Escolar Documentos
Profissional Documentos
Cultura Documentos
Michael Bonitz
February 9, 2015
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
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
Bibliography 293
Chapter 2
Introduction to second
quantization
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
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.
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
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)
8π
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
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.
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.
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
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
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
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
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
Ĥ 1
= N̂ + . (2.32)
~ω 2
[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)
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
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
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)
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 .
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 .
left and right neighbor via springs with constant k.10 , see Fig. 2.2.
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
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
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
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)
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.
∂
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
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
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
20
Thus we have formally introduced N + 1 lattice points but only N are different.
82 CHAPTER 2. SECOND QUANTIZATION
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
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.
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
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 .
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
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.
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
87
88 CHAPTER 3. FERMIONS AND BOSONS
Obviously, Pkl† = Pkl , so the eigenvalue λkl is real. Then, from Eqs. (3.5) and
(3.6) immediately follows
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.
|Ψj1 ,j2 i± = C12 {|Ψj1 ,j2 i + A12 P12 |Ψj1 ,j2 i} , (3.8)
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
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
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,
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.
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
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
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.
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
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
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)
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.
the creation operator(s). For example, single and two-particle states with the
proper normalization are obtained via
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 ! . . .
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
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
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
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
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
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
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 .
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
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
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
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
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
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
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
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
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.
where the two form an orthonormal basis with h0|0i = h1|1i = 1 and h0|1i = 0.
3.4. SECOND QUANTIZATION FOR FERMIONS 111
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
where the original prefactor 1 − n0k has been transformed into an additional
Kronecker delta for nk . The matrix of the annihilation operator is
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
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
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
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
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
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
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
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
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
∞
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.
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.
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
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
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)
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
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 ).
where we took into account that the integral over the finite volume V equals
zero for k 6= k0 and V otherwise.
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
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
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
X ~2 k 2 X
Ĥ = a†kσ akσ + ṽk−k0 a†kσ ak0 σ
kσ
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
5. Discuss what happened to the sum over α in the derivation of Eq. (3.48).
139
140 CHAPTER 5. DYNAMICS OF FIELD OPERATORS
where Ĥ is the full N -particle hamiltonian. We also give the adjoint equation,
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)
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
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)
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,
† ~ 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
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.
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
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
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.
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
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,
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.
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
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
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
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).
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).
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
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:
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
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].
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:
The definition (5.71) contains all relevant cases. Let us discuss some of
them explicitly.
ii) The diagonal elements of the single-particle density operator (5.73) yield
the ensemble averaged occupations of the single-particle orbitals |ii,
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)
iv) All the above results are directly extended to time-dependent situations.
We simply have to introduce the Heisenberg operators in standard man-
ner,
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).
5.6.6 BBGKY-hierarchy
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
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 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,
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
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 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
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
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.
293
294 BIBLIOGRAPHY
[MG64] A.M.L. Messiah and O.W. Greenberg. Phys. Rev., 136:248, 1964.
[MG65] A.M.L. Messiah and O.W. Greenberg. Phys. Rev., 138:1155, 1965.
[Sla29] J.C. Slater. The theory of complex spectra. Phys. Rev., 34:1293–
1322, 1929.