Qn (t)Qn0 (t)
0
n=1 n =1
2m 2
3N  2 
X Pn (t) m 2 2
= + ωn Qn (t) ≡ H(P, Q), (2.78)
n=1
2m 2

where, in the last line, the orthogonality of the eigenvectors has been used.
Thus we have succeeded to diagonalize the hamiltonian of the N -particle
system with arbitrary interaction. Assuming weak excitations from a station-
ary state the hamiltonian can be written as a superposition of 3N normal
modes. This means, we can again apply the results from the case of uncou-
pled harmonic oscillators, Sec. 2.3.2, and immediately perform the “first” and
“second” quantization.
80 CHAPTER 2. SECOND QUANTIZATION

2.4.4 Quantization of the N -particle system


For the first quantization we have to replace the normal mode coordinates and
momenta by operators,

Qn (t) → Q̂n (t) = An cos{ωn t + Bn }Q̂n


Pn (t) → P̂n (t) = An sin{ωn t + Bn }P̂n , (2.79)

leaving the time-dependence of the classical system unchanged. Further we


have to make sure that the standard commutation relations are fulfilled, i.e.
[Q̂n , P̂m ] = i~δn,m . This should follow from the commutation relations of
the original particle coordinates and momenta, [xiα , pjβ ] = i~δi,j δα,β , where
α, β = 1, 2, 3 and i, j = 1, . . . N , see Problem 7, Sec. 2.6. Then, the Hamilton
operator becomes, in normal mode representation
3N
( )
X P̂n2 (t) m 2 2
Ĥ(P̂ , Q̂) = + ωn Q̂n (t) , (2.80)
n=1
2m 2

which allows us to directly


p n introduce the creation and annihilation operators
by introducing ξn = mω ~
Q̂n , n = 1, . . . 3N )
 
1 ∂
an = √ + ξn , (2.81)
2 ∂ξn
 
1 ∂
a†n = √ − + ξn , [an , a†k ] = δn,k . (2.82)
2 ∂ξn

Thus the hamiltonian and its eigenfunctions and eigenvalues can be written as
3N  
X 1
Ĥ = ~ωn a†n an +
n=1
2
an |0i = 0, n = 1, . . . 3N
1
ψn1 ,...n3N = |n1 . . . n3N i = √ (a†1 )n1 . . . (a†3N )n3N |0i
n1 ! . . . n3N !
3N  
X 1
E = ~ωn nn + .
n=1
2

Here |0i ≡ |0 . . . 0i = |0i . . . |0i [3N factors] denotes the ground state and a
general state |n1 . . . n3N i = |n1 i . . . |n3N i contains nn elementary excitations of
the normal mode n, created by nn times applying operator a†n to the ground
state.
2.5. CONTINUOUS SYSTEMS 81

In summary, in finding the normal modes of the interacting N -particle sys-


tem the description is reduced to a superposition of independent contributions
from 3N degrees of freedom. Depending on the system dimensionality, these
include (for a three-dimsional system) 3 translations of the center of mass and 3
rotations of the system as a whole around the coordinate axes. The remaining
normal modes correspond to excitations where the particle distances change.
Due to the stability of the stationary state with respect to weak excitations,
these relative excitations are harmonic oscillations which have been quantized.
In other words, we have 3N − 6 phonon modes associated with the correspond-
ing creation and annihilation operators and energy quanta. The frequencies of
the modes are determined by the local curvature of the total potential energy
(the diagonal elements of the Hesse matrix).

Additional discussions of the present concept are subject of problems 7 and 8,


cf. Sec. 2.6.

2.5 Continuous systems

2.5.1 Continuum limit of 1d chain

So far we have considered discrete systems containing N point particles. If the


number of particles grows and their spacing becomes small we will eventually
reach a continuous system – the 1d chain becomes a 1d string. We start with
assigning particle i a coordinate xj = ja where j = 0, . . . N , a is the constant
interparticle distance and the total length of the system is l = N a, see Fig.

We again consider a macroscopic system which is now periodically repeated


after length l, i.e. points x = 0 and x = l are identical20 . In the discrete
system we have an equally spaced distribution of masses m of point particles
with a linear mass density ρ = m/a. The interaction between the masses
is characterized by an elastic tension σ = κa where we relabeled the spring
constant by κ. The continuum limit is now performed by simulataneously
increasing the particle number and reducing a but requiring that the density

20
Thus we have formally introduced N + 1 lattice points but only N are different.
82 CHAPTER 2. SECOND QUANTIZATION

and the tension remain unchanged,

a, m −→ 0
N, κ −→ ∞
l, ρ, σ = const.

We now consider the central quantity, the displacement of the individual par-
ticles qi (t) which now transforms into a continuous displacement field q(x, t).
Further, with the continuum limit, differences become derivatives and the sum
over the particles is replaced by an integral according to

qj (t) −→ q(x, t)
∂q
qj+1 − qj −→ a
∂x
1 l
X Z
−→ dx.
j
a 0

Instead of the Hamilton function (2.47) we now consider the Lagrange


function which is the difference of kinetic and potential energy, L = T − V ,
which in the continuum limit transforms to
N n
X m κ 2 2
o
L(q, q̇) = (q̇j ) − (qj − qj+1 )
j=1
2 2
( 2 2 )
1 l
Z  
∂q(x, t) ∂q(x, t)
−→ dx ρ −σ (2.83)
2 0 ∂t ∂x

The advantage of using the Lagrange function which now is a functional of the
displacement field, L = L[q(x, t)], is that there exists a very general method of
finding the corresponding equations of motion – the minimal action principle.

2.5.2 Equation of motion of the 1d string


We now define the one-dimensional Lagrange density L
Z l
L= dx L[q̇(x, t), q 0 (x, t)], (2.84)
0

where Eq. (2.83) shows that Lagrange density of the spring depends only on
two fields – the time derivative q̇ and space derivative q 0 of the displacement
2.5. CONTINUOUS SYSTEMS 83

Figure 2.4: Illustration of the minimal action principle: the physical equa-
tion of motion corresponds to the tractory q(x, t) which minimizes the action,
Eq. (2.85) at fixed initial and final points (ti , 0) and (tf , l).

field. The action is defined as the time integral of the Lagrange function
between a fixed initial time ti and final time tf
Z tf Z tf Z l
S= dtL = dt dx L[q̇(x, t), q 0 (x, t)]. (2.85)
ti ti 0

The equation of motion of the 1d string follows from minimizing the action
with respect to the independent variables of L [this “minimal action principle”
will be discussed in detail in Chapter 1, Sec. 1.1], for illustration, see Fig. 2.4,

Z tf Z l  
δL δL
0 = δS = dt dx δ q̇ + 0 δq 0
ti 0 δ q̇ δq
Z tf Z l
= dt dx {ρq̇ δ q̇ − σq 0 δq 0 } . (2.86)
ti 0

We now change the order of differentiation and variation, δ q̇ = ∂t∂


δq and δq 0 =

∂x
δq and perform partial integrations with respect to t in the first term and x
in the second term of (2.86)
Z tf Z l
0=− dt dx {ρq̈ − σq 00 } δq, (2.87)
ti 0

where the boundary values vanish because one requires that the variation
δq(x, t) are zero at the border of the integration region, δq(0, t) = δq(l, t) ≡ 0.
Since this equation has to be fulfilled for any fluctuation δq(x, t) the term in
the parantheses has to vanish which yields the equation of motion of the 1d
string
r
∂ 2 q(x, t) 2 r
∂ q(x, t) σ κ
2
− c2 2
= 0, with c = =a . (2.88)
∂t ∂x ρ m

This is a linear wave equation for the displacement field, and we introduced
the phase velocity, i.e. the sound speed c. The solution of this equation can
be written as
q(x, t) = q0 ei(kx−ωt) + c.c., (2.89)
84 CHAPTER 2. SECOND QUANTIZATION

Figure 2.5: Dispersion of the normal modes of the discrete 1D chain and of
the associated continuous system – the 1D string. The dispersions agree for
small k up to a kmax=π/a .

which, inserted into Eq. (2.88), yields the dispersion relation

ω(k) = c · k, (2.90)

i.e., the displacement of the string performs a wave motion with linear disper-
sion – we observe an acoustic wave where the wave number k is continuous.
It is now interesting to compare this result with the behavior of the original
discrete N −particle system. There the oscillation frequencies ωn were given
by Eq. (2.52), and the wave numbers are discrete21 kn = 2πn/N a with n =
±1, · · · ± N/2, and the maximum wave number is kmax = π/a. Obviously, the
discrete system does not have a linear dispersion, but we may consider the
small k limit and expand the sin to first order:
2
c2 akn

2 κ  πn 2
ωn ≈ 4 =4 2 = ckn , (2.91)
m N a 2

i.e. for small k the discrete system has exactly the same dispersion as the con-
tinuous system. The comparison with the discrete system also gives a hint at
the existence of an upper limit for the wave number in the continuous system.
In fact, k cannot be larger than π/amin where amin is the minimal distance
of neighboring particles in the “continuous medium”. The two dispersions are
shown in Fig. 2.5.
One may, of course, ask whether a continuum model has its own right of ex-
istence, without being a limit of a discrete system. In other words, this would
correspond to a system with an infinite particle number and, correspondingly,
an infinite number M of normal modes. While we have not yet discussed how
to quantize continuum systems it is immediately clear that there should be
problems if the number of modes is unlimited. In fact, the total energy con-
tains a zero point contribution for each mode which, with M going to infinity,
will diverge. This problem does not occur for any realistic system because the
particle number is always finite (though, possibly large). But a pure contin-
uum model will be only physically relevant if such divergencies are avoided.
The solution is found by co-called “renormalization” procedures where a max-
imum k-value (a cut-off) is introduced. This maybe not easy to derive for any
specific field theory, however, based on the information from discrete systems,
21
The wave number follows from the mode numbers ln by dividing by a
2.6. PROBLEMS TO CHAPTER 2 85

such a cut-off can always be motivated by choosing a physically relevant par-


ticle number, as we have seen in this chapter.

Thus we have succeeded to perform the continuum limit of the 1d chain


– the 1d string and derive and solve its equation of motion. The solution is
a continuum of acoustic waves which are the normal modes of the medium
which replace the discrete normal modes of the linear chain. Now the ques-
tion remains how to perform a quantization of the continuous system, how to
introduce creation and annihilation operators. To this end we have to develop
a more general formalism which is called canonical quatization and which will
be discussed in the next chapter.

2.6 Problems to chapter 2


1. Calculate the explicit form of the ground state wave function by using
Eq. (2.37).

2. Show that the matrix elements of a† are given by n + 1|a† |n = n + 1,

where n = 0, 1, . . . , and are zero otherwise.



3. Show that the matrix elements of a are given by hn − 1|a|ni = n, where
n = 0, 1, . . . , and are zero otherwise.

4. Proof relation (2.40).

5. Proof the orthogonality relation (2.55).

6. The commutation relation (2.63) which was derived to satisfy the com-
mutation relations of coordinates and momenta is that of bosons. This
result was independent of whether the particles in the chain are fermions
or bosons. Discuss this seeming contradiction.

7. Proof the commutation relation [Q̂n , P̂m ] = i~δn,m .

8. Apply the concept of the eigenvalue problem of the Hesse matrix to the
solution of the normal modes of the 1d chain. Rederive the normal mode
representation of the hamiltonian and check if the time dependencies
vanish.
86 CHAPTER 2. SECOND QUANTIZATION
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 = i |φi i, i = 1, 2, . . . (3.1)
where the eigenvalues of the hamiltonian are ordered, 1 < 2 < 3 . . . . 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 ≡ |Ψ0{j} i, ∀k, l = 1, . . . N, (3.4)
where we have to require
hΨ0{j} |Ψ0{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 = |Ψ0{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 SN

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. 3.7

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}|{n0 }i = δ{n},{n0 } = δn1 ,n01 δn2 ,n02 . . .


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}|{n0 }i = δn1 ,n01 δn2 ,n02 . . . ,
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 SN

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 = |{n0 }ih{n0 }|âi |n1 n2 . . . ni . . . i
{n0 }
X
= |{n0 }ihn1 n2 . . . ni . . . |â†i |n01 . . . n0i . . . i∗ =
{n0 }
Xp
i 0
= n0i + 1 δ{n},{n0 } δni ,n0 +1 |{n }i =
i
{n0 }

= 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},{n0} = δn1 ,n01 . . . δni−1 ,n0i−1 δni+1 ,n0i+1 . . . . (3.32)
ik
δ{n},{n0} = δn1 ,n01 . . . δni−1 ,n0i−1 δni+1 ,n0i+1 . . . .δnk−1 ,n0k−1 δnk+1 ,n0k+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 exciations 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  n1  n2
|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 =
i=1 ni |{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 operator 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 operator10
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
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+ 11
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 in the product state gives
rise to an overall factor of nj . Finally, 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 Λ1...N differs by nj / ni + 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 ni 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)
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

11
From the definition (3.41) it is obvious that Π̂ij is totally symmetric in all particle
indices.
102 CHAPTER 3. FERMIONS AND BOSONS

which, together with the definition (3.45), proves the theorem12 .


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
|iji = |φi i|φj i,

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

12
See problem 2.
3.3. SECOND QUANTIZATION FOR BOSONS 103

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
= âi âj 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)13 .

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

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.
13
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

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)]
 n1  n2
|n1 , n2 , . . . i = Λ− |i
1...N 1 . . . 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 bosons14 . 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
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)
14
The prefactors are always equal to unity because 1! = 1
15
This was introduced by P. Jordan and E. Wigner in 1927.
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 k .

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 as16
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
set of anti-symmetric states and using (3.60)
X
âk | . . . , nk , . . . i = |{n0 }ih{n0 }|âk | . . . , nk , . . . i =
{n0 }
X
= |{n0 }ih{n}|â†k |{n0 }i∗
{n0 }
0
X
= (1 − n0k )(−1)αk δ{n
k 0
0 },{n} δnk ,n0 +1 |{n }i
k
{n0 }

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

where, in the third line, we used definition (3.32). Also, αk0 = 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
16
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

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,

and thus the anti-commutator vanishes as well. Consider now the case17 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.

17
This covers the general case of i 6= k, since i and k are arbitrary.
3.4. SECOND QUANTIZATION FOR FERMIONS 107

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


cf. Sec. ??.
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 state18 .
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.

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.


18
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

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 πSN

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
“move” the (empty) orbital |ji
one in the k-th orbital. To this end we first P
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
lower then Ei leading to αi pair exchanges and sign changes19 . Taking into

19
Note that, if i > j, the occupation numbers occuring in αi have changed by one compared
to those in αj .
3.4. SECOND QUANTIZATION FOR FERMIONS 109

account the definitions (3.60) and (3.61) we obtain20

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

= 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 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).
20
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

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

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.
3.4. SECOND QUANTIZATION FOR FERMIONS 111

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,21
 
0 0 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 0
nk âk nk = = δnk ,1 δnk ,n0k +1 ≡ A†k , (3.84)
1 0
 
0 0 1
hnk |âk | nk i = = δnk ,0 δnk ,n0k −1 ≡ Ak , (3.85)
0 0

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 δn0k ,1 in the space of single-particle
orbitals |φk i 22 .
21
The first [second] row corresponds to the case hn| = h0| [hn| = h1|], whereas the first
[second] column corresponds to |ni = |0i [|ni = |1i].
22
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:
112 CHAPTER 3. FERMIONS AND BOSONS

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 {n0 } = (−1)αk δ{n},{n
k †
0 } Ak (3.86)

where the original prefactor 1 − n0k has been transformed into an additional
Kronecker delta for nk . The matrix of the annihilation operator is

h{n} |âk | {n0 }i = (−1)αk δ{n},{n


k
0 } 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
and (3.86) for the creator successively we obtain, for the case k 6= l,
D E XD E
{n} â†l âk {n0 } = {n} â†l {n̄} h{n̄} |âk | {n0 }i =

{n̄}
α0k
X
= (−1) (−1)ᾱl δn̄k ,0 δ{n̄},{n
k l
0 } δn̄k ,n0 −1 δnl ,1 δ{n̄},{n} δn̄l +1,nl
k
{n̄}
α0k
X
kl
= (−1) δnl ,1 δ{n},{n0} (−1)ᾱl δn̄k ,0 δn̄k ,nk δn̄l ,n0l δn̄k ,n0k −1 δn̄l +1,nl
n̄,n̄k

X X
= (−1)αk0 l δ{n},{n
kl
0 } Al Ak , αk0 l = n0m + nm , (3.88)
m<k m<l

 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 Ak = = (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

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 αk0 l
are restricted by the Kronecker symbols. For the case k = l we recover the
matrix of the particle number operator which is completely diagonal23
D E
† 0
{n} âk âk {n } = h{n} |n̂k | {n0 }i = nk δ{n},{n0 } . (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
blk {n} â†l âk {n0 }
0
{n} B̂1 {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
diag 0
{n} B̂1 {n } = δ{n},{n0 } bk nk = δ{n},{n0 } bn k . (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 .
For the general case of a non-diagonal operator it follows from (3.90)24
( N
D E X
0
{n} B̂1 {n } = δ{n},{n0 } bnk nk +
k=1
N
)
X nk nl †
+ (−1)k+l+γkl bnl nk δ{n},{n0 } Anl Ank , . (3.92)
k6=l=1

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


23
ThisPresult is contained in expression (3.88). Indeed, in the special case k = l we obtain
αk0 l → m<k (n0m + nm ), δ{n},{n
kl k
0 } → δ{n},{n0 } and the matrix product in k-orbital space

yields A†k Ak → nk δnk ,n0k [cf. property 2 in footnote 22] which combines to the results (3.89).

24
The non-diagonal matrix elements are transformed to summation over occupied orbitals
as
∞ D E N
X † 0 X
bnl nk {n} â†nl ânk {n0 } ,


blk {n} âl âk {n } =
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 .
114 CHAPTER 3. FERMIONS AND BOSONS

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
† † 0 † † 0
{n} âi âl âj âk {n } = {n} âi âl {n̄} {n̄} âj âk {n } =
{n̄}
X jk
= (−1)αil̄ δ{n},{n̄}
il
δni ,1 δn̄i ,0 δnl ,0 δn̄l ,1 × (−1)αj̄k0 δ{n̄},{n 0 } δn̄j ,1 δn0 ,0 δn̄k ,0 δn0 ,1 ,
j k
{n̄}

where αj̄k0 = p<j n̄p + p<k n0 etc. Performing the summation, with the help
P P

of the Kronecker deltas we obtain the final result25


D E
† † 0 iljk † †
{n} âi âl âj âk {n } = (−1)αilj0 k0 δ{n},{n0 } Ai Al Aj Ak (3.94)
X X X X
with αilj 0 k0 = np + np + n0p + n0p .
p<i p<l p<j p<k

This is a general result which also contains the cases of equal index pairs.
Then, proceeding as in footnote 23, we obtain the results for the special cases.
jk †
i=l: (−1)αj0 k0 δ{n},{n0 } ni Aj Ak


j=k: (−1)αil δ{n},{n
il
0 } nj Ai Al


l=j: (−1)αik0 δ{n},{n
ik
0 } (1 − nl )Ai Ak

i=l, j=k: δ{n},{n0 } ni nj



lj
k=i: (−1)αlj0 δ{n},{n0 } ni Al Aj + (−1) δ{n},{n0 } δij A†i Al
αil il

25
We first rewrite
X X
il
δ{n},{n̄ δ jk
p } {n̄p },{n0 }
= iljk
δ{n},{n 0 } δnj ,n̄j δnk ,n̄k δn̄i ,n0 δn̄l ,n0 ,
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 ,n0i δn̄i ,0 = δn0i ,0 and so on.
3.4. SECOND QUANTIZATION FOR FERMIONS 115

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 progress26 . 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
Eq. (3.96)27

X ∞
X
V̂ = −
wijkl â†j â†i âk âl , (3.100)
1≤i<j 1≤k<l

wijkl = wijkl − wijlk , (3.101)
26
M. Heimsoth contributed to this section.
27
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
116 CHAPTER 3. FERMIONS AND BOSONS

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 |{n0 }i

X ∞
X
0
h{n}|V̂ |{n }i = −
wijkl h{n}|â†j â†i âk âl |{n0 }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 (m01 , m02 . . . m0N ), respectively,28

h{n}|V̂ |{n0 }i → h{m}|V̂ |{m0 }i =


XN XN
− † † 0
= wm 0 0 h{m}|âm âm âm0 âm0 |{m }i. (3.103)
i mj m m k jl i k l
1≤i<j 1≤k<l

Using the definitions of the creation and annihilation operators, Eqs. (3.60),
(3.61), and taking advantage of the operator order in (3.103)29 , the operators
can be evaluated, with the result
N
X N
X
0 − 0
h{m}|V̂ |{m }i = (−1)i+j+k+l wm 0
i mj m m
0 h{m}|mi ,mj |{m }im0 ,m0 ,
k l
k l
1≤i<j 1≤k<l
(3.104)
0
where the notation |{m }im0k ,m0l means that the single-particle orbitals with
number m0k and m0l are missing in the state |{m0 }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 = m03 , m4 = m04 , . . . .
28
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 |{n0 }i is diagonal in all orbitals missing simultaneously in h{m}|
and |{m0 }i.
29
Since i < j and k < l, the signs produced by the first and second operators are inde-
pendent of each other.
3.4. SECOND QUANTIZATION FOR FERMIONS 117

Finally, expression (3.104) will be only non-zero if the missing orbitals fall
in one of three cases30 :

1. The two states are identical, {n} ≡ {n0 } and, consequently {m} ≡ {m0 }.
Then Eq. (3.104) yields
N
X
h{n}|V̂ |{n0 }i = δ{n},{n0 } −
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 |{m0 }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) yields31
N −1
m m0
X

h{n}|V̂ |{n0 }i = δ{n},{n
p r †
0 } Amp Am0r (−1)p+r · Θ(p, r, i) wm 0
i mp mi mr
1≤i,i6=p,r
(3.106)
Here Θ(p, r, i) = −1, if either mp < mi or m0r
< mi , otherwise Θ(p, r, i) =
1. This case describes single-particle excitations where |{n0 }i = |{n}rp i.

3. The two states are identical except for two orbitals with the numbers mp
and mq in h{m}| and m0r and m0s in |{m0 }i, respectively. Without loss of
generality we can use mp < mq and m0r < m0s . Then Eq. (3.104) yields
m m m0 m0s −
h{n}|V̂ |{n0 }i = δ{n},{n
p q r
A†mp Am0r A†mq Am0s (−1)p+q+r+s wm
0} 0 0
p mq mr ms
(3.107)
0 rs
This case describes two-particle excitations where |{n }i = |{n}pq 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.
30
Thereby we return to the full vectors (including the empty orbitals) and restore the
delta functions.
31
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 |{n0 }i, respectively and count the number of transpositions (difference).
118 CHAPTER 3. FERMIONS AND BOSONS

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

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(x0 ) = 0, (3.110)

h i
ψˆ† (x), ψˆ† (x0 ) = 0, (3.111)
h i∓
ψ̂(x), ψˆ† (x0 ) = δ(x − x0 ). (3.112)

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.

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 † (x0 ) = φi (x)φ∗j (x0 ) âi , â†j =
∓ ∓
i,j=1
X ∞
= φi (x)φ∗i (x0 ) = δ(x − x0 ) = δ(r − r0 )δσ,σ0 ,
i=1

where, in the last line, we used the representation of the delta function in
terms of a complete set of functions.

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
120 CHAPTER 3. FERMIONS AND BOSONS

We now transform the matrix element to coordinate representation:


Z
hi|b̂|ji = dxdx0 φ∗i (x)hx|b̂|x0 iφj (x0 ), (3.114)

and obtain for the operator, taking into account the definitions (3.108) and
(3.109),
∞ Z
X
B̂1 = dxdx0 a†i φ∗i (x)hx|b̂|x0 iφj (x0 )aj =
i,j=1
Z
= dxdx0 ψ̂ † (x)hx|b̂|x0 iψ̂(x0 ). (3.115)

For the important case that the matrix is diagonal, hx|b̂|x0 i = b̂(x)δ(x − x0 ),
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

and the expectation value in a certain N -particle state Ψ(x1 , x2 , . . . xN ) is32


N
X
hn̂i(x) = h Ψ| δ(x − xα )|Ψ i
Z α=1
= 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 − x0 ), i.e.
Z
n̂(x) = dx0 ψ̂ † (x0 )δ(x − x0 )ψ̂(x0 ) = ψ̂ † (x)ψ̂(x), (3.119)

32
This is the example of an (anti-)symmetrized pure state which is easily extended to
mixed states.
3.5. FIELD OPERATORS 121

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
Z  
† 1 2
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

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),
∞ Z
1 X
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
Z
1
B̂2 = dx1 dx2 ψ̂ † (x1 )ψ̂ † (x2 )b̂(x1 , x2 )ψ̂(x2 )ψ̂(x1 ) (3.125)
2
122 CHAPTER 3. FERMIONS AND BOSONS

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
Z
1 0
X
hφk,s |φk0 ,s0 i = d3 r ei(k −k)r δs,σ δs0 ,σ = δk,k0 δs,s0 , (3.127)
V V σ

where we took into account that the integral over the finite volume V equals
zero for k 6= k0 and V otherwise.

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) = φk0 ,σ0 (x)ak0 ,σ0 .
k0 σ 0

Multiplication by φ∗k,σ (x) and integrating over x yields, with the help of con-
dition (3.127),
Z Z
∗ 1
ak,σ = dx φk0 σ0 ψ̂(x) = 1/2 d3 r e−ik·r ψ̂(r, σ), (3.128)
V V
3.6. MOMENTUM REPRESENTATION 123

and, similarly for the creation operator,


Z
† 1
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), x0 = (r0 , s0 ),
XX †
B̂1 = akσ hkσ|b̂|k0 σ 0 i ak0 σ0
kσ k0 σ 0
XXZ
= dx dx0 a†kσ hkσ|xihx|b̂|x0 ihx0 |k0 σ 0 i ak0 σ0
kσ k0 σ 0
Z
1 XX 0 0
= dx dx0 a†kσ e−ikr hx|b̂|x0 ieik r ak0 σ0 δσ,s δσ0 ,s0 , (3.130)
V kσ k0 σ0

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|x0 i → − ~2m δ(x − x0 ), and we obtain, using the property (3.127),
Z 2 02
1 XX 3 † −ikr ~ k 0
T̂ = d r akσ e eik r ak0 σ
V kσ k0 V 2m
X ~ 2 k2 †
= akσ akσ . (3.131)

2m
124 CHAPTER 3. FERMIONS AND BOSONS

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


hx|b̂|x0 i → v(r)δ(x − x0 ),
Z
XX † 1 0
V̂ = akσ ak0 σ d3 r e−ikr v(r) eik r
kσ k0
V V
XX
= ṽk−k0 a†kσ ak0 σ , (3.132)
kσ k0

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
Z
1 X 1 0
= a†k0 σ akσ d3 r ei(k−k )r e−iqr
V σkk0 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

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|k01 σ10 k02 σ20 i ak02 σ20 ak01 σ10 (3.135)
2! k σ k σ 0 0 0 0
1 1 2 2 k1 σ1 k2 σ2

We now apply this result to the interaction potential where the matrix element
in momentum representation was computed before, hk1 σ1 k2 σ2 |ŵ|k01 σ10 k02 σ20 i =
w̃(k1 − k01 )δk1 +k2 −k01 −k02 δσ1 ,σ10 δσ2 ,σ20 , 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. 3.7. Inserting this into Eq. (3.135) and intro-
ducing the momentum transfer q = k01 − k1 = k2 − k02 , 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
3.6. MOMENTUM REPRESENTATION 125

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 = a†kσ akσ + ṽk−k0 a†kσ ak0 σ

2m kk0 σ
1 X X
+ w̃(q)a†k1 σ1 a†k2 σ2 ak2 −q,σ2 ak1 +q,σ1 . (3.137)
2! k
1 k2 q σ1 σ2

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


matter physics, quantum plasmas or nuclear matter.
After investigating the basic properties of the method of second quantiza-
tion 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.

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 2
k = ~2mk → ~2 k 2 c2 + m2 c4 , where m is the rest mass. In the ultra-relativistic
limit, k = ~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 k− = − ~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.
126 CHAPTER 3. FERMIONS AND BOSONS

3.7 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).

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.


Chapter 5

Dynamics of the creation and


annihilation operators

After considering the description of a many-particle system in thermodynamic


equilibrium we now extend the formalism of second quantization to nonequilib-
rium. We obtain the equations of motion for the second quantization operators
where we consider fermions and bosons in a common approach. The only dis-
tinction will enter through the different (anti-)commutation properties of the
respective operators.

5.1 Equation of motion of the field operators


We start by considering the dynamics of the field operators. Their time-
dependent form is obtained by transforming to the Heisenberg representation
of quantum mechanics according to1 .

ψ̂H (x, t) = U † (t, t0 )ψ̂(x)U (t, t0 ) (5.1)

where ψ̂(x) is the (time-independent) field operator in the Schrödinger picture,


i.e. the value of the Heisenberg operator ψ̂H (x, t) at a chosen initial time t0 .
Furthermore, U (t, t0 ) is the N -particle Schrödinger time evolution operator
that obeys

i~∂t U (t, t0 ) − Ĥ(t)U (t, t0 ) = 0, (5.2)


U (t, t) = 1̂, (5.3)
1
A critical discussion ot the Heisenberg representation of the field operators is given in
Sec. 5.4.

139
140 CHAPTER 5. DYNAMICS OF FIELD OPERATORS

where Ĥ is the full N -particle hamiltonian. We also give the adjoint equation,

0 = −i~∂t U † (t, t0 ) − U † (t, t0 )Ĥ(t) = −i~∂t U (t0 , t) − U (t0 , t)Ĥ(t)


= −i~∂t0 U (t, t0 ) − U (t, t0 )Ĥ(t0 ), (5.4)

where we used [U (t, t0 )]† = U (t0 , t) and, in the last line, renamed the time
arguments t ↔ t0 and understand H to act to the left.
The time evolution of the field operators is governed by the hamiltonian for
which we use a general expression containing kinetic energy, potential energy
and pair interaction energy which we write in second quantization (x = (r, σ),
see chapter 3)
~2 0 2
Z  
0 † 0
Ĥ = T̂ + Û + Ŵ = dx ψ̂ (x ) − ∇ + v(r ) ψ̂(x0 ) +
0
2m
Z Z
1 0
= dx dx00 ψ̂ † (x0 )ψ̂ † (x00 )w(r0 , r00 )ψ̂(x00 )ψ̂(x0 ). (5.5)
2
The evolution equation of the field operators is given by Heisenberg’s equation
(see problem 5.1, Sec. 5.7) 2

i~∂t ψ̂H (x, t) = −[ĤH , ψ̂H (x, t)] = −U † (t, t0 )[Ĥ, ψ̂(x)]U (t, t0 ). (5.7)

We now evaluate the commutator which is the sum of three commutators


involving T̂ , Û and Ŵ , respectively. This will lead to commutators of different
combinations of field operators which we will simplify using the commutation
(anticommutation) relations for bosonic (fermionic) operators.
We start the derivation by noting the following properties of commutators,

[ÂB̂, Ĉ] = Â[B̂, Ĉ] + [Â, Ĉ]B̂, (5.8)


[ÂB̂, Ĉ] = Â[B̂, Ĉ]∓ ± [Â, Ĉ]∓ B̂, (5.9)
[ψ̂ † (x0 ), ψ̂(x)]∓ = ∓δ(x − x0 ), (5.10)

where the first two are verified by direct evaluation of the left and right-hand
sides (see problem 5.2, Sec. 5.7) and the third follows from the standard (anti-
)commutation relations3 .
2
The derivation starts from the r.h.s. of Heisenberg’s equation that involves two Heisen-
berg operators

−[U † (t, t0 )ĤU (t, t0 ), U † (t, t0 )ψ̂(x)U (t, t0 )], (5.6)

and uses the property U (t, t0 )U † (t, t0 ) = 1.


3
In the second and third line the upper (lower) sign refers to bosons (fermions), i.e. to
the commutator (anti-commutator).
5.1. EQUATION OF MOTION OF THE FIELD OPERATORS 141

Consider first the commutator with the external potential which is simpli-
fied with the help of Eq. (5.9),
Z
[V̂ , ψ̂(x)] = dx0 [ψ̂ † (x0 )v(r0 )ψ̂(x0 ), ψ̂(x)] =
Z n o
dx0 v(r0 ) ψ̂ † (x0 )[ψ̂(x0 ), ψ̂(x)]∓ ± [ψ̂ † (x0 ), ψ̂(x)]∓ ψ̂(x0 )

= −v(r)ψ̂(x), (5.11)
where we took into account that the first commutator vanishes and the second
is evaluated according to Eq. (5.10). The same derivation applies to the kinetic
energy term with the result
~2 2
 
[T̂ , ψ̂(x)] = − − ∇ ψ̂(x). (5.12)
2m
Finally, we transform the commutator with the interaction energy using rela-
tion (5.8),
Z Z
0
2[Ŵ , ψ̂(x)] = dx dx00 [ψ̂ † (x0 )ψ̂ † (x00 )w(r0 , r00 )ψ̂(x00 )ψ̂(x0 ), ψ̂(x)] =
Z Z 
0
= dx dx w(r , r ) ψ̂ † (x0 )ψ̂ † (x00 )[ψ̂(x00 )ψ̂(x0 ), ψ̂(x)] +
00 0 00


† 0 † 00 00 0
+ [ψ̂ (x )ψ̂ (x ), ψ̂(x)]ψ̂(x )ψ̂(x ) . (5.13)

The first commutator vanishes as it involves only annihilation operators whereas


the second is transformed, using Eqs. (5.9) and (5.10),
[ψ̂ † (x0 )ψ̂ † (x00 ), ψ̂(x)] = ψ̂ † (x0 )[ψ̂ † (x00 ), ψ̂(x)]∓ ± [ψ̂ † (x0 ), ψ̂(x)]∓ ψ̂ † (x00 )
= ∓ψ̂ † (x0 )δ(x00 − x) − δ(x0 − x)ψ̂ † (x00 ), (5.14)
and the second term in the integral (5.13) becomes
[ψ̂ † (x0 )ψ̂ † (x00 ), ψ̂(x)]ψ̂(x00 )ψ̂(x0 ) = −2δ(x0 − x)ψ̂ † (x00 )ψ̂(x00 )ψ̂(x0 ),
where the first term in Eq. (5.14) is transformed by exchanging x0 ↔ x00 , after
which it becomes identically equal to the second one4 . With this the final
result for the commutator becomes
Z
[Ŵ , ψ̂(x)] = − dx00 w(r, r00 )ψ̂ † (x00 )ψ̂(x00 )ψ̂(x). (5.15)

4
The derivation assumes w(r0 , r00 ) = w(r00 , r0 ), and the sign change, in the case of
fermions, arises from exchanging the order of the two annihilation operators.
142 CHAPTER 5. DYNAMICS OF FIELD OPERATORS

Inserting the results for the three commutators into Eq. (5.7) and applying the
time evolution operators (assuming ∂H/∂t = 0 it follows U † v(r) = v(r)U † ; for
the general case, see Sec. 5.4 and problem 2) we obtain the equation of motion
of the field operator,

~2 2
 
ind
i~∂t ψ̂H (x, t) = − ∇ + v(r) + ÛH (x, t) ψ̂H (x, t) (5.16)
2m
Z

ÛH (x, t) = dx00 w(r, r00 )ψ̂H
ind
(x00 , t)ψ̂H (x00 , t). (5.17)

eff
Thus the field operator is subject to an effective single-particle potential v̂H =
ind
v(r) + ÛH .
This is an exact result, valid both for fermions and bosons. Remarkably,
this equation which was derived from the Heisenberg equation (5.7) has the
form of a one-particle time-dependent Schrödinger equation, just as for the
wave function, and it shares the same basic properties. First, the equation for
the creation operator is obtained by hermitean conjugation of Eq. (5.16):

~2 2
 
† † ind
i~∂t ψ̂H (x, t) = −ψ̂H (x, t) − ∇ + v(r) + ÛH (x, t) (5.18)
2m

where the operators ∇ and ÛHind act on the field operator to the left, and we
took into account that (ÛHind )† = ÛHind which is a consequence of the fact that

the density operator, n̂H = ψ̂H ψ̂H , appearing in ÛHind , is hermitean.
Theorem: As the Schrödinger equation in quantum mechanics, Eq. (5.16)
is associated with an operator continuity equation describing local particle num-
ber conservation,

∂t n̂H (x, t) + ∇ĵH (x, t) = 0 (5.19)

† ~ n † 

 o
n̂H = ψ̂H ψ̂H , ĵH (x, t) = ψ̂H ∇ψ̂H − ∇ψ̂H ψ̂H (5.20)
2im

While in the continuity equation for the single-particle wave function of stan-
dard quantum mechanics the quantities n and j describe the probability den-
sity and probability current density, here the analogous quantities refer to an
N -particle system5 .
5
While the probability density is normalized to 1 (the particle number equals one), here
the integral of n̂ over the volume yields the total particle number N .
5.2. GENERAL OPERATOR DYNAMICS 143

Proof: We compute the time-derivative of the density operator and use the
equations of motion (5.16), (5.18), dropping the arguments x, t

˙n̂H = ψ̂ † ψ̂˙ H + ψ̂˙ † ψ̂H = − ~


n   o
† 2 2 †
H H ψ̂H ∇ ψ̂H − ∇ ψ̂H ψ̂H =
2im
~ n   o
† †
= − ∇ ψ̂H ∇ψ̂H − ∇ψ̂H ψ̂H ,
2im

and the expression in the brackets is just the current density operator (5.20)6 .
The key difference between the familiar one-particle Schrödinger equation
and Eq. (5.16) for the field operator is the appearance of an effective potential
ÛHeff = v + ÛHind instead of the external potential v. This “induced” potential
includes the whole many-body problem. It has exactly the form of a mean
field (Hartree) potential that is created by all particles, as in the case of the
quantum Vlasov equation (Hartree equation)7 . Thus this equation is the sim-
plest formulation of the nonequilibrium many-body problem for fermions and
bosons in its full generality. This simple form arises from the nature of the
creation and annihilation operators that are well adapted to this problem.
Unfortunately, a direct solution of Eq. (5.16) is impossible due to its op-
erator character. The standard procedure is, therefore, to introduce suitable
expectation values. This will be considered in Sec. 5.6. An independent ap-
proach that is based on a stochastic approach to this equation will be discussed
in Sec. 5.4. But before that we generalize the equation of motion for the field
operators to a general basis and derive the equations of motion for the creation
and annihilation operators.

5.2 Dynamics of the creation and annihilation


operators in an arbitrary representation
After considering the dynamics of the second quantization operators in co-
ordinate representation, we now generalize this result to an arbitrary basis of
single-particle states {|ii}. The N -particle states belong to the Fock space and
are again written in occupation number representation |n1 n2 . . . i, cf. Chapter
3. The creation and annihilation operators associated to orbital i are ai and
ai † and obey the standard (anti-)commutation relations.
6
In the derivation we took into account that the terms with the potentials cancel.
7
Interestingly, the same general structure of an exact mean-field type form of the many-
body problem was obtained before in Ch. 2 for classical systems when we discussed the
phase space density N (r, p, t), cf. Eq. (2.20).
144 CHAPTER 5. DYNAMICS OF FIELD OPERATORS

We start with the same hamiltonian as before, Eq. (5.5), for which we use
the general second quantization representation,

Ĥ = T̂ + Û + Ŵ , (5.21)
X∞ ∞
X

T̂ + Û = ai (tij + vij ) aj = hij a†i aj , (5.22)
i,j=1 i,j=1

1 X † †
Ŵ = a a wijkl al ak . (5.23)
2 i,j,k,l=1 i j

Proceeding as in Sec. 5.1 we introduce Heisenberg operators,


âi (t) = U † (t, t0 )âi U (t, t0 ), and consider the Heisenberg equation of motion8

i~∂t ai (t) = −U † (t, t0 )[Ĥ, ai ]U (t, t0 ), ai (t0 ) = ai . (5.24)

Evaluating the three commutators in Eq. (5.24) we finally obtain (see problem
5.4, Sec. 5.7)
X X
i~∂t ai (t) = (til + vil )al (t) + wimln a†m (t)an (t)al (t) (5.25)
l lmn

where all operators are now Heisenberg operators. This is the generalization
of the coordinate space result (5.16) to a general basis representation. All
the results discussed before (induced potential, adjoint equation, continuity
equation etc.) remain valid. Again we may introduce an effective potential
and rewrite the equation of motion in the form of an effective single-particle
problem
X
eff

i~∂t ai (t) = til + v̂H,il (t) al (t), (5.26)
l
X
eff
v̂H,il (t) = vil + wimln n̂mn (t). (5.27)
mn

5.3 Extension to time-dependent hamiltonians


So far we have assumed that the hamiltonian does not depend explicitly on
time. This was used when applying the time evolution on the final step of the
derivation. We now remove this restriction and generalize our results to the
case of a time-dependent single-particle potential, such as an external electro-
magnetic field. Then the only term that changes is the the one involving the
8
As before, we assume ∂t H = 0. For the general case see Sec. 5.4
5.4. SCHRÖDINGER DYNAMICS OF THE FIELD OPERATORS 145

potential Û (t), cf. Eq. (5.22), and the contribution to the r.h.s. of Eq. (5.24)
becomes
X
−U † (t, t0 )[Û , ai ]U (t, t0 ) = U † (t, t0 ) vil (t) al U (t, t0 ) (5.28)
l
X X

= U (t, t0 )vil (t)U (t, t0 ) al (t) = v̂H,il (t) al (t).
l l

where, in the last line we inserted a unity operator between vil and al . Note
that, for the general case of a time-depdendent potential v(t) does not commute
with the time evolution operator, v(t)U (t, t0 ) 6= U (t, t0 )v(t), and the result,
therefore, contains the Heisenberg operator vH,il (t). Thus, our previous result,
Eq. (5.27) is generalized to
X
eff

i~∂t ai (t) = til + v̂H,il (t) al (t), (5.29)
l
X
eff
v̂H,il (t) = v̂H,il (t) + wimln n̂mn (t), (5.30)
mn

where the time dependence of v̂H,il (t) = U † (t, t0 )vil (t)U (t, t0 ) is due, both, to
the explicit time dependence of the potential v and the two time evolution
operators.

5.4 Schrödinger dynamics of the creation and


annihilation operators
In the previous sections we used the Heisenberg picture for the creation and
annihilation operators9 . While this is common practice in many text books,
this approach has to be critically assessed. The problem is that the “standard”
Heisenberg operator âH (t) = U † (tt0 ) â U (tt0 ) has, strictly speaking, no clear
mathematical meaning if the Hamilton operator (and, similarly, the evolution
operator U ) refers to a fixed particle number N . Suppose we act with âH (t)
on an arbitrary state |ψN i of the N -particle Hilbert state HN . Then we will,
obviously, understand U as an N -particle time evolution operator associated
with the N -particle hamiltonian ĤN . The action of U produces again a state
from HN . Acting now with â produces a state from the Hilbert space HN −1 .
The final action of U † , which is again associated with ĤN , is then, however,
ill-defined. Thus, the use of the standard Heisenberg picture for the operators
9
This aspect and the following results have been worked out together with S. Hermanns
and C. Hinz.
146 CHAPTER 5. DYNAMICS OF FIELD OPERATORS

â and ↠is only possible if ĤN and U do not refer to a fixed N but are defined
in Fock space10 .
Alternatively, if the Hamiltonian is defined in Hilbert space HN , the dy-
namics of creation and annihilation operators should be formulated in the
Schrödinger picture where no such problem occurs since it involves only a sin-
gle evolution operator UN . Let us now consider how this is accomplished and
compare the results with those of the previous sections of this chapter.
We start with an arbitrary complete set of single-particle states |ii for which
the operators âi and â†i are defined as before. With these operators we can
again produce the second quantization respresentation of arbitrary operators,
in particular, for the generic N -particle hamiltonian Ĥ, cf. Eq. (5.21). We
proceed by constructing properly (anti-)symmetrized N -particle states |{n}i
and defining the N -particle evolution operator U , as before, via Eq. (5.16).
Now we define the time-dependent annihilation and creation operators that
evolve from the operators âi and â†i , leaving out the hats

ai (t) = ai U (t, t0 ) (5.35)

a†i (t) = U † (t, t0 )a†i (5.36)


10
One possible way to define Heisenberg-type operators with hamiltonians for a fixed N
is to work with different Hilbert spaces:

aH
k (t) = UN −1 (t, t0 )ak UN (t, t0 ). (5.31)

Then, the equation of motion is given by


† †
i∂t aH
k (t) = i∂t UN −1 ak UN + UN −1 ak i∂t UN
† †
= −UN −1 HN −1 ak UN + UN −1 ak HN UN
H H H H
= −HN −1 (t)ak (t) + ak (t)HN (t) (5.32)

where, in the third line, we inserted unity according to UN −1 UN −1 = 1̂. The density matrix
operator is then given by
†,H † † † †
nH H
kl (t) = ak (t)al (t) = UN ak UN −1 UN −1 al UN = UN nkl UN , (5.33)

which is a proper Heisenberg operator in N -particle Hilbert space that evolves according to
the Heisenberg equation of motion

i~∂t nH H H
kl (t) = [nkl (t), Hkl (t)]. (5.34)

Thus this modified Heisenberg dynamics of the creation and annihilation operators lead to
the same equations of motion for the density matrix operator. Furthermore, it is clear that
this modified Heisenberg dynamics will approach the standard definition in the macroscopic
limit, N → ∞ when N − 1 → N , and the r.h.s. of Eq. (5.32) approaches the commutator
[aH H
k (t), HN (t)].
5.5. DYNAMICS OF THE DENSITY MATRIX OPERATOR 147

where the second line follows by hermitean adjungation of the first one. These
definitions mean that the annihilation and creation operators behave like wave
functions of first quantization evolving according to the time-dependent N −par-
ticle Schrödinger equation,

i~∂t ai (t) = ai H(t)U (t, t0 ), (5.37)


−i~∂t a†i (t) = U † (t, t0 )H(t)a†i . (5.38)

These equations are well defined when U is an N -particle operator11 .


Let us now see how the corresponding density matrix operator looks like
and what its properties are. One immediately finds

nji (t) = a†j (t)ai (t) = U † (t, t0 )a†j ai U (t, t0 ) = nH


ji (t), (5.39)
n†ji (t) = nij (t). (5.40)

The first line shows that the density matrix operator defined with Eqs. (5.35)
and (5.36) is a proper Heisenberg operator and its equation of motion is given
by the Heisenberg equation (5.34).
This way we have at our disposal two independent dynamical equations
of the creation and annihilation operators – a Schrödinger equation and a
Heisenberg equation. Both have a different applicability range: the first corre-
sponds to Hamiltonians (and time evolution operators) acting in the N -particle
Hilbert space, whereas the second assumes operators defined in Fock space
with a variable particle number. Both approaches have their advantages and
disadvantages for numerical applications as we discuss below.

5.5 Dynamics of the density matrix operator


n̂nm(t)
We now consider the dynamics of the operator n̂nm (t). This operator is directly
related to observable quantities in quantum many-body systems in nonequilib-
rium and thus of prime importance. Since n̂nm (t) is a Heisenberg operator the
ambiguity in the dynamics of the field operators – Heisenberg vs. Schrödinger
dynamics – does not play a role here. Both representaions lead to the same
results for the density matrix operator. We start from the Heisenberg equation

i~∂t nij (t) = −U † (t, t0 )[Ĥs (t), nij ]U (t, t0 ), nij (t0 ) = nij . (5.41)
11
This is not a restriction. N can be chosen arbitrary, only U has to be chosen corre-
spondingly.
148 CHAPTER 5. DYNAMICS OF FIELD OPERATORS

and evaluate the three commutators in Eq. (5.41), using again the relations
(5.8), (5.9) and [a†i , aj ]∓ = ∓δi,j ,
X n o
[T̂ + Û , nij ] = hkl (t) a†k [al , a†i aj ] + [a†k , a†i aj ]al =
kl
X n o
= hkl (t) ∓a†k [a†i , al ]∓ aj − a†i [aj , a†k ]∓ al
kl
X n o
† †
= hkl (t) ak aj δil − ai al δjk
kl
Xn o
= hki (t) a†k aj − hjk (t) a†i ak (5.42)
k
X
nik h∗kj (t) − h∗ik (t) nkj = n̂h∗ (t) − h∗ (t)n̂, (5.43)

= −
k

where, in the last expression, we introduced standard matrix notation. The


commutator with the interaction energy is transformed similarly,
X n o
2[Ŵ , a†i aj ] = wklmn a†k a†l [an am , a†i aj ] + [a†k a†l , a†i aj ]an am =
klmn
X n o
= wklmn −a†k a†l [a†i , an am ]aj − a†i [aj , a†k a†l ]an am =
klmn
X n   o
† † † † †
= wklmn ak al (an δmi ± am δni ) aj − ai al δkj ± ak δlj an am
klmn
Xn o
= −2 wjnkl a†i a†n al ak − winkl

a†k a†l an aj . (5.44)
kln

In the third line, the first terms in the parantheses are equal to the second
ones – this is shown by exchanging (k, m) ↔ (l, n) and using the symmetries
am an = ±an am and wklmn = wlknm .
What remains now is to apply the time evolution operators. There are
two ways to proceed. The first is to apply the evolution operators only to the
outermost field operators. To this end we use the results for the commutators
in the form (5.42) and (5.44) and combine them as follows
X
i~∂t nij (t) = U † (t, t0 )a†i heff
jk (t)ak U (t, t0 ) −
k
X
− U (t, t0 )a†k heff

ki (t)aj U (t, t0 ) (5.45)
k
X
heff
jk
ind
= hjk (t) + Ŵjk , ind
Ŵjk = wjnkl a†n al , (5.46)
ln
5.5. DYNAMICS OF THE DENSITY MATRIX OPERATOR 149

where we introduced the same operators of the induced potential and effec-
tive single-particle potential as before, cf. Sec. 5.3. Note, however, that here
the induced potential is still time-independent. This is our first result. It is
particularly useful when we consider computation of suitabel averages. Sup-
pose we are interested in the average dynamics of the density matrix opera-
tor, i.e. the dnamics of the density matrix nij , in a given time-independent
N -particle state |Ψi. When the density matrix operator is averaged with
|Ψi, we can, for each term, combine the pair of time evolution operators,
hΨ|U (t0 , t) . . . U (t, t0 )|Ψi = hΨ(t)| . . . |Ψ(t)i with the state vectors to yield
time-dependent N -particle states, where the dots denote a time-independent
operator, except for the intrinsic time-dependence of ĥ(t). This brings us back
to a Schrödinger-type description of the time evolution which is the basis for
Configuration Interaction approaches.
The second approach consists in reordering the field operators in the inter-
action term such that this term can be expressed via density matrix operators.
Eventually we will also try to achieve a compact matrix equation, as was done
for the single-particle terms in Eq. (5.43). To this end we transform the first
four-operator product, using nnl ak = ak nnl − δkn al

a†i a†n al ak = nik nnl − δnk nil


= ± (nil nnk − δln nik )
1 1
= (nik nnl ± nil nnk ) − (δnk nil ± δln nik ) . (5.47)
2 2

The first two lines correspond to the two options to pair creation and anni-
hilation operators which are both equivalent. Therefore, below we will use
the (anti-)symmetrized form given in the third line. Analogously, the second
four-operator product becomes

1 1
a†k a†l an aj = (nln nkj ± nkn nlj ) − (δnk nlj ± δln nkj ) . (5.48)
2 2

The next step is to apply the two time evolution operators which simply leads
to the replacement of all density matrix operators be time-dependent (Heisen-
berg) operators. Finally, we take into account the induced potential and trans-
150 CHAPTER 5. DYNAMICS OF FIELD OPERATORS

form, using Eq. (5.47),


X X wjnkl
a†i ind
Ŵjk ak = {(nik nnl ± nil nnk ) − (δnk nil ± δln nik )} .
k kln
2
X ∗
X wkljn X ∗
X wkljn
= nik nnl ± nil nnk
k ln
2 l kn
2
∗ ∗
X X wlkjn ± wkljn
− nik δln
k ln
2
∗ ∗
X X wkljn ± wlkjn
= nik {nnl ∓ δln }
k ln
2
= n̂Û± ,
∗ ∗
±
X wkljn ± wlkjn
with the definition Ûkj = {n̂nl ∓ δln } ,
ln
2
X wjnkl ± wjnlk
= {n̂nl ∓ δln } , (5.49)
ln
2

where, in the two terms containing nil , we exchanged the summation indices
l ↔ k. In Eq. (5.49) we introduced the operator of the (anti-)symmetrized
induced potential.
Similarly, the second term becomes
X X wklin
a†k Ŵkiind aj = {(nln nkj ± nkn nlj ) − (δnk nlj ± δln nkj )} .
k
2
kln
X X wklin ± wlkin
= {nln ∓ δln } nkj .
k ln
2
= Û± n̂. (5.50)

One readily verifies the potential U ± is exactly the one introduced in Eq. (5.49).12
12
Starting from the definition (5.49) we readily transform to the expression (5.50) by, first,
exchanging the summation indices n, l and then using, in the second term, the property of
the matrix elements of the interaction, wklni = wlkin
X wknil ± wknli
±
Uik = {n̂nl ∓ δln }
2
ln
X wklin ± wklni X wklin ± wlkin
= {n̂ln ∓ δln } = {n̂ln ∓ δln } .
2 2
ln ln
5.6. FLUCTUATIONS AND CORRELATIONS 151

Collecting all the results, we obtain, after applying the time evolution op-
erators,
h n oi h i
i~∂t n̂(t) = n̂(t), h∗H (t) + Û±
H (t) = n̂(t), ĥ ±
H (t) (5.51)

where all operators are now Heisenberg operators, in particular, the induced
potential operator now contains Heisenberg creation and annihilation opera-
tors. The term in the curly brackets can again be understood as the operator
of an effective (Hartree-Fock-type) potential, ĥ± ∗ ±
H (t) = hH (t) + ÛH (t).

5.6 Ensemble average of the Heisenberg equa-


tion. Fluctuations and correlations
Despite the formal simplicity of the dynamical equation (5.51) which has the
form of a Hartree-Fock equation, the operator nature of the entering field
operators prohibits a direct access to observable physical quantities. There
are (at least) four solutions:

A. Computation of pure state averages using N -particle states and time prop-
agation of these states (expansion coefficients) in CI-manner, as discussed
in the context of Eq. (5.45).

B. Application of the field operators to suitable many-body states. Propaga-


tion of individual random trajaectories with subsequent ensemble aver-
aging. An example is the stochastic mean field approach of Ayik, Lacroix
and others which is discussed in Sec. 5.6.2.

C. Performing a suitable statistical average over field operators yielding results


in a mixed ensemble. This approach results in a hierarchy of equations for
reduced s-particle density matrices (BBGKY-hierarchy or for correlation
functions of fluctuations) and will be considered in Sec. 5.6.1.

D. Computation of statistical averages of field operator products taken at dif-


ferent times. This leads to the theory of nonequilibrium Green functions
and will be discussed in Chapter 7.

5.6.1 Fluctuations and correlations


We now perform a statistical average of the operator equation (5.51). We
will denote averages of operators by symbols without hat and fluctuations
152 CHAPTER 5. DYNAMICS OF FIELD OPERATORS

(deviations from the average) by the symbol δ, i.e.


hn̂nm i ≡ nnm . (5.52)
δn̂nm ≡ n̂nm − nnm . (5.53)
Since averaging is a linear operation, its application to the operator equation
of motion (5.51) does not change the equation, except for terms containing
products of density matrix operators. For arbitrary operators (or random
variables), the average of a product can be written as hÂB̂i = AB + hδ Âδ B̂i.
We now apply these results to the operator equation (5.51):
 Dh iE
i∂t n(t) − n(t), h± ±
≡ I± (t)

H (t) = δn̂(t), δ ÛH (t) (5.54)

Here the l.h.s. contains all (ensemble averaged) mean field terms and con-
stitutes a standard time-depdendent Hartree-Fock (TDHF) equation for the
density matrix. The r.h.s., in contrast, contains all terms going beyond TDHF.
By definition, these are correlation contributions. Here we see that these cor-
relation terms have a one to one correspondence with fluctuations of operator
pairs13 . We have also introduced the short notation I± for the collision integral.
The solution of this inhomogeneous linear (formally) equation, together
with the initial condition, n(t0 ) = n0 , is straightforward and given in terms of
Hartree-Fock propagators U HF (these are two-dimensional matrices and every-
where matrix multiplication is implied)
n(t) = U HF† (t, t0 ) n0 U HF (t, t0 ) + nI (t), (5.55)
1 t
Z
nI (t) = dt̄ U HF† (t, t̄) I± (t̄) U HF (t, t̄), (5.56)
i t0
i∂t U HF (t, t0 ) = h±
H (t)U
HF
(t, t0 ), U HF (t, t) = 1. (5.57)
We now can make further progress in evaluating the collision term I± by
directly computing the fluctuations δ n̂ and, from it, also the fluctuation of the
effective potential,
X wjnkl ± wjnlk
±
δ Ûkj = δn̂nl . (5.58)
ln
2
Indeed the equation of motion of δ n̂ follows immediately by taking the differ-
ence of Eqs. (5.51) and (5.54) [we suppress the time arguments]
i∂t (n̂ − n) = [n̂, h∗H ] − [n, h∗H ] +
h i   Dh iE
+ n̂, Û± H − n, U ±
H − δ n̂, δ Û±
H

13
This correspondence between correlations and fluctuations is well known from the kinetic
theory of classical plasmas and was established by Kadomtsev, Klimontovich and others.
5.6. FLUCTUATIONS AND CORRELATIONS 153

Using the linearity in the density matrix, this can be rewritten as


h i Dh iE
± ±
i∂t δ n̂ − [δ n̂, h∗H ] = δ n̂, δ ÛH − δ n̂, δ ÛH ≡ Ĵ± (5.59)

The term on the right can be understood as a higher order collision h integral
i
or as the fluctuation of the correlator of the fluctuations, Ĵ = δ δ n̂, δ Û±
±
H .
Equation (5.59), together with the initial condition δn̂(t0 ) = δn̂0 , is solved
like Eq. (5.54), but using ideal propagators instead of Hartree-Fock propaga-
tors:

δn̂(t) = U id† (t, t0 ) δ n̂0 U id (t, t0 ) + δ n̂J (t), (5.60)


1 t
Z
δ n̂J (t) = dt̄ U id† (t, t̄) Ĵ± (t̄) U id (t, t̄), (5.61)
i t0
i∂t U id (t, t0 ) = h∗H (t)U id (t, t0 ), U id (t, t) = 1. (5.62)

There are several ways how to proceed. One is to evaluate the r.h.s. of
Eq.(5.59) by using again the equation of motion (5.59), multiply by δ Û± to
derive the equation of motion for the product of fluctuations δ n̂δ Û± and for
their commutator. It is easy to see that this equation, on the r.h.s., will
contain products of three operator fluctuations. This shows that a hierarchy
of equations for the fluctuations emerges which, in fact, is analogous to the
BBGKY-hierarchy for the reduced density operators.
As an alternative, we can use the solution δn(t), Eq. (5.60), to compute
(α)
the commutator [δ n̂(t)δ Ûind (t)], for a given initial condition δn0 . This yields
a single random realization of the collision integral I±(α) in Eq. (5.54). Re-
peating this for a representative set of initial conditions we can compute the
expectation value by averaging over an ensemble of initial conditions,
M
±
Dh
±
iE 1 X Dh (α) ±(α)
iE
I (t) = δ n̂(t), δ Û (t) = lim δ n̂ (t), δ Û (t) , (5.63)
M →∞ M
α=1

where P(α) denotes the possible realizations that occur with probability pα ,
where α pα = 1. This set (α, pα ) specifies the ensemble.
With this, the r.h.s. of Eq. (5.54) is known and this equation can be
solved. Two problems remain. The first is how to specify a physically adequate
ensemble and the second, how to solve for δ n̂, considering the complicated
structure of the collision integral Ĵ± . A very simple and successful approach
has recently been proposed by Ayik and co-workers [Ayi08, Lac13] and will be
considered in the next section.
154 CHAPTER 5. DYNAMICS OF FIELD OPERATORS

5.6.2 Stochastic Mean Field Approximation


One problem in treating the fluctuations of the density matrix operator and
of the mean field potential is their time dependence. A first simplifying at-
tempt to understand the general physics is, therefore, to neglect this depen-
dence entirely. This can be done by approximating the collision intergral I± in
Eq. (5.54) by a local function according to I± (t) → I± (t0 )δ(t − t0 ). This means
only the initial fluctuations are taken into account. With this the solution for
the density matrix, Eq. (5.56) becomes
1 HF†
nI (t) = U (t, t0 ) I± (t0 ) U HF (t, t0 ),
i
and the total solution for the density matrix is given by
 iE
HF† 1 Dh ±
n(t) = U (t, t0 ) n0 + δn̂(t0 ), δ ÛH (t0 ) U HF (t, t0 ).
i
This means that the evolution of the density matrix n(t) is given by a pure
Hartree-Fock dynamics. However, the evolution does not startfrom the ini-
tial value of the density matrix, n(t0 ) but from a value that is shifted by the
second term in the parantheses. If we forget for a moment the angular brack-
ets we would have random realizations of initial values. Ayik had the idea
[Ayi08] to replace the complicated commutator by a semiclassical ensemble of
initial density fluctuations with given mean and variance such that the term in
(α)
parantheses becomes n0 +∆n0 , for a given realization (α). The corresponding
dynamics, starting from this initial state is given by
n o
HF† (α)
n̂(α) (t) = U(α) (t, t0 ) n0 + ∆n0 HF
U(α) (t, t0 ),

and the full result is then given by the ensemble average, i.e. by the sum over
all realizations, for all times,
M
1 X (α)
n(t) = lim n̂ (t). (5.64)
M →∞ M
α=1

Since only mean field trajectories are involved and the result is obtained from
a stochastic sampling over relizations this approach has been called Stochas-
tic Mean Field (SMF). Thereby, the incorporation of fluctuations reproduces
(part of) the correlations in the system. The most attractive feature is the
conceptional simplicity and computational efficiency: THDF propagations are
very simple and fast, and sampling of the initial states is very efficiently re-
alized with Monte Carlo methods. Finally, this sampling an be performed in
parallel on a large number of computer cores.
5.6. FLUCTUATIONS AND CORRELATIONS 155

Although the SMF concept is very crude since it restricts the fluctuations
to those of the initial state, neglecting decay of initial fluctaions and buildup of
correlations due to collisions, this method shows remarkable results. Tests for
simple Hubbard clusters have shown that the results are not only better than
pure time-dpendent Hartree-Fock (TDHF) but also more accurate than NEGF
results using selfenergies in second order Born approximation [LHHB14].

5.6.3 Iterative Improvement of Stochastic Mean Field


Approximation
Here we suggest a further improvement of SMF that allows to include the time-
dependence of the fluctuations in an iterative manner. A crucial observation
is that SMF does not only yield the one-body expectation value n(t) but a
full set of random trajectories. This means, we can also compute fluctuations
of the density, correlation functions, higher order density matrices and so on.
Using the entire ensemble of trajectories {n(α1) } we can immediately compute
the ensemble of fluctuations {δn(α1) } and {δU±(α1) }, cf. Eq. (5.58). Using
Eq. (5.63) we can directly evaluate the collision integral and thus compute the
evolution of the density matrix.
A further improvement would be to avoid the computation of the ensemble
average in Eq. (5.63) but instead, again, to propagate random realizations.
Then we would again have access to an ensemble of improved trajectories
{n(α2) } which can, again, be used as input into the collision integral. This way
an iterative procedure can be designed. It remains to be checked how good
convergence is.
The open problem is to work out an approximation how to compute the
commutator of {δn(α) } and {δU±(α) } that enters the collision integral.

5.6.4 Ensemble average of the field operators


Suppose our many-body system is in a mixed state characterized by some
time-independent probability distribution. In the most general case this is the
N -particle density operator ρN . Then we can compute averages, h. . . iρN =
Tr . . . ρN ,

hψ̂(r, σ, t)iρN = ψ(r, σ, t) (5.65)


hψ̂ † (r, σ, t)iρN = ψ ∗ (r, σ, t), (5.66)

which are already regular functions of coordinate, spin and time.


156 CHAPTER 5. DYNAMICS OF FIELD OPERATORS

5.6.5 Field operators and reduced density matrices


Consider an arbitrary s-particle operator, B̂s . To compute its expectation
values we have two options. First is to use the (anti-) symmetrized reduced
s-particle density operator Fs± that are defined via the full N -particle density
operator according to [Bon]
Fs± = Fs Λ±
1...s (5.67)
N! N!
Fs = Trs+1...N ρN , Tr1...s Fs = . (5.68)
(N − s)! (N − s)!
Here we introduced the (anti-)symmetrization operator defined in Eq. (3.14)
in Sec. 3. Note that Fs is an ensemble averaged quantity since it is computed
from ρN that incorporates a mixed state description with given probabilities
of the individual N -particle states.
Using the reduced density operator the expectation value of B̂s is computed
according to
1
hB̂s iρN = Tr1...s B̂s Fs± (5.69)
s!
∞ ∞
1 X X
= hi1 . . . is |Fs± |k1 . . . ks ihk1 . . . ks |b̂1...s |i1 . . . is i,
s! i ...i =1 k ...k =1
1 s 1 s

where, in the second line, the trace is performed using a complete set of s-
particle states |i1 . . . is i which we can always construct as products of single-
particle orbitals. This expression is equivalent14 to averaging over the full N -
particle density operator since the trace over the variables of particles s+1 . . . N
is trivially performed.
The second approach to compute this expecation value is to transform the
operator B̂s into second quantization representation, cf. Eq. (3.54),
∞ ∞
1 X X
B̂s = hk1 . . . ks |b̂1...s |i1 . . . is ia†i1 . . . a†is aks . . . ak1 ,
s! i ...i =1 k ...k =1
1 s 1 s

where the sums run over the complete set of single-particle orbitals. This is still
an operator expression. In order to obtain its expectation value in the relevant
statistical ensemble, we average this expression with the density operator ρN ,
taking into account that the matrix element of b̂ is a regular c-function,
∞ ∞
1 X X
hB̂s iρN = hk1 . . . ks |b̂1...s |i1 . . . iss iha†i1 . . . a†is aks . . . ak1 iρN .
s! i ...i =1 k ...k =1
1 s 1 s

(5.70)
14
Of course, it is equivalent only if the density operator Fs± is known exactly.
5.6. FLUCTUATIONS AND CORRELATIONS 157

Now, comparing the two results, Eq. (5.69) and (5.70), we can establish the
connection between the creation and annihiliation operators and the reduced
density operators:

hi1 . . . is |Fs± |k1 . . . ks i = ha†i1 . . . a†is aks . . . ak1 iρN . (5.71)

This is an important result as it establishes the connection between quantum


kinetic theory (reduced density operators) and second quantization and allows
us to construct the reduced density operators directly from the second quanti-
zation operators. Note that the appearance of the factor ns is a consequence of
our definition of the reduced density operators which obey the normalization
TrFs = V s that is convenient for macroscopic systems. From this we obtain
the normalization of the expression (5.71):

X N!
Tr1...s F̂s± = ha†i1 . . . a†is ais . . . ai1 iρN = . (5.72)
i1 ...is =1
(N − s)!

The definition (5.71) contains all relevant cases. Let us discuss some of
them explicitly.

i) The single-particle reduced density operator is obtained from setting, in


Eq. (5.71), s → 1:

hi|F1± |ki = ha†i ak iρN ≡ nik ≡ n, (5.73)

and its coordinate representation is obtained by using the field operators,


instead of a and a† , and a basis of coordinate-spin states (x = r, σ),

nhrσ|F1± |r0 σ 0 i = hψ † (r, σ)ψ(r0 σ 0 )iρN ≡ n(x, x0 ). (5.74)

For completeness, we give the normalization condition of the single-


particle density matrix in coordinate representation which follows di-
rectly from the general relation (5.72),
XZ XZ
±
N= dr hrσ|nF1 |rσi = dr hψ † (r, σ)ψ(rσ)iρN . (5.75)
σ σ

ii) The diagonal elements of the single-particle density operator (5.73) yield
the ensemble averaged occupations of the single-particle orbitals |ii,

ha†i ai iρN ≡ nii = ni , (5.76)


158 CHAPTER 5. DYNAMICS OF FIELD OPERATORS

whereas the diagonal elements in the coordinate representation yield the


local spin density

hψ † (r, σ)ψ(rσ)iρN ≡ n(x, x) = nσ (r). (5.77)

In contrast, the off-diagonal elements of expression (5.73) describe the


statistical probability of transitions between orbital |ki and |ii. Similarly,
the off-diagonal elements of the coordinate-space expression (5.74) are
related to the probability of a particle undergoing a transition from spin
orbital |r0 σ 0 i to |rσi.

iii) The second important case of (5.71) is the two-particle reduced density
operator (s = 2),

hi1 i2 |F2± |k1 k2 i = ha†i1 a†i2 ak2 ak1 iρN ≡ ni1 ,i2 ;k1 ,k2 ≡ n(2) ,
(2)
(5.78)

whereas its coordinate representation is,

hr1 σ1 r2 σ2 |F2± |r01 σ10 r02 σ20 i = (5.79)


† † 0 0 0 0 (2) 0 0
hψ (r1 , σ1 )ψ (r2 , σ2 )ψ(r2 σ2 )ψ(r1 σ1 )iρN ≡ n (x1 , x2 ; x1 , x2 ).

The two-particle density matrix is normalized according to [cf. Eq. (5.72)]



X
Tr12 n (2)
= ha†i1 . . . a†is ais . . . ai1 iρN = N (N − 1).
i1 i2 =1

iv) All the above results are directly extended to time-dependent situations.
We simply have to introduce the Heisenberg operators in standard man-
ner,

ai → aHi (t) ≡ U † (t, t0 )ai U (t, t0 ),


ψ(x) → ψH (x, t) ≡ U † (t, t0 )ψ(x)U (t, t0 ),

and so on. This will give rise to the time-dependent reduced density op-
(2)
erators Fs± (t), nij (t), nij (t), time-dependent densities ni (t) and nσ (r, t)
etc. Thereby, the underlying dynamics of the Heisenberg operators was
computed above: the field operators obey Eqs. (5.16) and (5.18) and the
general annihilation operator obeys Eq. (5.25).

As we just discussed, the time-dynamics of a many-body system can be


obtained from the time evolution of the second quantization operators in the
5.7. PROBLEMS TO CHAPTER 5 159

Heisenberg picture. Alternatively, the dynamics of the reduced density op-


erators Fs± (t) is known: it is given by the BBGKY-hierarchy which follows
from the equation of motion of the N -particle density operator ρN – the von
Neumann equation. Since we found a one-to-one relation between the Fs± (t)
and the second quantization operators, this BBGKY-hierarchy has to follow
from the dynamics of ai and a†i . This will be discussed below.

5.6.6 BBGKY-hierarchy

5.7 Problems to Chapter 5


Problem 5.1 Derive the equation

i∂t ψ̂H (x, t) = −U † (t, t0 )[Ĥ, ψ̂(x)]U (t, t0 ). (5.80)

Problem 5.2 Prove the identity (5.9): [ÂB̂, Ĉ] = Â[B̂, Ĉ]∓ ± [Â, Ĉ]∓ B̂

Problem 5.3 Discuss the derivation of Eq. (5.16) for the case of a time-
dependent hamiltonian. Consider a time-dependent single-particle po-
tential, v(r, t).

Problem 5.4 Derive the general equation of motion (5.25) for the creation
and annihilation operators for the case of a time-independent external
potential.
268 CHAPTER 5. DYNAMICS OF FIELD OPERATORS
Appendix A

Solutions to problems

A.1 Problems from chapter 2


Problem 1: A simple equation for ψ0 is readily obtained by inserting the
definition of a into Eq. (2.37),

0 = ψ00 (ξ) + ξψ0 (ξ), (A.1)


2
with the solution
R∞ ψ0 (ξ) = C0 e−ξ /2 , where C0 follows from the normal-
ization x0 −∞ dξψ02 = 1, with the result C0 = (π 1/2 /x0 )−1/2 , where the
phase is arbitrary and chosen to be zero.

Problem 2: Proof: Using hψ|a† = a|ψi and Eq. (2.40), direct computation
yields
1
ψn+1 |a† |ψn = p ψ0 |an+1 a† (a† )n |ψ0 .



n!(n + 1)!

The final result n + 1 is obtained by induction, starting with n = 0.

Problem 3: This problem reduces to the previous one by applying hermitean


conjugation ∗ √
hψn−1 |a|ψn i = ψn |a† |ψn−1 = n

A.2 Problems from chapter 3


Problem 1:

Problem 2:

Problem 3:

269
270 APPENDIX A. SOLUTIONS TO PROBLEMS

Problem 4: The Proof of relation (3.63), i.e. [âi , â†k ]+ = 0, for fermionic
creation and annihilation operators proceeds as follows:
Consider, this relation explicitly, in its action on a Fock state:
 
† † †
[âi , âk ]+ |{n}i = âi âk + âk âi |{n}i,

i) case i = k. Inserting the definitions (3.60) and (3.61) we obtain for


the first term
âi â†i | . . . ni . . . i = âi (1 − ni )(−1)αi | . . . ni + 1 . . . i (A.2)
2αi
= (ni + 1)(1 − ni )(−1) | . . . ni . . . i = δni ,0 | . . . ni . . . i.
Analogously, the second term becomes
â†i âi | . . . ni . . . i = â†i ni (−1)αi | . . . ni − 1 . . . i (A.3)
2αi
= (2 − ni )ni (−1) | . . . ni . . . i = δni ,1 | . . . ni . . . i.
Since δni ,1 + δni ,0 = 1, this proves relation (3.63), for i = k.
ii) case i 6= k. Without loss of generality we consider i < k and obtain,
as before,
âi â†k | . . . ni . . . nk . . . i = âi (1 − nk )(−1)αk | . . . ni . . . nk + 1 . . . i
= ni (1 − nk )(−1)αi +αk | . . . ni − 1 . . . nk + 1 . . . i.
For the second term of the anti-commutator, it follows
â†k âi | . . . ni . . . nk . . . i = â†k ni (−1)αi | . . . ni − 1 . . . nk . . . i
= (1 − nk )ni (−1)αi +(αk −1) | . . . ni − 1 . . . nk + 1 . . . i
= −âi â†k | . . . ni . . . nk . . . i,
which proves relation (3.63) for i 6= k. Note theP sign change in the
last line that results from the exponent αk − 1 = l<k n0l , where the n0l
are the occupation numbers after the earlier action of the operator âi
which causes a reduction by one. Thus we have proved the fermionic
anti-commutation relation (3.63).
Problem 5:
Problem 6: The momentum matrix element of the interaction potential is
derived as follows: Suppressing the spin variables (the matrix of the
interaction is diagonal in the spin indices of both particles) we have
Z
0 0 1 0 0 0 0
hk1 k2 |ŵ|k1 k2 i = 2
dr1 dr2 dr01 dr02 e−ik1 r1 −ik2 r2 hr1 r2 |ŵ|r01 r02 ieik1 r1 +ik2 r2
V
Z
1 −ik1 r1 −ik2 r2 ik01 r1 +ik02 r2
= dr1 dr2 w(r 1 − r2 )e e .
V2
A.3. PROBLEMS FROM CHAPTER 4 271

Introducing the distance of the two particles, r = r1 − r2 , we rewrite the


exponents according to r1 (k1 − k01 ) + r2 (k2 − k02 ) = r(k1 − k01 ) + r2 (k1 −
k01 + k2 − k02 ) and obtain
Z Z
0 0 1 −ir(k1 −k01 ) 0 0
hk1 k2 |ŵ|k1 k2 i = 2
dr w(r)e dr2 e−ir2 (k1 −k1 +k2 −k2 ) .
V

The second integral yields Vδk1 +k2 ,k01 +k02 and theRfirst is expressed by the
Fourier transform of the potential w̃(q) = V −1 dr w(r) e−iqr , with the
final result

hk1 k2 |ŵ|k01 k02 i = w̃(k1 − k01 )δk1 +k2 ,k01 +k02 .

A.3 Problems from chapter 4


Problem 1:

A.4 Problems from chapter 5


Problem 1:

Problem 2: The commutator identiy [ÂB̂, Ĉ] = Â[B̂, Ĉ]∓ ±[Â, Ĉ]∓ B̂ is proven
by dirct computation. The left hand side equals ÂB̂ Ĉ − Ĉ ÂB̂, whereas
the right hand side becomes
n o
ÂB̂ Ĉ ∓ ÂĈ B̂ ± ÂĈ B̂ ∓ Ĉ ÂB̂ .

The terms ÂĈ B̂ exactly cancel and we recover the expression on the left
hand side.

Problem 2:

Problem 3: The derivation for a time-dependent single-particle potential pro-


ceeds as follows.

Problem 4: The solution of the equation of motion for the annihilion operator
with respect to a general single-particle basis starts from the Heisenberg
equation

i~∂t ai (t) = −U † (t, t0 )[Ĥ, ai ]U (t, t0 ), ai (t0 ) = ai . (A.4)


272 APPENDIX A. SOLUTIONS TO PROBLEMS

We now evaluate the three commutators in Eq. (5.24) using the hamil-
tonian in second quantization (5.21, 5.22, 5.23) as well as the relations
(5.8), (5.9) and [a†i , aj ]∓ = ∓δi,j ,
X n o X
[T̂ + Û , ai ] = (tkl + vkl a†k [al , ai ]∓ ± [a†k , ai ]∓ al = − (til + vil )al .
k,l l

The commutator with the interaction energy is transformed similarly,


X n o
2[Ŵ , ai ] = wklmn a†k a†l [an am , ai ] + [a†k a†l , ai ]an am =
klmn
X n o
= wklmn a†k [a†l , ai ]∓ ± [a†k , ai ]∓ a†l an am =
klmn
X n o
= wklmn ∓a†k δl,i − a†l δk,i an am =
klmn
X X
= −2 wilmn a†l an am = −2 wimln a†m an al .
lmn lmn

In the third line the first term is equal to the second one – this is shown
by exchanging (k, m) ↔ (l, n) and using the symmetries am an = ±an am
and wklmn = wlknm . In the last line we exchanged l ↔ m.
Collecting all the results, we obtain from Eq. (A.4), after applying the
time evolution operators,
X X
i~∂t ai (t) = (til + vil )al (t) + wimln a†m (t)an (t)al (t),
l lmn

where all operators are now Heisenberg operators. This is the desired
result (5.25). which generalizes the coordinate space result (5.16) to a
general basis representation.

A.5 Problems from chapter 6


Problem 1:
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