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Quantization of the Electromagnetic Field
R. Guy Woolley
Volume 1, Part 7, Chapter 39, pp 657–678

in

Handbook of Molecular Physics and Quantum Chemistry

(ISBN 0 471 62374 1)

Edited by

Stephen Wilson

 John Wiley & Sons, Ltd, Chichester, 2003

Chapter 39
Quantization of the Electromagnetic Field
R. Guy Woolley
Nottingham Trent University, Nottingham, UK
1 Introduction 1 state |
is given by
2 Quantization for a Particle 2
3 Quantization for a Field 4 E(
, ) =
4 The Free Electromagnetic Field Quantized 6 |

5 Representation of States of the Field 8 where a|b
is the Hilbert space scalar product. More
6 Properties of the Field Operators 15
7 Angular Momentum and Polarization 18
8 Translations of the Field Variables 19
Notes 21
References 21
1 INTRODUCTION
In this chapter, we review the principal results of the appli-
cation of the quantum theory to the electromagnetic field.
In quantum mechanics, all observable physical quantities
correspond to self-adjoint operators. The only measurable
values of a physical observable are the various eigenval-
ues of the corresponding operator; in general, the spectrum
of an operator contains a discrete and a continuous part.
The state of a physical system is described completely by
a vector in a Hilbert space upon which the operators cor-
responding to observables act. If this state vector happens
to be an eigenvector of the measured observable, then the
result of the measurement will definitely (i.e., with proba-
bility 1) be the corresponding eigenvalue; more generally,
one has a probability distribution for finding eigenvalues.
Handbook of Molecular Physics and Quantum Chemistry,
Edited by Stephen Wilson. Volume 1: Fundamentals.  2003
John Wiley & Sons, Ltd. ISBN: 0-471-62374-1.
ˆ in the
The mean value of the result of measurement of

ˆ
|


(1)
generally the notion of a mixed state in classical statistical
mechanics translates into the use in quantum theory of a
density operator, ρ̂, that acts on vectors in the Hilbert space.
For mixed states, equation (1) becomes,
ˆ
E(
, ρ) = Tr(ρ̂
), Tr(ρ̂) = 1 (2)
Perhaps the most celebrated result of quantum mechanics
is the uncertainty principle,(1) according to which there is a
fundamental limit to the accuracy with which the position
and momentum of a particle can be known simultaneously
px ∼ h̄ (3)
Formally, the uncertainty relation (3) is an immediate con-
sequence of the fact that the observables x and p correspond
to a pair of non-commuting operators. It is more instruc-
tive, however, to consider an ideal experiment designed to
measure these quantities, for example, Heisenberg’s γ-ray
microscope. Although it is valid to use classical optics to
describe the path of a convergent light beam to its focus
in the microscope,(2) the light beam cannot be a classi-
cal Maxwell wave; if it were, the momentum of the light
could be made as small as desired so that the position of
the particle could be obtained exactly without transferring
momentum to it, and hence the restriction implied by equa-
tion (3) could be evaded by first measuring the momentum
exactly and then using the microscope to determine the
position. On the contrary, if the light beam is such that
2 Quantum electrodynamics of atoms and molecules
the position of the particle can be measured at the focus
with an accuracy of x, for consistency with equation (3),
the momentum of the light beam must have an uncertainty
given by
h̄
gx ∼ (4)
x
The uncertainty relation (3) also plays a critical role in
a discussion of the measurement of the field strengths E
and B; although they are written as point functions, they
cannot actually be measured at a specified space–time point
(x, t). In practice, they can only be measured as average
values for a small volume δV ∼ δl 3 over some time interval
t. Such a measurement can be achieved experimentally
by determining the effect of an electromagnetic field on
suitable charged test bodies, for example, the deflection of
particle beams. The deflection can be computed classically
using the Lorentz force law (Chapter 37, this Volume,
equation 120); however, the test particles are subject to the
fundamental condition (3), whatever their charge and mass,
and this limits the accuracy with which the deflection can
be measured. This leads to an uncertainty relation for the
field strengths in the same volume element
h
Ei Bj ≥ (5)
ε0 (δl)4
with cyclic permutation of (i, j ) for the other compon-
ents.(1,3) Consequently, the classical field strengths (E, B)

,
must be replaced by a pair of non-commuting operators (E

sented by a self-adjoint operator; ambiguities in the oper-
B ) consistent with equation (5).
We see therefore that the quantum properties of charged
particles and of the electromagnetic field are intimately
related. Quantization of the free field can be carried through
formally in close analogy with the simplest case in quan-
tum mechanics – the spinless particle, which is convenient
to review first. In the following section, we first give
a summary statement (Section 2.1) of canonical quanti-
zation for a particle described by Hamiltonian conjugate
variables (x, p), and then recall some important results
(Section 2.2) of the unitary group representation theory for
translations. ‘Translations’ of the variables describing the
electromagnetic field, for example, gauge transformations
(Chapter 37, this Volume, Section 3), play an important
role in the formalism of quantum electrodynamics (QED).
2 QUANTIZATION FOR A PARTICLE
2.1 Canonical quantization
According to Dirac’s canonical quantization scheme, we
may adapt the formalism of classical Hamiltonian mechan-
ics in the following way.(4) All observables for a spinless
particle can be constructed out of just two basic operators
corresponding to position and momentum, which we denote
as x̂ and p̂, respectively. Their classical Poisson-brackets
(Chapter 37, this Volume, equation 165) are replaced by
the Heisenberg commutation relations
[x̂, p̂] ≡ x̂ p̂ − p̂ x̂ = i h̄1̂ (6)
where 1̂ is the identity operator on the Hilbert space H, and
h̄ is the reduced Planck constant h/2π; this relation leads
directly to equation (3). It is easy to see that the position
and momentum operators have the formal properties
∂ ∂
x̂ = i h̄ , p̂ = −i h̄ (7)
∂ p̂ ∂ x̂
Classical functions of the canonical variables (x, p) such as
the Hamiltonian, H (x, p), become operators, H
(x̂, p̂), by
the direct replacements of x by x̂ and p by p̂. Furthermore,
canonical quantization postulates a direct correspondence
between classical Poisson-brackets and quantum commuta-
tors that is applied to all observables

B]
{A, B} = C ===⇒ [A,
= i h̄C

(8)
in this way quantum operators inherit the Lie group struc-
tures of the Poisson-brackets (Chapter 37, this Volume,
Section 6). We have to bear in mind, however, the require-
ment that an observable in quantum theory must be repre-
ators constructed according to the canonical quantization
rules are resolved as far as possible by the principle that
the operators describing invariances of the system should
have the same group theoretical properties as their classical
counterparts. Using equation (8), the equation of motion for
a time-independent classical variable is replaced by


dA
H
]
i h̄ = [A, (9)
dt
for the conjugate variables x and p this leads to
dx̂ ∂H
dp̂ ∂H

= , =− (10)
dt ∂ p̂ dt ∂ x̂
in exact correspondence with Hamilton’s equations of
motion (Chapter 37, this Volume, equation 156).
Although the quantum-mechanical formalism is based on
the vectors of an abstract Hilbert space, for many purposes
it is much more convenient to introduce a representation of
the Hilbert space; this is like the introduction of coordinates
in algebraic geometry. Accordingly, we often represent
the Hilbert space using complex-valued functions in a
 Quantization of the electromagnetic field 3

function space that are square-integrable with respect to |p 
of p̂ in the coordinate representation, x  |p 
; we have
an appropriate measure. Consider the basic observables for
d  
the particle; we have the eigenvalue equations, p  x  |p 
≡ x  |p̂p 
= −i h̄ x |p
(17)
dx
x̂|x 
= x  |x 
, x ∈ (11) so that
     
p̂|p
= p |p
, p ∈ (12) i  
x  |p 
= N exp px (18)
h̄
and we may represent the abstract Hilbert space using
vectors φ(x  ) ∈ L2 ( , µx  ) or ψ(p  ) ∈ L2 ( , µp ) where µ where N is a normalization constant.
is Lebesgue measure on the real line. If we use the functions
φ, we speak of the coordinate representation, whereas 2.2 Translations and unitary group
the functions ψ describe momentum representation. Since representations
x̂ and p̂ have continuous spectra, −∞ ≤ x  , p  ≤ +∞,
their associated representations are in terms of continuous Both operators x̂ and p̂ have spectra that can be endowed
functions on the whole real line. For systems with a finite with the group structure of the additive group of the real line
number of degrees of freedom, the choice of representation ( , +). For definiteness, let the additive group associated
has a purely kinematical character since, as proved by with the spectrum of x̂ be denoted by G; then for a fixed
von Neumann,(5) one can pass from one representation element a belonging to G, the unitary operator
to another by means of a unitary transformation. Clearly  

i
the physical description will not depend on the choice Ua = exp a p̂ (19)
h̄
of representation, which is therefore reduced purely to a
matter of convenience. This is also the case for the quantum is a true unitary representation of G since we have
theory of the free electromagnetic field but von Neumann’s

U




fundamental result does not hold generally in a quantum U a b = Ub Ua = Ua+b (20)
field theory if there are interactions.(6)
= 1̂
The functions φ, ψ may be thought of as arising from an U 0 (21)
abstract vector |
defined by some other operator, most
)−1 = U
(U
(22)
a −a
importantly the Hamiltonian operator and the Schrödinger
equation For every fixed p 

|
= E|


H (13) i 
χp (a) ≡ exp ap ≡ a|p 
(23)
h̄
and we have the following relations:
is a character, and every character may be obtained in this

φ(x ) = x |
,  
ψ(p ) = p |

(14) way. The set of characters form a group, G̃, called the
character group, that is dual to G. A unitary representation
of G̃ is given by
Thus, the scalar product x  |
≡ φ(x  ) is the value of
the function φ at the point x  ; it is in general a complex  

= exp i s x̂
V (24)
number and is said to be the representative of the ket |
s
h̄
in the coordinate representation. We recognize φ(x  ) as a
Schrödinger wave function for the particle. The abstract
on the basic ket |x
; if we
Now consider the effect of U a
kets {|x
, |p
} satisfy the following formal completeness write
and orthonormality relations for eigenkets

|x

|X
= U (25)
a
 
x|x
= δx,x  , p|p
= δp,p (15)
then
 
|x
x| = 1̂, |p
p| = 1̂ (16)
)|x
+ U
x|x

x p
x̂|X
= (x̂ U a a
 
∂U

where equation (16) follows from equation (15) since both = i h̄ a |x
+ U
x|x

a
∂ p̂
sides give the same result if applied onto a basic ket |x 

or |p 
. Finally, consider the representative of the eigenket = (x − a)|X
≡ (x − a)|x − a
(26)
4 Quantum electrodynamics of atoms and molecules

where we have put, equally to the position and momentum operators, and their
eigenvalues, so that, for example, the spatial translations

|x
= |X
= |x − a

U (27) are described by the operator
a
 
since |X
has the position eigenvalue (x − a). The opera-
i

is interpreted physically as the operator describing Ua = exp a·p̂ (33)
tor U a h̄
spatial translations, and it provides the regular representa-
tion of G, which is a locally compact Abelian group. We Quantization can also be formulated in this group theo-
can therefore write down a family of projection operators retical context as the statement of the Weyl commutation
associated with this representation using the standard group relations
 
theoretical result that for each χ ∈ G̃(7)

i
U

Ua Vs = exp a·s V s a (34)
 h̄
P
χ = da χ(a)p U

a (28)
where

where the integration over the group parameters is simply a = {a1 , a2 , . . . , an }, s = {s1 , s2 , . . . , sn } (35)
over Lebesgue measure on [1]. This operator acts as
follows on a basic ket, equation (34) is completely equivalent to the canonical
 quantization rule (6), but has the advantage of specifying


Pχ |x
= da χ(a)p U
|x
algebraic properties in terms of bounded operators.
a
 The unitary operator
= da χ(a)p |x − a
 

iv p̂
 Uu,v = exp iux̂ −
h̄
= χ(x)p da χ(a)p |a
≡ χ(x)p |p
(29)
≡V
U
eiuv/2 (36)
h̄u −v
If we choose the character labelled by the momentum
eigenvalue p, we see that it projects out the component in terms of equations (19) and (24), is called a Weyl
labelled by the eigenvalue p. In Dirac’s notation, we have operator. Its action on a vector |φ
in the Hilbert space
P
χ = |p
p| of course. Let Hχ be the range of P
χ ; then leads to a generalized coherent state parameterized by the
the Hχ are mutually orthogonal invariant subspaces of H pair (u, v),
such that
|φ

|u, v
= U (37)
u,v

H= ⊕Hχ (30)
If the position space wave function x|φ
is a Gaussian, this
χ∈

G
definition coincides with Glauber’s original definition(9) of
Accordingly we may write a coherent state for a mode of the electromagnetic field (see
Section 5.2).
 
|x
= P
χ |x
= χ(x)p |p
(31) When we relax the condition n < ∞, we are confronted
χ with much more difficult mathematics, since we can no
χ∈G̃
longer rely on von Neumann’s theorem for an unique
which shows explicitly that |x
and |p
are related by solution (up to unitary equivalence) for the operators ‘x̂’
Fourier transformation.(7,8) and ‘p̂’ satisfying the Weyl or Heisenberg commutation
These results can be extended directly to the n-dimen- relations. Moreover, we have to make use of the so-called
sional case (n < ∞) by considering n-tuples as vectors in functional calculus, that is, calculus on function spaces.
n
. The additive group G and its isomorphic dual G̃ are The following summary of field quantization is therefore
now the additive group of n-tuples, so that, for example, heuristic and simply uses a formal analogy with the finite-
we simply have to make replacements like, dimensional theory just discussed.

ap  −−−→ a1 p1 + a2 p2 + · · · + an pn ≡ a·p (32)

3 QUANTIZATION FOR A FIELD
using ordinary vector notation; they too are locally compact
Abelian groups with a well-developed unitary represen- We introduce a real function space of square-integrable test
tation theory. This generalization of the notation applies functions (Schwartz space) with elements f, g, . . . that has
 Quantization of the electromagnetic field 5

a scalar product where the square brackets denote functional dependence.

 From this, by analogy with equation (7) we can realize the
(f, g) = d3 u f (u)g(u) < ∞ (38) commutation relations (43) and (44) in terms of functional
derivatives,
Next, we have canonically conjugate operator-valued dis-
= i h̄ ∂ ===⇒ X(u)

δ

and P

, which are used to describe the field, X = i h̄ (48)
tributions X ∂ P
δP (u)
∂ δ

= X(u),
X
P
= P
(u) (39) P
= −i h̄ ===⇒ P
(u) = −i h̄ (49)
∂X
δX(u)

], P
and the corresponding operators X[f
[f ] in the dual
The completeness and orthonormality relations (15) and
space (16) formally generalize to
  
X[f ] = d u X(u)f (u), P [f ] = d3 u P
(u)f (u)

3

X|X
= δX,X ≡ δ[X − X ] = δ[X(u) − X(u) ]
u
(40)

and P

to be Hermitian and define the unitary (50)
We take X
   
operators, |X
X| = 1̂, ===⇒ dX ≡ δX(u) (51)
    X X

[f ] = exp i

[f ] = exp i

U P [f ] , V X[f ] (41)
h̄ h̄ implying functional integration over all possible functions
X(u). Similarly,
The Weyl commutation relations 
  P |P 
= δP ,P  ≡ δ[P − P  ] = δ[P (u) − P (u) ]

[f ]V

[g] = exp i
[g]U

[f ] u
U (f, g) V (42)
h̄ (52)
   
are then formally equivalent to the Heisenberg commutation |P
P | = 1̂, ===⇒ dP ≡ δP (u) (53)
relations P P

P
[X,
] = i h̄1̂ (43) Finally, we can generalize equations (17) and (18) to yield
the representative X |P 
of the eigenket |P 
of the
using coordinates this is operator P
in the ‘field coordinate representation’ as
 


[X(u), P
(u )] = i h̄δ3 (u − u ) (44)   i  
X |P
= N exp (X , P ) (54)
h̄
Formally at least, X
and P

define representations through
where
their eigenvalue equations as in equations (11) and (12) for 
the spinless particle (X , P  ) ≡ d3 u X(u) P (u) (55)


= X |X
,
X|X P
|P 
= P  |P 
(45)
is the Schwartz space scalar product.
Just as in the finite-dimensional case, we recognize that
which lead to an infinite system of equations that hold at
the functions in the Schwartz space can form an Abelian
all points in the space u, for example,
and
group, G, under addition. The unitary operators U


V in equation (41) provide the regular representations of


X(u)|X(u)
= X(u)|X(u)
(46) the group G and its dual G̃, respectively, on the Hilbert
space of states for the field; these groups, however, are
the eigenvalues are functions X(u) that also belong to the not even locally compact since they describe ‘translations’
Schwartz space. The states in quantum field theory are on an infinite-dimensional function space. An immediate
thus quantities that depend on these functions, that is, wave illustration of this feature is the difficulty of normalization.
functionals; for example, in the representation in which the Formally we may write the ‘group volume’

is diagonal, we have
operator X

X|
= [X] (47) V (G) = dX (56)
6 Quantum electrodynamics of atoms and molecules

in terms of which N in equation (54) should be using an expansion in an infinite set of discrete mode func-
tions such as that described for the free electromagnetic
1 field in Chapter 38, this Volume, Section 2.
N=√ (57)
V (G)

as in the finite-dimensional case, but here V (G) is of course 4 THE FREE ELECTROMAGNETIC
infinite. As a practical method of calculation, the functional FIELD QUANTIZED
calculus requires the careful separation out of such infinite
normalization terms. It is convenient to start with the classical Hamiltonian and
For fixed P and given X, the representative, equa- Poisson-brackets for the free field in terms of the mode
tion (54), variables [X(k)λ , P (k)λ ] (Chapter 38, this Volume, equa-
X|P
≡ χP (X) (58) tions 41 and 42) and, in the spirit of canonical quantization
just described (Section 3), reinterpret them as operators act-
is a character of G. We write its unitary representation on ing on a Hilbert space; thus,
H as 
 
= 1

[X] = exp i P
[X] Hrad [P
(k)2λ + ω2 X(k)

2]
λ (65)
U (59) 2 k,λ
h̄

[X] acts on a basic ‘coordinate’ ket

as in equation (26), U where we sum over both polarization directions, λ = 1, 2
by ‘translation’ and all wave vectors k, and



[X]|X
= |X − X

U (60)
[X(k)λ , P (k )λ ] = i h̄δλ,λ δk,k (66)

and all other equal-time commutators vanish. The Hamil-

The group projection operator may then be written as
tonian equation (65) is an infinite sum of independent
 harmonic oscillators, and to begin with we consider just


PχP ≡ |P
P | = dX χP (X)U
[X] (61) one term,

using equations (58) and (59). In terms of explicit functions,
=

H 1
P
(k)2 + ω2 X(k)

2 , ω = kc (67)
k 2
this is
    with Schrödinger equation
i
P
χP = δX(u) exp d3 u[P
(u) − P (u)]X(u)
h̄
|
= E |

H (68)
k nk nk nk
(62)
In quantum electrodynamics, the roles of the field opera- The solution of equation (68) for the harmonic oscillator is

and P
tors X
can be taken by the vector potential â and its
well known and will simply be stated; the energies are
conjugate π̂, for which ‘translations’ such as equation (60)
are important properties; for example, a gauge transforma- E n k = nk + 1
2 h̄ω, nk = 0, 1, 2, . . . (69)
tion is a translation of the vector potential by a longitudinal
vector field (Chapter 37, this Volume, Section 3) and is

and the Hermitian ‘coordinate’ operator X(k) has matrix
of this type. Finally, the field ‘coordinate’ and ‘momen- elements
tum’ representations are related by a generalized Fourier
transformation (cf. equation 31)
h̄n
n |X(k)| n−1
= (70)
 2ω
|X
= χP  (X)|P 
(63)

n |X(k)| 
n
= 0 if n  = n ± 1 (71)
χ∈G̃
Since P
(k) = dX(k)/dt

for an oscillator, the matrix ele-
where



ments of P (k) differ from those of X(k) only by factors of

===⇒ dP  (64) ±iω. The classical field momentum is proportional to the
χ energy (Chapter 38, this Volume, equation 47) and so the
state labelled by the integer nk has momentum eigenvalue
implies functional integration. As a practical matter, func-
tional integrations are usually done in quantum field theory gk = nk + 1
2 h̄k (72)
 Quantization of the electromagnetic field 7

The energy and momentum for the field are then simply h̄ω and momentum h̄k where |k| = h̄/λ. The concept of
obtained by summing equations (69) and (72), respectively, the photon derives purely from the integer quantum num-
over all the modes. bers that appear in the quantization formulae (69) and (72)
These formulae present an obvious difficulty. The state for the modes; hence photons are indistinguishable particles
of the field of lowest energy and momentum is obtained and their numbers are unlimited. Every mode of the field
by putting all nk = 0; this state is called the vacuum state can be described in this way and a state of the quantized
of the electromagnetic field. In this state, each mode still field can be specified by giving the number of (indis-
contributes an energy (1/2)h̄kc and momentum (1/2)h̄k to tinguishable) photons associated with each mode. This is
the field; these are the zero-point energy and momentum exactly how a Bose–Einstein ensemble is specified in sta-
of the field. Since the number of radiation oscillators for a tistical mechanics, and so the photon is a boson particle [2].
given volume is infinite, this leads to an infinite energy Having obtained the quantized mode energies, we
and momentum for the vacuum state. This unpleasant can now revisit the problem of blackbody radiation
feature of field quantization is difficult to account for (Chapter 38, this Volume, Section 2). The particle
satisfactorily. Fortunately the absolute values of the field interpretation of black body radiation in a cavity is
energy and momentum are not of physical interest; in simply that it consists of a gas of photons in thermal
physical processes, we are only concerned with changes equilibrium with their surroundings. In thermal equilibrium
in the energy and momentum eigenvalues of the field. at temperature T , the probability that the mode with wave
Finite changes in the zero-point energy are caused by vector k is thermally excited to the state with nk photons
changes in the cavity volume and by polarizable material is given by the Boltzmann formula
bodies, as shown by, for example, the Casimir–Polder
effect(10,11) and long-range intermolecular forces.(12) When exp(−Enk /kB T )
p(nk ) =  (75)
the zero-point energy is not of interest, the difficulty can exp(−Enk /kB T )
be eliminated by the simple expedient of striking out the nk
infinite contributions and writing
  We substitute the quantized mode energy, equation (69), in
E= nk,λ h̄ω, g= nk,λ h̄k (73) equation (75) and writing
k,λ k,λ  
−h̄ω
It is customary, and very appealing, to introduce a new x = exp (76)
kB T
physical interpretation of these results. To begin with,
suppose there is only one mode with wave vector k and obtain
frequency ω in the field that has the energy equation (69)
identified by the integer nk . We prefer to give a ‘particle’ p(nk ) = (1 − x)x nk (77)
interpretation for equation (69) saying that the field consists
of nk quanta (particles); these quanta are called photons since the denominator of equation (75) is a simple geo-
and each has energy Eph = h̄ω. Increasing or decreasing nk metric series in x. The average energy of the mode at
changes the energy in the mode, and we say that photons temperature T is thus
have been created or annihilated, respectively. In addition, 
there is the zero-point energy (1/2)h̄ω present even when Ek = Enk p(nk ) (78)
nk
there are no photons. At the same time, according to
equation (72), we can reinterpret the wave vector k of the
and this is(13)
mode in terms of the momentum of the photon, pph =
h̄k. The photon’s energy and momentum behave under E k = nk h̄ω (79)
Lorentz transformations as the components of a 4-vector
kµ = (pph , iEph /c) with the property where the mean photon number is
2
Eph 1
kµ kµ ≡ h̄k·h̄k − =0 (74) nk = (80)
c2 exp(h̄ω/kB T ) − 1

This equation is characteristic of a particle with zero rest Thus, the mean energy density at temperature T of modes
mass that has speed c in all reference frames. Thus, the with frequencies in the interval ω to ω + dω is obtained
result of quantization is that a plane wave of light behaves from equation (48) of Chapter 38, this Volume by simply
as though it were a beam of nk particles each with energy replacing the classical value kB T by equation (78); this
8 Quantum electrodynamics of atoms and molecules

yields the Planck formula, which describes the spectral Experimentally, it is the intensity, I , of black body radiation
distribution in the cavity correctly leaving a small area of the surface of the cavity that is
   more directly accessible rather than the energy density in
h̄ω3 dω the cavity; the two are, however, closely related since
E(ω) dω = (81)
π2 c3 exp(h̄ω/kB T ) − 1
I = 14 cW = σT 4 (88)
It is now straightforward to characterize the fluctuations in
the black body radiation. Accepting the ergodic theorem where σ = cA/4 is the Stefan–Boltzmann constant ex-
we can think of the mean photon number (equation 80) as pressed in terms of fundamental constants.
either the long-time average of the number of photons in a The average energy of the mode k at temperature T ,
cavity mode with wave vector k or as an ensemble average. (equations 78 and 79) tends to the classical value given by
The thermal distribution equation (75) can be expressed in the equipartition theorem, kB T , for those modes satisfying
terms of n̄k using equations (76) and (77) as
h̄ω  kB T (89)
(nk )nk
p(nk ) = (82)
(nk + 1)nk +1 which makes
nk  1 (90)
The extent of the fluctuations in the photon numbers is
given by the dispersion σ of this distribution; this is easily
In this limit, the Planck distribution coincides with the
found to be
Rayleigh–Jeans law (Chapter 38, this Volume, equa-
σk = nk (nk + 1) (83) tion 76). This is an example of the heuristic rule that
the ‘classical limit’ corresponds to quantum numbers  1.
√
hence the fluctuation nk = σk is always greater than the Another form of the condition for the field to be quasi-
average photon number, n̄k .(13,14) As regards fluctuations of classical can be obtained as follows. As noted earlier
the energy in the cavity, thermodynamics gives a general (Section 1), in practice we can measure values of the field
relation between the dispersion in E(ω) and the temperature averaged over some time interval t, which must be less
derivative of its average value,(15) than the time over which the field varies appreciably. Only
frequencies such that ωt ≤ 1 will contribute to the aver-
dE(ω) age value of E (or B) so we only need consider modes
E(ω)2 = kB T 2 (84) with frequencies less than ωmax = 1/t. The total energy
dT
density, which is proportional to |E |2 , may be written as
With the aid of equation (81), this gives
 ωmax  ωmax
 2 nh̄ω4max
W = dωρω nωh̄ω ∼ n dω ρωh̄ω =
E(ω) 0 0 π2 c3
E(ω)2 = h̄ωE(ω) + (85) (91)
ρω dω Then in order of magnitude

The first term, which disappears in the classical limit, √

h̄c
can be associated with the photons; the second appears in n  1 requires |E |  (92)
(ct)2
Maxwell’s theory, and the occurrence of both types of term
in the quantum theory result, equation 85, reminds us of the Thus, for classical behaviour of the time-averaged field,
limitations of the classical particle and wave concepts.(1) |E | must reach a minimum value, which increases as
The average total energy density in the cavity, W , is t decreases. A time-varying field, if sufficiently weak,
obtained by summing up the contributions from all the can never be classical; on the other hand, a static elec-
modes; this is an integral over the Planck distribution tromagnetic field is always classical since we can take
(equation 81) for all positive frequencies, t → ∞.(16)
 ∞
W = E(ω) dω = AT 4 (86) 5 REPRESENTATION OF STATES OF
0
THE FIELD
where
π2 kB4 So far nothing has been said about the representation of the
A= (87) field eigenstates |n
; let us initially choose a ‘coordinate’
15h̄3 c3
 Quantization of the electromagnetic field 9

representation in which X(k) is diagonal. The Schrödinger More generally, ĉk and ĉk+ act as ladder operators for the
equation (68) for the mode may then be realized as an oscillator, stepping down and up the mode index, or photon
ordinary differential equation, number, n; they are called, respectively, the annihilation
  and creation operators for the mode k.
d2 Using equations (66), (67), (95), and (96), we easily find
−h̄2 + ω X(k) n (X) = En n (X)
2 2
(93)
dX(k)2  
1
− 1 h̄ω
ĉk+ ĉk = H k (101)
and solved using the standard harmonic oscillator theory. h̄ω 2
The ground state, for example, is  
+ 1
1
  ĉk ĉk = Hk + h̄ω (102)
−ωX(k)2 h̄ω 2
0 (X) = N exp (94)
2h̄ from which we infer
There is such a wave function for every k and so the
= ĉ+ ĉ + 1
Hk k k 2 h̄ω (103)
vacuum state of the field is an infinite product of Gaussians
(equation 94); this can be rewritten as an exponential with
and
an infinite sum in its exponent. In the continuum limit,
the sum becomes an integral over a continuous variable k [ĉk , ĉk+ ] = 1̂ (104)
and so the vacuum state |0
in this representation is a
functional 0 [X] of the field X(k) [3]. The matrix elements of the annihilation and creation oper-

is repre-
Although the oscillator coordinate operator X(k) ators are simply,
sented by the Hermitian matrix equation (70) and is there- √
fore formally an ‘observable’, it is of no direct physical n−1 |ĉk |n
= n |ĉk+ |n−1
= n (105)
interest. It is much more rewarding for the development of
the quantum theory to make a linear transformation from They form a pair of adjoint operators and are not observ-


the mode operators X(k), P
(k) to new variables by setting ables. The bilinear combination occurring in equation (103)
(cf. Chapter 37, this Volume, equation 172),
n̂k = ĉk+ ĉk (106)
1

ĉk = √ [ωX(k) + i P
(k)] (95)
2h̄ω is usually called the photon number operator; it is Hermi-
1 tian and its eigenvalues are the integers in equation (69).
ĉk+ = √

[ωX(k) − i P
(k)] (96) This representation is so important in field theory that we
2h̄ω
next describe its formal details.
or inversely,

h̄ 5.1 The Fock space construction

X(k) = (ĉ + ĉk+ ) (97)
2ω k
According to general quantum-mechanical principles, a
h̄ω
P
(k) = −i (ĉ − ĉk+ ) (98) particle is fully described by the specification of a complete
2 k set of commuting observables. For the photon, this is very
simple for we can specify just the momentum, h̄k, and
Consider now the action of ĉk and ĉk+ on the vacuum state
polarization state, λ [4]. Let a state of definite momentum
(equation 94); we have
and polarization be denoted as
 
1 d
ĉk 0 (X) = √ ωX(k) + h̄ 0 (X) = 0 |wi
= |k, λ
(107)
2h̄ω dX(k)
(99)
To describe the state of the quantized field, we only need to
whereas
specify the number of photons, ni , in each state |wi
since
 
+ 1 d photons are non-interacting and indistinguishable particles.
ĉk 0 (X) = √ ωX(k) − h̄ 0 (X)
2h̄ω dX(k) The photon is a boson particle, so the ni are unrestricted
 integers (0, 1, 2, . . .). The Fock space construction formal-
2ω izes this physical picture in terms of operators acting on a
= X(k)0 (X) ≡ 1 (X) (100)
h̄ Hilbert space.
10 Quantum electrodynamics of atoms and molecules

We introduce a set of basis vectors |n1 , n2 , . . .
that are
normalized and orthogonal
n1 , n2 , . . . |n1 , n2 , . . .
= δn ,n1 δn ,n2 · · ·
1 2
Then, given the operators defined by equations (111)
and (112), all other states of the system can be constructed
by repeated action of the creation operator on the vacuum
(108) state,

1
The space generated by this set of vectors is a separable |n1 , n2 , . . . , ni , . . .
=  (ĉ1+ )n1 · · ·
Hilbert space provided only that n1 !
 1
ni < ∞ (109) ×  (ĉi+ )ni · · · |0
(118)
ni !
i

We can define self-adjoint number operators n̂i that are This can be checked by applying the number operator n̂i
diagonal in the basis, equation (108), to both sides of equation (118); use of the commutation
relation
n̂i |n1 , n2 , . . . , ni , . . .
= ni |n1 , n2 , . . . , ni , . . .
(110)
[n̂i , ĉi+ ] = ĉi+ (119)
They form a complete set of commuting operators since a
shows that the vector, equation (118), satisfies equa-
basis vector is fully characterized by giving the eigenvalues
tion (110). An extremely useful concept in calculations
of the number operators. We can also define annihilation
and creation operators as linear operators that reduce by using the Fock basis is that of the normal ordered product.
one and increase by one the number of photons in a given Every observable for the oscillator is a (operator-valued)
function of X
and P
, and hence will be a function of
state
sums of products of the annihilation and creation operators.
√ Normal ordering is the process based on the use of the com-
ĉi |n1 , n2 , . . . , ni , . . .
= ni |n1 , n2 , . . . , ni − 1, . . .

mutation relation (113) whereby all the creation operators
ni > 0 are brought to stand to the left of all the annihilation opera-
= 0 for ni = 0 (111) tors. When this has been achieved, the evaluation of matrix
 elements is straightforward using equations (111) and (112)
ĉi+ |n1 , n2 , . . . , ni , . . .
= ni + 1 and the orthogonality of the basis.
× |n1 , n2 , . . . , ni + 1, . . .
A photon in the state |wi
has well-defined energy h̄ωi ,
and so the field Hamiltonian must be
(112)
ĉi+ is the adjoint of ĉi . They have the following canonical 

=
H n̂i h̄ωi (120)
commutation relations (CCR) rad
i

[ĉi , ĉj+ ] = δij (113)

The equation of motion of the annihilation operator is then
[ĉi , ĉj ] = [ĉi+ , ĉj+ ] =0 (114) (cf. equation 9)

The number operator n̂i can be expressed in terms of the dĉi
] = h̄ω ĉ
i h̄ = [ĉi , Hrad i i (121)
annihilation and creation operators dt

n̂i = ĉi+ ĉi , n̂i + 1̂ = ĉi ĉi+ (115) with solution

ĉ(t)i = e−iωi t ĉ(0)i (122)

since according to equations (111) and (112)
This description is extremely convenient for physical pro-
ĉi+ ĉi |n1 , n2 , . . . , ni , . . .
= ni |n1 , n2 , . . . , ni , . . .
(116)
cesses in which the number of particles is not conserved;
for example, if a particle is created in some process,
in agreement with equation (110).
it is only necessary to give the quantum numbers of
The Fock representation can be characterized by postu-
the added particle, leaving the description of the original
lating the existence of a unique vacuum state |0
, which
particles unchanged. The basis consisting of the vectors
is such that
|n1 , n2 , . . . , ni , . . .
is called the Fock basis or the occupa-
ĉi |0
= 0, all i (117) tion number basis; it can be pictured as an inverted pyramid
 Quantization of the electromagnetic field 11

above the vacuum state |0
(13,14) Then the coherent state X|λ
can be parameterized by u
and v and written as
1 1
√ (ĉ1+ )3 |0
, √ (ĉ1+ )2 ĉ2+ |0
, . . .  1/4  
3! 2! ω ω
X|u, v
= exp − (X − u) + ivX (130)
2

1 πh̄ 2h̄
√ (ĉ1 )2 |0
, ĉ1+ ĉ2+ |0
, . . . (123)
2! The coordinate representative of the vacuum state for the
ĉ1+ |0
, ĉ2+ |0
, . . . oscillator in this notation is X|0, 0
, so that the coherent
state |u, v
can be written as a unitary transform of the
|0
vacuum state

|

|u, v
= U (131)
u,v 0
5.2 Coherent states
where the Weyl operator
In this section, we initially confine attention to a single  

− iuP
iv X

mode of the field with definite polarization; then we may

U = exp (132)
u,v
drop the labels k and λ. We now wish to investigate further h̄
the properties of the adjoint pair of operators ĉ and ĉ+ for
an oscillator of frequency ω. The coherent states of the is closely related to the Weyl commutation relation and
oscillator are the eigenstates of the annihilation operator ĉ, the translation operators [6], as discussed in Section 2.2. In
terms of the annihilation and creation operators, we have
ĉ|λ
= λ|λ
(124)

→U
U
≡ exp λĉ+ − λ∗ ĉ (133)
u,v λ
since ĉ is not self-adjoint, the eigenvalues λ will in general
be complex numbers. In the coordinate (X) representation with which we easily derive
for the oscillator, we have, using equation (93)

−1 ĉU
U
= ĉ + λ
λ λ
 
i ω

−1 ĉ+ U

= ĉ+ + λ∗
√ P
+ X |λ
= λ|λ
(125) U λ λ (134)
2h̄ω 2h̄

is therefore commonly known as the coherent-state
U λ
so that the representative X|λ
satisfies a first-order displacement operator. We also recopy equation (131) as
differential equation
 
|

|λ
= U (135)
λ 0
h̄ d ω
+ X X|λ
= λX|λ
(126)
2ω dX 2h̄ The relationship of the coherent states to the number
states {|n
} can be established in the following way. The
with normalized solution Baker–Campbell–Hausdorff formula

 1/4  2
ω ω e

A+

B
= e

A

eB e−[

A,

B ]/2
(136)
X|λ
= exp  − X − λR
πh̄ 2h̄

and B
is an operator identity provided A
both commute
 
B].

In view of equation (113), this identity can be
with [A,
2ω
+i λ X (127) applied to the displacement operator to yield
h̄ I

= eλĉ+ eλ∗ ĉ e−|λ|2 /2
U (137)
λ
where we have separated λ into real (λR ) and imaginary
(λI ) parts [5]. Now
Since λ|P
|λ
and λ|X|λ


are both real, we can put ∗
eλ ĉ |0
= |0
(138)
ω
ω
λR = λ|X|λ
≡ u (128) from the defining property of the vacuum state equa-
2h̄ 2h̄
tion (117), and so we can rewrite equation (135) as
1 h̄
λI = √ λ|P
|λ
≡ v (129) /2 λĉ+
|λ
= e−|λ|
2
2h̄ω 2ω e |0
(139)
12 Quantum electrodynamics of atoms and molecules

The exponential operator is defined as This can be checked by inserting the lhs of equation (146)
into the orthonormality condition for the number states,
A
n that is,
e

A
= (140)
n
n! n|1̂|n
= δnn (148)

and therefore the coherent state |λ
can be expressed as a and using equation (141) to verify its validity. In terms
superposition in the Fock space basis of the position and momentum parameters (u, v), the
equivalent condition reads
 λn (ĉ+ )n 
|λ
= e−|λ|
2
/2
√ · √ |0

n n! n! dµ(u, v)|u, v
u, v| = 1̂ (149)
 λn
≡ e−|λ|
2
/2
√ |n
(141) where
n n!
1
dµ(u, v) = du dv, −∞ ≤ u, v ≤ ∞ (150)
Using equation (141) we calculate for a single mode 2π
On the other hand, it is evident from their relationship to the

|λ
= |λ|2 ,
N = λ|N
2 |λ
= |λ|4 − |λ|2
N 2 = λ|N number states (equation 141) that they form an overcom-
(142) plete set of states; their non-orthogonality equation (144) is
giving a dispersion one manifestation of this.

N 2 − (N )2 = |λ|2 ≡ N (143)
5.3 The number and phase representation
the mean particle number. The expansion (141) can be used
A classical electromagnetic field is conveniently described
to characterize the formal properties of the coherent states
in terms of its amplitude and phase; it is of interest
since we know that the number states are eigenstates of
therefore to establish the limitations imposed on such
a self-adjoint operator, and are therefore a complete set
a description by the quantum theory. In Chapter 37,
of orthonormal states. From their definition, the coherent-
this Volume, Section 6, we noted that there exists a
states are normalized; however, they are not orthogonal
classical transformation that reduces the Hamiltonian for
because, using equation (141) we have
an oscillator to cyclic form (Chapter 37, this Volume,
 (λ∗ λ )n equation 177); this involves a canonical transformation
/2−|λ |2 /2
λ|λ
= e−|λ|
2
from position (x) and momentum (p) variables to action-
n
n! angle variables (J , θ). In quantum theory, the analogous
−|λ|2 /2−|λ |2 /2+λ∗ λ transformation is to the number operator, n̂, and a conjugate
=e
 2
phase angle variable θ̂; however, the transformation is not
+i Imλ∗ λ
= e−|λ−λ | (144) unitary since x̂ and p̂ have continuous spectra (Section 2),
whereas n̂ has a discrete spectrum consisting of 0 and the
The coherent states have the valuable property that a positive integers, and θ̂ is not Hermitian. As in the classical
general matrix element of a normally ordered product, N , case, the transformation is conveniently performed via the
of annihilation and creation operators can be evaluated annihilation and creation operators. We set
immediately  1
ĉ = n̂ + 1 ei θ̂ ===⇒ ei θ̂ = √ ĉ (151)
+ 
λ|N (ĉ , ĉ)|λ
= N (λ , λ )λ|λ
∗  
(145) n̂ + 1
which has the adjoint equation,
The completeness condition for the coherent states reads
+
 + 1
 ĉ+ = e−i θ̂ n̂ + 1 ===⇒ e−i θ̂ = ĉ+ √ (152)
dµ(λ)|λ
λ| = 1̂ (146) n̂ + 1
The ordering of the factors is important here since n̂ and θ
where the measure is do not commute,

1 + 1 +
dµ(λ) = dλ dλ , −∞ ≤ λR , λI ≤ ∞ (147) [n̂, e−i θ̂ ] = [n̂, ĉ+ ] √ = e−i θ̂ (153)
π R I n̂ + 1
 Quantization of the electromagnetic field 13

using equation (119), whereas These operators are used for the description of the phase
properties of the quantized electromagnetic field.(13) In a
1 Fock state |n
, the uncertainty in the photon number is
[n̂, ei θ̂ ] = √ [n̂, ĉ] = −ei θ̂ (154)
n̂ + 1 clearly zero,

The exponential phase operator is not unitary since although n = 0 (163)

+ and the corresponding uncertainties in sin(θ̂) and cos(θ̂) can

ei θ̂ e−i θ̂ = 1̂ (155) then be shown to be given by

the product of operators in reverse order yields  sin(θ̂) =  cos(θ̂) = √1 (164)

2

+ 1
e−i θ̂ ei θ̂ = ĉ+ ĉ (156) corresponding to a phase angle θ that is equally likely to
n̂ + 1 have any value in [0, 2π].
The spectrum of the number operator has the symmetry
The matrix elements of equation (156) in the Fock basis
of an infinite cyclic group, the additive group of the
 integers; the character group of the integers is isomorphic
+ δnm , m = n
n|e−i θ̂ ei θ̂ |m
= (157) to the group of rotations in the plane, and every character
0, m=0
is of the form
show that we may rewrite it as
χ(θ)n = einθ , n = integer, 0 ≤ θ ≤ 2π (165)
e−i θ̂ ei θ̂ = 1̂ − P
0
+
(158)
We choose a phase angle representation in which θ̂ is
diagonal, and then for every θ the operator
where P
0 is the projector onto the vacuum state. We see
therefore that formally n̂h̄ and θ̂ are conjugate operators
= ei n̂θ
U (166)
θ
satisfying a CCR
[n̂h̄, θ̂] = i h̄ (159) is a true unitary representation of the cyclic group; with it
we may form the projection operator on the number states
but this is not realized as a unitary representation since θ̂ (cf. Section 2.2),
is not Hermitian  2π
1
+ P
n =

dθ χ(θ)n U θ (167)
θ̂ = θ̂ (160) 2π 0

Equation (159) does not yield the usual uncertainty If the exponential operator (166) is represented using equa-
relation for conjugate variables since the angle θ lies tion (140), it may be brought to normal ordered form,
in [0, 2π]. Nevertheless, these relations imply that we  1
ei

Nθ k
cannot have states of the oscillator for which both the = eiθ − 1 (ĉ+ )k (ĉ)k (168)
k!
number of quanta and the phase have sharp values. A k=0
useful uncertainty relation can be formulated in terms of
the sum and difference combinations of the exponential and performing the θ integration yields the projection
phase operators that are usually, and loosely, called sin operator as
and cos,
1  (−1)k + n+k n+k
  P
n = (ĉ ) (ĉ) (169)
+ n! k=0 k!
cos(θ̂) = 12 ei θ̂ + e−i θ̂
 +

sin(θ̂) = 2i1 ei θ̂ − e−i θ̂ (161)
5.4 Coherence of the electromagnetic field
and are obviously Hermitian with matrix elements,
The coherence properties of the electromagnetic field are
n| cos(θ̂)|n − 1
= n − 1| cos(θ̂)|n
= 1 described in terms of the properties of the mean values
2
of polynomials of the field strength operators, in direct
n| sin(θ̂)|n − 1
= −n − 1| sin(θ̂)|n
= − 2i1 (162) analogy with classical electromagnetism. These operators
14 Quantum electrodynamics of atoms and molecules

will involve products of the annihilation and creation Since all the modes are independent, and the coherent states
operators (ĉi , ĉj+ ) for the modes of the field that can have the property (145), it is evident that
be brought to normal ordered form. Thus, the study of
coherence from the theoretical point of view requires |αi |2ni
p(ni ) = e−|αi |
2
(176)
evaluation of the correlation functions of the annihilation ni !
and creation operators,
which is a Poisson distribution about a mean |αi |2 and p{n}
ĉi+1 · · · ĉi+n ĉin+1 · · · ĉin+m
has the product form (174). However, from equation (143)
this is
= G(n,m) (i1 , . . . , in , in+1 , . . . , in+m ) (170)
(Ni )ni
p(ni ) = e−Ni (177)
ˆ according to equation (2). The state of ni !
and 

= Tr(ρ̂
)
the electromagnetic field described by the density operator and the dispersion of the distribution obtained from the
ρ̂ is said to be fully coherent if there exists a sequence of coherent state is just the mean photon number
complex numbers {zi : z1 , z2 , . . .} such that for every value
of n and for every set of indices i1 , . . . , in , in+1 , . . . , i2n σ 2 = Ni (178)
we have
States of the field that are not fully coherent have greater

n 
2n
dispersions than the Poisson distribution; examples of
G(n,n) (i1 , . . . , in , in+1 , . . . , i2n ) = zi∗k zim (171)
incoherent radiation include black body radiation for which
k=1 m=n+1
the dispersion is given by equation (83) and a pure Fock
If the correlation functions (170) possess this property only state with definite occupation numbers.
for n ≤ M, we say that the state of the field has only Mth Quantum theory accounts for classical interference exper-
order coherence.(14) iments in which two light beams are combined to produce
Some of the higher-order correlation functions are acces- interference fringes through the superposition of photon
sible through photon-counting experiments. Let p{n} be the probability amplitudes. The fringe visibility, v, is defined
probability that the state ρ̂ has n1 photons in mode 1; n2 in terms of the intensity variation
photons in mode 2; . . ., and ni photons in mode i [7]. This Imax − Imin
is simply the mean value of the projection operator that v= (179)
Imax + Imin
projects onto the Fock space vector with the occupation
numbers n1 , n2 , . . . , ni , . . . Equation (167) can be general- For simplicity, we restrict ourselves to just two modes of the
ized to give field; their quantum properties are described by annihilation
and creation operators ĉi , ĉi+ , i = 1, 2. The Fock basis will
 1  (−1)k
P
{n} = (ĉi+ )ni +k (ĉi )ni +k (172) then be vectors |n1
|n2
specifying the number of photons
i=1
n i ! k=0
k! in each mode. We have in mind a monochromatic beam of
light falling on two pinholes, as in Young’s experiment, or
According to the definition (169), a fully coherent state has two plane waves with wave vectors k1 and k2 (k1 = k2 ) that
 intersect at an angle θ for which interference fringes may
p{n} = p(ni ) (173) be observed along the direction r perpendicular to k1 . The
i=1 quantum theory of photodetection shows that the intensity
in each mode separately, that is, when no superposition
where is allowed, is determined by the traces of their respective
  number operators
p{n} = Tr ρ̂P
{n} (174)

),
I1 ∝ Tr(ρ̂N
)
I2 ∝ Tr(ρ̂N (180)
1 2
These considerations provide the justification for the name
coherent state introduced in Section 5.2. Suppose that the and v is proportional to the first-order correlation function
field is described by a coherent-state vector ({αi }) labelled
by the eigenvalues {αi } of all annihilation operators {ĉi }; v ∝ Tr(ρ̂ĉ1+ ĉ2 ) (181)
then the density operator is
It is clear that for v = 0 we require ρ̂ to contain
ρ̂ = |({αi })
({αi })| (175) contributions from modes differing by one photon. For
 Quantization of the electromagnetic field 15

simplicity, let the detected field be in a pure state strengths, can be quantized in exactly the same way as the
with state vector |ψ
so that the density operator is a energy and momentum. It is convenient to use the annihila-
projector

tion and creation operators just introduced in place of X(k)


and P (k). For general mode and polarization indices, their
ρ̂ = |ψ
ψ| (182)
commutation relation is
One way in which a non-zero v can be obtained is if
+
|ψ
is a superposition of one-photon states from the two [ĉk,λ , ĉq,λ ] = δλ,λ δk,q (185)
modes,
For the Coulomb gauge vector potential A(x), (Chapter 38,
|ψ
= a1 |1
|0
+ a2 |0
|1
(183)
this Volume, equation 44), and its conjugate π(x),
This result shows that the interference pattern can be built (Chapter 38, this Volume, equation 45), there results
up from a sequence of one-photon experiments, for exam- 
ple, by using a light source of such weak intensity that
h̄  ε̂(k)λ
A(x) = √
on average only one photon at a time is in the appara- 2ε0 V c k,λ k
tus. Clearly, if we take |ψ
= |n1
|n2
corresponding to
+
two independent beams in Fock states there is no corre- × ĉk,λ eik·x + ĉk,λ e−ik·x (186)
lation (v = 0). On the other hand, a simple product of
ε0 h̄c  √
two coherent states |ψ
= |α1
|α2
can give interference π̂(x) = −i k ε̂(k)λ
fringes provided the relative phase of the two beams is 2V k,λ
sufficiently slowly varying for the fringes to be observed. +
× ĉk,λ eik·x − ĉk,λ e−ik·x (187)
This is because the number of photons in a coherent
state is indefinite with a Poisson distribution (cf. equa-
tion 141). Such a state can be realized with two single-mode and so the field strengths have the following operator
lasers.(13,17) expansions,
The field measured at the detector belongs to the 
whole apparatus including the sources and the detec-
(x) = i h̄c  √
E k ε̂(k)λ
tor, such that it is not possible for a photon to con- 2ε0 V k,λ
tribute to the interference effect and be assigned to one
+
or other source. The uncertainty relation (4) is relevant × ĉk,λ eik·x − ĉk,λ e−ik·x (188)
here; if the photon can be detected with an uncertainty 
in position x, it has an uncertainty in momentum k
h̄  k ∧ ε̂(k)λ
B (x) = i √
such that 2ε0 V c k,λ k
xk ∼ h̄ (184) +
× ĉk,λ eik·x − ĉk,λ e−ik·x (189)

An analysis of the experiment then shows that if the

The coefficient of the annihilation operator in the expansion
resolution in position is better than one fringe width so
of the vector potential, (equation 186)
that fringes can be observed, the uncertainty in momen-
tum is such that it is no longer possible to assign 
the photon to a particular source. Conversely, if the h̄
Ak,λ = ε̂(k)λ eik·x (190)
momentum is known sufficiently accurately to determine 2ε0 V ω
which beam the photon is associated with, the uncer-
tainty in x is great enough to wash out the fringe can be interpreted as a wave function for the photon
pattern. in momentum representation. The vector wave functions
Ak,λ are orthogonal if integrated over the quantization
volume,
6 PROPERTIES OF THE FIELD

OPERATORS h̄
d3 x A∗k,λ ·Ak ,λ = δ δ  (191)
V 20 ω k,k λ,λ
Other classical variables for the free field that were
discussed in Chapter 38, this Volume using the mode This normalization can be given a physical interpretation by
expansion, for example, the vector potential and the field defining analogous quantities for the electric field strength
16 Quantum electrodynamics of atoms and molecules

and the magnetic induction, where we have explicitly included the time dependence
resulting from equation (122) and set
Ek,λ = iωAk,λ , Bk,λ = ik ∧ Ak,λ (192)
αk = |αk | eiθk (200)
in terms of which equations (188) and (189) become
 Similarly,

(x) =
E ∗
Ek,λ ĉk,λ + Ek,λ +
ĉk,λ (193)
k,λ

2 |α
= h̄kc {4|α |2 sin2 (k·x − ωt + θ ) + 1}
αk |E

(x) =
B Bk,λ ĉk,λ + ∗
Bk,λ +
ĉk,λ (194) k
20 V k k

k,λ (201)
In the limit |αk | → ∞, equation (197) becomes a stable
Inserting these expansions in the classical energy expression classical wave with a well-defined phase angle θk , and
(Chapter 38, this Volume, equation 10) yields the quan- electric field amplitude
tized Hamiltonian as,

 2h̄kc

= 1
H ĉ ĉ+ + ĉk,λ
+
ĉk,λ E0 = |α | (202)
rad
2 0 k,λ k,λ k,λ 0 V k

× d3 x |Ek,λ |2 + c2 |Bk,λ |2 (195) This rests on the fact that the uncertainty in the phase angle
V for the coherent state varies as |α|−1 for large |α|. If we
choose θk = −π/2, then
Using the explicit forms (190) and (192) the integration
yields

|α
= E cos(k·x − ωt)
αk |E (203)
k 0
0 d3 x |Ek,λ |2 + c2 |Bk,λ |2 = h̄ω (196)
V
is a solution of the classical Maxwell equations for the
The integral on the lhs is the mean value of the energy in the free field. There are of course off-diagonal matrix elements
state having the wave function Ak,λ and this is equal to the of E
; these are proportional to the overlap integrals of
energy of one photon in the mode k, λ; the normalization the coherent states involved, which from equation (142)
can be interpreted as ‘one photon per unit volume’.(16) behave as
The matrix elements of the field operators for the Fock
and coherent-state representations are easily established |αk |βk
|2 = exp(−|αk − βk |2 ) (204)
using the properties of the annihilation and creation opera-
tors. We give the results for just the electric field strength and so only become negligible for |αk − βk | → ∞. Finally

. For a single mode, k, with exactly n photons,
operator, E k it is easy to see that in the vacuum state |0

we find

|
= 0,
0 |E
2 |
= ∞
0 |E (205)

|n
= 0
nk |E 0 0
k
 

2 |n
= h̄kc 1 – a result that sharply circumscribes any proposed physical
nk |E nk + (197)
k
ε0 V 2 interpretation of the field operators.
We have emphasized the photon picture of the quan-
with no time dependence. Thus, the amplitude of the field is tized electromagnetic field because it provides a powerful
   basis for calculations. By using the mode expansion, the
2h̄kc 1 functional calculus can be kept in the background of the
E0 = nk + (198)
ε0 V 2 calculations. It is, however, only a representation, and there
are others that emphasize the ‘wave’ aspects of radiation,
while the phase is completely uncertain. For a single-mode for example, one can use the fields themselves as ‘coordi-
coherent state |αk
, we obtain (ignoring the polarization nates’. We conclude this section with a brief introduction
state) to how this may be done. In Section 1, we saw that a con-
 sistent quantum theory of charges and radiation requires

|α
= − 2h̄kc that the field strengths be replaced by operators that satisfy
αk |E |α | sin(k·x − ωt + θk ) (199)
k
0 V k equation (5). Using equations (185), (188), and (189) we
 Quantization of the electromagnetic field 17

compute their commutator directly, The commutation relation (210) with equation (213)
implies that the field operators themselves can be


 h̄  represented using functional differentiation, and in this
[E(x)i , B(x )j ] = ˆ (k)λi (k ∧ ˆ (k)λ )j
20 V k,λ representation the magnetic induction operator is
× (eik·x − e−ik·x ) (206) δ

(x) = − i h̄ ∈ ∇
B (215)
i
0 ij k k δE (x)j
The sum over the polarization vectors can be performed
with the relation(13,18)
Now consider the Hamiltonian for the free field,
 ki kj
ˆ (k)λi ˆ (k)λj = δij − (207) 
λ
k2
= 1
H d3 x E
+ c2 B

·E
·B

(216)
rad
2 0
Now
where both fields are transverse,
(k ∧ ˆ (k)λ )j = ∈j mn km ˆ (k)λn (208)

= ∇·B
∇·E
=0 (217)
where ∈j mn is the Levi–Civita antisymmetric tensor [8],
and so using equation (207)
Once again, we can factorize the Hamiltonian into what are

ˆ (k)λi (k ∧ ˆ (k)λ )j = ∈j mi km (209) effectively annihilation and creation operators; the obvious
λ factorization of x 2 + y 2 = (x + iy)(x − iy) used earlier is
not useful here because we have to accommodate the Curl
since k ∧ k = 0. The factor of k may be removed from the operator in the representation (215).
sum by replacing it with −i∂/∂x, so that the exponentials Instead, we write the Hamiltonian as,(19)
can be combined, and the commutator reduces to

i h̄ ∂ 1  ik·x−x
= 1
H d3 x ˆ + ·ˆ (218)


 rad
2 0
[E(x)i , B(x )j ] = ∈ij m e (210)
0 ∂xm V k
where
With periodic boundary conditions for the volume V ,
we have 
(y)
ˆ
(x) + i ∇ ∧ E
1  ik·x−x (x) = cB d3 y (219)
e = δx,x (211) 2π2 |x − y|2
V k
This odd-looking formula is easily understood if we intro-
In the continuum limit the Fourier series for the field duce Fourier transforms; a straightforward calculation using
variables (equations 186 to 189) must be written as integrals the expansions of the fields (equations 188 and 189) yields
with the replacement 
 ˆ
(k) = ˆ
d3 x (x)e −ik·x
1  1
√ −−−→  d3 k (212) 
V k (2π)3
h̄c(2π)3 
=i k̂ ∧ ˆ (k)λ ĉ(k)λ (220)
and equation (211) becomes 20 k λ

1  ik·x−x 1 
e −−−→ d3 k eik·x−x = δ3 (x − x ) where ĉ(k)λ is the annihilation operator for the mode with
V k (2π)3 wave vector k and polarization λ, with k now treated as
(213) a continuous variable. In momentum space, the Fourier
All other commutators of the field strength operators vanish; transforms of the Curl operation (∇∧) and of 1/|x|2 are
this result is consistent with equation (5).(1,3) just what are required to equalize the coefficients of ĉ(k)λ
Suppose we choose a representation in which the electric in the expansions of E(x) and B(x) (see equation 192).
field strength operator is diagonal, so that its eigenvalues The vacuum state of the field is then the vector that is
are ordinary (classical) electric fields, ˆ
annihilated by ,

(x)|E
= E (x)|E

E (214) ˆ
(x)| 0
= 0 (221)
18 Quantum electrodynamics of atoms and molecules

In the {|E
} representation this is for EJ -photons commute with those for MJ photons. The
   angular momentum representation is particularly convenient
i h̄c δ i E (y) for describing multipole radiation.(3,16,20)
− ∈ ∇ − ∈ ∇ 3
d y
0 ij k k δE (x)j 2π2 ij k k |x − y|2 The polarization properties of the classical electromag-
netic field are completely described by the Stokes parame-
× [E ]0 = 0 (222) ters discussed in Chapter 38, this Volume, Section 3; they
were expressed in terms of the oscillator variables for a
with solution,
single mode k. After quantization of the field, we have to
    regard the Stokes parameters {Si } as the expectation values
0 E (x)·E (y)
[E ]0 = N exp − 3
d x 3
d y of corresponding Stokes operators,
4π2 h̄c |x − y|2
(223) ˆ i)
Si = Tr(ρ̂ (225)
Power(12) has shown how this form of the vacuum state can
be used in a perturbation theory description of intermolec- where ρ̂ is the density matrix for the light beam. Using
ular forces that arise as finite shifts in the zero-point energy equations (97) and (98) of this chapter we can write down
of the field, without recourse to (virtual) photons. directly the Stokes operators for the mode in terms of
annihilation and creation operators for the two orthogonal
polarization states, λ = 1, 2; thus (cf. Chapter 38, this
7 ANGULAR MOMENTUM AND Volume, equations 51 to 53),
POLARIZATION
ˆ
(k) + +
1 = h̄(ĉ(k)1 ĉ(k)1 − ĉ(k)2 ĉ(k)2 )
In Chapter 38, this Volume, we derived expansions of the
≡ h̄(n̂(k)1 − n̂(k)2 ) (226)
vector potential A(x) in terms of a complete orthogonal set
of transverse vector functions with definite angular momen- ˆ
(k) + +
2 = h̄(ĉ(k)1 ĉ(k)2 + ĉ(k)2 ĉ(k)1 ) (227)
tum (J M) and definite parity (Chapter 38, this Volume,
ˆ
(k) + +
3 = −i h̄(ĉ(k)1 ĉ(k)2 − ĉ(k)2 ĉ(k)1 ) (228)
equations 120 and 121). These functions are composed of
vector spherical harmonics and appropriately chosen radial
The only non-zero commutator of the mode operators is
functions; they can be regarded as wave functions for the
photon in the angular momentum representation that are
[ĉ(k)+
λ , ĉ(k)λ ] = δλ,λ , λ, λ = 1, 2 (229)
analogous to equation (190). Such expansions can be quan-
tized in exactly the same way as the expansion of the field
and so the commutation relations of the Stokes opera-
in terms of plane waves, (Section 5.5). Instead of a box
tors are
of volume V , we quantize the field in a large sphere of
radius R. The coefficients of the orthogonal vector func- ˆ
[(k) ˆ ˆ
i , (k)j ] = i h̄(k)n (230)
tions are interpreted as annihilation and creation operators
for photons with definite angular momentum and parity. For for a cyclic permutation of i, j , n, which will be recognized
each frequency ω and fixed parity, we have a commutation as the defining relation for the SU(2) Lie group associated
relation that replaces equation (185), with the quantum theory of angular momentum. If we set

+ 1

[ĉωJ M , ĉωJ  M  ] = δJ J  δMM  (224) ˆ
(k)0 = H ≡ h̄ n̂(k)1 + n̂(k)2 (231)
ω k
with all other commutators vanishing. For a definite value
is the Hamiltonian for the mode (the zero-point
where H k
of J , the energy EJ of the field is determined by an
energy is dropped), the group invariant is easily checked
integral over the radial function (Chapter 38, this Volume,
to be
equation 128), and this can be used to fix the normalization
of the wave functions by setting EJ equal to the energy ˆ
(k) ˆ 2 ˆ 2 ˆ
0 = (k)1 + (k)2 + (k)3
2 2
(232)
h̄ω of a photon. A photon with angular momentum J
and parity (−1)J is usually referred to as an electric ˆ 1 is diagonal with respect to the Fock space vectors |1, 0

2J -pole (or EJ ) photon; one with parity (−1)J +1 is and |0, 1
with eigenvalues of +1 and −1, respectively (in
called a magnetic 2J -pole or (MJ ) photon. Thus, a parity units of h̄) and so ˆ 1 can be identified as the z-component
even state with J = 1 corresponds to a magnetic dipole of the angular momentum operator. Thus, the photon can be
photon, and one with J = 2 corresponds to an electric regarded as a spin 1 particle; as it has zero mass, the eigen-
quadrupole photon. The boson operators in equation (224) value 0 for Jz does not appear. Strictly speaking, the spin
 Quantization of the electromagnetic field 19

and orbital angular momentum of the field cannot be sepa- down from equation (62), and if the functional integration
rated; the eigenstates of angular momentum are proportional is restricted to just longitudinal vector fields, it will project
to the solid spherical harmonics defined in Chapter 38, this out gauge-invariant states from arbitrary wave functionals
Volume, which are combinations of the polarization vectors depending on the vector potential.
(representing ‘spin’) and spherical harmonics (representing The gauge-invariant states, that is, the kets that satisfy
the ‘orbital’ component). The Stokes operator formalism
was used extensively in a comprehensive account of molec-
[K]|
= |

U (241)
ular light scattering by Atkins and co-workers.(21 – 25)
are the physical states of the system. If we write K(x) in
the form (239), and make an integration by parts, we may
8 TRANSLATIONS OF THE FIELD
as
rewrite U
  
VARIABLES

[f ] = exp − i
U d3 xf (x)[∇·π(x)] (242)
h̄
The vector potential a(x) can be regarded as a ‘coordinate’
function for the field, while its conjugate π(x) is the and |
will be gauge-invariant provided that
corresponding ‘momentum’; in terms of the formalism
described in Section 2, we make the identifications, ∇·π(x)|
= 0 (243)

â ↔ X, π̂ ↔ P
(233) This is the quantum-mechanical version of Dirac’s equation
of constraint in the classical Hamiltonian theory for the free
When no gauge condition is specified, they satisfy an equal- field (Chapter 37, this Volume, equation 201 with zero
time CCR, charge density)

2 = ∇·π ≈ 0 (244)
[â(x)r , π̂(x )s ] = i h̄δrs δ3 (x − x ) (234)
If there are charges present, equation (242) must be modi-
and so may be realized in terms of functional derivatives, fied to read
  
δ δ
i
â(x) −−−→ i h̄ , π̂(x) −−−→ −i h̄ (235) Uρ [f ] = exp − d xf (x)[∇·π̂(x) + ρ̂(x)]
3
(245)
δπ(x) δa(x) h̄

According to the discussion in Section 2.2, ‘translations’ of corresponding to the Dirac constraint for the interacting
the vector potential operator system,

2 = ∇·π + ρ ≈ 0 (246)
â(x) −−−→ â(x) = â(x) + K(x) (236)
Suppose now we have a wave functional in a representation
are induced by the unitary operator (cf. equation 59) that is diagonal in the particle coordinates, and the vector
   potential

i 3   
U [K] = exp d x π̂(x )·K(x ) (237)
h̄ {xn }, a(x)|
= ({xn }, [a(x)]) (247)
For vector fields {K(x)} restricted to the class of longitudi-
, this state transforms as
Under the action of U ρ
nal vector fields,

|

|
= U ρ
∇ ∧ K(x) = 0 (238)  
i 
K(x) = ∇f (x) (239) = exp − e f (xn ) ({xn }, [a(x )])
h̄ n n
where f (x) is single-valued and square-integrable, such  
i 
transformations describe a symmetry of the system since ≡ exp − e f (xn ) ({xn }, [a(x) − ∇f (x)])
h̄ n n

,U
{H
[K  ]} = 0 (240) (248)
rad
where we have used the charge density for point charges
These are the gauge transformations of the vector potential. (Chapter 37, this Volume, equation 67), that is, in the
The corresponding projection operator is easily written transformed representation the state is a functional of the
20 Quantum electrodynamics of atoms and molecules

translated vector potential and acquires a phase determined The requirement that S[a(x)] be the functional derivative
by the charges present. Provided that charge is conserved, of the expression in braces in equation (255) strongly
there is unrestricted validity for the quantum-mechanical restricts the from of the functional T, since if we write
superposition principle because the phase factor is the same equation (255) in the form
for all possible states. Conversely one cannot have super-
positions of states associated with different charge densities δV [a(x)]
S[a(x)] = (257)
since their relative phases could be changed by a mere δa(x)
gauge transformation – this is the quantum-mechanical for-
then S must satisfy an integrability condition
mulation of the principle of charge conservation in terms
of the states of the system. δS[a(x)] δS[a(y)]
A physical state |
for the interacting system must = (258)
δa(y) δa(x)
satisfy the condition
and this implies that
(∇·π̂ + ρ)|
= 0 (249)   
i
T[a(x)] = t[a(x)] exp + d3 x a(x )·P (x ) (259)
We again choose a representation diagonal in the vector h̄
potential and the particle coordinates, so that ρ̂ can be
replaced by the classical charge density and π̂ can be where t is a transverse vector function of a(x). Thus, we
represented by equation (235). In terms of the electric must have(26)
polarization field (Chapter 37, this Volume, equation 72),   
i
[a(x)] = exp + d3 x a(x )·P (x )
h̄
ρ = −∇·P (250)  a(x)
× δa(x) ·t[a(x) ]
we may write equation (249) as
  
i 3   
∇·[π̂(x) − P (x)]|
= 0 (251) ≡ exp + d x a(x )·P (x ) [{xn }, a(x)]
h̄
(260)
Clearly, we cannot require the state |
to be an eigenstate The phase factor involving the electric polarization field
of π̂(x) with eigenvalue P(x); however, equation (251) will that appears in the gauge-invariant state (equation 260)
be satisfied if we can write will be recognized as the action that guarantees the gauge
invariance of the classical Lagrangian (Chapter 37, this
π̂(x)|
= P (x)|
+ T[a(x)] (252) Volume, equation 136). It is associated with the unitary
operator
where T, a functional of the vector potential, is transverse,
  
ˆ ] = exp i
[P d3 x a(x )·P (x ) (261)
∇·T[a(x)] = 0 (253) h̄

Equation (252) can now be written as a first-order func- that induces ‘translations’ of the conjugate field ‘momen-
tional differential equation, tum’ π̂,
  ˆ ]π̂ [P
[P ˆ ]−1 = π̂ − P (262)
δ i i
− P(x) [a(x)] = T[a(x)] (254)
δa(x) h̄ h̄ This, however, is not a symmetry of the system since H

rad
ˆ
does not commute with [P ].
which may be solved by introducing an integrating factor,
A similar discussion is possible when the vector potential
writing
is subject to a definite gauge condition which may be
     formulated as the requirement that the vector potential
δ i 3   
exp − d x a(x )·P (x ) [a(x)] = S[a(x)] should have a specified divergence (Chapter 37, this
δa(x) h̄
(255) Volume, Section 3). One may ask if gauge transformations
where are still possible when this restriction is applied. We fix the
  vector potential by setting

i i
S[a(x)] = T[a(x)] exp − d3 x a(x )·P (x ) (256)
h̄ h̄ ∇·a = Z (263)
 Quantization of the electromagnetic field 21

and then make a gauge transformation, [5] This shows at once that there is no eigenvalue problem
in Hilbert space for the creation operator ĉ+ ; because
a −−−→ a = a + ∇f (264) ĉ+ is the adjoint of ĉ, the differential equation for
ĉ+ corresponding to equation (125) must have −i in
Equation (263) will be satisfied provided f (x) is a solution the first factor, and this translates into the exponent
of Laplace’s equation, of the Gaussian solution like equation (127) having a
positive quadratic part, and so the solution cannot be
∇ 2 f (x) = 0 (265) normalized.
[6] Recall that
We achieve uniqueness of the vector potential by demand-
ing that |a(x)| → 0 as |x| → ∞, for then Laplace’s equa- e−iuP̂ /h̄ φ(x) = φ(x − u)
tion has only the trivial solution f = 0.(18)
When a gauge is fixed, the commutation relation of [7] The subscript i is being used as in equation (107)
the vector potential and its conjugate is obtained from [8] ∈j mn = +1 for a cyclic permutation of j , m, n,
the corresponding classical Dirac-bracket (Chapter 37, this ∈j mn = −1 for a non-cyclic permutation, and ∈j mn = 0
Volume, Section 6); although â and π̂ can no longer be if two or more subscripts are the same.
represented as simple functional derivative operators (equa-
tion 235), the commutation relation is sufficient to deter-
ˆ ] (equation 261). A
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