Quantum Mechanics

:
A graduate level course
Richard Fitzpatrick
Associate Professor of Physics
The University of Texas at Austin
Contents
1 Introduction 5
1.1 Major sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2 Fundamental concepts 6
2.1 The breakdown of classical physics . . . . . . . . . . . . . . . . . . 6
2.2 The polarization of photons . . . . . . . . . . . . . . . . . . . . . . 7
2.3 The fundamental principles of quantum mechanics . . . . . . . . . 9
2.4 Ket space . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.5 Bra space . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.6 Operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.7 The outer product . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.8 Eigenvalues and eigenvectors . . . . . . . . . . . . . . . . . . . . . 20
2.9 Observables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.10 Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.11 Expectation values . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.12 Degeneracy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.13 Compatible observables . . . . . . . . . . . . . . . . . . . . . . . . 27
2.14 The uncertainty relation . . . . . . . . . . . . . . . . . . . . . . . . 28
2.15 Continuous spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3 Position and momentum 33
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.2 Poisson brackets . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.3 Wave-functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.4 Schr¨ odinger’s representation - I . . . . . . . . . . . . . . . . . . . . 39
3.5 Schr¨ odinger’s representation - II . . . . . . . . . . . . . . . . . . . 43
3.6 The momentum representation . . . . . . . . . . . . . . . . . . . . 46
3.7 The uncertainty relation . . . . . . . . . . . . . . . . . . . . . . . . 48
3.8 Displacement operators . . . . . . . . . . . . . . . . . . . . . . . . 50
4 Quantum dynamics 55
4.1 Schr¨ odinger’s equations of motion . . . . . . . . . . . . . . . . . . 55
4.2 Heisenberg’s equations of motion . . . . . . . . . . . . . . . . . . . 59
2
4.3 Ehrenfest’s theorem . . . . . . . . . . . . . . . . . . . . . . . . . . 61
4.4 Schr¨ odinger’s wave-equation . . . . . . . . . . . . . . . . . . . . . 65
5 Angular momentum 71
5.1 Orbital angular momentum . . . . . . . . . . . . . . . . . . . . . . 71
5.2 Eigenvalues of angular momentum . . . . . . . . . . . . . . . . . . 74
5.3 Rotation operators . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
5.4 Eigenfunctions of orbital angular momentum . . . . . . . . . . . . 81
5.5 Motion in a central field . . . . . . . . . . . . . . . . . . . . . . . . 84
5.6 Energy levels of the hydrogen atom . . . . . . . . . . . . . . . . . . 86
5.7 Spin angular momentum . . . . . . . . . . . . . . . . . . . . . . . 89
5.8 Wave-function of a spin one-half particle . . . . . . . . . . . . . . . 91
5.9 Rotation operators in spin space . . . . . . . . . . . . . . . . . . . 93
5.10 Magnetic moments . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
5.11 Spin precession . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
5.12 Pauli two-component formalism . . . . . . . . . . . . . . . . . . . . 99
5.13 Spin greater than one-half systems . . . . . . . . . . . . . . . . . . 105
5.14 Addition of angular momentum . . . . . . . . . . . . . . . . . . . . 110
6 Approximation methods 120
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
6.2 The two-state system . . . . . . . . . . . . . . . . . . . . . . . . . . 120
6.3 Non-degenerate perturbation theory . . . . . . . . . . . . . . . . . 122
6.4 The quadratic Stark effect . . . . . . . . . . . . . . . . . . . . . . . 124
6.5 Degenerate perturbation theory . . . . . . . . . . . . . . . . . . . . 129
6.6 The linear Stark effect . . . . . . . . . . . . . . . . . . . . . . . . . 132
6.7 Fine structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
6.8 The Zeeman effect . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
6.9 Time-dependent perturbation theory . . . . . . . . . . . . . . . . . 144
6.10 The two-state system . . . . . . . . . . . . . . . . . . . . . . . . . . 146
6.11 Spin magnetic resonance . . . . . . . . . . . . . . . . . . . . . . . 149
6.12 The Dyson series . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
6.13 Constant perturbations . . . . . . . . . . . . . . . . . . . . . . . . . 154
6.14 Harmonic perturbations . . . . . . . . . . . . . . . . . . . . . . . . 158
6.15 Absorption and stimulated emission of radiation . . . . . . . . . . 159
3
6.16 The electric dipole approximation . . . . . . . . . . . . . . . . . . . 162
6.17 Energy-shifts and decay-widths . . . . . . . . . . . . . . . . . . . . 165
7 Scattering theory 170
7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
7.2 The Lipmann-Schwinger equation . . . . . . . . . . . . . . . . . . 170
7.3 The Born approximation . . . . . . . . . . . . . . . . . . . . . . . . 175
7.4 Partial waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
7.5 The optical theorem . . . . . . . . . . . . . . . . . . . . . . . . . . 181
7.6 Determination of phase-shifts . . . . . . . . . . . . . . . . . . . . . 182
7.7 Hard sphere scattering . . . . . . . . . . . . . . . . . . . . . . . . . 184
7.8 Low energy scattering . . . . . . . . . . . . . . . . . . . . . . . . . 186
7.9 Resonances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
4
1 INTRODUCTION
1 Introduction
1.1 Major sources
The textbooks which I have consulted most frequently while developing course
material are:
The principles of quantum mechanics, P.A.M. Dirac, 4th Edition (revised), (Ox-
ford University Press, Oxford, UK, 1958).
The Feynman lectures on physics, R.P. Feynman, R.B. Leighton, and M. Sands,
Volume III (Addison-Wesley, Reading MA, 1965).
Quantum mechanics, E. Merzbacher, 2nd Edition (John Wiley & Sons, New York
NY, 1970).
Modern quantum mechanics, J.J. Sakurai, (Benjamin/Cummings, Menlo Park
CA, 1985).
5
2 FUNDAMENTAL CONCEPTS
2 Fundamental concepts
2.1 The breakdown of classical physics
The necessity for a departure from classical mechanics is clearly demonstrated
by:
1. The anomalous stability of atoms and molecules: According to classical physics,
an electron orbiting a nucleus should lose energy by emission of synchrotron
radiation, and gradually spiral in towards the nucleus. Experimentally, this
is not observed to happen.
2. The anomalously low specific heats of atoms and molecules: According to the
equipartition theorem of classical physics, each degree of freedom of an
atomic or molecular system should contribute R/2 to its molar specific heat,
where R is the ideal gas constant. In fact, only the translational and some
rotational degrees of freedom seem to contribute. The vibrational degrees
of freedom appear to make no contribution at all (except at high temper-
atures). Incidentally, this fundamental problem with classical physics was
known and appreciated in the middle of the nineteenth century. Stories that
physicists at the start of the twentieth century thought that classical physics
explained everything, and that there was nothing left to discover, are largely
apocryphal (see Feynman, Vol. I, Cha. 40).
3. The ultraviolet catastrophe: According to classical physics, the energy density
of an electromagnetic field in vacuum is infinite due to a divergence of en-
ergy carried by short wave-length modes. Experimentally, there is no such
divergence, and the total energy density is finite.
4. Wave-particle duality: Classical physics can deal with waves or particles. How-
ever, various experiments (e.g., light interference, the photo-electric effect,
electron diffraction) show quite clearly that waves sometimes act as if they
were streams of particles, and streams of particles sometimes act as if they
were waves. This is completely inexplicable within the framework of classi-
cal physics.
6
2.2 The polarization of photons 2 FUNDAMENTAL CONCEPTS
2.2 The polarization of photons
It is known experimentally that when plane polarized light is used to eject photo-
electrons there is a preferred direction of emission of the electrons. Clearly, the
polarization properties of light, which are more usually associated with its wave-
like behaviour, also extend to its particle-like behaviour. In particular, a polariza-
tion can be ascribed to each individual photon in a beam of light.
Consider the following well-known experiment. A beam of plane polarized
light is passed through a polaroid film, which has the property that it is only
transparent to light whose plane of polarization lies perpendicular to its optic
axis. Classical electromagnetic wave theory tells us that if the beam is polarized
perpendicular to the optic axis then all of the light is transmitted, if the beam is
polarized parallel to the optic axis then none of the light is transmitted, and if the
light is polarized at an angle α to the axis then a fraction sin
2
α of the beam is
transmitted. Let us try to account for these observations at the individual photon
level.
A beam of light which is plane polarized in a certain direction is made up of a
stream of photons which are each plane polarized in that direction. This picture
leads to no difficulty if the plane of polarization lies parallel or perpendicular
to the optic axis of the polaroid. In the former case, none of the photons are
transmitted, and, in the latter case, all of the photons are transmitted. But, what
happens in the case of an obliquely polarized incident beam?
The above question is not very precise. Let us reformulate it as a question
relating to the result of some experiment which we could perform. Suppose that
we were to fire a single photon at a polaroid film, and then look to see whether
or not it emerges from the other side. The possible results of the experiment are
that either a whole photon, whose energy is equal to the energy of the incident
photon, is observed, or no photon is observed. Any photon which is transmitted
though the film must be polarized perpendicular to the optic axis. Furthermore,
it is impossible to imagine (in physics) finding part of a photon on the other side
of the film. If we repeat the experiment a great number of times then, on average,
a fraction sin
2
α of the photons are transmitted through the film, and a fraction
7
2.2 The polarization of photons 2 FUNDAMENTAL CONCEPTS
cos
2
α are absorbed. Thus, we conclude that a photon has a probability sin
2
α of
being transmitted as a photon polarized in the plane perpendicular to the optic
axis, and a probability cos
2
α of being absorbed. These values for the probabilities
lead to the correct classical limit for a beamcontaining a large number of photons.
Note that we have only been able to preserve the individuality of photons,
in all cases, by abandoning the determinacy of classical theory, and adopting a
fundamentally probabilistic approach. We have no way of knowing whether an
individual obliquely polarized photon is going to be absorbed by or transmitted
through a polaroid film. We only know the probability of each event occurring.
This is a fairly sweeping statement, but recall that the state of a photon is fully
specified once its energy, direction of propagation, and polarization are known.
If we imagine performing experiments using monochromatic light, normally in-
cident on a polaroid film, with a particular oblique polarization, then the state of
each individual photon in the beam is completely specified, and there is nothing
left over to uniquely determine whether the photon is transmitted or absorbed by
the film.
The above discussion about the results of an experiment with a single obliquely
polarized photon incident on a polaroid film answers all that can be legitimately
asked about what happens to the photon when it reaches the film. Questions as
to what decides whether the photon is transmitted or not, or how it changes its
direction of polarization, are illegitimate, since they do not relate to the outcome
of a possible experiment. Nevertheless, some further description is needed in
order to allow the results of this experiment to be correlated with the results of
other experiments which can be performed using photons.
The further description provided by quantum mechanics is as follows. It is
supposed that a photon polarized obliquely to the optic axis can be regarded as
being partly in a state of polarization parallel to the axis, and partly in a state of
polarization perpendicular to the axis. In other words, the oblique polarization
state is some sort of superposition of two states of parallel and perpendicular
polarization. Since there is nothing special about the orientation of the optic
axis in our experiment, we must conclude that any state of polarization can be
regarded as a superposition of two mutually perpendicular states of polarization.
8
2.3 The fundamental principles of quantum mechanics 2 FUNDAMENTAL CONCEPTS
When we make the photon encounter a polaroid film, we are subjecting it
to an observation. In fact, we are observing whether it is polarized parallel or
perpendicular to the optic axis. The effect of making this observation is to force
the photon entirely into a state of parallel or perpendicular polarization. In other
words, the photon has to jump suddenly from being partly in each of these two
states to being entirely in one or the other of them. Which of the two states it will
jump into cannot be predicted, but is governed by probability laws. If the photon
jumps into a state of parallel polarization then it is absorbed. Otherwise, it is
transmitted. Note that, in this example, the introduction of indeterminacy into
the problem is clearly connected with the act of observation. In other words, the
indeterminacy is related to the inevitable disturbance of the system associated
with the act of observation.
2.3 The fundamental principles of quantum mechanics
There is nothing special about the transmission and absorption of photons through
a polaroid film. Exactly the same conclusions as those outlined above are ob-
tained by studying other simple experiments, such as the interference of photons
(see Dirac, Sect. I.3), and the Stern-Gerlach experiment (see Sakurai, Cha. 1;
Feynman, Cha. 5). The study of these simple experiments leads us to formulate
the following fundamental principles of quantum mechanics:
1. Dirac’s razor: Quantum mechanics can only answer questions regarding the
outcome of possible experiments. Any other questions lie beyond the realms
of physics.
2. The principle of superposition of states: Any microscopic system (i.e., an atom,
molecule, or particle) in a given state can be regarded as being partly in
each of two or more other states. In other words, any state can be regarded
as a superposition of two or more other states. Such superpositions can be
performed in an infinite number of different ways.
3. The principle of indeterminacy: An observation made on a microscopic system
causes it to jump into one or more particular states (which are related to
9
2.4 Ket space 2 FUNDAMENTAL CONCEPTS
the type of observation). It is impossible to predict into which final state
a particular system will jump, however the probability of a given system
jumping into a given final state can be predicted.
The first of these principles was formulated by quantum physicists (such as Dirac)
in the 1920s to fend off awkward questions such as “How can a system suddenly
jump from one state into another?”, or “How does a system decide which state to
jump into?”. As we shall see, the second principle is the basis for the mathemat-
ical formulation of quantum mechanics. The final principle is still rather vague.
We need to extend it so that we can predict which possible states a system can
jump into after a particular type of observation, as well as the probability of the
system making a particular jump.
2.4 Ket space
Consider a microscopic system composed of particles or bodies with specific prop-
erties (mass, moment of inertia, etc.) interacting according to specific laws of
force. There will be various possible motions of the particles or bodies consistent
with the laws of force. Let us term each such motion a state of the system. Accord-
ing to the principle of superposition of states, any given state can be regarded as
a superposition of two or more other states. Thus, states must be related to math-
ematical quantities of a kind which can be added together to give other quantities
of the same kind. The most obvious examples of such quantities are vectors.
Let us consider a particular microscopic system in a particular state, which we
label A: e.g., a photon with a particular energy, momentum, and polarization.
We can represent this state as a particular vector, which we also label A, residing
in some vector space, where the other elements of the space represent all of the
other possible states of the system. Such a space is called a ket space (after Dirac).
The state vector A is conventionally written
|A`. (2.1)
Suppose that state A is, in fact, the superposition of two different states, B and
10
2.4 Ket space 2 FUNDAMENTAL CONCEPTS
C. This interrelation is represented in ket space by writing
|A` = |B` + |C`, (2.2)
where |B` is the vector relating to the state B, etc. For instance, state |B` might
represent a photon propagating in the z-direction, and plane polarized in the x-
direction, and state |C` might represent a similar photon plane polarized in the
y-direction. In this case, the sum of these two states represents a photon whose
plane of polarization makes an angle of 45

with both the x- and y-directions (by
analogy with classical physics). This latter state is represented by |B` + |C` in ket
space.
Suppose that we want to construct a state whose plane of polarization makes
an arbitrary angle α with the x-direction. We can do this via a suitably weighted
superposition of states B and C. By analogy with classical physics, we require
cos α of state B, and sinα of state C. This new state is represented by
cos α|B` + sinα|C` (2.3)
in ket space. Note that we cannot form a new state by superposing a state with
itself. For instance, a photon polarized in the y-direction superposed with another
photon polarized in the y-direction (with the same energy and momentum) gives
the same photon. This implies that the ket vector
c
1
|A` +c
2
|A` = (c
1
+c
2
)|A` (2.4)
corresponds to the same state that |A` does. Thus, ket vectors differ from con-
ventional vectors in that their magnitudes, or lengths, are physically irrelevant.
All the states of the system are in one to one correspondence with all the possi-
ble directions of vectors in the ket space, no distinction being made between the
directions of the ket vectors |A` and −|A`. There is, however, one caveat to the
above statements. If c
1
+ c
2
= 0 then the superposition process yields nothing at
all: i.e., no state. The absence of a state is represented by the null vector |0` in
ket space. The null vector has the fairly obvious property that
|A` + |0` = |A`, (2.5)
for any vector |A`. The fact that ket vectors pointing in the same direction repre-
sent the same state relates ultimately to the quantization of matter: i.e., the fact
11
2.4 Ket space 2 FUNDAMENTAL CONCEPTS
that it comes in irreducible packets called photons, electrons, atoms, etc. If we ob-
serve a microscopic system then we either see a state (i.e., a photon, or an atom,
or a molecule, etc.) or we see nothing—we can never see a fraction or a multiple
of a state. In classical physics, if we observe a wave then the amplitude of the
wave can take any value between zero and infinity. Thus, if we were to represent
a classical wave by a vector, then the magnitude, or length, of the vector would
correspond to the amplitude of the wave, and the direction would correspond to
the frequency and wave-length, so that two vectors of different lengths pointing
in the same direction would represent different wave states.
We have seen, in Eq. (2.3), that any plane polarized state of a photon can
be represented as a linear superposition of two orthogonal polarization states
in which the weights are real numbers. Suppose that we want to construct a
circularly polarized photon state. Well, we know from classical physics that a cir-
cularly polarized wave is a superposition of two waves of equal amplitude, plane
polarized in orthogonal directions, which are in phase quadrature. This suggests
that a circularly polarized photon is the superposition of a photon polarized in
the x-direction (state B) and a photon polarized in the y-direction (state C), with
equal weights given to the two states, but with the proviso that state C is 90

out of phase with state B. By analogy with classical physics, we can use complex
numbers to simultaneously represent the weighting and relative phase in a linear
superposition. Thus, a circularly polarized photon is represented by
|B` + i |C` (2.6)
in ket space. A general elliptically polarized photon is represented by
c
1
|B` +c
2
|C`, (2.7)
where c
1
and c
2
are complex numbers. We conclude that a ket space must be
a complex vector space if it is to properly represent the mutual interrelations
between the possible states of a microscopic system.
Suppose that the ket |R` is expressible linearly in terms of the kets |A` and |B`,
so that
|R` = c
1
|A` +c
2
|B`. (2.8)
12
2.4 Ket space 2 FUNDAMENTAL CONCEPTS
We say that |R` is dependent on |A` and |B`. It follows that the state R can be
regarded as a linear superposition of the states A and B. So, we can also say that
state R is dependent on states A and B. In fact, any ket vector (or state) which
is expressible linearly in terms of certain others is said to be dependent on them.
Likewise, a set of ket vectors (or states) are termed independent if none of them
are expressible linearly in terms of the others.
The dimensionality of a conventional vector space is defined as the number
of independent vectors contained in the space. Likewise, the dimensionality of
a ket space is equivalent to the number of independent ket vectors it contains.
Thus, the ket space which represents the possible polarization states of a photon
propagating in the z-direction is two-dimensional (the two independent vectors
correspond to photons plane polarized in the x- and y-directions, respectively).
Some microscopic systems have a finite number of independent states (e.g., the
spin states of an electron in a magnetic field). If there are N independent states,
then the possible states of the system are represented as an N-dimensional ket
space. Some microscopic systems have a denumerably infinite number of inde-
pendent states (e.g., a particle in an infinitely deep, one-dimensional potential
well). The possible states of such a system are represented as a ket space whose
dimensions are denumerably infinite. Such a space can be treated in more or less
the same manner as a finite-dimensional space. Unfortunately, some microscopic
systems have a nondenumerably infinite number of independent states (e.g., a
free particle). The possible states of such a system are represented as a ket space
whose dimensions are nondenumerably infinite. This type of space requires a
slightly different treatment to spaces of finite, or denumerably infinite, dimen-
sions.
In conclusion, the states of a general microscopic system can be represented as
a complex vector space of (possibly) infinite dimensions. Such a space is termed
a Hilbert space by mathematicians.
13
2.5 Bra space 2 FUNDAMENTAL CONCEPTS
2.5 Bra space
A snack machine inputs coins plus some code entered on a key pad, and (hope-
fully) outputs a snack. It also does so in a deterministic manner: i.e., the same
money plus the same code produces the same snack (or the same error message)
time after time. Note that the input and output of the machine have completely
different natures. We can imagine building a rather abstract snack machine which
inputs ket vectors and outputs complex numbers in a deterministic fashion. Math-
ematicians call such a machine a functional. Imagine a general functional, labeled
F, acting on a general ket vector, labeled A, and spitting out a general complex
number φ
A
. This process is represented mathematically by writing
'F|(|A`) = φ
A
. (2.9)
Let us narrow our focus to those functionals which preserve the linear dependen-
cies of the ket vectors upon which they operate. Not surprisingly, such functionals
are termed linear functionals. A general linear functional, labeled F, satisfies
'F|(|A` + |B`) = 'F|(|A`) +'F|(|B`), (2.10)
where |A` and |B` are any two kets in a given ket space.
Consider an N-dimensional ket space [i.e., a finite-dimensional, or denumer-
ably infinite dimensional (i.e., N → ∞), space]. Let the |i` (where i runs from 1
to N) represent N independent ket vectors in this space. A general ket vector can
be written
1
|A` =
N
¸
i=1
α
i
|i`, (2.11)
where the α
i
are an arbitrary set of complex numbers. The only way the func-
tional F can satisfy Eq. (2.10) for all vectors in the ket space is if
'F|(|A`) =
N
¸
i=1
f
i
α
i
, (2.12)
1
Actually, this is only strictly true for finite-dimensional spaces. Only a special subset of denumerably infinite
dimensional spaces have this property (i.e., they are complete), but since a ket space must be complete if it is to
represent the states of a microscopic system, we need only consider this special subset.
14
2.5 Bra space 2 FUNDAMENTAL CONCEPTS
where the f
i
are a set of complex numbers relating to the functional.
Let us define N basis functionals 'i| which satisfy
'i|(|j`) = δ
ij
. (2.13)
It follows from the previous three equations that
'F| =
N
¸
i=1
f
i
'i|. (2.14)
But, this implies that the set of all possible linear functionals acting on an N-
dimensional ket space is itself an N-dimensional vector space. This type of vector
space is called a bra space (after Dirac), and its constituent vectors (which are
actually functionals of the ket space) are called bra vectors. Note that bra vectors
are quite different in nature to ket vectors (hence, these vectors are written in
mirror image notation, ' | and | `, so that they can never be confused). Bra
space is an example of what mathematicians call a dual vector space (i.e., it is
dual to the original ket space). There is a one to one correspondence between
the elements of the ket space and those of the related bra space. So, for every
element A of the ket space, there is a corresponding element, which it is also
convenient to label A, in the bra space. That is,
|A`
DC
←→'A|, (2.15)
where DC stands for dual correspondence.
There are an infinite number of ways of setting up the correspondence between
vectors in a ket space and those in the related bra space. However, only one
of these has any physical significance. For a general ket vector A, specified by
Eq. (2.11), the corresponding bra vector is written
'A| =
N
¸
i=1
α

i
'i|, (2.16)
where the α

i
are the complex conjugates of the α
i
. 'A| is termed the dual vector
to |A`. It follows, from the above, that the dual to c'A| is c

|A`, where c is a
complex number. More generally,
c
1
|A` +c
2
|B`
DC
←→c

1
'A| +c

2
'B|. (2.17)
15
2.5 Bra space 2 FUNDAMENTAL CONCEPTS
Recall that a bra vector is a functional which acts on a general ket vector, and
spits out a complex number. Consider the functional which is dual to the ket
vector
|B` =
N
¸
i=1
β
i
|i` (2.18)
acting on the ket vector |A`. This operation is denoted 'B|(|A`). Note, however,
that we can omit the round brackets without causing any ambiguity, so the oper-
ation can also be written 'B||A`. This expression can be further simplified to give
'B|A`. According to Eqs. (2.11), (2.12), (2.16), and (2.18),
'B|A` =
N
¸
i=1
β

i
α
i
. (2.19)
Mathematicians term 'B|A` the inner product of a bra and a ket.
2
An inner prod-
uct is (almost) analogous to a scalar product between a covariant and contravari-
ant vector in some curvilinear space. It is easily demonstrated that
'B|A` = 'A|B`

. (2.20)
Consider the special case where |B` →|A`. It follows from Eqs. (2.12) and (2.20)
that 'A|A` is a real number, and that
'A|A` ≥ 0. (2.21)
The equality sign only holds if |A` is the null ket [i.e., if all of the α
i
are zero in
Eq. (2.11)]. This property of bra and ket vectors is essential for the probabilistic
interpretation of quantum mechanics, as will become apparent later.
Two kets |A` and |B` are said to be orthogonal if
'A|B` = 0, (2.22)
which also implies that 'B|A` = 0.
Given a ket |A` which is not the null ket, we can define a normalized ket |
˜
A`,
where
|
˜
A` =

¸
1

'A|A`
¸

|A`, (2.23)
2
We can now appreciate the elegance of Dirac’s notation. The combination of a bra and a ket yields a “bra(c)ket”
(which is just a number).
16
2.6 Operators 2 FUNDAMENTAL CONCEPTS
with the property
'
˜
A|
˜
A` = 1. (2.24)
Here,

'A|A` is known as the norm or “length” of |A`, and is analogous to the
length, or magnitude, of a conventional vector. Since |A` and c|A` represent
the same physical state, it makes sense to require that all kets corresponding to
physical states have unit norms.
It is possible to define a dual bra space for a ket space of nondenumerably
infinite dimensions in much the same manner as that described above. The main
differences are that summations over discrete labels become integrations over
continuous labels, Kronecker delta-functions become Dirac delta-functions, com-
pleteness must be assumed (it cannot be proved), and the normalization conven-
tion is somewhat different. More of this later.
2.6 Operators
We have seen that a functional is a machine which inputs a ket vector and spits
out a complex number. Consider a somewhat different machine which inputs a
ket vector and spits out another ket vector in a deterministic fashion. Mathemati-
cians call such a machine an operator. We are only interested in operators which
preserve the linear dependencies of the ket vectors upon which they act. Such
operators are termed linear operators. Consider an operator labeled X. Suppose
that when this operator acts on a general ket vector |A` it spits out a new ket
vector which is denoted X|A`. Operator X is linear provided that
X(|A` + |B`) = X|A` +X|B`, (2.25)
for all ket vectors |A` and |B`, and
X(c|A`) = cX|A`, (2.26)
for all complex numbers c. Operators X and Y are said to be equal if
X|A` = Y|A` (2.27)
17
2.6 Operators 2 FUNDAMENTAL CONCEPTS
for all kets in the ket space in question. Operator X is termed the null operator if
X|A` = |0` (2.28)
for all ket vectors in the space. Operators can be added together. Such addition
is defined to obey a commutative and associate algebra:
X +Y = Y +X, (2.29)
X + (Y +Z) = (X +Y) +Z. (2.30)
Operators can also be multiplied. The multiplication is associative:
X(Y|A`) = (XY)|A` = XY|A`, (2.31)
X(Y Z) = (XY)Z = XY Z. (2.32)
However, in general, it is noncommutative:
XY = Y X. (2.33)
So far, we have only considered linear operators acting on ket vectors. We can
also give a meaning to their operating on bra vectors. Consider the inner product
of a general bra 'B| with the ket X|A`. This product is a number which depends
linearly on |A`. Thus, it may be considered to be the inner product of |A` with
some bra. This bra depends linearly on 'B|, so we may look on it as the result of
some linear operator applied to 'B|. This operator is uniquely determined by the
original operator X, so we might as well call it the same operator acting on |B`. A
suitable notation to use for the resulting bra when X operates on 'B| is 'B|X. The
equation which defines this vector is
('B|X)|A` = 'B|(X|A`) (2.34)
for any |A` and 'B|. The triple product of 'B|, X, and |A` can be written 'B|X|A`
without ambiguity, provided we adopt the convention that the bra vector always
goes on the left, the operator in the middle, and the ket vector on the right.
Consider the dual bra to X|A`. This bra depends antilinearly on |A` and must
therefore depend linearly on 'A|. Thus, it may be regarded as the result of some
18
2.7 The outer product 2 FUNDAMENTAL CONCEPTS
linear operator applied to 'A|. This operator is termed the adjoint of X, and is
denoted X

. Thus,
X|A`
DC
←→'A|X

. (2.35)
It is readily demonstrated that
'B|X

|A` = 'A|X|B`

, (2.36)
plus
(XY)

= Y

X

. (2.37)
It is also easily seen that the adjoint of the adjoint of a linear operator is equiva-
lent to the original operator. A Hermitian operator ξ has the special property that
it is its own adjoint: i.e.,
ξ = ξ

. (2.38)
2.7 The outer product
So far we have formed the following products: 'B|A`, X|A`, 'A|X, XY, 'B|X|A`.
Are there any other products we are allowed to form? How about
|B`'A| ? (2.39)
This clearly depends linearly on the ket |A` and the bra |B`. Suppose that we
right-multiply the above product by the general ket |C`. We obtain
|B`'A|C` = 'A|C`|B`, (2.40)
since 'A|C` is just a number. Thus, |B`'A| acting on a general ket |C` yields
another ket. Clearly, the product |B`'A| is a linear operator. This operator also
acts on bras, as is easily demonstrated by left-multiplying the expression (2.39)
by a general bra 'C|. It is also easily demonstrated that
(|B`'A|)

= |A`'B|. (2.41)
Mathematicians term the operator |B`'A| the outer product of |B` and 'A|. The
outer product should not be confused with the inner product, 'A|B`, which is just
a number.
19
2.8 Eigenvalues and eigenvectors 2 FUNDAMENTAL CONCEPTS
2.8 Eigenvalues and eigenvectors
In general, the ket X|A` is not a constant multiple of |A`. However, there are
some special kets known as the eigenkets of operator X. These are denoted
|x

`, |x

`, |x

` . . . , (2.42)
and have the property
X|x

` = x

|x

`, X|x

` = x

|x

` . . . , (2.43)
where x

, x

, . . . are numbers called eigenvalues. Clearly, applying X to one of its
eigenkets yields the same eigenket multiplied by the associated eigenvalue.
Consider the eigenkets and eigenvalues of a Hermitian operator ξ. These are
denoted
ξ|ξ

` = ξ

`, (2.44)
where |ξ

` is the eigenket associated with the eigenvalue ξ

. Three important
results are readily deduced:
(i) The eigenvalues are all real numbers, and the eigenkets corresponding to
different eigenvalues are orthogonal. Since ξ is Hermitian, the dual equation to
Eq. (2.44) (for the eigenvalue ξ

) reads

|ξ = ξ

|. (2.45)
If we left-multiply Eq. (2.44) by 'ξ

|, right-multiply the above equation by |ξ

`,
and take the difference, we obtain

−ξ

)'ξ

` = 0. (2.46)
Suppose that the eigenvalues ξ

and ξ

are the same. It follows from the above
that
ξ

= ξ

, (2.47)
where we have used the fact that |ξ

` is not the null ket. This proves that the
eigenvalues are real numbers. Suppose that the eigenvalues ξ

and ξ

are differ-
ent. It follows that

` = 0, (2.48)
20
2.9 Observables 2 FUNDAMENTAL CONCEPTS
which demonstrates that eigenkets corresponding to different eigenvalues are
orthogonal.
(ii) The eigenvalues associated with eigenkets are the same as the eigenvalues
associated with eigenbras. An eigenbra of ξ corresponding to an eigenvalue ξ

is
defined

|ξ = 'ξ

. (2.49)
(iii) The dual of any eigenket is an eigenbra belonging to the same eigenvalue,
and conversely.
2.9 Observables
We have developed a mathematical formalism which comprises three types of
objects—bras, kets, and linear operators. We have already seen that kets can be
used to represent the possible states of a microscopic system. However, there is
a one to one correspondence between the elements of a ket space and its dual
bra space, so we must conclude that bras could just as well be used to repre-
sent the states of a microscopic system. What about the dynamical variables of
the system (e.g., its position, momentum, energy, spin, etc.)? How can these be
represented in our formalism? Well, the only objects we have left over are oper-
ators. We, therefore, assume that the dynamical variables of a microscopic system
are represented as linear operators acting on the bras and kets which correspond to
the various possible states of the system. Note that the operators have to be linear,
otherwise they would, in general, spit out bras/kets pointing in different direc-
tions when fed bras/kets pointing in the same direction but differing in length.
Since the lengths of bras and kets have no physical significance, it is reasonable
to suppose that non-linear operators are also without physical significance.
We have seen that if we observe the polarization state of a photon, by placing
a polaroid film in its path, the result is to cause the photon to jump into a state
of polarization parallel or perpendicular to the optic axis of the film. The former
state is absorbed, and the latter state is transmitted (which is how we tell them
apart). In general, we cannot predict into which state a given photon will jump
21
2.9 Observables 2 FUNDAMENTAL CONCEPTS
(except in a statistical sense). However, we do know that if the photon is initially
polarized parallel to the optic axis then it will definitely be absorbed, and if it is
initially polarized perpendicular to the axis then it will definitely be transmitted.
We also known that after passing though the film a photon must be in a state of
polarization perpendicular to the optic axis (otherwise it would not have been
transmitted). We can make a second observation of the polarization state of
such a photon by placing an identical polaroid film (with the same orientation of
the optic axis) immediately behind the first film. It is clear that the photon will
definitely be transmitted through the second film.
There is nothing special about the polarization states of a photon. So, more
generally, we can say that when a dynamical variable of a microscopic system
is measured the system is caused to jump into one of a number of independent
states (note that the perpendicular and parallel polarization states of our photon
are linearly independent). In general, each of these final states is associated with
a different result of the measurement: i.e., a different value of the dynamical
variable. Note that the result of the measurement must be a real number (there
are no measurement machines which output complex numbers). Finally, if an
observation is made, and the system is found to be a one particular final state,
with one particular value for the dynamical variable, then a second observation,
made immediately after the first one, will definitely find the system in the same
state, and yield the same value for the dynamical variable.
How can we represent all of these facts in our mathematical formalism? Well,
by a fairly non-obvious leap of intuition, we are going to assert that a measure-
ment of a dynamical variable corresponding to an operator X in ket space causes
the system to jump into a state corresponding to one of the eigenkets of X. Not
surprisingly, such a state is termed an eigenstate. Furthermore, the result of the
measurement is the eigenvalue associated with the eigenket into which the system
jumps. The fact that the result of the measurement must be a real number implies
that dynamical variables can only be represented by Hermitian operators (since only
Hermitian operators are guaranteed to have real eigenvalues). The fact that the
eigenkets of a Hermitian operator corresponding to different eigenvalues (i.e., dif-
ferent results of the measurement) are orthogonal is in accordance with our ear-
lier requirement that the states into which the system jumps should be mutually
22
2.9 Observables 2 FUNDAMENTAL CONCEPTS
independent. We can conclude that the result of a measurement of a dynamical
variable represented by a Hermitian operator ξ must be one of the eigenvalues of
ξ. Conversely, every eigenvalue of ξ is a possible result of a measurement made
on the corresponding dynamical variable. This gives us the physical significance
of the eigenvalues. (From now on, the distinction between a state and its rep-
resentative ket vector, and a dynamical variable and its representative operator,
will be dropped, for the sake of simplicity.)
It is reasonable to suppose that if a certain dynamical variable ξ is measured
with the system in a particular state, then the states into which the system may
jump on account of the measurement are such that the original state is dependent
on them. This fairly innocuous statement has two very important corollaries.
First, immediately after an observation whose result is a particular eigenvalue ξ

,
the system is left in the associated eigenstate. However, this eigenstate is orthog-
onal to (i.e., independent of) any other eigenstate corresponding to a different
eigenvalue. It follows that a second measurement made immediately after the
first one must leave the system in an eigenstate corresponding to the eigenvalue
ξ

. In other words, the second measurement is bound to give the same result as
the first. Furthermore, if the system is in an eigenstate of ξ, corresponding to an
eigenvalue ξ

, then a measurement of ξ is bound to give the result ξ

. This follows
because the system cannot jump into an eigenstate corresponding to a different
eigenvalue of ξ, since such a state is not dependent on the original state. Second,
it stands to reason that a measurement of ξ must always yield some result. It fol-
lows that no matter what the initial state of the system, it must always be able to
jump into one of the eigenstates of ξ. In other words, a general ket must always
be dependent on the eigenkets of ξ. This can only be the case if the eigenkets
form a complete set (i.e., they span ket space). Thus, in order for a Hermitian oper-
ator ξ to be observable its eigenkets must form a complete set. A Hermitian operator
which satisfies this condition is termed an observable. Conversely, any observable
quantity must be a Hermitian operator with a complete set of eigenstates.
23
2.10 Measurements 2 FUNDAMENTAL CONCEPTS
2.10 Measurements
We have seen that a measurement of some observable ξ of a microscopic system
causes the system to jump into one of the eigenstates of ξ. The result of the
measurement is the associated eigenvalue (or some function of this quantity). It
is impossible to determine into which eigenstate a given system will jump, but it is
possible to predict the probability of such a transition. So, what is the probability
that a system in some initial state |A` makes a transition to an eigenstate |ξ

` of an
observable ξ, as a result of a measurement made on the system? Let us start with
the simplest case. If the system is initially in an eigenstate |ξ

` then the transition
probability to a eigenstate |ξ

` corresponding to a different eigenvalue is zero,
and the transition probability to the same eigenstate |ξ

` is unity. It is convenient
to normalize our eigenkets such that they all have unit norms. It follows from the
orthogonality property of the eigenkets that

` = δ
ξ

ξ
, (2.50)
where δ
ξ

ξ
is unity if ξ

= ξ

, and zero otherwise. For the moment, we are
assuming that the eigenvalues of ξ are all different.
Note that the probability of a transition from an initial eigenstate |ξ

` to a fi-
nal eigenstate |ξ

` is the same as the value of the inner product 'ξ

`. Can we
use this correspondence to obtain a general rule for calculating transition prob-
abilities? Well, suppose that the system is initially in a state |A` which is not an
eigenstate of ξ. Can we identify the transition probability to a final eigenstate

` with the inner product 'A|ξ

`? The straight answer is “no”, since 'A|ξ

` is, in
general, a complex number, and complex probabilities do not make much sense.
Let us try again. How about if we identify the transition probability with the mod-
ulus squared of the inner product, |'A|ξ

`|
2
? This quantity is definitely a positive
number (so it could be a probability). This guess also gives the right answer for
the transition probabilities between eigenstates. In fact, it is the correct guess.
Since the eigenstates of an observable ξ form a complete set, we can express
any given state |A` as a linear combination of them. It is easily demonstrated that
|A` =
¸
ξ

`'ξ

|A`, (2.51)
24
2.11 Expectation values 2 FUNDAMENTAL CONCEPTS
'A| =
¸
ξ

'A|ξ

`'ξ

|, (2.52)
'A|A` =
¸
ξ

'A|ξ

`'ξ

|A` =
¸
ξ

|'A|ξ

`|
2
, (2.53)
where the summation is over all the different eigenvalues of ξ, and use has been
made of Eq. (2.20), and the fact that the eigenstates are mutually orthogonal.
Note that all of the above results follow from the extremely useful (and easily
proved) result
¸
ξ

`'ξ

| = 1, (2.54)
where 1 denotes the identity operator. The relative probability of a transition to
an eigenstate |ξ

`, which is equivalent to the relative probability of a measure-
ment of ξ yielding the result ξ

, is
P(ξ

) ∝ |'A|ξ

`|
2
. (2.55)
The absolute probability is clearly
P(ξ

) =
|'A|ξ

`|
2
¸
ξ

|'A|ξ

`|
2
=
|'A|ξ

`|
2
'A|A`
. (2.56)
If the ket |A` is normalized such that its norm is unity, then this probability simply
reduces to
P(ξ

) = |'A|ξ

`|
2
. (2.57)
2.11 Expectation values
Consider an ensemble of microscopic systems prepared in the same initial state
|A`. Suppose a measurement of the observable ξ is made on each system. We
know that each measurement yields the value ξ

with probability P(ξ

). What is
the mean value of the measurement? This quantity, which is generally referred
to as the expectation value of ξ, is given by
'ξ` =
¸
ξ

ξ

P(ξ

) =
¸
ξ

ξ

|'A|ξ

`|
2
25
2.12 Degeneracy 2 FUNDAMENTAL CONCEPTS
=
¸
ξ

ξ

'A|ξ

`'ξ

|A` =
¸
ξ

'A|ξ|ξ

`'ξ

|A`, (2.58)
which reduces to
'ξ` = 'A|ξ|A` (2.59)
with the aid of Eq. (2.54).
Consider the identity operator, 1. All states are eigenstates of this operator
with the eigenvalue unity. Thus, the expectation value of this operator is always
unity: i.e.,
'A|1|A` = 'A|A` = 1, (2.60)
for all |A`. Note that it is only possible to normalize a given ket |A` such that
Eq. (2.60) is satisfied because of the more general property (2.21) of the norm.
This property depends on the particular correspondence (2.16), that we adopted
earlier, between the elements of a ket space and those of its dual bra space.
2.12 Degeneracy
Suppose that two different eigenstates |ξ

a
` and |ξ

b
` of ξ correspond to the same
eigenvalue ξ

. These are termed degenerate eigenstates. Degenerate eigenstates
are necessarily orthogonal to any eigenstates corresponding to different eigen-
values, but, in general, they are not orthogonal to each other (i.e., the proof of
orthogonality given in Sect. 2.8 does not work in this case). This is unfortunate,
since much of the previous formalism depends crucially on the mutual orthogo-
nality of the different eigenstates of an observable. Note, however, that any linear
combination of |ξ

a
` and |ξ

b
` is also an eigenstate corresponding to the eigenvalue
ξ

. It follows that we can always construct two mutually orthogonal degenerate
eigenstates. For instance,

1
` = |ξ

a
`, (2.61)

2
` =

b
` −'ξ

a

b
`|ξ

a
`
1 − |'ξ

a

b
`|
2
. (2.62)
26
2.13 Compatible observables 2 FUNDAMENTAL CONCEPTS
This result is easily generalized to the case of more than two degenerate eigen-
states. We conclude that it is always possible to construct a complete set of mu-
tually orthogonal eigenstates for any given observable.
2.13 Compatible observables
Suppose that we wish to simultaneously measure two observables, ξ and η, of
a microscopic system? Let us assume that we possess an apparatus which is ca-
pable of measuring ξ, and another which can measure η. For instance, the two
observables in question might be the projection in the x- and z-directions of the
spin angular momentum of a spin one-half particle. These could be measured us-
ing appropriate Stern-Gerlach apparatuses (see Sakurai, Sect. 1.1). Suppose that
we make a measurement of ξ, and the system is consequently thrown into one
of the eigenstates of ξ, |ξ

`, with eigenvalue ξ

. What happens if we now make
a measurement of η? Well, suppose that the eigenstate |ξ

` is also an eigenstate
of η, with eigenvalue η

. In this case, a measurement of η will definitely give the
result η

. A second measurement of ξ will definitely give the result ξ

, and so on.
In this sense, we can say that the observables ξ and η simultaneously have the
values ξ

and η

, respectively. Clearly, if all eigenstates of ξ are also eigenstates
of η then it is always possible to make a simultaneous measurement of ξ and η.
Such observables are termed compatible.
Suppose, however, that the eigenstates of ξ are not eigenstates of η. Is it
still possible to measure both observables simultaneously? Let us again make an
observation of ξ which throws the system into an eigenstate |ξ

`, with eigenvalue
ξ

. We can now make a second observation to determine η. This will throw
the system into one of the (many) eigenstates of η which depend on |ξ

`. In
principle, each of these eigenstates is associated with a different result of the
measurement. Suppose that the system is thrown into an eigenstate |η

`, with
the eigenvalue η

. Another measurement of ξ will throw the system into one
of the (many) eigenstates of ξ which depend on |η

`. Each eigenstate is again
associated with a different possible result of the measurement. It is clear that if
the observables ξ and η do not possess simultaneous eigenstates then if the value
27
2.14 The uncertainty relation 2 FUNDAMENTAL CONCEPTS
of ξ is known (i.e., the system is in an eigenstate of ξ) then the value of η is
uncertain (i.e., the system is not in an eigenstate of η), and vice versa. We say
that the two observables are incompatible.
We have seen that the condition for two observables ξ and η to be simultane-
ously measurable is that they should possess simultaneous eigenstates (i.e., every
eigenstate of ξ should also be an eigenstate of η). Suppose that this is the case.
Let a general eigenstate of ξ, with eigenvalue ξ

, also be an eigenstate of η, with
eigenvalue η

. It is convenient to denote this simultaneous eigenstate |ξ

η

`. We
have
ξ|ξ

η

` = ξ

η

`, (2.63)
η|ξ

η

` = η

η

`. (2.64)
We can left-multiply the first equation by η, and the second equation by ξ, and
then take the difference. The result is
(ξ η −ηξ)|ξ

η

` = |0` (2.65)
for each simultaneous eigenstate. Recall that the eigenstates of an observable
must form a complete set. It follows that the simultaneous eigenstates of two
observables must also form a complete set. Thus, the above equation implies that
(ξ η −ηξ)|A` = |0`, (2.66)
where |A` is a general ket. The only way that this can be true is if
ξ η = ηξ. (2.67)
Thus, the condition for two observables ξ and η to be simultaneously measurable is
that they should commute.
2.14 The uncertainty relation
We have seen that if ξ and η are two noncommuting observables, then a deter-
mination of the value of ξ leaves the value of η uncertain, and vice versa. It is
28
2.14 The uncertainty relation 2 FUNDAMENTAL CONCEPTS
possible to quantify this uncertainty. For a general observable ξ, we can define a
Hermitian operator
∆ξ = ξ −'ξ`, (2.68)
where the expectation value is taken over the particular physical state under con-
sideration. It is obvious that the expectation value of ∆ξ is zero. The expectation
value of (∆ξ)
2
≡ ∆ξ ∆ξ is termed the variance of ξ, and is, in general, non-zero.
In fact, it is easily demonstrated that
'(∆ξ)
2
` = 'ξ
2
` −'ξ`
2
. (2.69)
The variance of ξ is a measure of the uncertainty in the value of ξ for the particu-
lar state in question (i.e., it is a measure of the width of the distribution of likely
values of ξ about the expectation value). If the variance is zero then there is no
uncertainty, and a measurement of ξ is bound to give the expectation value, 'ξ`.
Consider the Schwarz inequality
'A|A`'B|B` ≥ |'A|B`|
2
, (2.70)
which is analogous to
|a|
2
| b|
2
≥ |a b|
2
(2.71)
in Euclidian space. This inequality can be proved by noting that
('A| +c

'B|)(|A` +c|B`) ≥ 0, (2.72)
where c is any complex number. If c takes the special value −'B|A`/'B|B` then
the above inequality reduces to
'A|A`'B|B` − |'A|B`|
2
≥ 0, (2.73)
which is the same as the Schwarz inequality.
Let us substitute
|A` = ∆ξ| `, (2.74)
|B` = ∆η| `, (2.75)
29
2.14 The uncertainty relation 2 FUNDAMENTAL CONCEPTS
into the Schwarz inequality, where the blank ket | ` stands for any general ket.
We find
'(∆ξ)
2
`'(∆η)
2
` ≥ |'∆ξ ∆η`|
2
, (2.76)
where use has been made of the fact that ∆ξ and ∆η are Hermitian operators.
Note that
∆ξ ∆η =
1
2
[∆ξ, ∆η] +
1
2
{∆ξ, ∆η} , (2.77)
where the commutator, [∆ξ, ∆η], and the anti-commutator, {∆ξ, ∆η}, are defined
[∆ξ, ∆η] ≡ ∆ξ ∆η −∆η∆ξ, (2.78)
{∆ξ, ∆η} ≡ ∆ξ ∆η +∆η∆ξ. (2.79)
The commutator is clearly anti-Hermitian,
([∆ξ, ∆η])

= (∆ξ ∆η −∆η∆ξ)

= ∆η∆ξ −∆ξ ∆η = − [∆ξ, ∆η] , (2.80)
whereas the anti-commutator is obviously Hermitian. Now, it is easily demon-
strated that the expectation value of a Hermitian operator is a real number,
whereas the expectation value of an anti-Hermitian operator is a pure imaginary
number. It is clear that the right hand side of
'∆ξ ∆η` =
1
2
'[∆ξ, ∆η]` +
1
2
'{∆ξ, ∆η}`, (2.81)
consists of the sum of a purely real and a purely imaginary number. Taking the
modulus squared of both sides gives
|'∆ξ ∆η`|
2
=
1
4
|'[ξ, η]`|
2
+
1
4
|'{∆ξ, ∆η}`|
2
, (2.82)
where use has been made of '∆ξ` = 0, etc. The final term in the above expression
is positive definite, so we can write
'(∆ξ)
2
`'(∆η)
2
` ≥
1
4
|'[ξ, η]`|
2
, (2.83)
where use has been made of Eq. (2.76). The above expression is termed the
uncertainty relation. According to this relation, an exact knowledge of the value
of ξ implies no knowledge whatsoever of the value of η, and vice versa. The one
exception to this rule is when ξ and η commute, in which case exact knowledge
of ξ does not necessarily imply no knowledge of η.
30
2.15 Continuous spectra 2 FUNDAMENTAL CONCEPTS
2.15 Continuous spectra
Up to now, we have studiously avoided dealing with observables possessing eigen-
values which lie in a continuous range, rather than having discrete values. The
reason for this is because continuous eigenvalues imply a ket space of nonde-
numerably infinite dimension. Unfortunately, continuous eigenvalues are un-
avoidable in quantum mechanics. In fact, the most important observables of all,
namely position and momentum, generally have continuous eigenvalues. Fortu-
nately, many of the results we obtained previously for a finite-dimensional ket
space with discrete eigenvalues can be generalized to ket spaces of nondenumer-
ably infinite dimensions.
Suppose that ξ is an observable with continuous eigenvalues. We can still
write the eigenvalue equation as
ξ|ξ

` = ξ

`. (2.84)
But, ξ

can now take a continuous range of values. Let us assume, for the sake of
simplicity, that ξ

can take any value. The orthogonality condition (2.50) gener-
alizes to

` = δ(ξ

−ξ

), (2.85)
where δ(x) denotes the famous Dirac delta-function. Note that there are clearly a
nondenumerably infinite number of mutually orthogonal eigenstates of ξ. Hence,
the dimensionality of ket space is nondenumerably infinite. Note, also, that eigen-
states corresponding to a continuous range of eigenvalues cannot be normalized
so that they have unit norms. In fact, these eigenstates have infinite norms: i.e.,
they are infinitely long. This is the major difference between eigenstates in a
finite-dimensional and an infinite-dimensional ket space. The extremely useful
relation (2.54) generalizes to
¸

`'ξ

| = 1. (2.86)
Note that a summation over discrete eigenvalues goes over into an integral over
a continuous range of eigenvalues. The eigenstates |ξ

` must form a complete set
if ξ is to be an observable. It follows that any general ket can be expanded in
31
2.15 Continuous spectra 2 FUNDAMENTAL CONCEPTS
terms of the |ξ

`. In fact, the expansions (2.51)–(2.53) generalize to
|A` =
¸

`'ξ

|A`, (2.87)
'A| =
¸

'A|ξ

`'ξ

|, (2.88)
'A|A` =
¸

'A|ξ

`'ξ

|A` =
¸

|'A|ξ

`|
2
. (2.89)
These results also follow simply from Eq. (2.86). We have seen that it is not possi-
ble to normalize the eigenstates |ξ

` such that they have unit norms. Fortunately,
this convenient normalization is still possible for a general state vector. In fact,
according to Eq. (2.89), the normalization condition can be written
'A|A` =
¸

|'A|ξ

`|
2
= 1. (2.90)
We have now studied observables whose eigenvalues can take a discrete num-
ber of values as well as those whose eigenvalues can take any value. There are
number of other cases we could look at. For instance, observables whose eigen-
values can only take a finite range of values, or observables whose eigenvalues
take on a finite range of values plus a set of discrete values. Both of these cases
can be dealt with using a fairly straight-forward generalization of the previous
analysis (see Dirac, Cha. II and III).
32
3 POSITION AND MOMENTUM
3 Position and momentum
3.1 Introduction
So far, we have considered general dynamical variables represented by general
linear operators acting in ket space. However, in classical mechanics the most
important dynamical variables are those involving position and momentum. Let
us investigate the role of such variables in quantum mechanics.
In classical mechanics, the position q and momentum p of some component
of a dynamical system are represented as real numbers which, by definition, com-
mute. In quantum mechanics, these quantities are represented as noncommuting
linear Hermitian operators acting in a ket space which represents all of the pos-
sible states of the system. Our first task is to discover a quantum mechanical
replacement for the classical result qp − pq = 0. Do the position and momen-
tum operators commute? If not, what is the value of qp −pq?
3.2 Poisson brackets
Consider a dynamic system whose state at a particular time t is fully specified
by N independent classical coordinates q
i
(where i runs from 1 to N). Associ-
ated with each generalized coordinate q
i
is a classical canonical momentum p
i
.
For instance, a Cartesian coordinate has an associated linear momentum, an an-
gular coordinate has an associated angular momentum, etc. As is well-known,
the behaviour of a classical system can be specified in terms of Lagrangian or
Hamiltonian dynamics. For instance, in Hamiltonian dynamics,
dq
i
dt
=
∂H
∂p
i
, (3.1)
dp
i
dt
= −
∂H
∂q
i
, (3.2)
where the function H(q
i
, p
i
, t) is the energy of the system at time t expressed
in terms of the classical coordinates and canonical momenta. This function is
33
3.2 Poisson brackets 3 POSITION AND MOMENTUM
usually referred to as the Hamiltonian of the system.
We are interested in finding some construct of classical dynamics which con-
sists of products of dynamical variables. If such a construct exists we hope to
generalize it somehow to obtain a rule describing how dynamical variables com-
mute with one another in quantum mechanics. There is, indeed, one well-known
construct in classical dynamics which involves products of dynamical variables.
The Poisson bracket of two dynamical variables u and v is defined
[u, v] =
N
¸
i=1

∂u
∂q
i
∂v
∂p
i

∂u
∂p
i
∂v
∂q
i

, (3.3)
where u and v are regarded as functions of the coordinates and momenta q
i
and
p
i
. It is easily demonstrated that
[q
i
, q
j
] = 0, (3.4)
[p
i
, p
j
] = 0, (3.5)
[q
i
, p
j
] = δ
ij
. (3.6)
The time evolution of a dynamical variable can also be written in terms of a
Poisson bracket by noting that
du
dt
=
N
¸
i=1

∂u
∂q
i
dq
i
dt
+
∂u
∂p
i
dp
i
dt

=
N
¸
i=1

∂u
∂q
i
∂H
∂p
i

∂u
∂p
i
∂H
∂q
i

= [u, H], (3.7)
where use has been made of Hamilton’s equations.
Can we construct a quantum mechanical Poisson bracket in which u and v are
noncommuting operators, instead of functions? Well, the main properties of the
classical Poisson bracket are as follows:
[u, v] = −[v, u], (3.8)
34
3.2 Poisson brackets 3 POSITION AND MOMENTUM
[u, c] = 0, (3.9)
[u
1
+u
2
, v] = [u
1
, v] + [u
2
, v], (3.10)
[u, v
1
+v
2
] = [u, v
1
] + [u, v
2
] (3.11)
[u
1
u
2
, v] = [u
1
, v]u
2
+u
1
[u
2
, v], (3.12)
[u, v
1
v
2
] = [u, v
1
]v
2
+v
1
[u, v
2
], (3.13)
and
[u, [v, w]] + [v, [w, u]] + [w, [u, v]] = 0. (3.14)
The last relation is known as the Jacobi identity. In the above, u, v, w, etc.,
represent dynamical variables, and c represents a number. Can we find some
combination of noncommuting operators u and v, etc., which satisfies all of the
above relations?
Well, we can evaluate the Poisson bracket [u
1
u
2
, v
1
v
2
] in two different ways,
since we can use either of the formulae (3.12) or (3.13) first. Thus,
[u
1
u
2
, v
1
v
2
] = [u
1
, v
1
v
2
]u
2
+u
1
[u
2
, v
1
v
2
] (3.15)
= {[u
1
, v
1
]v
2
+v
1
[u
1
, v
2
]} u
2
+u
1
{[u
2
, v
1
]v
2
+v
1
[u
2
, v
2
]}
= [u
1
, v
1
]v
2
u
2
+v
1
[u
1
, v
2
]u
2
+u
1
[u
2
, v
1
]v
2
+u
1
v
1
[u
2
, v
2
],
and
[u
1
u
2
, v
1
v
2
] = [u
1
u
2
, v
1
]v
2
+v
1
[u
1
u
2
, v
2
] (3.16)
= [u
1
, v
1
]u
2
v
2
+u
1
[u
2
, v
1
]v
2
+v
1
[u
1
, v
2
]u
2
+v
1
u
1
[u
2
, v
2
].
Note that the order of the various factors has been preserved, since they now
represent noncommuting operators. Equating the above two results yields
[u
1
, v
1
](u
2
v
2
−v
2
u
2
) = (u
1
v
1
−v
1
u
1
)[u
2
, v
2
]. (3.17)
Since this relation must hold for u
1
and v
1
quite independent of u
2
and v
2
, it
follows that
u
1
v
1
−v
1
u
1
= i ¯h[u
1
, v
1
], (3.18)
u
2
v
2
−v
2
u
2
= i ¯h[u
2
, v
2
], (3.19)
35
3.2 Poisson brackets 3 POSITION AND MOMENTUM
where ¯h does not depend on u
1
, v
1
, u
2
, v
2
, and also commutes with (u
1
v
1
−v
1
u
1
).
Since u
1
, etc., are quite general operators, it follows that ¯h is just a number. We
want the quantum mechanical Poisson bracket of two Hermitian operators to
be an Hermitian operator itself, since the classical Poisson bracket of two real
dynamical variables is real. This requirement is satisfied if ¯h is a real number.
Thus, the quantum mechanical Poisson bracket of two dynamical variables u and
v is given by
[u, v] =
uv −v u
i ¯h
, (3.20)
where ¯h is a new universal constant of nature. Quantum mechanics agrees with
experiments provided that ¯h takes the value h/2π, where
h = 6.6261 10
−34
J s (3.21)
is Planck’s constant. Somewhat confusingly, the notation [u, v] is convention-
ally reserved for the commutator uv − v u in quantum mechanics. We will use
[u, v]
quantum
to denote the quantum Poisson bracket. Thus,
[u, v]
quantum
=
[u, v]
i ¯h
. (3.22)
It is easily demonstrated that the quantum mechanical Poisson bracket, as defined
above, satisfies all of the relations (3.8)–(3.14).
The strong analogy we have found between the classical Poisson bracket,
defined in Eq. (3.3), and the quantum mechanical Poisson bracket, defined in
Eq. (3.22), leads us to make the assumption that the quantum mechanical bracket
has the same value as the corresponding classical bracket, at least for the simplest
cases. In other words, we are assuming that Eqs. (3.4)–(3.6) hold for quantum
mechanical as well as classical Poisson brackets. This argument yields the funda-
mental commutation relations
[q
i
, q
j
] = 0, (3.23)
[p
i
, p
j
] = 0, (3.24)
[q
i
, p
j
] = i ¯hδ
ij
. (3.25)
These results provide us with the basis for calculating commutation relations be-
tween general dynamical variables. For instance, if two dynamical variables, ξ
36
3.3 Wave-functions 3 POSITION AND MOMENTUM
and η, can both be written as a power series in the q
i
and p
i
, then repeated
application of Eqs. (3.8)–(3.13) allows [ξ, η] to be expressed in terms of the fun-
damental commutation relations (3.23)–(3.25).
Equations (3.23)–(3.25) provide the foundation for the analogy between quan-
tum mechanics and classical mechanics. Note that the classical result (that every-
thing commutes) is obtained in the limit ¯h → 0. Thus, classical mechanics can be
regarded as the limiting case of quantum mechanics when ¯h goes to zero. In classi-
cal mechanics, each pair of generalized coordinate and its conjugate momentum,
q
i
and p
i
, correspond to a different classical degree of freedom of the system. It is
clear from Eqs. (3.23)–(3.25) that in quantum mechanics the dynamical variables
corresponding to different degrees of freedom all commute. It is only those variables
corresponding to the same degree of freedom which may fail to commute.
3.3 Wave-functions
Consider a simple system with one classical degree of freedom, which corre-
sponds to the Cartesian coordinate x. Suppose that x is free to take any value
(e.g., x could be the position of a free particle). The classical dynamical vari-
able x is represented in quantum mechanics as a linear Hermitian operator which
is also called x. Moreover, the operator x possesses eigenvalues x

lying in the
continuous range −∞ < x

< +∞ (since the eigenvalues correspond to all the
possible results of a measurement of x). We can span ket space using the suit-
ably normalized eigenkets of x. An eigenket corresponding to the eigenvalue x

is denoted |x

`. Moreover, [see Eq. (2.85)]
'x

|x

` = δ(x

−x

). (3.26)
The eigenkets satisfy the extremely useful relation [see Eq. (2.86)]
¸
+∞
−∞
dx

|x

`'x

| = 1. (3.27)
This formula expresses the fact that the eigenkets are complete, mutually orthog-
onal, and suitably normalized.
37
3.3 Wave-functions 3 POSITION AND MOMENTUM
A state ket |A` (which represents a general state A of the system) can be
expressed as a linear superposition of the eigenkets of the position operator using
Eq. (3.27). Thus,
|A` =
¸
+∞
−∞
dx

'x

|A`|x

` (3.28)
The quantity 'x

|A` is a complex function of the position eigenvalue x

. We can
write
'x

|A` = ψ
A
(x

). (3.29)
Here, ψ
A
(x

) is the famous wave-function of quantum mechanics. Note that state
A is completely specified by its wave-function ψ
A
(x

) [since the wave-function
can be used to reconstruct the state ket |A` using Eq. (3.28)]. It is clear that
the wave-function of state A is simply the collection of the weights of the cor-
responding state ket |A`, when it is expanded in terms of the eigenkets of the
position operator. Recall, from Sect. 2.10, that the probability of a measurement
of a dynamical variable ξ yielding the result ξ

when the system is in state A is
given by |'ξ

|A`|
2
, assuming that the eigenvalues of ξ are discrete. This result is
easily generalized to dynamical variables possessing continuous eigenvalues. In
fact, the probability of a measurement of x yielding a result lying in the range
x

to x

+ dx

when the system is in a state |A` is |'x

|A`|
2
dx

. In other words,
the probability of a measurement of position yielding a result in the range x

to
x

+dx

when the wave-function of the system is ψ
A
(x

) is
P(x

, dx

) = |ψ
A
(x

)|
2
dx

. (3.30)
This formula is only valid if the state ket |A` is properly normalized: i.e., if
'A|A` = 1. The corresponding normalization for the wave-function is
¸
+∞
−∞

A
(x

)|
2
dx

= 1. (3.31)
Consider a second state B represented by a state ket |B` and a wave-function
ψ
B
(x

). The inner product 'B|A` can be written
'B|A` =
¸
+∞
−∞
dx

'B|x

`'x

|A` =
¸
+∞
−∞
ψ

B
(x

) ψ

A
(x

) dx

, (3.32)
38
3.4 Schr¨ odinger’s representation - I 3 POSITION AND MOMENTUM
where use has been made of Eqs. (3.27) and (3.29). Thus, the inner product of
two states is related to the overlap integral of their wave-functions.
Consider a general function f(x) of the observable x [e.g., f(x) = x
2
]. If |B` =
f(x)|A` then it follows that
ψ
B
(x

) = 'x

|f(x)
¸
+∞
−∞
dx

ψ
A
(x

)|x

`
=
¸
+∞
−∞
dx

f(x

) ψ
A
(x

)'x

|x

`, (3.33)
giving
ψ
B
(x

) = f(x

) ψ
A
(x

), (3.34)
where use has been made of Eq. (3.26). Here, f(x

) is the same function of the
position eigenvalue x

that f(x) is of the position operator x: i.e., if f(x) = x
2
then
f(x

) = x
2
. It follows, from the above result, that a general state ket |A` can be
written
|A` = ψ
A
(x)`, (3.35)
where ψ
A
(x) is the same function of the operator x that the wave-function ψ
A
(x

)
is of the position eigenvalue x

, and the ket ` has the wave-function ψ(x

) = 1.
The ket ` is termed the standard ket. The dual of the standard ket is termed the
standard bra, and is denoted '. It is easily seen that


A
(x)
DC
←→ψ
A
(x)`. (3.36)
Note, finally, that ψ
A
(x)` is often shortened to ψ
A
`, leaving the dependence on
the position operator x tacitly understood.
3.4 Schr¨ odinger’s representation - I
Consider the simple system described in the previous section. A general state ket
can be written ψ(x)`, where ψ(x) is a general function of the position operator x,
and ψ(x

) is the associated wave-function. Consider the ket whose wave-function
39
3.4 Schr¨ odinger’s representation - I 3 POSITION AND MOMENTUM
is dψ(x

)/dx

. This ket is denoted dψ/dx`. The new ket is clearly a linear func-
tion of the original ket, so we can think of it as the result of some linear operator
acting on ψ`. Let us denote this operator d/dx. It follows that
d
dx
ψ` =

dx
`. (3.37)
Any linear operator which acts on ket vectors can also act on bra vectors.
Consider d/dx acting on a general bra 'φ(x). According to Eq. (2.34), the bra
'φd/dx satisfies


d
dx

ψ` = 'φ

d
dx
ψ`

. (3.38)
Making use of Eqs. (3.27) and (3.29), we can write
¸
+∞
−∞

d
dx
|x

` dx

ψ(x

) =
¸
+∞
−∞
φ(x

) dx

dψ(x

)
dx

. (3.39)
The right-hand side can be transformed via integration by parts to give
¸
+∞
−∞

d
dx
|x

` dx

ψ(x

) = −
¸
+∞
−∞
dφ(x

)
dx

dx

ψ(x

), (3.40)
assuming that the contributions from the limits of integration vanish. It follows
that

d
dx
|x

` = −
dφ(x

)
dx

, (3.41)
which implies

d
dx
= −'

dx
. (3.42)
The neglect of contributions from the limits of integration in Eq. (3.40) is rea-
sonable because physical wave-functions are square-integrable [see Eq. (3.31)].
Note that
d
dx
ψ` =

dx
`
DC
←→'


dx
= −'ψ

d
dx
, (3.43)
where use has been made of Eq. (3.42). It follows, by comparison with Eqs. (2.35)
and (3.36), that

d
dx


= −
d
dx
. (3.44)
40
3.4 Schr¨ odinger’s representation - I 3 POSITION AND MOMENTUM
Thus, d/dx is an anti-Hermitian operator.
Let us evaluate the commutation relation between the operators x and d/dx.
We have
d
dx
x ψ` =
d(x ψ)
dx
` = x
d
dx
ψ` +ψ`. (3.45)
Since this holds for any ket ψ`, it follows that
d
dx
x −x
d
dx
= 1. (3.46)
Let p be the momentumconjugate to x (for the simple systemunder consideration
p is a straight-forward linear momentum). According to Eq. (3.25), x and p
satisfy the commutation relation
x p −px = i ¯h. (3.47)
It can be seen, by comparison with Eq. (3.46), that the Hermitian operator
−i ¯hd/dx satisfies the same commutation relation with x that p does. The most
general conclusion which may be drawn from a comparison of Eqs. (3.46) and
(3.47) is that
p = −i ¯h
d
dx
+f(x), (3.48)
since (as is easily demonstrated) a general function f(x) of the position operator
automatically commutes with x.
We have chosen to normalize the eigenkets and eigenbras of the position oper-
ator so that they satisfy the normalization condition (3.26). However, this choice
of normalization does not uniquely determine the eigenkets and eigenbras. Sup-
pose that we transform to a new set of eigenbras which are related to the old set
via
'x

|
new
= e
i γ

'x

|
old
, (3.49)
where γ

≡ γ(x

) is a real function of x

. This transformation amounts to a
rearrangement of the relative phases of the eigenbras. The new normalization
condition is
'x

|x

`
new
= 'x

|e
i γ

e
−i γ

|x

`
old
= e
i (γ

−γ

)
'x

|x

`
old
= e
i (γ

−γ

)
δ(x

−x

) = δ(x

−x

). (3.50)
41
3.4 Schr¨ odinger’s representation - I 3 POSITION AND MOMENTUM
Thus, the new eigenbras satisfy the same normalization condition as the old
eigenbras.
By definition, the standard ket ` satisfies 'x

|` = 1. It follows from Eq. (3.49)
that the new standard ket is related to the old standard ket via
`
new
= e
−i γ
`
old
, (3.51)
where γ ≡ γ(x) is a real function of the position operator x. The dual of the
above equation yields the transformation rule for the standard bra,
'
new
= '
old
e
i γ
. (3.52)
The transformation rule for a general operator A follows from Eqs. (3.51) and
(3.52), plus the requirement that the triple product 'A` remain invariant (this
must be the case, otherwise the probability of a measurement yielding a certain
result would depend on the choice of eigenbras). Thus,
A
new
= e
−i γ
A
old
e
i γ
. (3.53)
Of course, if A commutes with x then A is invariant under the transformation. In
fact, d/dx is the only operator (we know of) which does not commute with x, so
Eq. (3.53) yields

d
dx

new
= e
−i γ
d
dx
e
i γ
=
d
dx
+ i

dx
, (3.54)
where the subscript “old” is taken as read. It follows, from Eq. (3.48), that the
momentum operator p can be written
p = −i ¯h

d
dx

new
− ¯h

dx
+f(x). (3.55)
Thus, the special choice
¯hγ(x) =
¸
x
f(x) dx (3.56)
yields
p = −i ¯h

d
dx

new
. (3.57)
42
3.5 Schr¨ odinger’s representation - II 3 POSITION AND MOMENTUM
Equation (3.56) fixes γ to within an arbitrary additive constant: i.e., the special
eigenkets and eigenbras for which Eq. (3.57) is true are determined to within an
arbitrary common phase-factor.
In conclusion, it is possible to find a set of basis eigenkets and eigenbras of
the position operator x which satisfy the normalization condition (3.26), and for
which the momentum conjugate to x can be represented as the operator
p = −i ¯h
d
dx
. (3.58)
A general state ket is written ψ(x)`, where the standard ket ` satisfies 'x

|` =
1, and where ψ(x

) = 'x

|ψ(x)` is the wave-function. This scheme of things is
known as Schr¨ odinger’s representation, and is the basis of wave mechanics.
3.5 Schr¨ odinger’s representation - II
In the preceding sections, we have developed Schr¨ odinger’s representation for
the case of a single operator x corresponding to a classical Cartesian coordinate.
However, this scheme can easily be extended. Consider a system with N general-
ized coordinates, q
1
q
N
, which can all be simultaneously measured. These are
represented as N commuting operators, q
1
q
N
, each with a continuous range
of eigenvalues, q

1
q

N
. Ket space is conveniently spanned by the simultaneous
eigenkets of q
1
q
N
, which are denoted |q

1
q

N
`. These eigenkets must form
a complete set, otherwise the q
1
q
N
would not be simultaneously observable.
The orthogonality condition for the eigenkets [i.e., the generalization of Eq. (3.26)]
is
'q

1
q

N
|q

1
q

N
` = δ(q

1
−q

1
) δ(q

2
−q

2
) δ(q

N
−q

N
). (3.59)
The completeness condition [i.e., the generalization of Eq. (3.27)] is
¸
+∞
−∞

¸
+∞
−∞
dq

1
dq

N
|q

1
q

N
`'q

1
q

N
| = 1. (3.60)
The standard ket ` is defined such that
'q

1
q

N
|` = 1. (3.61)
43
3.5 Schr¨ odinger’s representation - II 3 POSITION AND MOMENTUM
The standard bra ' is the dual of the standard ket. A general state ket is written
ψ(q
1
q
N
)`. (3.62)
The associated wave-function is
ψ(q

1
q

N
) = 'q

1
q

N
|ψ`. (3.63)
Likewise, a general state bra is written
'φ(q
1
q
N
), (3.64)
where
φ(q

1
q

N
) = 'φ|q

1
q

N
`. (3.65)
The probability of an observation of the system finding the first coordinate in the
range q

1
to q

1
+dq

1
, the second coordinate in the range q

2
to q

2
+dq

2
, etc., is
P(q

1
q

N
; dq

1
dq

N
) = |ψ(q

1
q

N
)|
2
dq

1
dq

N
. (3.66)
Finally, the normalization condition for a physical wave-function is
¸
+∞
−∞

¸
+∞
−∞
|ψ(q

1
q

N
)|
2
dq

1
dq

N
= 1. (3.67)
The N linear operators ∂/∂q
i
(where i runs from 1 to N) are defined

∂q
i
ψ` =
∂ψ
∂q
i
`. (3.68)
These linear operators can also act on bras (provided the associated wave-functions
are square integrable) in accordance with [see Eq. (3.42)]


∂q
i
= −'
∂φ
∂q
i
. (3.69)
Corresponding to Eq. (3.46), we can derive the commutation relations

∂q
i
q
j
−q
j

∂q
i
= δ
ij
. (3.70)
44
3.5 Schr¨ odinger’s representation - II 3 POSITION AND MOMENTUM
It is also clear that

∂q
i

∂q
j
ψ` =

2
ψ
∂q
i
∂q
j
` =

∂q
j

∂q
i
ψ`, (3.71)
showing that

∂q
i

∂q
j
=

∂q
j

∂q
i
. (3.72)
It can be seen, by comparison with Eqs. (3.23)–(3.25), that the linear oper-
ators −i ¯h∂/∂q
i
satisfy the same commutation relations with the q’s and with
each other that the p’s do. The most general conclusion we can draw from this
coincidence of commutation relations is (see Dirac)
p
i
= −i ¯h

∂q
i
+
∂F(q
1
q
N
)
∂q
i
. (3.73)
However, the function F can be transformed away via a suitable readjustment of
the phases of the basis eigenkets (see Sect. 3.4, and Dirac). Thus, we can always
construct a set of simultaneous eigenkets of q
1
q
N
for which
p
i
= −i ¯h

∂q
i
. (3.74)
This is the generalized Schr¨ odinger representation.
It follows from Eqs. (3.61), (3.68), and (3.74) that
p
i
` = 0. (3.75)
Thus, the standard ket in Schr¨ odinger’s representation is a simultaneous eigenket
of all the momentum operators belonging to the eigenvalue zero. Note that
'q

1
q

N
|

∂q
i
ψ` = 'q

1
q

N
|
∂ψ
∂q
i
` =
∂ψ(q

1
q

N
)
∂q

i
=

∂q

i
'q

1
q

N
|ψ`. (3.76)
Hence,
'q

1
q

N
|

∂q
i
=

∂q

i
'q

1
q

N
|, (3.77)
so that
'q

1
q

N
|p
i
= −i ¯h

∂q

i
'q

1
q

N
|. (3.78)
45
3.6 The momentum representation 3 POSITION AND MOMENTUM
The dual of the above equation gives
p
i
|q

1
q

N
` = i ¯h

∂q

i
|q

1
q

N
`. (3.79)
3.6 The momentum representation
Consider a system with one degree of freedom, describable in terms of a coordi-
nate x and its conjugate momentum p, both of which have a continuous range
of eigenvalues. We have seen that it is possible to represent the system in terms
of the eigenkets of x. This is termed Schr¨ odinger’s representation. However, it is
also possible to represent the system in terms of the eigenkets of p.
Consider the eigenkets of p which belong to the eigenvalues p

. These are
denoted |p

`. The orthogonality relation for the momentum eigenkets is
'p

|p

` = δ(p

−p

), (3.80)
and the corresponding completeness relation is
¸
+∞
−∞
dp

|p

`'p

| = 1. (3.81)
A general state ket can be written
φ(p)` (3.82)
where the standard ket ` satisfies
'p

|` = 1. (3.83)
Note that the standard ket in this representation is quite different to that in
Schr¨ odinger’s representation. The momentum space wave-function φ(p

) sat-
isfies
φ(p

) = 'p

|φ`. (3.84)
The probability that a measurement of the momentum yields a result lying in the
range p

to p

+dp

is given by
P(p

, dp

) = |φ(p

)|
2
dp

. (3.85)
46
3.6 The momentum representation 3 POSITION AND MOMENTUM
Finally, the normalization condition for a physical momentumspace wave-function
is
¸
+∞
−∞
|φ(p

)|
2
dp

= 1. (3.86)
The fundamental commutation relations (3.23)–(3.25) exhibit a particular
symmetry between coordinates and their conjugate momenta. If all the coor-
dinates are transformed into their conjugate momenta, and vice versa, and i is
then replaced by −i, the commutation relations are unchanged. It follows from
this symmetry that we can always choose the eigenkets of p in such a manner
that the coordinate x can be represented as (see Sect. 3.4)
x = i ¯h
d
dp
. (3.87)
This is termed the momentum representation.
The above result is easily generalized to a system with more than one degree
of freedom. Suppose the system is specified by N coordinates, q
1
q
N
, and
N conjugate momenta, p
1
p
N
. Then, in the momentum representation, the
coordinates can be written as
q
i
= i ¯h

∂p
i
. (3.88)
We also have
q
i
` = 0, (3.89)
and
'p

1
p

N
|q
i
= i ¯h

∂p

i
'p

1
p

N
|. (3.90)
The momentum representation is less useful than Schr¨ odinger’s representa-
tion for a very simple reason. The energy operator (i.e., the Hamiltonian) of
most simple systems takes the form of a sum of quadratic terms in the momenta
(i.e., the kinetic energy) plus a complicated function of the coordinates (i.e., the
potential energy). In Schr¨ odinger’s representation, the eigenvalue problem for
the energy translates into a second-order differential equation in the coordinates,
with a complicated potential function. In the momentum representation, the
47
3.7 The uncertainty relation 3 POSITION AND MOMENTUM
problem transforms into a high-order differential equation in the momenta, with
a quadratic potential. With the mathematical tools at our disposal, we are far bet-
ter able to solve the former type of problem than the latter. Hence, Schr¨ odinger’s
representation is generally more useful than the momentum representation.
3.7 The uncertainty relation
How is a momentum space wave-function related to the corresponding coordi-
nate space wave-function? To answer this question, let us consider the represen-
tative 'x

|p

` of the momentum eigenkets |p

` in Schr¨ odinger’s representation for
a system with a single degree of freedom. This representative satisfies
p

'x

|p

` = 'x

|p|p

` = −i ¯h
d
dx

'x

|p

`, (3.91)
where use has been made of Eq. (3.78) (for the case of a system with one degree
of freedom). The solution of the above differential equation is
'x

|p

` = c

exp(i p

x

/¯h), (3.92)
where c

= c

(p

). It is easily demonstrated that
'p

|p

` =
¸
+∞
−∞
'p

|x

` dx

'x

|p

` = c

c

¸

−∞
exp[−i (p

−p

) x

/¯h] dx

. (3.93)
The well-known mathematical result
¸
+∞
−∞
exp(i ax) dx = 2πδ(a), (3.94)
yields
'p

|p

` = |c

|
2
hδ(p

−p

). (3.95)
This is consistent with Eq. (3.80), provided that c

= h
−1/2
. Thus,
'x

|p

` = h
−1/2
exp(i p

x

/¯h). (3.96)
48
3.7 The uncertainty relation 3 POSITION AND MOMENTUM
Consider a general state ket |A` whose coordinate wave-function is ψ(x

), and
whose momentum wave-function is Ψ(p

). In other words,
ψ(x

) = 'x

|A`, (3.97)
Ψ(p

) = 'p

|A`. (3.98)
It is easily demonstrated that
ψ(x

) =
¸
+∞
−∞
dp

'x

|p

`'p

|A`
=
1
h
1/2
¸
+∞
−∞
Ψ(p

) exp(i p

x

/¯h) dp

(3.99)
and
Ψ(p

) =
¸
+∞
−∞
dx

'p

|x

`'x

|A`
=
1
h
1/2
¸
+∞
−∞
ψ(x

) exp(−i p

x

/¯h) dx

, (3.100)
where use has been made of Eqs. (3.27), (3.81), (3.94), and (3.96). Clearly, the
momentum space wave-function is the Fourier transform of the coordinate space
wave-function.
Consider a state whose coordinate space wave-function is a wave-packet. In
other words, the wave-function only has non-negligible amplitude in some spa-
tially localized region of extent ∆x. As is well-know, the Fourier transform of a
wave-packet fills up a wave-number band of approximate extent δk ∼ 1/∆x. Note
that in Eq. (3.99) the role of the wave-number k is played by the quantity p

/¯h. It
follows that the momentum space wave-function corresponding to a wave-packet
in coordinate space extends over a range of momenta ∆p ∼ ¯h/∆x. Clearly, a mea-
surement of x is almost certain to give a result lying in a range of width ∆x.
Likewise, measurement of p is almost certain to yield a result lying in a range of
width ∆p. The product of these two uncertainties is
∆x ∆p ∼ ¯h. (3.101)
This result is called Heisenberg’s uncertainty principle.
49
3.8 Displacement operators 3 POSITION AND MOMENTUM
Actually, it is possible to write Heisenberg’s uncertainty principle more exactly
by making use of Eq. (2.83) and the commutation relation (3.47). We obtain
'(∆x)
2
`'(∆p)
2
` ≥
¯h
2
4
(3.102)
for any general state. It is easily demonstrated that the minimum uncertainty
states, for which the equality sign holds in the above relation, correspond to
Gaussian wave-packets in both coordinate and momentum space.
3.8 Displacement operators
Consider a system with one degree of freedom corresponding to the Cartesian
coordinate x. Suppose that we displace this system some distance along the x-
axis. We could imagine that the system is on wheels, and we just give it a little
push. The final state of the system is completely determined by its initial state,
together with the direction and magnitude of the displacement. Note that the
type of displacement we are considering is one in which everything to do with the
system is displaced. So, if the system is subject to an external potential, then the
potential must be displaced.
The situation is not so clear with state kets. The final state of the system
only determines the direction of the displaced state ket. Even if we adopt the
convention that all state kets have unit norms, the final ket is still not completely
determined, since it can be multiplied by a constant phase-factor. However, we
know that the superposition relations between states remain invariant under the
displacement. This follows because the superposition relations have a physical
significance which is unaffected by a displacement of the system. Thus, if
|R` = |A` + |B` (3.103)
in the undisplaced system, and the displacement causes ket |R` to transform to
ket |Rd`, etc., then in the displaced system we have
|Rd` = |Ad` + |Bd`. (3.104)
50
3.8 Displacement operators 3 POSITION AND MOMENTUM
Incidentally, this determines the displaced kets to within a single arbitrary phase-
factor to be multiplied into all of them. The displaced kets cannot be multiplied
by individual phase-factors, because this would wreck the superposition relations.
Since Eq. (3.104) holds in the displaced system whenever Eq. (3.103) holds in
the undisplaced system, it follows that the displaced ket |Rd` must be the result
of some linear operator acting on the undisplaced ket |R`. In other words,
|Rd` = D|R`, (3.105)
where D an operator which depends only on the nature of the displacement. The
arbitrary phase-factor by which all displaced kets may be multiplied results in D
being undetermined to an arbitrary multiplicative constant of modulus unity.
We now adopt the ansatz that any combination of bras, kets, and dynamical
variables which possesses a physical significance is invariant under a displace-
ment of the system. The normalization condition
'A|A` = 1 (3.106)
for a state ket |A` certainly has a physical significance. Thus, we must have
'Ad|Ad` = 1. (3.107)
Now, |Ad` = D|A` and 'Ad| = 'A|D

, so
'A|D

D|A` = 1. (3.108)
Since this must hold for any state ket |A`, it follows that
D

D = 1. (3.109)
Hence, the displacement operator is unitary. Note that the above relation implies
that
|A` = D

|Ad`. (3.110)
The equation
v |A` = |B`, (3.111)
51
3.8 Displacement operators 3 POSITION AND MOMENTUM
where the operator v represents a dynamical variable, has some physical signifi-
cance. Thus, we require that
v
d
|Ad` = |Bd`, (3.112)
where v
d
is the displaced operator. It follows that
v
d
|Ad` = D|B` = Dv |A` = Dv D

|Ad`. (3.113)
Since this is true for any ket |Ad`, we have
v
d
= Dv D

. (3.114)
Note that the arbitrary numerical factor in D does not affect either of the results
(3.109) and (3.114).
Suppose, now, that the system is displaced an infinitesimal distance δx along
the x-axis. We expect that the displaced ket |Ad` should approach the undisplaced
ket |A` in the limit as δx →0. Thus, we expect the limit
lim
δx→0
|Ad` − |A`
δx
= lim
δx→0
D−1
δx
|A` (3.115)
to exist. Let
d
x
= lim
δx→0
D−1
δx
, (3.116)
where d
x
is denoted the displacement operator along the x-axis. The fact that D
can be replaced by Dexp(i γ), where γ is a real phase-angle, implies that d
x
can
be replaced by
lim
δx→0
Dexp(i γ) −1
δx
= lim
δx→0
D−1 + i γ
δx
= d
x
+ i a
x
, (3.117)
where a
x
is the limit of γ/δx. We have assumed, as seems reasonable, that γ tends
to zero as δx → 0. It is clear that the displacement operator is undetermined to
an arbitrary imaginary additive constant.
For small δx, we have
D = 1 +δx d
x
. (3.118)
52
3.8 Displacement operators 3 POSITION AND MOMENTUM
It follows from Eq. (3.109) that
(1 +δx d

x
)(1 +δx d
x
) = 1. (3.119)
Neglecting order (δx)
2
, we obtain
d

x
+d
x
= 0. (3.120)
Thus, the displacement operator is anti-Hermitian. Substituting into Eq. (3.114),
and again neglecting order (δx)
2
, we find that
v
d
= (1 +δx d
x
) v (1 −δx d
x
) = v +δx (d
x
v −v d
x
), (3.121)
which implies
lim
δx→0
v
d
−v
δx
= d
x
v −v d
x
. (3.122)
Let us consider a specific example. Suppose that a state has a wave-function
ψ(x

). If the system is displaced a distance δx along the x-axis then the new
wave-function is ψ(x

− δx) (i.e., the same shape shifted in the x-direction by a
distance δx). Actually, the new wave-function can be multiplied by an arbitrary
number of modulus unity. It can be seen that the new wave-function is obtained
from the old wave-function according to the prescription x

→x

−δx. Thus,
x
d
= x −δx. (3.123)
A comparison with Eq. (3.122), using x = v, yields
d
x
x −x d
x
= −1. (3.124)
It follows that i ¯hd
x
obeys the same commutation relation with x that p
x
, the
momentum conjugate to x, does [see Eq. (3.25)]. The most general conclusion
we can draw from this observation is that
p
x
= i ¯hd
x
+f(x), (3.125)
where f is Hermitian (since p
x
is Hermitian). However, the fact that d
x
is unde-
termined to an arbitrary additive imaginary constant (which could be a function
of x) enables us to transform the function f out of the above equation, leaving
p
x
= i ¯hd
x
. (3.126)
53
3.8 Displacement operators 3 POSITION AND MOMENTUM
Thus, the displacement operator in the x-direction is proportional to the momen-
tum conjugate to x. We say that p
x
is the generator of translations along the
x-axis.
A finite translation along the x-axis can be constructed from a series of very
many infinitesimal translations. Thus, the operator D(∆x) which translates the
system a distance ∆x along the x-axis is written
D(∆x) = lim
N→∞

1 − i
∆x
N
p
x
¯h

N
, (3.127)
where use has been made of Eqs. (3.118) and (3.126). It follows that
D(∆x) = exp(−i p
x
∆x/¯h) . (3.128)
The unitary nature of the operator is now clearly apparent.
We can also construct displacement operators which translate the system along
the y- and z-axes. Note that a displacement a distance ∆x along the x-axis com-
mutes with a displacement a distance ∆y along the y-axis. In other words, if the
system is moved ∆x along the x-axis, and then ∆y along the y-axis then it ends
up in the same state as if it were moved ∆y along the y-axis, and then ∆x along
the x-axis. The fact that translations in independent directions commute is clearly
associated with the fact that the conjugate momentum operators associated with
these directions also commute [see Eqs. (3.24) and (3.128)].
54
4 QUANTUM DYNAMICS
4 Quantum dynamics
4.1 Schr¨ odinger’s equations of motion
Up to now, we have only considered systems at one particular instant of time. Let
us now investigate how quantum mechanical systems evolve with time.
Consider a system in a state A which evolves in time. At time t the state of the
system is represented by the ket |At`. The label A is needed to distinguish the
ket from any other ket (|Bt`, say) which is evolving in time. The label t is needed
to distinguish the different states of the system at different times.
The final state of the system at time t is completely determined by its initial
state at time t
0
plus the time interval t − t
0
(assuming that the system is left
undisturbed during this time interval). However, the final state only determines
the direction of the final state ket. Even if we adopt the convention that all state
kets have unit norms, the final ket is still not completely determined, since it
can be multiplied by an arbitrary phase-factor. However, we expect that if a
superposition relation holds for certain states at time t
0
then the same relation
should hold between the corresponding time-evolved states at time t, assuming
that the system is left undisturbed between times t
0
and t. In other words, if
|Rt
0
` = |At
0
` + |Bt
0
` (4.1)
for any three kets, then we should have
|Rt` = |At` + |Bt`. (4.2)
This rule determines the time-evolved kets to within a single arbitrary phase-
factor to be multiplied into all of them. The evolved kets cannot be multiplied by
individual phase-factors, since this would invalidate the superposition relation at
later times.
According to Eqs. (4.1) and (4.2), the final ket |Rt` depends linearly on the
initial ket |Rt
0
`. Thus, the final ket can be regarded as the result of some linear
operator acting on the initial ket: , i.e.,
|Rt` = T|Rt
0
`, (4.3)
55
4.1 Schr¨ odinger’s equations of motion 4 QUANTUM DYNAMICS
where T is a linear operator which depends only on the times t and t
0
. The
arbitrary phase-factor by which all time evolved kets may be multiplied results
in T(t, t
0
) being undetermined to an arbitrary multiplicative constant of modulus
unity.
Since we have adopted a convention in which the norm of any state ket is
unity, it make sense to define the time evolution operator T in such a manner
that it preserves the length of any ket upon which it acts (i.e., if a ket is prop-
erly normalized at time t then it will remain normalized at all subsequent times
t > t
0
). This is always possible, since the length of a ket possesses no physical
significance. Thus, we require that
'At
0
|At
0
` = 'At|At` (4.4)
for any ket A, which immediately yields
T

T = 1. (4.5)
Hence, the time evolution operator T is a unitary operator.
Up to now, the time evolution operator T looks very much like the spatial
displacement operator D introduced in the previous section. However, there are
some important differences between time evolution and spatial displacement.
In general, we do expect the expectation value of some observable ξ to evolve
with time, even if the system is left in a state of undisturbed motion (after all,
time evolution has no meaning unless something observable changes with time).
The triple product 'A|ξ|A` can evolve either because the ket |A` evolves and the
operator ξ stays constant, the ket |A` stays constant and the operator ξ evolves,
or both the ket |A` and the operator ξ evolve. Since we are already committed to
evolving state kets, according to Eq. (4.3), let us assume that the time evolution
operator T can be chosen in such a manner that the operators representing the
dynamical variables of the system do not evolve in time (unless they contain some
specific time dependence).
We expect, from physical continuity, that as t → t
0
then |At` → |At
0
` for any
ket A. Thus, the limit
lim
t→t
0
|At` − |At
0
`
t −t
0
= lim
t→t
0
T −1
t −t
0
|At
0
` (4.6)
56
4.1 Schr¨ odinger’s equations of motion 4 QUANTUM DYNAMICS
should exist. Note that this limit is simply the derivative of |At
0
` with respect to
t
0
. Let
τ(t
0
) = lim
t→t
0
T(t, t
0
) −1
t −t
0
. (4.7)
It is easily demonstrated from Eq. (4.5) that τ is anti-Hermitian: i.e.,
τ

+τ = 0. (4.8)
The fact that T can be replaced by T exp(i γ) (where γ is real) implies that τ is
undetermined to an arbitrary imaginary additive constant (see previous section).
Let us define the Hermitian operator H(t
0
) = i ¯hτ. This operator is undetermined
to an arbitrary real additive constant. It follows from Eqs. (4.6) and (4.7) that
i ¯h
d|At
0
`
dt
0
= i ¯h lim
t→t
0
|At` − |At
0
`
t −t
0
= i ¯hτ(t
0
)|At
0
` = H(t
0
)|At
0
`. (4.9)
When written for general t this equation becomes
i ¯h
d|At`
dt
= H(t)|At`. (4.10)
Equation (4.10) gives the general law for the time evolution of a state ket in
a scheme in which the operators representing the dynamical variables remain
fixed. This equation is denoted Schr¨ odinger’s equation of motion. It involves a
Hermitian operator H(t) which is, presumably, a characteristic of the dynamical
system under investigation.
We saw, in the previous section, that if the operator D(x, x
0
) displaces the
system along the x-axis from x
0
to x then
p
x
= i ¯h lim
x→x
0
D(x, x
0
) −1
x −x
0
, (4.11)
where p
x
is the operator representing the momentum conjugate to x. We now
have that if the operator T(t, t
0
) evolves the system in time from t
0
to t then
H(t
0
) = i ¯h lim
t→t
0
T(t, t
0
) −1
t −t
0
. (4.12)
57
4.1 Schr¨ odinger’s equations of motion 4 QUANTUM DYNAMICS
Thus, the dynamical variable corresponding to the operator H stands to time t as
the momentum p
x
stands to the coordinate x. By analogy with classical physics,
this suggests that H(t) is the operator representing the total energy of the system.
(Recall that, in classical physics, if the equations of motion of a system are in-
variant under an x-displacement of the system then this implies that the system
conserves momentum in the x-direction. Likewise, if the equations of motion are
invariant under a temporal displacement then this implies that the system con-
serves energy.) The operator H(t) is usually called the Hamiltonian of the system.
The fact that the Hamiltonian is undetermined to an arbitrary real additive con-
stant is related to the well-known phenomenon that energy is undetermined to
an arbitrary additive constant in physics (i.e., the zero of potential energy is not
well-defined).
Substituting |At` = T|At
0
` into Eq. (4.10) yields
i ¯h
dT
dt
|At
0
` = H(t) T|At
0
`. (4.13)
Since this must hold for any initial state |At
0
` we conclude that
i ¯h
dT
dt
= H(t) T. (4.14)
This equation can be integrated to give
T(t, t
0
) = exp

¸
−i
¸
t
t
0
H(t

) dt

/¯h
¸

, (4.15)
where use has been made of Eqs. (4.5) and (4.6). (Here, we assume that Hamil-
tonian operators evaluated at different times commute with one another). It is
now clear how the fact that H is undetermined to an arbitrary real additive con-
stant leaves T undetermined to a phase-factor. Note that, in the above analysis,
time is not an operator (we cannot observe time, as such), it is just a parameter
(or, more accurately, a continuous label). Since we are only dealing with non-
relativistic quantum mechanics, the fact that position is an operator, but time is
only a label, need not worry us unduly. In relativistic quantum mechanics, time
and space coordinates are treated on the same footing by relegating position from
being an operator to being just a label.
58
4.2 Heisenberg’s equations of motion 4 QUANTUM DYNAMICS
4.2 Heisenberg’s equations of motion
We have seen that in Schr¨ odinger’s scheme the dynamical variables of the system
remain fixed during a period of undisturbed motion, whereas the state kets evolve
according to Eq. (4.10). However, this is not the only way in which to represent
the time evolution of the system.
Suppose that a general state ket A is subject to the transformation
|A
t
` = T

(t, t
0
)|A`. (4.16)
This is a time-dependent transformation, since the operator T(t, t
0
) obviously
depends on time. The subscript t is used to remind us that the transformation is
time-dependent. The time evolution of the transformed state ket is given by
|A
t
t` = T

(t, t
0
)|At` = T

(t, t
0
) T(t, t
0
)|At
0
` = |A
t
t
0
`, (4.17)
where use has been made of Eqs. (4.3), (4.5), and the fact that T(t
0
, t
0
) = 1.
Clearly, the transformed state ket does not evolve in time. Thus, the transforma-
tion (4.16) has the effect of bringing all kets representing states of undisturbed
motion of the system to rest.
The transformation must also be applied to bras. The dual of Eq. (4.16) yields
'A
t
| = 'A|T. (4.18)
The transformation rule for a general observable v is obtained from the require-
ment that the expectation value 'A|v|A` should remain invariant. It is easily seen
that
v
t
= T

v T. (4.19)
Thus, a dynamical variable, which corresponds to a fixed linear operator in Schr¨ o-
dinger’s scheme, corresponds to a moving linear operator in this new scheme. It
is clear that the transformation (4.16) leads us to a scenario in which the state
of the system is represented by a fixed vector, and the dynamical variables are
represented by moving linear operators. This is termed the Heisenberg picture, as
opposed to the Schr¨ odinger picture, which is outlined in Sect. 4.1.
59
4.2 Heisenberg’s equations of motion 4 QUANTUM DYNAMICS
Consider a dynamical variable v corresponding to a fixed linear operator in the
Schr¨ odinger picture. According to Eq. (4.19), we can write
T v
t
= v T. (4.20)
Differentiation with respect to time yields
dT
dt
v
t
+T
dv
t
dt
= v
dT
dt
. (4.21)
With the help of Eq. (4.14), this reduces to
HT v
t
+ i ¯hT
dv
t
dt
= v HT, (4.22)
or
i ¯h
dv
t
dt
= T

v HT −T

HT v
t
= v
t
H
t
−H
t
v
t
, (4.23)
where
H
t
= T

HT. (4.24)
Equation (4.23) can be written
i ¯h
dv
t
dt
= [v
t
, H
t
]. (4.25)
Equation (4.25) shows how the dynamical variables of the system evolve in
the Heisenberg picture. It is denoted Heisenberg’s equation of motion. Note that
the time-varying dynamical variables in the Heisenberg picture are usually called
Heisenberg dynamical variables to distinguish them from Schr¨ odinger dynamical
variables (i.e., the corresponding variables in the Schr¨ odinger picture), which do
not evolve in time.
According to Eq. (3.22), the Heisenberg equation of motion can be written
dv
t
dt
= [v
t
, H
t
]
quantum
, (4.26)
where [ ]
quantum
denotes the quantumPoisson bracket. Let us compare this equa-
tion with the classical time evolution equation for a general dynamical variable
v, which can be written in the form [see Eq. (3.7)]
dv
dt
= [v, H]
classical
. (4.27)
60
4.3 Ehrenfest’s theorem 4 QUANTUM DYNAMICS
Here, [ ]
classical
is the classical Poisson bracket, and H denotes the classical
Hamiltonian. The strong resemblance between Eqs. (4.26) and (4.27) provides
us with further justification for our identification of the linear operator H with
the energy of the system in quantum mechanics.
Note that if the Hamiltonian does not explicitly depend on time (i.e., the sys-
tem is not subject to some time-dependent external force) then Eq. (4.15) yields
T(t, t
0
) = exp [−i H(t −t
0
)/¯h] . (4.28)
This operator manifestly commutes with H, so
H
t
= T

HT = H. (4.29)
Furthermore, Eq. (4.25) gives
i ¯h
dH
dt
= [H, H] = 0. (4.30)
Thus, if the energy of the system has no explicit time-dependence then it is rep-
resented by the same non-time-varying operator H in both the Schr¨ odinger and
Heisenberg pictures.
Suppose that v is an observable which commutes with the Hamiltonian (and,
hence, with the time evolution operator T). It follows from Eq. (4.19) that v
t
= v.
Heisenberg’s equation of motion yields
i ¯h
dv
dt
= [v, H] = 0. (4.31)
Thus, any observable which commutes with the Hamiltonian is a constant of the mo-
tion (hence, it is represented by the same fixed operator in both the Schr¨ odinger
and Heisenberg pictures). Only those observables which do not commute with
the Hamiltonian evolve in time in the Heisenberg picture.
4.3 Ehrenfest’s theorem
We have now derived all of the basic elements of quantum mechanics. The only
thing which is lacking is some rule to determine the form of the quantum mechan-
ical Hamiltonian. For a physical system which possess a classical analogue, we
61
4.3 Ehrenfest’s theorem 4 QUANTUM DYNAMICS
generally assume that the Hamiltonian has the same form as in classical physics
(i.e., we replace the classical coordinates and conjugate momenta by the corre-
sponding quantum mechanical operators). This scheme guarantees that quantum
mechanics yields the correct classical equations of motion in the classical limit.
Whenever an ambiguity arises because of non-commuting observables, this can
usually be resolved by requiring the Hamiltonian H to be an Hermitian oper-
ator. For instance, we would write the quantum mechanical analogue of the
classical product x p, appearing in the Hamiltonian, as the Hermitian product
(1/2)(x p + px). When the system in question has no classical analogue then we
are reduced to guessing a form for H which reproduces the observed behaviour
of the system.
Consider a three-dimensional systemcharacterized by three independent Carte-
sian position coordinates x
i
(where i runs from 1 to 3), with three corresponding
conjugate momenta p
i
. These are represented by three commuting position op-
erators x
i
, and three commuting momentum operators p
i
, respectively. The com-
mutation relations satisfied by the position and momentum operators are [see
Eq. (3.25)]
[x
i
, p
j
] = i ¯hδ
ij
. (4.32)
It is helpful to denote (x
1
, x
2
, x
3
) as x and (p
1
, p
2
, p
3
) as p. The following useful
formulae,
[x
i
, F(p)] = i ¯h
∂F
∂p
i
, (4.33)
[p
i
, G(x)] = −i ¯h
∂G
∂x
i
, (4.34)
where F and G are functions which can be expanded as power series, are easily
proved using the fundamental commutation relations Eq. (4.32).
Let us now consider the three-dimensional motion of a free particle of mass m
in the Heisenberg picture. The Hamiltonian is assumed to have the same form as
in classical physics:
H =
p
2
2 m
=
1
2 m
3
¸
i=1
p
2
i
. (4.35)
62
4.3 Ehrenfest’s theorem 4 QUANTUM DYNAMICS
In the following, all dynamical variables are assumed to be Heisenberg dynamical
variables, although we will omit the subscript t for the sake of clarity. The time
evolution of the momentum operator p
i
follows from Heisenberg’s equation of
motion (4.25). We find that
dp
i
dt
=
1
i ¯h
[p
i
, H] = 0, (4.36)
since p
i
automatically commutes with any function of the momentum operators.
Thus, for a free particle the momentum operators are constants of the motion,
which means that p
i
(t) = p
i
(0) at all times t (for i is 1 to 3). The time evolution
of the position operator x
i
is given by
dx
i
dt
=
1
i ¯h
[x
i
, H] =
1
i ¯h
1
2 m
i ¯h

∂p
i

¸
¸
3
¸
j=1
p
2
j
¸

=
p
i
m
=
p
i
(0)
m
, (4.37)
where use has been made of Eq. (4.33). It follows that
x
i
(t) = x
i
(0) +

p
i
(0)
m
¸
¸
t, (4.38)
which is analogous to the equation of motion of a classical free particle. Note
that even though
[x
i
(0), x
j
(0)] = 0, (4.39)
where the position operators are evaluated at equal times, the x
i
do not commute
when evaluated at different times. For instance,
[x
i
(t), x
i
(0)] =

p
i
(0) t
m
, x
i
(0)
¸
¸
=
−i ¯ht
m
. (4.40)
Combining the above commutation relation with the uncertainty relation (2.83)
yields
'(∆x
i
)
2
`
t
'(∆x
i
)
2
`
t=0

¯h
2
t
2
4 m
2
. (4.41)
This result implies that even if a particle is well-localized at t = 0, its position
becomes progressively more uncertain with time. This conclusion can also be
obtained by studying the propagation of wave-packets in wave mechanics.
63
4.3 Ehrenfest’s theorem 4 QUANTUM DYNAMICS
Let us now add a potential V(x) to our free particle Hamiltonian:
H =
p
2
2 m
+V(x). (4.42)
Here, V is some function of the x
i
operators. Heisenberg’s equation of motion
gives
dp
i
dt
=
1
i ¯h
[p
i
, V(x)] = −
∂V(x)
∂x
i
, (4.43)
where use has been made of Eq. (4.34). On the other hand, the result
dx
i
dt
=
p
i
m
(4.44)
still holds, because the x
i
all commute with the new term V(x) in the Hamilto-
nian. We can use the Heisenberg equation of motion a second time to deduce
that
d
2
x
i
dt
2
=
1
i ¯h
¸
dx
i
dt
, H
¸
=
1
i ¯h
¸
p
i
m
, H
¸
=
1
m
dp
i
dt
= −
1
m
∂V(x)
∂x
i
. (4.45)
In vectorial form, this equation becomes
m
d
2
x
dt
2
=
dp
dt
= −∇V(x). (4.46)
This is the quantum mechanical equivalent of Newton’s second law of motion.
Taking the expectation values of both sides with respect to a Heisenberg state ket
that does not move with time, we obtain
m
d
2
'x`
dt
2
=
d'p`
dt
= −'∇V(x)`. (4.47)
This is known as Ehrenfest’s theorem. When written in terms of expectation
values, this result is independent of whether we are using the Heisenberg or
Schr¨ odinger picture. In contrast, the operator equation (4.46) only holds if x and
p are understood to be Heisenberg dynamical variables. Note that Eq. (4.47) has
no dependence on ¯h. In fact, it guarantees to us that the centre of a wave-packet
always moves like a classical particle.
64
4.4 Schr¨ odinger’s wave-equation 4 QUANTUM DYNAMICS
4.4 Schr¨ odinger’s wave-equation
Let us nowconsider the motion of a particle in three dimensions in the Schr¨ odinger
picture. The fixed dynamical variables of the system are the position operators
x ≡ (x
1
, x
2
, x
3
), and the momentum operators p ≡ (p
1
, p
2
, p
3
). The state of the
system is represented as some time evolving ket |At`.
Let |x

` represent a simultaneous eigenket of the position operators belonging
to the eigenvalues x

≡ (x

1
, x

2
, x

3
). Note that, since the position operators are
fixed in the Schr¨ odinger picture, we do not expect the |x

` to evolve in time. The
wave-function of the system at time t is defined
ψ(x

, t) = 'x

|At`. (4.48)
The Hamiltonian of the system is taken to be
H =
p
2
2 m
+V(x). (4.49)
Schr¨ odinger’s equation of motion (4.10) yields
i ¯h
∂'x

|At`
∂t
= 'x

|H|At`, (4.50)
where use has been made of the time independence of the |x

`. We adopt Schr¨ od-
inger’s representation in which the momentum conjugate to the position operator
x
i
is written [see Eq. (3.74)]
p
i
= −i ¯h

∂x
i
. (4.51)
Thus,

x

p
2
2 m

At
¸
= −

¸
¯h
2
2 m
¸


2
'x

|At`, (4.52)
where use has been made of Eq. (3.78). Here, ∇

≡ (∂/∂x

, ∂/∂y

, ∂/∂z

) denotes
the gradient operator written in terms of the position eigenvalues. We can also
write
'x

|V(x) = V(x

)'x

|, (4.53)
65
4.4 Schr¨ odinger’s wave-equation 4 QUANTUM DYNAMICS
where V(x

) is a scalar function of the position eigenvalues. Combining Eqs. (4.49),
(4.50), (4.52), and (4.53), we obtain
i ¯h
∂'x

|At`
∂t
= −

¸
¯h
2
2 m
¸


2
'x

|At` +V(x

)'x

|At`, (4.54)
which can also be written
i ¯h
∂ψ(x

, t)
∂t
= −

¸
¯h
2
2 m
¸


2
ψ(x

, t) +V(x

) ψ(x

, t). (4.55)
This is Schr¨ odinger’s famous wave-equation, and is the basis of wave mechanics.
Note, however, that the wave-equation is just one of many possible representa-
tions of quantum mechanics. It just happens to give a type of equation which we
know how to solve. In deriving the wave-equation, we have chosen to represent
the system in terms of the eigenkets of the position operators, instead of those
of the momentum operators. We have also fixed the relative phases of the |x

`
according to Schr¨ odinger’s representation, so that Eq. (4.51) is valid. Finally, we
have chosen to work in the Schr¨ odinger picture, in which state kets evolve and
dynamical variables are fixed, instead of the Heisenberg picture, in which the
opposite is true.
Suppose that the ket |At` is an eigenket of the Hamiltonian belonging to the
eigenvalue H

:
H|At` = H

|At`. (4.56)
Schr¨ odinger’s equation of motion (4.10) yields
i ¯h
d|At`
dt
= H

|At`. (4.57)
This can be integrated to give
|At` = exp[−i H

(t −t
0
)/¯h]|At
0
`. (4.58)
Note that |At` only differs from |At
0
` by a phase-factor. The direction of the
vector remains fixed in ket space. This suggests that if the system is initially in an
eigenstate of the Hamiltonian then it remains in this state for ever, as long as the
66
4.4 Schr¨ odinger’s wave-equation 4 QUANTUM DYNAMICS
system is undisturbed. Such a state is called a stationary state. The wave-function
of a stationary state satisfies
ψ(x

, t) = ψ(x

, t
0
) exp[−i H

(t −t
0
)/¯h]. (4.59)
Substituting the above relation into Schr¨ odinger’s wave equation (4.55), we
obtain

¸
¯h
2
2 m
¸


2
ψ
0
(x

) + (V(x

) −E) ψ
0
(x

) = 0, (4.60)
where ψ
0
(x

) ≡ ψ(x

, t
0
), and E = H

is the energy of the system. This is
Schr¨ odinger’s time-independent wave-equation. A bound state solution of the
above equation, in which the particle is confined within a finite region of space,
satisfies the boundary condition
ψ
0
(x

) →0 as |x

| →∞. (4.61)
Such a solution is only possible if
E < lim
|x

|→∞
V(x

). (4.62)
Since it is conventional to set the potential at infinity equal to zero, the above
relation implies that bound states are equivalent to negative energy states. The
boundary condition (4.61) is sufficient to uniquely specify the solution of Eq. (4.60).
The quantity ρ(x

, t), defined by
ρ(x

, t) = |ψ(x

, t)|
2
, (4.63)
is termed the probability density. Recall, from Eq. (3.30), that the probability of
observing the particle in some volume element d
3
x

around position x

is propor-
tional to ρ(x

, t) d
3
x

. The probability is equal to ρ(x

, t) d
3
x

if the wave-function
is properly normalized, so that
¸
ρ(x

, t) d
3
x

= 1. (4.64)
Schr¨ odinger’s time-dependent wave-equation, (4.55), can easily be written in
the form of a conservation equation for the probability density:
∂ρ
∂t
+∇

j = 0. (4.65)
67
4.4 Schr¨ odinger’s wave-equation 4 QUANTUM DYNAMICS
The probability current j takes the form
j(x

, t) = −

i ¯h
2 m



ψ− (∇

ψ

) ψ] =

¯h
m

Im(ψ

ψ). (4.66)
We can integrate Eq. (4.65) over all space, using the divergence theorem, and the
boundary condition ρ →0 as |x

| →∞, to obtain

∂t
¸
ρ(x

, t) d
3
x

= 0. (4.67)
Thus, Schr¨ odinger’s wave-equation conserves probability. In particular, if the
wave-function starts off properly normalized, according to Eq. (4.64), then it
remains properly normalized at all subsequent times. It is easily demonstrated
that
¸
j(x

, t) d
3
x

=
'p`
t
m
, (4.68)
where 'p`
t
denotes the expectation value of the momentum evaluated at time t.
Clearly, the probability current is indirectly related to the particle momentum.
In deriving Eq. (4.65) we have, naturally, assumed that the potential V(x

) is
real. Suppose, however, that the potential has an imaginary component. In this
case, Eq. (4.65) generalizes to
∂ρ
∂t
+∇

j =
2 Im(V)
¯h
ρ, (4.69)
giving

∂t
¸
ρ(x

, t) d
3
x

=
2
¯h
Im
¸
V(x

) ρ(x

, t) d
3
x

. (4.70)
Thus, if Im(V) < 0 then the total probability of observing the particle anywhere
in space decreases monotonically with time. Thus, an imaginary potential can
be used to account for the disappearance of a particle. Such a potential is often
employed to model nuclear reactions in which incident particles can be absorbed
by nuclei.
The wave-function can always be written in the form
ψ(x

, t) =

ρ(x

, t) exp

i S(x

, t)
¯h
¸
¸
, (4.71)
68
4.4 Schr¨ odinger’s wave-equation 4 QUANTUM DYNAMICS
where ρ and S are both real functions. The interpretation of ρ as a probability
density has already been given. What is the interpretation of S? Note that
ψ

ψ =

ρ ∇

(

ρ) +

i
¯h

ρ∇

S. (4.72)
It follows from Eq. (4.66) that
j =
ρ ∇

S
m
. (4.73)
Thus, the gradient of the phase of the wave-function determines the direction of
the probability current. In particular, the probability current is locally normal to
the contours of the phase-function S.
Let us substitute Eq. (4.71) into Schr¨ odinger’s time-dependent wave-equation.
We obtain

1
2 m

¯h
2

2

ρ +2i ¯h∇

(

ρ)∇

S −

ρ |∇

S|
2
+ i ¯h

ρ ∇
2
S

+

ρ V
=
¸
i ¯h


ρ
∂t


ρ
∂S
∂t
¸
. (4.74)
Let us treat ¯h as a small quantity. To lowest order, Eq. (4.74) yields

∂S(x

, t)
∂t
=
1
2 m
|∇

S(x

, t)|
2
+V(x

, t) = H(x

, ∇

S, t), (4.75)
where H(x, p, t) is the Hamiltonian operator. The above equation is known as the
Hamilton-Jacobi equation, and is one of the many forms in which we can write
the equations of classical mechanics. In classical mechanics, S is the action (i.e.,
the path-integral of the Lagrangian). Thus, in the limit ¯h → 0, wave mechanics
reduces to classical mechanics. It is a good approximation to neglect the terms
involving ¯h in Eq. (4.74) provided that
¯h|∇
2
S| <|∇

S|
2
. (4.76)
Note that, according to Eq. (4.71),
¯ λ =
¯h
|∇

S|
, (4.77)
69
4.4 Schr¨ odinger’s wave-equation 4 QUANTUM DYNAMICS
where ¯ λ is the de Broglie wave-length divided by 2π. The inequality (4.76) is
equivalent to
|∇

¯ λ| <1. (4.78)
In other words, quantum mechanics reduces to classical mechanics whenever
the de Broglie wave-length is small compared to the characteristic distance over
which things (other than the quantum phase) vary. This distance is usually set by
the variation scale-length of the potential.
70
5 ANGULAR MOMENTUM
5 Angular momentum
5.1 Orbital angular momentum
Consider a particle described by the Cartesian coordinates (x, y, z) ≡ r and their
conjugate momenta (p
x
, p
y
, p
z
) ≡ p. The classical definition of the orbital angular
momentum of such a particle about the origin is L = r p, giving
L
x
= yp
z
−z p
y
, (5.1)
L
y
= z p
x
−x p
z
, (5.2)
L
z
= x p
y
−yp
x
. (5.3)
Let us assume that the operators (L
x
, L
y
, L
z
) ≡ L which represent the compo-
nents of orbital angular momentum in quantum mechanics can be defined in an
analogous manner to the corresponding components of classical angular momen-
tum. In other words, we are going to assume that the above equations specify
the angular momentum operators in terms of the position and linear momentum
operators. Note that L
x
, L
y
, and L
z
are Hermitian, so they represent things which
can, in principle, be measured. Note, also, that there is no ambiguity regard-
ing the order in which operators appear in products on the right-hand sides of
Eqs. (5.1)–(5.3), since all of the products consist of operators which commute.
The fundamental commutation relations satisfied by the position and linear
momentum operators are [see Eqs. (3.23)–(3.25)]
[x
i
, x
j
] = 0, (5.4)
[p
i
, p
j
] = 0, (5.5)
[x
i
, p
j
] = i ¯hδ
ij
, (5.6)
where i and j stand for either x, y, or z. Consider the commutator of the operators
L
x
and L
z
:
[L
x
, L
y
] = [(yp
z
−z p
y
), (z p
x
−x p
z
)] = y[p
z
, z] p
x
+x p
y
[z, p
z
]
= i ¯h(−yp
x
+x p
y
) = i ¯hL
z
. (5.7)
71
5.1 Orbital angular momentum 5 ANGULAR MOMENTUM
The cyclic permutations of the above result yield the fundamental commutation
relations satisfied by the components of an angular momentum:
[L
x
, L
y
] = i ¯hL
z
, (5.8)
[L
y
, L
z
] = i ¯hL
x
, (5.9)
[L
z
, L
x
] = i ¯hL
y
. (5.10)
These can be summed up more succinctly by writing
L L = i ¯hL. (5.11)
The three commutation relations (5.8)–(5.10) are the foundation for the whole
theory of angular momentum in quantum mechanics. Whenever we encounter
three operators having these commutation relations, we know that the dynamical
variables which they represent have identical properties to those of the compo-
nents of an angular momentum (which we are about to derive). In fact, we shall
assume that any three operators which satisfy the commutation relations (5.8)–
(5.10) represent the components of an angular momentum.
Suppose that there are N particles in the system, with angular momentum
vectors L
i
(where i runs from 1 to N). Each of these vectors satisfies Eq. (5.11),
so that
L
i
L
i
= i ¯hL
i
. (5.12)
However, we expect the angular momentum operators belonging to different par-
ticles to commute, since they represent different degrees of freedom of the sys-
tem. So, we can write
L
i
L
j
+L
j
L
i
= 0, (5.13)
for i = j. Consider the total angular momentum of the system, L =
¸
N
i=1
L
i
. It is
clear from Eqs. (5.12) and (5.13) that
L L =
N
¸
i=1
L
i

N
¸
j=1
L
j
=
N
¸
i=1
L
i
L
i
+
1
2
N
¸
i,j=1
(L
i
L
j
+L
j
L
i
)
= i ¯h
N
¸
i=1
L
i
= i ¯hL. (5.14)
72
5.1 Orbital angular momentum 5 ANGULAR MOMENTUM
Thus, the sum of two or more angular momentum vectors satisfies the same
commutation relation as a primitive angular momentum vector. In particular,
the total angular momentum of the system satisfies the commutation relation
(5.11).
The immediate conclusion which can be drawn from the commutation rela-
tions (5.8)–(5.10) is that the three components of an angular momentum vector
cannot be specified (or measured) simultaneously. In fact, once we have speci-
fied one component, the values of other two components become uncertain. It is
conventional to specify the z-component, L
z
.
Consider the magnitude squared of the angular momentum vector, L
2
≡ L
2
x
+
L
2
y
+L
2
z
. The commutator of L
2
and L
z
is written
[L
2
, L
z
] = [L
2
x
, L
z
] + [L
2
y
, L
z
] + [L
2
z
, L
z
]. (5.15)
It is easily demonstrated that
[L
2
x
, L
z
] = −i ¯h(L
x
L
y
+L
y
L
x
), (5.16)
[L
2
y
, L
z
] = +i ¯h(L
x
L
y
+L
y
L
x
), (5.17)
[L
2
z
, L
z
] = 0, (5.18)
so
[L
2
, L
z
] = 0. (5.19)
Since there is nothing special about the z-axis, we conclude that L
2
also commutes
with L
x
and L
y
. It is clear from Eqs. (5.8)–(5.10) and (5.19) that the best we can
do in quantum mechanics is to specify the magnitude of an angular momentum
vector along with one of its components (by convention, the z-component).
It is convenient to define the shift operators L
+
and L

:
L
+
= L
x
+ i L
y
, (5.20)
L

= L
x
− i L
y
. (5.21)
Note that
[L
+
, L
z
] = −¯hL
+
, (5.22)
73
5.2 Eigenvalues of angular momentum 5 ANGULAR MOMENTUM
[L

, L
z
] = +¯hL

, (5.23)
[L
+
, L

] = 2 ¯hL
z
. (5.24)
Note, also, that both shift operators commute with L
2
.
5.2 Eigenvalues of angular momentum
Suppose that the simultaneous eigenkets of L
2
and L
z
are completely specified by
two quantum numbers, l and m. These kets are denoted |l, m`. The quantum
number m is defined by
L
z
|l, m` = m¯h|l, m`. (5.25)
Thus, m is the eigenvalue of L
z
divided by ¯h. It is possible to write such an
equation because ¯h has the dimensions of angular momentum. Note that m is a
real number, since L
z
is an Hermitian operator.
We can write
L
2
|l, m` = f(l, m) ¯h
2
|l, m`, (5.26)
without loss of generality, where f(l, m) is some real dimensionless function of l
and m. Later on, we will show that f(l, m) = l (l +1). Now,
'l, m|L
2
−L
2
z
|l, m` = 'l, m|f(l, m) ¯h
2
−m
2
¯h
2
|l, m` = [f(l, m) −m
2
]¯h
2
, (5.27)
assuming that the |l, m` have unit norms. However,
'l, m|L
2
−L
2
z
|l, m` = 'l, m|L
2
x
+L
2
y
|l, m`
= 'l, m|L
2
x
|l, m` +'l, m|L
2
y
|l, m`. (5.28)
It is easily demonstrated that
'A|ξ
2
|A` ≥ 0, (5.29)
where |A` is a general ket, and ξ is an Hermitian operator. The proof follows
from the observation that
'A|ξ
2
|A` = 'A|ξ

ξ|A` = 'B|B`, (5.30)
74
5.2 Eigenvalues of angular momentum 5 ANGULAR MOMENTUM
where |B` = ξ|A`, plus the fact that 'B|B` ≥ 0 for a general ket |B` [see Eq. (2.21)].
It follows from Eqs. (5.27)–(5.29) that
m
2
≤ f(l, m). (5.31)
Consider the effect of the shift operator L
+
on the eigenket |l, m`. It is easily
demonstrated that
L
2
(L
+
|l, m`) = ¯h
2
f(l, m) (L
+
|l, m`), (5.32)
where use has been made of Eq. (5.26), plus the fact that L
2
and L
z
commute. It
follows that the ket L
+
|l, m` has the same eigenvalue of L
2
as the ket |l, m`. Thus,
the shift operator L
+
does not affect the magnitude of the angular momentum of
any eigenket it acts upon. Note that
L
z
L
+
|l, m` = (L
+
L
z
+ [L
z
, L
+
])|l, m` = (L
+
L
z
+ ¯hL
+
)|l, m`
= (m+1) ¯hL
+
|l, m`, (5.33)
where use has been made of Eq. (5.22). The above equation implies that L
+
|l, m`
is proportional to |l, m+1`. We can write
L
+
|l, m` = c
+
l,m
¯h|l, m+1`, (5.34)
where c
+
l,m
is a number. It is clear that when the operator L
+
acts on a simulta-
neous eigenstate of L
2
and L
z
, the eigenvalue of L
2
remains unchanged, but the
eigenvalue of L
z
is increased by ¯h. For this reason, L
+
is called a raising operator.
Using similar arguments to those given above, it is possible to demonstrate
that
L

|l, m` = c

l,m
¯h|l, m−1`. (5.35)
Hence, L

is called a lowering operator.
The shift operators step the value of m up and down by unity each time they
operate on one of the simultaneous eigenkets of L
2
and L
z
. It would appear, at
first sight, that any value of m can be obtained by applying the shift operators a
sufficient number of times. However, according to Eq. (5.31), there is a definite
upper bound to the values that m
2
can take. This bound is determined by the
75
5.2 Eigenvalues of angular momentum 5 ANGULAR MOMENTUM
eigenvalue of L
2
[see Eq. (5.26)]. It follows that there is a maximum and a
minimum possible value which m can take. Suppose that we attempt to raise
the value of m above its maximum value m
max
. Since there is no state with
m > m
max
, we must have
L
+
|l, m
max
` = |0`. (5.36)
This implies that
L

L
+
|l, m
max
` = |0`. (5.37)
However,
L

L
+
= L
2
x
+L
2
y
+ i [L
x
, L
y
] = L
2
−L
2
z
− ¯hL
z
, (5.38)
so Eq. (5.37) yields
(L
2
−L
2
z
− ¯hL
z
)|l, m
max
` = |0`. (5.39)
The above equation can be rearranged to give
L
2
|l, m
max
` = (L
2
z
+ ¯hL
z
)|l, m
max
` = m
max
(m
max
+1) ¯h
2
|l, m
max
`. (5.40)
Comparison of this equation with Eq. (5.26) yields the result
f(l, m
max
) = m
max
(m
max
+1). (5.41)
But, when L

operates on |n, m
max
` it generates |n, m
max
− 1`, |n, m
max
− 2`, etc.
Since the lowering operator does not change the eigenvalue of L
2
, all of these
states must correspond to the same value of f, namely m
max
(m
max
+1). Thus,
L
2
|l, m` = m
max
(m
max
+1) ¯h
2
|l, m`. (5.42)
At this stage, we can give the unknown quantum number l the value m
max
, with-
out loss of generality. We can also write the above equation in the form
L
2
|l, m` = l (l +1) ¯h
2
|l, m`. (5.43)
It is easily seen that
L

L
+
|l, m` = (L
2
−L
2
z
− ¯hL
z
)|l, m` = ¯h
2
[l (l +1) −m(m+1)]|l, m`. (5.44)
Thus,
'l, m|L

L
+
|l, m` = ¯h
2
[l (l +1) −m(m+1)]. (5.45)
76
5.2 Eigenvalues of angular momentum 5 ANGULAR MOMENTUM
However, we also know that
'l, m|L

L
+
|l, m` = 'l, m|L

¯hc
+
l,m
|l, m+1` = ¯h
2
c
+
l,m
c

l,m+1
, (5.46)
where use has been made of Eqs. (5.34) and (5.35). It follows that
c
+
l,m
c

l,m+1
= [l (l +1) −m(m+1)]. (5.47)
Consider the following:
'l, m|L

|l, m+1` = 'l, m|L
x
|l, m+1` − i 'l, m|L
y
|l, m+1`
= 'l, m+1|L
x
|l, m`

− i 'l, m+1|L
y
|l, m`

= ('l, m+1|L
x
|l, m` + i 'l, m+1|L
y
|l, m`)

= 'l, m+1|L
+
|l, m`

, (5.48)
where use has been made of the fact that L
x
and L
y
are Hermitian. The above
equation reduces to
c

l,m+1
= (c
+
l,m
)

(5.49)
with the aid of Eqs. (5.34) and (5.35).
Equations (5.47) and (5.49) can be combined to give
|c
+
l,m
|
2
= [l (l +1) −m(m+1)]. (5.50)
The solution of the above equation is
c
+
l,m
=

l (l +1) −m(m+1). (5.51)
Note that c
+
l,m
is undetermined to an arbitrary phase-factor [i.e., we can replace
c
+
l,m
, given above, by c
+
l,m
exp(i γ), where γ is real, and we still satisfy Eq. (5.50)].
We have made the arbitrary, but convenient, choice that c
+
l,m
is real and posi-
tive. This is equivalent to choosing the relative phases of the eigenkets |l, m`.
According to Eq. (5.49),
c

l,m
= (c
+
l,m−1
)

=

l (l +1) −m(m−1). (5.52)
We have already seen that the inequality (5.31) implies that there is a maxi-
mum and a minimum possible value of m. The maximum value of m is denoted
77
5.3 Rotation operators 5 ANGULAR MOMENTUM
l. What is the minimum value? Suppose that we try to lower the value of m
below its minimum value m
min
. Since there is no state with m < m
min
, we must
have
L

|l, m
min
` = 0. (5.53)
According to Eq. (5.35), this implies that
c

l,m
min
= 0. (5.54)
It can be seen from Eq. (5.52) that m
min
= −l. We conclude that m can take a
“ladder” of discrete values, each rung differing from its immediate neighbours by
unity. The top rung is l, and the bottom rung is −l. There are only two possible
choices for l. Either it is an integer (e.g., l = 2, which allows m to take the values
−2, −1, 0, 1, 2), or it is a half-integer (e.g., l = 3/2, which allows m to take the
values −3/2, −1/2, 1/2, 3/2). We will prove in the next section that an orbital
angular momentum can only take integer values of l.
In summary, using just the fundamental commutation relations (5.8)–(5.10),
plus the fact that L
x
, L
y
, and L
z
are Hermitian operators, we have shown that the
eigenvalues of L
2
≡ L
2
x
+L
2
y
+L
2
z
can be written l (l +1) ¯h
2
, where l is an integer,
or a half-integer. We have also demonstrated that the eigenvalues of L
z
can only
take the values m¯h, where m lies in the range −l, −l + 1, l − 1, l. Let |l, m`
denote a properly normalized simultaneous eigenket of L
2
and L
z
, belonging to
the eigenvalues l (l +1) ¯h
2
and m¯h, respectively. We have shown that
L
+
|l, m` =

l (l +1) −m(m+1) ¯h|l, m+1` (5.55)
L

|l, m` =

l (l +1) −m(m−1) ¯h|l, m−1`, (5.56)
where L
±
= L
x
±i L
y
are the so-called shift operators.
5.3 Rotation operators
Consider a particle described by the spherical polar coordinates (r, θ, ϕ). The
classical momentum conjugate to the azimuthal angle ϕ is the z-component of
angular momentum, L
z
. According to Sect. 3.5, in quantum mechanics we can
78
5.3 Rotation operators 5 ANGULAR MOMENTUM
always adopt Schr¨ odinger’s representation, for which ket space is spanned by the
simultaneous eigenkets of the position operators r, θ, and φ, and L
z
takes the
form
L
z
= −i ¯h

∂ϕ
. (5.57)
We can do this because there is nothing in Sect. 3.5 which specifies that we
have to use Cartesian coordinates—the representation (3.74) works for any well-
defined set of coordinates.
Consider an operator R(∆ϕ) which rotates the system an angle ∆ϕabout the z-
axis. This operator is very similar to the operator D(∆x), introduced in Sect. 3.8,
which translates the system a distance ∆x along the x axis. We were able to
demonstrate in Sect. 3.8 that
p
x
= i ¯h lim
δx→0
D(δx) −1
δx
, (5.58)
where p
x
is the linear momentum conjugate to x. There is nothing in our deriva-
tion of this result which specifies that x has to be a Cartesian coordinate. Thus,
the result should apply just as well to an angular coordinate. We conclude that
L
z
= i ¯h lim
δϕ→0
R(δϕ) −1
δϕ
. (5.59)
According to Eq. (5.59), we can write
R(δϕ) = 1 − i L
z
δϕ/¯h (5.60)
in the limit δϕ → 0. In other words, the angular momentum operator L
z
can be
used to rotate the system about the z-axis by an infinitesimal amount. We say
that L
z
is the generator of rotations about the z-axis. The above equation implies
that
R(∆ϕ) = lim
N→∞

1 − i
∆ϕ
N
L
z
¯h

N
, (5.61)
which reduces to
R(∆ϕ) = exp(−i L
z
∆ϕ/¯h). (5.62)
79
5.3 Rotation operators 5 ANGULAR MOMENTUM
Note that R(∆ϕ) has all of the properties we would expect of a rotation operator
R(0) = 1, (5.63)
R(∆ϕ) R(−∆ϕ) = 1, (5.64)
R(∆ϕ
1
) R(∆ϕ
2
) = R(∆ϕ
1
+∆ϕ
2
). (5.65)
Suppose that the system is in a simultaneous eigenstate of L
2
and L
z
. As before,
this state is represented by the eigenket |l, m`, where the eigenvalue of L
2
is
l (l + 1) ¯h
2
, and the eigenvalue of L
z
is m¯h. We expect the wave-function to
remain unaltered if we rotate the system 2π degrees about the z-axis. Thus,
R(2π)|l, m` = exp(−i L
z
2π/¯h)|l, m` = exp(−i 2 πm)|l, m` = |l, m`. (5.66)
We conclude that m must be an integer. This implies, from the previous section,
that l must also be an integer. Thus, orbital angular momentum can only take on
integer values of the quantum numbers l and m.
Consider the action of the rotation operator R(∆ϕ) on an eigenstate possessing
zero angular momentum about the z-axis (i.e., an m = 0 state). We have
R(∆ϕ)|l, 0` = exp(0)|l, 0` = |l, 0`. (5.67)
Thus, the eigenstate is invariant to rotations about the z-axis. Clearly, its wave-
function must be symmetric about the z-axis.
There is nothing special about the z-axis, so we can write
R
x
(∆ϕ
x
) = exp(−i L
x
∆ϕ
x
/¯h), (5.68)
R
y
(∆ϕ
y
) = exp(−i L
y
∆ϕ
y
/¯h), (5.69)
R
z
(∆ϕ
y
) = exp(−i L
z
∆ϕ
z
/¯h), (5.70)
by analogy with Eq. (5.62). Here, R
x
(∆ϕ
x
) denotes an operator which rotates the
system by an angle ∆ϕ
x
about the x-axis, etc. Suppose that the system is in an
eigenstate of zero overall orbital angular momentum (i.e., an l = 0 state). We
know that the system is also in an eigenstate of zero orbital angular momentum
about any particular axis. This follows because l = 0 implies m = 0, according
80
5.4 Eigenfunctions of orbital angular momentum 5 ANGULAR MOMENTUM
to the previous section, and we can choose the z-axis to point in any direction.
Thus,
R
x
(∆ϕ
x
)|0, 0` = exp(0)|0, 0` = |0, 0`, (5.71)
R
y
(∆ϕ
y
)|0, 0` = exp(0)|0, 0` = |0, 0`, (5.72)
R
z
(∆ϕ
z
)|0, 0` = exp(0)|0, 0` = |0, 0`. (5.73)
Clearly, a zero angular momentum state is invariant to rotations about any axis.
Such a state must possess a spherically symmetric wave-function.
Note that a rotation about the x-axis does not commute with a rotation about
the y-axis. In other words, if the system is rotated an angle ∆ϕ
x
about the x-axis,
and then ∆ϕ
y
about the y-axis, it ends up in a different state to that obtained
by rotating an angle ∆ϕ
y
about the y-axis, and then ∆ϕ
x
about the x-axis. In
quantum mechanics, this implies that R
y
(∆ϕ
y
) R
x
(∆ϕ
x
) = R
x
(∆ϕ
x
) R
y
(∆ϕ
y
), or
L
y
L
x
= L
x
L
y
, [see Eqs. (5.68)–(5.70)]. Thus, the noncommuting nature of the
angular momentum operators is a direct consequence of the fact that rotations
do not commute.
5.4 Eigenfunctions of orbital angular momentum
In Cartesian coordinates, the three components of orbital angular momentum can
be written
L
x
= −i ¯h

y

∂z
−z

∂y

, (5.74)
L
y
= −i ¯h

z

∂x
−x

∂z

, (5.75)
L
z
= −i ¯h

x

∂y
−y

∂x

, (5.76)
using the Schr¨ odinger representation. Transforming to standard spherical polar
coordinates,
x = r sinθ cos ϕ, (5.77)
81
5.4 Eigenfunctions of orbital angular momentum 5 ANGULAR MOMENTUM
y = r sinθ sinϕ, (5.78)
z = r cos θ, (5.79)
we obtain
L
x
= i ¯h

sinϕ

∂θ
+ cot θcos ϕ

∂ϕ

(5.80)
L
y
= −i ¯h

cos ϕ

∂θ
− cot θsinϕ

∂ϕ

(5.81)
L
z
= −i ¯h

∂ϕ
. (5.82)
Note that Eq. (5.82) accords with Eq. (5.57). The shift operators L
±
= L
x
± i L
y
become
L
±
= ±¯h exp(±i ϕ)


∂θ
±i cot θ

∂ϕ

. (5.83)
Now,
L
2
= L
2
x
+L
2
y
+L
2
z
= L
2
z
+ (L
+
L

+L

L
+
)/2, (5.84)
so
L
2
= −¯h
2

¸
1
sinθ

∂θ
sinθ

∂θ
+
1
sin
2
θ

2
∂ϕ
2
¸

. (5.85)
The eigenvalue problem for L
2
takes the form
L
2
ψ = λ ¯h
2
ψ, (5.86)
where ψ(r, θ, ϕ) is the wave-function, and λ is a number. Let us write
ψ(r, θ, ϕ) = R(r) Y(θ, ϕ). (5.87)
Equation (5.86) reduces to

¸
1
sinθ

∂θ
sinθ

∂θ
+
1
sin
2
θ

2
∂ϕ
2
¸

Y +λ Y = 0, (5.88)
where use has been made of Eq. (5.85). As is well-known, square integrable
solutions to this equation only exist when λ takes the values l (l + 1), where l is
an integer. These solutions are known as spherical harmonics, and can be written
Y
m
l
(θ, ϕ) =

2 l +1

(l −m)!
(l +m)!
(−1)
m
e
i mϕ
P
m
l
(cos ϕ), (5.89)
82
5.4 Eigenfunctions of orbital angular momentum 5 ANGULAR MOMENTUM
where m is a positive integer lying in the range 0 ≤ m ≤ l. Here, P
m
l
(ξ) is an
associated Legendre function satisfying the equation
d

¸
(1 −ξ
2
)
dP
m
l

¸

m
2
1 −ξ
2
P
m
l
+l (l +1) P
m
l
= 0. (5.90)
We define
Y
−m
l
= (−1)
m
(Y
m
l
)

, (5.91)
which allows m to take the negative values −l ≤ m < 0. The spherical harmonics
are orthogonal functions, and are properly normalized with respect to integration
over the entire solid angle:
¸
π
0
¸

0
Y
m∗
l
(θ, ϕ) Y
m

l
(θ, ϕ) sinθdθdϕ = δ
ll
δ
mm
. (5.92)
The spherical harmonics also form a complete set for representing general func-
tions of θ and ϕ.
By definition,
L
2
Y
m
l
= l (l +1) ¯h
2
Y
m
l
, (5.93)
where l is an integer. It follows from Eqs. (5.82) and (5.89) that
L
z
Y
m
l
= m¯hY
m
l
, (5.94)
where m is an integer lying in the range −l ≤ m ≤ l. Thus, the wave-function
ψ(r, θ, ϕ) = R(r) Y
m
l
(θ, φ), where R is a general function, has all of the expected
features of the wave-function of a simultaneous eigenstate of L
2
and L
z
belonging
to the quantum numbers l and m. The well-known formula
dP
m
l

=
1

1 −ξ
2
P
m+1
l


1 −ξ
2
P
m
l
= −
(l +m)(l −m+1)

1 −ξ
2
P
m−1
l
+

1 −ξ
2
P
m
l
(5.95)
can be combined with Eqs. (5.83) and (5.89) to give
L
+
Y
m
l
=

l (l +1) −m(m+1) ¯hY
m+1
l
, (5.96)
L

Y
m
l
=

l (l +1) −m(m−1) ¯hY
m−1
l
. (5.97)
83
5.5 Motion in a central field 5 ANGULAR MOMENTUM
These equations are equivalent to Eqs. (5.55)–(5.56). Note that a spherical har-
monic wave-function is symmetric about the z-axis (i.e., independent of ϕ) when-
ever m = 0, and is spherically symmetric whenever l = 0 (since Y
0
0
= 1/

4π).
In summary, by solving directly for the eigenfunctions of L
2
and L
z
in Schr¨ od-
inger’s representation, we have been able to reproduce all of the results of Sect. 5.2.
Nevertheless, the results of Sect. 5.2 are more general than those obtained in this
section, because they still apply when the quantum number l takes on half-integer
values.
5.5 Motion in a central field
Consider a particle of mass M moving in a spherically symmetric potential. The
Hamiltonian takes the form
H =
p
2
2 M
+V(r). (5.98)
Adopting Schr¨ odinger’s representation, we can write p = −(i/¯h)∇. Hence,
H = −
¯h
2
2 M

2
+V(r). (5.99)
When written in spherical polar coordinates, the above equation becomes
H = −
¯h
2
2 M

1
r
2

∂r
r
2

∂r
+
1
r
2
sinθ

∂θ
sinθ

∂θ
+
1
r
2
sin
2
θ

2
∂ϕ
2
¸
¸
+V(r). (5.100)
Comparing this equation with Eq. (5.85), we find that
H =
¯h
2
2 M


1
r
2

∂r
r
2

∂r
+
L
2
¯h
2
r
2
¸
¸
+V(r). (5.101)
Now, we know that the three components of angular momentum commute
with L
2
(see Sect. 5.1). We also know, from Eqs. (5.80)–(5.82), that L
x
, L
y
,
and L
z
take the form of partial derivative operators of the angular coordinates,
84
5.5 Motion in a central field 5 ANGULAR MOMENTUM
when written in terms of spherical polar coordinates using Schr¨ odinger’s repre-
sentation. It follows from Eq. (5.101) that all three components of the angular
momentum commute with the Hamiltonian:
[L, H] = 0. (5.102)
It is also easily seen that L
2
commutes with the Hamiltonian:
[L
2
, H] = 0. (5.103)
According to Sect. 4.2, the previous two equations ensure that the angular mo-
mentum L and its magnitude squared L
2
are both constants of the motion. This
is as expected for a spherically symmetric potential.
Consider the energy eigenvalue problem
Hψ = Eψ, (5.104)
where E is a number. Since L
2
and L
z
commute with each other and the Hamil-
tonian, it is always possible to represent the state of the system in terms of the
simultaneous eigenstates of L
2
, L
z
, and H. But, we already know that the most
general form for the wave-function of a simultaneous eigenstate of L
2
and L
z
is
(see previous section)
ψ(r, θ, ϕ) = R(r) Y
m
l
(θ, ϕ). (5.105)
Substituting Eq. (5.105) into Eq. (5.101), and making use of Eq. (5.93), we ob-
tain

¯h
2
2 M

¸

1
r
2
d
dr
r
2
d
dr
+
l (l +1)
r
2
¸

+V(r) −E
¸
¸
R = 0. (5.106)
This is a Sturm-Liouville equation for the function R(r). We know, from the gen-
eral properties of this type of equation, that if R(r) is required to be well-behaved
at r = 0 and as r → ∞ then solutions only exist for a discrete set of values of E.
These are the energy eigenvalues. In general, the energy eigenvalues depend on
the quantum number l, but are independent of the quantum number m.
85
5.6 Energy levels of the hydrogen atom 5 ANGULAR MOMENTUM
5.6 Energy levels of the hydrogen atom
Consider a hydrogen atom, for which the potential takes the specific form
V(r) = −
e
2

0
r
. (5.107)
The radial eigenfunction R(r) satisfies Eq. (5.106), which can be written

¯h
2
2 µ

¸

1
r
2
d
dr
r
2
d
dr
+
l (l +1)
r
2
¸


e
2

0
r
−E
¸
¸
R = 0. (5.108)
Here, µ = m
e
m
p
/(m
e
+m
p
) is the reduced mass, which takes into account the fact
that the electron (of mass m
e
) and the proton (of mass m
p
) both rotate about a
common centre, which is equivalent to a particle of mass µ rotating about a fixed
point. Let us write the product r R(r) as the function P(r). The above equation
transforms to
d
2
P
dr
2

2 µ
¯h
2

¸
l (l +1)¯h
2
2 µr
2

e
2

0
r
−E
¸

P = 0, (5.109)
which is the one-dimensional Schr¨ odinger equation for a particle of mass µ mov-
ing in the effective potential
V
eff
(r) = −
e
2

0
r
+
l (l +1) ¯h
2
2 µr
2
. (5.110)
The effective potential has a simple physical interpretation. The first part is the
attractive Coulomb potential, and the second part corresponds to the repulsive
centrifugal force.
Let
a =

−¯h
2
2 µE
, (5.111)
and y = r/a, with
P(r) = f(y) exp(−y). (5.112)
Here, it is assumed that the energy eigenvalue E is negative. Equation (5.109)
transforms to

¸
d
2
dy
2
−2
d
dy

l (l +1)
y
2
+
2 µe
2
a

0
¯h
2
y
¸

f = 0. (5.113)
86
5.6 Energy levels of the hydrogen atom 5 ANGULAR MOMENTUM
Let us look for a power-law solution of the form
f(y) =
¸
n
c
n
y
n
. (5.114)
Substituting this solution into Eq. (5.113), we obtain
¸
n
c
n

n(n −1) y
n−2
−2 ny
n−1
−l (l +1) y
n−2
+
2 µe
2
a

0
¯h
2
y
n−1
¸
= 0. (5.115)
Equating the coefficients of y
n−2
gives
c
n
[n(n −1) −l (l +1)] = c
n−1

2 (n −1) −
2 µe
2
a

0
¯h
2
¸
¸
. (5.116)
Now, the power law series (5.114) must terminate at small n, at some positive
value of n, otherwise f(y) behaves unphysically as y →0. This is only possible if
[n
min
(n
min
−1)−l (l+1)] = 0, where the first term in the series is c
n
min
y
n
min
. There
are two possibilities: n
min
= −l or n
min
= l + 1. The former predicts unphysical
behaviour of the wave-function at y = 0. Thus, we conclude that n
min
= l + 1.
Note that for an l = 0 state there is a finite probability of finding the electron at
the nucleus, whereas for an l > 0 state there is zero probability of finding the
electron at the nucleus (i.e., |ψ|
2
= 0 at r = 0, except when l = 0). Note, also,
that it is only possible to obtain sensible behaviour of the wave-function as r →0
if l is an integer.
For large values of y, the ratio of successive terms in the series (5.114) is
c
n
y
c
n−1
=
2 y
n
, (5.117)
according to Eq. (5.116). This is the same as the ratio of successive terms in the
series
¸
n
(2 y)
n
n!
, (5.118)
which converges to exp(2 y). We conclude that f(y) → exp(2 y) as y → ∞. It
follows from Eq. (5.112) that R(r) → exp(r/a)/r as r → ∞. This does not cor-
respond to physically acceptable behaviour of the wave-function, since

|ψ|
2
dV
must be finite. The only way in which we can avoid this unphysical behaviour is
87
5.6 Energy levels of the hydrogen atom 5 ANGULAR MOMENTUM
if the series (5.114) terminates at some maximum value of n. According to the
recursion relation (5.116), this is only possible if
µe
2
a

0
¯h
2
= n, (5.119)
where the last term in the series is c
n
y
n
. It follows from Eq. (5.111) that the
energy eigenvalues are quantized, and can only take the values
E = −
µe
4
32π
2

2
0
¯h
2
n
2
. (5.120)
Here, n is a positive integer which must exceed the quantum number l, otherwise
there would be no terms in the series (5.114).
It is clear that the wave-function for a hydrogen atom can be written
ψ(r, θ, ϕ) = R(r/a) Y
m
l
(θ, ϕ), (5.121)
where
a =
n4π
0
¯h
2
µe
2
= 5.3 10
−11
n meters, (5.122)
and R(x) is a well-behaved solution of the differential equation

¸
1
x
2
d
dx
x
2
d
dx

l (l +1)
x
2
+
2 n
x
−1
¸

R = 0. (5.123)
Finally, the Y
m
l
are spherical harmonics. The restrictions on the quantum numbers
are |m| ≤ l < n. Here, n is a positive integer, l is a non-negative integer, and m
is an integer.
The ground state of hydrogen corresponds to n = 1. The only permissible
values of the other quantum numbers are l = 0 and m = 0. Thus, the ground
state is a spherically symmetric, zero angular momentum state. The energy of
the ground state is
E
0
= −
µe
4
32π
2

2
0
¯h
2
= −13.6 electron volts. (5.124)
88
5.7 Spin angular momentum 5 ANGULAR MOMENTUM
The next energy level corresponds to n = 2. The other quantum numbers are
allowed to take the values l = 0, m = 0 or l = 1, m = −1, 0, 1. Thus, there are
n = 2 states with non-zero angular momentum. Note that the energy levels given
in Eq. (5.120) are independent of the quantum number l, despite the fact that l
appears in the radial eigenfunction equation (5.123). This is a special property
of a 1/r Coulomb potential.
In addition to the quantized negative energy state of the hydrogen atom, which
we have just found, there is also a continuum of unbound positive energy states.
5.7 Spin angular momentum
Up to now, we have tacitly assumed that the state of a particle in quantum me-
chanics can be completely specified by giving the wave-function ψ as a function
of the spatial coordinates x, y, and z. Unfortunately, there is a wealth of experi-
mental evidence which suggests that this simplistic approach is incomplete.
Consider an isolated system at rest, and let the eigenvalue of its total angular
momentum be j (j +1) ¯h
2
. According to the theory of orbital angular momentum
outlined in Sects. 5.4 and 5.5, there are two possibilities. For a system consisting
of a single particle, j = 0. For a system consisting of two (or more) particles, j is
a non-negative integer. However, this does not agree with observations, because
we often find systems which appear to be structureless, and yet have j = 0. Even
worse, systems where j has half-integer values abound in nature. In order to
explain this apparent discrepancy between theory and experiments, Gouldsmit
and Uhlenbeck (in 1925) introduced the concept of an internal, purely quantum
mechanical, angular momentum called spin. For a particle with spin, the total
angular momentum in the rest frame is non-vanishing.
Let us denote the three components of the spin angular momentum of a par-
ticle by the Hermitian operators (S
x
, S
y
, S
z
) ≡ S. We assume that these operators
obey the fundamental commutation relations (5.8)–(5.10) for the components of
an angular momentum. Thus, we can write
S S = i ¯hS. (5.125)
89
5.7 Spin angular momentum 5 ANGULAR MOMENTUM
We can also define the operator
S
2
= S
2
x
+S
2
y
+S
2
z
. (5.126)
According to the quite general analysis of Sect. 5.1,
[S, S
2
] = 0. (5.127)
Thus, it is possible to find simultaneous eigenstates of S
2
and S
z
. These are
denoted |s, s
z
`, where
S
z
|s, s
z
` = s
z
¯h|s, s
z
`, (5.128)
S
2
|s, s
z
` = s (s +1) ¯h
2
|s, s
z
`. (5.129)
According to the equally general analysis of Sect. 5.2, the quantum number s can,
in principle, take integer or half-integer values, and the quantum number s
z
can
only take the values s, s −1 −s +1, −s.
Spin angular momentum clearly has many properties in common with orbital
angular momentum. However, there is one vitally important difference. Spin
angular momentum operators cannot be expressed in terms of position and mo-
mentum operators, like in Eqs. (5.1)–(5.3), since this identification depends on
an analogy with classical mechanics, and the concept of spin is purely quantum
mechanical: i.e., it has no analogy in classical physics. Consequently, the re-
striction that the quantum number of the overall angular momentum must take
integer values is lifted for spin angular momentum, since this restriction (found
in Sects. 5.3 and 5.4) depends on Eqs. (5.1)–(5.3). In other words, the quantum
number s is allowed to take half-integer values.
Consider a spin one-half particle, for which
S
z
|±` = ±
¯h
2
|±`, (5.130)
S
2
|±` =
3 ¯h
2
4
|±`. (5.131)
Here, the |±` denote eigenkets of the S
z
operator corresponding to the eigen-
values ±¯h/2. These kets are orthonormal (since S
z
is an Hermitian operator),
so
'+|−` = 0. (5.132)
90
5.8 Wave-function of a spin one-half particle 5 ANGULAR MOMENTUM
They are also properly normalized and complete, so that
'+|+` = '−|−` = 1, (5.133)
and
|+`'+| + |−`'−| = 1. (5.134)
It is easily verified that the Hermitian operators defined by
S
x
=
¯h
2
( |+`'−| + |−`'+| ) , (5.135)
S
y
=
i ¯h
2
( − |+`'−| + |−`'+| ) , (5.136)
S
z
=
¯h
2
( |+`'+| − |−`'−| ) , (5.137)
satisfy the commutation relations (5.8)–(5.10) (with the L
j
replaced by the S
j
).
The operator S
2
takes the form
S
2
=
3 ¯h
2
4
. (5.138)
It is also easily demonstrated that S
2
and S
z
, defined in this manner, satisfy the
eigenvalue relations (5.130)–(5.131). Equations (5.135)–(5.138) constitute a re-
alization of the spin operators S and S
2
(for a spin one-half particle) in spin space
(i.e., that Hilbert sub-space consisting of kets which correspond to the different
spin states of the particle).
5.8 Wave-function of a spin one-half particle
The state of a spin one-half particle is represented as a vector in ket space.
Let us suppose that this space is spanned by the basis kets |x

, y

, z

, ±`. Here,
|x

, y

, z

, ±` denotes a simultaneous eigenstate of the position operators x, y, z,
and the spin operator S
z
, corresponding to the eigenvalues x

, y

, z

, and ±¯h/2,
respectively. The basis kets are assumed to satisfy the completeness relation
¸¸¸
( |x

, y

, z

, +`'x

, y

, z

, +| + |x

, y

, z

, −`'x

, y

, z

, −| ) dx

dy

dz

= 1.
(5.139)
91
5.8 Wave-function of a spin one-half particle 5 ANGULAR MOMENTUM
It is helpful to think of the ket |x

, y

, z

, +` as the product of two kets—a
position space ket |x

, y

, z

`, and a spin space ket |+`. We assume that such a
product obeys the commutative and distributive axioms of multiplication:
|x

, y

, z

`|+` = |+`|x

, y

, z

`, (5.140)
(c

|x

, y

, z

` +c

|x

, y

, z

`) |+` = c

|x

, y

, z

`|+`
+c

|x

, y

, z

`|+` (5.141)
|x

, y

, z

` (c
+
|+` +c

|−`) = c
+
|x

, y

, z

`|+`
+c

|x

, y

, z

`|−`, (5.142)
where the c’s are numbers. We can give meaning to any position space operator
(such as L
z
) acting on the product |x

, y

, z

`|+` by assuming that it operates only
on the |x

, y

, z

` factor, and commutes with the |+` factor. Similarly, we can give
a meaning to any spin operator (such as S
z
) acting on |x

, y

, z

`|+` by assuming
that it operates only on |+`, and commutes with |x

, y

, z

`. This implies that every
position space operator commutes with every spin operator. In this manner, we
can give meaning to the equation
|x

, y

, z

, ±` = |x

, y

, z

`|±` = |±`|x

, y

, z

`. (5.143)
The multiplication in the above equation is of quite a different type to any
which we have encountered previously. The ket vectors |x

, y

, z

` and |±` are
in two quite separate vector spaces, and their product |x

, y

, z

`|±` is in a third
vector space. In mathematics, the latter space is termed the product space of the
former spaces, which are termed factor spaces. The number of dimensions of a
product space is equal to the product of the number of dimensions of each of the
factor spaces. A general ket of the product space is not of the form (5.143), but
is instead a sum or integral of kets of this form.
A general state A of a spin one-half particle is represented as a ket ||A`` in the
product of the spin and position spaces. This state can be completely specified by
two wavefunctions:
ψ
+
(x

, y

, z

) = 'x

, y

, z

|'+||A``, (5.144)
ψ

(x

, y

, z

) = 'x

, y

, z

|'−||A``. (5.145)
92
5.9 Rotation operators in spin space 5 ANGULAR MOMENTUM
The probability of observing the particle in the region x

to x

+dx

, y

to y

+dy

,
and z

to z

+ dz

, with s
z
= +1/2 is |ψ
+
(x

, y

, z

)|
2
dx

dy

dz

. Likewise, the
probability of observing the particle in the region x

to x

+ dx

, y

to y

+ dy

,
and z

to z

+dz

, with s
z
= −1/2 is |ψ

(x

, y

, z

)|
2
dx

dy

dz

. The normalization
condition for the wavefunctions is
¸¸¸


+
|
2
+ |ψ

|
2

dx

dy

dz

= 1. (5.146)
5.9 Rotation operators in spin space
Let us, for the moment, forget about the spatial position of the particle, and
concentrate on its spin state. A general spin state A is represented by the ket
|A` = '+|A`|+` +'−|A`|−` (5.147)
in spin space. In Sect. 5.3, we were able to construct an operator R
z
(∆ϕ) which
rotates the system by an angle ∆ϕ about the z-axis in position space. Can we also
construct an operator T
z
(∆ϕ) which rotates the system by an angle ∆ϕ about
the z-axis in spin space? By analogy with Eq. (5.62), we would expect such an
operator to take the form
T
z
(∆ϕ) = exp(−i S
z
∆ϕ/¯h). (5.148)
Thus, after rotation, the ket |A` becomes
|A
R
` = T
z
(∆ϕ)|A`. (5.149)
To demonstrate that the operator (5.148) really does rotate the spin of the
system, let us consider its effect on 'S
x
`. Under rotation, this expectation value
changes as follows:
'S
x
` →'A
R
|S
x
|A
R
` = 'A|T

z
S
x
T
z
|A`. (5.150)
Thus, we need to compute
exp( i S
z
∆ϕ/¯h) S
x
exp(−i S
z
∆ϕ/¯h). (5.151)
93
5.9 Rotation operators in spin space 5 ANGULAR MOMENTUM
This can be achieved in two different ways.
First, we can use the explicit formula for S
x
given in Eq. (5.135). We find that
Eq. (5.151) becomes
¯h
2
exp( i S
z
∆ϕ/¯h) ( |+`'−| + |−`'+| ) exp(−i S
z
∆ϕ/¯h), (5.152)
or
¯h
2

e
i ∆ϕ/2
|+`'−| e
i ∆ϕ/2
+ e
−i ∆ϕ/2
|−`'+| e
−i ∆ϕ/2

, (5.153)
which reduces to
S
x
cos ∆ϕ−S
y
sin∆ϕ, (5.154)
where use has been made of Eqs. (5.135)–(5.137).
A second approach is to use the so called Baker-Hausdorff lemma. This takes
the form
exp( i Gλ) A exp(−i Gλ) = A+ i λ[G, A] +

¸
i
2
λ
2
2!
¸

[G, [G, A]] + (5.155)
+

i
n
λ
n
n!

[G, [G, [G, [G, A]]] ],
where G is a Hermitian operator, and λ is a real parameter. The proof of this
lemma is left as an exercise. Applying the Baker-Hausdorff lemma to Eq. (5.151),
we obtain
S
x
+

i ∆ϕ
¯h

[S
z
, S
x
] +

1
2!

i ∆ϕ
¯h

2
[S
z
, [S
z
, S
x
]] + , (5.156)
which reduces to
S
x

1 −
∆ϕ
2
2!
+
¸
¸
−S
y

ϕ−
∆ϕ
3
3!
+
¸
¸
, (5.157)
or
S
x
cos ∆ϕ−S
y
sin∆ϕ, (5.158)
where use has been made of Eq. (5.125). The second proof is more general than
the first, since it only uses the fundamental commutation relation (5.125), and is,
therefore, valid for systems with spin angular momentum higher than one-half.
94
5.9 Rotation operators in spin space 5 ANGULAR MOMENTUM
For a spin one-half system, both methods imply that
'S
x
` →'S
x
` cos ∆ϕ−'S
y
` sin∆ϕ (5.159)
under the action of the rotation operator (5.148). It is straight-forward to show
that
'S
y
` →'S
y
` cos ∆ϕ+'S
x
` sin∆ϕ. (5.160)
Furthermore,
'S
z
` →'S
z
`, (5.161)
since S
z
commutes with the rotation operator. Equations (5.159)–(5.161) demon-
strate that the operator (5.148) rotates the expectation value of S by an angle ∆ϕ
about the z-axis. In fact, the expectation value of the spin operator behaves like
a classical vector under rotation:
'S
k
` →
¸
l
R
kl
'S
l
`, (5.162)
where the R
kl
are the elements of the conventional rotation matrix for the rotation
in question. It is clear, from our second derivation of the result (5.159), that this
property is not restricted to the spin operators of a spin one-half system. In fact,
we have effectively demonstrated that
'J
k
` →
¸
l
R
kl
'J
l
`, (5.163)
where the J
k
are the generators of rotation, satisfying the fundamental commuta-
tion relation J J = i ¯hJ, and the rotation operator about the kth axis is written
R
k
(∆ϕ) = exp(−i J
k
∆ϕ/¯h).
Consider the effect of the rotation operator (5.148) on the state ket (5.147).
It is easily seen that
T
z
(∆ϕ)|A` = e
−i ∆ϕ/2
'+|A`|+` + e
i ∆ϕ/2
'−|A`|−`. (5.164)
Consider a rotation by 2π radians. We find that
|A` →T
z
(2π)|A` = −|A`. (5.165)
95
5.10 Magnetic moments 5 ANGULAR MOMENTUM
Note that a ket rotated by 2π radians differs from the original ket by a minus
sign. In fact, a rotation by 4π radians is needed to transform a ket into itself.
The minus sign does not affect the expectation value of S, since S is sandwiched
between 'A| and |A`, both of which change sign. Nevertheless, the minus sign
does give rise to observable consequences, as we shall see presently.
5.10 Magnetic moments
Consider a particle of charge q and velocity v performing a circular orbit of radius
r in the x-y plane. The charge is equivalent to a current loop of radius r in the
x-y plane carrying current I = qv/2πr. The magnetic moment µ of the loop is of
magnitude πr
2
I and is directed along the z-axis. Thus, we can write
µ =
q
2
r v, (5.166)
where r and v are the vector position and velocity of the particle, respectively.
However, we know that p = v/m, where p is the vector momentum of the parti-
cle, and m is its mass. We also know that L = rp, where L is the orbital angular
momentum. It follows that
µ =
q
2 m
L. (5.167)
Using the usual analogy between classical and quantum mechanics, we expect the
above relation to also hold between the quantum mechanical operators, µ and L,
which represent magnetic moment and orbital angular momentum, respectively.
This is indeed found to the the case.
Does spin angular momentum also give rise to a contribution to the magnetic
moment of a charged particle? The answer is “yes”. In fact, relativistic quantum
mechanics actually predicts that a charged particle possessing spin should also
possess a magnetic moment (this was first demonstrated by Dirac). We can write
µ =
q
2 m
(L +gS) , (5.168)
where g is called the gyromagnetic ratio. For an electron this ratio is found to be
g
e
= 2

¸
1 +
1

e
2

0
¯hc
¸

. (5.169)
96
5.11 Spin precession 5 ANGULAR MOMENTUM
The factor 2 is correctly predicted by Dirac’s relativistic theory of the electron.
The small correction 1/(2π137), derived originally by Schwinger, is due to quan-
tum field effects. We shall ignore this correction in the following, so
µ · −
e
2 m
e
(L +2 S) (5.170)
for an electron (here, e > 0).
5.11 Spin precession
The Hamiltonian for an electron at rest in a z-directed magnetic field, B = B ^z, is
H = −µB =

e
m
e

SB = ωS
z
, (5.171)
where
ω =
e B
m
e
. (5.172)
According to Eq. (4.28), the time evolution operator for this system is
T(t, 0) = exp(−i Ht/¯h) = exp(−i S
z
ωt/¯h). (5.173)
It can be seen, by comparison with Eq. (5.148), that the time evolution operator
is precisely the same as the rotation operator for spin, with ∆ϕ set equal to ωt.
It is immediately clear that the Hamiltonian (5.171) causes the electron spin to
precess about the z-axis with angular frequency ω. In fact, Eqs. (5.159)–(5.161)
imply that
'S
x
`
t
= 'S
x
`
t=0
cos ωt −'S
y
`
t=0
sinωt, (5.174)
'S
y
`
t
= 'S
y
`
t=0
cos ωt +'S
x
`
t=0
sinωt, (5.175)
'S
z
`
t
= 'S
z
`
t=0
. (5.176)
The time evolution of the state ket is given by analogy with Eq. (5.164):
|A, t` = e
−i ωt/2
'+|A, 0`|+` + e
i ωt/2
'−|A, 0`|−`. (5.177)
97
5.11 Spin precession 5 ANGULAR MOMENTUM
Note that it takes time t = 4π/ω for the state ket to return to its original state. By
contrast, it only takes times t = 2π/ω for the spin vector to point in its original
direction.
We now describe an experiment to detect the minus sign in Eq. (5.165). An
almost monoenergetic beam of neutrons is split in two, sent along two different
paths, A and B, and then recombined. Path A goes through a magnetic field free
region. However, path B enters a small region where a static magnetic field is
present. As a result, a neutron state ket going along path B acquires a phase-shift
exp(∓i ωT/2) (the ∓ signs correspond to s
z
= ±1/2 states). Here, T is the time
spent in the magnetic field, and ω is the spin precession frequency
ω =
g
n
e B
m
p
. (5.178)
This frequency is defined in an analogous manner to Eq. (5.172). The gyro-
magnetic ratio for a neutron is found experimentally to be g
n
= −1.91. (The
magnetic moment of a neutron is entirely a quantum field effect). When neu-
trons from path A and path B meet they undergo interference. We expect the
observed neutron intensity in the interference region to exhibit a cos(±ωT/2+δ)
variation, where δ is the phase difference between paths A and B in the absence
of a magnetic field. In experiments, the time of flight T through the magnetic
field region is kept constant, while the field-strength B is varied. It follows that
the change in magnetic field required to produce successive maxima is
∆B =
4π¯h
e g
n
¯ λ l
, (5.179)
where l is the path-length through the magnetic field region, and ¯ λ is the de
Broglie wavelength over 2π of the neutrons. The above prediction has been ver-
ified experimentally to within a fraction of a percent. This prediction depends
crucially on the fact that it takes a 4π rotation to return a state ket to its original
state. If it only took a 2π rotation then ∆B would be half of the value given above,
which does not agree with the experimental data.
98
5.12 Pauli two-component formalism 5 ANGULAR MOMENTUM
5.12 Pauli two-component formalism
We have seen, in Sect. 5.4, that the eigenstates of orbital angular momentum
can be conveniently represented as spherical harmonics. In this representation,
the orbital angular momentum operators take the form of differential operators
involving only angular coordinates. It is conventional to represent the eigenstates
of spin angular momentum as column (or row) matrices. In this representation,
the spin angular momentum operators take the form of matrices.
The matrix representation of a spin one-half system was introduced by Pauli in
1926. Recall, from Sect. 5.9, that a general spin ket can be expressed as a linear
combination of the two eigenkets of S
z
belonging to the eigenvalues ±¯h/2. These
are denoted |±`. Let us represent these basis eigenkets as column matrices:
|+` →

¸
1
0
¸

≡ χ
+
, (5.180)
|−` →

¸
0
1
¸

≡ χ

. (5.181)
The corresponding eigenbras are represented as row matrices:
'+| → (1, 0) ≡ χ

+
, (5.182)
'−| → (0, 1) ≡ χ


. (5.183)
In this scheme, a general bra takes the form
|A` = '+|A`|+` +'−|A`|−` →

¸
'+|A`
'−|A`
¸

, (5.184)
and a general ket becomes
'A| = 'A|+`'+| +'A|−`'−| →('A|+`, 'A|−`). (5.185)
The column matrix (5.184) is called a two-component spinor, and can be written
χ ≡

¸
'+|A`
'−|A`
¸

=

¸
c
+
c

¸

= c
+
χ
+
+c

χ

, (5.186)
99
5.12 Pauli two-component formalism 5 ANGULAR MOMENTUM
where the c
±
are complex numbers. The row matrix (5.185) becomes
χ

≡ ('A|+`, 'A|−`) = (c

+
, c


) = c

+
χ

+
+c


χ


. (5.187)
Consider the ket obtained by the action of a spin operator on ket A:
|A

` = S
k
|A`. (5.188)
This ket is represented as
|A

` →

¸
'+|A

`
'−|A

`
¸

≡ χ

. (5.189)
However,
'+|A

` = '+|S
k
|+`'+|A` +'+|S
k
|−`'−|A`, (5.190)
'−|A

` = '−|S
k
|+`'+|A` +'−|S
k
|−`'−|A`, (5.191)
or

¸
'+|A

`
'−|A

`
¸

=

¸
'+|S
k
|+` '+|S
k
|−`
'−|S
k
|+` '−|S
k
|−`
¸

¸
'+|A`
'−|A`
¸

. (5.192)
It follows that we can represent the operator/ket relation (5.188) as the matrix
relation
χ

=

¯h
2

σ
k
χ, (5.193)
where the σ
k
are the matrices of the '±|S
k
|±` values divided by ¯h/2. These
matrices, which are called the Pauli matrices, can easily be evaluated using the
explicit forms for the spin operators given in Eqs. (5.135)–(5.137). We find that
σ
1
=

¸
0 1
1 0
¸

, (5.194)
σ
2
=

¸
0 −i
i 0
¸

, (5.195)
σ
3
=

¸
1 0
0 −1
¸

. (5.196)
100
5.12 Pauli two-component formalism 5 ANGULAR MOMENTUM
Here, 1, 2, and 3 refer to x, y, and z, respectively. Note that, in this scheme, we
are effectively representing the spin operators in terms of the Pauli matrices:
S
k

¯h
2

σ
k
. (5.197)
The expectation value of S
k
can be written in terms of spinors and the Pauli
matrices:
'S
k
` = 'A|S
k
|A` =
¸
±
'A|±`'±|S
k
|±`'±|A` =

¯h
2

χ

σ
k
χ. (5.198)
The fundamental commutation relation for angular momentum, Eq. (5.125),
can be combined with (5.197) to give the following commutation relation for the
Pauli matrices:
σ σ = 2 i σ. (5.199)
It is easily seen that the matrices (5.194)–(5.196) actually satisfy these relations
(i.e., σ
1
σ
2
−σ
2
σ
1
= 2 i σ
3
, plus all cyclic permutations). It is also easily seen that
the Pauli matrices satisfy the anti-commutation relations

i
, σ
j
} = 2 δ
ij
. (5.200)
Let us examine how the Pauli scheme can be extended to take into account the
position of a spin one-half particle. Recall, from Sect. 5.8, that we can represent
a general basis ket as the product of basis kets in position space and spin space:
|x

, y

, z

, ±` = |x

, y

, z

`|±` = |±`|x

, y

, z

`. (5.201)
The ket corresponding to state A is denoted ||A``, and resides in the product
space of the position and spin ket spaces. State A is completely specified by the
two wave-functions
ψ
+
(x

, y

, z

) = 'x

, y

, z

|'+||A``, (5.202)
ψ

(x

, y

, z

) = 'x

, y

, z

|'−||A``. (5.203)
Consider the operator relation
||A

`` = S
k
||A``. (5.204)
101
5.12 Pauli two-component formalism 5 ANGULAR MOMENTUM
It is easily seen that
'x

, y

, z

|'+|A

`` = '+|S
k
|+`'x

, y

, z

|'+||A``
+'+|S
k
|−`'x

, y

, z

|'−||A``, (5.205)
'x

, y

, z

|'−|A

`` = '−|S
k
|+`'x

, y

, z

|'+||A``
+'−|S
k
|−`'x

, y

, z

|'−||A``, (5.206)
where use has been made of the fact that the spin operator S
k
commutes with
the eigenbras 'x

, y

, z

|. It is fairly obvious that we can represent the operator
relation (5.204) as a matrix relation if we generalize our definition of a spinor by
writing
||A`` →

¸
ψ
+
(r

)
ψ

(r

)
¸

≡ χ, (5.207)
and so on. The components of a spinor are now wave-functions, instead of com-
plex numbers. In this scheme, the operator equation (5.204) becomes simply
χ

=

¯h
2

σ
k
χ. (5.208)
Consider the operator relation
||A

`` = p
k
||A``. (5.209)
In the Schr¨ odinger representation, we have
'x

, y

, z

|'+|A

`` = 'x

, y

, z

|p
k
'+||A``
= −i ¯h

∂x

k
'x

, y

, z

|'+||A``, (5.210)
'x

, y

, z

|'−|A

`` = 'x

, y

, z

|p
k
'−||A``
= −i ¯h

∂x

k
'x

, y

, z

|'−||A``, (5.211)
where use has been made of Eq. (3.78). The above equation reduces to

¸
ψ

+
(r

)
ψ


(r

)
¸

=

¸
−i ¯h∂ψ
+
(r

)/∂x

k
−i ¯h∂ψ

(r

)/∂x

k
¸

. (5.212)
102
5.12 Pauli two-component formalism 5 ANGULAR MOMENTUM
Thus, the operator equation (5.209) can be written
χ

= p
k
χ, (5.213)
where
p
k
→−i ¯h

∂x

k
I. (5.214)
Here, I is the 2 2 unit matrix. In fact, any position operator (e.g., p
k
or L
k
)
is represented in the Pauli scheme as some differential operator of the position
eigenvalues multiplied by the 2 2 unit matrix.
What about combinations of position and spin operators? The most commonly
occurring combination is a dot product: e.g., S L = (¯h/2) σ L. Consider the
hybrid operator σa, where a ≡ (a
x
, a
y
, a
z
) is some vector position operator. This
quantity is represented as a 2 2 matrix:
σa ≡
¸
k
a
k
σ
k
=

¸
+a
3
a
1
− i a
2
a
1
+ i a
2
−a
3
¸

. (5.215)
Since, in the Schr¨ odinger representation, a general position operator takes the
form of a differential operator in x

, y

, or z

, it is clear that the above quantity
must be regarded as a matrix differential operator which acts on spinors of the
general form (5.207). The important identity
(σa) (σb) = ab + i σ(a b) (5.216)
follows fromthe commutation and anti-commutation relations (5.199) and (5.200).
Thus,
¸
j
σ
j
a
j
¸
k
σ
k
b
k
=
¸
j
¸
k

1
2

j
, σ
k
} +
1
2

j
, σ
k
]

a
j
b
k
=
¸
j
¸
k

jk
+ i
jkl
σ
l
) a
j
b
k
= ab + i σ(a b). (5.217)
A general rotation operator in spin space is written
T(∆φ) = exp(−i Sn∆ϕ/¯h) , (5.218)
103
5.12 Pauli two-component formalism 5 ANGULAR MOMENTUM
by analogy with Eq. (5.148), where n is a unit vector pointing along the axis of
rotation, and ∆ϕ is the angle of rotation. Here, n can be regarded as a trivial
position operator. The rotation operator is represented
exp(−i Sn∆ϕ/¯h) →exp(−i σn∆ϕ/2) (5.219)
in the Pauli scheme. The term on the right-hand side of the above expression is
the exponential of a matrix. This can easily be evaluated using the Taylor series
for an exponential, plus the rules
(σn)
n
= 1 for n even, (5.220)
(σn)
n
= (σn) for n odd. (5.221)
These rules follow trivially from the identity (5.216). Thus, we can write
exp (−i σn∆ϕ/2) =

1 −
(σn)
2
2!

∆ϕ
2

2
+
(σn)
4
4!

∆ϕ
2

4
+
¸
¸
−i

(σ n)

∆ϕ
2


(σn)
3
3!

∆ϕ
2

3
+
¸
¸
= cos(∆ϕ/2) I − i sin(∆ϕ/2) σn. (5.222)
The explicit 2 2 form of this matrix is

¸
cos(∆ϕ/2) − i n
z
sin(∆ϕ/2) (−i n
x
−n
y
) sin(∆ϕ/2)
(−i n
x
+n
y
) sin(∆ϕ/2) cos(∆ϕ/2) + i n
z
sin(∆ϕ/2)
¸

. (5.223)
Rotation matrices act on spinors in much the same manner as the corresponding
rotation operators act on state kets. Thus,
χ

= exp(−i σn∆ϕ/2) χ, (5.224)
where χ

denotes the spinor obtained after rotating the spinor χ an angle ∆ϕ
about the n-axis. The Pauli matrices remain unchanged under rotations. How-
ever, the quantity χ

σ
k
χ is proportional to the expectation value of S
k
[see
Eq. (5.198)], so we would expect it to transform like a vector under rotation
(see Sect. 5.9). In fact, we require


σ
k
χ)

≡ (χ

)

σ
k
χ

=
¸
l
R
kl


σ
l
χ), (5.225)
104
5.13 Spin greater than one-half systems 5 ANGULAR MOMENTUM
where the R
kl
are the elements of a conventional rotation matrix. This is easily
demonstrated, since
exp

i σ
3
∆ϕ
2

σ
1
exp

−i σ
3
∆ϕ
2

= σ
1
cos ∆ϕ−σ
2
sin∆ϕ (5.226)
plus all cyclic permutations. The above expression is the 2 2 matrix analogue
of (see Sect. 5.9)
exp

i S
z
∆ϕ
¯h

S
x
exp

−i S
z
∆ϕ
¯h

= S
x
cos ∆ϕ−S
y
sin∆ϕ. (5.227)
The previous two formulae can both be validated using the Baker-Hausdorff
lemma, (5.156), which holds for Hermitian matrices, in addition to Hermitian
operators.
5.13 Spin greater than one-half systems
In the absence of spin, the Hamiltonian can be written as some function of the
position and momentum operators. Using the Schr¨ odinger representation, in
which p →−i ¯h∇, the energy eigenvalue problem,
H|E` = E|E`, (5.228)
can be transformed into a partial differential equation for the wave-function
ψ(r

) ≡ 'r

|E`. This function specifies the probability density for observing the
particle at a given position, r

. In general, we find
Hψ = Eψ, (5.229)
where H is now a partial differential operator. The boundary conditions (for a
bound state) are obtained from the normalization constraint
¸
|ψ|
2
dV = 1. (5.230)
This is all very familiar. However, we now know how to generalize this scheme
to deal with a spin one-half particle. Instead of representing the state of the par-
ticle by a single wave-function, we use two wave-functions. The first, ψ
+
(r

),
105
5.13 Spin greater than one-half systems 5 ANGULAR MOMENTUM
specifies the probability density of observing the particle at position r

with spin
angular momentum +¯h/2 in the z-direction. The second, ψ

(r

), specifies the
probability density of observing the particle at position r

with spin angular mo-
mentum −¯h/2 in the z-direction. In the Pauli scheme, these wave-functions are
combined into a spinor, χ, which is simply the row vector of ψ
+
and ψ

. In gen-
eral, the Hamiltonian is a function of the position, momentum, and spin opera-
tors. Adopting the Schr¨ odinger representation, and the Pauli scheme, the energy
eigenvalue problem reduces to
Hχ = Eχ, (5.231)
where χ is a spinor (i.e., a 1 2 matrix of wave-functions) and H is a 2 2 matrix
partial differential operator [see Eq. (5.215)]. The above spinor equation can
always be written out explicitly as two coupled partial differential equations for
ψ
+
and ψ

.
Suppose that the Hamiltonian has no dependence on the spin operators. In this
case, the Hamiltonian is represented as diagonal 2 2 matrix partial differential
operator in the Schr¨ odinger/Pauli scheme [see Eq. (5.214)]. In other words, the
partial differential equation for ψ
+
decouples from that for ψ

. In fact, both
equations have the same form, so there is only really one differential equation.
In this situation, the most general solution to Eq. (5.231) can be written
χ = ψ(r

)

¸
c
+
c

¸

. (5.232)
Here, ψ(r

) is determined by the solution of the differential equation, and the
c
±
are arbitrary complex numbers. The physical significance of the above ex-
pression is clear. The Hamiltonian determines the relative probabilities of finding
the particle at various different positions, but the direction of its spin angular
momentum remains undetermined.
Suppose that the Hamiltonian depends only on the spin operators. In this
case, the Hamiltonian is represented as a 2 2 matrix of complex numbers in
the Schr¨ odinger/Pauli scheme [see Eq. (5.197)], and the spinor eigenvalue equa-
tion (5.231) reduces to a straight-forward matrix eigenvalue problem. The most
106
5.13 Spin greater than one-half systems 5 ANGULAR MOMENTUM
general solution can again be written
χ = ψ(r

)

¸
c
+
c

¸

. (5.233)
Here, the ratio c
+
/c

is determined by the matrix eigenvalue problem, and the
wave-function ψ(r

) is arbitrary. Clearly, the Hamiltonian determines the direc-
tion of the particle’s spin angular momentum, but leaves its position undeter-
mined.
In general, of course, the Hamiltonian is a function of both position and
spin operators. In this case, it is not possible to decompose the spinor as in
Eqs. (5.232) and (5.233). In other words, a general Hamiltonian causes the di-
rection of the particle’s spin angular momentum to vary with position in some
specified manner. This can only be represented as a spinor involving different
wave-functions, ψ
+
and ψ

.
But, what happens if we have a spin one or a spin three-halves particle? It
turns out that we can generalize the Pauli two-component scheme in a fairly
straight-forward manner. Consider a spin-s particle: i.e., a particle for which the
eigenvalue of S
2
is s (s + 1) ¯h
2
. Here, s is either an integer, or a half-integer.
The eigenvalues of S
z
are written s
z
¯h, where s
z
is allowed to take the values
s, s − 1, , −s + 1, −s. In fact, there are 2 s + 1 distinct allowed values of s
z
.
Not surprisingly, we can represent the state of the particle by 2 s + 1 different
wave-functions, denoted ψ
s
z
(r

). Here, ψ
s
z
(r

) specifies the probability density
for observing the particle at position r

with spin angular momentum s
z
¯h in the
z-direction. More exactly,
ψ
s
z
(r

) = 'r

|'s, s
z
||A``, (5.234)
where ||A`` denotes a state ket in the product space of the position and spin op-
erators. The state of the particle can be represented more succinctly by a spinor,
χ, which is simply the 2 s + 1 component row vector of the ψ
s
z
(r

). Thus, a spin
one-half particle is represented by a two-component spinor, a spin one particle
by a three-component spinor, a spin three-halves particle by a four-component
spinor, and so on.
107
5.13 Spin greater than one-half systems 5 ANGULAR MOMENTUM
In this extended Schr¨ odinger/Pauli scheme, position space operators take the
form of diagonal (2 s + 1) (2 s + 1) matrix differential operators. Thus, we can
represent the momentum operators as [see Eq. (5.214)]
p
k
→−i ¯h

∂x

k
I, (5.235)
where I is the (2 s +1) (2 s +1) unit matrix. We represent the spin operators as
S
k
→s ¯hσ
k
, (5.236)
where the (2 s +1) (2 s +1) extended Pauli matrix σ
k
has elements

k
)
jl
=
's, j|S
k
|s, l`
s ¯h
. (5.237)
Here, j, l are integers, or half-integers, lying in the range −s to +s. But, how can
we evaluate the brackets 's, j|S
k
|s, l` and, thereby, construct the extended Pauli
matrices? In fact, it is trivial to construct the σ
z
matrix. By definition,
S
z
|s, j` = j ¯h|s, j`. (5.238)
Hence,

z
)
jl
=
's, j|S
z
|s, l`
s ¯h
=
j
s
δ
jl
, (5.239)
where use has been made of the orthonormality property of the |s, j`. Thus, σ
z
is the suitably normalized diagonal matrix of the eigenvalues of S
z
. The matrix
elements of σ
x
and σ
y
are most easily obtained by considering the shift operators,
S
±
= S
x
±i S
y
. (5.240)
We know, from Eqs. (5.55)–(5.56), that
S
+
|s, j` =

s (s +1) −j (j +1) ¯h|s, j +1`, (5.241)
S

|s, j` =

s (s +1) −j (j −1) ¯h|s, j −1`. (5.242)
It follows from Eqs. (5.237), and (5.240)–(5.242), that

x
)
jl
=

s (s +1) −j (j −1) δ
j,l+1
2 s
108
5.13 Spin greater than one-half systems 5 ANGULAR MOMENTUM
+

s (s +1) −j (j +1) δ
j,l−1
2 s
, (5.243)

y
)
jl
=

s (s +1) −j (j −1) δ
j,l+1
2 i s

s (s +1) −j (j +1) δ
j,l−1
2 i s
. (5.244)
According to Eqs. (5.239) and (5.243)–(5.244), the Pauli matrices for a spin one-
half (s = 1/2) particle are
σ
x
=

¸
0 1
1 0
¸

, (5.245)
σ
y
=

¸
0 −i
i 0
¸

, (5.246)
σ
z
=

¸
1 0
0 −1
¸

, (5.247)
as we have seen previously. For a spin one (s = 1) particle, we find that
σ
x
=
1

2

¸
¸
¸
¸
0 1 0
1 0 1
0 1 0
¸

, (5.248)
σ
y
=
1

2

¸
¸
¸
¸
0 −i 0
i 0 −i
0 i 0
¸

, (5.249)
σ
z
=

¸
¸
¸
¸
1 0 0
0 0 0
0 0 −1
¸

. (5.250)
In fact, we can now construct the Pauli matrices for a spin anything particle.
This means that we can convert the general energy eigenvalue problem for a
spin-s particle, where the Hamiltonian is some function of position and spin op-
erators, into 2 s + 1 coupled partial differential equations involving the 2 s + 1
wave-functions ψ
s
z
(r

). Unfortunately, such a system of equations is generally
too complicated to solve exactly.
109
5.14 Addition of angular momentum 5 ANGULAR MOMENTUM
5.14 Addition of angular momentum
Consider a hydrogen atom in an l = 1 state. The electron possesses orbital angu-
lar momentum of magnitude ¯h, and spin angular momentum of magnitude ¯h/2.
So, what is the total angular momentum of the system?
In order to answer this question, we are going to have to learn how to add
angular momentum operators. Let us consider the most general case. Suppose
that we have two sets of angular momentum operators, J
1
and J
2
. By definition,
these operators are Hermitian, and obey the fundamental commutation relations
J
1
J
1
= i ¯hJ
1
, (5.251)
J
2
J
2
= i ¯hJ
2
. (5.252)
We assume that the two groups of operators correspond to different degrees of
freedom of the system, so that
[J
1i
, J
2j
] = 0, (5.253)
where i, j stand for either x, y, or z. For instance, J
1
could be an orbital angular
momentum operator, and J
2
a spin angular momentum operator. Alternatively, J
1
and J
2
could be the orbital angular momentum operators of two different parti-
cles in a multi-particle system. We know, from the general properties of angular
momentum, that the eigenvalues of J
2
1
and J
2
2
can be written j
1
(j
1
+ 1) ¯h
2
and
j
2
(j
2
+1) ¯h
2
, respectively, where j
1
and j
2
are either integers, or half-integers. We
also know that the eigenvalues of J
1z
and J
2z
take the form m
1
¯h and m
2
¯h, respec-
tively, where m
1
and m
2
are numbers lying in the ranges j
1
, j
1
−1, , −j
1
+1, −j
1
and j
2
, j
2
−1, , −j
2
+1, −j
2
, respectively.
Let us define the total angular momentum operator
J = J
1
+J
2
. (5.254)
Now J is an Hermitian operator, since it is the sum of Hermitian operators. Ac-
cording to Eqs. (5.11) and (5.14), J satisfies the fundamental commutation rela-
tion
J J = i ¯hJ. (5.255)
110
5.14 Addition of angular momentum 5 ANGULAR MOMENTUM
Thus, J possesses all of the expected properties of an angular momentum opera-
tor. It follows that the eigenvalue of J
2
can be written j (j + 1) ¯h
2
, where j is an
integer, or a half-integer. The eigenvalue of J
z
takes the form m¯h, where m lies
in the range j, j −1, , −j +1, −j. At this stage, we do not know the relationship
between the quantum numbers of the total angular momentum, j and m, and
those of the individual angular momenta, j
1
, j
2
, m
1
, and m
2
.
Now
J
2
= J
2
1
+J
2
2
+2 J
1
J
2
. (5.256)
We know that
[J
2
1
, J
1i
] = 0, (5.257)
[J
2
2
, J
2i
] = 0, (5.258)
and also that all of the J
1i
operators commute with the J
2i
operators. It follows
from Eq. (5.256) that
[J
2
, J
2
1
] = [J
2
, J
2
2
] = 0. (5.259)
This implies that the quantum numbers j
1
, j
2
, and j can all be measured simulta-
neously. In other words, we can know the magnitude of the total angular momen-
tum together with the magnitudes of the component angular momenta. However,
it is clear from Eq. (5.256) that
[J
2
, J
1z
] = 0, (5.260)
[J
2
, J
2z
] = 0. (5.261)
This suggests that it is not possible to measure the quantum numbers m
1
and
m
2
simultaneously with the quantum number j. Thus, we cannot determine the
projections of the individual angular momenta along the z-axis at the same time
as the magnitude of the total angular momentum.
It is clear, from the preceding discussion, that we can form two alternate
groups of mutually commuting operators. The first group is J
2
1
, J
2
2
, J
1z
, and J
2z
.
The second group is J
2
1
, J
2
2
, J
2
, and J
z
. These two groups of operators are in-
compatible with one another. We can define simultaneous eigenkets of each
operator group. The simultaneous eigenkets of J
2
1
, J
2
2
, J
1z
, and J
2z
are denoted
111
5.14 Addition of angular momentum 5 ANGULAR MOMENTUM
|j
1
, j
2
; m
1
, m
2
`, where
J
2
1
|j
1
, j
2
; m
1
, m
2
` = j
1
(j
1
+1) ¯h
2
|j
1
, j
2
; m
1
, m
2
`, (5.262)
J
2
2
|j
1
, j
2
; m
1
, m
2
` = j
2
(j
2
+1) ¯h
2
|j
1
, j
2
; m
1
, m
2
`, (5.263)
J
1z
|j
1
, j
2
; m
1
, m
2
` = m
1
¯h|j
1
, j
2
; m
1
, m
2
`, (5.264)
J
2z
|j
1
, j
2
; m
1
, m
2
` = m
2
¯h|j
1
, j
2
; m
1
, m
2
`. (5.265)
The simultaneous eigenkets of J
2
1
, J
2
2
, J
2
and J
z
are denoted |j
1
, j
2
; j, m`, where
J
2
1
|j
1
, j
2
; j, m` = j
1
(j
1
+1) ¯h
2
|j
1
, j
2
; j, m`, (5.266)
J
2
2
|j
1
, j
2
; j, m` = j
2
(j
2
+1) ¯h
2
|j
1
, j
2
; j, m`, (5.267)
J
2
|j
1
, j
2
; j, m` = j (j +1) ¯h
2
|j
1
, j
2
; j, m`, (5.268)
J
z
|j
1
, j
2
; j, m` = m¯h|j
1
, j
2
; j, m`. (5.269)
Each set of eigenkets are complete, mutually orthogonal (for eigenkets corre-
sponding to different sets of eigenvalues), and have unit norms. Since the op-
erators J
2
1
and J
2
2
are common to both operator groups, we can assume that the
quantum numbers j
1
and j
2
are known. In other words, we can always determine
the magnitudes of the individual angular momenta. In addition, we can either
know the quantum numbers m
1
and m
2
, or the quantum numbers j and m, but
we cannot know both pairs of quantum numbers at the same time. We can write
a conventional completeness relation for both sets of eigenkets:
¸
m
1
¸
m
2
|j
1
, j
2
; m
1
, m
2
`'j
1
, j
2
; m
1
, m
2
| = 1, (5.270)
¸
j
¸
m
|j
1
, j
2
; j, m`'j
1
, j
2
; j, m| = 1, (5.271)
where the right-hand sides denote the identity operator in the ket space corre-
sponding to states of given j
1
and j
2
. The summation is over all allowed values of
m
1
, m
2
, j, and m.
The operator group J
2
1
, J
2
2
, J
2
, and J
z
is incompatible with the group J
2
1
, J
2
2
,
J
1z
, and J
2z
. This means that if the system is in a simultaneous eigenstate of the
former group then, in general, it is not in an eigenstate of the latter. In other
112
5.14 Addition of angular momentum 5 ANGULAR MOMENTUM
words, if the quantum numbers j
1
, j
2
, j, and m are known with certainty, then a
measurement of the quantum numbers m
1
and m
2
will give a range of possible
values. We can use the completeness relation (5.270) to write
|j
1
, j
2
; j, m` =
¸
m
1
¸
m
2
'j
1
, j
2
; m
1
, m
2
|j
1
, j
2
; j, m`|j
1
, j
2
; m
1
, m
2
`. (5.272)
Thus, we can write the eigenkets of the first group of operators as a weighted
sum of the eigenkets of the second set. The weights, 'j
1
, j
2
; m
1
, m
2
|j
1
, j
2
; j, m`,
are called the Clebsch-Gordon coefficients. If the system is in a state where a
measurement of J
2
1
, J
2
2
, J
2
, and J
z
is bound to give the results j
1
(j
1
+1) ¯h
2
, j
2
(j
2
+
1) ¯h
2
, j (j + 1) ¯h
2
, and j
z
¯h, respectively, then a measurement of J
1z
and J
2z
will
give the results m
1
¯h and m
2
¯h with probability |'j
1
, j
2
; m
1
, m
2
|j
1
, j
2
; j, m`|
2
.
The Clebsch-Gordon coefficients possess a number of very important proper-
ties. First, the coefficients are zero unless
m = m
1
+m
2
. (5.273)
To prove this, we note that
(J
z
−J
1z
−J
2z
)|j
1
, j
2
; j, m` = 0. (5.274)
Forming the inner product with 'j
1
, j
2
; m
1
, m
2
|, we obtain
(m−m
1
−m
2
)'j
1
, j
2
; m
1
, m
2
|j
1
, j
2
; j, m` = 0, (5.275)
which proves the assertion. Thus, the z-components of different angular mo-
menta add algebraically. So, an electron in an l = 1 state, with orbital angular
momentum ¯h, and spin angular momentum ¯h/2, projected along the z-axis, con-
stitutes a state whose total angular momentum projected along the z-axis is 3¯h/2.
What is uncertain is the magnitude of the total angular momentum.
Second, the coefficients vanish unless
|j
1
−j
2
| ≤ j ≤ j
1
+j
2
. (5.276)
We can assume, without loss of generality, that j
1
≥ j
2
. We know, fromEq. (5.273),
that for given j
1
and j
2
the largest possible value of m is j
1
+ j
2
(since j
1
is the
113
5.14 Addition of angular momentum 5 ANGULAR MOMENTUM
largest possible value of m
1
, etc.). This implies that the largest possible value of j
is j
1
+j
2
(since, by definition, the largest value of m is equal to j). Now, there are
(2 j
1
+1) allowable values of m
1
and (2 j
2
+1) allowable values of m
2
. Thus, there
are (2 j
1
+ 1) (2 j
2
+ 1) independent eigenkets, |j
1
, j
2
; m
1
, m
2
`, needed to span the
ket space corresponding to fixed j
1
and j
2
. Since the eigenkets |j
1
, j
2
; j, m` span
the same space, they must also form a set of (2 j
1
+1) (2 j
2
+1) independent kets.
In other words, there can only be (2 j
1
+ 1) (2 j
2
+ 1) distinct allowable values of
the quantum numbers j and m. For each allowed value of j, there are 2 j + 1
allowed values of m. We have already seen that the maximum allowed value of
j is j
1
+ j
2
. It is easily seen that if the minimum allowed value of j is j
1
− j
2
then
the total number of allowed values of j and m is (2 j
1
+1) (2 j
2
+1): i.e.,
j
1
+j
2
¸
j=j
1
−j
2
(2 j +1) ≡ (2 j
1
+1) (2 j
2
+1). (5.277)
This proves our assertion.
Third, the sum of the modulus squared of all of the Clebsch-Gordon coeffi-
cients is unity: i.e.,
¸
m
1
¸
m
2
|'j
1
, j
2
; m
1
, m
2
|j
1
, j
2
; j, m`|
2
= 1. (5.278)
This assertion is proved as follows:
'j
1
, j
2
; j, m|j
1
, j
2
; j, m` =
¸
m
1
¸
m
2
'j
1
, j
2
; j, m|j
1
, j
2
; m
1
, m
2
`'j
1
, j
2
; m
1
, m
2
|j
1
, j
2
; j, m`
=
¸
m
1
¸
m
2
|'j
1
, j
2
; m
1
, m
2
|j
1
, j
2
; j, m`|
2
= 1, (5.279)
where use has been made of the completeness relation (5.270).
Finally, the Clebsch-Gordon coefficients obey two recursion relations. To ob-
tain these relations we start from
J
±
|j
1
, j
2
; j, m` = (J
±
1
+J
±
2
) (5.280)

¸
m

1
¸
m

2
'j
1
, j
2
; m

1
, m

2
|j
1
, j
2
; j, m`|j
1
, j
2
; m

1
, m

2
`.
114
5.14 Addition of angular momentum 5 ANGULAR MOMENTUM
Making use of the well-known properties of the shift operators, which are speci-
fied by Eqs. (5.55)–(5.56), we obtain

j (j +1) −m(m±1) |j
1
, j
2
; j, m±1` =
¸
m

1
¸
m

2

j
1
(j
1
+1) −m

1
(m

1
±1) |j
1
, j
2
; m

1
±1, m

2
`
+

j
2
(j
2
+1) −m

2
(m

2
±1) |j
1
, j
2
; m

1
, m

2
±1`

'j
1
, j
2
; m

1
, m

2
|j
1
, j
2
; j, m`. (5.281)
Taking the inner product with 'j
1
, j
2
; m
1
, m
2
|, and making use of the orthonormal-
ity property of the basis eigenkets, we obtain the desired recursion relations:

j (j +1) −m(m±1) 'j
1
, j
2
; m
1
, m
2
|j
1
, j
2
; j, m±1` =

j
1
(j
1
+1) −m
1
(m
1
∓1) 'j
1
, j
2
; m
1
∓1, m
2
|j
1
, j
2
; j, m`
+

j
2
(j
2
+1) −m
2
(m
2
∓1) 'j
1
, j
2
; m
1
, m
2
∓1|j
1
, j
2
; j, m`. (5.282)
It is clear, from the absence of complex coupling coefficients in the above re-
lations, that we can always choose the Clebsch-Gordon coefficients to be real
numbers. This is a convenient choice, since it ensures that the inverse Clebsch-
Gordon coefficients, 'j
1
, j
2
; j, m|j
1
, j
2
; m
1
, m
2
`, are identical to the Clebsch-Gordon
coefficients. In other words,
'j
1
, j
2
; j, m|j
1
, j
2
; m
1
, m
2
` = 'j
1
, j
2
; m
1
, m
2
|j
1
, j
2
; j, m`. (5.283)
The inverse Clebsch-Gordon coefficients are the weights in the expansion of the
|j
1
, j
2
; m
1
, m
2
` in terms of the |j
1
, j
2
; j, m`:
|j
1
, j
2
; m
1
, m
2
` =
¸
j
¸
m
'j
1
, j
2
; j, m|j
1
, j
2
; m
1
, m
2
`|j
1
, j
2
; j, m`. (5.284)
It turns out that the recursion relations (5.282), together with the normal-
ization condition (5.278), are sufficient to completely determine the Clebsch-
Gordon coefficients to within an arbitrary sign (multiplied into all of the coeffi-
cients). This sign is fixed by convention. The easiest way of demonstrating this
assertion is by considering some specific examples.
115
5.14 Addition of angular momentum 5 ANGULAR MOMENTUM
Let us add the angular momentum of two spin one-half systems: e.g., two
electrons at rest. So, j
1
= j
2
= 1/2. We know, from general principles, that
|m
1
| ≤ 1/2 and |m
2
| ≤ 1/2. We also know, from Eq. (5.276), that 0 ≤ j ≤ 1,
where the allowed values of j differ by integer amounts. It follows that either
j = 0 or j = 1. Thus, two spin one-half systems can be combined to form either a
spin zero system or a spin one system. It is helpful to arrange all of the possibly
non-zero Clebsch-Gordon coefficients in a table:
m
1
m
2
1/2 1/2 ? ? ? ?
1/2 -1/2 ? ? ? ?
-1/2 1/2 ? ? ? ?
-1/2 -1/2 ? ? ? ?
j
1
=1/2 j 1 1 1 0
j
2
=1/2 m 1 0 -1 0
The box in this table corresponding to m
1
= 1/2, m
2
= 1/2, j = 1, m = 1
gives the Clebsch-Gordon coefficient '1/2, 1/2; 1/2, 1/2|1/2, 1/2; 1, 1`, or the in-
verse Clebsch-Gordon coefficient '1/2, 1/2; 1, 1|1/2, 1/2; 1/2, 1/2`. All the boxes
contain question marks because we do not know any Clebsch-Gordon coefficients
at the moment.
A Clebsch-Gordon coefficient is automatically zero unless m
1
+ m
2
= m. In
other words, the z-components of angular momentum have to add algebraically.
Many of the boxes in the above table correspond to m
1
+m
2
= m. We immediately
conclude that these boxes must contain zeroes: i.e.,
m
1
m
2
1/2 1/2 ? 0 0 0
1/2 -1/2 0 ? 0 ?
-1/2 1/2 0 ? 0 ?
-1/2 -1/2 0 0 ? 0
j
1
=1/2 j 1 1 1 0
j
2
=1/2 m 1 0 -1 0
The normalization condition (5.278) implies that the sum of the squares of all
116
5.14 Addition of angular momentum 5 ANGULAR MOMENTUM
the rows and columns of the above table must be unity. There are two rows and
two columns which only contain a single non-zero entry. We conclude that these
entries must be ±1, but we have no way of determining the signs at present.
Thus,
m
1
m
2
1/2 1/2 ±1 0 0 0
1/2 -1/2 0 ? 0 ?
-1/2 1/2 0 ? 0 ?
-1/2 -1/2 0 0 ±1 0
j
1
=1/2 j 1 1 1 0
j
2
=1/2 m 1 0 -1 0
Let us evaluate the recursion relation (5.282) for j
1
= j
2
= 1/2, with j = 1,
m = 0, m
1
= m
2
= ±1/2, taking the upper/lower sign. We find that
'1/2, −1/2|1, 0` +'−1/2, 1/2|1, 0` =

2 '1/2, 1/2|1, 1` = ±

2, (5.285)
and
'1/2, −1/2|1, 0` +'−1/2, 1/2|1, 0` =

2 '−1/2, −1/2|1, −1` = ±

2. (5.286)
Here, the j
1
and j
2
labels have been suppressed for ease of notation. We also
know that
'1/2, −1/2|1, 0`
2
+'−1/2, 1/2|1, 0`
2
= 1, (5.287)
from the normalization condition. The only real solutions to the above set of
equations are

2 '1/2, −1/2|1, 0` =

2 '−1/2, 1/2|1, 0`
= '1/2, 1/2|1, 1` = '1/2, 1/2|1, −1` = ±1. (5.288)
The choice of sign is arbitrary—the conventional choice is a positive sign. Thus,
117
5.14 Addition of angular momentum 5 ANGULAR MOMENTUM
our table now reads
m
1
m
2
1/2 1/2 1 0 0 0
1/2 -1/2 0 1/

2 0 ?
-1/2 1/2 0 1/

2 0 ?
-1/2 -1/2 0 0 1 0
j
1
=1/2 j 1 1 1 0
j
2
=1/2 m 1 0 -1 0
We could fill in the remaining unknown entries of our table by using the re-
cursion relation again. However, an easier method is to observe that the rows
and columns of the table must all be mutually orthogonal. That is, the dot prod-
uct of a row with any other row must be zero. Likewise, for the dot product of
a column with any other column. This follows because the entries in the table
give the expansion coefficients of one of our alternative sets of eigenkets in terms
of the other set, and each set of eigenkets contains mutually orthogonal vectors
with unit norms. The normalization condition tells us that the dot product of a
row or column with itself must be unity. The only way that the dot product of the
fourth column with the second column can be zero is if the unknown entries are
equal and opposite. The requirement that the dot product of the fourth column
with itself is unity tells us that the magnitudes of the unknown entries have to
be 1/

2. The unknown entries are undetermined to an arbitrary sign multiplied
into them both. Thus, the final form of our table (with the conventional choice
of arbitrary signs) is
m
1
m
2
1/2 1/2 1 0 0 0
1/2 -1/2 0 1/

2 0 1/

2
-1/2 1/2 0 1/

2 0 -1/

2
-1/2 -1/2 0 0 1 0
j
1
=1/2 j 1 1 1 0
j
2
=1/2 m 1 0 -1 0
The table can be read in one of two ways. The columns give the expansions of
118
5.14 Addition of angular momentum 5 ANGULAR MOMENTUM
the eigenstates of overall angular momentum in terms of the eigenstates of the
individual angular momenta of the two component systems. Thus, the second
column tells us that
|1, 0` =
1

2
( |1/2, −1/2` + | −1/2, 1/2` ) . (5.289)
The ket on the left-hand side is a |j, m` ket, whereas those on the right-hand side
are |m
1
, m
2
` kets. The rows give the expansions of the eigenstates of individual
angular momentum in terms of those of overall angular momentum. Thus, the
second row tells us that
|1/2, −1/2` =
1

2
( |1, 0` + |0, 0` ) . (5.290)
Here, the ket on the left-hand side is a |m
1
, m
2
` ket, whereas those on the right-
hand side are |j, m` kets.
Note that our table is really a combination of two sub-tables, one involving
j = 0 states, and one involving j = 1 states. The Clebsch-Gordon coefficients cor-
responding to two different choices of j are completely independent: i.e., there is
no recursion relation linking Clebsch-Gordon coefficients corresponding to differ-
ent values of j. Thus, for every choice of j
1
, j
2
, and j we can construct a table of
Clebsch-Gordon coefficients corresponding to the different allowed values of m
1
,
m
2
, and m (subject to the constraint that m
1
+m
2
= m). A complete knowledge
of angular momentum addition is equivalent to a knowing all possible tables of
Clebsch-Gordon coefficients. These tables are listed (for moderate values of j
1
, j
2
and j) in many standard reference books.
119
6 APPROXIMATION METHODS
6 Approximation methods
6.1 Introduction
We have developed techniques by which the general energy eigenvalue problem
can be reduced to a set of coupled partial differential equations involving various
wave-functions. Unfortunately, the number of such problems which yield exactly
soluble equations is comparatively small. Clearly, we need to develop some tech-
niques for finding approximate solutions to otherwise intractable problems.
Consider the following problem, which is very common. The Hamiltonian of a
system is written
H = H
0
+H
1
. (6.1)
Here, H
0
is a simple Hamiltonian for which we know the exact eigenvalues and
eigenstates. H
1
introduces some interesting additional physics into the problem,
but it is sufficiently complicated that when we add it to H
0
we can no longer
find the exact energy eigenvalues and eigenstates. However, H
1
can, in some
sense (which we shall specify more exactly later on), be regarded as being small
compared to H
0
. Can we find the approximate eigenvalues and eigenstates of the
modified Hamiltonian, H
0
+H
1
, by performing some sort of perturbation analysis
about the eigenvalues and eigenstates of the original Hamiltonian, H
0
? Let us
investigate.
6.2 The two-state system
Let us begin by considering time-independent perturbation theory, in which the
modification to the Hamiltonian, H
1
, has no explicit dependence on time. It is
usually assumed that the unperturbed Hamiltonian, H
0
, is also time-independent.
Consider the simplest non-trivial system, in which there are only two indepen-
dent eigenkets of the unperturbed Hamiltonian. These are denoted
H
0
|1` = E
1
|1`, (6.2)
120
6.2 The two-state system 6 APPROXIMATION METHODS
H
0
|2` = E
2
|2`. (6.3)
It is assumed that these states, and their associated eigenvalues, are known. Since
H
0
is, by definition, an Hermitian operator, its two eigenkets are orthonormal and
form a complete set. The lengths of these eigenkets are both normalized to unity.
Let us now try to solve the modified energy eigenvalue problem
(H
0
+H
1
)|E` = E|E`. (6.4)
In fact, we can solve this problem exactly. Since, the eigenkets of H
0
form a
complete set, we can write
|E` = '1|E`|1` +'2|E`|2`. (6.5)
Right-multiplication of Eq. (6.4) by '1| and '2| yields two coupled equations,
which can be written in matrix form:

¸
E
1
−E +e
11
e
12
e

12
E
2
−E +e
22
¸

¸
'1|E`
'2|E`
¸

=

¸
0
0
¸

. (6.6)
Here,
e
11
= '1|H
1
|1`, (6.7)
e
22
= '2|H
1
|2`, (6.8)
e
12
= '1|H
1
|2`. (6.9)
In the special (but common) case of a perturbing Hamiltonian whose diagonal
matrix elements (in the unperturbed eigenstates) are zero, so that
e
11
= e
22
= 0, (6.10)
the solution of Eq. (6.6) (obtained by setting the determinant of the matrix equal
to zero) is
E =
(E
1
+E
2
) ±

(E
1
−E
2
)
2
+4 |e
12
|
2
2
. (6.11)
Let us expand in the supposedly small parameter
=
|e
12
|
|E
1
−E
2
|
. (6.12)
121
6.3 Non-degenerate perturbation theory 6 APPROXIMATION METHODS
We obtain
E ·
1
2
(E
1
+E
2
) ±
1
2
(E
1
−E
2
)(1 +2
2
+ ). (6.13)
The above expression yields the modifications to the energy eigenvalues due to
the perturbing Hamiltonian:
E

1
= E
1
+
|e
12
|
2
E
1
−E
2
+ , (6.14)
E

2
= E
2

|e
12
|
2
E
1
−E
2
+ . (6.15)
Note that H
1
causes the upper eigenvalue to rise, and the lower eigenvalue to
fall. It is easily demonstrated that the modified eigenkets take the form
|1`

= |1` +
e

12
E
1
−E
2
|2` + , (6.16)
|2`

= |2` −
e
12
E
1
−E
2
|1` + . (6.17)
Thus, the modified energy eigenstates consist of one of the unperturbed eigen-
states with a slight admixture of the other. Note that the series expansion in
Eq. (6.13) only converges if 2 || < 1. This suggests that the condition for the
validity of the perturbation expansion is
|e
12
| <
|E
1
−E
2
|
2
. (6.18)
In other words, when we say that H
1
needs to be small compared to H
0
, what we
really mean is that the above inequality needs to be satisfied.
6.3 Non-degenerate perturbation theory
Let us now generalize our perturbation analysis to deal with systems possessing
more than two energy eigenstates. The energy eigenstates of the unperturbed
Hamiltonian, H
0
, are denoted
H
0
|n` = E
n
|n`, (6.19)
122
6.3 Non-degenerate perturbation theory 6 APPROXIMATION METHODS
where n runs from 1 to N. The eigenkets |n` are orthonormal, form a complete
set, and have their lengths normalized to unity. Let us now try to solve the energy
eigenvalue problem for the perturbed Hamiltonian:
(H
0
+H
1
)|E` = E|E`. (6.20)
We can express |E` as a linear superposition of the unperturbed energy eigenkets,
|E` =
¸
k
'k|E`|k`, (6.21)
where the summation is from k = 1 to N. Substituting the above equation into
Eq. (6.20), and right-multiplying by 'm|, we obtain
(E
m
+e
mm
−E)'m|E` +
¸
k=m
e
mk
'k|E` = 0, (6.22)
where
e
mk
= 'm|H
1
|k`. (6.23)
Let us now develop our perturbation expansion. We assume that
|e
mk
|
E
m
−E
k
∼ O(), (6.24)
for all m = k, where <1 is our expansion parameter. We also assume that
|e
mm
|
E
m
∼ O(), (6.25)
for all m. Let us search for a modified version of the nth unperturbed energy
eigenstate, for which
E = E
n
+O(), (6.26)
and
'n|E` = 1, (6.27)
'm|E` ∼ O(), (6.28)
for m = n. Suppose that we write out Eq. (6.22) for m = n, neglecting terms
which are O(
2
) according to our expansion scheme. We find that
(E
m
−E
n
)'m|E` +e
mn
· 0, (6.29)
123
6.4 The quadratic Stark effect 6 APPROXIMATION METHODS
giving
'm|E` · −
e
mn
E
m
−E
n
. (6.30)
Substituting the above expression into Eq. (6.22), evaluated for m = n, and
neglecting O(
3
) terms, we obtain
(E
n
+e
nn
−E) −
¸
k=n
|e
nk
|
2
E
k
−E
n
= 0. (6.31)
Thus, the modified nth energy eigenstate possesses an eigenvalue
E

n
= E
n
+e
nn
+
¸
k=n
|e
nk
|
2
E
n
−E
k
+O(
3
), (6.32)
and a eigenket
|n`

= |n` +
¸
k=n
e
kn
E
n
−E
k
|k` +O(
2
). (6.33)
Note that
'm|n`

= δ
mn
+
e

nm
E
m
−E
n
+
e
mn
E
n
−E
m
+O(
2
) = δ
mn
+O(
2
). (6.34)
Thus, the modified eigenkets remain orthonormal and properly normalized to
O(
2
).
6.4 The quadratic Stark effect
Suppose that a one-electron atom [i.e., either a hydrogen atom, or an alkali metal
atom (which possesses one valance electron orbiting outside a closed, spher-
ically symmetric shell)] is subjected to a uniform electric field in the positive
z-direction. The Hamiltonian of the system can be split into two parts. The un-
perturbed Hamiltonian,
H
0
=
p
2
2 m
e
+V(r), (6.35)
and the perturbing Hamiltonian,
H
1
= e |E| z. (6.36)
124
6.4 The quadratic Stark effect 6 APPROXIMATION METHODS
It is assumed that the unperturbed energy eigenvalues and eigenstates are
completely known. The electron spin is irrelevant in this problem (since the spin
operators all commute with H
1
), so we can ignore the spin degrees of freedom of
the system. This implies that the system possesses no degenerate energy eigen-
values. This is not true for the n = 1 energy levels of the hydrogen atom, due to
the special properties of a pure Coulomb potential. It is necessary to deal with
this case separately, because the perturbation theory presented in Sect. 6.3 breaks
down for degenerate unperturbed energy levels.
An energy eigenket of the unperturbed Hamiltonian is characterized by three
quantum numbers—the radial quantum number n, and the two angular quantum
numbers l and m (see Sect. 5.6). Let us denote such a ket |n, l, m`, and let its
energy level be E
nlm
. According to Eq. (6.32), the change in this energy level
induced by a small electric field is given by
∆E
nlm
= e |E| 'n, l, m|z|n, l, m`
+e
2
|E|
2
¸
n

,l

,m

=n,l,m
|'n, l, m|z|n,

l

, m

`|
2
E
nlm
−E
n

l

m

. (6.37)
Now, since
L
z
= x p
y
−yp
x
, (6.38)
it follows that
[L
z
, z] = 0. (6.39)
Thus,
'n, l, m|[L
z
, z]|n

, l

, m

` = 0, (6.40)
giving
(m−m

)'n, l, m|z|n

, l

, m

` = 0, (6.41)
since |n, l, m` is, by definition, an eigenstate of L
z
with eigenvalue m¯h. It is
clear, from the above relation, that the matrix element 'n, l, m|z|n

, l

, m

` is zero
unless m

= m. This is termed the selection rule for the quantum number m.
Let us now determine the selection rule for l. We have
[L
2
, z] = [L
2
x
, z] + [L
2
y
, z]
125
6.4 The quadratic Stark effect 6 APPROXIMATION METHODS
= L
x
[L
x
, z] + [L
x
, z]L
x
+L
y
[L
y
, z] + [L
y
, z]L
y
= i ¯h(−L
x
y −yL
x
+L
y
x +x L
y
)
= 2 i ¯h(L
y
x −L
x
y + i ¯hz)
= 2 i ¯h(L
y
x −yL
x
) = 2 i ¯h(x L
y
−L
x
y), (6.42)
where use has been made of Eqs. (5.1)–(5.6). Similarly,
[L
2
, y] = 2 i ¯h(L
x
z −x L
z
), (6.43)
[L
2
, x] = 2 i ¯h(yL
z
−L
y
z). (6.44)
Thus,
[L
2
, [L
2
, z]] = 2 i ¯h

L
2
, L
y
x −L
x
y + i ¯hz

= 2 i ¯h

L
y
[L
2
, x] −L
x
[L
2
, y] + i ¯h[L
2
, z]

,
= −4 ¯h
2
L
y
(yL
z
−L
y
z) +4 ¯h
2
L
x
(L
x
z −x L
z
)
−2 ¯h
2
(L
2
z −z L
2
). (6.45)
This reduces to
[L
2
, [L
2
, z]] = −¯h
2

4 (L
x
x +L
y
y +L
z
z)L
z
−4 (L
2
x
+L
2
y
+L
2
z
) z
+2 (L
2
z −z L
2
)

. (6.46)
However, it is clear from Eqs. (5.1)–(5.3) that
L
x
x +L
y
y +L
z
z = 0. (6.47)
Hence, we obtain
[L
2
, [L
2
, z]] = 2 ¯h
2
(L
2
z +z L
2
). (6.48)
Finally, the above expression expands to give
L
4
z −2 L
2
z L
2
+z L
4
−2 ¯h
2
(L
2
z +z L
2
) = 0. (6.49)
Equation (6.49) implies that
'n, l, m|L
4
z −2 L
2
z L
2
+z L
4
−2 ¯h
2
(L
2
z +z L
2
)|n

, l

, m

` = 0. (6.50)
126
6.4 The quadratic Stark effect 6 APPROXIMATION METHODS
This expression yields

l
2
(l +1)
2
−2 l (l +1) l

(l

+1) +l
2
(l

+1)
2
−2 l (l +1) −2 l

(l

+1)] 'n, l, m|z|n

, l

, m

` = 0, (6.51)
which reduces to
(l +l

+2) (l +l

) (l −l

+1) (l −l

−1)'n, l, m|z|n

, l

, m

` = 0. (6.52)
According to the above formula, the matrix element 'n, l, m|z|n

, l

, m

` vanishes
unless l = l

= 0 or l

= l ±1. This matrix element can be written
'n, l, m|z|n

, l

, m

` =
¸¸¸
ψ

nlm
(r

, θ

, ϕ

) r

cos θ

ψ
n

m

l
(r

, θ

, ϕ

) dV

, (6.53)
where ψ
nlm
(r

) = 'r

|n, l, m`. Recall, however, that the wave-function of an l = 0
state is spherically symmetric (see Sect. 5.3): i.e., ψ
n00
(r

) = ψ
n00
(r

). It follows
from Eq. (6.53) that the matrix element vanishes by symmetry when l = l

= 0.
In conclusion, the matrix element 'n, l, m|z|n

, l

, m

` is zero unless l

= l ± 1.
This is the selection rule for the quantum number l.
Application of the selection rules to Eq. (6.37) yields
∆E
nlm
= e
2
|E|
2
¸
n

¸
l

=l±1
|'n, l, m|z|n

, l

, m`|
2
E
nlm
−E
n

l

m
. (6.54)
Note that all of the terms in Eq. (6.37) which vary linearly with the electric field-
strength vanish by symmetry, according to the selection rules. Only those terms
which vary quadratically with the field-strength survive. The polarizability of an
atom is defined in terms of the energy-shift of the atomic state as follows:
∆E = −
1
2
α|E|
2
. (6.55)
Consider the ground state of a hydrogen atom. (Recall, that we cannot address
the n > 1 excited states because they are degenerate, and our theory cannot
handle this at present). The polarizability of this state is given by
α = 2 e
2
¸
n>1
|'1, 0, 0|z|n, 1, 0`|
2
E
n00
−E
100
. (6.56)
127
6.4 The quadratic Stark effect 6 APPROXIMATION METHODS
Here, we have made use of the fact that E
n10
= E
n00
for a hydrogen atom.
The sum in the above expression can be evaluated approximately by noting
that [see Eq. (5.120)]
E
n00
= −
e
2

0
a
0
n
2
(6.57)
for a hydrogen atom, where
a
0
=

0
¯h
2
µe
2
= 5.3 10
−11
meters (6.58)
is the Bohr radius. We can write
E
n00
−E
100
≥ E
200
−E
100
=
3
4
e
2

0
a
0
. (6.59)
Thus,
α <
16
3

0
a
0
¸
n>1
|'1, 0, 0|z|n, 1, 0`|
2
. (6.60)
However,
¸
n>1
|'1, 0, 0|z|n, 1, 0`|
2
=
¸
n

,l

,m

'1, 0, 0|z|n

, l

, m

`'n

, m

, l

|z|1, 0, 0`
= '1, 0, 0|z
2
|1, 0, 0`, (6.61)
where we have made use of the fact that the wave-functions of a hydrogen atom
form a complete set. It is easily demonstrated from the actual form of the ground
state wave-function that
'1, 0, 0|z
2
|1, 0, 0` = a
2
0
. (6.62)
Thus, we conclude that
α <
16
3

0
a
3
0
· 5.3 4π
0
a
3
0
. (6.63)
The true result is
α =
9
2

0
a
3
0
= 4.5 4π
0
a
3
0
. (6.64)
It is actually possible to obtain this answer, without recourse to perturbation the-
ory, by solving Schr¨ odinger’s equation exactly in parabolic coordinates.
128
6.5 Degenerate perturbation theory 6 APPROXIMATION METHODS
6.5 Degenerate perturbation theory
Let us now consider systems in which the eigenstates of the unperturbed Hamil-
tonian, H
0
, possess degenerate energy levels. It is always possible to represent
degenerate energy eigenstates as the simultaneous eigenstates of the Hamilto-
nian and some other Hermitian operator (or group of operators). Let us denote
this operator (or group of operators) L. We can write
H
0
|n, l` = E
n
|n, l`, (6.65)
and
L|n, l` = L
nl
|n, l`, (6.66)
where [H
0
, L] = 0. Here, the E
n
and the L
nl
are real numbers which depend on
the quantum numbers n, and n and l, respectively. It is always possible to find a
sufficient number of operators which commute with the Hamiltonian in order to
ensure that the L
nl
are all different. In other words, we can choose L such that
the quantum numbers n and l uniquely specify each eigenstate. Suppose that for
each value of n there are N
n
different values of l: i.e., the nth energy eigenstate
is N
n
-fold degenerate.
In general, L does not commute with the perturbing Hamiltonian, H
1
. This
implies that the modified energy eigenstates are not eigenstates of L. In this situ-
ation, we expect the perturbation to split the degeneracy of the energy levels, so
that each modified eigenstate |n, l`

acquires a unique energy eigenvalue E

nl
. Let
us naively attempt to use the standard perturbation theory of Sect. 6.3 to evalu-
ate the modified energy eigenstates and energy levels. A direct generalization of
Eqs. (6.32) and (6.33) yields
E

nl
= E
n
+e
nlnl
+
¸
n

,l

=n,l
|e
n

l

nl
|
2
E
n
−E
n

+O(
3
), (6.67)
and
|n, l`

= |n, l` +
¸
n

,l

=n,l
e
n

l

nl
E
n
−E
n

|n

, l

` +O(
2
), (6.68)
where
e
n

l

nl
= 'n

, l

|H
1
|n, l`. (6.69)
129
6.5 Degenerate perturbation theory 6 APPROXIMATION METHODS
It is fairly obvious that the summations in Eqs. (6.67) and (6.68) are not well-
behaved if the nth energy level is degenerate. The problem terms are those
involving unperturbed eigenstates labeled by the same value of n, but different
values of l: i.e., those states whose unperturbed energies are E
n
. These terms
give rise to singular factors 1/(E
n
− E
n
) in the summations. Note, however, that
this problem would not exist if the matrix elements, e
nl

nl
, of the perturbing
Hamiltonian between distinct, degenerate, unperturbed energy eigenstates cor-
responding to the eigenvalue E
n
were zero. In other words, if
'n, l

|H
1
|n, l` = λ
nl
δ
ll
, (6.70)
then all of the singular terms in Eqs. (6.67) and (6.68) would vanish.
In general, Eq. (6.70) is not satisfied. Fortunately, we can always redefine the
unperturbed energy eigenstates belonging to the eigenvalue E
n
in such a manner
that Eq. (6.70) is satisfied. Let us define N
n
new states which are linear combina-
tions of the N
n
original degenerate eigenstates corresponding to the eigenvalue
E
n
:
|n, l
(1)
` =
N
n
¸
k=1
'n, k|n, l
(1)
`|n, k`. (6.71)
Note that these new states are also degenerate energy eigenstates of the unper-
turbed Hamiltonian corresponding to the eigenvalue E
n
. The |n, l
(1)
` are chosen
in such a manner that they are eigenstates of the perturbing Hamiltonian, H
1
.
Thus,
H
1
|n, l
(1)
` = λ
nl
|n, l
(1)
`. (6.72)
The |n, l
(1)
` are also chosen so that they are orthonormal, and have unit lengths.
It follows that
'n, l
(1)
|H
1
|n, l
(1)
` = λ
nl
δ
ll
. (6.73)
Thus, if we use the new eigenstates, instead of the old ones, then we can employ
Eqs. (6.67) and (6.68) directly, since all of the singular terms vanish. The only
remaining difficulty is to determine the new eigenstates in terms of the original
ones.
130
6.5 Degenerate perturbation theory 6 APPROXIMATION METHODS
Now
N
n
¸
l=1
|n, l`'n, l| = 1, (6.74)
where 1 denotes the identity operator in the sub-space of all unperturbed energy
eigenkets corresponding to the eigenvalue E
n
. Using this completeness relation,
the operator eigenvalue equation (6.72) can be transformed into a straightfor-
ward matrix eigenvalue equation:
N
n
¸
l

=1
'n, l

|H
1
|n, l

`'n, l

|n, l
(1)
` = λ
nl
'n, l

|n, l
(1)
`. (6.75)
This can be written more transparently as
Ux = λ x, (6.76)
where the elements of the N
n
N
n
Hermitian matrix U are
U
jk
= 'n, j|H
1
|n, k`. (6.77)
Provided that the determinant of U is non-zero, Eq. (6.76) can always be solved
to give N
n
eigenvalues λ
nl
(for l = 1 to N
n
), with N
n
corresponding eigenvectors
x
nl
. The eigenvectors specify the weights of the new eigenstates in terms of the
original eigenstates: i.e.,
(x
nl
)
k
= 'n, k|n, l
(1)
`, (6.78)
for k = 1 to N
n
. In our new scheme, Eqs. (6.67) and (6.68) yield
E

nl
= E
n

nl
+
¸
n

=n,l

|e
n

l

nl
|
2
E
n
−E
n

+O(
3
), (6.79)
and
|n, l
(1)
`

= |n, l
(1)
` +
¸
n

=n,l

e
n

l

nl
E
n
−E
n

|n

, l

` +O(
2
). (6.80)
There are no singular terms in these expressions, since the summations are over
n

= n: i.e., they specifically exclude the problematic, degenerate, unperturbed
energy eigenstates corresponding to the eigenvalue E
n
. Note that the first-order
energy shifts are equivalent to the eigenvalues of the matrix equation (6.76).
131
6.6 The linear Stark effect 6 APPROXIMATION METHODS
6.6 The linear Stark effect
Let us examine the effect of an electric field on the excited energy levels of a
hydrogen atom. For instance, consider the n = 2 states. There is a single l =
0 state, usually referred to as 2s, and three l = 1 states (with m = −1, 0, 1),
usually referred to as 2p. All of these states possess the same energy, E
200
=
−e
2
/(32π
0
a
0
). As in Sect. 6.4, the perturbing Hamiltonian is
H
1
= e |E| z. (6.81)
In order to apply perturbation theory, we have to solve the matrix eigenvalue
equation
Ux = λ x, (6.82)
where U is the array of the matrix elements of H
1
between the degenerate 2s and
2p states. Thus,
U = e |E|

¸
¸
¸
¸
¸
¸
¸
0 '2, 0, 0|z|2, 1, 0` 0 0
'2, 1, 0|z|2, 0, 0` 0 0 0
0 0 0 0
0 0 0 0
¸

, (6.83)
where the rows and columns correspond to the |2, 0, 0`, |2, 1, 0`, |2, 1, 1`, and
|2, 1, −1` states, respectively. Here, we have made use of the selection rules,
which tell us that the matrix element of z between two hydrogen atom states is
zero unless the states possess the same m quantum number, and l quantum num-
bers which differ by unity. It is easily demonstrated, from the exact forms of the
2s and 2p wave-functions, that
'2, 0, 0|z|2, 1, 0` = '2, 1, 0|z|2, 0, 0` = 3 a
0
. (6.84)
It can be seen, by inspection, that the eigenvalues of U are λ
1
= 3 e a
0
|E|,
λ
2
= −3 e a
0
|E|, λ
3
= 0, and λ
4
= 0. The corresponding eigenvectors are
x
1
=

¸
¸
¸
¸
¸
¸
¸
1/

2
1/

2
0
0
¸

, (6.85)
132
6.6 The linear Stark effect 6 APPROXIMATION METHODS
x
2
=

¸
¸
¸
¸
¸
¸
¸
1/

2
−1/

2
0
0
¸

, (6.86)
x
3
=

¸
¸
¸
¸
¸
¸
¸
0
0
1
0
¸

, (6.87)
x
4
=

¸
¸
¸
¸
¸
¸
¸
0
0
0
1
¸

. (6.88)
It follows from Sect. 6.5 that the simultaneous eigenstates of the unperturbed
Hamiltonian and the perturbing Hamiltonian take the form
|1` =
|2, 0, 0` + |2, 1, 0`

2
, (6.89)
|2` =
|2, 0, 0` − |2, 1, 0`

2
, (6.90)
|3` = |2, 1, 1`, (6.91)
|4` = |2, 1, −1`. (6.92)
In the absence of an electric field, all of these states possess the same energy, E
200
.
The first-order energy shifts induced by an electric field are given by
∆E
1
= +3 e a
0
|E|, (6.93)
∆E
2
= −3 e a
0
|E|, (6.94)
∆E
3
= 0, (6.95)
∆E
4
= 0. (6.96)
Thus, the energies of states 1 and 2 are shifted upwards and downwards, respec-
tively, by an amount 3 e a
0
|E| in the presence of an electric field. States 1 and
2 are orthogonal linear combinations of the original 2s and 2p(m = 0) states.
133
6.7 Fine structure 6 APPROXIMATION METHODS
Note that the energy shifts are linear in the electric field-strength, so this is a
much larger effect that the quadratic effect described in Sect. 6.4. The energies
of states 3 and 4 (which are equivalent to the original 2p(m = 1) and 2p(m = −1)
states, respectively) are not affected to first-order. Of course, to second-order the
energies of these states are shifted by an amount which depends on the square of
the electric field-strength.
Note that the linear Stark effect depends crucially on the degeneracy of the 2s
and 2p states. This degeneracy is a special property of a pure Coulomb potential,
and, therefore, only applies to a hydrogen atom. Thus, alkali metal atoms do not
exhibit the linear Stark effect.
6.7 Fine structure
Let us now consider the energy levels of hydrogen-like atoms (i.e., alkali metal
atoms) in more detail. The outermost electron moves in a spherically symmetric
potential V(r) due to the nuclear charge and the charges of the other electrons
(which occupy spherically symmetric closed shells). The shielding effect of the
inner electrons causes V(r) to depart from the pure Coulomb form. This splits the
degeneracy of states characterized by the same value of n, but different values of
l. In fact, higher l states have higher energies.
Let us examine a phenomenon known as fine structure, which is due to inter-
action between the spin and orbital angular momenta of the outermost electron.
This electron experiences an electric field
E =
∇V
e
. (6.97)
However, a charge moving in an electric field also experiences an effective mag-
netic field
B = −v E. (6.98)
Now, an electron possesses a spin magnetic moment [see Eq. (5.170)]
µ = −
e S
m
e
. (6.99)
134
6.7 Fine structure 6 APPROXIMATION METHODS
We, therefore, expect a spin-orbit contribution to the Hamiltonian of the form
H
LS
= −µB
= −
e S
m
e
v

1
e
r
r
dV
dr

=
1
m
2
e
r
dV
dr
LS, (6.100)
where L = m
e
rv is the orbital angular momentum. When the above expression
is compared to the observed spin-orbit interaction, it is found to be too large by
a factor of two. There is a classical explanation for this, due to spin precession,
which we need not go into. The correct quantummechanical explanation requires
a relativistically covariant treatment of electron dynamics (this is achieved using
the so-called Dirac equation).
Let us now apply perturbation theory to a hydrogen-like atom, using H
LS
as
the perturbation (with H
LS
taking one half of the value given above), and
H
0
=
p
2
2 m
e
+V(r) (6.101)
as the unperturbed Hamiltonian. We have two choices for the energy eigenstates
of H
0
. We can adopt the simultaneous eigenstates of H
0
, L
2
, S
2
, L
z
and S
z
, or the
simultaneous eigenstates of H
0
, L
2
, S
2
, J
2
, and J
z
, where J = L + S is the total
angular momentum. Although the departure of V(r) from a pure 1/r form splits
the degeneracy of same n, different l, states, those states characterized by the
same values of n and l, but different values of m
l
, are still degenerate. (Here,
m
l
, m
s
, and m
j
are the quantum numbers corresponding to L
z
, S
z
, and J
z
, respec-
tively.) Moreover, with the addition of spin degrees of freedom, each state is
doubly degenerate due to the two possible orientations of the electron spin (i.e.,
m
s
= ±1/2). Thus, we are still dealing with a highly degenerate system. We
know, from Sect. 6.6, that the application of perturbation theory to a degenerate
system is greatly simplified if the basis eigenstates of the unperturbed Hamilto-
nian are also eigenstates of the perturbing Hamiltonian. Now, the perturbing
Hamiltonian, H
LS
, is proportional to LS, where
LS =
J
2
−L
2
−S
2
2
. (6.102)
135
6.7 Fine structure 6 APPROXIMATION METHODS
It is fairly obvious that the first group of operators (H
0
, L
2
, S
2
, L
z
and S
z
) does not
commute with H
LS
, whereas the second group (H
0
, L
2
, S
2
, J
2
, and J
z
) does. In
fact, LS is just a combination of operators appearing in the second group. Thus,
it is advantageous to work in terms of the eigenstates of the second group of
operators, rather than those of the first group.
We now need to find the simultaneous eigenstates of H
0
, L
2
, S
2
, J
2
, and J
z
. This
is equivalent to finding the eigenstates of the total angular momentum resulting
from the addition of two angular momenta: j
1
= l, and j
2
= s = 1/2. According
to Eq. (5.276), the allowed values of the total angular momentum are j = l +1/2
and j = l −1/2. We can write
|l +1/2, m` = cos α|m−1/2, 1/2` + sinα|m+1/2, −1/2`, (6.103)
|l −1/2, m` = −sinα|m−1/2, 1/2` + cos α|m+1/2, −1/2`. (6.104)
Here, the kets on the left-hand side are |j, m
j
` kets, whereas those on the right-
hand side are |m
l
, m
s
` kets (the j
1
, j
2
labels have been dropped, for the sake of
clarity). We have made use of the fact that the Clebsch-Gordon coefficients are
automatically zero unless m
j
= m
l
+ m
s
. We have also made use of the fact that
both the |j, m
j
` and |m
l
, m
s
` kets are orthonormal, and have unit lengths. We
now need to determine
cos α = 'm−1/2, 1/2|l +1/2, m`, (6.105)
where the Clebsch-Gordon coefficient is written in 'm
l
, m
s
|j, m
j
` form.
Let us now employ the recursion relation for Clebsch-Gordon coefficients,
Eq. (5.282), with j
1
= l, j
2
= 1/2, j = l + 1/2, m
1
= m − 1/2, m
2
= 1/2 (lower
sign). We obtain

(l +1/2) (l +3/2) −m(m+1) 'm−1/2, 1/2|l +1/2, m`
=

l (l +1) − (m−1/2) (m+1/2) 'm+1/2, 1/2|l +1/2, m+1`, (6.106)
which reduces to
'm−1/2, 1/2|l +1/2, m` =

l +m+1/2
l +m+3/2
'm+1/2, 1/2|l +1/2, m+1`. (6.107)
136
6.7 Fine structure 6 APPROXIMATION METHODS
We can use this formula to successively increase the value of m
l
. For instance,
'm−1/2, 1/2|l +1/2, m` =

l +m+1/2
l +m+3/2

l +m+3/2
l +m+5/2
'm+3/2, 1/2|l +1/2, m+2`. (6.108)
This procedure can be continued until m
l
attains its maximum possible value, l.
Thus,
'm−1/2, 1/2|l +1/2, m` =

l +m+1/2
2 l +1
'l, 1/2|l +1/2, l +1/2`. (6.109)
Consider the situation in which m
l
and m both take their maximum values,
l and 1/2, respectively. The corresponding value of m
j
is l + 1/2. This value is
possible when j = l +1/2, but not when j = l −1/2. Thus, the |m
l
, m
s
` ket |l, 1/2`
must be equal to the |j, m
j
` ket |l + 1/2, l + 1/2`, up to an arbitrary phase-factor.
By convention, this factor is taken to be unity, giving
'l, 1/2|l +1/2, l +1/2` = 1. (6.110)
It follows from Eq. (6.109) that
cos α = 'm−1/2, 1/2|l +1/2, m` =

l +m+1/2
2 l +1
. (6.111)
Now,
sin
2
α = 1 −
l +m+1/2
2 l +1
=
l −m+1/2
2 l +1
. (6.112)
We now need to determine the sign of sinα. A careful examination of the
recursion relation, Eq. (5.282), shows that the plus sign is appropriate. Thus,
|l +1/2, m` =

l +m+1/2
2 l +1
|m−1/2, 1/2`
+

l −m+1/2
2 l +1
|m+1/2, −1/2`, (6.113)
137
6.7 Fine structure 6 APPROXIMATION METHODS
|l −1/2, m` = −

l −m+1/2
2 l +1
|m−1/2, 1/2`
+

l +m+1/2
2 l +1
|m+1/2, −1/2`. (6.114)
It is convenient to define so called spin-angular functions using the Pauli two-
component formalism:
\
j=l±1/2,m
l
= ±

l ±m+1/2
2 l +1
Y
m−1/2
l
(θ, ϕ) χ
+
+

l ∓m+1/2
2 l +1
Y
m+1/2
l
(θ, ϕ) χ

=
1

2 l +1

¸
¸
±

l ±m+1/2 Y
m−1/2
l
(θ, ϕ)

l ∓m+1/2 Y
m+1/2
l
(θ, ϕ)
¸

. (6.115)
These functions are eigenfunctions of the total angular momentum for spin one-
half particles, just as the spherical harmonics are eigenfunctions of the orbital
angular momentum. A general wave-function for an energy eigenstate in a
hydrogen-like atom is written
ψ
nlm±
= R
nl
(r) \
j=l±1/2,m
. (6.116)
The radial part of the wave-function, R
nl
(r), depends on the radial quantum num-
ber n and the angular quantum number l. The wave-function is also labeled by
m, which is the quantum number associated with J
z
. For a given choice of l, the
quantum number j (i.e., the quantum number associated with J
2
) can take the
values l ±1/2.
The |l ±1/2, m` kets are eigenstates of LS, according to Eq. (6.102). Thus,
LS|j = l ±1/2, m
j
= m` =
¯h
2
2
[j (j +1) −l (l +1) −3/4] |j, m`, (6.117)
giving
LS|l +1/2, m` =
l ¯h
2
2
|l +1/2, m`, (6.118)
LS|l −1/2, m` = −
(l +1) ¯h
2
2
|l −1/2, m`. (6.119)
138
6.7 Fine structure 6 APPROXIMATION METHODS
It follows that
¸
(\
l+1/2,m
)

LS\
l+1/2,m
dΩ =
l ¯h
2
2
, (6.120)
¸
(\
l−1/2,m
)

LS\
l−1/2,m
dΩ = −
(l +1) ¯h
2
2
, (6.121)
where the integrals are over all solid angle.
Let us nowapply degenerate perturbation theory to evaluate the shift in energy
of a state whose wave-function is ψ
nlm±
due to the spin-orbit Hamiltonian H
LS
.
To first-order, the energy-shift is given by
∆E
nlm±
=
¸

nlm±
)

H
LS
ψ
nlm±
dV, (6.122)
where the integral is over all space. Equations (6.100) (remember the factor of
two), (6.116), and (6.120)–(6.121) yield
∆E
nlm+
= +
1
2 m
2
e

1
r
dV
dr
¸
l ¯h
2
2
, (6.123)
∆E
nlm−
= −
1
2 m
2
e

1
r
dV
dr
¸
(l +1) ¯h
2
2
, (6.124)
where

1
r
dV
dr
¸
=
¸
(R
nl
)

1
r
dV
dr
R
nl
r
2
dr. (6.125)
Equations (6.123)–(6.124) are known as Lande’s interval rule.
Let us now apply the above result to the case of a sodium atom. In chemist’s
notation, the ground state is written
(1s)
2
(2s)
2
(2p)
6
(3s). (6.126)
The inner ten electrons effectively form a spherically symmetric electron cloud.
We are interested in the excitation of the eleventh electron from 3s to some
higher energy state. The closest (in energy) unoccupied state is 3p. This state
has a higher energy than 3s due to the deviations of the potential from the pure
139
6.8 The Zeeman effect 6 APPROXIMATION METHODS
Coulomb form. In the absence of spin-orbit interaction, there are six degenerate
3p states. The spin-orbit interaction breaks the degeneracy of these states. The
modified states are labeled (3p)
1/2
and (3p)
3/2
, where the subscript refers to the
value of j. The four (3p)
3/2
states lie at a slightly higher energy level than the two
(3p)
1/2
states, because the radial integral (6.125) is positive. The splitting of the
(3p) energy levels of the sodium atom can be observed using a spectroscope. The
well-known sodium D line is associated with transitions between the 3p and 3s
states. The fact that there are two slightly different 3p energy levels (note that
spin-orbit coupling does not split the 3s energy levels) means that the sodium D
line actually consists of two very closely spaced spectroscopic lines. It is easily
demonstrated that the ratio of the typical spacing of Balmer lines to the splitting
brought about by spin-orbit interaction is about 1 : α
2
, where
α =
e
2
2
0
hc
=
1
137
(6.127)
is the fine structure constant. Note that Eqs. (6.123)–(6.124) are not entirely
correct, since we have neglected an effect (namely, the relativistic mass correction
of the electron) which is the same order of magnitude as spin-orbit coupling.
6.8 The Zeeman effect
Consider a hydrogen-like atom placed in a uniform z-directed magnetic field. The
change in energy of the outermost electron is
H
B
= −µB, (6.128)
where
µ = −
e
2 m
e
(L +2 S) (6.129)
is its magnetic moment, including both the spin and orbital contributions. Thus,
H
B
=
e B
2 m
e
(L
z
+2 S
z
). (6.130)
Suppose that the energy-shifts induced by the magnetic field are much smaller
than those induced by spin-orbit interaction. In this situation, we can treat H
B
as
140
6.8 The Zeeman effect 6 APPROXIMATION METHODS
a small perturbation acting on the eigenstates of H
0
+H
LS
. Of course, these states
are the simultaneous eigenstates of J
2
and J
z
. Let us consider one of these states,
labeled by the quantum numbers j and m, where j = l ± 1/2. From standard
perturbation theory, the first-order energy-shift in the presence of a magnetic
field is
∆E
nlm±
= 'l ±1/2, m|H
B
|l ±1/2, m`. (6.131)
Since
L
z
+2 S
z
= J
z
+S
z
, (6.132)
we find that
∆E
nlm±
=
e B
2 m
e
(m¯h +'l ±1/2, m|S
z
|l ±1/2, m` ) . (6.133)
Now, from Eqs. (6.113)–(6.114),
|l ±1/2, m` = ±

l ±m+1/2
2 l +1
|m−1/2, 1/2`
+

l ∓m+1/2
2 l +1
|m+1/2, −1/2`. (6.134)
It follows that
'l ±1/2, m|S
z
|l ±1/2, m` =
¯h
2 (2 l +1)
[(l ±m+1/2) − (l ∓m+1/2)]
= ±
m¯h
2 l +1
. (6.135)
Thus, we obtain Lande’s formula for the energy-shift induced by a weak magnetic
field:
∆E
nlm±
=
e ¯hB
2 m
e
m
¸
1 ±
1
2 l +1
¸
. (6.136)
Let us apply this theory to the sodium atom. We have already seen that the
non-Coulomb potential splits the degeneracy of the 3s and 3p states, the latter
states acquiring a higher energy. The spin-orbit interaction splits the six 3p states
into two groups, with four j = 3/2 states lying at a slightly higher energy than
two j = 1/2 states. According to Eq. (6.136), a magnetic field splits the (3p)
3/2
141
6.8 The Zeeman effect 6 APPROXIMATION METHODS
quadruplet of states, each state acquiring a different energy. In fact, the energy of
each state becomes dependent on the quantum number m, which measures the
projection of the total angular momentum along the z-axis. States with higher
m values have higher energies. A magnetic field also splits the (3p)
1/2
doublet
of states. However, it is evident from Eq. (6.136) that these states are split by a
lesser amount than the j = 3/2 states.
Suppose that we increase the strength of the magnetic field, so that the energy-
shift due to the magnetic field becomes comparable to the energy-shift induced
by spin-orbit interaction. Clearly, in this situation, it does not make much sense to
think of H
B
as a small interaction term operating on the eigenstates of H
0
+H
LS
.
In fact, this intermediate case is very difficult to analyze. Let us consider the
extreme limit in which the energy-shift due to the magnetic field greatly exceeds
that induced by spin-orbit effects. This is called the Paschen-Back limit.
In the Paschen-Back limit we can think of the spin-orbit Hamiltonian, H
LS
, as
a small interaction term operating on the eigenstates of H
0
+ H
B
. Note that the
magnetic Hamiltonian, H
B
, commutes with L
2
, S
2
, L
z
, S
z
, but does not commute
with L
2
, S
2
, J
2
, J
z
. Thus, in an intense magnetic field, the energy eigenstates of a
hydrogen-like atom are approximate eigenstates of the spin and orbital angular
momenta, but are not eigenstates of the total angular momentum. We can label
each state by the quantum numbers n (the energy quantum number), l, m
l
,
and m
s
. Thus, our energy eigenkets are written |n, l, m
l
, m
s
`. The unperturbed
Hamiltonian, H
0
, causes states with different values of the quantum numbers n
and l to have different energies. However, states with the same value of n and l,
but different values of m
l
and m
s
, are degenerate. The shift in energy due to the
magnetic field is simply
∆E
nlm
l
m
s
= 'n, l, m
l
, m
s
|H
B
|n, l, m
l
, m
s
`
=
e ¯hB
2 m
e
(m
l
+2 m
s
). (6.137)
Thus, states with different values of m
l
+2 m
s
acquire different energies.
Let us apply this result to a sodium atom. In the absence of a magnetic field,
the six 3p states form two groups of four and two states, depending on the values
142
6.8 The Zeeman effect 6 APPROXIMATION METHODS
of their total angular momentum. In the presence of an intense magnetic field
the 3p states are split into five groups. There is a state with m
l
+2 m
s
= 2, a state
with m
l
+2 m
s
= 1, two states with m
l
+2 m
s
= 0, a state with m
l
+2 m
s
= −1,
and a state with m
l
+2 m
s
= −2. These groups are equally spaced in energy, the
energy difference between adjacent groups being e ¯hB/2 m
e
.
The energy-shift induced by the spin-orbit Hamiltonian is given by
∆E
nl m
l
m
s
= 'n, l, m
l
, m
s
|H
LS
|n, l, m
l
, m
s
`, (6.138)
where
H
LS
=
1
2 m
2
e
1
r
dV
dr
LS. (6.139)
Now,
'LS` = ' L
z
S
z
+ (L
+
S

+L

S
+
)/2 `
= ¯h
2
m
l
m
s
, (6.140)
since
'L
±
` = 'S
±
` = 0 (6.141)
for expectation values taken between the simultaneous eigenkets of L
z
and S
z
.
Thus,
∆E
nlm
l
m
s
=
¯h
2
m
l
m
s
2 m
2
e

1
r
dV
dr
¸
. (6.142)
Let us apply the above result to a sodium atom. In the presence of an intense
magnetic field, the 3p states are split into five groups with (m
l
, m
s
) quantum
numbers (1, 1/2), (0, 1/2), (1, −1/2), or (−1, 1/2), (0, −1/2), and (−1, −1/2), re-
spectively, in order of decreasing energy. The spin-orbit term increases the en-
ergy of the highest energy state, does not affect the next highest energy state,
decreases, but does not split, the energy of the doublet, does not affect the next
lowest energy state, and increases the energy of the lowest energy state. The net
result is that the five groups of states are no longer equally spaced in energy.
The sort of magnetic field-strength needed to get into the Paschen-Bach limit
is given by
B
PB
∼ α
2
e m
e

0
ha
0
· 25 tesla. (6.143)
143
6.9 Time-dependent perturbation theory 6 APPROXIMATION METHODS
Obviuously, this is an extremely large field-strength.
6.9 Time-dependent perturbation theory
Suppose that the Hamiltonian of the system under consideration can be written
H = H
0
+H
1
(t), (6.144)
where H
0
does not contain time explicitly, and H
1
is a small time-dependent
perturbation. It is assumed that we are able to calculate the eigenkets of the
unperturbed Hamiltonian:
H
0
|n` = E
n
|n`. (6.145)
We know that if the system is in one of the eigenstates of H
0
then, in the ab-
sence of the external perturbation, it remains in this state for ever. However,
the presence of a small time-dependent perturbation can, in principle, give rise
to a finite probability that a system initially in some eigenstate |i` of the unper-
turbed Hamiltonian is found in some other eigenstate at a subsequent time (since
|i` is no longer an exact eigenstate of the total Hamiltonian), In other words, a
time-dependent perturbation causes the system to make transitions between its
unperturbed energy eigenstates. Let us investigate this effect.
Suppose that at t = t
0
the state of the system is represented by
|A` =
¸
n
c
n
|n`, (6.146)
where the c
n
are complex numbers. Thus, the initial state is some linear su-
perposition of the unperturbed energy eigenstates. In the absence of the time-
dependent perturbation, the time evolution of the system is given by
|A, t
0
, t` =
¸
n
c
n
exp([−i E
n
(t −t
0
)/¯h] |n`. (6.147)
Now, the probability of finding the system in state |n` at time t is
P
n
(t) = |c
n
exp[−i E
n
(t −t
0
)/¯h]|
2
= |c
n
|
2
= P
n
(t
0
). (6.148)
144
6.9 Time-dependent perturbation theory 6 APPROXIMATION METHODS
Clearly, with H
1
= 0, the probability of finding the system in state |n` at time t is
exactly the same as the probability of finding the system in this state at the initial
time t
0
. However, with H
1
= 0, we expect P
n
(t) to vary with time. Thus, we can
write
|A, t
0
, t` =
¸
n
c
n
(t) exp[−i E
n
(t −t
0
)/¯h] |n`, (6.149)
where P
n
(t) = |c
n
(t)|
2
. Here, we have carefully separated the fast phase oscilla-
tion of the eigenkets, which depends on the unperturbed Hamiltonian, from the
slow variation of the amplitudes c
n
(t), which depends entirely on the perturba-
tion (i.e., c
n
is constant if H
1
= 0). Note that in Eq. (6.149) the eigenkets |n` are
time-independent (they are actually the eigenkets of H
0
evaluated at the time t
0
).
Schr¨ odinger’s time evolution equation yields
i ¯h

∂t
|A, t
0
, t` = H|A, t
0
, t` = (H
0
+H
1
) |A, t
0
, t`. (6.150)
It follows from Eq. (6.149) that
(H
0
+H
1
)|A, t
0
, t` =
¸
m
c
m
(t) exp[−i E
m
(t −t
0
)/¯h] (E
m
+H
1
) |m`. (6.151)
We also have
i ¯h

∂t
|A, t
0
, t` =
¸
m

i ¯h
dc
m
dt
+c
m
(t) E
m

exp[−i E
m
(t −t
0
)/¯h] |m`, (6.152)
where use has been made of the time-independence of the kets |m`. According
to Eq. (6.150), we can equate the right-hand sides of the previous two equations
to obtain
¸
m
i ¯h
dc
m
dt
exp[−i E
m
(t −t
0
)/¯h]|m` =
¸
m
c
m
(t) exp[−i E
m
(t −t
0
)/¯h] H
1
|m`.
(6.153)
Left-multiplication by 'n| yields
i ¯h
dc
n
dt
=
¸
m
H
nm
(t) exp[i ω
nm
(t −t
0
)] c
m
(t), (6.154)
where
H
nm
(t) = 'n|H
1
(t)|m`, (6.155)
145
6.10 The two-state system 6 APPROXIMATION METHODS
and
ω
nm
=
E
n
−E
m
¯h
. (6.156)
Here, we have made use of the standard orthonormality result, 'n|m` = δ
nm
.
Suppose that there are N linearly independent eigenkets of the unperturbed
Hamiltonian. According to Eq. (6.154), the time variation of the coefficients
c
n
, which specify the probability of finding the system in state |n` at time t, is de-
termined by N coupled first-order differential equations. Note that Eq. (6.154) is
exact—we have made no approximations at this stage. Unfortunately, we cannot
generally find exact solutions to this equation, so we have to obtain approximate
solutions via suitable expansions in small quantities. However, for the particu-
larly simple case of a two-state system (i.e., N = 2), it is actually possible to
solve Eq. (6.154) without approximation. This solution is of enormous practical
importance.
6.10 The two-state system
Consider a system in which the time-independent Hamiltonian possesses two
eigenstates, denoted
H
0
|1` = E
1
|1`, (6.157)
H
0
|2` = E
2
|2`. (6.158)
Suppose, for the sake of simplicity, that the diagonal matrix elements of the in-
teraction Hamiltonian, H
1
, are zero:
'1|H
1
|1` = '2|H
1
|2` = 0. (6.159)
The off-diagonal matrix elements are assumed to oscillate sinusoidally at some
frequency ω:
'1|H
1
|2` = '2|H
1
|1`

= γexp(i ωt), (6.160)
where γ and ω are real. Note that it is only the off-diagonal matrix elements
which give rise to the effect which we are interested in—namely, transitions be-
tween states 1 and 2.
146
6.10 The two-state system 6 APPROXIMATION METHODS
For a two-state system, Eq. (6.154) reduces to
i ¯h
dc
1
dt
= γexp[+i (ω−ω
21
) t ] c
2
, (6.161)
i ¯h
dc
2
dt
= γexp[−i (ω−ω
21
) t ] c
1
, (6.162)
where ω
21
= (E
2
− E
1
)/¯h, and assuming that t
0
= 0. Equations (6.161) and
(6.162) can be combined to give a second-order differential equation for the
time variation of the amplitude c
2
:
d
2
c
2
dt
2
+ i (ω−ω
21
)
dc
2
dt
+
γ
2
¯h
2
c
2
= 0. (6.163)
Once we have solved for c
2
, we can use Eq. (6.162) to obtain the amplitude c
1
.
Let us look for a solution in which the system is certain to be in state 1 at time
t = 0. Thus, our boundary conditions are c
1
(0) = 1 and c
2
(0) = 0. It is easily
demonstrated that the appropriate solutions are
c
2
(t) =
−i γ/¯h

γ
2
/¯h
2
+ (ω−ω
21
)
2
/4
exp[−i (ω−ω
21
) t/2]
sin

γ
2
/¯h
2
+ (ω−ω
21
)
2
/4 t

, (6.164)
c
1
(t) = exp[ i (ω−ω
21
) t/2] cos

γ
2
/¯h
2
+ (ω−ω
21
)
2
/4 t


i (ω−ω
21
)/2

γ
2
/¯h
2
+ (ω−ω
21
)
2
/4
exp[ i (ω−ω
21
) t/2]
sin

γ
2
/¯h
2
+ (ω−ω
21
)
2
/4 t

. (6.165)
Now, the probability of finding the system in state 1 at time t is simply P
1
(t) =
|c
1
|
2
. Likewise, the probability of finding the system in state 2 at time t is P
2
(t) =
|c
2
|
2
. It follows that
P
2
(t) =
γ
2
/¯h
2
γ
2
/¯h
2
+ (ω−ω
21
)
2
/4
147
6.10 The two-state system 6 APPROXIMATION METHODS
sin
2

γ
2
/¯h
2
+ (ω−ω
21
)
2
/4 t

, (6.166)
P
1
(t) = 1 −P
2
(t). (6.167)
This result is known as Rabi’s formula.
Equation (6.166) exhibits all the features of a classic resonance. At resonance,
when the oscillation frequency of the perturbation, ω, matches the frequency
ω
21
, we find that
P
1
(t) = cos
2
(γt/¯h), (6.168)
P
2
(t) = sin
2
(γt/¯h). (6.169)
According to the above result, the system starts off at t = 0 in state 1. After a
time interval π¯h/2 γ it is certain to be in state 2. After a further time interval
π¯h/2 γ it is certain to be in state 1, and so on. Thus, the system periodically
flip-flops between states 1 and 2 under the influence of the time-dependent per-
turbation. This implies that the system alternatively absorbs and emits energy
from the source of the perturbation.
The absorption-emission cycle also take place away from the resonance, when
ω = ω
21
. However, the amplitude of oscillation of the coefficient c
2
is reduced.
This means that the maximum value of P
2
(t) is no longer unity, nor is the mini-
mum value of P
1
(t) zero. In fact, if we plot the maximum value of P
2
(t) as a func-
tion of the applied frequency, ω, we obtain a resonance curve whose maximum
(unity) lies at the resonance, and whose full-width half-maximum (in frequency)
is 4 γ/¯h. Thus, if the applied frequency differs from the resonant frequency by
substantially more than 2 γ/¯h then the probability of the system jumping from
state 1 to state 2 is very small. In other words, the time-dependent perturbation
is only effective at causing transitions between states 1 and 2 if its frequency of
oscillation lies in the approximate range ω
21
± 2 γ/¯h. Clearly, the weaker the
perturbation (i.e., the smaller γ becomes), the narrower the resonance.
148
6.11 Spin magnetic resonance 6 APPROXIMATION METHODS
6.11 Spin magnetic resonance
Consider a spin one-half system (e.g., a bound electron) placed in a uniform z-
directed magnetic field, and then subjected to a small time-dependent magnetic
field rotating in the x-y plane. Thus,
B = B
0
^z +B
1
(cos ωt ^ x + sinωt ^ y), (6.170)
where B
0
and B
1
are constants, with B
1
< B
0
. The rotating magnetic field usu-
ally represents the magnetic component of an electromagnetic wave propagating
along the z-axis. In this system, the electric component of the wave has no effect.
The Hamiltonian is written
H = −µB = H
0
+H
1
, (6.171)
where
H
0
=
e B
0
m
e
S
z
, (6.172)
and
H
1
=
e B
1
m
e
(cos ωt S
x
+ sinωt S
y
) . (6.173)
The eigenstates of the unperturbed Hamiltonian are the ‘spin up’ and ‘spin
down’ states, denoted |+` and |−`, respectively. Thus,
H
0
|±` = ±
e ¯hB
0
2 m
e
|±`. (6.174)
The time-dependent Hamiltonian can be written
H
1
=
e B
1
2 m
e

exp( i ωt) S

+ exp(−i ωt) S
+

, (6.175)
where S
+
and S

are the conventional raising and lowering operators for the spin
angular momentum. It follows that
'+|H
1
|+` = '−|H
1
|−` = 0, (6.176)
and
'−|H
1
|+` = '+|H
1
|−`

=
e ¯hB
1
2 m
e
exp( i ωt). (6.177)
149
6.12 The Dyson series 6 APPROXIMATION METHODS
It can be seen that this system is exactly the same as the two-state system
discussed in the previous section, provided that we make the identifications
|1` → |−`, (6.178)
|2` → |+`, (6.179)
ω
21

e B
0
m
e
, (6.180)
γ →
e ¯hB
1
2 m
e
. (6.181)
The resonant frequency, ω
21
, is simply the spin precession frequency for an elec-
tron in a uniform magnetic field of strength B
0
. In the absence of the perturba-
tion, the expectation values of S
x
and S
y
oscillate because of the spin precession,
but the expectation value of S
z
remains invariant. If we now apply a magnetic
perturbation rotating at the resonant frequency then, according to the analysis of
the previous section, the system undergoes a succession of spin-flops, |+`
÷
÷|−`,
in addition to the spin precession. We also know that if the oscillation frequency
of the applied field is very different from the resonant frequency then there is
virtually zero probability of the field triggering a spin-flop. The width of the
resonance (in frequency) is determined by the strength of the oscillating mag-
netic perturbation. Experimentalist are able to measure the magnetic moments
of electrons, and other spin one-half particles, to a high degree of accuracy by
placing the particles in a magnetic field, and subjecting them to an oscillating
magnetic field whose frequency is gradually scanned. By determining the reso-
nant frequency (i.e., the frequency at which the particles absorb energy from the
oscillating field), it is possible to calculate the magnetic moment.
6.12 The Dyson series
Let us now try to find approximate solutions of Eq. (6.154) for a general system.
It is convenient to work in terms of the time evolution operator, U(t
0
, t), which is
defined
|A, t
0
, t` = U(t
0
, t) |A`. (6.182)
150
6.12 The Dyson series 6 APPROXIMATION METHODS
Here, |A, t
0
, t` is the state ket of the system at time t, given that the state ket at
the initial time t
0
is |A`. It is easily seen that the time evolution operator satisfies
the differential equation
i ¯h
∂U(t
0
, t)
∂t
= (H
0
+H
1
) U(t
0
, t), (6.183)
subject to the boundary condition
U(t
0
, t
0
) = 1. (6.184)
In the absence of the external perturbation, the time evolution operator re-
duces to
U(t
0
, t) = exp[−i H
0
(t −t
0
)/¯h]. (6.185)
Let us switch on the perturbation and look for a solution of the form
U(t
0
, t) = exp[−i H
0
(t −t
0
)/¯h] U
I
(t
0
, t). (6.186)
It is readily demonstrated that U
I
satisfies the differential equation
i ¯h
∂U
I
(t
0
, t)
∂t
= H
I
(t
0
, t) U
I
(t
0
, t), (6.187)
where
H
I
(t
0
, t) = exp[+i H
0
(t −t
0
)/¯h] H
1
exp[−i H
0
(t −t
0
)/¯h], (6.188)
subject to the boundary condition
U
I
(t
0
, t
0
) = 1. (6.189)
Note that U
I
specifies that component of the time evolution operator which is due
to the time-dependent perturbation. Thus, we would expect U
I
to contain all of
the information regarding transitions between different eigenstates of H
0
caused
by the perturbation.
Suppose that the system starts off at time t
0
in the eigenstate |i` of the un-
perturbed Hamiltonian. The subsequent evolution of the state ket is given by
Eq. (6.149),
|i, t
0
, t` =
¸
m
c
m
(t) exp[−i E
m
(t −t
0
)/¯h] |m`. (6.190)
151
6.12 The Dyson series 6 APPROXIMATION METHODS
However, we also have
|i, t
0
, t` = exp[−i H
0
(t −t
0
)/¯h] U
I
(t
0
, t) |i`. (6.191)
It follows that
c
n
(t) = 'n|U
I
(t
0
, t)|i`, (6.192)
where use has been made of 'n|m` = δ
nm
. Thus, the probability that the system
is found in state |n` at time t, given that it is definitely in state |i` at time t
0
, is
simply
P
i→n
(t
0
, t) = |'n|U
I
(t
0
, t)|i`|
2
. (6.193)
This quantity is usually termed the transition probability between states |i` and
|n`.
Note that the differential equation (6.187), plus the boundary condition (6.189),
are equivalent to the following integral equation,
U
I
(t
0
, t) = 1 −
i
¯h
¸
t
t
0
H
I
(t
0
, t

) U
I
(t
0
, t

) dt

. (6.194)
We can obtain an approximate solution to this equation by iteration:
U
I
(t
0
, t) · 1 −
i
¯h
¸
t
t
0
H
I
(t
0
, t

)

1 −
i
¯h
¸
t

t
0
H
I
(t
0
, t

) U
I
(t
0
, t

)
¸
¸
dt

· 1 −
i
¯h
¸
t
t
0
H
I
(t
0
, t

) dt

+

−i
¯h

2
¸
t
t
0
dt

¸
t

t
0
H
I
(t
0
, t

) H
I
(t
0
, t

) dt

+ . (6.195)
This expansion is known as the Dyson series. Let
c
n
= c
(0)
n
+c
(1)
n
+c
(2)
n
+ , (6.196)
where the superscript
(1)
refers to a first-order term in the expansion, etc. It
follows from Eqs. (6.192) and (6.195) that
c
(0)
n
(t) = δ
in
, (6.197)
152
6.12 The Dyson series 6 APPROXIMATION METHODS
c
(1)
n
(t) = −
i
¯h
¸
t
t
0
'n|H
I
(t
0
, t

)|i` dt

, (6.198)
c
(2)
n
(t) =

−i
¯h

2
¸
t
t
0
dt

¸
t

t
0
'n|H
I
(t
0
, t

) H
I
(t
0
, t

)|i` dt

. (6.199)
These expressions simplify to
c
(0)
n
(t) = δ
in
, (6.200)
c
(1)
n
(t) = −
i
¯h
¸
t
t
0
exp[ i ω
ni
(t

−t
0
)] H
ni
(t

) dt

, (6.201)
c
(2)
n
(t) =

−i
¯h

2
¸
m
¸
t
t
0
dt

¸
t

t
0
dt

exp[ i ω
nm
(t

−t
0
)]
H
nm
(t

) exp[ i ω
mi
(t

−t
0
)] H
mi
(t

), (6.202)
where
ω
nm
=
E
n
−E
m
¯h
, (6.203)
and
H
nm
(t) = 'n|H
1
(t)|m`. (6.204)
The transition probability between states i and n is simply
P
i→n
(t
0
, t) = |c
(0)
n
+c
(1)
n
+c
(2)
n
+ |
2
. (6.205)
According to the above analysis, there is no chance of a transition between
states |i` and |n` (i = n) to zeroth-order (i.e., in the absence of the perturbation).
To first-order, the transition probability is proportional to the time integral of the
matrix element 'n|H
1
|i`, weighted by some oscillatory phase-factor. Thus, if the
matrix element is zero, then there is no chance of a first-order transition between
states |i` and |n`. However, to second-order, a transition between states |i` and
|n` is possible even when the matrix element 'n|H
1
|i` is zero.
153
6.13 Constant perturbations 6 APPROXIMATION METHODS
6.13 Constant perturbations
Consider a constant perturbation which is suddenly switched on at time t = 0:
H
1
(t) = 0 for t < 0
H
1
(t) = H
1
for t ≥ 0, (6.206)
where H
1
is time-independent, but is generally a function of the position, mo-
mentum, and spin operators. Suppose that the system is definitely in state |i` at
time t = 0. According to Eqs. (6.200)–(6.202) (with t
0
= 0),
c
(0)
n
(t) = δ
in
, (6.207)
c
(1)
n
(t) = −
i
¯h
H
ni
¸
t
0
exp[ i ω
ni
(t

−t)] dt

=
H
ni
E
n
−E
i
[1 − exp( i ω
ni
t)], (6.208)
giving
P
i→n
(t) · |c
(1)
n
|
2
=
4 |H
ni
|
2
|E
n
−E
i
|
2
sin
2

(E
n
−E
i
) t
2 ¯h
¸
¸
, (6.209)
for i = n. The transition probability between states |i` and |n` can be written
P
i→n
(t) =
|H
ni
|
2
t
2
¯h
2
sinc
2

(E
n
−E
i
) t
2 ¯h
¸
¸
, (6.210)
where
sinc(x) =
sinx
x
. (6.211)
The sinc function is highly oscillatory, and decays like 1/|x| at large |x|. It is a
good approximation to say that sinc(x) is small except when |x|
<

π. It follows
that the transition probability, P
i→n
, is small except when
|E
n
−E
i
|
<

2π¯h
t
. (6.212)
Note that in the limit t → ∞ only those transitions which conserve energy (i.e.,
E
n
= E
i
) have an appreciable probability of occurrence. At finite t, is is possible
to have transitions which do not exactly conserve energy, provided that
∆E∆t
<

¯h, (6.213)
154
6.13 Constant perturbations 6 APPROXIMATION METHODS
where ∆E = |E
n
− E
i
| is change in energy of the system associated with the
transition, and ∆t = t is the time elapsed since the perturbation was switched
on. Clearly, this result is just a manifestation of the well-known uncertainty re-
lation for energy and time. This uncertainty relation is fundamentally different
to the position-momentum uncertainty relation, since in non-relativistic quan-
tum mechanics position and momentum are operators, whereas time is merely a
parameter.
The probability of a transition which conserves energy (i.e., E
n
= E
i
) is
P
i→n
(t) =
|H
in
|
2
t
2
¯h
2
, (6.214)
where use has been made of sinc(0) = 1. Note that this probability grows quadrat-
ically with time. This result is somewhat surprising, since it implies that the prob-
ability of a transition occurring in a fixed time interval, t to t +dt, grows linearly
with t, despite the fact that H
1
is constant for t > 0. In practice, there is usually
a group of final states, all possessing nearly the same energy as the energy of the
initial state |i`. It is helpful to define the density of states, ρ(E), where the num-
ber of final states lying in the energy range E to E+dE is given by ρ(E) dE. Thus,
the probability of a transition from the initial state i to any of the continuum of
possible final states is
P
i→
(t) =
¸
P
i→n
(t) ρ(E
n
) dE
n
, (6.215)
giving
P
i→
(t) =
2 t
¯h
¸
|H
ni
|
2
ρ(E
n
) sinc
2
(x) dx, (6.216)
where
x = (E
n
−E
i
) t/2 ¯h, (6.217)
and use has been made of Eq. (6.210). We know that in the limit t → ∞ the
function sinc(x) is only non-zero in an infinitesimally narrow range of final ener-
gies centred on E
n
= E
i
. It follows that, in this limit, we can take ρ(E
n
) and |H
ni
|
2
out of the integral in the above formula to obtain
P
i→[n]
(t) =

¯h
|H
ni
|
2
ρ(E
n
) t

E
n
E
i
, (6.218)
155
6.13 Constant perturbations 6 APPROXIMATION METHODS
where P
i→[n]
denotes the transition probability between the initial state |i` and
all final states |n` which have approximately the same energy as the initial state.
Here, |H
ni
|
2
is the average of |H
ni
|
2
over all final states with approximately the
same energy as the initial state. In deriving the above formula, we have made
use of the result
¸

−∞
sinc
2
(x) dx = π. (6.219)
Note that the transition probability, P
i→[n]
, is now proportional to t, instead of t
2
.
It is convenient to define the transition rate, which is simply the transition
probability per unit time. Thus,
w
i→[n]
=
dP
i→[n]
dt
, (6.220)
giving
w
i→[n]
=

¯h
|H
ni
|
2
ρ(E
n
)

E
n
E
i
. (6.221)
This appealingly simple result is known as Fermi’s golden rule. Note that the
transition rate is constant in time (for t > 0): i.e., the probability of a transition
occurring in the time interval t to t + dt is independent of t for fixed dt. Fermi’s
golden rule is sometimes written
w
i→n
=

¯h
|H
ni
|
2
δ(E
n
−E), (6.222)
where it is understood that this formula must be integrated with

ρ(E
n
) dE
n
to
obtain the actual transition rate.
Let us now calculate the second-order term in the Dyson series, using the
constant perturbation (6.206). From Eq. (6.202) we find that
c
(2)
n
(t) =

−i
¯h

2
¸
m
H
nm
H
mi
¸
t
0
dt

exp( i ω
nm
t

)
¸
t

0
dt

exp( i ω
mi
t )
=
i
¯h
¸
m
H
nm
H
mi
E
m
−E
i
¸
t
0
[exp( i ω
ni
t

) − exp( i ω
nm
t

] ) dt

=
i t
¯h
¸
m
H
nm
H
mi
E
m
−E
i
[exp( i ω
ni
t/2) sinc(ω
ni
t/2)
156
6.13 Constant perturbations 6 APPROXIMATION METHODS
−exp( i ω
nm
t/2) sinc(ω
nm
t/2)] . (6.223)
Thus,
c
n
(t) = c
(1)
n
+c
(2)
n
=
i t
¯h
exp( i ω
ni
t/2)

¸
H
ni
+
¸
m
H
nm
H
mi
E
m
−E
i
¸

sinc(ω
ni
t/2)

¸
m
H
nm
H
mi
E
m
−E
i
exp( i ω
im
t/2) sinc(ω
nm
t/2)
¸
¸
, (6.224)
where use has been made of Eq. (6.208). It follows, by analogy with the previous
analysis, that
w
i→[n]
=

¯h

H
ni
+
¸
m
H
nm
H
mi
E
m
−E
i

2
ρ(E
n
)

E
n
E
i
, (6.225)
where the transition rate is calculated for all final states, |n`, with approximately
the same energy as the initial state, |i`, and for intermediate states, |m` whose
energies differ from that of the initial state. The fact that E
m
= E
i
causes the
last term on the right-hand side of Eq. (6.224) to average to zero (due to the
oscillatory phase-factor) during the evaluation of the transition probability.
According to Eq. (6.225), a second-order transition takes place in two steps.
First, the system makes a non-energy-conserving transition to some intermedi-
ate state |m`. Subsequently, the system makes another non-energy-conserving
transition to the final state |n`. The net transition, from |i` to |n`, conserves en-
ergy. The non-energy-conserving transitions are generally termed virtual transi-
tions, whereas the energy conserving first-order transition is termed a real transi-
tion. The above formula clearly breaks down if H
nm
H
mi
= 0 when E
m
= E
i
.
This problem can be avoided by gradually turning on the perturbation: i.e.,
H
1
→ exp(ηt) H
1
(where η is very small). The net result is to change the en-
ergy denominator in Eq. (6.225) from E
i
−E
m
to E
i
−E
m
+ i ¯hη.
157
6.14 Harmonic perturbations 6 APPROXIMATION METHODS
6.14 Harmonic perturbations
Consider a perturbation which oscillates sinusoidally in time. This is usually
called a harmonic perturbation. Thus,
H
1
(t) = V exp( i ωt) +V

exp(−i ωt), (6.226)
where V is, in general, a function of position, momentum, and spin operators.
Let us initiate the system in the eigenstate |i` of the unperturbed Hamiltonian,
H
0
, and switch on the harmonic perturbation at t = 0. It follows from Eq. (6.201)
that
c
(1)
n
=
−i
¯h
¸
t
0
¸
V
ni
exp(i ωt

) +V

ni
exp(−i ωt

)

exp( i ω
ni
t

) dt

, (6.227)
=
1
¯h

¸
1 − exp[ i (ω
ni
+ω) t]
ω
ni

V
ni
+
1 − exp[ i (ω
ni
−ω) t]
ω
ni
−ω
V

ni
¸

,
where
V
ni
= 'n|V|i`, (6.228)
V

ni
= 'n|V

|i` = 'i|V|n`

. (6.229)
This formula is analogous to Eq. (6.208), provided that
ω
ni
=
E
n
−E
i
¯h
→ω
ni
±ω. (6.230)
Thus, it follows fromthe previous analysis that the transition probability P
i→n
(t) =
|c
(1)
n
|
2
is only appreciable in the limit t →∞if
ω
ni
+ω · 0 or E
n
· E
i
− ¯hω, (6.231)
ω
ni
−ω · 0 or E
n
· E
i
+ ¯hω. (6.232)
Clearly, (6.231) corresponds to the first termon the right-hand side of Eq. (6.227),
and (6.232) corresponds to the second term. The former term describes a process
by which the system gives up energy ¯hω to the perturbing field, whilst making a
transition to a final state whose energy level is less than that of the initial state
158
6.15 Absorption and stimulated emission of radiation 6 APPROXIMATION METHODS
by ¯hω. This process is known as stimulated emission. The latter term describes
a process by which the system gains energy ¯hω from the perturbing field, whilst
making a transition to a final state whose energy level exceeds that of the initial
state by ¯hω. This process is known as absorption. In both cases, the total energy
(i.e., that of the system plus the perturbing field) is conserved.
By analogy with Eq. (6.221),
w
i→[n]
=

¯h
|V
ni
|
2
ρ(E
n
)

E
n
=E
i
−¯hω
, (6.233)
w
i→[n]
=

¯h
|V

ni
|
2
ρ(E
n
)

E
n
=E
i
+¯hω
. (6.234)
Equation (6.233) specifies the transition rate for stimulated emission, whereas
Eq. (6.234) gives the transition rate for absorption. These equations are more
usually written
w
i→n
=

¯h
|V
ni
|
2
δ(E
n
−E
i
+ ¯hω), (6.235)
w
i→n
=

¯h
|V

ni
|
2
δ(E
n
−E
i
− ¯hω). (6.236)
It is clear from Eqs. (6.228)-(6.229) that |V

ni
|
2
= |V
ni
|
2
. It follows from
Eqs. (6.233)–(6.234) that
w
i→[n]
ρ(E
n
)
=
w
n→[i]
ρ(E
i
)
. (6.237)
In other words, the rate of stimulated emission, divided by the density of final
states for stimulated emission, equals the rate of absorption, divided by the den-
sity of final states for absorption. This result, which expresses a fundamental
symmetry between absorption and stimulated emission, is known as detailed bal-
ancing, and is very important in statistical mechanics.
6.15 Absorption and stimulated emission of radiation
Let us use some of the results of time-dependent perturbation theory to inves-
tigate the interaction of an atomic electron with classical (i.e., non-quantized)
159
6.15 Absorption and stimulated emission of radiation 6 APPROXIMATION METHODS
electromagnetic radiation.
The unperturbed Hamiltonian is
H
0
=
p
2
2 m
e
+V
0
(r). (6.238)
The standard classical prescription for obtaining the Hamiltonian of a particle of
charge q in the presence of an electromagnetic field is
p → p +qA, (6.239)
H → H−qφ, (6.240)
where A(r) is the vector potential and φ(r) is the scalar potential. Note that
E = −∇φ −
∂A
∂t
, (6.241)
B = ∇A. (6.242)
This prescription also works in quantum mechanics. Thus, the Hamiltonian of an
atomic electron placed in an electromagnetic field is
H =
(p −e A)
2
2 m
e
+e φ +V
0
(r), (6.243)
where A and φ are functions of the position operators. The above equation can
be written
H =

p
2
−e Ap −e pA +e
2
A
2

2 m
e
+e φ +V
0
(r). (6.244)
Now,
pA = Ap, (6.245)
provided that we adopt the gauge ∇A = 0. Hence,
H =
p
2
2 m
e

e Ap
m
e
+
e
2
A
2
2 m
e
+e φ +V
0
(r). (6.246)
Suppose that the perturbation corresponds to a monochromatic plane-wave,
for which
φ = 0, (6.247)
A = 2 A
0
cos

ω
c
nr −ωt

, (6.248)
160
6.15 Absorption and stimulated emission of radiation 6 APPROXIMATION METHODS
where and n are unit vectors which specify the direction of polarization and
the direction of propagation, respectively. Note that n = 0. The Hamiltonian
becomes
H = H
0
+H
1
(t), (6.249)
with
H
0
=
p
2
2 m
e
+V(r), (6.250)
and
H
1
· −
e Ap
m
e
, (6.251)
where the A
2
term, which is second order in A
0
, has been neglected.
The perturbing Hamiltonian can be written
H
1
= −
e A
0
p
m
e
(exp[ i (ω/c) nr − i ωt] + exp[−i (ω/c) nr + i ωt]) . (6.252)
This has the same form as Eq. (6.226), provided that
V = −
e A
0
p
m
e
exp[−i (ω/c) nr ] (6.253)
It is clear, by analogy with the previous analysis, that the first term on the right-
hand side of Eq. (6.252) describes the absorption of a photon of energy ¯hω,
whereas the second term describes the stimulated emission of a photon of energy
¯hω. It follows from Eq. (6.236) that the rate of absorption is
w
i→n
=

¯h
e
2
m
2
e
|A
0
|
2
|'n| exp[ i (ω/c) nr] p|i`|
2
δ(E
n
−E
i
− ¯hω). (6.254)
The absorption cross-section is defined as the ratio of the power absorbed by
the atom to the incident power per unit area in the electromagnetic field. Now
the energy density of an electromagnetic field is
U =
1
2

¸

0
E
2
0
2
+
B
2
0
2 µ
0
¸

, (6.255)
161
6.16 The electric dipole approximation 6 APPROXIMATION METHODS
where E
0
and B
0
= E
0
/c = 2 A
0
ω/c are the peak electric and magnetic field-
strengths, respectively. The incident power per unit area of the electromagnetic
field is
c U = 2
0
c ω
2
|A
0
|
2
. (6.256)
Now,
σ
abs
=
¯hωw
i→n
c U
, (6.257)
so
σ
abs
=
πe
2

0
m
2
e
ωc
|'n| exp[ i (ω/c) nr] p|i`|
2
δ(E
n
−E
i
− ¯hω). (6.258)
6.16 The electric dipole approximation
In general, the wave-length of the type of electromagnetic radiation which in-
duces, or is emitted during, transitions between different atomic energy levels is
much larger than the typical size of a light atom. Thus,
exp[ i (ω/c) nr] = 1 + i
ω
c
nr + , (6.259)
can be approximated by its first term, unity (remember that ω/c = 2π/λ). This
approximation is known as the electric dipole approximation. It follows that
'n| exp[ i (ω/c) nr] p|i` · 'n|p|i`. (6.260)
It is readily demonstrated that
[r, H
0
] =
i ¯hp
m
e
, (6.261)
so
'n|p|i` = −i
m
e
¯h
'n|[r, H
0
]|i` = i m
e
ω
ni
'n|r|i`. (6.262)
Using Eq. (6.258), we obtain
σ
abs
= 4π
2
αω
ni
|'n|r|i`|
2
δ(ω−ω
ni
), (6.263)
162
6.16 The electric dipole approximation 6 APPROXIMATION METHODS
where α = e
2
/(2
0
hc) = 1/137 is the fine structure constant. It is clear that if
the absorption cross-section is regarded as a function of the applied frequency,
ω, then it exhibits a sharp maximum at ω = ω
ni
= (E
n
−E
i
)/¯h.
Suppose that the radiation is polarized in the z-direction, so that = ^z. We
have already seen, from Sect. 6.4, that 'n|z|i` = 0 unless the initial and final
states satisfy
∆l = ±1, (6.264)
∆m = 0. (6.265)
Here, l is the quantum number describing the total orbital angular momentum
of the electron, and m is the quantum number describing the projection of the
orbital angular momentum along the z-axis. It is easily demonstrated that 'n|x|i`
and 'n|y|i` are only non-zero if
∆l = ±1, (6.266)
∆m = ±1. (6.267)
Thus, for generally directed radiation 'n|r|i` is only non-zero if
∆l = ±1, (6.268)
∆m = 0, ±1. (6.269)
These are termed the selection rules for electric dipole transitions. It is clear, for
instance, that the electric dipole approximation allows a transition from a 2p
state to a 1s state, but disallows a transition from a 2s to a 1s state. The latter
transition is called a forbidden transition.
Forbidden transitions are not strictly forbidden. Instead, they take place at a
far lower rate than transitions which are allowed according to the electric dipole
approximation. After electric dipole transitions, the next most likely type of tran-
sition is a magnetic dipole transition, which is due to the interaction between the
electron spin and the oscillating magnetic field of the incident electromagnetic
radiation. Magnetic dipole transitions are typically about 10
5
times more unlikely
than similar electric dipole transitions. The first-order term in Eq. (6.259) yields
163
6.16 The electric dipole approximation 6 APPROXIMATION METHODS
so-called electric quadrupole transitions. These are typically about 10
8
times more
unlikely than electric dipole transitions. Magnetic dipole and electric quadrupole
transitions satisfy different selection rules than electric dipole transitions: for
instance, the selection rules for electric quadrupole transitions are ∆l = 0, ±2.
Thus, transitions which are forbidden as electric dipole transitions may well be
allowed as magnetic dipole or electric quadrupole transitions.
Integrating Eq. (6.263) over all possible frequencies of the incident radiation
yields
¸
σ
abs
(ω) dω =
¸
n

2
αω
ni
|'n|r|i`|
2
. (6.270)
Suppose, for the sake of definiteness, that the incident radiation is polarized in
the x-direction. It is easily demonstrated that
[x, [x, H
0
] ] = −
¯h
2
m
e
. (6.271)
Thus,
'i|[x, [x, H
0
] ]|i` = 'i|x
2
H
0
+H
0
x
2
−2 x H
0
x|i` = −
¯h
2
m
e
, (6.272)
giving
2
¸
n
('i|x|n`E
i
'n|x|i` −'i|x|n`E
n
'n|x|i`) = −
¯h
2
m
e
. (6.273)
It follows that
2 m
e
¯h
¸
n
ω
ni
|'n|x|i`|
2
= 1. (6.274)
This is known as the Thomas-Reiche-Kuhn sum rule. According to this rule,
Eq. (6.270) reduces to
¸
σ
abs
(ω) dω =

2
α¯h
m
e
=
πe
2
2
0
m
e
c
. (6.275)
Note that ¯h has dropped out of the final result. In fact, the above formula is ex-
actly the same as that obtained classically by treating the electron as an oscillator.
164
6.17 Energy-shifts and decay-widths 6 APPROXIMATION METHODS
6.17 Energy-shifts and decay-widths
We have examined how a state |n`, other than the initial state |i`, becomes popu-
lated as a result of some time-dependent perturbation applied to the system. Let
us now consider how the initial state becomes depopulated.
It is convenient to gradually turn on the perturbation from zero at t = −∞.
Thus,
H
1
(t) = exp(ηt) H
1
, (6.276)
where η is small and positive, and H
1
is a constant.
In the remote past, t →−∞, the system is assumed to be in the initial state |i`.
Thus, c
i
(t → −∞) = 1, and c
n=i
(t → −∞) = 0. Basically, we want to calculate
the time evolution of the coefficient c
i
(t). First, however, let us check that our
previous Fermi golden rule result still applies when the perturbing potential is
turned on slowly, instead of very suddenly. For c
n=i
(t) we have fromEqs. (6.200)–
(6.201) that
c
(0)
n
(t) = 0, (6.277)
c
(1)
n
(t) = −
i
¯h
H
ni
¸
t
−∞
exp[ (η + i ω
ni
)t

] dt

= −
i
¯h
H
ni
exp[ (η + i ω
ni
)t ]
η + i ω
ni
, (6.278)
where H
ni
= 'n|H
1
|i`. It follows that, to first-order, the transition probability
from state |i` to state |n` is
P
i→n
(t) = |c
(1)
n
|
2
=
|H
ni
|
2
¯h
2
exp(2 ηt)
η
2

2
ni
. (6.279)
The transition rate is given by
w
i→n
(t) =
dP
i→n
dt
=
2 |H
ni
|
2
¯h
2
ηexp(2 ηt)
η
2

2
ni
. (6.280)
Consider the limit η →0. In this limit, exp(ηt) →1, but
lim
η→0
η
η
2

2
ni
= πδ(ω
ni
) = π¯hδ(E
n
−E
i
). (6.281)
165
6.17 Energy-shifts and decay-widths 6 APPROXIMATION METHODS
Thus, Eq. (6.280) yields the standard Fermi golden rule result
w
i→n
=

¯h
|H
ni
|
2
δ(E
n
−E
i
). (6.282)
It is clear that the delta-function in the above formula actually represents a func-
tion which is highly peaked at some particular energy. The width of the peak is
determined by how fast the perturbation is switched on.
Let us now calculate c
i
(t) using Eqs. (6.200)–(6.202). We have
c
(0)
i
(t) = 1, (6.283)
c
(1)
i
(t) = −
i
¯h
H
ii
¸
t
−∞
exp(ηt

) dt

= −
i
¯h
H
ii
exp(ηt)
η
, (6.284)
c
(2)
i
(t) =

−i
¯h

2
¸
m
|H
mi
|
2
¸
t
−∞
dt

¸
t

−∞
dt

exp[ (η + i ω
im
)t

] exp[ (η + i ω
mi
)t

],
=

−i
¯h

2
¸
m
|H
mi
|
2
exp(2 ηt)
2 η(η + i ω
mi
)
. (6.285)
Thus, to second-order we have
c
i
(t) · 1 +

−i
¯h

H
ii
exp(ηt)
η
+

−i
¯h

2
|H
ii
|
2
exp(2 ηt)
2 η
2
+

−i
¯h

¸
m=i
|H
mi
|
2
exp(2 ηt)
2 η(E
i
−E
m
+ i ¯hη)
. (6.286)
Let us now consider the ratio ˙ c
i
/c
i
, where ˙ c
i
≡ dc
i
/dt. Using Eq. (6.286), we
can evaluate this ratio in the limit η →0. We obtain
˙ c
i
c
i
·

−i
¯h

H
ii
+

−i
¯h

2
|H
ii
|
2
η
+

−i
¯h

¸
m=i
|H
mi
|
2
E
i
−E
m
+ i ¯hη
¸
¸
¸

1 −
i
¯h
H
ii
η

·

−i
¯h

H
ii
+ lim
η→0

−i
¯h

¸
m=i
|H
mi
|
2
E
i
−E
m
+ i ¯hη
. (6.287)
166
6.17 Energy-shifts and decay-widths 6 APPROXIMATION METHODS
This result is formally correct to second-order in perturbed quantities. Note that
the right-hand side of Eq. (6.287) is independent of time. We can write
˙ c
i
c
i
=

−i
¯h


i
, (6.288)
where

i
= H
ii
+ lim
η→0
¸
m=i
|H
mi
|
2
E
i
−E
m
+ i ¯hη
(6.289)
is a constant. According to a well-known result in pure mathematics,
lim
→0
1
x + i
= P
1
x
− i πδ(x), (6.290)
where > 0, and P denotes the principle part. It follows that

i
= H
ii
+P
¸
m=i
|H
mi
|
2
E
i
−E
m
− i π
¸
m=i
|H
mi
|
2
δ(E
i
−E
m
). (6.291)
It is convenient to normalize the solution of Eq. (6.288) so that c
i
(0) = 1.
Thus, we obtain
c
i
(t) = exp

−i ∆
i
t
¯h

. (6.292)
According to Eq. (6.149), the time evolution of the initial state ket |i` is given by
|i, t` = exp[−i (∆
i
+E
i
) t/¯h] |i`. (6.293)
We can rewrite this result as
|i, t` = exp(−i [E
i
+ Re(∆
i
) ] t/¯h) exp[ Im(∆
i
) t/¯h] |i`. (6.294)
It is clear that the real part of ∆
i
gives rise to a simple shift in energy of state |i`,
whereas the imaginary part of ∆
i
governs the growth or decay of this state. Thus,
|i, t` = exp[−i (E
i
+∆E
i
) t/¯h] exp(−Γ
i
t/2¯h) |i`, (6.295)
where
∆E
i
= Re(∆
i
) = H
ii
+P
¸
m=i
|H
mi
|
2
E
i
−E
m
, (6.296)
167
6.17 Energy-shifts and decay-widths 6 APPROXIMATION METHODS
and
Γ
i
¯h
= −
2 Im(∆
i
)
¯h
=

¯h
¸
m=i
|H
mi
|
2
δ(E
i
−E
m
). (6.297)
Note that the energy-shift ∆E
i
is the same as that predicted by standard time-
independent perturbation theory.
The probability of observing the system in state |i` at time t > 0, given that it
is definately in state |i` at time t = 0, is given by
P
i→i
(t) = |c
i
|
2
= exp(−Γ
i
t/¯h), (6.298)
where
Γ
i
¯h
=
¸
m=i
w
i→m
. (6.299)
Here, use has been made of Eq. (6.222). Clearly, the rate of decay of the initial
state is a simple function of the transition rates to the other states. Note that the
system conserves probability up to second-order in perturbed quantities, since
|c
i
|
2
+
¸
m=i
|c
m
|
2
· (1 −Γ
i
t/¯h) +
¸
m=i
w
i→m
t = 1. (6.300)
The quantity ∆
i
is called the decay-width of state |i`. It is closely related to the
mean lifetime of this state,
τ
i
=
¯h
Γ
i
, (6.301)
where
P
i→i
= exp(−t/τ
i
). (6.302)
According to Eq. (6.294), the amplitude of state |i` both oscillates and decays as
time progresses. Clearly, state |i` is not a stationary state in the presence of the
time-dependent perturbation. However, we can still represent it as a superposi-
tion of stationary states (whose amplitudes simply oscillate in time). Thus,
exp[−i (E
i
+∆E
i
) t/¯h] exp(−Γ
i
t/2¯h) =
¸
f(E) exp(−i Et/¯h) dE, (6.303)
168
6.17 Energy-shifts and decay-widths 6 APPROXIMATION METHODS
where f(E) is the weight of the stationary state with energy E in the superposition.
The Fourier inversion theorem yields
|f(E)|
2

1
(E − [E
i
+ Re(∆
i
)])
2

2
i
/4
. (6.304)
In the absence of the perturbation, |f(E)|
2
is basically a delta-function centred on
the unperturbed energy E
i
of state |i`. In other words, state |i` is a stationary state
whose energy is completely determined. In the presence of the perturbation, the
energy of state |i` is shifted by Re(∆
i
). The fact that the state is no longer station-
ary (i.e., it decays in time) implies that its energy cannot be exactly determined.
Indeed, the energy of the state is smeared over some region of width (in energy)
Γ
i
centred around the shifted energy E
i
+Re(∆
i
). The faster the decay of the state
(i.e., the larger Γ
i
), the more its energy is spread out. This effect is clearly a man-
ifestation of the energy-time uncertainty relation ∆E∆t ∼ ¯h. One consequence of
this effect is the existence of a natural width of spectral lines associated with the
decay of some excited state to the ground state (or any other lower energy state).
The uncertainty in energy of the excited state, due to its propensity to decay, gives
rise to a slight smearing (in wave-length) of the spectral line associated with the
transition. Strong lines, which correspond to fast transitions, are smeared out
more that weak lines. For this reason, spectroscopists generally favour forbid-
den lines for Doppler shift measurements. Such lines are not as bright as those
corresponding to allowed transitions, but they are a lot sharper.
169
7 SCATTERING THEORY
7 Scattering theory
7.1 Introduction
Historically, data regarding quantum phenomena has been obtained from two
main sources—the study of spectroscopic lines, and scattering experiments. We
have already developed theories which account for some aspects of the spectra of
hydrogen-like atoms. Let us now examine the quantum theory of scattering.
7.2 The Lipmann-Schwinger equation
Consider time-independent scattering theory, for which the Hamiltonian of the
system is written
H = H
0
+H
1
, (7.1)
where H
0
is the Hamiltonian of a free particle of mass m,
H
0
=
p
2
2 m
, (7.2)
and H
1
represents the non-time-varying source of the scattering. Let |φ` be an
energy eigenket of H
0
,
H
0
|φ` = E|φ`, (7.3)
whose wave-function 'r

|φ` is φ(r

). This state is a plane-wave state or, possibly,
a spherical-wave state. Schr¨ odinger’s equation for the scattering problem is
(H
0
+H
1
)|ψ` = E|ψ`, (7.4)
where |ψ` is an energy eigenstate of the total Hamiltonian whose wave-function
'r

|ψ` is ψ(r

). In general, both H
0
and H
0
+ H
1
have continuous energy spectra:
i.e., their energy eigenstates are unbound. We require a solution of Eq. (7.4)
which satisfies the boundary condition |ψ` → |φ` as H
1
→ 0. Here, |φ` is a
solution of the free particle Schr¨ odinger equation, (7.3), corresponding to the
same energy eigenvalue.
170
7.2 The Lipmann-Schwinger equation 7 SCATTERING THEORY
Formally, the desired solution can be written
|ψ` = |φ` +
1
E −H
0
H
1
|ψ`. (7.5)
Note that we can recover Eq. (7.4) by operating on the above equation with
E − H
0
, and making use of Eq. (7.3). Furthermore, the solution satisfies the
boundary condition |ψ` →|φ` as H
1
→0. Unfortunately, the operator (E −H
0
)
−1
is singular: i.e., it produces infinities when it operates on an eigenstate of H
0
corresponding to the eigenvalue E. We need a prescription for dealing with these
infinities, otherwise the above solution is useless. The standard prescription is to
make the energy eigenvalue E slightly complex. Thus,

±
` = |φ` +
1
E −H
0
±i
H
1

±
`, (7.6)
where is real, positive, and small. Equation (7.6) is called the Lipmann-Schwinger
equation, and is non-singular as long as > 0. The physical significance of the ±
signs will become apparent later on.
The Lipmann-Schwinger equation can be converted into an integral equation
via left multiplication by 'r|. Thus,
ψ
±
(r) = φ(r) +
¸

r

1
E −H
0
±i

r

¸
'r

|H
1

±
` d
3
r

. (7.7)
Adopting the Schr¨ odinger representation, we can write the scattering problem
(7.4) in the form
(∇
2
+k
2
) ψ(r) =
2 m
¯h
2
'r|H
1
|ψ`, (7.8)
where
E =
¯h
2
k
2
2 m
. (7.9)
This equation is called Helmholtz’s equation, and can be inverted using standard
Green’s function techniques. Thus,
ψ(r) = φ(r) +
2 m
¯h
2
¸
G(r, r

)'r

|H
1
|ψ` d
3
r

, (7.10)
171
7.2 The Lipmann-Schwinger equation 7 SCATTERING THEORY
where
(∇
2
+k
2
) G(r, r

) = δ(r −r

). (7.11)
Note that the solution (7.10) satisfies the boundary condition |ψ` →|φ` as H
1

0. As is well-known, the Green’s function for the Helmholtz problem is given by
G(r, r

) = −
exp(±i k |r −r

| )
4π|r −r

|
. (7.12)
Thus, Eq. (7.10) becomes
ψ
±
(r) = φ(r) −
2 m
¯h
2
¸
exp(±i k |r −r

| )
4π|r −r

|
'r

|H
1
|ψ` d
3
r

. (7.13)
A comparison of Eqs. (7.7) and (7.13) suggests that the kernel to Eq. (7.7) takes
the form

r

1
E −H
0
±i

r

¸
= −
2 m
¯h
2
exp(±i k |r −r

| )
4π|r −r

|
. (7.14)
It is not entirely clear that the ± signs correspond on both sides of this equation.
In fact, they do, as is easily proved by a more rigorous derivation of this result.
Let us suppose that the scattering Hamiltonian, H
1
, is only a function of the
position operators. This implies that
'r

|H
1
|r` = V(r) δ(r −r

). (7.15)
We can write
'r

|H
1

±
` =
¸
'r

|H
1
|r

`'r


±
` d
3
r

= V(r

) ψ
±
(r

). (7.16)
Thus, the integral equation (7.13) simplifies to
ψ
±
(r) = φ(r) −
2 m
¯h
2
¸
exp(±i k |r −r

|)
4π|r −r

|
V(r

) ψ
±
(r

) d
3
r

. (7.17)
Suppose that the initial state |φ` is a plane-wave with wave-vector k (i.e., a
stream of particles of definite momentum p = ¯hk). The ket corresponding to
this state is denoted |k`. The associated wave-function takes the form
'r|k` =
exp( i kr)
(2π)
3/2
. (7.18)
172
7.2 The Lipmann-Schwinger equation 7 SCATTERING THEORY
The wave-function is normalized such that
'k|k

` =
¸
'k|r`'r|k

` d
3
r
=
¸
exp[−i r(k −k

)]
(2π)
3
d
3
r = δ(k −k

). (7.19)
Suppose that the scattering potential V(r) is only non-zero in some relatively
localized region centred on the origin (r = 0). Let us calculate the wave-function
ψ(r) a long way from the scattering region. In other words, let us adopt the
ordering r r

. It is easily demonstrated that
|r −r

| · r − ^rr

(7.20)
to first-order in r

/r, where
^r =
r
r
(7.21)
is a unit vector which points from the scattering region to the observation point.
Let us define
k

= k^r. (7.22)
Clearly, k

is the wave-vector for particles which possess the same energy as the
incoming particles (i.e., k

= k), but propagate from the scattering region to the
observation point. Note that
exp(±i k |r −r

| ) · exp(±i k r) exp(∓i k

r

). (7.23)
In the large-r limit, Eq. (7.17) reduces to
ψ(r)
±
·
exp( i kr)
(2π)
3/2

m
2π¯h
2
exp(±i k r)
r
¸
exp(∓i k

r

) V(r

) ψ
±
(r

) d
3
r

. (7.24)
The first term on the right-hand side is the incident wave. The second term
represents a spherical wave centred on the scattering region. The plus sign (on
ψ
±
) corresponds to a wave propagating away from the scattering region, whereas
the minus sign corresponds to a wave propagating towards the scattering region.
173
7.2 The Lipmann-Schwinger equation 7 SCATTERING THEORY
It is obvious that the former represents the physical solution. Thus, the wave-
function a long way from the scattering region can be written
ψ(r) =
1
(2π)
3/2

exp( i kr) +
exp( i kr)
r
f(k

, k)
¸
¸
, (7.25)
where
f(k

, k) = −
(2π)
2
m
¯h
2
¸
exp(−i k

r

)
(2π)
3/2
V(r

) ψ(r

) d
3
r

= −
(2π)
2
m
¯h
2
'k

|H
1
|ψ`. (7.26)
Let us define the differential cross-section dσ/dΩ as the number of particles
per unit time scattered into an element of solid angle dΩ, divided by the incident
flux of particles. Recall, from Sect. 4, that the probability flux (i.e., the particle
flux) associated with a wave-function ψ is
j =
¯h
m
Im(ψ

∇ψ). (7.27)
Thus, the probability flux associated with the incident wave-function,
exp( i kr)
(2π)
3/2
, (7.28)
is
j
inci
=
¯h
(2π)
3
m
k. (7.29)
Likewise, the probability flux associated with the scattered wave-function,
exp( i k r)
(2π)
3/2
f(k

, k)
r
, (7.30)
is
j
scat
=
¯h
(2π)
3
m
|f(k

, k)|
2
r
2
k^r. (7.31)
Now,

dΩ
dΩ =
r
2
dΩ|j
scat
|
|j
inci
|
, (7.32)
174
7.3 The Born approximation 7 SCATTERING THEORY
giving

dΩ
= |f(k

, k)|
2
. (7.33)
Thus, |f(k

, k)|
2
gives the differential cross-section for particles with incident mo-
mentum ¯hk to be scattered into states whose momentum vectors are directed in
a range of solid angles dΩ about ¯hk

. Note that the scattered particles possess
the same energy as the incoming particles (i.e., k

= k). This is always the case
for scattering Hamiltonians of the form shown in Eq. (7.15).
7.3 The Born approximation
Equation (7.33) is not particularly useful, as it stands, because the quantity
f(k

, k) depends on the unknown ket |ψ`. Recall that ψ(r) = 'r|ψ` is the solu-
tion of the integral equation
ψ(r) = φ(r) −
m
2π¯h
2
exp( i k r)
r
¸
exp(−i k

r

) V(r

) ψ(r

) d
3
r

, (7.34)
where φ(r) is the wave-function of the incident state. According to the above
equation the total wave-function is a superposition of the incident wave-function
and lots of spherical-waves emitted from the scattering region. The strength of
the spherical-wave emitted at a given point is proportional to the local value of
the scattering potential, V, as well as the local value of the wave-function, ψ.
Suppose that the scattering is not particularly strong. In this case, it is reason-
able to suppose that the total wave-function, ψ(r), does not differ substantially
from the incident wave-function, φ(r). Thus, we can obtain an expression for
f(k

, k) by making the substitution
ψ(r) →φ(r) =
exp( i kr)
(2π)
3/2
. (7.35)
This is called the Born approximation.
The Born approximation yields
f(k

, k) · −
m
2π¯h
2
¸
exp[ i (k −k

)r

] V(r

) d
3
r

. (7.36)
175
7.3 The Born approximation 7 SCATTERING THEORY
Thus, f(k

, k) is proportional to the Fourier transform of the scattering potential
V(r) with respect to the wave-vector q ≡ k −k

.
For a spherically symmetric potential,
f(k

, k) · −
m
2π¯h
2
¸¸¸
exp( i qr

cos θ

) V(r

) r
2
dr

sinθ

, (7.37)
giving
f(k

, k) · −
2 m
¯h
2
q
¸

0
r

V(r

) sin(qr

) dr

. (7.38)
Note that f(k

, k) is just a function of q for a spherically symmetric potential. It is
easily demonstrated that
q ≡ |k −k

| = 2 k sin(θ/2), (7.39)
where θ is the angle subtended between the vectors k and k

. In other words, θ
is the angle of scattering. Recall that the vectors k and k

have the same length
by energy conservation.
Consider scattering by a Yukawa potential
V(r) =
V
0
exp(−µr)
µr
, (7.40)
where V
0
is a constant and 1/µ measures the “range” of the potential. It follows
from Eq. (7.38) that
f(θ) = −
2 mV
0
¯h
2
µ
1
q
2

2
, (7.41)
since
¸

0
exp(−µr

) sin(qr

) dr

=
q
µ
2
+q
2
. (7.42)
Thus, in the Born approximation, the differential cross-section for scattering by a
Yukawa potential is

dΩ
·

¸
2 mV
0
¯h
2
µ
¸

2
1
[2 k
2
(1 − cos θ) +µ
2
]
2
, (7.43)
given that
q
2
= 4 k
2
sin
2
(θ/2) = 2 k
2
(1 − cos θ). (7.44)
176
7.3 The Born approximation 7 SCATTERING THEORY
The Yukawa potential reduces to the familiar Coulomb potential as µ → 0,
provided that V
0
/µ → ZZ

e
2
/4π
0
. In this limit the Born differential cross-
section becomes

dΩ
·

¸
2 mZZ

e
2

0
¯h
2
¸

2
1
16 k
4
sin
4
(θ/2)
. (7.45)
Recall that ¯hk is equivalent to |p|, so the above equation can be rewritten

dΩ
·

¸
ZZ

e
2
16π
0
E
¸

2
1
sin
4
(θ/2)
, (7.46)
where E = p
2
/2 m is the kinetic energy of the incident particles. Equation (7.46)
is the classical Rutherford scattering cross-section formula.
The Born approximation is valid provided that ψ(r) is not too different from
φ(r) in the scattering region. It follows, from Eq. (7.17), that the condition for
ψ(r) · φ(r) in the vicinity of r = 0 is

m
2π¯h
2
¸
exp( i k r

)
r

V(r

) d
3
r

<1. (7.47)
Consider the special case of the Yukawa potential. At low energies, (i.e., k < µ)
we can replace exp( i k r

) by unity, giving
2 m
¯h
2
|V
0
|
µ
2
<1 (7.48)
as the condition for the validity of the Born approximation. The condition for the
Yukawa potential to develop a bound state is
2 m
¯h
2
|V
0
|
µ
2
≥ 2.7, (7.49)
where V
0
is negative. Thus, if the potential is strong enough to form a bound
state then the Born approximation is likely to break down. In the high-k limit,
Eq. (7.47) yields
2 m
¯h
2
|V
0
|
µk
<1. (7.50)
This inequality becomes progressively easier to satisfy as k increases, implying
that the Born approximation is more accurate at high incident particle energies.
177
7.4 Partial waves 7 SCATTERING THEORY
7.4 Partial waves
We can assume, without loss of generality, that the incident wave-function is
characterized by a wave-vector k which is aligned parallel to the z-axis. The
scattered wave-function is characterized by a wave-vector k

which has the same
magnitude as k, but, in general, points in a different direction. The direction of k

is specified by the polar angle θ (i.e., the angle subtended between the two wave-
vectors), and an azimuthal angle ϕ about the z-axis. Equation (7.38) strongly
suggests that for a spherically symmetric scattering potential [i.e., V(r) = V(r)]
the scattering amplitude is a function of θ only:
f(θ, ϕ) = f(θ). (7.51)
It follows that neither the incident wave-function,
φ(r) =
exp( i k z)
(2π)
3/2
=
exp( i k r cos θ)
(2π)
3/2
, (7.52)
nor the total wave-function,
ψ(r) =
1
(2π)
3/2

exp( i k r cos θ) +
exp( i k r) f(θ)
r
¸
¸
, (7.53)
depend on the azimuthal angle ϕ.
Outside the range of the scattering potential, both φ(r) and ψ(r) satisfy the
free space Schr¨ odinger equation
(∇
2
+k
2
) ψ = 0. (7.54)
What is the most general solution to this equation in spherical polar coordinates
which does not depend on the azimuthal angle ϕ? Separation of variables yields
ψ(r, θ) =
¸
l
R
l
(r) P
l
(cos θ), (7.55)
since the Legendre functions P
l
(cos θ) form a complete set in θ-space. The Leg-
endre functions are related to the spherical harmonics introduced in Sect. 5 via
P
l
(cos θ) =


2 l +1
Y
0
l
(θ, ϕ). (7.56)
178
7.4 Partial waves 7 SCATTERING THEORY
Equations (7.54) and (7.55) can be combined to give
r
2
d
2
R
l
dr
2
+2 r
dR
l
dr
+ [k
2
r
2
−l (l +1)]R
l
= 0. (7.57)
The two independent solutions to this equation are called a spherical Bessel func-
tion, j
l
(k r), and a Neumann function, η
l
(k r). It is easily demonstrated that
j
l
(y) = y
l


1
y
d
dy

l
siny
y
, (7.58)
η
l
(y) = −y
l


1
y
d
dy

l
cos y
y
. (7.59)
Note that spherical Bessel functions are well-behaved in the limit y →0 , whereas
Neumann functions become singular. The asymptotic behaviour of these func-
tions in the limit y →∞is
j
l
(y) →
sin(y −l π/2)
y
, (7.60)
η
l
(y) → −
cos(y −l π/2)
y
. (7.61)
We can write
exp( i k r cos θ) =
¸
l
a
l
j
l
(k r) P
l
(cos θ), (7.62)
where the a
l
are constants. Note there are no Neumann functions in this expan-
sion, because they are not well-behaved as r → 0. The Legendre functions are
orthonormal,
¸
1
−1
P
n
(µ) P
m
(µ) dµ =
δ
nm
n +1/2
, (7.63)
so we can invert the above expansion to give
a
l
j
l
(k r) = (l +1/2)
¸
1
−1
exp( i k r µ) P
l
(µ) dµ. (7.64)
It is well-known that
j
l
(y) =
(−i)
l
2
¸
1
−1
exp( i yµ) P
l
(µ) dµ, (7.65)
179
7.4 Partial waves 7 SCATTERING THEORY
where l = 0, 1, 2, [see Abramowitz and Stegun (Dover, New York NY, 1965),
Eq. 10.1.14]. Thus,
a
l
= i
l
(2 l +1), (7.66)
giving
exp( i k r cos θ) =
¸
l
i
l
(2 l +1) j
l
(k r) P
l
(cos θ). (7.67)
The above expression tells us how to decompose a plane-wave into a series of
spherical-waves (or “partial waves”).
The most general solution for the total wave-function outside the scattering
region is
ψ(r) =
1
(2π)
3/2
¸
l
[A
l
j
l
(k r) +B
l
η
l
(k r)] P
l
(cos θ), (7.68)
where the A
l
and B
l
are constants. Note that the Neumann functions are allowed
to appear in this expansion, because its region of validity does not include the
origin. In the large-r limit, the total wave-function reduces to
ψ(r) ·
1
(2π)
3/2
¸
l

A
l
sin(k r −l π/2)
k r
−B
l
cos(k r −l π/2)
k r
¸
¸
P
l
(cos θ), (7.69)
where use has been made of Eqs. (7.60)–(7.61). The above expression can also
be written
ψ(r) ·
1
(2π)
3/2
¸
l
C
l
sin(k r −l π/2 +δ
l
)
k r
P
l
(cos θ), (7.70)
where the sine and cosine functions have been combined to give a sine function
which is phase-shifted by δ
l
.
Equation (7.70) yields
ψ(r) ·
1
(2π)
3/2
¸
l
C
l
exp[ i (k r −l π/2 +δ
l
)] − exp[−i (k r −l π/2 +δ
l
)]
2 i k r
P
l
(cos θ), (7.71)
which contains both incoming and outgoing spherical-waves. What is the source
of the incoming waves? Obviously, they must be part of the large-r asymptotic
180
7.5 The optical theorem 7 SCATTERING THEORY
expansion of the incident wave-function. In fact, it is easily seen that
φ(r) ·
1
(2π)
3/2
¸
l
i
l
(2l +1)
exp[ i (k r −l π/2)] − exp[−i (k r −l π/2)]
2 i k r
P
l
(cos θ) (7.72)
in the large-r limit. Now, Eqs. (7.52) and (7.53) give
(2π)
3/2
[ψ(r) −φ(r)] =
exp( i k r)
r
f(θ). (7.73)
Note that the right-hand side consists only of an outgoing spherical wave. This
implies that the coefficients of the incoming spherical waves in the large-r ex-
pansions of ψ(r) and φ(r) must be equal. It follows from Eqs. (7.71) and (7.72)
that
C
l
= (2 l +1) exp[ i (δ
l
+l π/2)]. (7.74)
Thus, Eqs. (7.71)–(7.73) yield
f(θ) =

¸
l=0
(2 l +1)
exp( i δ
l
)
k
sinδ
l
P
l
(cos θ). (7.75)
Clearly, determining the scattering amplitude f(θ) via a decomposition into par-
tial waves (i.e., spherical-waves) is equivalent to determining the phase-shifts δ
l
.
7.5 The optical theorem
The differential scattering cross-section dσ/dΩ is simply the modulus squared of
the scattering amplitude f(θ). The total cross-section is given by
σ
total
=
¸
|f(θ)|
2
dΩ
=
1
k
2


¸
1
−1

¸
l
¸
l

(2 l +1) (2 l

+1) exp[ i (δ
l
−δ
l
]
sinδ
l
sinδ
l
P
l
(µ) P
l
(µ), (7.76)
181
7.6 Determination of phase-shifts 7 SCATTERING THEORY
where µ = cos θ. It follows that
σ
total
=

k
2
¸
l
(2 l +1) sin
2
δ
l
, (7.77)
where use has been made of Eq. (7.63). A comparison of this result with Eq. (7.75)
yields
σ
total
=

k
Im[f(0)] , (7.78)
since P
l
(1) = 1. This result is known as the optical theorem. It is a reflection
of the fact that the very existence of scattering requires scattering in the forward
(θ = 0) direction in order to interfere with the incident wave, and thereby reduce
the probability current in this direction.
It is usual to write
σ
total
=

¸
l=0
σ
l
, (7.79)
where
σ
l
=

k
2
(2 l +1) sin
2
δ
l
(7.80)
is the lth partial cross-section: i.e., the contribution to the total cross-section from
the lth partial wave. Note that the maximumvalue for the lth partial cross-section
occurs when the phase-shift δ
l
takes the value π/2.
7.6 Determination of phase-shifts
Let us now consider how the phase-shifts δ
l
can be evaluated. Consider a spher-
ically symmetric potential V(r) which vanishes for r > a, where a is termed
the range of the potential. In the region r > a, the wave-function ψ(r) satisfies
the free-space Schr¨ odinger equation (7.54). The most general solution which is
consistent with no incoming spherical-waves is
ψ(r) =
1
(2π)
3/2

¸
l=0
i
l
(2 l +1) A
l
(r) P
l
(cos θ), (7.81)
182
7.6 Determination of phase-shifts 7 SCATTERING THEORY
where
A
l
(r) = exp( i δ
l
) [ cos δ
l
j
l
(k r) − sinδ
l
η
l
(k r) ] . (7.82)
Note that Neumann functions are allowed to appear in the above expression,
because its region of validity does not include the origin (where V = 0). The
logarithmic derivative of the lth radial wave-function A
l
(r) just outside the range
of the potential is given by
β
l+
= k a

cos δ
l
j

l
(k a) − sinδ
l
η

l
(k a)
cos δ
l
j
l
(k a) − sinδ
l
η
l
(k a)
¸
¸
, (7.83)
where j

l
(x) denotes dj
l
(x)/dx, etc. The above equation can be inverted to give
tanδ
l
=
k aj

l
(k a) −β
l+
j
l
(k a)
k aη

l
(k a) −β
l+
η
l
(k a)
. (7.84)
Thus, the problem of determining the phase-shift δ
l
is equivalent to that of ob-
taining β
l+
.
The most general solution to Schr¨ odinger’s equation inside the range of the
potential (r < a) which does not depend on the azimuthal angle ϕ is
ψ(r) =
1
(2π)
3/2

¸
l=0
i
l
(2 l +1) R
l
(r) P
l
(cos θ), (7.85)
where
R
l
(r) =
u
l
(r)
r
, (7.86)
and
d
2
u
l
dr
2
+

k
2

2m
¯h
2
V −
l (l +1)
r
2
¸
¸
u
l
= 0. (7.87)
The boundary condition
u
l
(0) = 0 (7.88)
ensures that the radial wave-function is well-behaved at the origin. We can
launch a well-behaved solution of the above equation from r = 0, integrate out
to r = a, and form the logarithmic derivative
β
l−
=
1
(u
l
/r)
d(u
l
/r)
dr

r=a
. (7.89)
183
7.7 Hard sphere scattering 7 SCATTERING THEORY
Since ψ(r) and its first derivatives are necessarily continuous for physically ac-
ceptible wave-functions, it follows that
β
l+
= β
l−
. (7.90)
The phase-shift δ
l
is obtainable from Eq. (7.84).
7.7 Hard sphere scattering
Let us test out this scheme using a particularly simple example. Consider scatter-
ing by a hard sphere, for which the potential is infinite for r < a, and zero for
r > a. It follows that ψ(r) is zero in the region r < a, which implies that u
l
= 0
for all l. Thus,
β
l−
= β
l+
= ∞, (7.91)
for all l. It follows from Eq. (7.84) that
tanδ
l
=
j
l
(k a)
η
l
(k a)
. (7.92)
Consider the l = 0 partial wave, which is usually referred to as the s-wave.
Equation (7.92) yields
tanδ
0
=
sin(k a)/k a
−cos(k a)/ka
= −tank a, (7.93)
where use has been made of Eqs. (7.58)–(7.59). It follows that
δ
0
= −k a. (7.94)
The s-wave radial wave function is
A
0
(r) = exp(−i k a)
[cos k a sink r − sink a cos k r]
k r
= exp(−i k a)
sin[k (r −a)]
k r
. (7.95)
The corresponding radial wave-function for the incident wave takes the form
˜
A
0
(r) =
sink r
k r
. (7.96)
184
7.7 Hard sphere scattering 7 SCATTERING THEORY
It is clear that the actual l = 0 radial wave-function is similar to the incident l = 0
wave-function, except that it is phase-shifted by k a.
Let us consider the low and high energy asymptotic limits of tanδ
l
. Low energy
means k a < 1. In this regime, the spherical Bessel functions and Neumann
functions reduce to:
j
l
(k r) ·
(k r)
l
(2 l +1)!!
, (7.97)
η
l
(k r) · −
(2 l −1)!!
(k r)
l+1
, (7.98)
where n!! = n(n −2) (n −4) 1. It follows that
tanδ
l
=
−(k a)
2 l+1
(2 l +1) [(2 l −1)!!]
2
. (7.99)
It is clear that we can neglect δ
l
, with l > 0, with respect to δ
0
. In other words,
at low energy only s-wave scattering (i.e., spherically symmetric scattering) is
important. It follows from Eqs. (7.33), (7.75), and (7.94) that

dΩ
=
sin
2
k a
k
2
· a
2
(7.100)
for k a <1. Note that the total cross-section
σ
total
=
¸

dΩ
dΩ = 4πa
2
(7.101)
is four times the geometric cross-section πa
2
(i.e., the cross-section for classical
particles bouncing off a hard sphere of radius a). However, low energy scattering
implies relatively long wave-lengths, so we do not expect to obtain the classical
result in this limit.
Consider the high energy limit k a 1. At high energies, all partial waves
up to l
max
= k a contribute significantly to the scattering cross-section. It follows
from Eq. (7.77) that
σ
total
=

k
2
l
max
¸
l=0
(2 l +1) sin
2
δ
l
. (7.102)
185
7.8 Low energy scattering 7 SCATTERING THEORY
With so many l values contributing, it is legitimate to replace sin
2
δ
l
by its average
value 1/2. Thus,
σ
total
=
ka
¸
l=0

k
2
(2 l +1) · 2πa
2
. (7.103)
This is twice the classical result, which is somewhat surprizing, since we might ex-
pect to obtain the classical result in the short wave-length limit. For hard sphere
scattering, incident waves with impact parameters less than a must be deflected.
However, in order to produce a “shadow” behind the sphere, there must be scat-
tering in the forward direction (recall the optical theorem) to produce destruc-
tive interference with the incident plane-wave. In fact, the interference is not
completely destructive, and the shadow has a bright spot in the forward direc-
tion. The effective cross-section associated with this bright spot is πa
2
which,
when combined with the cross-section for classical reflection, πa
2
, gives the ac-
tual cross-section of 2πa
2
.
7.8 Low energy scattering
At low energies (i.e., when 1/k is much larger than the range of the potential)
partial waves with l > 0, in general, make a negligible contribution to the scatter-
ing cross-section. It follows that, at these energies, with a finite range potential,
only s-wave scattering is important.
As a specific example, let us consider scattering by a finite potential well, char-
acterized by V = V
0
for r < a, and V = 0 for r ≥ a. Here, V
0
is a constant.
The potential is repulsive for V
0
> 0, and attractive for V
0
< 0. The outside
wave-function is given by [see Eq. (7.82)]
A
0
(r) = exp( i δ
0
) [j
0
(k r) cos δ
0
−η
0
(k r) sinδ
0
] (7.104)
=
exp( i δ
0
) sin(k r +δ
0
)
k r
, (7.105)
where use has been made of Eqs. (7.58)–(7.59). The inside wave-function follows
186
7.8 Low energy scattering 7 SCATTERING THEORY
from Eq. (7.87). We obtain
A
0
(r) = B
sink

r
r
, (7.106)
where use has been made of the boundary condition (7.88). Here, B is a constant,
and
E −V
0
=
¯h
2
k
2
2 m
. (7.107)
Note that Eq. (7.106) only applies when E > V
0
. For E < V
0
, we have
A
0
(r) = B
sinhκ r
r
, (7.108)
where
V
0
−E =
¯h
2
κ
2
2 m
. (7.109)
Matching A
0
(r), and its radial derivative at r = a, yields
tan(k a +δ
0
) =
k
k

tank

a (7.110)
for E > V
0
, and
tan(k a +δ
0
) =
k
κ
tanhκ a (7.111)
for E < V
0
.
Consider an attractive potential, for which E > V
0
. Suppose that |V
0
| E
(i.e., the depth of the potential well is much larger than the energy of the inci-
dent particles), so that k

k. It follows from Eq. (7.110) that, unless tank

a
becomes extremely large, the right-hand side is much less that unity, so replacing
the tangent of a small quantity with the quantity itself, we obtain
k a +δ
0
·
k
k

tank

a. (7.112)
This yields
δ
0
· k a

¸
tank

a
k

a
−1
¸

. (7.113)
187
7.9 Resonances 7 SCATTERING THEORY
According to Eq. (7.102), the scattering cross-section is given by
σ
total
·

k
2
sin
2
δ
0
= 4πa
2

¸
tank

a
k

a
−1
¸

2
. (7.114)
Now
k

a =

k
2
a
2
+
2 m|V
0
| a
2
¯h
2
, (7.115)
so for sufficiently small values of k a,
k

a ·

2 m|V
0
| a
2
¯h
2
. (7.116)
It follows that the total (s-wave) scattering cross-section is independent of the
energy of the incident particles (provided that this energy is sufficiently small).
Note that there are values of k

a (e.g., k

a · 4.49) at which δ
0
→ π, and the
scattering cross-section (7.114) vanishes, despite the very strong attraction of the
potential. In reality, the cross-section is not exactly zero, because of contributions
from l > 0 partial waves. But, at low incident energies, these contributions are
small. It follows that there are certain values of V
0
and k which give rise to almost
perfect transmission of the incident wave. This is called the Ramsauer-Townsend
effect, and has been observed experimentally.
7.9 Resonances
There is a significant exception to the independence of the cross-section on en-
ergy. Suppose that the quantity

2 m|V
0
| a
2
/¯h
2
is slightly less than π/2. As the
incident energy increases, k

a, which is given by Eq. (7.115), can reach the value
π/2. In this case, tank

a becomes infinite, so we can no longer assume that the
right-hand side of Eq. (7.110) is small. In fact, at the value of the incident energy
when k

a = π/2, it follows from Eq. (7.110) that k a + δ
0
= π/2, or δ
0
· π/2
(since we are assuming that k a <1). This implies that
σ
total
=

k
2
sin
2
δ
0
= 4πa
2

1
k
2
a
2

. (7.117)
188
7.9 Resonances 7 SCATTERING THEORY
Note that the cross-section now depends on the energy. Furthermore, the mag-
nitude of the cross-section is much larger than that given in Eq. (7.114) for
k

a = π/2 (since k a <1).
The origin of this rather strange behaviour is quite simple. The condition

2 m|V
0
| a
2
¯h
2
=
π
2
(7.118)
is equivalent to the condition that a spherical well of depth V
0
possesses a bound
state at zero energy. Thus, for a potential well which satisfies the above equation,
the energy of the scattering system is essentially the same as the energy of the
bound state. In this situation, an incident particle would like to form a bound
state in the potential well. However, the bound state is not stable, since the
system has a small positive energy. Nevertheless, this sort of resonance scattering
is best understood as the capture of an incident particle to form a metastable
bound state, and the subsequent decay of the bound state and release of the
particle. The cross-section for resonance scattering is generally far higher than
that for non-resonance scattering.
We have seen that there is a resonant effect when the phase-shift of the s-wave
takes the value π/2. There is nothing special about the l = 0 partial wave, so it
is reasonable to assume that there is a similar resonance when the phase-shift of
the lth partial wave is π/2. Suppose that δ
l
attains the value π/2 at the incident
energy E
0
, so that
δ
l
(E
0
) =
π
2
. (7.119)
Let us expand cot δ
l
in the vicinity of the resonant energy:
cot δ
l
(E) = cot δ
l
(E
0
) +

dcot δ
l
dE

E=E
0
(E −E
0
) + (7.120)
= −

¸
1
sin
2
δ
l

l
dE
¸

E=E
0
(E −E
0
) + . (7.121)
Defining

¸

l
(E)
dE
¸

E=E
0
=
2
Γ
, (7.122)
189
7.9 Resonances 7 SCATTERING THEORY
we obtain
cot δ
l
(E) = −
2
Γ
(E −E
0
) + . (7.123)
Recall, from Eq. (7.80), that the contribution of the lth partial wave to the scat-
tering cross-section is
σ
l
=

k
2
(2 l +1) sin
2
δ
l
=

k
2
(2 l +1)
1
1 + cot
2
δ
l
. (7.124)
Thus,
σ
l
·

k
2
(2 l +1)
Γ
2
/4
(E −E
0
)
2

2
/4
. (7.125)
This is the famous Breit-Wigner formula. The variation of the partial cross-section
σ
l
with the incident energy has the form of a classical resonance curve. The
quantity Γ is the width of the resonance (in energy). We can interpret the Breit-
Wigner formula as describing the absorption of an incident particle to form a
metastable state, of energy E
0
, and lifetime τ = ¯h/Γ (see Sect. 6.17).
190

Contents
1 Introduction 1.1 Major sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Fundamental concepts 2.1 The breakdown of classical physics . . . . . . . . . 2.2 The polarization of photons . . . . . . . . . . . . . 2.3 The fundamental principles of quantum mechanics 2.4 Ket space . . . . . . . . . . . . . . . . . . . . . . . 2.5 Bra space . . . . . . . . . . . . . . . . . . . . . . . 2.6 Operators . . . . . . . . . . . . . . . . . . . . . . . 2.7 The outer product . . . . . . . . . . . . . . . . . . 2.8 Eigenvalues and eigenvectors . . . . . . . . . . . . 2.9 Observables . . . . . . . . . . . . . . . . . . . . . . 2.10 Measurements . . . . . . . . . . . . . . . . . . . . 2.11 Expectation values . . . . . . . . . . . . . . . . . . 2.12 Degeneracy . . . . . . . . . . . . . . . . . . . . . . 2.13 Compatible observables . . . . . . . . . . . . . . . 2.14 The uncertainty relation . . . . . . . . . . . . . . . 2.15 Continuous spectra . . . . . . . . . . . . . . . . . . 3 Position and momentum 3.1 Introduction . . . . . . . . . . . 3.2 Poisson brackets . . . . . . . . . 3.3 Wave-functions . . . . . . . . . . 3.4 Schr¨dinger’s representation - I . o 3.5 Schr¨dinger’s representation - II o 3.6 The momentum representation . 3.7 The uncertainty relation . . . . . 3.8 Displacement operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 5 6 6 7 9 10 14 17 19 20 21 24 25 26 27 28 31 33 33 33 37 39 43 46 48 50

4 Quantum dynamics 55 4.1 Schr¨dinger’s equations of motion . . . . . . . . . . . . . . . . . . 55 o 4.2 Heisenberg’s equations of motion . . . . . . . . . . . . . . . . . . . 59
2

4.3 4.4

Ehrenfest’s theorem . . . . . . . . . . . . . . . . . . . . . . . . . . 61 Schr¨dinger’s wave-equation . . . . . . . . . . . . . . . . . . . . . 65 o . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71 71 74 78 81 84 86 89 91 93 96 97 99 105 110 120 120 120 122 124 129 132 134 140 144 146 149 150 154 158 159

5 Angular momentum 5.1 Orbital angular momentum . . . . . . . . . . 5.2 Eigenvalues of angular momentum . . . . . . 5.3 Rotation operators . . . . . . . . . . . . . . . 5.4 Eigenfunctions of orbital angular momentum 5.5 Motion in a central field . . . . . . . . . . . . 5.6 Energy levels of the hydrogen atom . . . . . . 5.7 Spin angular momentum . . . . . . . . . . . 5.8 Wave-function of a spin one-half particle . . . 5.9 Rotation operators in spin space . . . . . . . 5.10 Magnetic moments . . . . . . . . . . . . . . . 5.11 Spin precession . . . . . . . . . . . . . . . . . 5.12 Pauli two-component formalism . . . . . . . . 5.13 Spin greater than one-half systems . . . . . . 5.14 Addition of angular momentum . . . . . . . .

6 Approximation methods 6.1 Introduction . . . . . . . . . . . . . . . . . . . . 6.2 The two-state system . . . . . . . . . . . . . . . . 6.3 Non-degenerate perturbation theory . . . . . . . 6.4 The quadratic Stark effect . . . . . . . . . . . . . 6.5 Degenerate perturbation theory . . . . . . . . . . 6.6 The linear Stark effect . . . . . . . . . . . . . . . 6.7 Fine structure . . . . . . . . . . . . . . . . . . . . 6.8 The Zeeman effect . . . . . . . . . . . . . . . . . 6.9 Time-dependent perturbation theory . . . . . . . 6.10 The two-state system . . . . . . . . . . . . . . . . 6.11 Spin magnetic resonance . . . . . . . . . . . . . 6.12 The Dyson series . . . . . . . . . . . . . . . . . . 6.13 Constant perturbations . . . . . . . . . . . . . . . 6.14 Harmonic perturbations . . . . . . . . . . . . . . 6.15 Absorption and stimulated emission of radiation
3

. . . . . . . . . .16 The electric dipole approximation . . 170 170 170 175 178 181 182 184 186 188 4 . .3 The Born approximation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9 Resonances . . . . . 7. .8 Low energy scattering . . . . . 7. . . . . . . . . . . . . . . . . . . . . . .1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7. . . . . . . . . . . . . . . . . . . . . . . .2 The Lipmann-Schwinger equation 7. . . . . . . . .6. . .5 The optical theorem . . . . . . 7. . . . 162 6. . 7. 7. . . . .6 Determination of phase-shifts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .17 Energy-shifts and decay-widths . . . . . . 165 7 Scattering theory 7. . . . . . . . . . . . . . . . . . . . . .7 Hard sphere scattering . . . . . . . .4 Partial waves . 7. . . . . . . . . . . . . . . . .

J. UK. Volume III (Addison-Wesley. 1958). 5 . 1970). Oxford. Sands.P Feynman.J. 2nd Edition (John Wiley & Sons. . 1965). R.A. R.M. (Benjamin/Cummings. Leighton. 1985). Sakurai. P ford University Press. and M.B. Dirac.1 Major sources The textbooks which I have consulted most frequently while developing course material are: . Merzbacher. New York NY. (OxThe principles of quantum mechanics. 4th Edition (revised). Modern quantum mechanics.1 INTRODUCTION 1 Introduction 1. Quantum mechanics. The Feynman lectures on physics. Reading MA. Menlo Park CA. E.

Cha. Experimentally. The vibrational degrees of freedom appear to make no contribution at all (except at high temperatures). 3. Incidentally. light interference. The anomalous stability of atoms and molecules: According to classical physics. Wave-particle duality: Classical physics can deal with waves or particles. Vol. Experimentally. The anomalously low specific heats of atoms and molecules: According to the equipartition theorem of classical physics. This is completely inexplicable within the framework of classical physics.g. are largely apocryphal (see Feynman. the energy density of an electromagnetic field in vacuum is infinite due to a divergence of energy carried by short wave-length modes. However.2 FUNDAMENTAL CONCEPTS 2 Fundamental concepts 2. and gradually spiral in towards the nucleus. various experiments (e. electron diffraction) show quite clearly that waves sometimes act as if they were streams of particles. The ultraviolet catastrophe: According to classical physics. and streams of particles sometimes act as if they were waves. 6 .1 The breakdown of classical physics The necessity for a departure from classical mechanics is clearly demonstrated by: 1. 2. 4. the photo-electric effect. only the translational and some rotational degrees of freedom seem to contribute. In fact. and the total energy density is finite. Stories that physicists at the start of the twentieth century thought that classical physics explained everything. each degree of freedom of an atomic or molecular system should contribute R/2 to its molar specific heat. and that there was nothing left to discover. 40). this is not observed to happen. an electron orbiting a nucleus should lose energy by emission of synchrotron radiation. there is no such divergence. I.. where R is the ideal gas constant. this fundamental problem with classical physics was known and appreciated in the middle of the nineteenth century.

The possible results of the experiment are that either a whole photon. the polarization properties of light. and then look to see whether or not it emerges from the other side. But. This picture leads to no difficulty if the plane of polarization lies parallel or perpendicular to the optic axis of the polaroid. what happens in the case of an obliquely polarized incident beam? The above question is not very precise. Clearly. If we repeat the experiment a great number of times then. Consider the following well-known experiment. Let us reformulate it as a question relating to the result of some experiment which we could perform. a fraction sin2 α of the photons are transmitted through the film. Suppose that we were to fire a single photon at a polaroid film. if the beam is polarized parallel to the optic axis then none of the light is transmitted.2. and if the light is polarized at an angle α to the axis then a fraction sin 2 α of the beam is transmitted. none of the photons are transmitted. also extend to its particle-like behaviour. In particular. Any photon which is transmitted though the film must be polarized perpendicular to the optic axis. all of the photons are transmitted. and. Classical electromagnetic wave theory tells us that if the beam is polarized perpendicular to the optic axis then all of the light is transmitted. Furthermore. A beam of plane polarized light is passed through a polaroid film. is observed.2 The polarization of photons It is known experimentally that when plane polarized light is used to eject photoelectrons there is a preferred direction of emission of the electrons. Let us try to account for these observations at the individual photon level. in the latter case. and a fraction 7 . In the former case. or no photon is observed. whose energy is equal to the energy of the incident photon. it is impossible to imagine (in physics) finding part of a photon on the other side of the film.2 The polarization of photons 2 FUNDAMENTAL CONCEPTS 2. on average. which has the property that it is only transparent to light whose plane of polarization lies perpendicular to its optic axis. A beam of light which is plane polarized in a certain direction is made up of a stream of photons which are each plane polarized in that direction. a polarization can be ascribed to each individual photon in a beam of light. which are more usually associated with its wavelike behaviour.

In other words. Questions as to what decides whether the photon is transmitted or not. Since there is nothing special about the orientation of the optic axis in our experiment. the oblique polarization state is some sort of superposition of two states of parallel and perpendicular polarization. and a probability cos2 α of being absorbed. and there is nothing left over to uniquely determine whether the photon is transmitted or absorbed by the film. by abandoning the determinacy of classical theory. The further description provided by quantum mechanics is as follows. Thus. or how it changes its direction of polarization. then the state of each individual photon in the beam is completely specified. direction of propagation. but recall that the state of a photon is fully specified once its energy. are illegitimate. some further description is needed in order to allow the results of this experiment to be correlated with the results of other experiments which can be performed using photons. We only know the probability of each event occurring. The above discussion about the results of an experiment with a single obliquely polarized photon incident on a polaroid film answers all that can be legitimately asked about what happens to the photon when it reaches the film. This is a fairly sweeping statement. These values for the probabilities lead to the correct classical limit for a beam containing a large number of photons. in all cases. normally incident on a polaroid film. with a particular oblique polarization. Nevertheless. If we imagine performing experiments using monochromatic light. and adopting a fundamentally probabilistic approach. since they do not relate to the outcome of a possible experiment. we must conclude that any state of polarization can be regarded as a superposition of two mutually perpendicular states of polarization. We have no way of knowing whether an individual obliquely polarized photon is going to be absorbed by or transmitted through a polaroid film. Note that we have only been able to preserve the individuality of photons. and polarization are known.2 The polarization of photons 2 FUNDAMENTAL CONCEPTS cos2 α are absorbed. we conclude that a photon has a probability sin 2 α of being transmitted as a photon polarized in the plane perpendicular to the optic axis. 8 . and partly in a state of polarization perpendicular to the axis.2. It is supposed that a photon polarized obliquely to the optic axis can be regarded as being partly in a state of polarization parallel to the axis.

but is governed by probability laws. 2. Sect.2. an atom.3 The fundamental principles of quantum mechanics There is nothing special about the transmission and absorption of photons through a polaroid film. the introduction of indeterminacy into the problem is clearly connected with the act of observation. Note that. If the photon jumps into a state of parallel polarization then it is absorbed. molecule. we are observing whether it is polarized parallel or perpendicular to the optic axis. Exactly the same conclusions as those outlined above are obtained by studying other simple experiments. The principle of indeterminacy: An observation made on a microscopic system causes it to jump into one or more particular states (which are related to 9 . Feynman. we are subjecting it to an observation. it is transmitted. Cha. In other words. The effect of making this observation is to force the photon entirely into a state of parallel or perpendicular polarization. any state can be regarded as a superposition of two or more other states. Any other questions lie beyond the realms of physics. Which of the two states it will jump into cannot be predicted. Otherwise. in this example. The study of these simple experiments leads us to formulate the following fundamental principles of quantum mechanics: 1. I. or particle) in a given state can be regarded as being partly in each of two or more other states.3). 1. Dirac’s razor: Quantum mechanics can only answer questions regarding the outcome of possible experiments. In other words. Cha. 2. In other words.. such as the interference of photons (see Dirac. and the Stern-Gerlach experiment (see Sakurai. 5).e. The principle of superposition of states: Any microscopic system (i. In fact. the photon has to jump suddenly from being partly in each of these two states to being entirely in one or the other of them. the indeterminacy is related to the inevitable disturbance of the system associated with the act of observation. 3.3 The fundamental principles of quantum mechanics 2 FUNDAMENTAL CONCEPTS When we make the photon encounter a polaroid film. Such superpositions can be performed in an infinite number of different ways.

any given state can be regarded as a superposition of two or more other states. There will be various possible motions of the particles or bodies consistent with the laws of force. The most obvious examples of such quantities are vectors.. The first of these principles was formulated by quantum physicists (such as Dirac) in the 1920s to fend off awkward questions such as “How can a system suddenly jump from one state into another?”. We need to extend it so that we can predict which possible states a system can jump into after a particular type of observation. which we also label A. momentum. B and 10 . As we shall see. According to the principle of superposition of states. The state vector A is conventionally written |A . The final principle is still rather vague. Let us consider a particular microscopic system in a particular state. where the other elements of the space represent all of the other possible states of the system. and polarization. residing in some vector space. We can represent this state as a particular vector. Let us term each such motion a state of the system. which we label A: e.) interacting according to specific laws of force.4 Ket space Consider a microscopic system composed of particles or bodies with specific properties (mass.1) Suppose that state A is. the superposition of two different states. or “How does a system decide which state to jump into?”. moment of inertia. however the probability of a given system jumping into a given final state can be predicted. as well as the probability of the system making a particular jump.g. the second principle is the basis for the mathematical formulation of quantum mechanics. (2.4 Ket space 2 FUNDAMENTAL CONCEPTS the type of observation). It is impossible to predict into which final state a particular system will jump. Thus. Such a space is called a ket space (after Dirac).2. etc. a photon with a particular energy. states must be related to mathematical quantities of a kind which can be added together to give other quantities of the same kind. 2. in fact.

. ket vectors differ from conventional vectors in that their magnitudes.e.5) for any vector |A . (2. and sin α of state C. and state |C might represent a similar photon plane polarized in the y-direction. Thus. no distinction being made between the directions of the ket vectors |A and −|A . we require cos α of state B. This latter state is represented by |B + |C in ket space.3) in ket space.2. no state. Suppose that we want to construct a state whose plane of polarization makes an arbitrary angle α with the x-direction. are physically irrelevant.2) where |B is the vector relating to the state B.4) corresponds to the same state that |A does. Note that we cannot form a new state by superposing a state with itself. By analogy with classical physics. etc. This interrelation is represented in ket space by writing |A = |B + |C . We can do this via a suitably weighted superposition of states B and C. and plane polarized in the xdirection. or lengths. For instance. If c1 + c2 = 0 then the superposition process yields nothing at all: i. a photon polarized in the y-direction superposed with another photon polarized in the y-direction (with the same energy and momentum) gives the same photon.and y-directions (by analogy with classical physics). one caveat to the above statements. (2. All the states of the system are in one to one correspondence with all the possible directions of vectors in the ket space.4 Ket space 2 FUNDAMENTAL CONCEPTS C. The absence of a state is represented by the null vector |0 in ket space.e. state |B might represent a photon propagating in the z-direction. however. In this case.. The null vector has the fairly obvious property that |A + |0 = |A . The fact that ket vectors pointing in the same direction represent the same state relates ultimately to the quantization of matter: i. This implies that the ket vector c1 |A + c2 |A = (c1 + c2 )|A (2. This new state is represented by cos α |B + sin α |C (2. the sum of these two states represents a photon whose plane of polarization makes an angle of 45◦ with both the x. There is. For instance. the fact 11 .

or a molecule. if we were to represent a classical wave by a vector. plane polarized in orthogonal directions. we can use complex numbers to simultaneously represent the weighting and relative phase in a linear superposition. atoms. (2.7) (2. and the direction would correspond to the frequency and wave-length. if we observe a wave then the amplitude of the wave can take any value between zero and infinity. with equal weights given to the two states. Thus. so that |R = c1 |A + c2 |B . If we observe a microscopic system then we either see a state (i. By analogy with classical physics. We conclude that a ket space must be a complex vector space if it is to properly represent the mutual interrelations between the possible states of a microscopic system.3). of the vector would correspond to the amplitude of the wave. A general elliptically polarized photon is represented by c1 |B + c2 |C . Well. In classical physics. in Eq. This suggests that a circularly polarized photon is the superposition of a photon polarized in the x-direction (state B) and a photon polarized in the y-direction (state C).e. Thus. (2.4 Ket space 2 FUNDAMENTAL CONCEPTS that it comes in irreducible packets called photons.. which are in phase quadrature. then the magnitude. that any plane polarized state of a photon can be represented as a linear superposition of two orthogonal polarization states in which the weights are real numbers. We have seen. a circularly polarized photon is represented by |B + i |C in ket space. Suppose that the ket |R is expressible linearly in terms of the kets |A and |B . etc. (2. or an atom.2.) or we see nothing—we can never see a fraction or a multiple of a state.6) where c1 and c2 are complex numbers. so that two vectors of different lengths pointing in the same direction would represent different wave states. a photon. but with the proviso that state C is 90 ◦ out of phase with state B. or length. electrons. we know from classical physics that a circularly polarized wave is a superposition of two waves of equal amplitude. Suppose that we want to construct a circularly polarized photon state.8) 12 . etc.

we can also say that state R is dependent on states A and B. the spin states of an electron in a magnetic field). The possible states of such a system are represented as a ket space whose dimensions are nondenumerably infinite.and y-directions. The possible states of such a system are represented as a ket space whose dimensions are denumerably infinite. Likewise. Such a space can be treated in more or less the same manner as a finite-dimensional space. It follows that the state R can be regarded as a linear superposition of the states A and B. Likewise. or denumerably infinite. The dimensionality of a conventional vector space is defined as the number of independent vectors contained in the space. one-dimensional potential well). Some microscopic systems have a finite number of independent states (e.g.. In fact. some microscopic systems have a nondenumerably infinite number of independent states (e. the ket space which represents the possible polarization states of a photon propagating in the z-direction is two-dimensional (the two independent vectors correspond to photons plane polarized in the x.g. This type of space requires a slightly different treatment to spaces of finite. 13 . In conclusion.2. the dimensionality of a ket space is equivalent to the number of independent ket vectors it contains. Such a space is termed a Hilbert space by mathematicians. a free particle). Some microscopic systems have a denumerably infinite number of independent states (e. a particle in an infinitely deep. So.. then the possible states of the system are represented as an N-dimensional ket space. respectively).g. Unfortunately. dimensions.. the states of a general microscopic system can be represented as a complex vector space of (possibly) infinite dimensions.4 Ket space 2 FUNDAMENTAL CONCEPTS We say that |R is dependent on |A and |B . a set of ket vectors (or states) are termed independent if none of them are expressible linearly in terms of the others. any ket vector (or state) which is expressible linearly in terms of certain others is said to be dependent on them. Thus. If there are N independent states.

(2. Only a special subset of denumerably infinite dimensional spaces have this property (i.5 Bra space 2 FUNDAMENTAL CONCEPTS 2..9) Let us narrow our focus to those functionals which preserve the linear dependencies of the ket vectors upon which they operate. N → ∞). satisfies F|(|A + |B ) = F|(|A ) + F|(|B ). labeled F. (2. (2. and (hopefully) outputs a snack. such functionals are termed linear functionals.10) |A = i=1 αi |i . It also does so in a deterministic manner: i. (2.e.5 Bra space A snack machine inputs coins plus some code entered on a key pad. but since a ket space must be complete if it is to represent the states of a microscopic system. Not surprisingly. 14 .. where |A and |B are any two kets in a given ket space. the same money plus the same code produces the same snack (or the same error message) time after time.. labeled A. Imagine a general functional. we need only consider this special subset. The only way the functional F can satisfy Eq. acting on a general ket vector. We can imagine building a rather abstract snack machine which inputs ket vectors and outputs complex numbers in a deterministic fashion. this is only strictly true for finite-dimensional spaces. and spitting out a general complex number φA . A general linear functional. A general ket vector can be written1 N (2.e. Let the |i (where i runs from 1 to N) represent N independent ket vectors in this space.12) Actually. Consider an N-dimensional ket space [i.11) where the αi are an arbitrary set of complex numbers.10) for all vectors in the ket space is if N F|(|A ) = i=1 1 fi αi . Note that the input and output of the machine have completely different natures. a finite-dimensional. Mathematicians call such a machine a functional. labeled F. space].. or denumerably infinite dimensional (i.e.e. This process is represented mathematically by writing F|(|A ) = φA . they are complete).2.

e. So. that the dual to c A| is c∗ |A .14) But. A| is termed the dual vector to |A .2. It follows. Note that bra vectors are quite different in nature to ket vectors (hence. There are an infinite number of ways of setting up the correspondence between vectors in a ket space and those in the related bra space. DC (2. and its constituent vectors (which are actually functionals of the ket space) are called bra vectors. (2. where c is a complex number. these vectors are written in mirror image notation. it is dual to the original ket space). Let us define N basis functionals i| which satisfy i|(|j ) = δij . the corresponding bra vector is written N A| = i=1 α∗ i|.16) where the are the complex conjugates of the αi .17) . However.13) F| = i=1 fi i|. i (2.15) where DC stands for dual correspondence. It follows from the previous three equations that N (2. 1 2 15 DC α∗ i (2..11). |A ←→ A|. There is a one to one correspondence between the elements of the ket space and those of the related bra space. For a general ket vector A. this implies that the set of all possible linear functionals acting on an Ndimensional ket space is itself an N-dimensional vector space. there is a corresponding element. in the bra space. That is. (2. c1 |A + c2 |B ←→ c∗ A| + c∗ B|. from the above. More generally. · · · | and | · · · . which it is also convenient to label A. only one of these has any physical significance.5 Bra space 2 FUNDAMENTAL CONCEPTS where the fi are a set of complex numbers relating to the functional. so that they can never be confused). for every element A of the ket space. specified by Eq. Bra space is an example of what mathematicians call a dual vector space (i. This type of vector space is called a bra space (after Dirac).

e. It follows from Eqs. According to Eqs. as will become apparent later. if all of the α i are zero in Eq. and spits out a complex number.21) (2.18) acting on the ket vector |A . (2.5 Bra space 2 FUNDAMENTAL CONCEPTS Recall that a bra vector is a functional which acts on a general ket vector. where   1  ˜ |A . which also implies that B|A = 0. 2 An inner product is (almost) analogous to a scalar product between a covariant and contravariant vector in some curvilinear space.12). so the operation can also be written B||A . (2. however.16). This property of bra and ket vectors is essential for the probabilistic interpretation of quantum mechanics. ˜ Given a ket |A which is not the null ket. 2 A|A ≥ 0. i (2. Consider the functional which is dual to the ket vector N |B = i=1 βi |i (2.18). and that The equality sign only holds if |A is the null ket [i. This operation is denoted B|(|A ).22) 16 . N B|A = i=1 β∗ α i .. (2.11). (2. (2.19) Mathematicians term B|A the inner product of a bra and a ket. (2.12) and (2. and (2. It is easily demonstrated that B|A = A|B ∗ . This expression can be further simplified to give B|A .23) |A =  A|A We can now appreciate the elegance of Dirac’s notation. Note.20) that A|A is a real number. Two kets |A and |B are said to be orthogonal if A|B = 0. The combination of a bra and a ket yields a “bra(c)ket” (which is just a number). we can define a normalized ket | A . that we can omit the round brackets without causing any ambiguity.2. (2.20) Consider the special case where |B → |A .11)]. (2.

More of this later. of a conventional vector. We are only interested in operators which preserve the linear dependencies of the ket vectors upon which they act. for all complex numbers c. The main differences are that summations over discrete labels become integrations over continuous labels. and X(c|A ) = cX|A .24) Here. Suppose that when this operator acts on a general ket vector |A it spits out a new ket vector which is denoted X|A .25) 17 . Mathematicians call such a machine an operator. and is analogous to the length. and the normalization convention is somewhat different. Since |A and c|A represent the same physical state. (2. It is possible to define a dual bra space for a ket space of nondenumerably infinite dimensions in much the same manner as that described above. it makes sense to require that all kets corresponding to physical states have unit norms.26) (2. Consider a somewhat different machine which inputs a ket vector and spits out another ket vector in a deterministic fashion. Operators X and Y are said to be equal if X|A = Y|A (2. 2. for all ket vectors |A and |B . Such operators are termed linear operators.2.6 Operators We have seen that a functional is a machine which inputs a ket vector and spits out a complex number. or magnitude. completeness must be assumed (it cannot be proved).27) (2. A|A is known as the norm or “length” of |A . Kronecker delta-functions become Dirac delta-functions.6 Operators 2 FUNDAMENTAL CONCEPTS with the property ˜ ˜ A|A = 1. Consider an operator labeled X. Operator X is linear provided that X(|A + |B ) = X|A + X|B .

Operators can be added together.34) for any |A and B|. However. Consider the dual bra to X|A . we have only considered linear operators acting on ket vectors. X(Y Z) = (X Y)Z = X Y Z. and |A can be written B|X|A without ambiguity.33) (2. X + (Y + Z) = (X + Y) + Z. it is noncommutative: X Y = Y X. The equation which defines this vector is ( B|X)|A = B|(X|A ) (2.32) (2. it may be considered to be the inner product of |A with some bra. the operator in the middle.2. This bra depends linearly on B|. The multiplication is associative: X(Y|A ) = (X Y)|A = X Y|A . The triple product of B|.28) for all ket vectors in the space. This bra depends antilinearly on |A and must therefore depend linearly on A|.31) (2. (2. A suitable notation to use for the resulting bra when X operates on B| is B|X. provided we adopt the convention that the bra vector always goes on the left. in general.6 Operators 2 FUNDAMENTAL CONCEPTS for all kets in the ket space in question. so we may look on it as the result of some linear operator applied to B|. Thus. Thus. Operator X is termed the null operator if X|A = |0 (2. X. so we might as well call it the same operator acting on |B . This operator is uniquely determined by the original operator X. Consider the inner product of a general bra B| with the ket X|A . We can also give a meaning to their operating on bra vectors.30) So far. it may be regarded as the result of some 18 . and the ket vector on the right. Such addition is defined to obey a commutative and associate algebra: X + Y = Y + X.29) (2. This product is a number which depends linearly on |A . Operators can also be multiplied.

(2. DC X|A ←→ A|X† . and is denoted X† .40) since A|C is just a number. (2.7 The outer product 2 FUNDAMENTAL CONCEPTS linear operator applied to A|. (2.41) Mathematicians term the operator |B A| the outer product of |B and A|. This operator also acts on bras. ξ = ξ† . Thus. A Hermitian operator ξ has the special property that it is its own adjoint: i. plus (X Y)† = Y † X† .2. Suppose that we right-multiply the above product by the general ket |C . Are there any other products we are allowed to form? How about |B A| ? (2. It is also easily demonstrated that (|B A|)† = |A B|. A|B . as is easily demonstrated by left-multiplying the expression (2. Thus. 19 .39) This clearly depends linearly on the ket |A and the bra |B . |B A| acting on a general ket |C yields another ket. B|X|A .35) It is readily demonstrated that B|X† |A = A|X|B ∗ .e. We obtain |B A|C = A|C |B .36) 2.. (2. A|X. the product |B A| is a linear operator.38) (2. which is just a number. X Y.39) by a general bra C|. Clearly. The outer product should not be confused with the inner product.37) It is also easily seen that the adjoint of the adjoint of a linear operator is equivalent to the original operator. X|A .7 The outer product So far we have formed the following products: B|A . This operator is termed the adjoint of X. (2.

It follows that ξ |ξ = 0. These are denoted ξ|ξ = ξ |ξ . Consider the eigenkets and eigenvalues of a Hermitian operator ξ. and the eigenkets corresponding to different eigenvalues are orthogonal. |x . the ket X|A is not a constant multiple of |A .2.44) where |ξ is the eigenket associated with the eigenvalue ξ . x .47) where we have used the fact that |ξ is not the null ket. |x and have the property X|x = x |x . there are some special kets known as the eigenkets of operator X. (2. .44) by ξ |. X|x = x |x .48) 20 . These are denoted |x . However. are numbers called eigenvalues. applying X to one of its eigenkets yields the same eigenket multiplied by the associated eigenvalue. the dual equation to Eq.. (2... (2.44) (for the eigenvalue ξ ) reads ξ |ξ = ξ ∗ ξ |. This proves that the eigenvalues are real numbers.8 Eigenvalues and eigenvectors 2 FUNDAMENTAL CONCEPTS 2.43) .45) If we left-multiply Eq.46) Suppose that the eigenvalues ξ and ξ are the same. (2. . (2.8 Eigenvalues and eigenvectors In general. Three important results are readily deduced: (i) The eigenvalues are all real numbers. Since ξ is Hermitian. Clearly. (2. and take the difference. right-multiply the above equation by |ξ . (2.. we obtain (ξ − ξ ∗ ) ξ |ξ = 0. (2.. (2. It follows from the above that ξ = ξ ∗. Suppose that the eigenvalues ξ and ξ are different.42) where x . ..

etc. by placing a polaroid film in its path. the only objects we have left over are operators. it is reasonable to suppose that non-linear operators are also without physical significance.)? How can these be represented in our formalism? Well. the result is to cause the photon to jump into a state of polarization parallel or perpendicular to the optic axis of the film. so we must conclude that bras could just as well be used to represent the states of a microscopic system.49) (iii) The dual of any eigenket is an eigenbra belonging to the same eigenvalue.g. there is a one to one correspondence between the elements of a ket space and its dual bra space. we cannot predict into which state a given photon will jump 21 . its position. and conversely.. and linear operators. We. (ii) The eigenvalues associated with eigenkets are the same as the eigenvalues associated with eigenbras. However. momentum. in general. therefore. otherwise they would. (2. 2. The former state is absorbed. spit out bras/kets pointing in different directions when fed bras/kets pointing in the same direction but differing in length. We have already seen that kets can be used to represent the possible states of a microscopic system. kets. assume that the dynamical variables of a microscopic system are represented as linear operators acting on the bras and kets which correspond to the various possible states of the system. spin.2. and the latter state is transmitted (which is how we tell them apart). We have seen that if we observe the polarization state of a photon. energy. Since the lengths of bras and kets have no physical significance.9 Observables We have developed a mathematical formalism which comprises three types of objects—bras.9 Observables 2 FUNDAMENTAL CONCEPTS which demonstrates that eigenkets corresponding to different eigenvalues are orthogonal. An eigenbra of ξ corresponding to an eigenvalue ξ is defined ξ |ξ = ξ |ξ . In general. Note that the operators have to be linear. What about the dynamical variables of the system (e.

It is clear that the photon will definitely be transmitted through the second film. if an observation is made. In general. Note that the result of the measurement must be a real number (there are no measurement machines which output complex numbers). However.. more generally.e. we can say that when a dynamical variable of a microscopic system is measured the system is caused to jump into one of a number of independent states (note that the perpendicular and parallel polarization states of our photon are linearly independent). Not surprisingly. then a second observation. we do know that if the photon is initially polarized parallel to the optic axis then it will definitely be absorbed. by a fairly non-obvious leap of intuition. and yield the same value for the dynamical variable. each of these final states is associated with a different result of the measurement: i.. the result of the measurement is the eigenvalue associated with the eigenket into which the system jumps.9 Observables 2 FUNDAMENTAL CONCEPTS (except in a statistical sense). Finally. There is nothing special about the polarization states of a photon. made immediately after the first one. will definitely find the system in the same state. different results of the measurement) are orthogonal is in accordance with our earlier requirement that the states into which the system jumps should be mutually 22 . Furthermore. such a state is termed an eigenstate. a different value of the dynamical variable. with one particular value for the dynamical variable.2. we are going to assert that a measurement of a dynamical variable corresponding to an operator X in ket space causes the system to jump into a state corresponding to one of the eigenkets of X. and the system is found to be a one particular final state.e. The fact that the result of the measurement must be a real number implies that dynamical variables can only be represented by Hermitian operators (since only Hermitian operators are guaranteed to have real eigenvalues). We can make a second observation of the polarization state of such a photon by placing an identical polaroid film (with the same orientation of the optic axis) immediately behind the first film. So. and if it is initially polarized perpendicular to the axis then it will definitely be transmitted. The fact that the eigenkets of a Hermitian operator corresponding to different eigenvalues (i. We also known that after passing though the film a photon must be in a state of polarization perpendicular to the optic axis (otherwise it would not have been transmitted). How can we represent all of these facts in our mathematical formalism? Well.

independent of) any other eigenstate corresponding to a different eigenvalue. since such a state is not dependent on the original state.2. they span ket space). A Hermitian operator which satisfies this condition is termed an observable. for the sake of simplicity.e. the system is left in the associated eigenstate. every eigenvalue of ξ is a possible result of a measurement made on the corresponding dynamical variable. It follows that no matter what the initial state of the system. this eigenstate is orthogonal to (i. Conversely. 23 . Thus. In other words. the distinction between a state and its representative ket vector. then a measurement of ξ is bound to give the result ξ . it must always be able to jump into one of the eigenstates of ξ.. Conversely. if the system is in an eigenstate of ξ. it stands to reason that a measurement of ξ must always yield some result.e. will be dropped. This can only be the case if the eigenkets form a complete set (i. It follows that a second measurement made immediately after the first one must leave the system in an eigenstate corresponding to the eigenvalue ξ . a general ket must always be dependent on the eigenkets of ξ. in order for a Hermitian operator ξ to be observable its eigenkets must form a complete set. This follows because the system cannot jump into an eigenstate corresponding to a different eigenvalue of ξ. the second measurement is bound to give the same result as the first. In other words. then the states into which the system may jump on account of the measurement are such that the original state is dependent on them. immediately after an observation whose result is a particular eigenvalue ξ . However.. We can conclude that the result of a measurement of a dynamical variable represented by a Hermitian operator ξ must be one of the eigenvalues of ξ. First. This gives us the physical significance of the eigenvalues.9 Observables 2 FUNDAMENTAL CONCEPTS independent. and a dynamical variable and its representative operator. any observable quantity must be a Hermitian operator with a complete set of eigenstates. corresponding to an eigenvalue ξ . Second.) It is reasonable to suppose that if a certain dynamical variable ξ is measured with the system in a particular state. (From now on. This fairly innocuous statement has two very important corollaries. Furthermore.

It is convenient to normalize our eigenkets such that they all have unit norms. we are assuming that the eigenvalues of ξ are all different. Let us try again.51) . but it is possible to predict the probability of such a transition. | A|ξ |2 ? This quantity is definitely a positive number (so it could be a probability). It is easily demonstrated that |A = ξ |ξ ξ |A . It follows from the orthogonality property of the eigenkets that ξ |ξ = δξ ξ . Can we use this correspondence to obtain a general rule for calculating transition probabilities? Well. in general. as a result of a measurement made on the system? Let us start with the simplest case. we can express any given state |A as a linear combination of them. 24 (2. it is the correct guess. So. Can we identify the transition probability to a final eigenstate |ξ with the inner product A|ξ ? The straight answer is “no”. For the moment. Note that the probability of a transition from an initial eigenstate |ξ to a final eigenstate |ξ is the same as the value of the inner product ξ |ξ . (2. what is the probability that a system in some initial state |A makes a transition to an eigenstate |ξ of an observable ξ.2. How about if we identify the transition probability with the modulus squared of the inner product.10 Measurements We have seen that a measurement of some observable ξ of a microscopic system causes the system to jump into one of the eigenstates of ξ. Since the eigenstates of an observable ξ form a complete set. The result of the measurement is the associated eigenvalue (or some function of this quantity). In fact. This guess also gives the right answer for the transition probabilities between eigenstates. suppose that the system is initially in a state |A which is not an eigenstate of ξ. since A|ξ is. and zero otherwise. It is impossible to determine into which eigenstate a given system will jump.10 Measurements 2 FUNDAMENTAL CONCEPTS 2. If the system is initially in an eigenstate |ξ then the transition probability to a eigenstate |ξ corresponding to a different eigenvalue is zero. and complex probabilities do not make much sense.50) where δξ ξ is unity if ξ = ξ . and the transition probability to the same eigenstate |ξ is unity. a complex number.

(2. (2. We know that each measurement yields the value ξ with probability P(ξ ). (2. Suppose a measurement of the observable ξ is made on each system. which is equivalent to the relative probability of a measurement of ξ yielding the result ξ .54) ξ where 1 denotes the identity operator.57) 2. is given by ξ = ξ ξ P(ξ ) = ξ ξ | A|ξ |2 25 . is P(ξ ) ∝ | A|ξ |2 . ξ |A = ξ (2. = 2 A|A ξ | A|ξ | (2. What is the mean value of the measurement? This quantity. The absolute probability is clearly P(ξ ) = | A|ξ |2 | A|ξ |2 . and the fact that the eigenstates are mutually orthogonal.53) A|A = where the summation is over all the different eigenvalues of ξ. The relative probability of a transition to an eigenstate |ξ . which is generally referred to as the expectation value of ξ.55) If the ket |A is normalized such that its norm is unity.52) | A|ξ |2 .56) (2.11 Expectation values Consider an ensemble of microscopic systems prepared in the same initial state |A . Note that all of the above results follow from the extremely useful (and easily proved) result |ξ ξ | = 1.2. and use has been made of Eq.20). then this probability simply reduces to P(ξ ) = | A|ξ |2 .11 Expectation values 2 FUNDAMENTAL CONCEPTS A| = ξ A|ξ A|ξ ξ ξ |. (2.

This property depends on the particular correspondence (2. the proof of orthogonality given in Sect. (2.61) (2. |ξ1 |ξ2 = |ξa . in general. Note that it is only possible to normalize a given ket |A such that Eq. 1. they are not orthogonal to each other (i. but. Degenerate eigenstates are necessarily orthogonal to any eigenstates corresponding to different eigenvalues.60) is satisfied because of the more general property (2.. All states are eigenstates of this operator with the eigenvalue unity. however. Thus.12 Degeneracy 2 FUNDAMENTAL CONCEPTS = ξ ξ A|ξ ξ |A = ξ A|ξ|ξ ξ |A . (2. It follows that we can always construct two mutually orthogonal degenerate eigenstates.12 Degeneracy Suppose that two different eigenstates |ξa and |ξb of ξ correspond to the same eigenvalue ξ .54). (2. (2.16).8 does not work in this case).e. Note.59) 2.60) for all |A . since much of the previous formalism depends crucially on the mutual orthogonality of the different eigenstates of an observable. between the elements of a ket space and those of its dual bra space. (2.2. that we adopted earlier. For instance. This is unfortunate. Consider the identity operator. 1 − | ξa |ξb |2 (2. 2.. that any linear combination of |ξa and |ξb is also an eigenstate corresponding to the eigenvalue ξ . A|1|A = A|A = 1. the expectation value of this operator is always unity: i.58) which reduces to ξ = A|ξ|A with the aid of Eq.62) 26 . = |ξb − ξa |ξb |ξa . These are termed degenerate eigenstates.e.21) of the norm.

Is it still possible to measure both observables simultaneously? Let us again make an observation of ξ which throws the system into an eigenstate |ξ .13 Compatible observables Suppose that we wish to simultaneously measure two observables.and z-directions of the spin angular momentum of a spin one-half particle. We conclude that it is always possible to construct a complete set of mutually orthogonal eigenstates for any given observable. Sect. with the eigenvalue η . What happens if we now make a measurement of η? Well. 1. suppose that the eigenstate |ξ is also an eigenstate of η. Another measurement of ξ will throw the system into one of the (many) eigenstates of ξ which depend on |η . |ξ . and another which can measure η. Such observables are termed compatible.2. however. Suppose. In principle. if all eigenstates of ξ are also eigenstates of η then it is always possible to make a simultaneous measurement of ξ and η. that the eigenstates of ξ are not eigenstates of η. Each eigenstate is again associated with a different possible result of the measurement. Clearly. Suppose that we make a measurement of ξ. These could be measured using appropriate Stern-Gerlach apparatuses (see Sakurai. A second measurement of ξ will definitely give the result ξ . with eigenvalue ξ . In this case. we can say that the observables ξ and η simultaneously have the values ξ and η . 2. and so on. with eigenvalue η . It is clear that if the observables ξ and η do not possess simultaneous eigenstates then if the value 27 . each of these eigenstates is associated with a different result of the measurement. ξ and η. of a microscopic system? Let us assume that we possess an apparatus which is capable of measuring ξ. Suppose that the system is thrown into an eigenstate |η . a measurement of η will definitely give the result η . respectively. We can now make a second observation to determine η. with eigenvalue ξ . and the system is consequently thrown into one of the eigenstates of ξ. For instance. This will throw the system into one of the (many) eigenstates of η which depend on |ξ .1).13 Compatible observables 2 FUNDAMENTAL CONCEPTS This result is easily generalized to the case of more than two degenerate eigenstates. In this sense. the two observables in question might be the projection in the x.

14 The uncertainty relation 2 FUNDAMENTAL CONCEPTS of ξ is known (i.e. the system is not in an eigenstate of η).66) Thus. It is 28 . and vice versa. It follows that the simultaneous eigenstates of two observables must also form a complete set.67) (2. We have seen that the condition for two observables ξ and η to be simultaneously measurable is that they should possess simultaneous eigenstates (i. Let a general eigenstate of ξ. the above equation implies that (ξ η − η ξ)|A = |0 . then a determination of the value of ξ leaves the value of η uncertain.. The result is (ξ η − η ξ)|ξ η = |0 (2.e. the condition for two observables ξ and η to be simultaneously measurable is that they should commute. 2.2.14 The uncertainty relation We have seen that if ξ and η are two noncommuting observables. Recall that the eigenstates of an observable must form a complete set. Thus. (2.e. also be an eigenstate of η..63) (2. every eigenstate of ξ should also be an eigenstate of η). where |A is a general ket. with eigenvalue ξ . It is convenient to denote this simultaneous eigenstate |ξ η . = η |ξ η .. and then take the difference.64) We can left-multiply the first equation by η. with eigenvalue η . and vice versa. We say that the two observables are incompatible. and the second equation by ξ.65) for each simultaneous eigenstate. Suppose that this is the case. The only way that this can be true is if ξ η = η ξ. (2. the system is in an eigenstate of ξ) then the value of η is uncertain (i. We have ξ|ξ η η|ξ η = ξ |ξ η .

we can define a Hermitian operator ∆ξ = ξ − ξ . non-zero.74) (2. which is analogous to in Euclidian space.e. it is a measure of the width of the distribution of likely values of ξ about the expectation value).14 The uncertainty relation 2 FUNDAMENTAL CONCEPTS possible to quantify this uncertainty.70) where c is any complex number.68) where the expectation value is taken over the particular physical state under consideration. The expectation value of (∆ξ)2 ≡ ∆ξ ∆ξ is termed the variance of ξ.72) |a|2 | b|2 ≥ |a · b|2 (2.73) 29 . = ∆η| . and is..69) The variance of ξ is a measure of the uncertainty in the value of ξ for the particular state in question (i. and a measurement of ξ is bound to give the expectation value. (2. Let us substitute |A |B = ∆ξ| . In fact. (2. (2. Consider the Schwarz inequality A|A B|B ≥ | A|B |2 . (2. ξ . It is obvious that the expectation value of ∆ξ is zero. which is the same as the Schwarz inequality. If the variance is zero then there is no uncertainty. This inequality can be proved by noting that ( A| + c∗ B|)(|A + c|B ) ≥ 0.75) (2. it is easily demonstrated that (∆ξ)2 = ξ2 − ξ 2 .71) (2.2. For a general observable ξ. If c takes the special value − B|A / B|B then the above inequality reduces to A|A B|B − | A|B |2 ≥ 0. in general.

Taking the modulus squared of both sides gives ∆ξ ∆η = 1 1 | ∆ξ ∆η |2 = | [ξ. (2. ∆η}. (2. 2 2 where the commutator. ∆η] ≡ ∆ξ ∆η − ∆η ∆ξ. (2. so we can write 1 (∆ξ)2 (∆η)2 ≥ | [ξ. It is clear that the right hand side of 1 1 [∆ξ. (2. {∆ξ.76). in which case exact knowledge of ξ does not necessarily imply no knowledge of η. Now.82) 4 4 where use has been made of ∆ξ = 0. ∆η])† = (∆ξ ∆η − ∆η ∆ξ)† = ∆η ∆ξ − ∆ξ ∆η = − [∆ξ. and the anti-commutator. The commutator is clearly anti-Hermitian.83) 4 where use has been made of Eq. 30 . ∆η} .81) 2 2 consists of the sum of a purely real and a purely imaginary number.76) {∆ξ. η] |2 . ∆η} .80) whereas the anti-commutator is obviously Hermitian. ∆η] . whereas the expectation value of an anti-Hermitian operator is a pure imaginary number. ∆η] + {∆ξ. [∆ξ.78) (2. (2. ∆η} ≡ ∆ξ ∆η + ∆η ∆ξ. η] |2 + | {∆ξ.14 The uncertainty relation 2 FUNDAMENTAL CONCEPTS where use has been made of the fact that ∆ξ and ∆η are Hermitian operators.79) into the Schwarz inequality. We find (∆ξ)2 (∆η)2 ≥ | ∆ξ ∆η |2 . (2. The above expression is termed the uncertainty relation. where the blank ket | stands for any general ket. Note that 1 1 (2. etc. The one exception to this rule is when ξ and η commute. (2. The final term in the above expression is positive definite. ∆η] + {∆ξ. and vice versa. ∆η]. are defined [∆ξ. ([∆ξ.2.77) ∆ξ ∆η = [∆ξ. it is easily demonstrated that the expectation value of a Hermitian operator is a real number. ∆η} |2 . an exact knowledge of the value of ξ implies no knowledge whatsoever of the value of η. According to this relation.

We can still write the eigenvalue equation as ξ|ξ = ξ |ξ . This is the major difference between eigenstates in a finite-dimensional and an infinite-dimensional ket space. these eigenstates have infinite norms: i. The reason for this is because continuous eigenvalues imply a ket space of nondenumerably infinite dimension. (2. Hence. also.50) generalizes to ξ |ξ = δ(ξ − ξ ). that eigenstates corresponding to a continuous range of eigenvalues cannot be normalized so that they have unit norms. Let us assume.85) where δ(x) denotes the famous Dirac delta-function. that ξ can take any value. In fact. the most important observables of all. (2. the dimensionality of ket space is nondenumerably infinite.2. (2. In fact. The eigenstates |ξ must form a complete set if ξ is to be an observable.54) generalizes to dξ |ξ ξ | = 1. many of the results we obtained previously for a finite-dimensional ket space with discrete eigenvalues can be generalized to ket spaces of nondenumerably infinite dimensions. The extremely useful relation (2. generally have continuous eigenvalues. Note. Unfortunately. Fortunately. ξ can now take a continuous range of values.84) But. namely position and momentum. Note that there are clearly a nondenumerably infinite number of mutually orthogonal eigenstates of ξ.15 Continuous spectra Up to now. continuous eigenvalues are unavoidable in quantum mechanics. we have studiously avoided dealing with observables possessing eigenvalues which lie in a continuous range. Suppose that ξ is an observable with continuous eigenvalues. The orthogonality condition (2.e. rather than having discrete values.15 Continuous spectra 2 FUNDAMENTAL CONCEPTS 2. It follows that any general ket can be expanded in 31 .86) Note that a summation over discrete eigenvalues goes over into an integral over a continuous range of eigenvalues. for the sake of simplicity.. they are infinitely long.

II and III).2.15 Continuous spectra 2 FUNDAMENTAL CONCEPTS terms of the |ξ .51)–(2. observables whose eigenvalues can only take a finite range of values. We have seen that it is not possible to normalize the eigenstates |ξ such that they have unit norms.53) generalize to |A = dξ |ξ ξ |A .88) (2. There are number of other cases we could look at. ξ |A = dξ | A|ξ |2 . (2. (2.90) We have now studied observables whose eigenvalues can take a discrete number of values as well as those whose eigenvalues can take any value. Cha. ξ |.89). the expansions (2. this convenient normalization is still possible for a general state vector. In fact. Both of these cases can be dealt with using a fairly straight-forward generalization of the previous analysis (see Dirac. (2. For instance.89) A| = A|A = dξ A|ξ dξ A|ξ These results also follow simply from Eq. In fact. Fortunately.86). (2. 32 .87) (2. the normalization condition can be written A|A = dξ | A|ξ |2 = 1. according to Eq. or observables whose eigenvalues take on a finite range of values plus a set of discrete values.

the behaviour of a classical system can be specified in terms of Lagrangian or Hamiltonian dynamics.1) (3. For instance. Let us investigate the role of such variables in quantum mechanics.2 Poisson brackets Consider a dynamic system whose state at a particular time t is fully specified by N independent classical coordinates qi (where i runs from 1 to N). a Cartesian coordinate has an associated linear momentum. In quantum mechanics. In classical mechanics. the position q and momentum p of some component of a dynamical system are represented as real numbers which. what is the value of q p − p q? 3. dt ∂qi (3. However.3 POSITION AND MOMENTUM 3 Position and momentum 3. we have considered general dynamical variables represented by general linear operators acting in ket space. in Hamiltonian dynamics. dqi ∂H = . in classical mechanics the most important dynamical variables are those involving position and momentum. For instance. by definition.2) where the function H(qi . these quantities are represented as noncommuting linear Hermitian operators acting in a ket space which represents all of the possible states of the system. t) is the energy of the system at time t expressed in terms of the classical coordinates and canonical momenta. Do the position and momentum operators commute? If not. commute. Associated with each generalized coordinate qi is a classical canonical momentum pi . As is well-known. etc. an angular coordinate has an associated angular momentum. pi . This function is 33 . dt ∂pi dpi ∂H = − . Our first task is to discover a quantum mechanical replacement for the classical result q p − p q = 0.1 Introduction So far.

[pi . ∂qi ∂pi ∂pi ∂qi (3. one well-known construct in classical dynamics which involves products of dynamical variables. H].7) = [u. There is. 34 (3. We are interested in finding some construct of classical dynamics which consists of products of dynamical variables. pj ] = 0. [qi . The Poisson bracket of two dynamical variables u and v is defined N [u.8) . It is easily demonstrated that [qi . u].3) where u and v are regarded as functions of the coordinates and momenta qi and pi . pj ] = δij . v] = i=1 ∂u ∂v ∂u ∂v − . v] = −[v. where use has been made of Hamilton’s equations. If such a construct exists we hope to generalize it somehow to obtain a rule describing how dynamical variables commute with one another in quantum mechanics.3.4) (3. instead of functions? Well. Can we construct a quantum mechanical Poisson bracket in which u and v are noncommuting operators. the main properties of the classical Poisson bracket are as follows: [u.6) The time evolution of a dynamical variable can also be written in terms of a Poisson bracket by noting that du = dt = i=1 N i=1 N ∂u dpi ∂u dqi + ∂qi dt ∂pi dt ∂u ∂H ∂u ∂H − ∂qi ∂pi ∂pi ∂qi (3. indeed.5) (3. (3.2 Poisson brackets 3 POSITION AND MOMENTUM usually referred to as the Hamiltonian of the system. qj ] = 0.

since they now represent noncommuting operators. w. u. etc.18) (3. we can evaluate the Poisson bracket [u1 u2 . v2 ]. v]. v2 ] (3. c] = 0.9) (3.13) (3. [u1 u2 .16) (3. Thus. v2 ].17) Since this relation must hold for u1 and v1 quite independent of u2 and v2 . and [u1 u2 . [u. [u1 + u2 .15) = [u1 . v2 ]u2 + v1 u1 [u2 . v1 ]v2 + v1 [u2 . which satisfies all of the above relations? Well..19) . v] = [u1 . [w. v1 v2 ] = [u. [u. v2 ] [u1 u2 . Note that the order of the various factors has been preserved. u]] + [w. and [u. v1 ]v2 + u1 v1 [u2 . (3. v] + [u2 . v. v2 ]} = [u1 .13) first. v] = [u1 . Equating the above two results yields [u1 . it follows that u1 v1 − v1 u1 = i ¯ [u1 . v1 v2 ] = [u1 . v1 ]v2 u2 + v1 [u1 . v1 ].. v2 ].10) (3. v1 v2 ]u2 + u1 [u2 . v2 ]} u2 + u1 {[u2 . v]u2 + u1 [u2 . [u. v2 ]. v1 ]v2 + v1 [u1 . and c represents a number.3. etc. v1 ]u2 v2 + u1 [u2 . w]] + [v. h 35 (3. v1 v2 ] = [u1 u2 . represent dynamical variables. v]] = 0. v2 ]u2 + u1 [u2 . In the above. v1 v2 ] = {[u1 .12) or (3.2 Poisson brackets 3 POSITION AND MOMENTUM [u.12) (3. v1 ]v2 + v1 [u1 . v]. v1 v2 ] in two different ways. v1 ] + [u. v1 + v2 ] = [u. (3. v2 ]. Can we find some combination of noncommuting operators u and v.14) The last relation is known as the Jacobi identity.11) (3. v1 ]v2 + v1 [u1 u2 . since we can use either of the formulae (3. v1 ]v2 + v1 [u. v1 ](u2 v2 − v2 u2 ) = (u1 v1 − v1 u1 )[u2 . [v. h u2 v2 − v2 u2 = i ¯ [u2 .

.22). We h want the quantum mechanical Poisson bracket of two Hermitian operators to be an Hermitian operator itself.6261 × 10−34 J s (3. (3. and the quantum mechanical Poisson bracket. leads us to make the assumption that the quantum mechanical bracket has the same value as the corresponding classical bracket.23) (3. This argument yields the fundamental commutation relations [qi . (3. (3. Thus.2 Poisson brackets 3 POSITION AND MOMENTUM where ¯ does not depend on u1 . the notation [u. etc. the quantum mechanical Poisson bracket of two dynamical variables u and v is given by uv − vu [u. pj ] = i ¯ δij . defined in Eq.8)–(3. [u. [pi .22) i¯ h It is easily demonstrated that the quantum mechanical Poisson bracket. Somewhat confusingly. as defined above. defined in Eq. ξ 36 . we are assuming that Eqs.21) is Planck’s constant. For instance. satisfies all of the relations (3. v] = . it follows that ¯ is just a number. v]quantum = The strong analogy we have found between the classical Poisson bracket. where h h = 6. pj ] = 0. v]quantum to denote the quantum Poisson bracket. v1 . v] . (3. if two dynamical variables. are quite general operators.20) i¯ h where ¯ is a new universal constant of nature. h (3. since the classical Poisson bracket of two real dynamical variables is real. v] is conventionally reserved for the commutator u v − v u in quantum mechanics. [qi . We will use [u. at least for the simplest cases. This requirement is satisfied if ¯ is a real number.6) hold for quantum mechanical as well as classical Poisson brackets.3. v2 . h Since u1 .24) (3.25) These results provide us with the basis for calculating commutation relations between general dynamical variables. (3. [u. h Thus. and also commutes with (u1 v1 −v1 u1 ).4)–(3. In other words.14). Quantum mechanics agrees with h experiments provided that ¯ takes the value h/2π.3). qj ] = 0. u2 .

Moreover. x could be the position of a free particle). correspond to a different classical degree of freedom of the system. Moreover. In classih cal mechanics.25).3 Wave-functions Consider a simple system with one classical degree of freedom.8)–(3.23)–(3.13) allows [ξ.25) that in quantum mechanics the dynamical variables corresponding to different degrees of freedom all commute. (3.3 Wave-functions 3 POSITION AND MOMENTUM and η. η] to be expressed in terms of the fundamental commutation relations (3.25) provide the foundation for the analogy between quantum mechanics and classical mechanics. which corresponds to the Cartesian coordinate x. then repeated application of Eqs. It is clear from Eqs. (3. Suppose that x is free to take any value (e. (2. the operator x possesses eigenvalues x lying in the continuous range −∞ < x < +∞ (since the eigenvalues correspond to all the possible results of a measurement of x). mutually orthogonal. (3. Thus.27) This formula expresses the fact that the eigenkets are complete..g. (2. [see Eq. can both be written as a power series in the qi and pi . An eigenket corresponding to the eigenvalue x is denoted |x . (3. qi and pi .86)] +∞ dx |x −∞ x | = 1. Note that the classical result (that everything commutes) is obtained in the limit ¯ → 0. 3.23)–(3. We can span ket space using the suitably normalized eigenkets of x.23)–(3. 37 . It is only those variables corresponding to the same degree of freedom which may fail to commute. and suitably normalized. classical mechanics can be h regarded as the limiting case of quantum mechanics when ¯ goes to zero.26) The eigenkets satisfy the extremely useful relation [see Eq. Equations (3.85)] x |x = δ(x − x ). each pair of generalized coordinate and its conjugate momentum.3. The classical dynamical variable x is represented in quantum mechanics as a linear Hermitian operator which is also called x.

In other words. ψA (x ) is the famous wave-function of quantum mechanics.3 Wave-functions 3 POSITION AND MOMENTUM A state ket |A (which represents a general state A of the system) can be expressed as a linear superposition of the eigenkets of the position operator using Eq.10.30) This formula is only valid if the state ket |A is properly normalized: i. if A|A = 1. (3. B (3. The corresponding normalization for the wave-function is +∞ |ψA (x )|2 dx = 1. +∞ |A = −∞ dx x |A |x (3. assuming that the eigenvalues of ξ are discrete. We can write x |A = ψA (x ). from Sect.3. (3. Note that state A is completely specified by its wave-function ψA (x ) [since the wave-function can be used to reconstruct the state ket |A using Eq..32) 38 . −∞ (3.e.28) The quantity x |A is a complex function of the position eigenvalue x . Thus. This result is easily generalized to dynamical variables possessing continuous eigenvalues. (3. when it is expanded in terms of the eigenkets of the position operator. 2. that the probability of a measurement of a dynamical variable ξ yielding the result ξ when the system is in state A is given by | ξ |A |2 . the probability of a measurement of x yielding a result lying in the range x to x + dx when the system is in a state |A is | x |A |2 dx .28)]. dx ) = |ψA (x )|2 dx .29) Here.31) Consider a second state B represented by a state ket |B and a wave-function ψB (x ). It is clear that the wave-function of state A is simply the collection of the weights of the corresponding state ket |A . (3. In fact. the probability of a measurement of position yielding a result in the range x to x + dx when the wave-function of the system is ψA (x ) is P(x . Recall. The inner product B|A can be written +∞ +∞ B|A = −∞ dx B|x x |A = −∞ ψ∗ (x ) ψA (x ) dx .27).

. −∞ giving ψB (x ) = f(x ) ψA (x ).4 Schr¨ dinger’s representation . It is easily seen that ∗ ψA (x) ←→ ψA (x) . Consider the ket whose wave-function 39 .4 Schr¨dinger’s representation . (3.36) Note. and is denoted . leaving the dependence on the position operator x tacitly understood. that ψA (x) is often shortened to ψA .27) and (3.I o Consider the simple system described in the previous section. (3. If |B = f(x)|A then it follows that +∞ ψB (x ) = = x |f(x) −∞ +∞ dx ψA (x )|x (3.29). and the ket has the wave-function ψ(x ) = 1.26). where ψ(x) is a general function of the position operator x. that a general state ket |A can be written |A = ψA (x) . from the above result.3. It follows. DC (3. The ket is termed the standard ket. and ψ(x ) is the associated wave-function.35) where ψA (x) is the same function of the operator x that the wave-function ψ A (x ) is of the position eigenvalue x .I o 3 POSITION AND MOMENTUM where use has been made of Eqs. (3.. Here. 3. A general state ket can be written ψ(x) . the inner product of two states is related to the overlap integral of their wave-functions. if f(x) = x 2 then f(x ) = x 2 . Consider a general function f(x) of the observable x [e. f(x ) is the same function of the position eigenvalue x that f(x) is of the position operator x: i. f(x) = x 2 ].34) where use has been made of Eq. Thus. finally.e. The dual of the standard ket is termed the standard bra.33) dx f(x ) ψA (x ) x |x . (3.g.

According to Eq.3. Let us denote this operator d/dx. (2.27) and (3. we can write +∞ −∞ d φ |x dx ψ(x ) = dx +∞ φ(x ) dx −∞ dψ(x ) . (3. Consider d/dx acting on a general bra φ(x).41) φ |x = − dx dx which implies d dφ φ =− .34). (3. (3.38) φ dx dx Making use of Eqs.31)]. (3. so we can think of it as the result of some linear operator acting on ψ .36). dx (3. (3. It follows that d dψ ψ = .42) dx dx The neglect of contributions from the limits of integration in Eq. (3.42).43) dx dx dx dx where use has been made of Eq. Note that d dψ DC dψ∗ d ψ = ←→ = − ψ∗ . by comparison with Eqs. dx dx (3. dx (3.40) assuming that the contributions from the limits of integration vanish. (3. that d † d =− .44) dx dx 40 .39) The right-hand side can be transformed via integration by parts to give +∞ −∞ d φ |x dx ψ(x ) = − dx +∞ −∞ dφ(x ) dx ψ(x ).29).40) is reasonable because physical wave-functions are square-integrable [see Eq.35) and (3. (3.I o 3 POSITION AND MOMENTUM is dψ(x )/dx .4 Schr¨dinger’s representation . It follows that dφ(x ) d . The new ket is clearly a linear function of the original ket. (2. (3. the bra φ d/dx satisfies d d ψ = φ ψ . This ket is denoted dψ/dx . It follows.37) Any linear operator which acts on ket vectors can also act on bra vectors.

3.4 Schr¨dinger’s representation - I o

3 POSITION AND MOMENTUM

Thus, d/dx is an anti-Hermitian operator. Let us evaluate the commutation relation between the operators x and d/dx. We have d d(x ψ) d xψ = =x ψ +ψ . (3.45) dx dx dx Since this holds for any ket ψ , it follows that d d x−x = 1. (3.46) dx dx Let p be the momentum conjugate to x (for the simple system under consideration p is a straight-forward linear momentum). According to Eq. (3.25), x and p satisfy the commutation relation xp − px = i¯. h (3.47)

It can be seen, by comparison with Eq. (3.46), that the Hermitian operator −i ¯ d/dx satisfies the same commutation relation with x that p does. The most h general conclusion which may be drawn from a comparison of Eqs. (3.46) and (3.47) is that d p = −i ¯ h + f(x), (3.48) dx since (as is easily demonstrated) a general function f(x) of the position operator automatically commutes with x. We have chosen to normalize the eigenkets and eigenbras of the position operator so that they satisfy the normalization condition (3.26). However, this choice of normalization does not uniquely determine the eigenkets and eigenbras. Suppose that we transform to a new set of eigenbras which are related to the old set via x |new = e i γ x |old , (3.49) where γ ≡ γ(x ) is a real function of x . This transformation amounts to a rearrangement of the relative phases of the eigenbras. The new normalization condition is x |x
new

=

x |e i γ e−i γ |x

old

= e i (γ −γ

)

x |x

old

= e i (γ −γ ) δ(x − x ) = δ(x − x ).
41

(3.50)

3.4 Schr¨dinger’s representation - I o

3 POSITION AND MOMENTUM

Thus, the new eigenbras satisfy the same normalization condition as the old eigenbras. By definition, the standard ket satisfies x | = 1. It follows from Eq. (3.49) that the new standard ket is related to the old standard ket via
new

= e−i γ

old ,

(3.51)

where γ ≡ γ(x) is a real function of the position operator x. The dual of the above equation yields the transformation rule for the standard bra,
new = old e iγ

.

(3.52)

The transformation rule for a general operator A follows from Eqs. (3.51) and (3.52), plus the requirement that the triple product A remain invariant (this must be the case, otherwise the probability of a measurement yielding a certain result would depend on the choice of eigenbras). Thus, Anew = e−i γ Aold e i γ . (3.53)

Of course, if A commutes with x then A is invariant under the transformation. In fact, d/dx is the only operator (we know of) which does not commute with x, so Eq. (3.53) yields d dγ d d +i , (3.54) = e−i γ e i γ = dx new dx dx dx where the subscript “old” is taken as read. It follows, from Eq. (3.48), that the momentum operator p can be written p = −i ¯ h Thus, the special choice ¯ γ(x) = h yields p = −i ¯ h d dx .
new

d dx

−¯ h
new x

dγ + f(x). dx

(3.55)

f(x) dx

(3.56)

(3.57)

42

3.5 Schr¨dinger’s representation - II o

3 POSITION AND MOMENTUM

Equation (3.56) fixes γ to within an arbitrary additive constant: i.e., the special eigenkets and eigenbras for which Eq. (3.57) is true are determined to within an arbitrary common phase-factor. In conclusion, it is possible to find a set of basis eigenkets and eigenbras of the position operator x which satisfy the normalization condition (3.26), and for which the momentum conjugate to x can be represented as the operator d . (3.58) dx A general state ket is written ψ(x) , where the standard ket satisfies x | = 1, and where ψ(x ) = x |ψ(x) is the wave-function. This scheme of things is known as Schr¨dinger’s representation, and is the basis of wave mechanics. o p = −i ¯ h

3.5 Schr¨ dinger’s representation - II o o In the preceding sections, we have developed Schr¨dinger’s representation for the case of a single operator x corresponding to a classical Cartesian coordinate. However, this scheme can easily be extended. Consider a system with N generalized coordinates, q1 · · · qN , which can all be simultaneously measured. These are represented as N commuting operators, q1 · · · qN , each with a continuous range of eigenvalues, q1 · · · qN . Ket space is conveniently spanned by the simultaneous eigenkets of q1 · · · qN , which are denoted |q1 · · · qN . These eigenkets must form a complete set, otherwise the q1 · · · qN would not be simultaneously observable. The orthogonality condition for the eigenkets [i.e., the generalization of Eq. (3.26)] is The completeness condition [i.e., the generalization of Eq. (3.27)] is
+∞ −∞ +∞

q1 · · · qN |q1 · · · qN = δ(q1 − q1 ) δ(q2 − q2 ) · · · δ(qN − qN ). ··· dq1 · · · dqN |q1 · · · qN q1 · · · qN | = 1.

(3.59)

(3.60)

−∞

The standard ket is defined such that q1 · · · qN | = 1.
43

(3.61)

is P(q1 · · · qN . The associated wave-function is ψ(q1 · · · qN ) = q1 · · · qN |ψ .68) These linear operators can also act on bras (provided the associated wave-functions are square integrable) in accordance with [see Eq.3.62) (3. (3. (3.65) φ(q1 · · · qN ) = φ|q1 · · · qN . we can derive the commutation relations ∂ ∂ qj − q j = δij . ∂qi ∂qi (3.67) The N linear operators ∂/∂qi (where i runs from 1 to N) are defined ∂ψ ∂ ψ = . Finally.70) . the normalization condition for a physical wave-function is +∞ −∞ +∞ (3. a general state bra is written φ(q1 · · · qN ). ∂qi ∂qi 44 (3. A general state ket is written ψ(q1 · · · qN ) . (3.69) Corresponding to Eq.II o 3 POSITION AND MOMENTUM The standard bra is the dual of the standard ket.64) (3. dq1 · · · dqN ) = |ψ(q1 · · · qN )|2 dq1 · · · dqN .66) ··· −∞ |ψ(q1 · · · qN )|2 dq1 · · · dqN = 1. the second coordinate in the range q2 to q2 + dq2 . ∂qi ∂qi (3.. where The probability of an observation of the system finding the first coordinate in the range q1 to q1 + dq1 .63) (3.42)] φ ∂ ∂φ =− .5 Schr¨dinger’s representation . Likewise.46). etc. (3.

(3. ∂qi ∂qj ∂qi ∂qj ∂qj ∂qi showing that ∂ ∂ ∂ ∂ = .5 Schr¨dinger’s representation . Thus. ∂qi 1 (3. o It follows from Eqs.76) ∂qi ∂qi ∂qi ∂qi 1 ∂ ∂ = q · · · qN |. and (3.78) . (3.4.25).23)–(3. q1 · · · q N | so that h q1 · · · qN |pi = −i ¯ 45 ∂ψ ∂ψ(q1 · · · qN ) ∂ ∂ ψ = q1 · · · qN | = = q · · · qN |ψ . that the linear operators −i ¯ ∂/∂qi satisfy the same commutation relations with the q’s and with h each other that the p’s do.73) However. the standard ket in Schr¨dinger’s representation is a simultaneous eigenket o of all the momentum operators belonging to the eigenvalue zero.61). Note that q1 · · · q N | Hence.74) that pi = 0. ∂qi ∂qi (3. 3. by comparison with Eqs. ∂qi (3. The most general conclusion we can draw from this coincidence of commutation relations is (see Dirac) pi = −i ¯ h ∂F(q1 · · · qN ) ∂ + .3.71) It can be seen. (3. we can always construct a set of simultaneous eigenkets of q1 · · · qN for which pi = −i ¯ h ∂ .77) (3. (3. ∂qi ∂qi 1 ∂ q · · · qN |. ∂qi ∂qj ∂qj ∂qi (3.II o 3 POSITION AND MOMENTUM It is also clear that ∂2 ψ ∂ ∂ ∂ ∂ ψ = = ψ. the function F can be transformed away via a suitable readjustment of the phases of the basis eigenkets (see Sect. and Dirac).74) This is the generalized Schr¨dinger representation.72) (3.75) Thus. (3.68).

(3. These are denoted |p . describable in terms of a coordinate x and its conjugate momentum p.3.83) (3. ∂qi 1 (3.6 The momentum representation Consider a system with one degree of freedom. The momentum space wave-function φ(p ) sato isfies φ(p ) = p |φ . (3. it is o also possible to represent the system in terms of the eigenkets of p. 46 (3.81) A general state ket can be written φ(p) where the standard ket satisfies p | = 1. both of which have a continuous range of eigenvalues.79) = δ(p − p ). Consider the eigenkets of p which belong to the eigenvalues p .85) .84) The probability that a measurement of the momentum yields a result lying in the range p to p + dp is given by P(p . (3. This is termed Schr¨dinger’s representation.6 The momentum representation 3 POSITION AND MOMENTUM The dual of the above equation gives pi |q1 · · · qN = i ¯ h 3.80) and the corresponding completeness relation is dp |p −∞ p | = 1.82) Note that the standard ket in this representation is quite different to that in Schr¨dinger’s representation. dp ) = |φ(p )|2 dp . (3. However. We have seen that it is possible to represent the system in terms of the eigenkets of x. The orthogonality relation for the momentum eigenkets is p |p +∞ ∂ |q · · · qN .

3.6 The momentum representation

3 POSITION AND MOMENTUM

Finally, the normalization condition for a physical momentum space wave-function is +∞ |φ(p )|2 dp = 1.
−∞

(3.86)

The fundamental commutation relations (3.23)–(3.25) exhibit a particular symmetry between coordinates and their conjugate momenta. If all the coordinates are transformed into their conjugate momenta, and vice versa, and i is then replaced by −i, the commutation relations are unchanged. It follows from this symmetry that we can always choose the eigenkets of p in such a manner that the coordinate x can be represented as (see Sect. 3.4) x = i¯ h d . dp (3.87)

This is termed the momentum representation. The above result is easily generalized to a system with more than one degree of freedom. Suppose the system is specified by N coordinates, q1 · · · qN , and N conjugate momenta, p1 · · · pN . Then, in the momentum representation, the coordinates can be written as ∂ qi = i ¯ h . (3.88) ∂pi We also have qi = 0, (3.89) and h p1 · · · pN |qi = i ¯ ∂ p · · · pN |. ∂pi 1 (3.90)

The momentum representation is less useful than Schr¨dinger’s representao tion for a very simple reason. The energy operator (i.e., the Hamiltonian) of most simple systems takes the form of a sum of quadratic terms in the momenta (i.e., the kinetic energy) plus a complicated function of the coordinates (i.e., the potential energy). In Schr¨dinger’s representation, the eigenvalue problem for o the energy translates into a second-order differential equation in the coordinates, with a complicated potential function. In the momentum representation, the
47

3.7 The uncertainty relation

3 POSITION AND MOMENTUM

problem transforms into a high-order differential equation in the momenta, with a quadratic potential. With the mathematical tools at our disposal, we are far better able to solve the former type of problem than the latter. Hence, Schr¨dinger’s o representation is generally more useful than the momentum representation.

3.7 The uncertainty relation How is a momentum space wave-function related to the corresponding coordinate space wave-function? To answer this question, let us consider the representative x |p of the momentum eigenkets |p in Schr¨dinger’s representation for o a system with a single degree of freedom. This representative satisfies p x |p = x |p|p = −i ¯ h d x |p , dx (3.91)

where use has been made of Eq. (3.78) (for the case of a system with one degree of freedom). The solution of the above differential equation is x |p = c exp(i p x /¯ ), h where c = c (p ). It is easily demonstrated that
+∞

(3.92)

p |p

=
−∞

p |x dx x |p

=c c

−∞

exp[−i (p − p ) x /¯ ] dx . h

(3.93)

The well-known mathematical result
+∞

exp(i a x) dx = 2π δ(a),
−∞

(3.94)

yields p |p = |c |2 h δ(p − p ). (3.95) This is consistent with Eq. (3.80), provided that c = h−1/2 . Thus, x |p = h−1/2 exp(i p x /¯ ). h (3.96)

48

3.7 The uncertainty relation

3 POSITION AND MOMENTUM

Consider a general state ket |A whose coordinate wave-function is ψ(x ), and whose momentum wave-function is Ψ(p ). In other words, ψ(x ) = Ψ(p ) = It is easily demonstrated that
+∞

x |A , p |A .

(3.97) (3.98)

ψ(x ) =
−∞

dp x |p
+∞

p |A (3.99)

1 = 1/2 h and
+∞

Ψ(p ) exp(i p x /¯ ) dp h
−∞

Ψ(p ) =
−∞

dx p |x
+∞

x |A (3.100)

1 = 1/2 h

ψ(x ) exp(−i p x /¯ ) dx , h
−∞

where use has been made of Eqs. (3.27), (3.81), (3.94), and (3.96). Clearly, the momentum space wave-function is the Fourier transform of the coordinate space wave-function. Consider a state whose coordinate space wave-function is a wave-packet. In other words, the wave-function only has non-negligible amplitude in some spatially localized region of extent ∆x. As is well-know, the Fourier transform of a wave-packet fills up a wave-number band of approximate extent δk ∼ 1/∆x. Note that in Eq. (3.99) the role of the wave-number k is played by the quantity p /¯ . It h follows that the momentum space wave-function corresponding to a wave-packet in coordinate space extends over a range of momenta ∆p ∼ ¯ /∆x. Clearly, a meah surement of x is almost certain to give a result lying in a range of width ∆x. Likewise, measurement of p is almost certain to yield a result lying in a range of width ∆p. The product of these two uncertainties is ∆x ∆p ∼ ¯ . h This result is called Heisenberg’s uncertainty principle.
49

(3.101)

correspond to Gaussian wave-packets in both coordinate and momentum space. It is easily demonstrated that the minimum uncertainty states. Suppose that we displace this system some distance along the xaxis. and we just give it a little push. it is possible to write Heisenberg’s uncertainty principle more exactly by making use of Eq. since it can be multiplied by a constant phase-factor. However.3. The final state of the system only determines the direction of the displaced state ket. 50 (3. if the system is subject to an external potential. We obtain (∆x) 2 (∆p) 2 ¯2 h ≥ 4 (3. then the potential must be displaced.47).8 Displacement operators 3 POSITION AND MOMENTUM Actually. This follows because the superposition relations have a physical significance which is unaffected by a displacement of the system. So. The final state of the system is completely determined by its initial state. we know that the superposition relations between states remain invariant under the displacement. the final ket is still not completely determined. (2. Note that the type of displacement we are considering is one in which everything to do with the system is displaced. for which the equality sign holds in the above relation..103) in the undisplaced system. Even if we adopt the convention that all state kets have unit norms.8 Displacement operators Consider a system with one degree of freedom corresponding to the Cartesian coordinate x.102) for any general state. etc. We could imagine that the system is on wheels. 3.83) and the commutation relation (3. then in the displaced system we have |Rd = |Ad + |Bd . Thus. and the displacement causes ket |R to transform to ket |Rd . The situation is not so clear with state kets. together with the direction and magnitude of the displacement.104) . if |R = |A + |B (3.

51 (3. it follows that D† D = 1. The normalization condition A|A = 1 (3. we must have Ad|Ad = 1.103) holds in the undisplaced system. this determines the displaced kets to within a single arbitrary phasefactor to be multiplied into all of them. it follows that the displaced ket |Rd must be the result of some linear operator acting on the undisplaced ket |R .105) where D an operator which depends only on the nature of the displacement. Since Eq.104) holds in the displaced system whenever Eq. The arbitrary phase-factor by which all displaced kets may be multiplied results in D being undetermined to an arbitrary multiplicative constant of modulus unity.111) . |Ad = D|A and Ad| = A|D† . and dynamical variables which possesses a physical significance is invariant under a displacement of the system. Now.108) (3. kets. the displacement operator is unitary.106) for a state ket |A certainly has a physical significance. |Rd = D|R . We now adopt the ansatz that any combination of bras.110) The equation v |A = |B . Since this must hold for any state ket |A . (3.109) (3. (3.3. (3. Thus. (3. because this would wreck the superposition relations.107) Hence. The displaced kets cannot be multiplied by individual phase-factors. In other words.8 Displacement operators 3 POSITION AND MOMENTUM Incidentally. (3. so A|D† D|A = 1. Note that the above relation implies that |A = D† |Ad .

(3.117) where ax is the limit of γ/δx. we expect the limit |Ad − |A D−1 = lim |A δx→0 δx→0 δx δx lim dx = lim to exist.116) δx→0 δx where dx is denoted the displacement operator along the x-axis. It follows that vd |Ad = D|B = D v |A = D v D† |Ad . that γ tends to zero as δx → 0. Since this is true for any ket |Ad . where γ is a real phase-angle. as seems reasonable.115) D−1 . Thus. where vd is the displaced operator. has some physical significance.3. that the system is displaced an infinitesimal distance δx along the x-axis.112) Note that the arbitrary numerical factor in D does not affect either of the results (3.114) (3. implies that d x can be replaced by D exp(i γ) − 1 D − 1 + iγ = lim = dx + i a x .109) and (3. δx→0 δx→0 δx δx lim (3. Let (3.8 Displacement operators 3 POSITION AND MOMENTUM where the operator v represents a dynamical variable. The fact that D can be replaced by D exp(i γ). Thus. we require that vd |Ad = |Bd . Suppose. we have D = 1 + δx dx . 52 (3. We have assumed. we have vd = D v D † .114). now. For small δx. It is clear that the displacement operator is undetermined to an arbitrary imaginary additive constant.113) (3.118) . We expect that the displaced ket |Ad should approach the undisplaced ket |A in the limit as δx → 0. (3.

However. using x = v. (3. h 53 (3. yields dx x − x dx = −1.122) Let us consider a specific example. Actually. leaving px = i ¯ d x .124) It follows that i ¯ dx obeys the same commutation relation with x that px . the new wave-function can be multiplied by an arbitrary number of modulus unity. the same shape shifted in the x-direction by a distance δx). (3. A comparison with Eq. the h momentum conjugate to x.e. Neglecting order (δx)2 . we find that vd = (1 + δx dx ) v (1 − δx dx ) = v + δx (dx v − v dx ). The most general conclusion we can draw from this observation is that px = i ¯ dx + f(x).123) (3.109) that (1 + δx dx† )(1 + δx dx ) = 1. and again neglecting order (δx)2 . (3. the displacement operator is anti-Hermitian.. Thus.119) Thus.125) where f is Hermitian (since px is Hermitian).3.121) (3.8 Displacement operators 3 POSITION AND MOMENTUM It follows from Eq. which implies vd − v = dx v − v d x . If the system is displaced a distance δx along the x-axis then the new wave-function is ψ(x − δx) (i. (3. Suppose that a state has a wave-function ψ(x ). xd = x − δx. the fact that dx is undetermined to an arbitrary additive imaginary constant (which could be a function of x) enables us to transform the function f out of the above equation. It can be seen that the new wave-function is obtained from the old wave-function according to the prescription x → x − δx.114). does [see Eq.25)].126) . (3. (3.122). δx→0 δx lim (3. h (3. Substituting into Eq. we obtain dx† + dx = 0.120) (3.

Note that a displacement a distance ∆x along the x-axis commutes with a displacement a distance ∆y along the y-axis. (3. (3.126). It follows that D(∆x) = exp (−i px ∆x/¯ ) . the displacement operator in the x-direction is proportional to the momentum conjugate to x. Thus. A finite translation along the x-axis can be constructed from a series of very many infinitesimal translations. if the system is moved ∆x along the x-axis.118) and (3. In other words.127) where use has been made of Eqs. The fact that translations in independent directions commute is clearly associated with the fact that the conjugate momentum operators associated with these directions also commute [see Eqs.24) and (3. (3. and then ∆y along the y-axis then it ends up in the same state as if it were moved ∆y along the y-axis. (3.3.and z-axes.128) 54 . We can also construct displacement operators which translate the system along the y. the operator D(∆x) which translates the system a distance ∆x along the x-axis is written D(∆x) = lim ∆x px 1−i N ¯ h N N→∞ . and then ∆x along the x-axis.128)]. h The unitary nature of the operator is now clearly apparent.8 Displacement operators 3 POSITION AND MOMENTUM Thus. We say that px is the generator of translations along the x-axis.

the final ket |Rt depends linearly on the initial ket |Rt0 . the final ket is still not completely determined. However. Thus. the final ket can be regarded as the result of some linear operator acting on the initial ket: . The label t is needed to distinguish the different states of the system at different times. i.. The evolved kets cannot be multiplied by individual phase-factors. Even if we adopt the convention that all state kets have unit norms. 55 (4. since this would invalidate the superposition relation at later times.1 Schr¨ dinger’s equations of motion o Up to now. (4. the final state only determines the direction of the final state ket. assuming that the system is left undisturbed between times t0 and t.2).3) .1) This rule determines the time-evolved kets to within a single arbitrary phasefactor to be multiplied into all of them.2) (4. According to Eqs. (4. The label A is needed to distinguish the ket from any other ket (|Bt . In other words. then we should have |Rt = |At + |Bt . we expect that if a superposition relation holds for certain states at time t0 then the same relation should hold between the corresponding time-evolved states at time t. if |Rt0 = |At0 + |Bt0 for any three kets. say) which is evolving in time. |Rt = T |Rt0 .1) and (4.4 QUANTUM DYNAMICS 4 Quantum dynamics 4. Consider a system in a state A which evolves in time. However.e. At time t the state of the system is represented by the ket |At . we have only considered systems at one particular instant of time. Let us now investigate how quantum mechanical systems evolve with time. since it can be multiplied by an arbitrary phase-factor. The final state of the system at time t is completely determined by its initial state at time t0 plus the time interval t − t0 (assuming that the system is left undisturbed during this time interval).

the time evolution operator T looks very much like the spatial displacement operator D introduced in the previous section. if a ket is properly normalized at time t then it will remain normalized at all subsequent times t > t0 ). from physical continuity. We expect. The triple product A|ξ|A can evolve either because the ket |A evolves and the operator ξ stays constant.6) lim t→t0 t − t0 t→t0 t − t0 56 (4. Thus. However. that as t → t0 then |At → |At0 for any ket A. which immediately yields T † T = 1. (4. Thus. t0 ) being undetermined to an arbitrary multiplicative constant of modulus unity. the ket |A stays constant and the operator ξ evolves..e. time evolution has no meaning unless something observable changes with time). the time evolution operator T is a unitary operator. Hence.4. according to Eq. This is always possible. Up to now. Since we are already committed to evolving state kets. In general. The arbitrary phase-factor by which all time evolved kets may be multiplied results in T (t. even if the system is left in a state of undisturbed motion (after all. since the length of a ket possesses no physical significance. Since we have adopted a convention in which the norm of any state ket is unity.4) (4. we require that At0 |At0 = At|At for any ket A. the limit T −1 |At − |At0 = lim |At0 (4. we do expect the expectation value of some observable ξ to evolve with time. or both the ket |A and the operator ξ evolve.3).1 Schr¨dinger’s equations of motion o 4 QUANTUM DYNAMICS where T is a linear operator which depends only on the times t and t0 . let us assume that the time evolution operator T can be chosen in such a manner that the operators representing the dynamical variables of the system do not evolve in time (unless they contain some specific time dependence). it make sense to define the time evolution operator T in such a manner that it preserves the length of any ket upon which it acts (i.5) . there are some important differences between time evolution and spatial displacement.

5) that τ is anti-Hermitian: i. Note that this limit is simply the derivative of |At 0 with respect to t0 .7) τ(t0 ) = lim t→t0 t − t0 It is easily demonstrated from Eq. in the previous section. τ† + τ = 0.e.. We now have that if the operator T (t.12) . It involves a o Hermitian operator H(t) which is. a characteristic of the dynamical system under investigation. t0 ) − 1 . (4. that if the operator D(x.8) The fact that T can be replaced by T exp(i γ) (where γ is real) implies that τ is undetermined to an arbitrary imaginary additive constant (see previous section).6) and (4. t→t0 t − t0 (4.11) where px is the operator representing the momentum conjugate to x. x0 ) displaces the system along the x-axis from x0 to x then px = i ¯ x→x h lim D(x.4.10) gives the general law for the time evolution of a state ket in a scheme in which the operators representing the dynamical variables remain fixed. dt (4. It follows from Eqs.10) Equation (4. Let us define the Hermitian operator H(t0 ) = i ¯ τ. 0 x − x0 (4.7) that i¯ h d|At0 |At − |At0 = i ¯ lim h = i ¯ τ(t0 )|At0 = H(t0 )|At0 . Let T (t. This operator is undetermined h to an arbitrary real additive constant. This equation is denoted Schr¨dinger’s equation of motion. t0 ) − 1 . (4. We saw. h t→t0 dt0 t − t0 (4.9) When written for general t this equation becomes i¯ h d|At = H(t)|At . x0 ) − 1 . (4. t0 ) evolves the system in time from t0 to t then H(t0 ) = i ¯ lim h 57 T (t. presumably.1 Schr¨dinger’s equations of motion o 4 QUANTUM DYNAMICS should exist. (4.

if the equations of motion of a system are invariant under an x-displacement of the system then this implies that the system conserves momentum in the x-direction.e. need not worry us unduly. Substituting |At = T |At0 into Eq. time and space coordinates are treated on the same footing by relegating position from being an operator to being just a label.15) where use has been made of Eqs.13) Since this must hold for any initial state |At0 we conclude that i¯ h dT = H(t) T. the zero of potential energy is not well-defined). Since we are only dealing with nonrelativistic quantum mechanics. the dynamical variable corresponding to the operator H stands to time t as the momentum px stands to the coordinate x. this suggests that H(t) is the operator representing the total energy of the system. In relativistic quantum mechanics. time is not an operator (we cannot observe time. t0 ) = exp −i  H(t ) dt /¯  .. It is now clear how the fact that H is undetermined to an arbitrary real additive constant leaves T undetermined to a phase-factor. The fact that the Hamiltonian is undetermined to an arbitrary real additive constant is related to the well-known phenomenon that energy is undetermined to an arbitrary additive constant in physics (i. Note that.) The operator H(t) is usually called the Hamiltonian of the system. 58 .5) and (4. Likewise. (4. it is just a parameter (or.10) yields i¯ h dT |At0 = H(t) T |At0 .1 Schr¨dinger’s equations of motion o 4 QUANTUM DYNAMICS Thus. a continuous label). (Here.14) This equation can be integrated to give T (t.4. dt t t0 (4. more accurately. the fact that position is an operator. in classical physics. h  (4. if the equations of motion are invariant under a temporal displacement then this implies that the system conserves energy. but time is only a label. dt (4.6). we assume that Hamiltonian operators evaluated at different times commute with one another). By analogy with classical physics. as such). (Recall that. (4. in the above analysis.

t0 ) = 1. o 59 . t0 ) T (t. The dual of Eq. 4. the transformation (4.16) has the effect of bringing all kets representing states of undisturbed motion of the system to rest. (4. (4. t0 )|A .19) Thus. (4. The transformation must also be applied to bras. Clearly. this is not the only way in which to represent the time evolution of the system. and the dynamical variables are represented by moving linear operators. This is termed the Heisenberg picture. Thus.1.16) This is a time-dependent transformation. (4.16) leads us to a scenario in which the state of the system is represented by a fixed vector. and the fact that T (t0 . (4.3). which is outlined in Sect. whereas the state kets evolve according to Eq.2 Heisenberg’s equations of motion 4 QUANTUM DYNAMICS 4.2 Heisenberg’s equations of motion We have seen that in Schr¨dinger’s scheme the dynamical variables of the system o remain fixed during a period of undisturbed motion. since the operator T (t. The time evolution of the transformed state ket is given by |At t = T † (t. It is clear that the transformation (4.4.16) yields At | = A|T. the transformed state ket does not evolve in time.18) The transformation rule for a general observable v is obtained from the requirement that the expectation value A|v|A should remain invariant.17) where use has been made of Eqs. t 0 ) obviously depends on time. Suppose that a general state ket A is subject to the transformation |At = T † (t. a dynamical variable. as opposed to the Schr¨dinger picture. It is easily seen that vt = T † v T. t0 )|At0 = |At t0 . (4. t0 )|At = T † (t.5). (4. (4. The subscript t is used to remind us that the transformation is time-dependent.10). corresponds to a moving linear operator in this new scheme. However. which corresponds to a fixed linear operator in Schr¨o dinger’s scheme.

the corresponding variables in the Schr¨dinger picture).27) .22). (3. It is denoted Heisenberg’s equation of motion. Differentiation with respect to time yields dvt dT dT vt + T =v . which can be written in the form [see Eq.. dt 60 (4. (4.25) shows how the dynamical variables of the system evolve in the Heisenberg picture. Let us compare this equation with the classical time evolution equation for a general dynamical variable v.7)] dv = [v. (3. H]classical . which do o not evolve in time.24) dvt = v H T.4. dt Equation (4. dt dt dt With the help of Eq. (4. this reduces to H T vt + i ¯ T h or i¯ h where Ht = T † H T.25) (4.2 Heisenberg’s equations of motion 4 QUANTUM DYNAMICS Consider a dynamical variable v corresponding to a fixed linear operator in the Schr¨dinger picture.26) dt where [· · ·]quantum denotes the quantum Poisson bracket. According to Eq. dt (4. we can write o T vt = v T. Ht ]quantum .21) (4.20) (4.14). According to Eq.19).23) dvt = T † v H T − T † H T v t = v t H t − H t vt . the Heisenberg equation of motion can be written dvt = [vt . dt (4. Equation (4. Note that the time-varying dynamical variables in the Heisenberg picture are usually called Heisenberg dynamical variables to distinguish them from Schr¨dinger dynamical o variables (i. (4.e.23) can be written i¯ h dvt = [vt . Ht ].22) (4.

4.. it is represented by the same fixed operator in both the Schr¨dinger o and Heisenberg pictures). (4.15) yields T (t.29) (4. It follows from Eq.31) dt Thus. the system is not subject to some time-dependent external force) then Eq. any observable which commutes with the Hamiltonian is a constant of the motion (hence. H] = 0.26) and (4. The only thing which is lacking is some rule to determine the form of the quantum mechanical Hamiltonian. Furthermore. h This operator manifestly commutes with H. with the time evolution operator T ). (4. Eq.19) that vt = v. we 61 .e. (4.3 Ehrenfest’s theorem 4 QUANTUM DYNAMICS Here. (4. so Ht = T † H T = H.30) dt Thus.28) 4. Heisenberg’s equation of motion yields dv i¯ h = [v. The strong resemblance between Eqs.25) gives dH = [H. i¯ h Suppose that v is an observable which commutes with the Hamiltonian (and. For a physical system which possess a classical analogue.27) provides us with further justification for our identification of the linear operator H with the energy of the system in quantum mechanics. Note that if the Hamiltonian does not explicitly depend on time (i. [· · ·]classical is the classical Poisson bracket. t0 ) = exp [−i H (t − t0 )/¯ ] . if the energy of the system has no explicit time-dependence then it is represented by the same non-time-varying operator H in both the Schr¨dinger and o Heisenberg pictures. (4.3 Ehrenfest’s theorem We have now derived all of the basic elements of quantum mechanics. and H denotes the classical Hamiltonian. H] = 0. hence. (4. Only those observables which do not commute with the Hamiltonian evolve in time in the Heisenberg picture. (4.

G(x)] = −i ¯ h . Consider a three-dimensional system characterized by three independent Cartesian position coordinates xi (where i runs from 1 to 3). with three corresponding conjugate momenta pi .35) H= pi 2 . as the Hermitian product (1/2)(x p + p x). ∂F .. F(p)] = i ¯ h (4. ∂pi ∂G [pi . we would write the quantum mechanical analogue of the classical product x p. Let us now consider the three-dimensional motion of a free particle of mass m in the Heisenberg picture. (3. and three commuting momentum operators pi . this can usually be resolved by requiring the Hamiltonian H to be an Hermitian operator. This scheme guarantees that quantum mechanics yields the correct classical equations of motion in the classical limit. These are represented by three commuting position operators xi . pj ] = i ¯ δij .3 Ehrenfest’s theorem 4 QUANTUM DYNAMICS generally assume that the Hamiltonian has the same form as in classical physics (i.4. When the system in question has no classical analogue then we are reduced to guessing a form for H which reproduces the observed behaviour of the system. The commutation relations satisfied by the position and momentum operators are [see Eq. (4. x2 . p3 ) as p. we replace the classical coordinates and conjugate momenta by the corresponding quantum mechanical operators). 2 m 2 m i=1 62 .34) where F and G are functions which can be expanded as power series. The following useful formulae.25)] [xi . For instance. respectively.33) (4.e. p2 .32). ∂xi [xi . appearing in the Hamiltonian. x3 ) as x and (p1 . are easily proved using the fundamental commutation relations Eq.32) It is helpful to denote (x1 . h (4. Whenever an ambiguity arises because of non-commuting observables. The Hamiltonian is assumed to have the same form as in classical physics: 3 1 p2 = (4.

33).41) 4 m2 This result implies that even if a particle is well-localized at t = 0. Thus. We find that dpi 1 = [pi . It follows that pi (0)  t. H] = i¯ h = . all dynamical variables are assumed to be Heisenberg dynamical variables.40) Combining the above commutation relation with the uncertainty relation (2. The time evolution of the momentum operator pi follows from Heisenberg’s equation of motion (4. The time evolution of the position operator xi is given by 1 1 1 ∂  pi (0) pi dxi   = [xi .37) (4. for a free particle the momentum operators are constants of the motion. which means that pi (t) = pi (0) at all times t (for i is 1 to 3).38) which is analogous to the equation of motion of a classical free particle. Note that even though [xi (0). although we will omit the subscript t for the sake of clarity. (4. dt i¯ h (4. xi (t) = xi (0) +  m    3  (4. pj 2  = dt i¯ h i¯ 2m h ∂pi j=1 m m where use has been made of Eq. m m   (4. H] = 0.3 Ehrenfest’s theorem 4 QUANTUM DYNAMICS In the following.83) yields ¯ 2 t2 h 2 2 (∆xi ) t (∆xi ) t=0 ≥ .25). This conclusion can also be obtained by studying the propagation of wave-packets in wave mechanics.36) since pi automatically commutes with any function of the momentum operators.39) where the position operators are evaluated at equal times. xi (0) = . its position becomes progressively more uncertain with time. (4. xi (0)] =  . xj (0)] = 0. pi (0) t −i ¯ t h [xi (t). 63 . For instance. the xi do not commute when evaluated at different times. (4.4.

34). Note that Eq. it guarantees to us that the centre of a wave-packet h always moves like a classical particle.47) This is known as Ehrenfest’s theorem. We can use the Heisenberg equation of motion a second time to deduce that 1 dxi 1 pi 1 dpi 1 ∂V(x) d2 x i = . (4.46) only holds if x and o p are understood to be Heisenberg dynamical variables. the operator equation (4.H = =− . Heisenberg’s equation of motion gives dpi 1 ∂V(x) = [pi . On the other hand. H= 2m (4. we obtain d2 x dp m = =− dt2 dt V(x) .45) dt2 i ¯ dt h i¯ m h m dt m ∂xi In vectorial form. When written in terms of expectation values. Taking the expectation values of both sides with respect to a Heisenberg state ket that does not move with time. V(x)] = − . In contrast. V is some function of the xi operators. m 2 = dt dt (4. (4. because the xi all commute with the new term V(x) in the Hamiltonian. (4.43) dt i¯ h ∂xi where use has been made of Eq. In fact. (4. (4. 64 . the result dxi pi = dt m (4. this result is independent of whether we are using the Heisenberg or Schr¨dinger picture.42) Here.44) still holds.4.46) This is the quantum mechanical equivalent of Newton’s second law of motion.47) has no dependence on ¯ . this equation becomes d2 x dp = − V(x).3 Ehrenfest’s theorem 4 QUANTUM DYNAMICS Let us now add a potential V(x) to our free particle Hamiltonian: p2 + V(x).H = .

and the momentum operators p ≡ (p1 . We adopt Schr¨do inger’s representation in which the momentum conjugate to the position operator xi is written [see Eq. x2 . ∂/∂z ) denotes the gradient operator written in terms of the position eigenvalues. Note that. we do not expect the |x to evolve in time. Let |x represent a simultaneous eigenket of the position operators belonging to the eigenvalues x ≡ (x1 . p2 . (3. (4. The fixed dynamical variables of the system are the position operators x ≡ (x1 .4.4 Schr¨dinger’s wave-equation o 4 QUANTUM DYNAMICS 4. x2 .49) (4. ∂t (4.   ¯2  2 h p2 At = −  x |At .53) 65 .51) ∂xi Thus. The state of the system is represented as some time evolving ket |At . 2m (4.48) Schr¨dinger’s equation of motion (4. x3 ).52) x 2m 2m where use has been made of Eq. p3 ).74)] ∂ pi = −i ¯ h . ∂/∂y .4 Schr¨ dinger’s wave-equation o Let us now consider the motion of a particle in three dimensions in the Schr¨dinger o picture. (4. t) = x |At . since the position operators are fixed in the Schr¨dinger picture.78). ≡ (∂/∂x . We can also write x |V(x) = V(x ) x |. (4. x3 ). The o wave-function of the system at time t is defined ψ(x . (3.50) where use has been made of the time independence of the |x . Here.10) yields o i¯ h ∂ x |At = x |H|At . The Hamiltonian of the system is taken to be H= p2 + V(x).

It just happens to give a type of equation which we know how to solve.10) yields o i¯ h This can be integrated to give |At = exp[−i H (t − t0 )/¯ ]|At0 .51) is valid.55) This is Schr¨dinger’s famous wave-equation.49). instead of those of the momentum operators. and is the basis of wave mechanics. h (4. (4. t) ¯2  h  i¯ h =− ∂t 2m   2 ψ(x .54) which can also be written ∂ψ(x . that the wave-equation is just one of many possible representations of quantum mechanics. (4. The direction of the vector remains fixed in ket space. (4.53). Finally.4 Schr¨dinger’s wave-equation o 4 QUANTUM DYNAMICS where V(x ) is a scalar function of the position eigenvalues. In deriving the wave-equation. Suppose that the ket |At is an eigenket of the Hamiltonian belonging to the eigenvalue H : H|At = H |At .57) Note that |At only differs from |At0 by a phase-factor.58) d|At = H |At .50). t) + V(x ) ψ(x .56) Schr¨dinger’s equation of motion (4. so that Eq. t). however. we obtain ¯2  h ∂ x |At  i¯ h =− ∂t 2m   2 x |At + V(x ) x |At . in which state kets evolve and o dynamical variables are fixed. Combining Eqs. o Note. (4. This suggests that if the system is initially in an eigenstate of the Hamiltonian then it remains in this state for ever. (4.52). and (4. we have chosen to work in the Schr¨dinger picture. dt (4. in which the opposite is true. We have also fixed the relative phases of the |x o according to Schr¨dinger’s representation. as long as the 66 . (4.4. we have chosen to represent the system in terms of the eigenkets of the position operators. (4. instead of the Heisenberg picture.

(4. the above relation implies that bound states are equivalent to negative energy states. t0 ) exp[−i H (t − t0 )/¯ ]. The boundary condition (4. can easily be written in o the form of a conservation equation for the probability density: ∂ρ + · j = 0. so that ρ(x .64) Schr¨dinger’s time-dependent wave-equation.61) (4. The quantity ρ(x . t) d3 x if the wave-function is properly normalized. This is Schr¨dinger’s time-independent wave-equation. A bound state solution of the o above equation. from Eq. Since it is conventional to set the potential at infinity equal to zero. t) d3 x = 1. (4. (4. in which the particle is confined within a finite region of space.65) ∂t 67 .4 Schr¨dinger’s wave-equation o 4 QUANTUM DYNAMICS system is undisturbed.60).63) is termed the probability density. defined by ρ(x . t) = |ψ(x . h (4.4. t) d3 x . t) = ψ(x . (4. t). t)|2 .62) E < lim V(x ). that the probability of observing the particle in some volume element d3 x around position x is proportional to ρ(x . t0 ). satisfies the boundary condition Such a solution is only possible if ψ0 (x ) → 0 |x |→∞ as |x | → ∞. we o obtain   ¯2  2 h ψ0 (x ) + (V(x ) − E) ψ0 (x ) = 0.30).55). The wave-function of a stationary state satisfies ψ(x . (4.55).60) − 2m where ψ0 (x ) ≡ ψ(x . Such a state is called a stationary state. (3. The probability is equal to ρ(x . (4.59) Substituting the above relation into Schr¨dinger’s wave equation (4. (4.61) is sufficient to uniquely specify the solution of Eq. and E = H is the energy of the system. Recall.

(4. t) = ρ(x . In particular.69) (4.66) We can integrate Eq. according to Eq. that the potential has an imaginary component. Eq. if the o wave-function starts off properly normalized. It is easily demonstrated that pt j(x .64). however. t) d3 x .65) over all space. (4. and the boundary condition ρ → 0 as |x | → ∞. t) exp  ¯ h 68   ·j= 2 Im(V) ρ. (4. Clearly. ψ(x .4. naturally. t) d3 x = 0.71) . the probability current is indirectly related to the particle momentum. t)  . ∂t ¯ h Thus. an imaginary potential can be used to account for the disappearance of a particle. Schr¨dinger’s wave-equation conserves probability. In deriving Eq. Such a potential is often employed to model nuclear reactions in which incident particles can be absorbed by nuclei. In this case.65) generalizes to ∂ρ + ∂t giving ∂ 2 (4. (4. t) d3 x = . Suppose.70) ρ(x . t) d3 x = Im V(x ) ρ(x .4 Schr¨dinger’s wave-equation o 4 QUANTUM DYNAMICS The probability current j takes the form j(x . ¯ h (4. assumed that the potential V(x ) is real. t) = − i¯ h [ψ∗ 2m ψ−( ψ∗ ) ψ] = ¯ h Im(ψ∗ m ψ).67) Thus. Thus.68) m where p t denotes the expectation value of the momentum evaluated at time t. (4. using the divergence theorem. The wave-function can always be written in the form i S(x .65) we have. if Im(V) < 0 then the total probability of observing the particle anywhere in space decreases monotonically with time. ∂t (4. to obtain ∂ ρ(x . then it remains properly normalized at all subsequent times. (4.

76) (4. (4. (4.4 Schr¨dinger’s wave-equation o 4 QUANTUM DYNAMICS where ρ and S are both real functions. (4.71). t) is the Hamiltonian operator. wave mechanics h reduces to classical mechanics. in the limit ¯ → 0.77) . t) = | ∂t 2m S(x . (4. p. Thus. | S| 69 2 S| | S|2 . (4. (4. It is a good approximation to neglect the terms involving ¯ in Eq.75) where H(x.66) that . the probability current is locally normal to the contours of the phase-function S. t)|2 + V(x .74) provided that h ¯| h Note that.73) m Thus. In classical mechanics. The above equation is known as the Hamilton-Jacobi equation. t).72) It follows from Eq. (4.e.71) into Schr¨dinger’s time-dependent wave-equation. The interpretation of ρ as a probability density has already been given. o We obtain − 1 ¯2 h 2m 2√ j= ρ + 2i ¯ h √ ( ρ)· S− √ ρ| √ √ S|2 + i ¯ ρ 2 S + ρ V h √ ∂ ρ √ ∂S = i¯ h . (4. according to Eq. In particular. and is one of the many forms in which we can write the equations of classical mechanics.74) − ρ ∂t ∂t Let us treat ¯ as a small quantity. What is the interpretation of S? Note that ψ∗ ψ= √ ρ √ ( ρ) + ρ S i ρ ¯ h S.74) yields h − 1 ∂S(x . S. To lowest order. (4.4. t) = H(x .. Eq. S is the action (i. the path-integral of the Lagrangian). Let us substitute Eq. the gradient of the phase of the wave-function determines the direction of the probability current. (4. λ= ¯ ¯ h .

70 . (4. quantum mechanics reduces to classical mechanics whenever the de Broglie wave-length is small compared to the characteristic distance over which things (other than the quantum phase) vary. This distance is usually set by the variation scale-length of the potential.4.4 Schr¨dinger’s wave-equation o 4 QUANTUM DYNAMICS where λ is the de Broglie wave-length divided by 2π.78) In other words.76) is ¯ equivalent to | λ| ¯ 1. The inequality (4.

2) (5. Note. (5. since all of the products consist of operators which commute. we are going to assume that the above equations specify the angular momentum operators in terms of the position and linear momentum operators.3). be measured. Lz ) ≡ L which represent the components of orbital angular momentum in quantum mechanics can be defined in an analogous manner to the corresponding components of classical angular momentum. z) ≡ r and their conjugate momenta (px .23)–(3. The classical definition of the orbital angular momentum of such a particle about the origin is L = r × p.3) Let us assume that the operators (Lx . Ly . h (5. so they represent things which can. h h 71 (5.6) where i and j stand for either x. [xi . Consider the commutator of the operators Lx and Lz : [Lx . Lz = x p y − y p x . (z px − x pz )] = y [pz .1) (5. y. pz ) ≡ p. In other words. Ly ] = [(y pz − z py ). z] px + x py [z. pj ] = 0. Ly = z p x − x p z .1)–(5. that there is no ambiguity regarding the order in which operators appear in products on the right-hand sides of Eqs. (5.1 Orbital angular momentum Consider a particle described by the Cartesian coordinates (x. pz ] = i ¯ (−y px + x py ) = i ¯ Lz . xj ] = 0. The fundamental commutation relations satisfied by the position and linear momentum operators are [see Eqs. y. (3. in principle. Note that Lx .25)] [xi . giving Lx = y p z − z p y . Ly .7) . pj ] = i ¯ δij . [pi . py .5 ANGULAR MOMENTUM 5 Angular momentum 5. and Lz are Hermitian. or z.4) (5. also.5) (5.

h (5.11) (5. h These can be summed up more succinctly by writing L × L = i ¯ L.14) 72 = i¯ h i=1 Li = i ¯ L. Ly ] = i ¯ Lz . Whenever we encounter three operators having these commutation relations. h (5.9) (5.11). h [Ly . In fact.5.8) (5.12) for i = j. (5. h [Lz .8)– (5.1 Orbital angular momentum 5 ANGULAR MOMENTUM The cyclic permutations of the above result yield the fundamental commutation relations satisfied by the components of an angular momentum: [Lx . we expect the angular momentum operators belonging to different particles to commute.10) are the foundation for the whole theory of angular momentum in quantum mechanics. (5. It is L×L = i=1 Li × N Lj = j=1 i=1 1 Li × L i + (Li × Lj + Lj × Li ) 2 i. h . since they represent different degrees of freedom of the system. (5.j=1 (5. Lz ] = i ¯ Lx . we can write Li × Lj + Lj × Li = 0. Each of these vectors satisfies Eq.10) The three commutation relations (5.12) and (5. Lx ] = i ¯ Ly . Suppose that there are N particles in the system. L = clear from Eqs. we shall assume that any three operators which satisfy the commutation relations (5.10) represent the components of an angular momentum. we know that the dynamical variables which they represent have identical properties to those of the components of an angular momentum (which we are about to derive). So. with angular momentum vectors Li (where i runs from 1 to N).13) that N N N N However. Consider the total angular momentum of the system.13) N i=1 Li .8)–(5. so that Li × L i = i ¯ L i .

L− = L x − i L y . Lz ]. (5. L2 ≡ Lx2 + Ly2 + Lz2 . h 73 (5. Lz ] = −i ¯ (Lx Ly + Ly Lx ).5.21) (5.17) (5. Consider the magnitude squared of the angular momentum vector. It is clear from Eqs. Lz ] = −¯ L+ . It is easily demonstrated that h [Lx2 . h [Ly2 .10) is that the three components of an angular momentum vector cannot be specified (or measured) simultaneously. the total angular momentum of the system satisfies the commutation relation (5.8)–(5. Lz ] = +i ¯ (Lx Ly + Ly Lx ). the values of other two components become uncertain. Lz .22) . (5. Lz ] + [Ly2 . Lz ] = 0. It is convenient to define the shift operators L+ and L− : L+ = L x + i L y . once we have specified one component. Note that [L+ . The commutator of L2 and Lz is written [L2 . In particular. The immediate conclusion which can be drawn from the commutation relations (5. It is conventional to specify the z-component. we conclude that L 2 also commutes with Lx and Ly .18) (5.20) (5.8)–(5.11).15) (5. In fact.10) and (5. so [L2 . the z-component).1 Orbital angular momentum 5 ANGULAR MOMENTUM Thus. Lz ] = [Lx2 .19) Since there is nothing special about the z-axis.19) that the best we can do in quantum mechanics is to specify the magnitude of an angular momentum vector along with one of its components (by convention.16) (5. Lz ] + [Lz2 . the sum of two or more angular momentum vectors satisfies the same commutation relation as a primitive angular momentum vector. Lz ] = 0. [Lz2 .

that both shift operators commute with L2 . However. assuming that the |l. The quantum number m is defined by Lz |l. m|L2 − Lz2 |l. l.2 Eigenvalues of angular momentum Suppose that the simultaneous eigenkets of L2 and Lz are completely specified by two quantum numbers. m = f(l. we will show that f(l. The proof follows from the observation that A|ξ2 |A = A|ξ† ξ|A = B|B . Later on. m is the eigenvalue of Lz divided by ¯ . h Note.26) without loss of generality. m) = l (l + 1). (5. h h h l. m . m|L2 − Lz2 |l. These kets are denoted |l. It is possible to write such an h equation because ¯ has the dimensions of angular momentum. where f(l. m) − m2 ]¯ 2 . Now. (5. m|Lx2 + Ly2 |l. m = [f(l. m) ¯ 2 |l.5. m . m l.30) .2 Eigenvalues of angular momentum 5 ANGULAR MOMENTUM [L− . h (5. also.25) Thus.23) (5. since Lz is an Hermitian operator. m|f(l. 74 (5. m = = It is easily demonstrated that A|ξ2 |A ≥ 0.24) 5. L− ] = 2 ¯ Lz . m = m ¯ |l. h (5. l and m. m .29) l. m + l. Note that m is a h real number. Lz ] = +¯ L− . h [L+ . m .28) (5. m have unit norms. m|Ly2 |l. m) ¯ 2 − m2 ¯ 2 |l. m) is some real dimensionless function of l and m. m = l. m|Lx2 |l. (5. We can write L2 |l. and ξ is an Hermitian operator.27) where |A is a general ket.

m = c+ ¯ |l. it is possible to demonstrate that (5. m ) = ¯ 2 f(l. m) (L+ |l. (5.32) where use has been made of Eq. m + 1 . L− is called a lowering operator. m has the same eigenvalue of L2 as the ket |l. (5. m .34) where c+ is a number.m h Hence.5. However. m . h (5. (2. L+ is called a raising operator. at first sight. It follows that the ket L+ |l. m − 1 . l. It follows from Eqs. It would appear.21)]. m ). h Using similar arguments to those given above. L+ ])|l. The shift operators step the value of m up and down by unity each time they operate on one of the simultaneous eigenkets of L2 and Lz . m = (L+ Lz + [Lz . but the eigenvalue of Lz is increased by ¯ .27)–(5. Note that Lz L+ |l.26). Thus. plus the fact that B|B ≥ 0 for a general ket |B [see Eq. h (5.33) where use has been made of Eq.m h (5.31).22). m). (5. m = c− ¯ |l. according to Eq.29) that m2 ≤ f(l. We can write L+ |l.31) Consider the effect of the shift operator L+ on the eigenket |l. there is a definite upper bound to the values that m2 can take. m = (L+ Lz + ¯ L+ )|l. m is proportional to |l. It is easily demonstrated that L2 (L+ |l. The above equation implies that L+ |l. that any value of m can be obtained by applying the shift operators a sufficient number of times. It is clear that when the operator L+ acts on a simultal. For this reason.35) L− |l. (5. the eigenvalue of L2 remains unchanged. m + 1 . m .2 Eigenvalues of angular momentum 5 ANGULAR MOMENTUM where |B = ξ|A . the shift operator L+ does not affect the magnitude of the angular momentum of any eigenket it acts upon.m neous eigenstate of L2 and Lz . m h = (m + 1) ¯ L+ |l. (5. l. This bound is determined by the 75 . plus the fact that L2 and Lz commute.

h The above equation can be rearranged to give L2 |l. m = ¯ 2 [l (l + 1) − m (m + 1)]. h h Thus. m . namely mmax (mmax + 1).36) This implies that L− L+ |l. mmax = |0 . L2 |l. m = ¯ 2 [l (l + 1) − m (m + 1)]|l. h h Comparison of this equation with Eq. (5. mmax .37) yields (L2 − Lz2 − ¯ Lz )|l. mmax = |0 . m = mmax (mmax + 1) ¯ 2 |l.40) (5. h (5. etc. (5. Since the lowering operator does not change the eigenvalue of L2 . Thus. Suppose that we attempt to raise the value of m above its maximum value mmax .26) yields the result f(l. all of these states must correspond to the same value of f. m = l (l + 1) ¯ 2 |l. mmax = |0 .45) . mmax ) = mmax (mmax + 1). m = (L2 − Lz2 − ¯ Lz )|l. (5.44) (5. It follows that there is a maximum and a minimum possible value which m can take. Since there is no state with m > mmax . we must have L+ |l. h so Eq.41) (5. |n. h 76 (5. Ly ] = L2 − Lz2 − ¯ Lz . (5. mmax = (Lz2 + ¯ Lz )|l.37) But. m|L− L+ |l.43) (5.5. mmax − 1 . However. m . (5. we can give the unknown quantum number l the value mmax . L− L+ = Lx2 + Ly2 + i [Lx .2 Eigenvalues of angular momentum 5 ANGULAR MOMENTUM eigenvalue of L2 [see Eq. mmax = mmax (mmax + 1) ¯ 2 |l. when L− operates on |n. We can also write the above equation in the form L2 |l. l. h It is easily seen that L− L+ |l.39) (5. without loss of generality.38) (5. mmax it generates |n.26)]. m .42) At this stage. mmax − 2 .

l.m ) with the aid of Eqs.52) We have already seen that the inequality (5. we also know that l. m )∗ (5. m + 1 l. This is equivalent to choosing the relative phases of the eigenkets |l.m l.m+1 where use has been made of Eqs. The maximum value of m is denoted 77 . According to Eq.m+1 = (cl. (5. m|Lx |l. h l. by c+ exp(i γ). m + 1|Ly |l.m The solution of the above equation is c+ = l (l + 1) − m (m + 1). m + 1|Lx |l. ∗ (5. given above. l. (5. m ∗ . m + 1 = = = l.47) and (5. l.m We have made the arbitrary. m|L− |l.e. m + i l. m + 1 = ¯ 2 c+ c− . It follows that c+ c− l.51) (5.m h l.m−1 l.5.48) where use has been made of the fact that Lx and Ly are Hermitian. m l.. m + 1|L+ |l.46) (5.47) = ( l. and we still satisfy Eq.35). m .34) and (5.m tive. m = l.35).m . m ∗ − i l. but convenient. m + 1|Lx |l.m + cl. c− = (c+ )∗ = l (l + 1) − m (m − 1).31) implies that there is a maximum and a minimum possible value of m. The above equation reduces to + ∗ (5.2 Eigenvalues of angular momentum 5 ANGULAR MOMENTUM However. we can replace l. m|Ly |l. choice that c+ is real and posil.m l. m|L− L+ |l.m (5. m + 1 − i l.50)]. l. m|L− ¯ c+ |l.50) Note that c+ is undetermined to an arbitrary phase-factor [i.49). (5. where γ is real.34) and (5.m (5.49) can be combined to give |c+ |2 = [l (l + 1) − m (m + 1)]. (5.49) c− l. Equations (5. m + 1|Ly |l.m+1 = [l (l + 1) − m (m + 1)]. Consider the following: l.

Either it is an integer (e. belonging to h h the eigenvalues l (l + 1) ¯ 2 and m ¯ . mmin = 0. which allows m to take the values −2. m − 1 . 0. 5.m (5. l = 2. There are only two possible choices for l. Since there is no state with m < mmin . 1. where l is an integer. in quantum mechanics we can 78 . l.. h (5. · · · l − 1.10).5.5. which allows m to take the values −3/2. or it is a half-integer (e.3 Rotation operators Consider a particle described by the spherical polar coordinates (r. In summary. each rung differing from its immediate neighbours by unity. we have shown that the eigenvalues of L2 ≡ Lx2 + Ly2 + Lz2 can be written l (l + 1) ¯ 2 . The classical momentum conjugate to the azimuthal angle ϕ is the z-component of angular momentum.53) According to Eq.g. According to Sect.35). 2). We conclude that m can take a “ladder” of discrete values. l. we must have L− |l.52) that mmin = −l. Ly . −1/2. 3/2). h or a half-integer. respectively. and Lz are Hermitian operators. What is the minimum value? Suppose that we try to lower the value of m below its minimum value mmin .54) It can be seen from Eq. We will prove in the next section that an orbital angular momentum can only take integer values of l. (5. plus the fact that Lx . m h denote a properly normalized simultaneous eigenket of L2 and Lz . and the bottom rung is −l. m = = l (l + 1) − m (m + 1) ¯ |l. −1. l = 3/2. m + 1 h l (l + 1) − m (m − 1) ¯ |l. 3. −l + 1. The top rung is l..8)–(5.g. where m lies in the range −l. ϕ). this implies that c− min = 0. (5. using just the fundamental commutation relations (5. (5. θ. 1/2.55) (5. We have shown that L+ |l. Let |l. m L− |l. Lz .56) where L± = Lx ± i Ly are the so-called shift operators.3 Rotation operators 5 ANGULAR MOMENTUM l. We have also demonstrated that the eigenvalues of L z can only take the values m ¯ .

θ. and φ. and L z takes the form ∂ Lz = −i ¯ h .58) where px is the linear momentum conjugate to x. (5.5. There is nothing in our derivation of this result which specifies that x has to be a Cartesian coordinate.5 which specifies that we have to use Cartesian coordinates—the representation (3. for which ket space is spanned by the o simultaneous eigenkets of the position operators r. the angular momentum operator Lz can be used to rotate the system about the z-axis by an infinitesimal amount. (5.74) works for any welldefined set of coordinates. 3. The above equation implies that ∆ϕ Lz N R(∆ϕ) = lim 1 − i . (5. h (5. This operator is very similar to the operator D(∆x).59) According to Eq. We conclude that Lz = i ¯ lim h R(δϕ) − 1 . the result should apply just as well to an angular coordinate.8 that px = i ¯ lim h D(δx) − 1 . 3.8. Thus. δϕ→0 δϕ (5. We say that Lz is the generator of rotations about the z-axis. introduced in Sect.60) in the limit δϕ → 0.62) 79 . Consider an operator R(∆ϕ) which rotates the system an angle ∆ϕ about the zaxis. δx→0 δx (5. We were able to demonstrate in Sect. 3.59). we can write R(δϕ) = 1 − i Lz δϕ/¯ h (5.61) N→∞ N ¯ h which reduces to R(∆ϕ) = exp(−i Lz ∆ϕ/¯ ).57) ∂ϕ We can do this because there is nothing in Sect. In other words.3 Rotation operators 5 ANGULAR MOMENTUM always adopt Schr¨dinger’s representation. which translates the system a distance ∆x along the x axis.

h (5. and the eigenvalue of Lz is m ¯ . an m = 0 state). according 80 . so we can write Rx (∆ϕx ) = exp(−i Lx ∆ϕx /¯ ).65) Suppose that the system is in a simultaneous eigenstate of L2 and Lz . 0 .e. its wavefunction must be symmetric about the z-axis. This implies. from the previous section. Consider the action of the rotation operator R(∆ϕ) on an eigenstate possessing zero angular momentum about the z-axis (i.. etc.69) (5.63) (5. m . Thus. Thus.62). Suppose that the system is in an eigenstate of zero overall orbital angular momentum (i. We expect the wave-function to h h remain unaltered if we rotate the system 2π degrees about the z-axis. that l must also be an integer. orbital angular momentum can only take on integer values of the quantum numbers l and m. h Rz (∆ϕy ) = exp(−i Lz ∆ϕz /¯ ). R(∆ϕ1 ) R(∆ϕ2 ) = R(∆ϕ1 + ∆ϕ2 ). Here. where the eigenvalue of L 2 is l (l + 1) ¯ 2 . m . h (5.5. There is nothing special about the z-axis. h Ry (∆ϕy ) = exp(−i Ly ∆ϕy /¯ ). We have R(∆ϕ)|l. (5. m = exp(−i Lz 2π/¯ )|l. We know that the system is also in an eigenstate of zero orbital angular momentum about any particular axis.66) We conclude that m must be an integer. Rx (∆ϕx ) denotes an operator which rotates the system by an angle ∆ϕx about the x-axis. (5. R(∆ϕ) R(−∆ϕ) = 1.3 Rotation operators 5 ANGULAR MOMENTUM Note that R(∆ϕ) has all of the properties we would expect of a rotation operator R(0) = 1. 0 = |l.e. This follows because l = 0 implies m = 0.68) (5. m = exp(−i 2 π m)|l. (5. R(2π)|l.. As before.64) (5.70) by analogy with Eq. the eigenstate is invariant to rotations about the z-axis. an l = 0 state).67) Thus. this state is represented by the eigenket |l. Clearly. m = |l. 0 = exp(0)|l.

the noncommuting nature of the angular momentum operators is a direct consequence of the fact that rotations do not commute. 0 Rz (∆ϕz )|0. 5. the three components of orbital angular momentum can be written Lx = −i ¯ y h Ly Lz ∂ ∂ −z . or Ly Lx = Lx Ly . a zero angular momentum state is invariant to rotations about any axis. 0 . 0 . it ends up in a different state to that obtained by rotating an angle ∆ϕy about the y-axis. In other words. 0 = |0.4 Eigenfunctions of orbital angular momentum 5 ANGULAR MOMENTUM to the previous section. 0 Ry (∆ϕy )|0. = exp(0)|0.68)–(5. In quantum mechanics. Rx (∆ϕx )|0. 0 = |0. 0 = exp(0)|0. ∂z ∂y ∂ ∂ = −i ¯ z h . Transforming to standard spherical polar o coordinates.74) (5. ∂y ∂x (5. Such a state must possess a spherically symmetric wave-function.72) (5. 0 = |0.76) using the Schr¨dinger representation.73) Clearly. Thus. if the system is rotated an angle ∆ϕx about the x-axis. 0 .71) (5. (5. this implies that Ry (∆ϕy ) Rx (∆ϕx ) = Rx (∆ϕx ) Ry (∆ϕy ). Note that a rotation about the x-axis does not commute with a rotation about the y-axis. and then ∆ϕy about the y-axis. Thus. (5.75) (5.4 Eigenfunctions of orbital angular momentum In Cartesian coordinates.77) . −x ∂x ∂z ∂ ∂ = −i ¯ x h −y . and we can choose the z-axis to point in any direction. = exp(0)|0. x = r sin θ cos ϕ. 81 (5. [see Eqs.5.70)]. and then ∆ϕx about the x-axis.

5.4 Eigenfunctions of orbital angular momentum

5 ANGULAR MOMENTUM

y = r sin θ sin ϕ, z = r cos θ, we obtain

(5.78) (5.79)

∂ ∂ + cot θ cos ϕ (5.80) ∂θ ∂ϕ ∂ ∂ − cot θ sin ϕ Ly = −i ¯ cos ϕ h (5.81) ∂θ ∂ϕ ∂ . (5.82) Lz = −i ¯ h ∂ϕ Note that Eq. (5.82) accords with Eq. (5.57). The shift operators L± = Lx ± i Ly become ∂ ∂ L± = ±¯ exp(±i ϕ) h ± i cot θ . (5.83) ∂θ ∂ϕ Now, L2 = Lx2 + Ly2 + Lz2 = Lz2 + (L+ L− + L− L+ )/2, (5.84) Lx = i ¯ sin ϕ h so ∂ ∂ 1 ∂2  2 1 2 L = −¯ h sin θ + . sin θ ∂θ ∂θ sin2 θ ∂ϕ2
 

(5.85)

The eigenvalue problem for L2 takes the form L2 ψ = λ ¯ 2 ψ, h where ψ(r, θ, ϕ) is the wave-function, and λ is a number. Let us write ψ(r, θ, ϕ) = R(r) Y(θ, ϕ). Equation (5.86) reduces to ∂ 1 ∂2  1 ∂  sin θ + Y + λ Y = 0, sin θ ∂θ ∂θ sin2 θ ∂ϕ2
 

(5.86) (5.87)

(5.88)

where use has been made of Eq. (5.85). As is well-known, square integrable solutions to this equation only exist when λ takes the values l (l + 1), where l is an integer. These solutions are known as spherical harmonics, and can be written Ylm (θ, ϕ) = 2 l + 1 (l − m)! m (−1)m e i m ϕ Pl (cos ϕ), 4π (l + m)!
82

(5.89)

5.4 Eigenfunctions of orbital angular momentum

5 ANGULAR MOMENTUM

m where m is a positive integer lying in the range 0 ≤ m ≤ l. Here, Pl (ξ) is an associated Legendre function satisfying the equation m m2 m d 2 dPl m (1 − ξ ) − P + l (l + 1) Pl = 0. 2 l dξ dξ 1−ξ

(5.90)

We define Yl−m = (−1)m (Ylm )∗ , (5.91) which allows m to take the negative values −l ≤ m < 0. The spherical harmonics are orthogonal functions, and are properly normalized with respect to integration over the entire solid angle:
π 0 2π

Ylm∗ (θ, ϕ) Ylm (θ, ϕ) sin θ dθ dϕ = δll δmm .
0

(5.92)

The spherical harmonics also form a complete set for representing general functions of θ and ϕ. By definition, L2 Ylm = l (l + 1) ¯ 2 Ylm , h where l is an integer. It follows from Eqs. (5.82) and (5.89) that h Lz Ylm = m ¯ Ylm , (5.94) (5.93)

where m is an integer lying in the range −l ≤ m ≤ l. Thus, the wave-function ψ(r, θ, ϕ) = R(r) Ylm (θ, φ), where R is a general function, has all of the expected features of the wave-function of a simultaneous eigenstate of L2 and Lz belonging to the quantum numbers l and m. The well-known formula
m dPl 1 mξ m m+1 = √ P Pl − dξ 1 − ξ2 l 1 − ξ2 mξ m (l + m)(l − m + 1) m−1 √ + Pl = − P 1 − ξ2 l 1 − ξ2

(5.95)

can be combined with Eqs. (5.83) and (5.89) to give h L+ Ylm = l (l + 1) − m (m + 1) ¯ Ylm+1 , h L− Ylm = l (l + 1) − m (m − 1) ¯ Ylm−1 .
83

(5.96) (5.97)

5.5 Motion in a central field

5 ANGULAR MOMENTUM

These equations are equivalent to Eqs. (5.55)–(5.56). Note that a spherical harmonic wave-function is symmetric about the z-axis (i.e., independent of ϕ) when√ 0 ever m = 0, and is spherically symmetric whenever l = 0 (since Y0 = 1/ 4π). In summary, by solving directly for the eigenfunctions of L2 and Lz in Schr¨do inger’s representation, we have been able to reproduce all of the results of Sect. 5.2. Nevertheless, the results of Sect. 5.2 are more general than those obtained in this section, because they still apply when the quantum number l takes on half-integer values.

5.5 Motion in a central field Consider a particle of mass M moving in a spherically symmetric potential. The Hamiltonian takes the form p2 + V(r). H= 2M (5.98)

Adopting Schr¨dinger’s representation, we can write p = −(i/¯ ) . Hence, o h ¯2 h H=− 2M
2

+ V(r).

(5.99)

When written in spherical polar coordinates, the above equation becomes 1 ∂ ∂ 1 ∂2  ¯2  1 ∂ 2 ∂ h + V(r). r + sin θ + H=− 2 M r2 ∂r ∂r r2 sin θ ∂θ ∂θ r2 sin2 θ ∂ϕ2
 

(5.100)

Comparing this equation with Eq. (5.85), we find that ¯2  1 ∂ 2 ∂ h L2 H= − 2 r + 2 2  + V(r). 2M r ∂r ∂r ¯ r h
 

(5.101)

Now, we know that the three components of angular momentum commute with L2 (see Sect. 5.1). We also know, from Eqs. (5.80)–(5.82), that Lx , Ly , and Lz take the form of partial derivative operators of the angular coordinates,
84

85 . 4. Since L2 and Lz commute with each other and the Hamiltonian. (5. H] = 0.93). ϕ) = R(r) Ylm (θ. we already know that the most general form for the wave-function of a simultaneous eigenstate of L2 and Lz is (see previous section) ψ(r. But. This is as expected for a spherically symmetric potential. and H. In general.102) According to Sect. We know. that if R(r) is required to be well-behaved at r = 0 and as r → ∞ then solutions only exist for a discrete set of values of E. the energy eigenvalues depend on the quantum number l. These are the energy eigenvalues. It follows from Eq. It is also easily seen that L2 commutes with the Hamiltonian: [L2 .103) (5. it is always possible to represent the state of the system in terms of the simultaneous eigenstates of L2 . Consider the energy eigenvalue problem H ψ = E ψ.106) − 2 r + V(r) − E R = 0. 2M r dr dr r2 This is a Sturm-Liouville equation for the function R(r). (5.2. (5. (5.101) that all three components of the angular momentum commute with the Hamiltonian: [L.105) Substituting Eq.101). but are independent of the quantum number m. ϕ). (5.5 Motion in a central field 5 ANGULAR MOMENTUM when written in terms of spherical polar coordinates using Schr¨dinger’s repreo sentation.105) into Eq. θ. (5. H] = 0. we obtain     ¯2  1 d 2 d h l (l + 1)   + (5. Lz .104) where E is a number. and making use of Eq. from the general properties of this type of equation. the previous two equations ensure that the angular momentum L and its magnitude squared L2 are both constants of the motion. (5.5.

and the second part corresponds to the repulsive centrifugal force. − 2 r 2 2µ r dr dr r 4π 0 r    (5. for which the potential takes the specific form V(r) = − e2 . which is equivalent to a particle of mass µ rotating about a fixed point. (5.113) dy2 dy y2 4π 0 ¯ 2 y h 86 −¯ 2 h . Let a= and y = r/a. it is assumed that the energy eigenvalue E is negative.5.112) Here.6 Energy levels of the hydrogen atom Consider a hydrogen atom. (5.109) transforms to   d l (l + 1) 2 µ e2 a  d2  −2 − + f = 0. which takes into account the fact that the electron (of mass me ) and the proton (of mass mp ) both rotate about a common centre. 4π 0 r  (5.108) Here. with P(r) = f(y) exp(−y). The first part is the attractive Coulomb potential. Let us write the product r R(r) as the function P(r). (5. 2µE (5. 4π 0 r 2 µ r2 (5. which can be written e2 l (l + 1)  ¯2  1 d 2 d h  − + − E R = 0. µ = me mp /(me +mp ) is the reduced mass.109) − 2 − − E P = 0.111) .6 Energy levels of the hydrogen atom 5 ANGULAR MOMENTUM 5.107) The radial eigenfunction R(r) satisfies Eq. The above equation transforms to   e2 d2 P 2 µ  l (l + 1)¯ 2 h (5.106).110) The effective potential has a simple physical interpretation. Equation (5. dr2 2 µ r2 4π 0 r ¯ h which is the one-dimensional Schr¨dinger equation for a particle of mass µ movo ing in the effective potential e2 l (l + 1) ¯ 2 h Veff (r) = − + .

This is the same as the ratio of successive terms in the series (2 y)n .115) Equating the coefficients of yn−2 gives 2 µ e2 a  2 (n − 1) − . cn−1 n (5. Note that for an l = 0 state there is a finite probability of finding the electron at the nucleus. (5. otherwise f(y) behaves unphysically as y → 0. except when l = 0). since |ψ|2 dV must be finite. whereas for an l > 0 state there is zero probability of finding the electron at the nucleus (i.116). (5. (5. Thus. (5.112) that R(r) → exp(r/a)/r as r → ∞. where the first term in the series is cnmin ynmin .114) Substituting this solution into Eq.6 Energy levels of the hydrogen atom 5 ANGULAR MOMENTUM Let us look for a power-law solution of the form f(y) = n c n yn . This is only possible if [nmin (nmin −1)−l (l+1)] = 0. We conclude that f(y) → exp(2 y) as y → ∞. (5.117) according to Eq. the ratio of successive terms in the series (5.. The only way in which we can avoid this unphysical behaviour is 87 . we conclude that nmin = l + 1. This does not correspond to physically acceptable behaviour of the wave-function.114) is cn y 2y = .116) Now. also. (5. Note. For large values of y. we obtain cn n (n − 1) y n n−2 − 2ny n−1 − l (l + 1) y n−2 2 µ e2 a n−1 y + 4π 0 ¯ 2 h = 0.114) must terminate at small n. The former predicts unphysical behaviour of the wave-function at y = 0.113).118) n! n which converges to exp(2 y). at some positive value of n. that it is only possible to obtain sensible behaviour of the wave-function as r → 0 if l is an integer. cn [n (n − 1) − l (l + 1)] = cn−1 4π 0 ¯ 2 h   (5.5.e. It follows from Eq. the power law series (5. There are two possibilities: nmin = −l or nmin = l + 1. |ψ|2 = 0 at r = 0.

n is a positive integer.122) Finally. Here. 2 µe and R(x) is a well-behaved solution of the differential equation  (5. θ. x2 dx dx x2 x  (5. Thus. otherwise there would be no terms in the series (5.123) (5. ϕ).114). (5.116).120) Here. The energy of the ground state is µ e4 E0 = − = −13.114) terminates at some maximum value of n. 32π2 02 ¯ 2 h 88 l (l + 1) 2 n 1 d 2d  x − + − 1 R = 0. zero angular momentum state. the ground state is a spherically symmetric.6 Energy levels of the hydrogen atom 5 ANGULAR MOMENTUM if the series (5. E=− h 32π2 02 ¯ 2 n2 (5.119) where the last term in the series is cn yn . It follows from Eq. ϕ) = R(r/a) Ylm (θ. 4π 0 ¯ 2 h (5.124) . the Ylm are spherical harmonics.5. The ground state of hydrogen corresponds to n = 1. It is clear that the wave-function for a hydrogen atom can be written ψ(r. l is a non-negative integer.6 electron volts. where n 4π 0 ¯ 2 h a= = 5. n is a positive integer which must exceed the quantum number l. and m is an integer. and can only take the values µ e4 . The only permissible values of the other quantum numbers are l = 0 and m = 0.121) (5. this is only possible if µ e2 a = n.3 × 10−11 n meters. The restrictions on the quantum numbers are |m| ≤ l < n.111) that the energy eigenvalues are quantized. According to the recursion relation (5.

purely quantum mechanical. 1. Gouldsmit and Uhlenbeck (in 1925) introduced the concept of an internal. the total angular momentum in the rest frame is non-vanishing.120) are independent of the quantum number l. there is a wealth of experimental evidence which suggests that this simplistic approach is incomplete. we have tacitly assumed that the state of a particle in quantum mechanics can be completely specified by giving the wave-function ψ as a function of the spatial coordinates x. m = −1. j is a non-negative integer.8)–(5. 5. 0. The other quantum numbers are allowed to take the values l = 0.7 Spin angular momentum 5 ANGULAR MOMENTUM The next energy level corresponds to n = 2. h 89 (5. and yet have j = 0.125) . Note that the energy levels given in Eq. In addition to the quantized negative energy state of the hydrogen atom. For a system consisting of a single particle. Let us denote the three components of the spin angular momentum of a particle by the Hermitian operators (Sx . 5. Consider an isolated system at rest. because we often find systems which appear to be structureless. Thus. For a particle with spin. For a system consisting of two (or more) particles. Sz ) ≡ S. despite the fact that l appears in the radial eigenfunction equation (5. there is also a continuum of unbound positive energy states.7 Spin angular momentum Up to now. (5. m = 0 or l = 1. we can write S × S = i ¯ S.5. this does not agree with observations. y. However. This is a special property of a 1/r Coulomb potential. there are n = 2 states with non-zero angular momentum. Even worse. Sy . Thus. In order to explain this apparent discrepancy between theory and experiments. and let the eigenvalue of its total angular momentum be j (j + 1) ¯ 2 . and z. According to the theory of orbital angular momentum h outlined in Sects.5. angular momentum called spin.4 and 5. systems where j has half-integer values abound in nature.123). We assume that these operators obey the fundamental commutation relations (5. there are two possibilities. Unfortunately. which we have just found. j = 0.10) for the components of an angular momentum.

Consequently. since this identification depends on an analogy with classical mechanics. S2 ] = 0. h = s (s + 1) ¯ 2 |s. take integer or half-integer values. 5. and the concept of spin is purely quantum mechanical: i.1)–(5. like in Eqs. These are denoted |s.129) (5..5. sz . (5. [S.e.1.7 Spin angular momentum 5 ANGULAR MOMENTUM We can also define the operator S2 = Sx2 + Sy2 + Sz2 . −s. According to the quite general analysis of Sect. the quantum number s can. the quantum number s is allowed to take half-integer values. However. since this restriction (found in Sects. These kets are orthonormal (since Sz is an Hermitian operator).1)–(5. h (5.130) 2 3¯2 h S2 |± = |± .4) depends on Eqs. it has no analogy in classical physics.3 and 5. (5. in principle. 5. (5. for which ¯ h Sz |± = ± |± . Spin angular momentum operators cannot be expressed in terms of position and momentum operators. where Sz |s.131) 4 Here.127) Thus. the restriction that the quantum number of the overall angular momentum must take integer values is lifted for spin angular momentum. it is possible to find simultaneous eigenstates of S2 and Sz . sz S2 |s. sz . In other words.126) According to the equally general analysis of Sect. sz . the |± denote eigenkets of the Sz operator corresponding to the eigenvalues ±¯ /2. Consider a spin one-half particle. and the quantum number s z can only take the values s. h so +|− = 0.132) 90 .3). (5.128) (5. 5. s − 1 · · · − s + 1. (5.3). (5. sz = sz ¯ |s.2. Spin angular momentum clearly has many properties in common with orbital angular momentum. there is one vitally important difference.

(5. (5. The operator S2 takes the form 3¯2 h S = . and ±¯ /2. h respectively.139) 91 . z. Here.138) constitute a realization of the spin operators S and S2 (for a spin one-half particle) in spin space (i. Equations (5. (5. ± . +| + |x . ± denotes a simultaneous eigenstate of the position operators x. y ..e. y .8)–(5. y . so that +|+ = −|− = 1.138) 4 It is also easily demonstrated that S2 and Sz . |x . z . z . corresponding to the eigenvalues x . y . z . 2 5.131). The basis kets are assumed to satisfy the completeness relation ( |x . (5.8 Wave-function of a spin one-half particle 5 ANGULAR MOMENTUM They are also properly normalized and complete.133) It is easily verified that the Hermitian operators defined by ¯ h ( |+ −| + |− +| ) . z .10) (with the Lj replaced by the Sj ).136) Sy = 2 ¯ h ( |+ +| − |− −| ) . − x . z . and the spin operator Sz .5.137) Sz = 2 satisfy the commutation relations (5. y . y .134) (5. z . y. (5. (5. and |+ +| + |− −| = 1.8 Wave-function of a spin one-half particle The state of a spin one-half particle is represented as a vector in ket space.130)–(5. y . −| ) dx dy dz = 1.135) Sx = 2 i¯ h ( − |+ −| + |− +| ) . that Hilbert sub-space consisting of kets which correspond to the different spin states of the particle). z . + x . satisfy the eigenvalue relations (5. defined in this manner.135)–(5. Let us suppose that this space is spanned by the basis kets |x .

A general state A of a spin one-half particle is represented as a ket ||A in the product of the spin and position spaces. which are termed factor spaces. The number of dimensions of a product space is equal to the product of the number of dimensions of each of the factor spaces. z + c |x . y .145) . z |± = |± |x . y . z . z |+ by assuming that it operates only on |+ . but is instead a sum or integral of kets of this form. y . y .141) (5. We assume that such a product obeys the commutative and distributive axioms of multiplication: |x . y . This implies that every position space operator commutes with every spin operator. y . Similarly. y . and their product |x . z . y . we can give meaning to the equation |x . We can give meaning to any position space operator (such as Lz ) acting on the product |x . y . z |+ +c |x . z | −||A . z |+ (c |x . y . ± = |x . A general ket of the product space is not of the form (5. z |+ +c− |x . 92 (5.8 Wave-function of a spin one-half particle 5 ANGULAR MOMENTUM It is helpful to think of the ket |x . y . In mathematics. y .142) (5. The ket vectors |x . z . y . y . This state can be completely specified by two wavefunctions: ψ+ (x . we can give a meaning to any spin operator (such as Sz ) acting on |x . z | +||A .143) The multiplication in the above equation is of quite a different type to any which we have encountered previously. z . y . z factor.144) (5. z (c+ |+ + c− |− ) = c+ |x . z |− . and commutes with |x . y . (5. y . z . (5. x . z ) = x . z |+ by assuming that it operates only on the |x . z |± is in a third vector space. = c |x . y .5. y . + as the product of two kets—a position space ket |x .143). z ) |+ = |+ |x . In this manner. z |+ |x . y . z and |± are in two quite separate vector spaces. and commutes with the |+ factor. y . z ) = ψ− (x . y . z . y . the latter space is termed the product space of the former spaces. y .140) where the c’s are numbers. and a spin space ket |+ .

(5. forget about the spatial position of the particle. and z to z + dz . y to y + dy .5.146) 5. the probability of observing the particle in the region x to x + dx . In Sect. y . (5.62).9 Rotation operators in spin space Let us.3. with sz = −1/2 is |ψ− (x . (5. with sz = +1/2 is |ψ+ (x . h Thus. for the moment. A general spin state A is represented by the ket |A = +|A |+ + −|A |− (5. and concentrate on its spin state. we would expect such an operator to take the form Tz (∆ϕ) = exp(−i Sz ∆ϕ/¯ ).150) Thus. and z to z + dz . y . the ket |A becomes |AR = Tz (∆ϕ)|A . (5. after rotation.9 Rotation operators in spin space 5 ANGULAR MOMENTUM The probability of observing the particle in the region x to x + dx .151) . this expectation value changes as follows: † Sx → AR |Sx |AR = A|Tz Sx Tz |A . y to y + dy .148) To demonstrate that the operator (5.147) in spin space.148) really does rotate the spin of the system. The normalization condition for the wavefunctions is |ψ+ |2 + |ψ− |2 dx dy dz = 1. z )|2 dx dy dz . we were able to construct an operator Rz (∆ϕ) which rotates the system by an angle ∆ϕ about the z-axis in position space. let us consider its effect on Sx . 5. h h 93 (5.149) (5. we need to compute exp( i Sz ∆ϕ/¯ ) Sx exp(−i Sz ∆ϕ/¯ ). Likewise. z )|2 dx dy dz . Under rotation. Can we also construct an operator Tz (∆ϕ) which rotates the system by an angle ∆ϕ about the z-axis in spin space? By analogy with Eq.

158) where use has been made of Eq. Sx ] + ¯ h 2! which reduces to ∆ϕ2 ∆ϕ3 1 −  − S ϕ − Sx + ··· + · · · .152) (5. [G. Applying the Baker-Hausdorff lemma to Eq. A second approach is to use the so called Baker-Hausdorff lemma. (5. [G. where use has been made of Eqs.5. This takes the form i 2 λ2   [G. (5.135)–(5. (5. and is. First. (5. (5.153) (5.155) exp( i G λ) A exp(−i G λ) = A + i λ[G. · · · [G. 94 .125). n! where G is a Hermitian operator. A]] + (5. Sx ]] + · · · . A]]] · · ·].151).137). The second proof is more general than the first. we obtain i ∆ϕ 1 Sx + [Sz . valid for systems with spin angular momentum higher than one-half.9 Rotation operators in spin space 5 ANGULAR MOMENTUM This can be achieved in two different ways.157) or Sx cos ∆ϕ − Sy sin ∆ϕ.135). [Sz . We find that Eq. (5. [G. since it only uses the fundamental commutation relation (5. we can use the explicit formula for Sx given in Eq. y 2! 3!     i ∆ϕ ¯ h 2 [Sz . A] + 2!   (5. The proof of this lemma is left as an exercise.154) i n λn ··· + [G. therefore. and λ is a real parameter.156) (5. (5. h h 2 or ¯ i ∆ϕ/2 h e |+ −| e i ∆ϕ/2 + e −i ∆ϕ/2 |− +| e −i ∆ϕ/2 .151) becomes ¯ h exp( i Sz ∆ϕ/¯ ) ( |+ −| + |− +| ) exp(−i Sz ∆ϕ/¯ ). 2 which reduces to Sx cos ∆ϕ − Sy sin ∆ϕ.125).

(5. the expectation value of the spin operator behaves like a classical vector under rotation: Sk → Rkl Sl .5.147).159).161) since Sz commutes with the rotation operator.148).161) demonstrate that the operator (5. 95 (5. from our second derivation of the result (5. (5.159)–(5. In fact. It is easily seen that Tz (∆ϕ)|A = e−i ∆ϕ/2 +|A |+ + e i ∆ϕ/2 −|A |− .159) under the action of the rotation operator (5. l (5. both methods imply that Sx → Sx cos ∆ϕ − Sy sin ∆ϕ (5. h Consider the effect of the rotation operator (5.165) . Sz → S z .160) Furthermore. we have effectively demonstrated that Jk → Rkl Jl . Consider a rotation by 2π radians. Equations (5. and the rotation operator about the kth axis is written h Rk (∆ϕ) = exp(−i Jk ∆ϕ/¯ ).162) where the Rkl are the elements of the conventional rotation matrix for the rotation in question. It is clear.9 Rotation operators in spin space 5 ANGULAR MOMENTUM For a spin one-half system.148) on the state ket (5. In fact.163) where the Jk are the generators of rotation. that this property is not restricted to the spin operators of a spin one-half system. satisfying the fundamental commutation relation J × J = i ¯ J. We find that |A → Tz (2π)|A = −|A . l (5.148) rotates the expectation value of S by an angle ∆ϕ about the z-axis.164) (5. It is straight-forward to show that Sy → Sy cos ∆ϕ + Sx sin ∆ϕ.

where L is the orbital angular momentum.167) µ= 2m Using the usual analogy between classical and quantum mechanics. (5.10 Magnetic moments 5 ANGULAR MOMENTUM Note that a ket rotated by 2π radians differs from the original ket by a minus sign. a rotation by 4π radians is needed to transform a ket into itself. Does spin angular momentum also give rise to a contribution to the magnetic moment of a charged particle? The answer is “yes”. respectively. Thus. the minus sign does give rise to observable consequences.166) 2 where r and v are the vector position and velocity of the particle. In fact. This is indeed found to the the case. relativistic quantum mechanics actually predicts that a charged particle possessing spin should also possess a magnetic moment (this was first demonstrated by Dirac). as we shall see presently. respectively. since S is sandwiched between A| and |A . we expect the above relation to also hold between the quantum mechanical operators. µ and L. It follows that q L. Nevertheless. (5. The charge is equivalent to a current loop of radius r in the x-y plane carrying current I = q v/2π r. 5. (5. We can write q µ= (L + g S) . The minus sign does not affect the expectation value of S. ge = 2 2π 4π 0 ¯ c h   (5.10 Magnetic moments Consider a particle of charge q and velocity v performing a circular orbit of radius r in the x-y plane.5. which represent magnetic moment and orbital angular momentum. For an electron this ratio is found to be e2  1 1 + . we can write q µ = r × v.169) 96 .168) 2m where g is called the gyromagnetic ratio. In fact. both of which change sign. However. where p is the vector momentum of the particle. and m is its mass. We also know that L = r × p. we know that p = v/m. The magnetic moment µ of the loop is of magnitude π r2 I and is directed along the z-axis.

In fact. (5. that the time evolution operator is precisely the same as the rotation operator for spin. It is immediately clear that the Hamiltonian (5. me (5. − Sy + Sx t=0 sin ωt. Eqs.171) eB . 0 |− . me According to Eq. The small correction 1/(2π 137).164): |A. the time evolution operator for this system is ω= T (t.177) .28). (4. derived originally by Schwinger.170) 5. with ∆ϕ set equal to ω t.173) It can be seen.5. t=0 sin ωt. 0) = exp(−i Ht/¯ ) = exp(−i Sz ω t/¯ ).175) (5. We shall ignore this correction in the following. 97 (5.11 Spin precession 5 ANGULAR MOMENTUM The factor 2 is correctly predicted by Dirac’s relativistic theory of the electron. h h (5. (5. t = e−i ω t/2 +|A. by comparison with Eq.148).161) imply that Sx Sy Sz t t t = = = Sx Sy Sz t=0 cos ωt t=0 cos ωt t=0 . (5. e > 0).159)–(5. so µ for an electron (here. 0 |+ + e i ω t/2 −|A. is z H = −µ·B = where e S·B = ω Sz .171) causes the electron spin to precess about the z-axis with angular frequency ω. is due to quantum field effects. B = B ^.176) The time evolution of the state ket is given by analogy with Eq.172) (5.174) (5. − e (L + 2 S) 2 me (5.11 Spin precession The Hamiltonian for an electron at rest in a z-directed magnetic field. (5.

The gyromagnetic ratio for a neutron is found experimentally to be gn = −1. a neutron state ket going along path B acquires a phase-shift exp( i ω T/2) (the signs correspond to sz = ±1/2 states). By contrast.179) where l is the path-length through the magnetic field region. 98 . sent along two different paths. mp (5. An almost monoenergetic beam of neutrons is split in two. (5. When neutrons from path A and path B meet they undergo interference. This prediction depends crucially on the fact that it takes a 4π rotation to return a state ket to its original state.172).165). We now describe an experiment to detect the minus sign in Eq. In experiments. If it only took a 2π rotation then ∆B would be half of the value given above. and ω is the spin precession frequency ω= gn e B . T is the time spent in the magnetic field. which does not agree with the experimental data. the time of flight T through the magnetic field region is kept constant. where δ is the phase difference between paths A and B in the absence of a magnetic field. (The magnetic moment of a neutron is entirely a quantum field effect). it only takes times t = 2π/ω for the spin vector to point in its original direction. We expect the observed neutron intensity in the interference region to exhibit a cos(±ω T/2 + δ) variation. The above prediction has been verified experimentally to within a fraction of a percent.91. path B enters a small region where a static magnetic field is present. Here. and then recombined. As a result. Path A goes through a magnetic field free region.178) This frequency is defined in an analogous manner to Eq. and λ is the de ¯ Broglie wavelength over 2π of the neutrons.11 Spin precession 5 ANGULAR MOMENTUM Note that it takes time t = 4π/ω for the state ket to return to its original state. (5.5. while the field-strength B is varied. However. e gn λ l ¯ (5. A and B. It follows that the change in magnetic field required to produce successive maxima is ∆B = 4π ¯ h .

181) The corresponding eigenbras are represented as row matrices: +| → (1. A|− ). These h are denoted |± . that a general spin ket can be expressed as a linear combination of the two eigenkets of Sz belonging to the eigenvalues ±¯ /2. Let us represent these basis eigenkets as column matrices: |+ |− 1 →   ≡ χ+ .184) The column matrix (5.12 Pauli two-component formalism We have seen. 1) ≡ χ† .180) (5.186) . in Sect. the orbital angular momentum operators take the form of differential operators involving only angular coordinates. + (5. It is conventional to represent the eigenstates of spin angular momentum as column (or row) matrices.185) c =  + = c χ +c χ . 5. − and a general ket becomes |A = +|A |+ + −|A |− →   +|A −|A  . +|A −|A  (5. the spin angular momentum operators take the form of matrices. + + − − c− 99   (5.182) (5. 5. 0     (5. In this representation. 0) ≡ χ† . (5. Recall. 1 In this scheme. The matrix representation of a spin one-half system was introduced by Pauli in 1926.184) is called a two-component spinor. and can be written χ≡  A| = A|+ +| + A|− −| → ( A|+ . that the eigenstates of orbital angular momentum can be conveniently represented as spherical harmonics.183) 0 →   ≡ χ− . from Sect.12 Pauli two-component formalism 5 ANGULAR MOMENTUM 5.4. In this representation. a general bra takes the form −| → (0.5.9.

189) However. + − (5.188) as the matrix relation ¯ h χ = σk χ. 1 0    = +|Sk |+ −|Sk |+ +|Sk |− −|Sk |−   +|A −|A  .193) 2 where the σk are the matrices of the ±|Sk |± values divided by ¯ /2.188) +|A −|A   ≡χ. = =   +|Sk |+ +|A + +|Sk |− −|A . −|Sk |+ +|A + −|Sk |− −|A . c− ) = c+ χ† + c− χ† . A|− ) = (c+ . These h matrices.192) (5.135)–(5. can easily be evaluated using the explicit forms for the spin operators given in Eqs. (5.137). 0 −1 100 0 −i  .  (5.5. =  i 0    .195) (5.190) (5. The row matrix (5. (5.194) (5. This ket is represented as |A →  +|A −|A or    (5.191) +|A −|A It follows that we can represent the operator/ket relation (5. (5.196) 1 0  =  . which are called the Pauli matrices. (5.185) becomes ∗ ∗ ∗ ∗ χ† ≡ ( A|+ .187) Consider the ket obtained by the action of a spin operator on ket A: |A = Sk |A . We find that σ1 σ2 σ3 0 1 =  .12 Pauli two-component formalism 5 ANGULAR MOMENTUM where the c± are complex numbers.

200) Let us examine how the Pauli scheme can be extended to take into account the position of a spin one-half particle.196) actually satisfy these relations (i. and z. respectively. State A is completely specified by the two wave-functions ψ+ (x . y . (5.198) 2 ± The fundamental commutation relation for angular momentum. Eq.125). z . y . y . in this scheme. x . from Sect. plus all cyclic permutations). y . σj } = 2 δij . z ) = Consider the operator relation ||A = Sk ||A . z .204) . and 3 refer to x. z | −||A . 2. ± = |x . 2 (5. z | +||A .12 Pauli two-component formalism 5 ANGULAR MOMENTUM Here.8. (5. (5.5. y. Note that. y .e. z ) = ψ− (x . 5. (5. It is also easily seen that the Pauli matrices satisfy the anti-commutation relations {σi . 1..202) (5. that we can represent a general basis ket as the product of basis kets in position space and spin space: |x . z |± = |± |x .197) The expectation value of Sk can be written in terms of spinors and the Pauli matrices: ¯ h † Sk = A|Sk |A = A|± ±|Sk |± ±|A = χ σk χ. and resides in the product space of the position and spin ket spaces. we are effectively representing the spin operators in terms of the Pauli matrices: Sk → ¯ h σk .194)–(5. can be combined with (5.203) (5. σ1 σ2 − σ2 σ1 = 2 i σ3 .197) to give the following commutation relation for the Pauli matrices: σ × σ = 2 i σ. (5.199) It is easily seen that the matrices (5.201) The ket corresponding to state A is denoted ||A . y . Recall. y . 101 x . (5.

y . y .208) In the Schr¨dinger representation.204) as a matrix relation if we generalize our definition of a spinor by writing   ψ+ (r )  ||A →  ≡ χ. = −i ¯ ∂ψ− (r )/∂xk h ψ− (r ) 102  (5. y . (3. instead of complex numbers. z | −|A = = +|Sk |+ x . z | +||A + +|Sk |− x .5. y . (5. In this scheme.207) ψ− (r ) and so on. z |. z | −||A . y . we have o x . It is fairly obvious that we can represent the operator relation (5. (5. The components of a spinor are now wave-functions.205) where use has been made of the fact that the spin operator Sk commutes with the eigenbras x .206) (5. y .209) ¯ h σk χ. y . = −i ¯ h ∂xk x . y .12 Pauli two-component formalism 5 ANGULAR MOMENTUM It is easily seen that x . (5. −|Sk |+ x .211) where use has been made of Eq. The above equation reduces to  h ψ (r )   −i ¯ ∂ψ+ (r )/∂xk   + . y . y . z | +|A x . 2 (5. z | −||A . z | −|A = (5. y . z | +||A . z |pk +||A ∂ x . y . ∂xk   (5.204) becomes simply χ = Consider the operator relation ||A = pk ||A .212) . z | −||A . z | +||A + −|Sk |− x . y .210) x .78). the operator equation (5. z |pk −||A ∂ = −i ¯ h x . z | +|A = x .

213) ∂ I.. or z . a general position operator takes the form of a differential operator in x . σk } + [σj .g. S · L = (¯ /2) σ · L. The important identity (σ·a) (σ·b) = a·b + i σ·(a × b) (5.g. σk ] aj bk 2 2 (σjk + i jkl σl ) aj bk = j k = a·b + i σ·(a × b). I is the 2 × 2 unit matrix. where pk → −i ¯ h (5. p k or Lk ) is represented in the Pauli scheme as some differential operator of the position eigenvalues multiplied by the 2 × 2 unit matrix. any position operator (e. A general rotation operator in spin space is written T (∆φ) = exp (−i S·n ∆ϕ/¯ ) .207).215) o Since.214) ∂xk Here. it is clear that the above quantity must be regarded as a matrix differential operator which acts on spinors of the general form (5. y .217) (5. Consider the h hybrid operator σ·a.218) . Thus.5. h 103 (5. (5. ak σ k =  a1 + i a 2 −a3   (5. What about combinations of position and spin operators? The most commonly occurring combination is a dot product: e. This quantity is represented as a 2 × 2 matrix: σ·a ≡ k +a3 a1 − i a 2 . in the Schr¨dinger representation.12 Pauli two-component formalism 5 ANGULAR MOMENTUM Thus.216) follows from the commutation and anti-commutation relations (5. where a ≡ (ax . az ) is some vector position operator. the operator equation (5. σ j aj j k σk bk = j k 1 1 {σj .199) and (5.. ay .200).209) can be written χ = pk χ. In fact.

12 Pauli two-component formalism 5 ANGULAR MOMENTUM by analogy with Eq.219) in the Pauli scheme. The rotation operator is represented exp (−i S·n ∆ϕ/¯ ) → exp (−i σ·n ∆ϕ/2) h (5. The explicit 2 × 2 form of this matrix is   (σ·n)3 ∆ϕ ∆ϕ (σ· n) − −i 2 3! 2 + · · ·   + · · · (5. Here. In fact. Thus. The Pauli matrices remain unchanged under rotations. we require (χ† σk χ) ≡ (χ† ) σk χ = 104 Rkl (χ† σl χ). n can be regarded as a trivial position operator.220) (5. The term on the right-hand side of the above expression is the exponential of a matrix. (5.225) . (5. the quantity χ† σk χ is proportional to the expectation value of Sk [see Eq.221) These rules follow trivially from the identity (5.198)]. This can easily be evaluated using the Taylor series for an exponential.224) . where n is a unit vector pointing along the axis of rotation.5.216).223) where χ denotes the spinor obtained after rotating the spinor χ an angle ∆ϕ about the n-axis. (5.9). (5. l (5. so we would expect it to transform like a vector under rotation (see Sect. we can write (σ·n)2 ∆ϕ 1 − exp (−i σ·n ∆ϕ/2) = 2! 2   2 (σ·n)4 ∆ϕ + 4! 2 3 4 = cos(∆ϕ/2) I − i sin(∆ϕ/2) σ·n.148).222) cos(∆ϕ/2) − i nz sin(∆ϕ/2) (−i nx − ny ) sin(∆ϕ/2) (−i nx + ny ) sin(∆ϕ/2) cos(∆ϕ/2) + i nz sin(∆ϕ/2)  Rotation matrices act on spinors in much the same manner as the corresponding rotation operators act on state kets. However. for n odd. plus the rules (σ·n)n = 1 (σ·n)n = (σ·n) for n even. and ∆ϕ is the angle of rotation. (5. Thus. 5. χ = exp (−i σ·n ∆ϕ/2) χ.

(5. since exp i σ3 ∆ϕ −i σ3 ∆ϕ σ1 exp = σ1 cos ∆ϕ − σ2 sin ∆ϕ 2 2 (5.229) (5. 5. ψ+ (r ). The boundary conditions (for a bound state) are obtained from the normalization constraint |ψ|2 dV = 1. 5. we now know how to generalize this scheme to deal with a spin one-half particle. r . we find H ψ = E ψ. However.5. (5. Instead of representing the state of the particle by a single wave-function.13 Spin greater than one-half systems 5 ANGULAR MOMENTUM where the Rkl are the elements of a conventional rotation matrix. in addition to Hermitian operators. ¯ h ¯ h (5. In general. The first.226) plus all cyclic permutations. the energy eigenvalue problem.228) where H is now a partial differential operator. Using the Schr¨dinger representation. This is easily demonstrated. The above expression is the 2 × 2 matrix analogue of (see Sect.9) exp −i Sz ∆ϕ i Sz ∆ϕ Sx exp = Sx cos ∆ϕ − Sy sin ∆ϕ. the Hamiltonian can be written as some function of the o position and momentum operators. 105 . h H |E = E |E . This function specifies the probability density for observing the particle at a given position. can be transformed into a partial differential equation for the wave-function ψ(r ) ≡ r |E .227) The previous two formulae can both be validated using the Baker-Hausdorff lemma. which holds for Hermitian matrices. (5. in which p → −i ¯ . we use two wave-functions.13 Spin greater than one-half systems In the absence of spin.230) This is all very familiar.156).

5. The above spinor equation can always be written out explicitly as two coupled partial differential equations for ψ+ and ψ− . Adopting the Schr¨dinger representation.197)]. but the direction of its spin angular momentum remains undetermined.e. Suppose that the Hamiltonian has no dependence on the spin operators. the energy eigenvalue problem reduces to H χ = E χ. In this case. (5. specifies the h probability density of observing the particle at position r with spin angular momentum −¯ /2 in the z-direction. (5. and the c± are arbitrary complex numbers. ψ− (r ). In this case. ψ(r ) is determined by the solution of the differential equation. these wave-functions are h combined into a spinor. In the Pauli scheme.231) reduces to a straight-forward matrix eigenvalue problem.231) where χ is a spinor (i. In other words. The second. which is simply the row vector of ψ+ and ψ− . In general. The Hamiltonian determines the relative probabilities of finding the particle at various different positions. a 1 × 2 matrix of wave-functions) and H is a 2 × 2 matrix partial differential operator [see Eq. the o partial differential equation for ψ+ decouples from that for ψ− . the Hamiltonian is represented as a 2 × 2 matrix of complex numbers in the Schr¨dinger/Pauli scheme [see Eq.232) Here. so there is only really one differential equation. In this situation. The physical significance of the above expression is clear. (5. both equations have the same form. In fact. momentum. c−   (5. Suppose that the Hamiltonian depends only on the spin operators..214)]. and the spinor eigenvalue equao tion (5.13 Spin greater than one-half systems 5 ANGULAR MOMENTUM specifies the probability density of observing the particle at position r with spin angular momentum +¯ /2 in the z-direction. The most 106 . the Hamiltonian is a function of the position.231) can be written c χ = ψ(r )  +  .215)]. the Hamiltonian is represented as diagonal 2 × 2 matrix partial differential operator in the Schr¨dinger/Pauli scheme [see Eq. the most general solution to Eq. χ. (5. and spin operao tors. and the Pauli scheme. (5.

c−   (5. Thus. and so on. the Hamiltonian determines the direction of the particle’s spin angular momentum. ψsz (r ) specifies the probability density for observing the particle at position r with spin angular momentum sz ¯ in the h z-direction. the ratio c+ /c− is determined by the matrix eigenvalue problem.233). But. a general Hamiltonian causes the direction of the particle’s spin angular momentum to vary with position in some specified manner. ψ+ and ψ− . a particle for which the eigenvalue of S2 is s (s + 1) ¯ 2 . Here. In other words. This can only be represented as a spinor involving different wave-functions. it is not possible to decompose the spinor as in Eqs. we can represent the state of the particle by 2 s + 1 different wave-functions. h The eigenvalues of Sz are written sz ¯ . s − 1. but leaves its position undetermined.232) and (5. −s. where sz is allowed to take the values h s. 107 . a spin one particle by a three-component spinor. In fact. of course.. · · · . −s + 1. and the wave-function ψ(r ) is arbitrary.13 Spin greater than one-half systems 5 ANGULAR MOMENTUM general solution can again be written c χ = ψ(r )  +  . which is simply the 2 s + 1 component row vector of the ψsz (r ).e. In general. The state of the particle can be represented more succinctly by a spinor. a spin three-halves particle by a four-component spinor. a spin one-half particle is represented by a two-component spinor.233) Here. Here. denoted ψsz (r ). there are 2 s + 1 distinct allowed values of s z . χ. sz ||A . the Hamiltonian is a function of both position and spin operators.5. Not surprisingly. s is either an integer. Clearly. what happens if we have a spin one or a spin three-halves particle? It turns out that we can generalize the Pauli two-component scheme in a fairly straight-forward manner. or a half-integer. ψsz (r ) = r | s. (5. (5. More exactly. Consider a spin-s particle: i. In this case.234) where ||A denotes a state ket in the product space of the position and spin operators.

13 Spin greater than one-half systems 5 ANGULAR MOMENTUM In this extended Schr¨dinger/Pauli scheme. h Hence. s. The matrix elements of σx and σy are most easily obtained by considering the shift operators. from Eqs.l+1 2s 108 . how can we evaluate the brackets s.237).237) Sk → s ¯ σ k . lying in the range −s to +s. (5. h (5.242). l . construct the extended Pauli matrices? In fact. ∂xk (5. it is trivial to construct the σz matrix. j|Sk |s. that (σx )jl = s (s + 1) − j (j − 1) δj.56). h s (s + 1) − j (j − 1) ¯ |s. j S− |s. j = j ¯ |s.242) (5. (5. j . j − 1 . We know.241) (5. (5. we can represent the momentum operators as [see Eq. By definition.55)–(5.214)] pk → −i ¯ h ∂ I.236) Here. that S+ |s. (5. Thus. We represent the spin operators as where the (2 s + 1) × (2 s + 1) extended Pauli matrix σk has elements (σk )jl = s. h (5. or half-integers. j|Sz |s. l are integers. j + 1 . j = = s (s + 1) − j (j + 1) ¯ |s. (σz )jl = S± = S x ± i S y . l and.240)–(5. l j = δjl . σ z is the suitably normalized diagonal matrix of the eigenvalues of Sz .239) s¯ h s where use has been made of the orthonormality property of the |s. But. position space operators take the o form of diagonal (2 s + 1) × (2 s + 1) matrix differential operators.240) (5.5. j . j.235) where I is the (2 s + 1) × (2 s + 1) unit matrix. thereby. Thus. s¯ h (5. and (5. j|Sk |s.238) It follows from Eqs. Sz |s.

246) (5.l−1 .l+1 (σy )jl = 2is s (s + 1) − j (j + 1) δj. (5. =  i 0    (5.250) In fact. (5.   0 0 −1   (5. the Pauli matrices for a spin onehalf (s = 1/2) particle are + σx σy σz 0 1 =  .243) 2s s (s + 1) − j (j − 1) δj. 2 0 i 0  1 0 0     = 0 0 0 . Unfortunately. 109 .243)–(5.5.247) as we have seen previously.245) (5. (5. This means that we can convert the general energy eigenvalue problem for a spin-s particle. 1 0    (5. such a system of equations is generally too complicated to solve exactly.239) and (5. where the Hamiltonian is some function of position and spin operators. 2 0 1 0    1 0  . we can now construct the Pauli matrices for a spin anything particle.13 Spin greater than one-half systems 5 ANGULAR MOMENTUM s (s + 1) − j (j + 1) δj. into 2 s + 1 coupled partial differential equations involving the 2 s + 1 wave-functions ψsz (r ).l−1 .249) σz (5. For a spin one (s = 1) particle.248)  σy 0 −i 0  1    = √  i 0 −i  .244).244) − 2is According to Eqs. we find that σx 0 1 0 1    = √ 1 0 1. =  0 −1 0 −i  .

5. Let us define the total angular momentum operator J = J 1 + J2 . h (5. since it is the sum of Hermitian operators. −j2 . respectively. and obey the fundamental commutation relations J1 × J 1 = i ¯ J 1 . Let us consider the most general case. According to Eqs. We know. The electron possesses orbital angular momentum of magnitude ¯ . Alternatively. or half-integers. where j1 and j2 are either integers. · · · . h h So.254) Now J is an Hermitian operator. what is the total angular momentum of the system? In order to answer this question. respectively. (5. y.14 Addition of angular momentum 5 ANGULAR MOMENTUM 5. we are going to have to learn how to add angular momentum operators. By definition.14 Addition of angular momentum Consider a hydrogen atom in an l = 1 state. J satisfies the fundamental commutation relation J × J = i ¯ J. −j1 and j2 . J1 could be an orbital angular momentum operator. these operators are Hermitian. h We assume that the two groups of operators correspond to different degrees of freedom of the system. J1 and J2 could be the orbital angular momentum operators of two different particles in a multi-particle system. that the eigenvalues of J12 and J22 can be written j1 (j1 + 1) ¯ 2 and h 2 j2 (j2 + 1) ¯ . and J2 a spin angular momentum operator.253) where i. We h also know that the eigenvalues of J1z and J2z take the form m1 ¯ and m2 ¯ . −j2 + 1. Suppose that we have two sets of angular momentum operators. (5. j1 − 1. j stand for either x. j2 − 1. from the general properties of angular momentum. where m1 and m2 are numbers lying in the ranges j1 . h (5.252) J2 × J 2 = i ¯ J 2 . For instance. J2j ] = 0.255) 110 . so that [J1i .11) and (5.14). J1 and J2 . or z. respech h tively. and spin angular momentum of magnitude ¯ /2. −j1 + 1. (5.251) (5. · · · .

−j + 1. it is clear from Eq.256) that [J2 . and Jz . J12 ] = [J 2 .256) (5. (5. we can know the magnitude of the total angular momentum together with the magnitudes of the component angular momenta.258) and also that all of the J1i operators commute with the J2i operators. J1i ] = 0. In other words. (5.257) (5. (5. j2 . [J2 . j1 . J22 . The simultaneous eigenkets of J12 . Thus. where m lies h in the range j. from the preceding discussion.259) This implies that the quantum numbers j1 . we do not know the relationship between the quantum numbers of the total angular momentum.261) This suggests that it is not possible to measure the quantum numbers m1 and m2 simultaneously with the quantum number j. J2i ] = 0. and J2z . J2z ] = 0. where j is an h integer.260) (5. J1z . (5. J 2 . j2 . that we can form two alternate groups of mutually commuting operators. It is clear. J1z ] = 0. J1z . and those of the individual angular momenta. [J12 . The first group is J12 . J22 . j − 1. J22 .14 Addition of angular momentum 5 ANGULAR MOMENTUM Thus. and m2 .5. or a half-integer. We can define simultaneous eigenkets of each operator group. J22 ] = 0. J possesses all of the expected properties of an angular momentum operator. It follows from Eq.256) that [J 2 . m1 . and j can all be measured simultaneously. Now We know that J 2 = J12 + J22 + 2 J1 ·J2 . · · · . At this stage. (5. The second group is J12 . However. The eigenvalue of Jz takes the form m ¯ . −j. we cannot determine the projections of the individual angular momenta along the z-axis at the same time as the magnitude of the total angular momentum. [J22 . It follows that the eigenvalue of J 2 can be written j (j + 1) ¯ 2 . These two groups of operators are incompatible with one another. j and m. and J2z are denoted 111 .

In addition. h = j2 (j2 + 1) ¯ 2 |j1 . J22 . h = m1 ¯ |j1 . m = j1 (j1 + 1) ¯ 2 |j1 .263) (5. We can write a conventional completeness relation for both sets of eigenkets: |j1 . h = j (j + 1) ¯ 2 |j1 .267) (5. we can either know the quantum numbers m1 and m2 . j2 . m1 . it is not in an eigenstate of the latter. h = m2 ¯ |j1 . h (5. m1 . j2 . j.271) |j1 . j. j2 . or the quantum numbers j and m. where J12 |j1 . where J12 |j1 . and J2z . j. j2 . j2 . j. j2 . j. j2 .264) (5. m2 . m1 . m1 . j. we can assume that the quantum numbers j1 and j2 are known.270) (5. Since the operators J12 and J22 are common to both operator groups. j2 . m1 . m1 . m . j. J1z . m2 j1 . mutually orthogonal (for eigenkets corresponding to different sets of eigenvalues). j2 . J22 . j m where the right-hand sides denote the identity operator in the ket space corresponding to states of given j1 and j2 . m1 . m . we can always determine the magnitudes of the individual angular momenta. j2 . j2 . m2 . m Jz |j1 . m1 m2 (5. In other words.262) (5. m2 J22 |j1 . m2 . j.14 Addition of angular momentum 5 ANGULAR MOMENTUM |j1 . m1 .266) (5.5. m2 J1z |j1 .265) The simultaneous eigenkets of J12 . m1 . h (5. j2 . j2 . This means that if the system is in a simultaneous eigenstate of the former group then. and m. j2 . h = j2 (j2 + 1) ¯ 2 |j1 . j. j2 . m . In other 112 . h = m ¯ |j1 . m2 | = 1. j. m1 . m2 . j. m2 = j1 (j1 + 1) ¯ 2 |j1 . j. j2 . J 2 . j2 .268) (5. m j1 . The summation is over all allowed values of m1 . j2 . m . The operator group J12 . m J2 |j1 . j2 . but we cannot know both pairs of quantum numbers at the same time. m . and have unit norms. m2 J2z |j1 . j2 . j2 . m1 . m2 . m J22 |j1 .269) Each set of eigenkets are complete. j2 . in general. and Jz is incompatible with the group J12 . m2 . m| = 1. J22 . J 2 and Jz are denoted |j1 .

the z-components of different angular momenta add algebraically. j2 . we obtain (m − m1 − m2 ) j1 . j. then a measurement of the quantum numbers m1 and m2 will give a range of possible values.5. J22 . m1 . m1 . First. j2 . h h The Clebsch-Gordon coefficients possess a number of very important properties. We know.272) Thus. (5. J 2 . So. j2 . an electron in an l = 1 state. we note that (Jz − J1z − J2z )|j1 . We can use the completeness relation (5. j. and m are known with certainty. j. from Eq. j2 . j2 . m2 |j1 . m2 |j1 . m1 . j1 . The weights. j2 .14 Addition of angular momentum 5 ANGULAR MOMENTUM words. m2 |j1 .273). j2 . without loss of generality. the coefficients are zero unless m = m 1 + m2 . j2 . j2 . j. j2 . Second. j. respectively. m = 0. If the system is in a state where a measurement of J12 . m1 . we can write the eigenkets of the first group of operators as a weighted sum of the eigenkets of the second set. m |2 . j2 . and spin angular momentum ¯ /2. with orbital angular momentum ¯ . m1 . m = 0. m2 . j2 .275) (5. j. To prove this. and Jz is bound to give the results j1 (j1 + 1) ¯ 2 . if the quantum numbers j1 . (5. then a measurement of J1z and J2z will h h h give the results m1 ¯ and m2 ¯ with probability | j1 .276) We can assume. m = m1 m2 j1 . (5. projected along the z-axis. and jz ¯ . j2 (j2 + h 2 2 1) ¯ . m2 |. Forming the inner product with j1 . h What is uncertain is the magnitude of the total angular momentum. m |j1 . (5.274) (5. that for given j1 and j2 the largest possible value of m is j1 + j2 (since j1 is the 113 . m2 |j1 . m1 . are called the Clebsch-Gordon coefficients.270) to write |j1 . j2 .273) which proves the assertion. m . the coefficients vanish unless |j1 − j2 | ≤ j ≤ j1 + j2 . Thus. j (j + 1) ¯ . that j1 ≥ j2 . j. conh h stitutes a state whose total angular momentum projected along the z-axis is 3¯ /2.

j. j2 . the Clebsch-Gordon coefficients obey two recursion relations. j2 . m m1 m2 = m1 m2 | j1 . m1 .270). m |j1 . m1 . there are (2 j1 + 1) (2 j2 + 1) independent eigenkets. m1 m2 (5. m2 . j. j2 . by definition. m|j1 .279) where use has been made of the completeness relation (5. m1 . m1 . j2 . the sum of the modulus squared of all of the Clebsch-Gordon coefficients is unity: i. m1 .5. |j1 . j2 . j2 . there are 2 j + 1 allowed values of m.). j2 .e. j2 .278) This assertion is proved as follows: j1 . m = (J± + J± ) 2 1 × j1 .. To obtain these relations we start from J± |j1 . j2 .e.14 Addition of angular momentum 5 ANGULAR MOMENTUM largest possible value of m1 . Finally. (5. m |2 = 1. j. m2 . m1 . Since the eigenkets |j1 . m1 m2 (5. j2 . j. It is easily seen that if the minimum allowed value of j is j1 − j2 then the total number of allowed values of j and m is (2 j1 + 1) (2 j2 + 1): i. m2 |j1 . j1 +j2 j=j1 −j2 (2 j + 1) ≡ (2 j1 + 1) (2 j2 + 1). m2 |j1 . m = j1 . j2 . m2 |j1 . j. j.277) This proves our assertion. they must also form a set of (2 j1 + 1) (2 j2 + 1) independent kets. there can only be (2 j1 + 1) (2 j2 + 1) distinct allowable values of the quantum numbers j and m. m2 |j1 . m |2 = 1.. For each allowed value of j. m2 j1 . j2 . j2 . there are (2 j1 + 1) allowable values of m1 and (2 j2 + 1) allowable values of m2 . j2 . j. etc. Now. needed to span the ket space corresponding to fixed j1 and j2 . m1 . | j1 . Thus. m span the same space.280) 114 . the largest value of m is equal to j). Third. j. We have already seen that the maximum allowed value of j is j1 + j2 . m|j1 . j2 . This implies that the largest possible value of j is j1 + j2 (since. In other words. (5. j2 . j.

j1 . In other words.284) It turns out that the recursion relations (5. j2 . j2 . j. m1 . j2 . m2 = j m j1 . m1 1. j. j2 . m2 |j1 . m1 . since it ensures that the inverse ClebschGordon coefficients. m1 . j2 . (5. m|j1 . j.5.282) 1) j1 . m : |j1 . (5. m2 |j1 . m1 . j. j2 . j2 .55)–(5. m2 = j1 . 115 . This is a convenient choice. j2 .282). This sign is fixed by convention. j2 . from the absence of complex coupling coefficients in the above relations. are identical to the Clebsch-Gordon coefficients.278). are sufficient to completely determine the ClebschGordon coefficients to within an arbitrary sign (multiplied into all of the coefficients). m . j. that we can always choose the Clebsch-Gordon coefficients to be real numbers. j2 . together with the normalization condition (5. j2 . m1 . j. m1 . m . j. j. m1 ± 1. (5.14 Addition of angular momentum 5 ANGULAR MOMENTUM Making use of the well-known properties of the shift operators. j2 . j2 . m1 . m1 . j2 . m . j2 . j2 . m 1|j1 . we obtain j (j + 1) − m (m ± 1) |j1 . m2 |j1 . which are specified by Eqs. j2 . m2 |j1 . m2 . and making use of the orthonormality property of the basis eigenkets. m2 It is clear. m2 in terms of the |j1 . m1 . m . m ± 1 = m1 m2 j1 (j1 + 1) − m1 (m1 ± 1) |j1 . m ± 1 = j1 (j1 + 1) − m1 (m1 + j2 (j2 + 1) − m2 (m2 1) j1 . m2 |j1 . j2 . j1 . j2 . m|j1 . j2 . (5. (5. m2 ± 1 × j1 .281) Taking the inner product with j1 . we obtain the desired recursion relations: j (j + 1) − m (m ± 1) j1 . m1 . The easiest way of demonstrating this assertion is by considering some specific examples. j. j2 . j2 . m|j1 . j. j2 . j2 . m2 |. m2 + j2 (j2 + 1) − m2 (m2 ± 1) |j1 . m1 . j.56).283) The inverse Clebsch-Gordon coefficients are the weights in the expansion of the |j1 .

In other words. the z-components of angular momentum have to add algebraically.276). 1. 1/2 ..14 Addition of angular momentum 5 ANGULAR MOMENTUM Let us add the angular momentum of two spin one-half systems: e. 1/2. A Clebsch-Gordon coefficient is automatically zero unless m1 + m2 = m. where the allowed values of j differ by integer amounts. 1/2. 1. All the boxes contain question marks because we do not know any Clebsch-Gordon coefficients at the moment. that |m1 | ≤ 1/2 and |m2 | ≤ 1/2. two electrons at rest.g. 1/2.. j1 = j2 = 1/2. Thus. (5. 1/2. We also know. 1 .278) implies that the sum of the squares of all 116 . 1|1/2. from Eq. two spin one-half systems can be combined to form either a spin zero system or a spin one system. that 0 ≤ j ≤ 1. from general principles. It follows that either j = 0 or j = 1. Many of the boxes in the above table correspond to m1 +m2 = m. 1/2|1/2. We immediately conclude that these boxes must contain zeroes: i. So.5. m = 1 gives the Clebsch-Gordon coefficient 1/2. 1/2. j = 1. We know. m1 m2 1/2 1/2 ? 0 1/2 -1/2 0 ? -1/2 1/2 0 ? -1/2 -1/2 0 0 j1 =1/2 j 1 1 j2 =1/2 m 1 0 0 0 0 ? 1 -1 0 ? ? 0 0 0 The normalization condition (5. m2 = 1/2.e. 1/2. It is helpful to arrange all of the possibly non-zero Clebsch-Gordon coefficients in a table: m1 m2 1/2 1/2 ? ? ? ? 1/2 -1/2 ? ? ? ? -1/2 1/2 ? ? ? ? -1/2 -1/2 ? ? ? ? j1 =1/2 j 1 1 1 0 j2 =1/2 m 1 0 -1 0 The box in this table corresponding to m1 = 1/2. or the inverse Clebsch-Gordon coefficient 1/2.

and 1/2. 1 = ± 2.282) for j1 = j2 = 1/2. 1/2|1.286) Here. m = 0. 1 = 1/2. 0 + −1/2. Thus. 1/2|1. 0 = √ √ 2 −1/2. 0 = 2 −1/2. 0 = 1/2.5. 1/2|1. taking the upper/lower sign. −1/2|1. 0 2 = 1. with j = 1. We also know that 1/2. (5. the j1 and j2 labels have been suppressed for ease of notation. We find that √ √ (5. 1/2|1. There are two rows and two columns which only contain a single non-zero entry. but we have no way of determining the signs at present. −1 = ±1. We conclude that these entries must be ±1.287) from the normalization condition. 0 = 2 1/2. The only real solutions to the above set of equations are √ √ 2 1/2. 1/2|1. 0 + −1/2. 117 . (5. −1/2|1.14 Addition of angular momentum 5 ANGULAR MOMENTUM the rows and columns of the above table must be unity. 1/2|1. m1 m2 1/2 1/2 ±1 0 0 0 1/2 -1/2 0 ? 0 ? -1/2 1/2 0 ? 0 ? -1/2 -1/2 0 0 ±1 0 j1 =1/2 j 1 1 1 0 j2 =1/2 m 1 0 -1 0 Let us evaluate the recursion relation (5. (5. −1/2|1. −1/2|1. m1 = m2 = ±1/2.285) 1/2.288) The choice of sign is arbitrary—the conventional choice is a positive sign. 0 2 + −1/2. −1 = ± 2. 1/2|1. Thus. −1/2|1.

5. The requirement that the dot product of the fourth column with itself is unity tells us that the magnitudes of the unknown entries have to √ be 1/ 2. and each set of eigenkets contains mutually orthogonal vectors with unit norms. Thus. The unknown entries are undetermined to an arbitrary sign multiplied into them both. the dot product of a row with any other row must be zero. an easier method is to observe that the rows and columns of the table must all be mutually orthogonal. The only way that the dot product of the fourth column with the second column can be zero is if the unknown entries are equal and opposite. The columns give the expansions of 118 . the final form of our table (with the conventional choice of arbitrary signs) is m1 m2 1/2 1/2 1 0 0 √ 0 √ 1/2 -1/2 0 1/√2 0 1/ √2 -1/2 1/2 0 1/ 2 0 -1/ 2 -1/2 -1/2 0 0 1 0 j1 =1/2 j 1 1 1 0 j2 =1/2 m 1 0 -1 0 The table can be read in one of two ways. Likewise. The normalization condition tells us that the dot product of a row or column with itself must be unity. for the dot product of a column with any other column. However.14 Addition of angular momentum 5 ANGULAR MOMENTUM our table now reads m1 m2 1/2 1/2 1 0 √ 1/2 -1/2 0 1/√2 -1/2 1/2 0 1/ 2 -1/2 -1/2 0 0 j1 =1/2 j 1 1 j2 =1/2 m 1 0 0 0 0 1 1 -1 0 ? ? 0 0 0 We could fill in the remaining unknown entries of our table by using the recursion relation again. That is. This follows because the entries in the table give the expansion coefficients of one of our alternative sets of eigenkets in terms of the other set.

for every choice of j1 . m2 ket. there is no recursion relation linking Clebsch-Gordon coefficients corresponding to different values of j. The Clebsch-Gordon coefficients corresponding to two different choices of j are completely independent: i. and one involving j = 1 states. m ket. j2 .e. whereas those on the righthand side are |j.. one involving j = 0 states.290) Here. 1/2 ) . m2 . Thus. m2 kets. 0 + |0. Note that our table is really a combination of two sub-tables. 2 (5. −1/2 + | − 1/2. m kets. Thus. A complete knowledge of angular momentum addition is equivalent to a knowing all possible tables of Clebsch-Gordon coefficients. the ket on the left-hand side is a |m1 .14 Addition of angular momentum 5 ANGULAR MOMENTUM the eigenstates of overall angular momentum in terms of the eigenstates of the individual angular momenta of the two component systems. j2 and j) in many standard reference books. These tables are listed (for moderate values of j 1 . and m (subject to the constraint that m1 + m2 = m). the second row tells us that 1 |1/2. 2 (5. 0 = √ ( |1/2. the second column tells us that 1 |1. Thus. 0 ) .5. The rows give the expansions of the eigenstates of individual angular momentum in terms of those of overall angular momentum.289) The ket on the left-hand side is a |j. 119 . and j we can construct a table of Clebsch-Gordon coefficients corresponding to the different allowed values of m 1 . whereas those on the right-hand side are |m1 . −1/2 = √ ( |1.

2 The two-state system Let us begin by considering time-independent perturbation theory. These are denoted H0 |1 = E1 |1 . Consider the simplest non-trivial system. The Hamiltonian of a system is written H = H 0 + H1 . has no explicit dependence on time. H1 can. 120 (6.6 APPROXIMATION METHODS 6 Approximation methods 6. H 0 ? Let us investigate. in which there are only two independent eigenkets of the unperturbed Hamiltonian. However. by performing some sort of perturbation analysis about the eigenvalues and eigenstates of the original Hamiltonian. the number of such problems which yield exactly soluble equations is comparatively small. but it is sufficiently complicated that when we add it to H0 we can no longer find the exact energy eigenvalues and eigenstates. 6.2) . Can we find the approximate eigenvalues and eigenstates of the modified Hamiltonian. H1 . It is usually assumed that the unperturbed Hamiltonian. we need to develop some techniques for finding approximate solutions to otherwise intractable problems. which is very common. Consider the following problem. be regarded as being small compared to H0 . H0 is a simple Hamiltonian for which we know the exact eigenvalues and eigenstates.1) Here. Clearly. H0 + H1 . H1 introduces some interesting additional physics into the problem.1 Introduction We have developed techniques by which the general energy eigenvalue problem can be reduced to a set of coupled partial differential equations involving various wave-functions. is also time-independent. in which the modification to the Hamiltonian. Unfortunately. (6. in some sense (which we shall specify more exactly later on). H0 .

|E1 − E2 | 121 (6.5) Right-multiplication of Eq.6. (6. 1|H1 |2 . (6.4) by 1| and 2| yields two coupled equations. an Hermitian operator. Since H0 is.7) (6.6) (obtained by setting the determinant of the matrix equal to zero) is (E1 + E2 ) ± (E1 − E2 )2 + 4 |e12 |2 E= . (6. (6. we can write |E = 1|E |1 + 2|E |2 . 2|H1 |2 .3) It is assumed that these states. so that e11 = e22 = 0.2 The two-state system 6 APPROXIMATION METHODS H0 |2 = E2 |2 . its two eigenkets are orthonormal and form a complete set.11) 2 Let us expand in the supposedly small parameter = |e12 | .12) . we can solve this problem exactly. which can be written in matrix form:   E1 − E + e11 e12 ∗ e12 E2 − E + e22   1|E 2|E Here.8) (6. Since.6) e11 = e22 = e12 = 1|H1 |1 . by definition. (6. Let us now try to solve the modified energy eigenvalue problem (H0 + H1 )|E = E |E .4) In fact. 0    (6. (6. are known. The lengths of these eigenkets are both normalized to unity. the eigenkets of H 0 form a complete set. 0  =  . and their associated eigenvalues. (6.10) the solution of Eq. (6.9) In the special (but common) case of a perturbing Hamiltonian whose diagonal matrix elements (in the unperturbed eigenstates) are zero.

6. (6.6.19) .16) (6.3 Non-degenerate perturbation theory 6 APPROXIMATION METHODS 1 1 (E1 + E2 ) ± (E1 − E2 )(1 + 2 2 + · · ·).13) 2 2 The above expression yields the modifications to the energy eigenvalues due to the perturbing Hamiltonian: E E1 |e12 |2 = E1 + + ···.14) (6. are denoted H0 |n = En |n . It is easily demonstrated that the modified eigenkets take the form |1 |2 = |1 + ∗ e12 |2 + · · · . H0 . the modified energy eigenstates consist of one of the unperturbed eigenstates with a slight admixture of the other. E1 − E 2 (6.3 Non-degenerate perturbation theory Let us now generalize our perturbation analysis to deal with systems possessing more than two energy eigenstates. 2 (6. 122 (6. and the lower eigenvalue to fall. E1 − E 2 |e12 |2 + ···.17) Thus. E1 − E 2 (6. (6.15) We obtain E2 = E 2 − Note that H1 causes the upper eigenvalue to rise. when we say that H1 needs to be small compared to H0 . The energy eigenstates of the unperturbed Hamiltonian.18) In other words. Note that the series expansion in Eq. what we really mean is that the above inequality needs to be satisfied. E1 − E 2 e12 = |2 − |1 + · · · .13) only converges if 2 | | < 1. This suggests that the condition for the validity of the perturbation expansion is |e12 | < |E1 − E2 | .

The eigenkets |n are orthonormal. Em (6. Let us search for a modified version of the nth unperturbed energy eigenstate. (6. (6. Em − E k for all m = k. for which E = En + O( ).20) We can express |E as a linear superposition of the unperturbed energy eigenkets.28) for m = n.25) for all m.6. (6. (6. we obtain (Em + emm − E) m|E + k=m emk k|E = 0. We find that (Em − En ) m|E + emn 123 0. (6. Suppose that we write out Eq.3 Non-degenerate perturbation theory 6 APPROXIMATION METHODS where n runs from 1 to N.22) for m = n. where |emm | ∼ O( ). |E = k k|E |k .23) 1 is our expansion parameter. We assume that |emk | ∼ O( ).22) where emk = m|H1 |k . and have their lengths normalized to unity.24) (6. (6. Substituting the above equation into Eq. and right-multiplying by m|. (6. ∼ O( ). neglecting terms which are O( 2 ) according to our expansion scheme.26) and n|E m|E = 1. form a complete set. Let us now develop our perturbation expansion. We also assume that (6.21) where the summation is from k = 1 to N. Let us now try to solve the energy eigenvalue problem for the perturbed Hamiltonian: (H0 + H1 )|E = E |E .20).27) (6.29) . (6.

evaluated for m = n.36) . (6.30) Em − E n Substituting the above expression into Eq.34) Thus. Ek − E n k=n Thus.32) ekn |k + O( 2 ). (6.31) (6. either a hydrogen atom. Em − E n En − E m giving (6.6. The Hamiltonian of the system can be split into two parts.4 The quadratic Stark effect 6 APPROXIMATION METHODS emn . we obtain m|E − |enk |2 (En + enn − E) − = 0.35) H0 = 2 me and the perturbing Hamiltonian. the modified eigenkets remain orthonormal and properly normalized to O( 2 ). and neglecting O( 3 ) terms. (6. the modified nth energy eigenstate possesses an eigenvalue |enk |2 + O( 3 ). The unperturbed Hamiltonian. spherically symmetric shell)] is subjected to a uniform electric field in the positive z-direction.22). 124 (6. p2 + V(r). 6. or an alkali metal atom (which possesses one valance electron orbiting outside a closed. H1 = e |E| z. En = En + enn + E − Ek k=n n and a eigenket |n = |n + Note that m|n = δmn + ∗ emn enm + + O( 2 ) = δmn + O( 2 ).e..4 The quadratic Stark effect Suppose that a one-electron atom [i. E − Ek k=n n (6.33) (6.

3 breaks down for degenerate unperturbed energy levels. l. This implies that the system possesses no degenerate energy eigenvalues. from the above relation. since Lz = x p y − y p x .6). that the matrix element n. z] + [Ly2 . m = 0. so we can ignore the spin degrees of freedom of the system. and the two angular quantum numbers l and m (see Sect.37) Now. m |2 +e |E| . the change in this energy level induced by a small electric field is given by ∆Enlm = e |E| n.m 2 2 (6. (6. n. m|z|n .41) since |n. 5. l . z]|n . m is. An energy eigenket of the unperturbed Hamiltonian is characterized by three quantum numbers—the radial quantum number n. The electron spin is irrelevant in this problem (since the spin operators all commute with H1 ). m = 0. l. it follows that [Lz . giving (m − m ) n.39) (6. l.38) (6. Enlm − En l m n . It is necessary to deal with this case separately. l. m|z|n. m | n. It is h clear. (6. by definition.m =n. l.l .32). m is zero unless m = m. z] = 0. l. l . l . Let us denote such a ket |n. m|[Lz . l. l . According to Eq. m|z|n. m . l. This is termed the selection rule for the quantum number m. m|z|n . z] = [Lx2 . Let us now determine the selection rule for l. z] 125 (6.4 The quadratic Stark effect 6 APPROXIMATION METHODS It is assumed that the unperturbed energy eigenvalues and eigenstates are completely known. and let its energy level be Enlm .l. 6. This is not true for the n = 1 energy levels of the hydrogen atom. Thus.6.40) . We have [L2 . due to the special properties of a pure Coulomb potential. because the perturbation theory presented in Sect. an eigenstate of Lz with eigenvalue m ¯ .

46) (6. x] = 2 i ¯ (y Lz − Ly z).44) (6. the above expression expands to give L4 z − 2 L2 z L2 + z L4 − 2 ¯ 2 (L2 z + z L2 ) = 0. we obtain [L2 .4 The quadratic Stark effect 6 APPROXIMATION METHODS = Lx [Lx . h [L2 .1)–(5. x] − Lx [L2 . h This reduces to [L2 . h h where use has been made of Eqs. m = 0. z]Ly = i ¯ (−Lx y − y Lx + Ly x + x Ly ) h = 2 i ¯ (Ly x − Lx y + i ¯ z) h h = 2 i ¯ (Ly x − y Lx ) = 2 i ¯ (x Ly − Lx y). m|L4 z − 2 L2 z L2 + z L4 − 2 ¯ 2 (L2 z + z L2 )|n . h Finally. z] + [Ly .47) (6. [L2 . [L2 .3) that Lx x + Ly y + Lz z = 0. [L2 .45) (6. h h = −4 ¯ 2 Ly (y Lz − Ly z) + 4 ¯ 2 Lx (Lx z − x Lz ) h h −2 ¯ 2 (L2 z − z L2 ). (5. z]] = −¯ 2 4 (Lx x + Ly y + Lz z)Lz − 4 (Lx2 + Ly2 + Lz2 ) z h +2 (L2 z − z L2 ) .48) (6. [L2 .43) (6.42) (6. Ly x − Lx y + i ¯ z h h = 2 i ¯ Ly [L2 .6. However.49) implies that n. it is clear from Eqs. y] = 2 i ¯ (Lx z − x Lz ).49) (6. (5. Hence. z] + [Lx . h 126 (6. l. z]Lx + Ly [Ly .50) . z] .1)–(5. l .6). h Thus. Similarly. h Equation (6. z]] = 2 ¯ 2 (L2 z + z L2 ). z]] = 2 i ¯ L2 . y] + i ¯ [L2 . [L2 .

(6. 0|z|n. m|z|n . m|z|n . l. (6. (Recall. l.e. l .56) .51) According to the above formula. according to the selection rules. En00 − E100 127 (6. Enlm − En l m l =l±1 (6.3): i. ψn00 (r ) = ψn00 (r ).53) that the matrix element vanishes by symmetry when l = l = 0. l .6. θ . 0. m|z|n . l. the matrix element n. 1. (6. The polarizability of this state is given by α = 2e 2 n>1 | 1. (6. (6. Recall. ϕ ) dV . m|z|n . Only those terms which vary quadratically with the field-strength survive. m is zero unless l = l ± 1. m|z|n . 5. m|z|n . 2 (6. m which reduces to (l + l + 2) (l + l ) (l − l + 1) (l − l − 1) n. the matrix element n. however. m |2 .52) = 0. θ . l. m = ψ∗ (r .54) Note that all of the terms in Eq..37) yields ∆Enlm = e2 |E|2 n | n.55) Consider the ground state of a hydrogen atom. (6.37) which vary linearly with the electric fieldstrength vanish by symmetry. that the wave-function of an l = 0 state is spherically symmetric (see Sect. l . m . It follows from Eq. l .53) nlm where ψnlm (r ) = r |n. Application of the selection rules to Eq.4 The quadratic Stark effect 6 APPROXIMATION METHODS This expression yields l2 (l + 1)2 − 2 l (l + 1) l (l + 1) + l 2 (l + 1)2 −2 l (l + 1) − 2 l (l + 1)] n. In conclusion. l . l. m = 0. 0 |2 . ϕ ) r cos θ ψn m l (r . that we cannot address the n > 1 excited states because they are degenerate. This matrix element can be written n. l. The polarizability of an atom is defined in terms of the energy-shift of the atomic state as follows: 1 ∆E = − α |E|2 . l . l. and our theory cannot handle this at present). This is the selection rule for the quantum number l. m vanishes unless l = l = 0 or l = l ± 1.

60) 1. (6. we have made use of the fact that En10 = En00 for a hydrogen atom.120)] e2 En00 = − (6. | 1. 0. Thus. 0 = a02 .4 The quadratic Stark effect 6 APPROXIMATION METHODS Here. o α= 128 . 0.57) 8π 0 a0 n2 for a hydrogen atom. 0.3 4π 3 0 a0 . 0 |2 = n>1 n .61) = where we have made use of the fact that the wave-functions of a hydrogen atom form a complete set. 0|z|n. (6.58) 3 e2 = . α< However. 0|z2 |1. 0 .64) 4π 0 a03 = 4. 2 It is actually possible to obtain this answer. m . 0.m (6. we conclude that α< The true result is 16 4π 3 3 0 a0 5. where 4π 0 ¯ 2 h = 5. 0.5 4π 0 a03 .59) 16 4π 3 0 a0 n>1 | 1. n . l . We can write En00 − E100 ≥ E200 − E100 Thus. 1.63) 9 (6. 0 (6. 0 |2 .l . m 1. 0. 0|z|n . 0.62) 1. The sum in the above expression can be evaluated approximately by noting that [see Eq. (5. It is easily demonstrated from the actual form of the ground state wave-function that (6. 0|z|n. 4 8π 0 a0 (6. 0.6.3 × 10−11 meters a0 = 2 µe is the Bohr radius. l |z|1. by solving Schr¨dinger’s equation exactly in parabolic coordinates. without recourse to perturbation theory. 1. 0|z2 |1.

the En and the Lnl are real numbers which depend on the quantum numbers n.5 Degenerate perturbation theory Let us now consider systems in which the eigenstates of the unperturbed Hamiltonian. we expect the perturbation to split the degeneracy of the energy levels.32) and (6. H0 . 129 (6. Let us denote this operator (or group of operators) L.33) yields Enl and |n. Suppose that for each value of n there are Nn different values of l: i. We can write H0 |n.67) (6. l = |n. the nth energy eigenstate is Nn -fold degenerate.65) |en l nl |2 + O( 3 ). and n and l. respectively. so that each modified eigenstate |n. E − En n . l = Lnl |n.l n (6. H1 .6. possess degenerate energy levels..5 Degenerate perturbation theory 6 APPROXIMATION METHODS 6.l n en l nl |n . Let us naively attempt to use the standard perturbation theory of Sect. = En + enlnl + E − En n . A direct generalization of Eqs. It is always possible to find a sufficient number of operators which commute with the Hamiltonian in order to ensure that the Lnl are all different. l acquires a unique energy eigenvalue Enl . L does not commute with the perturbing Hamiltonian.68) (6.e. l |H1 |n. (6. l .l =n. we can choose L such that the quantum numbers n and l uniquely specify each eigenstate. 6. l = En |n. It is always possible to represent degenerate energy eigenstates as the simultaneous eigenstates of the Hamiltonian and some other Hermitian operator (or group of operators). l . In other words. l + where en l nl = n . and L |n.3 to evaluate the modified energy eigenstates and energy levels. L] = 0. In this situation.l =n. l + O( 2 ). In general. Here.69) . This implies that the modified energy eigenstates are not eigenstates of L. l .66) where [H0 . (6.

l (1) |H1 |n. H 1 . In other words.70) is not satisfied.68) would vanish.70) |n. Eq.6.68) directly. l |H1 |n. if we use the new eigenstates.e. (6. (6. degenerate. l(1) . then we can employ Eqs.67) and (6. Let us define Nn new states which are linear combinations of the Nn original degenerate eigenstates corresponding to the eigenvalue En : Nn (6. l(1) = λnl |n. Note.67) and (6. however. of the perturbing Hamiltonian between distinct. k|n. but different values of l: i. l(1) are chosen in such a manner that they are eigenstates of the perturbing Hamiltonian. (6. l (1) = k=1 n. Thus. k . (6. then all of the singular terms in Eqs. l(1) are also chosen so that they are orthonormal. The problem terms are those involving unperturbed eigenstates labeled by the same value of n..72) The |n. Fortunately. It follows that (6. those states whose unperturbed energies are En . if n. unperturbed energy eigenstates corresponding to the eigenvalue En were zero. The only remaining difficulty is to determine the new eigenstates in terms of the original ones. l(1) = λnl δll . and have unit lengths.71) Note that these new states are also degenerate energy eigenstates of the unperturbed Hamiltonian corresponding to the eigenvalue En . instead of the old ones. (6. 130 . Thus. H1 |n. l = λnl δll . (6. (6.70) is satisfied. These terms give rise to singular factors 1/(En − En ) in the summations. that this problem would not exist if the matrix elements.68) are not wellbehaved if the nth energy level is degenerate.73) n.67) and (6.5 Degenerate perturbation theory 6 APPROXIMATION METHODS It is fairly obvious that the summations in Eqs. l(1) |n. we can always redefine the unperturbed energy eigenstates belonging to the eigenvalue En in such a manner that Eq. The |n. enl nl . since all of the singular terms vanish. In general.

unperturbed energy eigenstates corresponding to the eigenvalue En .e.74) where 1 denotes the identity operator in the sub-space of all unperturbed energy eigenkets corresponding to the eigenvalue En . l l =1 n.76). with Nn corresponding eigenvectors xnl . since the summations are over n = n: i.. l(1) = λnl n. (6. l |H1 |n. (6. 131 .76) |en l nl |2 + O( 3 ). The eigenvectors specify the weights of the new eigenstates in terms of the original eigenstates: i.79) and |n. l| = 1. k|n. l(1) + n =n.6.75) This can be written more transparently as U x = λ x. l + O( 2 ).68) yield Enl = En + λnl + n =n. l n. En − E n (6. l=1 (6. l(1) = |n.76) can always be solved to give Nn eigenvalues λnl (for l = 1 to Nn ).77) Provided that the determinant of U is non-zero. In our new scheme.5 Degenerate perturbation theory 6 APPROXIMATION METHODS Now Nn |n.72) can be transformed into a straightforward matrix eigenvalue equation: Nn n. Eq. l |n.l (6. k ..l en l nl |n . (xnl )k = n. En − E n (6. l |n. where the elements of the Nn × Nn Hermitian matrix U are Ujk = n.78) for k = 1 to Nn . they specifically exclude the problematic. (6.67) and (6. j|H1 |n.80) There are no singular terms in these expressions. (6. Note that the first-order energy shifts are equivalent to the eigenvalues of the matrix equation (6. the operator eigenvalue equation (6. Eqs. (6. Using this completeness relation. degenerate. l(1) .e. l(1) .

|2. (6. As in Sect. 0 = 2.    e |E|      U= 0 2. 1. 1. 0. 0 = 3 a0 . respectively. Thus. which tell us that the matrix element of z between two hydrogen atom states is zero unless the states possess the same m quantum number. consider the n = 2 states. we have to solve the matrix eigenvalue equation U x = λ x. (6. and |2.82) where U is the array of the matrix elements of H1 between the degenerate 2s and 2p states. usually referred to as 2s. Here. and three l = 1 states (with m = −1. 0. that the eigenvalues of U are λ1 = 3 e a0 |E|.    (6. and l quantum numbers which differ by unity. 1 . 6. 0|z|2. E200 = −e2 /(32π 0 a0 ). (6. |2.  (6. 0|z|2.6 The linear Stark effect Let us examine the effect of an electric field on the excited energy levels of a hydrogen atom. 1. 0. by inspection.81) In order to apply perturbation theory. we have made use of the selection rules. 1. that 2.4. 0. 0 0 0 2. 0 . 1. 0|z|2. It is easily demonstrated. −1 states.6 The linear Stark effect 6 APPROXIMATION METHODS 6. and λ4 = 0. 0.85) x1 =    0    0 132 . the perturbing Hamiltonian is H1 = e |E| z. λ2 = −3 e a0 |E|.84)    . from the exact forms of the 2s and 2p wave-functions. 0 . 0|z|2. 0. λ3 = 0. There is a single l = 0 state. All of these states possess the same energy. For instance. 0 0 0 0 0 0 0 0 0 0 0 0  where the rows and columns correspond to the |2.6. 1. 1). The corresponding eigenvectors are  √  1/√2      1/ 2  . usually referred to as 2p. 1.83) It can be seen.

87) x4 =         (6.92) In the absence of an electric field. the energies of states 1 and 2 are shifted upwards and downwards. 2 |2.93) (6.96) Thus.91) (6. 2 = |2. 0 + |2.88) It follows from Sect. 6. 0 √ = .95) (6. ∆E3 = 0. 0 √ . all of these states possess the same energy. by an amount 3 e a0 |E| in the presence of an electric field.94) (6.90) (6. −1 . 1 . 0. States 1 and 2 are orthogonal linear combinations of the original 2s and 2p(m = 0) states. 1. 133 .86) x3 = (6. respectively. 1.89) (6. (6. ∆E2 = −3 e a0 |E|. 1. 0 − |2.6. 0.        .5 that the simultaneous eigenstates of the unperturbed Hamiltonian and the perturbing Hamiltonian take the form |1 |2 |3 |4 = |2. ∆E4 = 0. E 200 . = |2.        . (6.    (6. The first-order energy shifts induced by an electric field are given by ∆E1 = +3 e a0 |E|.6 The linear Stark effect                 6 APPROXIMATION METHODS x2 = √ 1/ √ 2 −1/ 2 0 0 0 0 1 0 0 0 0 1     . 1.

to second-order the energies of these states are shifted by an amount which depends on the square of the electric field-strength.170)] µ=− eS .4..6. higher l states have higher energies. Thus. e (6. a charge moving in an electric field also experiences an effective magnetic field B = −v × E. alkali metal atoms do not exhibit the linear Stark effect.99) 134 . The shielding effect of the inner electrons causes V(r) to depart from the pure Coulomb form. an electron possesses a spin magnetic moment [see Eq. and. This degeneracy is a special property of a pure Coulomb potential. (5. The energies of states 3 and 4 (which are equivalent to the original 2p(m = 1) and 2p(m = −1) states. This electron experiences an electric field E= V . Note that the linear Stark effect depends crucially on the degeneracy of the 2s and 2p states. Let us examine a phenomenon known as fine structure. In fact. 6. me However.7 Fine structure Let us now consider the energy levels of hydrogen-like atoms (i. Of course. therefore. (6. but different values of l. which is due to interaction between the spin and orbital angular momenta of the outermost electron. respectively) are not affected to first-order.e. alkali metal atoms) in more detail. so this is a much larger effect that the quadratic effect described in Sect.97) Now. only applies to a hydrogen atom.7 Fine structure 6 APPROXIMATION METHODS Note that the energy shifts are linear in the electric field-strength. The outermost electron moves in a spherically symmetric potential V(r) due to the nuclear charge and the charges of the other electrons (which occupy spherically symmetric closed shells).98) (6. This splits the degeneracy of states characterized by the same value of n. 6.

we are still dealing with a highly degenerate system. Thus.100) where L = me r × v is the orbital angular momentum.. ms = ±1/2). and mj are the quantum numbers corresponding to Lz . and Jz . We know. HLS . The correct quantum mechanical explanation requires a relativistically covariant treatment of electron dynamics (this is achieved using the so-called Dirac equation). it is found to be too large by a factor of two. states. using H LS as the perturbation (with HLS taking one half of the value given above). L·S = 2 135 (6.7 Fine structure 6 APPROXIMATION METHODS We. S 2 . the perturbing Hamiltonian. We have two choices for the energy eigenstates of H0 .) Moreover. and Jz . There is a classical explanation for this. L2 . When the above expression is compared to the observed spin-orbit interaction. where J 2 − L2 − S 2 . Sz . 6. that the application of perturbation theory to a degenerate system is greatly simplified if the basis eigenstates of the unperturbed Hamiltonian are also eigenstates of the perturbing Hamiltonian. S2 . respectively. Although the departure of V(r) from a pure 1/r form splits the degeneracy of same n. Let us now apply perturbation theory to a hydrogen-like atom. = me2 r dr (6. where J = L + S is the total angular momentum. each state is doubly degenerate due to the two possible orientations of the electron spin (i. ms . Lz and Sz . Now. but different values of ml . those states characterized by the same values of n and l. or the simultaneous eigenstates of H0 . are still degenerate. from Sect. ml . is proportional to L·S.101) as the unperturbed Hamiltonian. with the addition of spin degrees of freedom.6. different l. therefore. J 2 . (Here. L2 .e. which we need not go into. due to spin precession. expect a spin-orbit contribution to the Hamiltonian of the form HLS = −µ·B 1 r dV eS ·v× = − me e r dr 1 dV L·S. We can adopt the simultaneous eigenstates of H0 . and p2 + V(r) H0 = 2 me (6.102) .6.

whereas those on the righthand side are |ml . We obtain (l + 1/2) (l + 3/2) − m (m + 1) m − 1/2. j2 = 1/2.107) l + m + 3/2 136 (6.6. ms |j. (5. m + 1 . mj kets. with j1 = l.106) which reduces to m − 1/2. m |l − 1/2. 1/2 + cos α |m + 1/2.276). mj and |ml . S 2 . L2 . We now need to determine cos α = m − 1/2. m1 = m − 1/2. Thus. and Jz . 1/2|l + 1/2. 1/2 + sin α |m + 1/2. 1/2|l + 1/2. and Jz ) does. S 2 . (6. m = cos α |m − 1/2. J 2 . (5. We have made use of the fact that the Clebsch-Gordon coefficients are automatically zero unless mj = ml + ms . We can write |l + 1/2. the allowed values of the total angular momentum are j = l + 1/2 and j = l − 1/2. j2 labels have been dropped.103) (6. m2 = 1/2 (lower sign). = − sin α |m − 1/2. 1/2|l + 1/2. Let us now employ the recursion relation for Clebsch-Gordon coefficients. Lz and Sz ) does not commute with HLS .282). the kets on the left-hand side are |j. According to Eq.104) Here. L2 . (6. where the Clebsch-Gordon coefficient is written in ml . whereas the second group (H0 . m .7 Fine structure 6 APPROXIMATION METHODS It is fairly obvious that the first group of operators (H0 . ms kets are orthonormal. it is advantageous to work in terms of the eigenstates of the second group of operators. Eq. m = l (l + 1) − (m − 1/2) (m + 1/2) m + 1/2. 1/2|l + 1/2. −1/2 . rather than those of the first group. S2 . In fact. ms kets (the j1 . m + 1 . −1/2 . L·S is just a combination of operators appearing in the second group. and have unit lengths. and j2 = s = 1/2. (6. We have also made use of the fact that both the |j. L2 . m = l + m + 1/2 m + 1/2.105) . We now need to find the simultaneous eigenstates of H0 . j = l + 1/2. This is equivalent to finding the eigenstates of the total angular momentum resulting from the addition of two angular momenta: j1 = l. mj form. J 2 . 1/2|l + 1/2. for the sake of clarity).

but not when j = l − 1/2.112) l + m + 1/2 . 2l + 1 137 (6.108) This procedure can be continued until ml attains its maximum possible value. m = l + m + 1/2 l + m + 3/2 l + m + 3/2 l + m + 5/2 × m + 3/2.109) Consider the situation in which ml and m both take their maximum values.113) . sin2 α = 1 − l + m + 1/2 l − m + 1/2 = . m + 2 . 1/2 must be equal to the |j. m = l + m + 1/2 l. l + 1/2 . Eq. l and 1/2. respectively. 1/2|l + 1/2. Thus.111) (6. ms ket |l. (5. m = + l + m + 1/2 |m − 1/2. 1/2|l + 1/2. (6. 2l + 1 (6. By convention. this factor is taken to be unity. 1/2 2l + 1 l − m + 1/2 |m + 1/2. 1/2|l + 1/2. |l + 1/2. 1/2|l + 1/2. l.7 Fine structure 6 APPROXIMATION METHODS We can use this formula to successively increase the value of ml . For instance. A careful examination of the recursion relation. It follows from Eq. m − 1/2. giving l. The corresponding value of mj is l + 1/2. −1/2 .282). Thus.110) We now need to determine the sign of sin α. (6. mj ket |l + 1/2. the |ml .6. This value is possible when j = l + 1/2. 2l + 1 2l + 1 (6. Thus. shows that the plus sign is appropriate.109) that cos α = m − 1/2. up to an arbitrary phase-factor. 1/2|l + 1/2. 2l + 1 (6. m − 1/2. l + 1/2 = 1. 1/2|l + 1/2. m = Now. l + 1/2 .

(6. Thus.m = ± + l ± m + 1/2 m−1/2 Yl (θ. just as the spherical harmonics are eigenfunctions of the orbital angular momentum. 2 giving L·S |l + 1/2.m . ϕ) χ− 2l + 1  m−1/2   . which is the quantum number associated with Jz . The wave-function is also labeled by m. (6. −1/2 . 1/2 2l + 1 l + m + 1/2 |m + 1/2. For a given choice of l. These functions are eigenfunctions of the total angular momentum for spin onehalf particles. m = − + l − m + 1/2 |m − 1/2. ϕ) 1  ± l ± m + 1/2 Yl  = √ m+1/2 2l + 1 l m + 1/2 Yl (θ.119) . ϕ) χ+ 2l + 1 l m + 1/2 m+1/2 Yl (θ. Rnl (r). = − 2 138 (θ.e. (6. m kets are eigenstates of L·S. the quantum number associated with J 2 ) can take the values l ± 1/2. ϕ) (6.116) The |l ± 1/2. mj = m = [j (j + 1) − l (l + 1) − 3/4] |j.7 Fine structure 6 APPROXIMATION METHODS |l − 1/2. (6..102). m L·S |l − 1/2. = 2 (l + 1) ¯ 2 h |l − 1/2.117) (6.6. according to Eq. A general wave-function for an energy eigenstate in a hydrogen-like atom is written The radial part of the wave-function. m . m . m l¯2 h |l + 1/2.118) (6.114) 2l + 1 It is convenient to define so called spin-angular functions using the Pauli twocomponent formalism: Yl j=l±1/2. ¯2 h L·S |j = l ± 1/2. the quantum number j (i.115) ψnlm± = Rnl (r) Y j=l±1/2. depends on the radial quantum number n and the angular quantum number l. m .

100) (remember the factor of two). In chemist’s notation.121) l−1/2.6.122) where the integral is over all space.120)–(6. 2 (6. To first-order. and (6. (6.121) yield ∆Enlm+ ∆Enlm− where 1 dV l ¯ 2 h 1 . (6. Equations (6.123)–(6. the ground state is written (1s)2 (2s)2 (2p)6 (3s).m l¯2 h .125) Let us now apply the above result to the case of a sodium atom. This state has a higher energy than 3s due to the deviations of the potential from the pure 139 .123) (6.120) (6.126) The inner ten electrons effectively form a spherically symmetric electron cloud.124) are known as Lande’s interval rule. r dr r dr Equations (6. the energy-shift is given by ∆Enlm± = (ψnlm± )† HLS ψnlm± dV. (6.m where the integrals are over all solid angle.124) 1 dV 1 dV = (Rnl )∗ Rnl r2 dr. 2 me2 r dr 2 (6.m † l−1/2. The closest (in energy) unoccupied state is 3p. We are interested in the excitation of the eleventh electron from 3s to some higher energy state. = + 2 me2 r dr 2 1 1 dV (l + 1) ¯ 2 h = − . dΩ = 2 (l + 1) ¯ 2 h dΩ = − .116).m † ) L·S Y ) L·S Y l+1/2.7 Fine structure 6 APPROXIMATION METHODS It follows that (Y (Y l+1/2. Let us now apply degenerate perturbation theory to evaluate the shift in energy of a state whose wave-function is ψnlm± due to the spin-orbit Hamiltonian HLS . (6.

8 The Zeeman effect Consider a hydrogen-like atom placed in a uniform z-directed magnetic field. In the absence of spin-orbit interaction.6.129) 2 me is its magnetic moment. Thus.8 The Zeeman effect 6 APPROXIMATION METHODS Coulomb form. there are six degenerate 3p states.123)–(6. The fact that there are two slightly different 3p energy levels (note that spin-orbit coupling does not split the 3s energy levels) means that the sodium D line actually consists of two very closely spaced spectroscopic lines. HB = eB (Lz + 2 Sz ). where 1 e2 = α= 2 0 h c 137 (6. Note that Eqs.127) is the fine structure constant. The modified states are labeled (3p)1/2 and (3p)3/2 . including both the spin and orbital contributions. It is easily demonstrated that the ratio of the typical spacing of Balmer lines to the splitting brought about by spin-orbit interaction is about 1 : α2 . The well-known sodium D line is associated with transitions between the 3p and 3s states. In this situation. 2 me (6. we can treat H B as 140 . the relativistic mass correction of the electron) which is the same order of magnitude as spin-orbit coupling. The change in energy of the outermost electron is HB = −µ·B.125) is positive. where the subscript refers to the value of j. 6. The splitting of the (3p) energy levels of the sodium atom can be observed using a spectroscope.128) e (L + 2 S) (6.130) Suppose that the energy-shifts induced by the magnetic field are much smaller than those induced by spin-orbit interaction. where µ=− (6. (6.124) are not entirely correct. because the radial integral (6. since we have neglected an effect (namely. The spin-orbit interaction breaks the degeneracy of these states. The four (3p)3/2 states lie at a slightly higher energy level than the two (3p)1/2 states.

m = ± + It follows that l ± 1/2. = ± 2l + 1 m + 1/2)] (6. a magnetic field splits the (3p)3/2 141 . m = ¯ h [(l ± m + 1/2) − (l 2 (2 l + 1) m¯ h . 2l + 1 (6. (6. 1/2 2l + 1 l m + 1/2 |m + 1/2. −1/2 .134) Thus. Let us consider one of these states. From standard perturbation theory. m|HB |l ± 1/2. We have already seen that the non-Coulomb potential splits the degeneracy of the 3s and 3p states. the latter states acquiring a higher energy.6.136) 2 me 2l + 1 Let us apply this theory to the sodium atom.132) we find that ∆Enlm± = eB (m ¯ + l ± 1/2.113)–(6. m|Sz |l ± 1/2.131) Lz + 2 S z = Jz + Sz .8 The Zeeman effect 6 APPROXIMATION METHODS Since a small perturbation acting on the eigenstates of H0 + HLS . we obtain Lande’s formula for the energy-shift induced by a weak magnetic field: e¯ B h 1 ∆Enlm± = m 1± .114). |l ± 1/2. where j = l ± 1/2. m . (6.136). (6. According to Eq.133) Now.135) l ± m + 1/2 |m − 1/2. (6. labeled by the quantum numbers j and m. The spin-orbit interaction splits the six 3p states into two groups. the first-order energy-shift in the presence of a magnetic field is ∆Enlm± = l ± 1/2. from Eqs. h 2 me (6. (6. m|Sz |l ± 1/2. with four j = 3/2 states lying at a slightly higher energy than two j = 1/2 states. these states are the simultaneous eigenstates of J 2 and Jz . Of course. m ) .

H LS . states with the same value of n and l. ms |HB |n. in an intense magnetic field. = 2 me (6. Note that the magnetic Hamiltonian.136) that these states are split by a lesser amount than the j = 3/2 states. H0 . S 2 . The unperturbed Hamiltonian. commutes with L2 . HB . This is called the Paschen-Back limit. causes states with different values of the quantum numbers n and l to have different energies. However. this intermediate case is very difficult to analyze. S 2 . states with different values of ml + 2 ms acquire different energies. l.137) Thus. The shift in energy due to the magnetic field is simply ∆Enlml ms = n. ml . In the absence of a magnetic field.8 The Zeeman effect 6 APPROXIMATION METHODS quadruplet of states. but different values of ml and ms . are degenerate. States with higher m values have higher energies. l. which measures the projection of the total angular momentum along the z-axis. Sz . it is evident from Eq. However. l. depending on the values 142 . ms . the energy eigenstates of a hydrogen-like atom are approximate eigenstates of the spin and orbital angular momenta. in this situation. ml . Let us consider the extreme limit in which the energy-shift due to the magnetic field greatly exceeds that induced by spin-orbit effects. but does not commute with L2 . but are not eigenstates of the total angular momentum. ms e¯ B h (ml + 2 ms ). the six 3p states form two groups of four and two states. Let us apply this result to a sodium atom. Suppose that we increase the strength of the magnetic field. Thus. Thus. Lz . In fact.6. and ms . J 2 . In fact. l. (6. the energy of each state becomes dependent on the quantum number m. each state acquiring a different energy. In the Paschen-Back limit we can think of the spin-orbit Hamiltonian. A magnetic field also splits the (3p)1/2 doublet of states. Clearly. our energy eigenkets are written |n. it does not make much sense to think of HB as a small interaction term operating on the eigenstates of H0 + HLS . so that the energyshift due to the magnetic field becomes comparable to the energy-shift induced by spin-orbit interaction. Jz . as a small interaction term operating on the eigenstates of H0 + HB . ml . We can label each state by the quantum numbers n (the energy quantum number). ml .

8 The Zeeman effect 6 APPROXIMATION METHODS of their total angular momentum. h since L± = S ± = 0 for expectation values taken between the simultaneous eigenkets of Lz and Sz . ml .142) 2 me2 r dr Let us apply the above result to a sodium atom. a state with ml + 2 ms = −1.139) 1 1 dV L·S. or (−1. (1. l. In the presence of an intense magnetic field the 3p states are split into five groups. and (−1. −1/2). In the presence of an intense magnetic field. but does not split. the 3p states are split into five groups with (ml . does not affect the next highest energy state. where HLS = Now. h The energy-shift induced by the spin-orbit Hamiltonian is given by ∆Enl ml ms = n. The net result is that the five groups of states are no longer equally spaced in energy. 1/2). The sort of magnetic field-strength needed to get into the Paschen-Bach limit is given by e me 25 tesla. ms |HLS |n. (6.140) (6. decreases. 1/2). two states with ml + 2 ms = 0. These groups are equally spaced in energy. the energy of the doublet. and a state with ml + 2 ms = −2. a state with ml + 2 ms = 1. Thus. There is a state with ml + 2 ms = 2. (0. and increases the energy of the lowest energy state.143) BPB ∼ α2 0 h a0 143 (6. in order of decreasing energy. ms ) quantum numbers (1. l. does not affect the next lowest energy state. 1/2). (6.6. (0. −1/2). ms . −1/2). ml . 2 me2 r dr .141) = ¯ 2 ml ms . respectively. The spin-orbit term increases the energy of the highest energy state. the energy difference between adjacent groups being e ¯ B/2 me .138) (6. ¯ 2 ml ms 1 dV h ∆Enlml ms = . L·S = Lz Sz + (L+ S− + L− S+ )/2 (6.

6.9 Time-dependent perturbation theory

6 APPROXIMATION METHODS

Obviuously, this is an extremely large field-strength.

6.9 Time-dependent perturbation theory Suppose that the Hamiltonian of the system under consideration can be written H = H0 + H1 (t), (6.144)

where H0 does not contain time explicitly, and H1 is a small time-dependent perturbation. It is assumed that we are able to calculate the eigenkets of the unperturbed Hamiltonian: H0 |n = En |n . (6.145) We know that if the system is in one of the eigenstates of H0 then, in the absence of the external perturbation, it remains in this state for ever. However, the presence of a small time-dependent perturbation can, in principle, give rise to a finite probability that a system initially in some eigenstate |i of the unperturbed Hamiltonian is found in some other eigenstate at a subsequent time (since |i is no longer an exact eigenstate of the total Hamiltonian), In other words, a time-dependent perturbation causes the system to make transitions between its unperturbed energy eigenstates. Let us investigate this effect. Suppose that at t = t0 the state of the system is represented by |A =
n

cn |n ,

(6.146)

where the cn are complex numbers. Thus, the initial state is some linear superposition of the unperturbed energy eigenstates. In the absence of the timedependent perturbation, the time evolution of the system is given by |A, t0 , t =
n

cn exp([−i En (t − t0 )/¯ ] |n . h

(6.147)

Now, the probability of finding the system in state |n at time t is Pn (t) = |cn exp[−i En (t − t0 )/¯ ]|2 = |cn |2 = Pn (t0 ). h
144

(6.148)

6.9 Time-dependent perturbation theory

6 APPROXIMATION METHODS

Clearly, with H1 = 0, the probability of finding the system in state |n at time t is exactly the same as the probability of finding the system in this state at the initial time t0 . However, with H1 = 0, we expect Pn (t) to vary with time. Thus, we can write |A, t0 , t = cn (t) exp[−i En (t − t0 )/¯ ] |n , h (6.149)
n

where Pn (t) = |cn (t)| . Here, we have carefully separated the fast phase oscillation of the eigenkets, which depends on the unperturbed Hamiltonian, from the slow variation of the amplitudes cn (t), which depends entirely on the perturbation (i.e., cn is constant if H1 = 0). Note that in Eq. (6.149) the eigenkets |n are time-independent (they are actually the eigenkets of H0 evaluated at the time t0 ). Schr¨dinger’s time evolution equation yields o ∂ |A, t0 , t = H |A, t0 , t = (H0 + H1 ) |A, t0 , t . ∂t It follows from Eq. (6.149) that i¯ h (H0 + H1 )|A, t0 , t =
m

2

(6.150)

cm (t) exp[−i Em (t − t0 )/¯ ] (Em + H1 ) |m . h

(6.151)

We also have ∂ i ¯ |A, t0 , t = h ∂t

i¯ h
m

dcm + cm (t) Em exp[−i Em (t − t0 )/¯ ] |m , h dt

(6.152)

where use has been made of the time-independence of the kets |m . According to Eq. (6.150), we can equate the right-hand sides of the previous two equations to obtain dcm exp[−i Em (t − t0 )/¯ ]|m = h cm (t) exp[−i Em (t − t0 )/¯ ] H1 |m . h i¯ h dt m m (6.153) Left-multiplication by n| yields i¯ h where Hnm (t) = n|H1 (t)|m ,
145

dcn = dt

Hnm (t) exp[i ωnm (t − t0 )] cm (t),
m

(6.154)

(6.155)

6.10 The two-state system

6 APPROXIMATION METHODS

En − E m . (6.156) ¯ h Here, we have made use of the standard orthonormality result, n|m = δ nm . Suppose that there are N linearly independent eigenkets of the unperturbed Hamiltonian. According to Eq. (6.154), the time variation of the coefficients cn , which specify the probability of finding the system in state |n at time t, is determined by N coupled first-order differential equations. Note that Eq. (6.154) is exact—we have made no approximations at this stage. Unfortunately, we cannot generally find exact solutions to this equation, so we have to obtain approximate solutions via suitable expansions in small quantities. However, for the particularly simple case of a two-state system (i.e., N = 2), it is actually possible to solve Eq. (6.154) without approximation. This solution is of enormous practical importance. ωnm =

and

6.10 The two-state system Consider a system in which the time-independent Hamiltonian possesses two eigenstates, denoted H0 |1 H0 |2 = E1 |1 , = E2 |2 . (6.157) (6.158)

Suppose, for the sake of simplicity, that the diagonal matrix elements of the interaction Hamiltonian, H1 , are zero: 1|H1 |1 = 2|H1 |2 = 0. (6.159)

The off-diagonal matrix elements are assumed to oscillate sinusoidally at some frequency ω: 1|H1 |2 = 2|H1 |1 ∗ = γ exp(i ω t), (6.160) where γ and ω are real. Note that it is only the off-diagonal matrix elements which give rise to the effect which we are interested in—namely, transitions between states 1 and 2.
146

h (6.162) to obtain the amplitude c1 .6. the probability of finding the system in state 1 at time t is simply P 1 (t) = |c1 |2 . our boundary conditions are c1 (0) = 1 and c2 (0) = 0. (6. i¯ h dt i¯ h (6. h γ2 /¯ 2 + (ω − ω21 )2 /4 t h exp[ i (ω − ω21 ) t/2] c1 (t) = exp[ i (ω − ω21 ) t/2] cos − i (ω − ω21 )/2 γ2 /¯ 2 + (ω − ω21 )2 /4 h × sin γ2 /¯ 2 + (ω − ω21 )2 /4 t .161) (6. Let us look for a solution in which the system is certain to be in state 1 at time t = 0. dt2 dt ¯ h (6.165) Now.10 The two-state system 6 APPROXIMATION METHODS For a two-state system.162) where ω21 = (E2 − E1 )/¯ .162) can be combined to give a second-order differential equation for the time variation of the amplitude c2 : dc2 γ2 d2 c 2 + i (ω − ω21 ) + 2 c2 = 0. the probability of finding the system in state 2 at time t is P 2 (t) = |c2 |2 . (6.154) reduces to dc1 = γ exp[+i (ω − ω21 ) t ] c2 . we can use Eq. Equations (6. Thus.164) γ2 /¯ 2 + (ω − ω21 )2 /4 t . dt dc2 = γ exp[−i (ω − ω21 ) t ] c1 . and assuming that t0 = 0.161) and h (6. Likewise.163) Once we have solved for c2 . It is easily demonstrated that the appropriate solutions are c2 (t) = −i γ/¯ h γ2 /¯ 2 + (ω − ω21 )2 /4 h × sin exp[−i (ω − ω21 ) t/2] (6. It follows that γ2 /¯ 2 h P2 (t) = 2 2 γ /¯ + (ω − ω21 )2 /4 h 147 . Eq.

Equation (6. the system periodically h flip-flops between states 1 and 2 under the influence of the time-dependent perturbation.168) (6. After a further time interval h π ¯ /2 γ it is certain to be in state 1. Clearly. nor is the minimum value of P1 (t) zero. the smaller γ becomes). we find that P1 (t) = cos2 (γ t/¯ ). Thus.167) P1 (t) = 1 − P2 (t). At resonance. ω. the weaker the h perturbation (i. if the applied frequency differs from the resonant frequency by h substantially more than 2 γ/¯ then the probability of the system jumping from h state 1 to state 2 is very small. However.169) According to the above result. In other words. h (6.6. ω. when the oscillation frequency of the perturbation. 148 . the system starts off at t = 0 in state 1. when ω = ω21 .10 The two-state system 6 APPROXIMATION METHODS × sin2 γ2 /¯ 2 + (ω − ω21 )2 /4 t .. This implies that the system alternatively absorbs and emits energy from the source of the perturbation. the amplitude of oscillation of the coefficient c2 is reduced. After a time interval π ¯ /2 γ it is certain to be in state 2. The absorption-emission cycle also take place away from the resonance. we obtain a resonance curve whose maximum (unity) lies at the resonance.166) (6. the narrower the resonance.166) exhibits all the features of a classic resonance. Thus. This means that the maximum value of P2 (t) is no longer unity. This result is known as Rabi’s formula. h (6. matches the frequency ω21 . if we plot the maximum value of P2 (t) as a function of the applied frequency.e. the time-dependent perturbation is only effective at causing transitions between states 1 and 2 if its frequency of oscillation lies in the approximate range ω21 ± 2 γ/¯ . In fact. and so on. and whose full-width half-maximum (in frequency) is 4 γ/¯ . h P2 (t) = sin2 (γ t/¯ ).

Thus.11 Spin magnetic resonance Consider a spin one-half system (e. where H0 = and H1 = e B0 Sz .174) The time-dependent Hamiltonian can be written H1 = e B1 exp( i ωt) S− + exp(−i ωt) S+ . It follows that +|H1 |+ = −|H1 |− = 0. the electric component of the wave has no effect. respectively.175) where S+ and S− are the conventional raising and lowering operators for the spin angular momentum. a bound electron) placed in a uniform zdirected magnetic field. 2 me (6.6..172) e B1 (cos ωt Sx + sin ωt Sy ) . The rotating magnetic field usually represents the magnetic component of an electromagnetic wave propagating along the z-axis. Thus. and then subjected to a small time-dependent magnetic field rotating in the x-y plane. me (6.176) (6. ^ ^ z B = B0 ^ + B1 (cos ωt x + sin ωt y). and −|H1 |+ = +|H1 |− ∗ (6. denoted |+ and |− . 2 me 149 . 2 me (6. (6. H0 |± = ± e ¯ B0 h |± . The Hamiltonian is written H = −µ·B = H0 + H1 .170) where B0 and B1 are constants. me (6.177) = e ¯ B1 h exp( i ωt).g. with B1 B0 . In this system.171) (6.173) The eigenstates of the unperturbed Hamiltonian are the ‘spin up’ and ‘spin down’ states.11 Spin magnetic resonance 6 APPROXIMATION METHODS 6.

t = U(t0 . to a high degree of accuracy by placing the particles in a magnetic field. If we now apply a magnetic perturbation rotating at the resonant frequency then. In the absence of the perturbation. (6. → |+ . and subjecting them to an oscillating magnetic field whose frequency is gradually scanned.181) The resonant frequency. 2 me 6. provided that we make the identifications |1 |2 → |− . it is possible to calculate the magnetic moment. (6. is simply the spin precession frequency for an electron in a uniform magnetic field of strength B0 . By determining the resonant frequency (i. We also know that if the oscillation frequency of the applied field is very different from the resonant frequency then there is virtually zero probability of the field triggering a spin-flop. Experimentalist are able to measure the magnetic moments of electrons. and other spin one-half particles. t) |A . the frequency at which the particles absorb energy from the oscillating field). in addition to the spin precession.154) for a general system. It is convenient to work in terms of the time evolution operator. the system undergoes a succession of spin-flops.e. but the expectation value of Sz remains invariant.179) (6. ω21 . t0 . (6. ω21 → me e ¯ B1 h γ → . |+ |− . according to the analysis of the previous section.6. t). The width of the resonance (in frequency) is determined by the strength of the oscillating magnetic perturbation.178) (6.182) 150 .12 The Dyson series Let us now try to find approximate solutions of Eq. which is defined |A.12 The Dyson series 6 APPROXIMATION METHODS It can be seen that this system is exactly the same as the two-state system discussed in the previous section. e B0 .180) (6. U(t 0 . the expectation values of Sx and Sy oscillate because of the spin precession..

t) UI (t0 .187) (6.6. ∂t (6. t is the state ket of the system at time t. given that the state ket at the initial time t0 is |A . t) = exp[−i H0 (t − t0 )/¯ ]. t). The subsequent evolution of the state ket is given by Eq.185) Let us switch on the perturbation and look for a solution of the form U(t0 . t) = HI (t0 .186) Note that UI specifies that component of the time evolution operator which is due to the time-dependent perturbation. |A.189) (6. t) = exp[−i H0 (t − t0 )/¯ ] UI (t0 . Thus.188) ∂UI (t0 . t0 . t) = exp[+i H0 (t − t0 )/¯ ] H1 exp[−i H0 (t − t0 )/¯ ].183) (6. h (6. (6. (6. the time evolution operator reduces to U(t0 .12 The Dyson series 6 APPROXIMATION METHODS Here. t = cm (t) exp[−i Em (t − t0 )/¯ ] |m . h It is readily demonstrated that UI satisfies the differential equation i¯ h where HI (t0 . t) = (H0 + H1 ) U(t0 . t). t).190) m 151 .184) In the absence of the external perturbation. t0 ) = 1.149). h (6. |i. t0 . t0 ) = 1. (6. It is easily seen that the time evolution operator satisfies the differential equation ∂U(t0 . ∂t subject to the boundary condition i¯ h U(t0 . h h subject to the boundary condition UI (t0 . we would expect UI to contain all of the information regarding transitions between different eigenstates of H 0 caused by the perturbation. Suppose that the system starts off at time t0 in the eigenstate |i of the unperturbed Hamiltonian.

(6.12 The Dyson series 6 APPROXIMATION METHODS However. t) |i . is simply Pi→n (t0 . t ) dt t0 2 t t dt t0 t0 HI (t0 . etc.194) We can obtain an approximate solution to this equation by iteration: UI (t0 . t0 (6. t0 .187). t)|i |2 . t ) dt . t ) UI (t0 .195) that c(0) (t) = δin .195) This expansion is known as the Dyson series. Note that the differential equation (6. t = exp[−i H0 (t − t0 )/¯ ] UI (t0 .192) where use has been made of n|m = δnm .189). Let cn = c(0) + c(1) + c(2) + · · · . t ) UI (t0 . Thus.191) HI (t0 . (6.196) where the superscript (1) refers to a first-order term in the expansion. the probability that the system is found in state |n at time t. (6. h It follows that cn (t) = n|UI (t0 . i UI (t0 . n 152 (6. n n n (6. t)|i . t) i 1− ¯ h i 1− ¯ h −i + ¯ h i HI (t0 . given that it is definitely in state |i at time t 0 . t ) dt  HI (t0 .192) and (6. It follows from Eqs. t ) HI (t0 . (6.193) This quantity is usually termed the transition probability between states |i and |n . we also have |i. t) = | n|UI (t0 . t ) dt + · · · . are equivalent to the following integral equation.197) . t ) 1 − ¯ h t0 t t  t t0 HI (t0 .6. plus the boundary condition (6. t) = 1 − ¯ h t (6.

t) = |c(0) + c(1) + c(2) + · · · |2 .e.204) (6.199) dt t0 t0 n|HI (t0 . However. t ) HI (t0 . there is no chance of a transition between states |i and |n (i = n) to zeroth-order (i. where ωnm = and Hnm (t) = n|H1 (t)|m . The transition probability between states i and n is simply Pi→n (t0 .12 The Dyson series 6 APPROXIMATION METHODS c(1) (t) n c(2) (t) n i = − ¯ h = −i ¯ h t n|HI (t0 . then there is no chance of a first-order transition between states |i and |n . ¯ h (6.200) t i = − ¯ h = −i ¯ h exp[ i ωni (t − t0 )] Hni (t ) dt . t )|i dt . weighted by some oscillatory phase-factor. 153 . the transition probability is proportional to the time integral of the matrix element n|H1 |i . Thus. in the absence of the perturbation). n n n En − E m .205) According to the above analysis. if the matrix element is zero.6. a transition between states |i and |n is possible even when the matrix element n|H1 |i is zero.201) (2) cn (t) dt t0 t0 dt exp[ i ωnm (t − t0 )] (6. t0 2 t t (6. t )|i dt . (1) cn (t) (6. t0 2 m t t (6.. to second-order.202) ×Hnm (t ) exp[ i ωmi (t − t0 )] Hmi (t ). To first-order.203) (6. These expressions simplify to (0) cn (t) = δin .198) (6.

En − E i   (6. The transition probability between states |i and |n can be written |Hni |2 t2 (En − Ei ) t  Pi→n (t) = .13 Constant perturbations 6 APPROXIMATION METHODS 6.206) where H1 is time-independent. According to Eqs. En = Ei ) have an appreciable probability of occurrence. ∼ h 154 where (6.207) (6. but is generally a function of the position.211) x The sinc function is highly oscillatory. (6. It is a good approximation to say that sinc(x) is small except when |x| < π. is small except when 2π ¯ h . provided that sinc(x) = ∆E ∆t < ¯ . and spin operators.213) . is is possible to have transitions which do not exactly conserve energy.202) (with t0 = 0).6. n c(1) (t) n t i = − Hni exp[ i ωni (t − t)] dt ¯ h 0 Hni = [1 − exp( i ωni t)]. (6. c(0) (t) = δin . Pi→n . (6. At finite t.208) giving (En − Ei ) t  4 |Hni |2 (1) 2 sin2  . momentum.210) sin x .212) |En − Ei | < ∼ t Note that in the limit t → ∞ only those transitions which conserve energy (i.e. sinc2  2¯ h ¯2 h   (6. and decays like 1/|x| at large |x|. (6. (6. It follows ∼ that the transition probability. Suppose that the system is definitely in state |i at time t = 0.209) Pi→n (t) |cn | = |En − Ei |2 2¯ h for i = n.13 Constant perturbations Consider a constant perturbation which is suddenly switched on at time t = 0: H1 (t) = 0 H1 (t) = H1 for t < 0 for t ≥ 0.200)–(6..

In practice.. t to t + dt. It is helpful to define the density of states. (6. this result is just a manifestation of the well-known uncertainty relation for energy and time. whereas time is merely a parameter.e. (6. we can take ρ(En ) and |Hni |2 out of the integral in the above formula to obtain Pi→[n] (t) = 2π |Hni |2 ρ(En ) t ¯ h En 155 Pi→n (t) ρ(En ) dEn . Thus. Ei (6.218) . ρ(E). grows linearly with t.13 Constant perturbations 6 APPROXIMATION METHODS where ∆E = |En − Ei | is change in energy of the system associated with the transition. Note that this probability grows quadratically with time. all possessing nearly the same energy as the energy of the initial state |i . We know that in the limit t → ∞ the function sinc(x) is only non-zero in an infinitesimally narrow range of final energies centred on En = Ei . E n = Ei ) is |Hin |2 t2 Pi→n (t) = . (6.210). ¯ h (6.214) ¯2 h where use has been made of sinc(0) = 1. since it implies that the probability of a transition occurring in a fixed time interval. since in non-relativistic quantum mechanics position and momentum are operators. It follows that. Clearly.215) 2t |Hni |2 ρ(En ) sinc2 (x) dx. in this limit. and ∆t = t is the time elapsed since the perturbation was switched on. This result is somewhat surprising. despite the fact that H1 is constant for t > 0.6.217) and use has been made of Eq. where the number of final states lying in the energy range E to E + dE is given by ρ(E) dE. there is usually a group of final states.216) . The probability of a transition which conserves energy (i. the probability of a transition from the initial state i to any of the continuum of possible final states is Pi→ (t) = giving Pi→ (t) = where x = (En − Ei ) t/2 ¯ . h (6. This uncertainty relation is fundamentally different to the position-momentum uncertainty relation.

dt (6. instead of t2 . It is convenient to define the transition rate. Thus.. |Hni |2 is the average of |Hni |2 over all final states with approximately the same energy as the initial state. Here. using the constant perturbation (6. From Eq. Note that the transition rate is constant in time (for t > 0): i.206). (6. Fermi’s golden rule is sometimes written wi→[n] = 2π |Hni |2 δ(En − E). ¯ h where it is understood that this formula must be integrated with obtain the actual transition rate.e. which is simply the transition probability per unit time. is now proportional to t.13 Constant perturbations 6 APPROXIMATION METHODS where Pi→[n] denotes the transition probability between the initial state |i and all final states |n which have approximately the same energy as the initial state. (6. wi→[n] = giving 2π |Hni |2 ρ(En ) .222) ρ(En ) dEn to dPi→[n] . wi→n = (6. the probability of a transition occurring in the time interval t to t + dt is independent of t for fixed dt.219) −∞ Note that the transition probability.221) ¯ h En E i This appealingly simple result is known as Fermi’s golden rule.6.220) Let us now calculate the second-order term in the Dyson series. we have made use of the result ∞ sinc2 (x) dx = π. Pi→[n] . (6. In deriving the above formula.202) we find that (2) cn (t) = −i ¯ h 2 t t Hnm Hmi m 0 t dt exp( i ωnm t ) 0 dt exp( i ωmi t ) i = ¯ h = it ¯ h m Hnm Hmi Em − E i [exp( i ωni t ) − exp( i ωnm t ] ) dt 0 m Hnm Hmi [exp( i ωni t/2) sinc(ωni t/2) Em − E i 156 .

by analogy with the previous analysis. (6. According to Eq. (6. and for intermediate states. (6. The above formula clearly breaks down if Hnm Hmi = 0 when Em = Ei . Subsequently.13 Constant perturbations 6 APPROXIMATION METHODS − exp( i ωnm t/2) sinc(ωnm t/2)] . En E i (6. with approximately the same energy as the initial state. First. Em − E i Hnm Hmi  sinc(ωni t/2) Em − E i   (6. whereas the energy conserving first-order transition is termed a real transition.223) + m Hnm Hmi exp( i ωim t/2) sinc(ωnm t/2) . |m whose energies differ from that of the initial state.224) to average to zero (due to the oscillatory phase-factor) during the evaluation of the transition probability. cn (t) = c(1) n + c(2) n it exp( i ωni t/2) = ¯ h − m  H ni (6. |i . that wi→[n] 2π = Hni + ¯ h Hnm Hmi ρ(En ) Em − E i 2 . conserves energy.e. The net result is to change the energy denominator in Eq. the system makes another non-energy-conserving transition to the final state |n . a second-order transition takes place in two steps.208). (6.225). It follows. The fact that Em = Ei causes the last term on the right-hand side of Eq.6.224) where use has been made of Eq. Thus. from |i to |n . The non-energy-conserving transitions are generally termed virtual transitions. H1 → exp(η t) H1 (where η is very small). This problem can be avoided by gradually turning on the perturbation: i. h 157 ..225) from Ei − Em to Ei − Em + i ¯ η. |n . the system makes a non-energy-conserving transition to some intermediate state |m . The net transition.225) m where the transition rate is calculated for all final states.

231) ωni − ω 0 or En Ei + ¯ ω. (6. ¯ h 0 or En (6.6. h (6. a function of position. (6. and spin operators. momentum.229) This formula is analogous to Eq.14 Harmonic perturbations Consider a perturbation which oscillates sinusoidally in time. (6. (6. H0 .201) that c(1) n −i = ¯ h  t 0  † Vni exp(i ωt ) + Vni exp(−i ωt ) exp( i ωni t ) dt . (6. and (6. and switch on the harmonic perturbation at t = 0. whilst making a h transition to a final state whose energy level is less than that of the initial state 158 . Let us initiate the system in the eigenstate |i of the unperturbed Hamiltonian. provided that ωni = En − E i → ωni ± ω. This is usually called a harmonic perturbation.14 Harmonic perturbations 6 APPROXIMATION METHODS 6.230) Thus.208). (6.232) corresponds to the second term. H1 (t) = V exp( i ωt) + V † exp(−i ωt).227).228) (6. Thus. The former term describes a process by which the system gives up energy ¯ ω to the perturbing field. n|V † |i = i|V|n ∗ .232) Clearly. in general. (6.227) 1  1 − exp[ i (ωni + ω) t] 1 − exp[ i (ωni − ω) t] †  = Vni + Vni .231) corresponds to the first term on the right-hand side of Eq. it follows from the previous analysis that the transition probability P i→n (t) = |c(1) |2 is only appreciable in the limit t → ∞ if n ωni + ω Ei − ¯ ω.226) where V is. h (6. ¯ h ωni + ω ωni − ω where Vni = † Vni = n|V|i . It follows from Eq.

15 Absorption and stimulated emission of radiation 6 APPROXIMATION METHODS by ¯ ω. whilst h making a transition to a final state whose energy level exceeds that of the initial state by ¯ ω. ¯ h En =Ei −¯ ω h 2π † 2 . This process is known as stimulated emission. divided by the density of final states for absorption. the rate of stimulated emission. h ¯ h 2π † 2 = |V | δ(En − Ei − ¯ ω). |V | ρ(En ) = ¯ h ni En =Ei +¯ ω h (6.e. It follows from Eqs.15 Absorption and stimulated emission of radiation Let us use some of the results of time-dependent perturbation theory to investigate the interaction of an atomic electron with classical (i.6.. By analogy with Eq. (6.228)-(6.229) that |Vni |2 = |Vni |2 . This process is known as absorption. is known as detailed balancing.233) specifies the transition rate for stimulated emission.221). In both cases. divided by the density of final states for stimulated emission. These equations are more usually written wi→n = wi→n 2π |Vni |2 δ(En − Ei + ¯ ω).234) Equation (6.234) that wi→[n] wn→[i] = .236) † It is clear from Eqs. h ¯ h ni (6.233)–(6. equals the rate of absorption. 6. whereas Eq.e. which expresses a fundamental symmetry between absorption and stimulated emission. (6. The latter term describes h a process by which the system gains energy ¯ ω from the perturbing field. that of the system plus the perturbing field) is conserved.233) (6.. non-quantized) 159 . wi→[n] = wi→[n] 2π |Vni |2 ρ(En ) . (6. (6. This result.237) ρ(En ) ρ(Ei ) In other words. (6. and is very important in statistical mechanics.234) gives the transition rate for absorption. the total energy h (i.235) (6.

244) 2 me Now.242) (p − e A)2 H= + e φ + V0 (r). (6.238) 2 me The standard classical prescription for obtaining the Hamiltonian of a particle of charge q in the presence of an electromagnetic field is H0 = H → H − q φ. the Hamiltonian of an atomic electron placed in an electromagnetic field is where A(r) is the vector potential and φ(r) is the scalar potential. (6. (6. The unperturbed Hamiltonian is p2 + V0 (r).239) (6. c (6.240) This prescription also works in quantum mechanics.248) .246) Suppose that the perturbation corresponds to a monochromatic plane-wave. (6. The above equation can be written p2 − e A·p − e p·A + e2 A2 H= + e φ + V0 (r). 2 me me 2 me ·A = 0.247) ω n·r − ωt . p·A = A·p.243) 2 me where A and φ are functions of the position operators. (6.15 Absorption and stimulated emission of radiation 6 APPROXIMATION METHODS electromagnetic radiation.241) E = − φ− ∂t B = × A. (6. A = 2 A0 cos 160 (6. p → p + q A. Hence.6. Thus. (6. (6.245) provided that we adopt the gauge p2 e A·p e2 A2 H= − + + e φ + V0 (r). for which φ = 0. Note that ∂A .

249) with H0 = and H1 − p2 + V(r). by analogy with the previous analysis. (6. that the first term on the righth hand side of Eq. The perturbing Hamiltonian can be written H1 = − e A0 ·p (exp[ i (ω/c) n·r − i ωt] + exp[−i (ω/c) n·r + i ωt]) . (6.250) (6. The Hamiltonian becomes H = H0 + H1 (t). which is second order in A0 . me (6.251) where the A2 term.236) that the rate of absorption is h wi→n 2π e2 = |A0 |2 | n| exp[ i (ω/c) n·r] ·p |i |2 δ(En − Ei − ¯ ω). Note that ·n = 0.252) describes the absorption of a photon of energy ¯ ω.226).252) This has the same form as Eq. (6. 2 me e A·p . It follows from Eq. h 2 ¯ me h (6. has been neglected.254) The absorption cross-section is defined as the ratio of the power absorbed by the atom to the incident power per unit area in the electromagnetic field.253) It is clear. respectively. 2 µ0  (6.15 Absorption and stimulated emission of radiation 6 APPROXIMATION METHODS where and n are unit vectors which specify the direction of polarization and the direction of propagation.6. provided that V =− e A0 ·p exp[−i (ω/c) n·r ] me (6. (6. whereas the second term describes the stimulated emission of a photon of energy ¯ ω. Now the energy density of an electromagnetic field is 1 U=  2  2 0 E0 2 B02  + .255) 161 . me (6.

(6. exp[ i (ω/c) n·r] = 1 + i ω n·r + · · · .258).263) .256) Now. Thus.16 The electric dipole approximation In general.258) ¯ ω wi→n h . we obtain σabs = 4π2 α ωni | n| ·r|i |2 δ(ω − ωni ). respectively. ¯ h (6. (6. the wave-length of the type of electromagnetic radiation which induces. H0 ] = so n|p|i = −i Using Eq.16 The electric dipole approximation 6 APPROXIMATION METHODS where E0 and B0 = E0 /c = 2 A0 ω/c are the peak electric and magnetic fieldstrengths. (6. me (6. H0 ]|i = i me ωni n|r|i . This approximation is known as the electric dipole approximation. h 2ωc 0 me (6.6.262) (6.257) 6. c (6. 162 · n|p|i . It follows that n| exp[ i (ω/c) n·r] ·p |i It is readily demonstrated that [r. transitions between different atomic energy levels is much larger than the typical size of a light atom. or is emitted during. The incident power per unit area of the electromagnetic field is c U = 2 0 c ω2 |A0 |2 .260) i¯ p h . cU (6.259) can be approximated by its first term. unity (remember that ω/c = 2π/λ). σabs = so σabs = π e2 | n| exp[ i (ω/c) n·r] ·p |i |2 δ(En − Ei − ¯ ω).261) me n|[r.

266) (6.264) (6. ∆l = ±1. the next most likely type of transition is a magnetic dipole transition. but disallows a transition from a 2s to a 1s state.267) ∆m = ±1. It is easily demonstrated that n|x|i and n|y|i are only non-zero if ∆l = ±1. and m is the quantum number describing the projection of the orbital angular momentum along the z-axis. After electric dipole transitions. ω.268) (6. (6. (6. then it exhibits a sharp maximum at ω = ωni = (En − Ei )/¯ . ±1. for instance. for generally directed radiation n| ·r|i is only non-zero if (6. Here. Forbidden transitions are not strictly forbidden. 6. l is the quantum number describing the total orbital angular momentum of the electron.6. so that = ^. The latter transition is called a forbidden transition. Magnetic dipole transitions are typically about 10 5 times more unlikely than similar electric dipole transitions. These are termed the selection rules for electric dipole transitions.259) yields 163 . It is clear that if the absorption cross-section is regarded as a function of the applied frequency. (6. that the electric dipole approximation allows a transition from a 2p state to a 1s state. It is clear. that n|z|i = 0 unless the initial and final states satisfy ∆l = ±1. We z have already seen. Instead. they take place at a far lower rate than transitions which are allowed according to the electric dipole approximation.265) ∆m = 0. Thus. which is due to the interaction between the electron spin and the oscillating magnetic field of the incident electromagnetic radiation. from Sect.16 The electric dipole approximation 6 APPROXIMATION METHODS where α = e2 /(2 0 h c) = 1/137 is the fine structure constant.269) ∆m = 0. h Suppose that the radiation is polarized in the z-direction.4. The first-order term in Eq.

273) It follows that (6. H0 ] ] = − .274) This is known as the Thomas-Reiche-Kuhn sum rule. [x. n (6. (6. the above formula is exh actly the same as that obtained classically by treating the electron as an oscillator. Magnetic dipole and electric quadrupole transitions satisfy different selection rules than electric dipole transitions: for instance. These are typically about 10 8 times more unlikely than electric dipole transitions. the selection rules for electric quadrupole transitions are ∆l = 0. H0 ] ]|i = i|x H0 + H0 x − 2 x H0 x|i = − . that the incident radiation is polarized in the x-direction. Thus. ±2. Eq. (6. = me 2 0 me c (6. According to this rule. [x. 164 .271) (6.6. (6. me 2 2 (6.272) giving 2 n ¯2 h ( i|x|n Ei n|x|i − i|x|n En n|x|i ) = − . Integrating Eq. for the sake of definiteness. h ¯2 i|[x. transitions which are forbidden as electric dipole transitions may well be allowed as magnetic dipole or electric quadrupole transitions.16 The electric dipole approximation 6 APPROXIMATION METHODS so-called electric quadrupole transitions. me 2 me ¯ h ωni | n|x|i |2 = 1. me Thus.270) reduces to σabs (ω) dω = 2π2 α ¯ h π e2 . In fact.263) over all possible frequencies of the incident radiation yields σabs (ω) dω = n 4π2 α ωni | n| ·r|i |2 . It is easily demonstrated that ¯2 h [x.270) Suppose.275) Note that ¯ has dropped out of the final result.

In the remote past.278) where Hni = n|H1 |i . ¯ h η + i ωni (6. let us check that our previous Fermi golden rule result still applies when the perturbing potential is turned on slowly. other than the initial state |i . but η h lim 2 2 = π δ(ωni ) = π ¯ δ(En − Ei ). (6. (6. dt η2 + ωni ¯2 h Consider the limit η → 0. In this limit. Let us now consider how the initial state becomes depopulated.201) that (0) cn (t) = 0.281) . we want to calculate the time evolution of the coefficient ci (t). the system is assumed to be in the initial state |i . It is convenient to gradually turn on the perturbation from zero at t = −∞. becomes populated as a result of some time-dependent perturbation applied to the system. For cn=i (t) we have from Eqs. and cn=i (t → −∞) = 0. Thus. instead of very suddenly. Thus.277) t i = − Hni ¯ h exp[ (η + i ωni )t ] dt −∞ i exp[ (η + i ωni )t ] = − Hni .280) (6. First. ¯ 2 η2 + ωni h (6. It follows that.17 Energy-shifts and decay-widths We have examined how a state |n . t → −∞. (1) cn (t) (6. the transition probability from state |i to state |n is Pi→n (t) = |c(1) |2 = n The transition rate is given by 2 |Hni |2 η exp(2 η t) dPi→n = wi→n (t) = 2 .6. η→0 η + ωni 165 |Hni |2 exp(2 η t) 2 . and H1 is a constant. however.200)– (6. H1 (t) = exp(η t) H1 .279) (6. ci (t → −∞) = 1. to first-order.276) where η is small and positive. exp(η t) → 1. Basically.17 Energy-shifts and decay-widths 6 APPROXIMATION METHODS 6.

¯ h η (6. (6. (6. We obtain ci ˙ ci    −i −i Hii + ¯ h ¯ h 1− 2 |Hii |2 −i + η ¯ h i Hii ¯ η h |Hmi |2   Ei − E m + i ¯ η h m=i  −i −i Hii + lim η→0 ¯ ¯ h h |Hmi |2 .200)–(6. we ˙ ˙ can evaluate this ratio in the limit η → 0. Ei − E m + i ¯ η h m=i 166 (6. We have ci (t) = 1. The width of the peak is determined by how fast the perturbation is switched on. |Hmi |2 exp(2 η t) . Let us now calculate ci (t) using Eqs.285) = Thus. Using Eq. (1) ci (t) (2) ci (t) (0) (6.286).280) yields the standard Fermi golden rule result 2π |Hni |2 δ(En − Ei ).282) wi→n = ¯ h It is clear that the delta-function in the above formula actually represents a function which is highly peaked at some particular energy.17 Energy-shifts and decay-widths 6 APPROXIMATION METHODS Thus. 2 η (Ei − Em + i ¯ η) h m=i Let us now consider the ratio ci /ci .6.286) |Hmi |2 exp(2 η t) . to second-order we have ci (t) exp(η t) −i −i Hii + 1+ ¯ h η ¯ h −i + ¯ h 2 |Hii |2 exp(2 η t) 2 η2 (6. Eq.287) .284) |Hmi | m 2 −∞ dt −∞ dt 2 m × exp[ (η + i ωim )t ] exp[ (η + i ωmi )t ].283) t i = − Hii ¯ h = −i ¯ h −i ¯ h 2 exp(η t ) dt = − −∞ t t i exp(η t) Hii .202). 2 η (η + i ωmi ) (6. (6. (6. where ci ≡ dci /dt.

It follows that |Hmi |2 ∆i = Hii + P − iπ |Hmi |2 δ(Ei − Em ). we obtain −i ∆i t ci (t) = exp .149). t = exp[−i (Ei + ∆Ei ) t/¯ ] exp(−Γi t/2¯ ) |i .295) (6.290) > 0. and P denotes the principle part.287) is independent of time. We can write ci ˙ −i ∆i . x (6.291) It is convenient to normalize the solution of Eq.293) It is clear that the real part of ∆i gives rise to a simple shift in energy of state |i . = ci ¯ h where |Hmi |2 ∆i = Hii + lim η→0 E − Em + i ¯ η h m=i i 1 →0 x + i 1 − i π δ(x). (6.296) . whereas the imaginary part of ∆i governs the growth or decay of this state. E − Em m=i i m=i (6. Note that the right-hand side of Eq. lim where =P (6. Thus. Ei − E m m=i 167 (6.17 Energy-shifts and decay-widths 6 APPROXIMATION METHODS This result is formally correct to second-order in perturbed quantities. t = exp(−i [Ei + Re(∆i ) ] t/¯ ) exp[ Im(∆i ) t/¯ ] |i . (6. |i. Thus.289) is a constant. the time evolution of the initial state ket |i is given by |i. h h (6. t = exp[−i (∆i + Ei ) t/¯ ] |i .6. (6. h We can rewrite this result as |i.288) (6.288) so that ci (0) = 1.294) (6. According to a well-known result in pure mathematics. (6.292) ¯ h According to Eq. h h where |Hmi |2 ∆Ei = Re(∆i ) = Hii + P .

since |ci |2 + m=i |cm |2 (1 − Γi t/¯ ) + h m=i wi→m t = 1. Clearly.300) The quantity ∆i is called the decay-width of state |i . h (6. ¯ h ¯ h ¯ m=i h (6.297) Note that the energy-shift ∆Ei is the same as that predicted by standard timeindependent perturbation theory.6.301) Γi where Pi→i = exp(−t/τi ). exp[−i (Ei + ∆Ei ) t/¯ ] exp(−Γi t/2¯ ) = h h f(E) exp(−i E t/¯ ) dE. (6. h where Γi = wi→m . (6. Note that the system conserves probability up to second-order in perturbed quantities. is given by Pi→i (t) = |ci |2 = exp(−Γi t/¯ ). the amplitude of state |i both oscillates and decays as time progresses. (6. However. the rate of decay of the initial state is a simple function of the transition rates to the other states.303) 168 .222). The probability of observing the system in state |i at time t > 0. ¯ h m=i (6.298) (6. (6.302) According to Eq.17 Energy-shifts and decay-widths 6 APPROXIMATION METHODS and Γi 2 Im(∆i ) 2π =− = |Hmi |2 δ(Ei − Em ). It is closely related to the mean lifetime of this state. we can still represent it as a superposition of stationary states (whose amplitudes simply oscillate in time). given that it is definately in state |i at time t = 0. ¯ h τi = . state |i is not a stationary state in the presence of the time-dependent perturbation. use has been made of Eq.294). Clearly.299) Here. Thus. (6.

One consequence of h this effect is the existence of a natural width of spectral lines associated with the decay of some excited state to the ground state (or any other lower energy state).6. the energy of the state is smeared over some region of width (in energy) Γi centred around the shifted energy Ei + Re(∆i ). the energy of state |i is shifted by Re(∆i ). |f(E)|2 is basically a delta-function centred on the unperturbed energy Ei of state |i . the more its energy is spread out.e. 169 .e. This effect is clearly a manifestation of the energy-time uncertainty relation ∆E ∆t ∼ ¯ .. state |i is a stationary state whose energy is completely determined.. gives rise to a slight smearing (in wave-length) of the spectral line associated with the transition. In the presence of the perturbation. The fact that the state is no longer stationary (i. Indeed. due to its propensity to decay. (E − [Ei + Re(∆i )])2 + Γi 2 /4 (6. are smeared out more that weak lines. which correspond to fast transitions. it decays in time) implies that its energy cannot be exactly determined.17 Energy-shifts and decay-widths 6 APPROXIMATION METHODS where f(E) is the weight of the stationary state with energy E in the superposition. The faster the decay of the state (i. but they are a lot sharper. spectroscopists generally favour forbidden lines for Doppler shift measurements. The uncertainty in energy of the excited state. Strong lines.304) In the absence of the perturbation. The Fourier inversion theorem yields |f(E)|2 ∝ 1 . the larger Γi ). For this reason. Such lines are not as bright as those corresponding to allowed transitions. In other words.

7. We require a solution of Eq. a spherical-wave state.3). We have already developed theories which account for some aspects of the spectra of hydrogen-like atoms. H0 = 2m (7. H0 |φ = E |φ . corresponding to the o same energy eigenvalue. Let us now examine the quantum theory of scattering. and scattering experiments. (7. their energy eigenstates are unbound. This state is a plane-wave state or. (7. Let |φ be an energy eigenket of H0 . In general. p2 .7 SCATTERING THEORY 7 Scattering theory 7.1 Introduction Historically.2) and H1 represents the non-time-varying source of the scattering.. (7.2 The Lipmann-Schwinger equation Consider time-independent scattering theory. Here. |φ is a solution of the free particle Schr¨dinger equation. Schr¨dinger’s equation for the scattering problem is o (H0 + H1 )|ψ = E |ψ .3) whose wave-function r |φ is φ(r ). data regarding quantum phenomena has been obtained from two main sources—the study of spectroscopic lines. both H0 and H0 + H1 have continuous energy spectra: i. (7.4) where |ψ is an energy eigenstate of the total Hamiltonian whose wave-function r |ψ is ψ(r ). 170 .e.1) where H0 is the Hamiltonian of a free particle of mass m. for which the Hamiltonian of the system is written H = H 0 + H1 . (7. possibly.4) which satisfies the boundary condition |ψ → |φ as H1 → 0.

and making use of Eq. and can be inverted using standard Green’s function techniques. ψ± (r) = φ(r) + r 1 E − H0 ± i r r |H1 |ψ± d3 r . ¯ h where ¯ 2 k2 h E= . the solution satisfies the boundary condition |ψ → |φ as H1 → 0.8) ( 2 + k2 ) ψ(r) = 2 r|H1 |ψ . Thus. Furthermore. and small. Unfortunately. r ) r |H1 |ψ d3 r .9) 2m This equation is called Helmholtz’s equation. 2 ¯ h 171 (7. E − H0 ± i (7. |ψ± = |φ + 1 H1 |ψ± . The physical significance of the ± signs will become apparent later on. E − H0 (7.2 The Lipmann-Schwinger equation 7 SCATTERING THEORY Formally. (7. Equation (7.5) Note that we can recover Eq. Thus.. we can write the scattering problem o (7. We need a prescription for dealing with these infinities. (7. and is non-singular as long as > 0.7. The Lipmann-Schwinger equation can be converted into an integral equation via left multiplication by r|.6) where is real. Thus.3). The standard prescription is to make the energy eigenvalue E slightly complex. ψ(r) = φ(r) + 2m G(r.7) Adopting the Schr¨dinger representation. the operator (E − H0 )−1 is singular: i.10) .4) in the form 2m (7.6) is called the Lipmann-Schwinger equation. (7. (7. otherwise the above solution is useless.4) by operating on the above equation with E − H0 .e. it produces infinities when it operates on an eigenstate of H 0 corresponding to the eigenvalue E. positive. the desired solution can be written |ψ = |φ + 1 H1 |ψ .

r ) = − Thus. (7.14) r E − H0 ± i 4π |r − r | ¯ h It is not entirely clear that the ± signs correspond on both sides of this equation. a stream of particles of definite momentum p = ¯ k). they do.e.10) satisfies the boundary condition |ψ → |φ as H1 → 0. In fact. (7. is only a function of the position operators.10) becomes 2 m exp(±i k |r − r | ) r |H1 |ψ d3 r . (7. Eq.13) 2 4π |r − r | ¯ h A comparison of Eqs. H1 . Thus.13) suggests that the kernel to Eq. (2π)3/2 172 (7. (7. the Green’s function for the Helmholtz problem is given by G(r.12) = V(r ) ψ± (r ).15) exp(±i k |r − r | ) . 4π |r − r | (7.7) and (7. This implies that r |H1 |r = V(r) δ(r − r ).16) (7. We can write r |H1 |ψ± = r |H1 |r r |ψ± d3 r (7.7) takes the form 2 m exp(±i k |r − r | ) 1 r =− 2 . the integral equation (7. The ket corresponding to h this state is denoted |k .2 The Lipmann-Schwinger equation 7 SCATTERING THEORY where ( 2 + k2 ) G(r.18) . r ) = δ(r − r ).11) Note that the solution (7.17) Suppose that the initial state |φ is a plane-wave with wave-vector k (i. The associated wave-function takes the form r|k = exp( i k·r) . (7.13) simplifies to ψ± (r) = φ(r) − 2m ¯2 h exp(±i k |r − r |) V(r ) ψ± (r ) d3 r .. As is well-known. ψ± (r) = φ(r) − Let us suppose that the scattering Hamiltonian.7. (7. 4π |r − r | (7. as is easily proved by a more rigorous derivation of this result.

let us adopt the ordering r r . The plus sign (on ψ± ) corresponds to a wave propagating away from the scattering region.e.2 The Lipmann-Schwinger equation 7 SCATTERING THEORY The wave-function is normalized such that k|k = = k|r r|k d3 r exp[−i r·(k − k )] 3 d r = δ(k − k ).21) r is a unit vector which points from the scattering region to the observation point. Note that exp(±i k |r − r | ) exp(±i k r) exp( i k ·r ). Eq. In other words. k = k). 173 . Let us calculate the wave-function ψ(r) a long way from the scattering region. where r − ^·r r (7. Let us define k = k ^.17) reduces to ψ(r)± exp( i k·r) m exp(±i k r) exp( i k ·r ) V(r ) ψ± (r ) d3 r .22) ^= r Clearly.24) − 2 3/2 (2π) r 2π ¯ h The first term on the right-hand side is the incident wave. whereas the minus sign corresponds to a wave propagating towards the scattering region. (7. but propagate from the scattering region to the observation point.7. k is the wave-vector for particles which possess the same energy as the incoming particles (i. (7. (7. (2π)3 (7.. It is easily demonstrated that |r − r | to first-order in r /r.19) Suppose that the scattering potential V(r) is only non-zero in some relatively localized region centred on the origin (r = 0). r (7. The second term represents a spherical wave centred on the scattering region.23) In the large-r limit.20) r (7.

k) = − ¯2 h exp(−i k ·r ) V(r ) ψ(r ) d3 r 3/2 (2π) (7.25) where (2π)2 m = − k |H1 |ψ . ¯2 h Let us define the differential cross-section dσ/dΩ as the number of particles per unit time scattered into an element of solid angle dΩ. that the probability flux (i. the particle flux) associated with a wave-function ψ is ¯ h Im(ψ∗ ψ). divided by the incident flux of particles. (2π)3/2 is jinci = (7. (7. Thus. (2π)3/2 r (7. the wavefunction a long way from the scattering region can be written 1  exp( i kr) f(k .26)   (7. the probability flux associated with the incident wave-function. k)|2 ¯ h k ^.28) ¯ h k. 4. the probability flux associated with the scattered wave-function.2 The Lipmann-Schwinger equation 7 SCATTERING THEORY It is obvious that the former represents the physical solution.32) .7. m Thus. k) .30) is jscat Now. from Sect. k) .27) (7. j= exp( i k·r) . dΩ |jinci | 174 (7. r = (2π)3 m r2 (7. ψ(r) = exp( i k·r) + (2π)3/2 r (2π)2 m f(k . exp( i k r) f(k . Recall..e. |f(k .29) (2π)3 m Likewise.31) dσ r2 dΩ |jscat | dΩ = .

(7. (2π)3/2 (7.33) dΩ Thus. This is always the case for scattering Hamiltonians of the form shown in Eq.34) 2 r 2π ¯ h where φ(r) is the wave-function of the incident state.3 The Born approximation Equation (7. k) depends on the unknown ket |ψ . According to the above equation the total wave-function is a superposition of the incident wave-function and lots of spherical-waves emitted from the scattering region. 175 (7. 7. does not differ substantially from the incident wave-function. we can obtain an expression for f(k . k)|2 . ψ. In this case. Thus. k) by making the substitution ψ(r) → φ(r) = exp( i k·r) .33) is not particularly useful.35) This is called the Born approximation. k)|2 gives the differential cross-section for particles with incident momentum ¯ k to be scattered into states whose momentum vectors are directed in h a range of solid angles dΩ about ¯ k . φ(r). V. because the quantity f(k .e. The Born approximation yields f(k . k) − m 2π ¯ 2 h exp [ i (k − k )·r ] V(r ) d3 r .. (7. Note that the scattered particles possess h the same energy as the incoming particles (i. it is reasonable to suppose that the total wave-function. (7. as well as the local value of the wave-function. ψ(r). as it stands. The strength of the spherical-wave emitted at a given point is proportional to the local value of the scattering potential. |f(k .7. ψ(r) = φ(r) − Suppose that the scattering is not particularly strong.15).3 The Born approximation 7 SCATTERING THEORY giving dσ = |f(k .36) . k = k). Recall that ψ(r) = r|ψ is the solution of the integral equation m exp( i k r) exp(−i k ·r ) V(r ) ψ(r ) d3 r .

3 The Born approximation 7 SCATTERING THEORY Thus. It is easily demonstrated that q ≡ |k − k | = 2 k sin(θ/2). For a spherically symmetric potential. θ is the angle of scattering. In other words.43) q2 = 4 k2 sin2 (θ/2) = 2 k2 (1 − cos θ). It follows from Eq. 176 (7. f(k . Recall that the vectors k and k have the same length by energy conservation. (7. µr (7. k) − 2 r V(r ) sin(q r ) dr .37) where θ is the angle subtended between the vectors k and k . in the Born approximation.40) where V0 is a constant and 1/µ measures the “range” of the potential.39) − m 2π ¯ 2 h exp( i q r cos θ ) V(r ) r 2 dr sin θ dθ dφ . k) is proportional to the Fourier transform of the scattering potential V(r) with respect to the wave-vector q ≡ k − k .7.44) .42) µ + q2 0 Thus. the differential cross-section for scattering by a Yukawa potential is dσ dΩ given that  2 m V0  1  . (7. k) is just a function of q for a spherically symmetric potential. (7. (7. (7. Consider scattering by a Yukawa potential V(r) = V0 exp(−µ r) . [2 k2 (1 − cos θ) + µ2 ]2 ¯2µ h 2 (7.41) ¯ µ q2 + µ 2 h since ∞ q exp(−µ r ) sin(q r ) dr = 2 . (7.38) ¯ q 0 h Note that f(k . k) giving 2m ∞ f(k . f(k .38) that 2 m V0 1 f(θ) = − 2 .

45) dΩ 4π 0 ¯ 2 h 16 k4 sin4 (θ/2) Recall that ¯ k is equivalent to |p|. At low energies. from Eq. 4 16π 0 E sin (θ/2)  2 (7.46) is the classical Rutherford scattering cross-section formula.50) ¯2 µk h This inequality becomes progressively easier to satisfy as k increases.7.. The Born approximation is valid provided that ψ(r) is not too different from φ(r) in the scattering region. (7. giving 2 m |V0 | ¯ 2 µ2 h 1 (7.47) µ) Consider the special case of the Yukawa potential. (7.47) yields 2 m |V0 | 1. provided that V0 /µ → Z Z e2 /4π 0 . k we can replace exp( i k r ) by unity. ¯ 2 µ2 h (7.48) as the condition for the validity of the Born approximation. 177 . Eq. so the above equation can be rewritten h dσ dΩ 1 Z Z e2   . Equation (7. implying that the Born approximation is more accurate at high incident particle energies.7. The condition for the Yukawa potential to develop a bound state is 2 m |V0 | ≥ 2. It follows. (7.46) where E = p2 /2 m is the kinetic energy of the incident particles.49) where V0 is negative. (i. (7. if the potential is strong enough to form a bound state then the Born approximation is likely to break down.17). In the high-k limit.e. (7.3 The Born approximation 7 SCATTERING THEORY The Yukawa potential reduces to the familiar Coulomb potential as µ → 0. In this limit the Born differential crosssection becomes 2  2 m Z Z e2  dσ 1  . that the condition for ψ(r) φ(r) in the vicinity of r = 0 is m 2π ¯ 2 h exp( i k r ) V(r ) d3 r r 1. Thus.

The Legendre functions are related to the spherical harmonics introduced in Sect. 5 via Pl (cos θ) = 4π Yl0 (θ. points in a different direction.e. ϕ).55) since the Legendre functions Pl (cos θ) form a complete set in θ-space.53) depend on the azimuthal angle ϕ. and an azimuthal angle ϕ about the z-axis. V(r) = V(r)] the scattering amplitude is a function of θ only: f(θ. 2l + 1 178 (7. 1  exp( i k r) f(θ)  ψ(r) = exp( i k r cos θ) + . The direction of k is specified by the polar angle θ (i.e.38) strongly suggests that for a spherically symmetric scattering potential [i.54) What is the most general solution to this equation in spherical polar coordinates which does not depend on the azimuthal angle ϕ? Separation of variables yields ψ(r. ϕ) = f(θ). Equation (7.4 Partial waves We can assume. φ(r) = nor the total wave-function. the angle subtended between the two wavevectors). (2π)3/2 r   (7. both φ(r) and ψ(r) satisfy the free space Schr¨dinger equation o ( 2 + k2 ) ψ = 0..4 Partial waves 7 SCATTERING THEORY 7.56) .7. that the incident wave-function is characterized by a wave-vector k which is aligned parallel to the z-axis. in general. (7. θ) = l Rl (r) Pl (cos θ). (2π)3/2 (2π)3/2 (7.52) (7.51) exp( i k z) exp( i k r cos θ) = . It follows that neither the incident wave-function. but. without loss of generality.. (7. The scattered wave-function is characterized by a wave-vector k which has the same magnitude as k. Outside the range of the scattering potential.

The Legendre functions are orthonormal. The asymptotic behaviour of these functions in the limit y → ∞ is sin(y − l π/2) . (7.57) + 2r 2 dr dr The two independent solutions to this equation are called a spherical Bessel function.62) where the al are constants. y cos(y − l π/2) ηl (y) → − . Note there are no Neumann functions in this expansion.63) Pn (µ) Pm (µ) dµ = n + 1/2 −1 so we can invert the above expansion to give 1 al jl (k r) = (l + 1/2) −1 exp( i k r µ) Pl (µ) dµ. y jl (y) → (7.60) (7. −1 (7.65) 179 . ηl (k r).55) can be combined to give dRl d2 Rl + [k2 r2 − l (l + 1)]Rl = 0. (7.58) (7.59) ηl (y) = −y 1 d − y dy cos y .64) It is well-known that (−i)l jl (y) = 2 1 exp( i y µ) Pl (µ) dµ.61) We can write exp( i k r cos θ) = l al jl (k r) Pl (cos θ).4 Partial waves 7 SCATTERING THEORY Equations (7. y l (7. and a Neumann function. because they are not well-behaved as r → 0. jl (k r). 1 δnm . (7.54) and (7. y Note that spherical Bessel functions are well-behaved in the limit y → 0 . whereas Neumann functions become singular. It is easily demonstrated that r2 jl (y) = y l 1 d − y dy l l sin y .7. (7.

· · · [see Abramowitz and Stegun (Dover. In the large-r limit. the total wave-function reduces to ψ(r) 1 (2π)3/2  l cos(k r − l π/2)  sin(k r − l π/2) A − Bl Pl (cos θ). New York NY. 1965).67) The above expression tells us how to decompose a plane-wave into a series of spherical-waves (or “partial waves”). (7. kr (7. The above expression can also be written ψ(r) 1 (2π)3/2 Cl l sin(k r − l π/2 + δl ) Pl (cos θ).70) where the sine and cosine functions have been combined to give a sine function which is phase-shifted by δl . 2. Equation (7. (7. (7. Eq.66) giving exp( i k r cos θ) = l il (2 l + 1) jl (k r) Pl (cos θ).71) × Pl (cos θ). The most general solution for the total wave-function outside the scattering region is 1 [Al jl (k r) + Bl ηl (k r)] Pl (cos θ).4 Partial waves 7 SCATTERING THEORY where l = 0.68) ψ(r) = (2π)3/2 l where the Al and Bl are constants.14]. What is the source of the incoming waves? Obviously. (7.70) yields ψ(r) 1 (2π)3/2 Cl l exp[ i (k r − l π/2 + δl )] − exp[−i (k r − l π/2 + δl )] 2ikr (7. which contains both incoming and outgoing spherical-waves. 10. because its region of validity does not include the origin.1.60)–(7. 1. they must be part of the large-r asymptotic 180 . al = il (2 l + 1).7. Thus.69) where use has been made of Eqs. l kr kr  (7.61). Note that the Neumann functions are allowed to appear in this expansion.

71)–(7. (7.75) Clearly. r (7.73) yield f(θ) = ∞ l=0 (2 l + 1) exp( i δl ) sin δl Pl (cos θ). 7.76) × sin δl sin δl Pl (µ) Pl (µ). (7.53) give (2π)3/2 [ψ(r) − φ(r)] = exp( i k r) f(θ). 181 .72) that Cl = (2 l + 1) exp[ i (δl + l π/2)]. The total cross-section is given by σtotal = |f(θ)|2 dΩ 1 1 = 2 k dϕ −1 dµ l l (2 l + 1) (2 l + 1) exp[ i (δl − δl ] (7. Eqs. (7. This implies that the coefficients of the incoming spherical waves in the large-r expansions of ψ(r) and φ(r) must be equal.e. k (7.5 The optical theorem The differential scattering cross-section dσ/dΩ is simply the modulus squared of the scattering amplitude f(θ). Now. spherical-waves) is equivalent to determining the phase-shifts δ l ..72) × Pl (cos θ) in the large-r limit. (7. Eqs. it is easily seen that φ(r) 1 (2π)3/2 il (2l + 1) l exp[ i (k r − l π/2)] − exp[−i (k r − l π/2)] 2ikr (7.7. In fact.5 The optical theorem 7 SCATTERING THEORY expansion of the incident wave-function.71) and (7.73) Note that the right-hand side consists only of an outgoing spherical wave. It follows from Eqs. determining the scattering amplitude f(θ) via a decomposition into partial waves (i.52) and (7.74) Thus.

In the region r > a.80) 2 k is the lth partial cross-section: i. It is usual to write σtotal = where ∞ l=0 σl .81) 182 . Note that the maximum value for the lth partial cross-section occurs when the phase-shift δl takes the value π/2.7. The most general solution which is o consistent with no incoming spherical-waves is 1 ψ(r) = (2π)3/2 ∞ l=0 il (2 l + 1) Al (r) Pl (cos θ).79) 4π (2 l + 1) sin2 δl (7. where a is termed the range of the potential. (7. (7. This result is known as the optical theorem. (7. the wave-function ψ(r) satisfies the free-space Schr¨dinger equation (7. (7. the contribution to the total cross-section from the lth partial wave.75) yields 4π σtotal = Im [f(0)] .6 Determination of phase-shifts 7 SCATTERING THEORY where µ = cos θ. It follows that σtotal = 4π k2 (2 l + 1) sin2 δl . σl = 7. A comparison of this result with Eq. (7. and thereby reduce the probability current in this direction. Consider a spherically symmetric potential V(r) which vanishes for r > a. It is a reflection of the fact that the very existence of scattering requires scattering in the forward (θ = 0) direction in order to interfere with the incident wave.54).e.63). l (7.77) where use has been made of Eq..78) k since Pl (1) = 1.6 Determination of phase-shifts Let us now consider how the phase-shifts δl can be evaluated.

ul (r) .89) . r  (7.7. The logarithmic derivative of the lth radial wave-function Al (r) just outside the range of the potential is given by βl+ cos δl jl (k a) − sin δl ηl (k a)  . and form the logarithmic derivative βl− = 1 d(ul /r) (ul /r) dr 183 .87) (7.82) Note that Neumann functions are allowed to appear in the above expression.85) (7. because its region of validity does not include the origin (where V = 0). the problem of determining the phase-shift δl is equivalent to that of obtaining βl+ . etc. dr2 r2 ¯ h The boundary condition ul (0) = 0 (7. integrate out to r = a. (7.88) ensures that the radial wave-function is well-behaved at the origin.84) Thus.6 Determination of phase-shifts 7 SCATTERING THEORY where Al (r) = exp( i δl ) [ cos δl jl (k r) − sin δl ηl (k r) ] .86) d2 ul  2 2m l (l + 1)  + k − 2 V− ul = 0. The above equation can be inverted to give (7. We can launch a well-behaved solution of the above equation from r = 0.83) where jl (x) denotes djl (x)/dx. The most general solution to Schr¨dinger’s equation inside the range of the o potential (r < a) which does not depend on the azimuthal angle ϕ is 1 ψ(r) = (2π)3/2 where Rl (r) = and  ∞ l=0 il (2 l + 1) Rl (r) Pl (cos θ). r=a (7. k a ηl (k a) − βl+ ηl (k a)   (7. = ka cos δl jl (k a) − sin δl ηl (k a) tan δl = k a jl (k a) − βl+ jl (k a) .

(7. It follows from Eq.7 Hard sphere scattering Let us test out this scheme using a particularly simple example. Equation (7. Consider scattering by a hard sphere. and zero for r > a. − cos(k a)/ka δ0 = −k a.94) (7. which is usually referred to as the s-wave.84) that tan δl = jl (k a) . (7. The s-wave radial wave function is [cos k a sin k r − sin k a cos k r] kr sin[k (r − a)] = exp(−i k a) .93) where use has been made of Eqs. (7. 7.7.92) yields tan δ0 = sin(k a)/k a = − tan k a. ηl (k a) (7.59).96) .7 Hard sphere scattering 7 SCATTERING THEORY Since ψ(r) and its first derivatives are necessarily continuous for physically acceptible wave-functions.95) kr The corresponding radial wave-function for the incident wave takes the form A0 (r) = exp(−i k a) sin k r ˜ . It follows that ψ(r) is zero in the region r < a. for which the potential is infinite for r < a.58)–(7. (7. it follows that βl+ = βl− . (7. which implies that u l = 0 for all l.91) for all l. The phase-shift δl is obtainable from Eq.90) Consider the l = 0 partial wave. Thus.92) (7.84). βl− = βl+ = ∞. It follows that (7. A0 (r) = kr 184 (7.

77) that l 4π max σtotal = 2 (2 l + 1) sin2 δl . Note that the total cross-section σtotal = dσ dΩ = 4π a2 dΩ (7. the cross-section for classical particles bouncing off a hard sphere of radius a). It follows from Eqs. In other words. Let us consider the low and high energy asymptotic limits of tan δl .e. It follows that −(k a)2 l+1 tan δl = . It follows from Eq. (7.98) where n!! = n (n − 2) (n − 4) · · · 1.7. (7. with l > 0. (k r)l+1 (7.102) k l=0 185 . Consider the high energy limit k a 1.. (7. (2 l + 1) [(2 l − 1)!!]2 (7.7 Hard sphere scattering 7 SCATTERING THEORY It is clear that the actual l = 0 radial wave-function is similar to the incident l = 0 wave-function.75). except that it is phase-shifted by k a. the spherical Bessel functions and Neumann functions reduce to: jl (k r) ηl (k r) (k r)l . In this regime.33). at low energy only s-wave scattering (i. At high energies. Low energy means k a 1. (2 l + 1)!! − (2 l − 1)!! .. so we do not expect to obtain the classical result in this limit. low energy scattering implies relatively long wave-lengths. all partial waves up to lmax = k a contribute significantly to the scattering cross-section.e.99) It is clear that we can neglect δl . (7. with respect to δ0 .97) (7. However.100) is four times the geometric cross-section π a2 (i. spherically symmetric scattering) is important.101) a2 (7. and (7.94) that dσ sin2 k a = dΩ k2 for k a 1.

Thus. and attractive for V0 < 0. In fact. make a negligible contribution to the scattering cross-section. in general.e. It follows that.58)–(7. in order to produce a “shadow” behind the sphere. As a specific example. when 1/k is much larger than the range of the potential) partial waves with l > 0. characterized by V = V0 for r < a. let us consider scattering by a finite potential well. and V = 0 for r ≥ a. The inside wave-function follows 186 . 7. V0 is a constant.8 Low energy scattering 7 SCATTERING THEORY With so many l values contributing.59).104) (7. when combined with the cross-section for classical reflection. However. (7. For hard sphere scattering. Here. ka 2π (2 l + 1) 2π a2 . it is legitimate to replace sin 2 δl by its average value 1/2.. at these energies. The outside wave-function is given by [see Eq.105) where use has been made of Eqs. The effective cross-section associated with this bright spot is π a 2 which. The potential is repulsive for V0 > 0. and the shadow has a bright spot in the forward direction. (7. which is somewhat surprizing. with a finite range potential.8 Low energy scattering At low energies (i. the interference is not completely destructive. only s-wave scattering is important. there must be scattering in the forward direction (recall the optical theorem) to produce destructive interference with the incident plane-wave. π a2 . gives the actual cross-section of 2π a2 . kr (7.103) σtotal = 2 k l=0 This is twice the classical result. (7.7. incident waves with impact parameters less than a must be deflected.82)] A0 (r) = exp( i δ0 ) [j0 (k r) cos δ0 − η0 (k r) sin δ0 ] = exp( i δ0 ) sin(k r + δ0 ) . since we might expect to obtain the classical result in the short wave-length limit.

e.106) where use has been made of the boundary condition (7. the right-hand side is much less that unity. (7. yields tan(k a + δ0 ) = k tan k a k k tanh κ a κ (7. we have A0 (r) = B where sinh κ r ..110) for E > V0 .107) E − V0 = 2m Note that Eq. For E < V0 . the depth of the potential well is much larger than the energy of the incik.87).113) . so replacing the tangent of a small quantity with the quantity itself.108) ¯ 2 κ2 h . and its radial derivative at r = a. so that k becomes extremely large. for which E > V0 . (7. We obtain A0 (r) = B sin k r .106) only applies when E > V0 . (7.111) Consider an attractive potential. we obtain k a + δ0 This yields δ0 tan k a ka − 1 .112) (7.8 Low energy scattering 7 SCATTERING THEORY from Eq. V0 − E = 2m Matching A0 (r).7. ka 187   k tan k a.110) that.88). r (7. r (7. (7. B is a constant. unless tan k a dent particles). k (7. and tan(k a + δ0 ) = for E < V0 .109) (7. and ¯2k 2 h . Suppose that |V0 | E (i. (7. It follows from Eq. Here.

102). ka 2 m |V0 | a2 . Suppose that the quantity 2 m |V0 | a2 /¯ 2 is slightly less than π/2. 7. ¯2 h (7.9 Resonances 7 SCATTERING THEORY According to Eq. + ¯2 h  2 (7. Note that there are values of k a (e.114) vanishes. and the scattering cross-section (7. (7. can reach the value π/2. tan k a becomes infinite.7.9 Resonances There is a significant exception to the independence of the cross-section on energy. It follows that there are certain values of V0 and k which give rise to almost perfect transmission of the incident wave. which is given by Eq. (7. In this case. k2 k a 188 (7. k a 4.. This is called the Ramsauer-Townsend effect. despite the very strong attraction of the potential. the cross-section is not exactly zero. 2 k ka ka= k 2 a2 2 m |V0 | a2 . because of contributions from l > 0 partial waves.115). But. This implies that σtotal = 4π 2 1 sin δ0 = 4π a2 2 2 . at low incident energies. (7.114) (7.49) at which δ0 → π.g. so we can no longer assume that the right-hand side of Eq. the scattering cross-section is given by σtotal Now tan k a 4π 2 sin δ0 = 4π a2  − 1 . In fact.110) that k a + δ0 = π/2.116) It follows that the total (s-wave) scattering cross-section is independent of the energy of the incident particles (provided that this energy is sufficiently small). As the h incident energy increases. or δ0 (since we are assuming that k a 1).115) so for sufficiently small values of k a. k a.117) . at the value of the incident energy π/2 when k a = π/2. and has been observed experimentally. In reality. it follows from Eq. these contributions are small.110) is small. (7.

Nevertheless. since the system has a small positive energy. this sort of resonance scattering is best understood as the capture of an incident particle to form a metastable bound state. (7.122) .114) for k a = π/2 (since k a 1). and the subsequent decay of the bound state and release of the particle. sin δl dE E=E0 Defining  2 dδl (E)   = .9 Resonances 7 SCATTERING THEORY Note that the cross-section now depends on the energy.119) 2 Let us expand cot δl in the vicinity of the resonant energy: cot δl (E) = cot δl (E0 ) +  d cot δl dE  E=E0 (E − E0 ) + · · · (7. We have seen that there is a resonant effect when the phase-shift of the s-wave takes the value π/2. Suppose that δl attains the value π/2 at the incident energy E0 .121) 1 dδl  = − 2 (E − E0 ) + · · · . dE E=E0 Γ 189  (7. an incident particle would like to form a bound state in the potential well. However. the magnitude of the cross-section is much larger than that given in Eq. so that π δl (E0 ) = . The condition π 2 m |V0 | a2 = 2 2 ¯ h (7. so it is reasonable to assume that there is a similar resonance when the phase-shift of the lth partial wave is π/2.7. The origin of this rather strange behaviour is quite simple. There is nothing special about the l = 0 partial wave. Thus. for a potential well which satisfies the above equation. The cross-section for resonance scattering is generally far higher than that for non-resonance scattering. In this situation. the bound state is not stable.118) is equivalent to the condition that a spherical well of depth V0 possesses a bound state at zero energy. the energy of the scattering system is essentially the same as the energy of the bound state. Furthermore. (7.120) (7.

Γ Recall. from Eq.7. (7. (2 l + 1) sin2 δl = 2 (2 l + 1) k2 k 1 + cot2 δl 4π Γ 2 /4 . (2 l + 1) k2 (E − E0 )2 + Γ 2 /4 (7. σl (7. that the contribution of the lth partial wave to the scattering cross-section is σl = 4π 1 4π .125) This is the famous Breit-Wigner formula. The quantity Γ is the width of the resonance (in energy).9 Resonances 7 SCATTERING THEORY we obtain 2 (7. 6. The variation of the partial cross-section σl with the incident energy has the form of a classical resonance curve.124) Thus.17). We can interpret the BreitWigner formula as describing the absorption of an incident particle to form a metastable state.123) cot δl (E) = − (E − E0 ) + · · · .80). h 190 . and lifetime τ = ¯ /Γ (see Sect. of energy E0 .

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