Definition of some units
Angstrom 1A=10"!%m (order of magnitude of
the atomic dimensions)
Fermi IF = 107! m (order of magnitude of
the nuclear dimensions)
Barn 1b = 10-8 m? = (10-4 AY = (10 FP
Electron Volt 1 eV = 1,602 189(5) x 107"? joule
Useful orders of magnitude
Electron rest energy : m,c? = 0.5 MeV [0.511 003(1) x 10% ev]
Proton rest energy : M,c? = {000 MeV [938.280(3) x 10° eV]
Neutron rest energy : Myc? = | 000 MeV [939.573(3) x 10° ev)
One electron volt corresponds to :
a frequency vy = 2.4 x 10" Hz through the relation E = Av
[2.417 970(7) x 10% Hz]
awavelength 2 = 12000A ‘through the relation 4 = c/v
[12 398.52(4) A]
a wave number i 8.000 em=! [8 065.48(2) cm-*]
atemperature T~12000K through the relation E = kg’
(11 604.5(4)K]
Ina | gauss magnetic field (10 * Tesla) :
the electron cyclotron frequency v, = w,/2x = — gB/2xm,
is v, = 2.8 MHz [2.799 225(8) x 106 Hz]
the orbital Larmor frequency vy, = «w,/2n = — pipBfh = v2
isv, = L4 MHz [1.399 612(4) x 10 Hz]
(this corresponds by definition to a g = 1 Landé factor)
itSome general physical constants
h= 6626 18(4) x 10-** joule second
Planck’s constant
he & = 1.054 589(6) x 10° joule second
Speed of light (in vacuum) cc = 2.997 924 58(1) x 10° m/s
Electron charge 4 = — 1,602 189(5) x 107'* coulomb
Electron mass m, = 9.109 53(5) x 1079! kg
Proton mass M, = 1.672 65(1) x 10727 kg
P
‘Neutron mass M, = 1.674 95(1) x 10-77 kg
M,
ape = 1 836.1515(7)
Ac = Wing: = 2426 309(8) = 107? A
Elect Ce jel
‘on Compton wavelength {i = fifmgc = 3861 591(7) x 10-2 A
Fine structure constant a a 1
(dimensionless) * = Tnedie he 1370360)
Bohr radius ay = & = 0.529177 1(5)A
Hydrogen atom ionization
energy (without proton recoil — E,, = am,c?/2 = 13.605 80(5) eV
effec)
Rydberg’s constant Ra, = — Ey, /he = 1.097 373 18(8) x 105 emt
” Classical” electron radius = — 2 = 2817 938(7) fermi
Aneym,c?
Bohr magneton Hy = Gh/2m, = — 9.274 08(4) x 10-* joule/tesla
Electron spin g factor 9, = 2 x 1.001 159 657(4)
‘Nuclear magneton My = — gh/2M, = 5.05082(2) x 10727 joule/testa
Boltzmann's constant ky = 1.380.66(4) x 107? joule/K
Avogadro's number N, = 6.022.05(3) x 1074Useful Identities
U : scalar field; A,B, ... : vector fields.
Vx (VU) =0 v.(VU) = AU
V.(Vx A)=0 Vx (Vx A)=V(V.A)—AA
A x (B x C) = (A. C)B — (A. BIC
Ax (Bx C)+Bx (Cx A) +C x (A x B)=0
(A x B).(C x D) = (A. C)(B.D) — (A. D.C)
(A x B)x(C x D) = [(A x B). DJc — [(A x B).C]D
= [(C x D). AJB - [(C x D).BJA
vy) =uws+vw
A (Uv) UAV + (VU). (VV) + VAU
Vv. (UA) UV.A+A.VU
vx (UA) UVxA+ (WU) A
V.(Ax B) =B.(VxA)—A.(VxB)
V (A.B) Ax (Vx B)+Bx (Vx A)+BV A+AV B
Vx (Ax B)=A (V.B)—B(V.A)+B.V A-A.V B
NB. : BVA vector field whose components are =
pas
Vax,
(BV A) = BPA, = 58
i= J,
(=PAG We = 2"'¥) +
=
e
yaa] = Av xa) afoa"ve ~ evo 2)
2[02"¥e~ 4 a
(ous si Lire vane us ~ 00%F2] = AV A) e"¥2— 22%) = Wea) ‘axpi¥e — 2H + 2
(ous siLaeeye — o2t"¥ 0 use] = IW * A) “re — #oo"¥0) = Wea) Mer 'H = QA 8 -
0 oy yas wy gE 2h apn Boy 248. gg
ae ert aie) "i aera ee 25
i2et (42 \eod ve ee 2
eee (yee. fee 93
ae 4 i 3
(6.08 92:02) = aa) ne = Maa) "4salne) + 3
sileeinel = aa) “oein2] = aa) ‘acne + 5
deine = Koa) 2
ota 'y Foun — = ein a
gus "y - 900% = 8 500'y +O .us"y ~ = *y (Oya 3
s00'y + ous'y = “r| us 'y + 6 500"7 =v (Cyt ay 7
y+ ey teV= Vv vee + v a ee 8
5
@ean= a Fon = a
jeoueyds OPUNAD, uersen1e9
swiaysAs 9}eUIps00DIntroduction
Structure and level of this text
It is hardly necessary to emphasize the importance of quantum mechanics
in modern physics and chemistry. Current university programs naturally reflect
this importance. In French universities, for example, an essentially qualitative
introduction to fundamental quantum mechanical ideas is given in the second year.
In the final year of the undergraduate physics program, basic quantum mechanics
and its most important applications are studied in detail.
This book is the direct result of several years of teaching quantum mechanics
in the final year of the undergraduate program, first in two parallel courses at the
Faculté des Sciences in Paris and then at the Universités Paris VI and Paris VII.
We felt it to be important to mark a clear separation, in the structure of this book,
between the two different but complementary aspects (lectures and recitations) of the
courses given during this time. This is why we have divided this text into two
distinct parts (see the “Directions for Use” at the beginning of the book).
On the one hand, the chapters are based on the lectures given in the two courses,
which we compared, discussed and expanded before writing the final version.
On the other hand, the “complements” grew out of the recitations, exercises and
problems given to the students, and reports that some of them prepared. Ideas
also came from other courses given under other circumstances or at other levels
(particularly in the graduate programs). As we pointed out in the “Directions for
Use”, the chapters as a whole constitute, more or less, a course we would
envisage teaching to fourth-year college students or those whose level is equivalent.
However, the complements are not intended to be treated in a single year. The
reader, teacher or student, must choose between them in accordance with his
interests, tastes and goals.
Throughout the writing of this book, our constant concern has been to
address ourselves to students majoring in physics, like those we have taught
over the past several years. Except in a few complements, we have not overstepped
those limits. In addition, we have endeavored to take into account what we
have seen of students’ difficulties in understanding and assimilating quantum
3mechanics, as well as their questions. We hope, of course, that this book will
also be of use to other readers such as graduate students, beginning research
workers and secondary schoo! teachers.
The reader is not required to be familiar with quantum physics : few of our
students were, However, we do think that the quantum mechanics course we propose
(see “General approach”, below) should be supplemented by a more descriptive and
more experimentally oriented course, in atomic physics for example.
General approach
We feel that familiarity with quantum mechanics can best be acquired by
using it to solve specific problems. We therefore introduce the postulates of quantum
mechanics very early (in chapter III), so as to be able to apply thei in the rest of
the book. Our teaching experience has shown it to be preferable to introduce all
the postulates together in the beginning rather than presenting them in several
stages. Similarly, we have chosen to use state spaces and Dirac notation from the
very beginning. This avoids the useless repetition which results from presenting
the more general bra-ket formalism only after having developed wave mechanics
uniquely in terms of wave functions. In addition, a belated change in the notation
runs the risk of confusing the student, and casting doubts on concepts which he
has only just acquired and not yet completely assimilated.
After a chapter of qualitative introduction to quantum mechanical ideas,
which uses simple optical analogies to familiarize the reader with these new concepts,
we present, in a systematic fashion, the mathematical tools (chapter [) and
postulates of quantum mechanics as well as a discussion of their physical content
(chapter III), This enables the reader, from the beginning, to have an overall view
of the physical consequences of the new postulates. Starting with the complements
of chapter III we take up applications, beginning with the simplest ones (two-level
systems, the harmonic oscillator, etc.) and becoming gradually more complicated
(the hydrogen atom, approximation methods, etc.). Our intention is to provide
illustrations of quantum mechanics by taking many examples from different fields
such as atomic physics, molecular physics and solid state physics. In these examples
we concentrate on the quantum mechanical aspect of the phenomena, often
neglecting specific details which are treated in more specialized texts. Whenever
possible, the quantum mechanical results are compared with the classical ones in
order to help the reader develop his intuition concerning quantum mechanical
effects.
This essentially deductive viewpoint has led us to avoid stressing the historical
introduction of quantum mechanical ideas, that is, the presentation and discussion
of experimental facts which force us to reject the classical ideas. We have thus had
to forego the inductive approach, which is nevertheless needed if physics is to be
faithfully portrayed as a science in continual evolution, provoked by constant
confrontation with experimental facts. Such an approach seems to us to be better
suited to an atomic physics text or an introductory quantum physics course on a
more elementary level.
Similarly, we have deliberately avoided any discussion of the philisophicalintropucTion
implications of quantum mechanics and of alternative interpretations that have
been proposed. Such discussions, while very interesting (see section 5 of the biblio-
graphy), scem to us to belong on another level. We feel that these questions can be
fruitfully considered only after one has mastered the “orthodox” quantum theory
whose impressive successes in all fields of physics and chemistry compelled its
acceptance.
Acknowledgements
‘The teaching experiences out of which this text grew were group efforts,
pursued over several years. We want to thank all the members of the various
‘groups and particularly, Jacques Dupont-Roc and Serge Haroche, for their friendly
collaboration, for the fruitful discussions we have had in our weekly meetings and
for the ideas for problems and exercises which they have suggested. Without their
enthusiasm and their valuable help, we would never have been able to undertake
and carry out the writing of this book.
Nor can we forget what we owe to the physicists who introduced us to
research, Alfred Kastler and Jean Brossel for two of us and Maurice Lévy for
the third. It was in the context of their laboratories that we discovered the
beauty and power of quantum mechanics. Neither have we forgotten the importance
to us of the modern physics taught at the C.E.A. by Albert Messiah, Claude Bloch
and Anatole Abragam, at a time when graduate studies were not yet incorporated
into French university programs.
We wish to express our gratitude to Ms. Aucher, Baudrit, Boy, Brodschi,
Emo, Heyvaerts, Lemirre, Touzeau for preparation of the manuscript.Foreword
This book is essentially a translation of the French edition which appeared at the end
of 1973,
‘The text has undergone a certain number of modifications. The most important one is an
addition of a detailed bibliography, with suggestions concerning its use appearing at the end of
cach chapter or complemeats.
This book was originally conceived for French students finishing their undergraduate
studies or beginning their research work. It seems to us however that the structure of this book
(Separation into chapters and complements — see the “Directions for use”) should make it
suitable for other groups of readers. For example, for an undergraduate elementary Quantum
Mechanics course, we would recommend using the most important chapters with their simplest
complements, For a more advanced course, one could add the remaining chapters and use more
1/4k, and the function to be integrated oscillates
several tots within the interval AK. In figure (b,x is fixed such that [x — xo] < I/Ak, and the
function tobe Integrated hardly otllats, eo that ite integral over fakes ona relatively large vale.
Consequently, the center of the wave packet [point where |y(x, 0)| is maximum) is situated at
When x moves away from the value xp, |y(x,0)| decreases. This decrease
becomes appreciable if ¢!~*"*-*) oscillates approximately once when & traverses
the domain 4k, that is, when:
Ak. (x = x9) = 1 (c-17)
If Ax is the approximate width of the wave packet, we therefore have :
Ak. Ax 21 (c-18)
We are thus brought back to a classical relation between the widths of two
functions which are Fourier transforms of each other. The important fact is
that the product 4x . 4k has a lower bound; the exact value of this bound clearly
depends on the precise definition of the widths Ax and Ak
A wave packet such as (C-7) thus represents the state of a particle whose
probability of presence, at the time ¢ = 0, is practically zero outside an interval
of approximate width Ax centered at the value xy.
COMMENT:
The preceding argument could lead one to believe that the product Ax. Ak
is always of the order of I [¢f. (C-17)]. Let us stress the fact that this is a lower
limit. Although it is impossible to construct wave packets for which the
product Ax . Ak is negligible compared to I, it is perfectly possible to construct
packets for which this product is as large as desired [see, for example,
complement G,, especially comment (ii) of §3-c]. This is why (C-18) is written
in the form of an inequality.C._WAVE PacKETs
3. Heisenberg uncertainty relation
In quantum mechanics, inequality (C-18) has extremely important physical
consequences. We intend to discuss these now (we shall stay, for simplicity, within
the framework of a one-dimensional model).
We have seen that a plane wave e'®*—°%" corresponds to a constant proba-
bility density for the particle’s presence along the Ox axis, for all values of 1.
This result can be roughly expressed by saying that the corresponding value
of 4x is infinite. On the other hand, only one angular frequency w, and one wave
vector k, are involved. According to the de Broglie relations, this means that the
energy and momentum of the particle are well-defined : E = fia, and p = hky.
Such a plane wave can, moreover, be considered to be a special case of (C-7), for
which g(k) is a « delta function » (appendix 11):
ak) = 5(k — ko) (c-19)
The corresponding value of Ak is then zero.
But this property can also be interpreted in the following manner, using the
principle of spectral decomposition (cf. § A-3 and B-2). To say that a particle,
described at = 0 by the wave function y(x,0) = 4c, has a well-determined
momentum, is to say that a measurement of the momentum at this time will
definitely yield p = hk. From this we deduce that e" characterizes the eigenstate
corresponding to p = hk. Since there exists a plane wave for every real value of k,
the eigenvalues which one can expect to find in a measurement of the momentum
on an arbitrary state include all real values. In this case, there is no quantization
of the possible results : as in classical mechanics, all values of the momentum are
allowed.
Now consider formula (C-8). In this formula, (x, 0) appears as a linear
superposition of the momentum eigenfunctions in which the coefficient of e!*
is a(k). We are thus led to interpret |a(k)|? (to within a constant factor) as the proba-
bility of finding p = hk if one measures, at = 0, the momentum of a particle whose
state is described by Y(x, £). In reality, the possible values of p, like those of x, form
a continuous set, and |g(k)|? is proportional to a probability density: the
probability d(x) of obtaining a value between hk and h(k + dk) is, to within a
constant factor, |a(k)|? dk. More precisely, if we rewrite formula (C-8) in the form:
Wx, 0) fro oh dp (C-20)
Vinh
we know that ¥(p) and y(x, 0) satisfy the Bessel-Parseval relation (appendix I):
Jes oF a [Wor (ca)
If the common value of these integrals is C, d%(x) 4 |W(x, 0)}? dx is the probability
of the particle being found, at ¢ = 0, between x and x + dx. In the same way :
(C22)
27CHAPTER |_WAVES AND PARTICLES
is the probability that the measurement of the momentum will yield a result included
between p and p + dp [relation (C-21) then insures that the total probability of
finding any value is indeed equal to 1].
Now let us go back to the inequality (C-18) We can write it as:
Ax. dp zh (C23)
(4p = hak is the width of the curve representing |/(p)|). Consider a particle whose
state is defined by the wave packet (C-20), We know that its position probability
at ¢ = 0, is appreciable only within a region of width 4x about x9: its position is
known within an uncertainty 4x. If one measures the momentum of this particle at
the same time, one will find a value between py + 42 and py — 4 since [¥(p)|?
2
is practically zero outside this interval : the uncertainty in the momentum is
therefore 4p. The interpretation of relation (C-23) is then the following : it is
impossible to define at a given time both the position of the particle and its momen-
tum to an arbitrary degree of accuracy. When the lower limit imposed by (C-23)
is reached, increasing the accuracy in the position (decreasing 4x) implies that the
accuracy in the momentum diminishes (4p increases), and vice versa, This relation
is called the Heisenberg uncertainty relation.
We know of nothing like this in classical mechanics. The limitation expressed
by (C-23) arises from the fact that h is not zero. It is the very small value of h on the
macroscopic scale which renders this limitation totally negligible in classical
‘mechanics (an example is discussed in detail in complement B,).
COMMENT
The inequality (C-18) with which we started is not an inherently quantum
‘mechanical principle. It merely expresses a general property of Fourier transforms,
‘numerous applications of which can be found in classical physics, For example, it is
well known from electromagnetic theory that there exists no train of electromagnetic
waves for which one can define the position and the wavelength with infinite accuracy
at the same time. Quantum mechanics enters in when one associates a wave with a
‘material particle and requires that the wavelength and the momentum satisfy de Broglie’s
relation.
4. Time evolution of a
wave packet
Until now, we have been concerned only with the form of a wave packet
at a given instant; in this paragraph, we are going to study its time evolution. Let
us return, therefore, to the case of a free particle whose state is described by the
one-dimensional wave packet (C-7).
A given plane wave e"* ~ “” propagates along the Ox axis with the velocity :
Yig=z (C24)
since it depends on x and ¢ only through (« =r): lk) is called the phase
velocity of the plane wave.
28We know that in the case of an electromagnetic wave propagating in a vacuum,
¥, is independent of k and equal to the speed of light c, All the waves which make up
a'wave packet move at the same velocity, so that the packet as a whole also moves
with the same velocity, without changing in shape. On the other hand, we know that
this is not true in a dispersive medium, where the phase velocity is given by :
Vk) = (C-25)
MN) = TH (C25)
n(k) being the index of the medium, which varies with the wavelength.
The case that we are considering here corresponds to a dispersive medium,
since the a a is equal to [¢f. equation (C-3)]:
Vfk) = pas (C-26)
We shall see that when the different waves thus have unequal phase velocities, the
velocity of the maximum x,, of the wave packet is not the average phase
velocity 22 Bho, contrary to what one might expect.
0
As we did before, we shall begin by trying to understand qualitatively what
happens, before taking a more general point of view. Therefore, let us return to
the superposition of three waves considered in § C-2. For arbitrary 1, Y(x, ¢) is
given by:
SS
We see, therefore, that the maximum of |¥(x, ¢)|, which was at x = 0 at ¢ = 0, is
now at the point :
42 (C-28)
and not at the point x = Re The physical origin of this result appears in figure 6.
Part a) of this figure represents the positon at time 1 = 0 of three adjacent
maxima (1), (2), (3) for the real parts of each of the three waves. Since the maxima
denoted by the index (2) coincide at x = 0, there is constructive interference at this
point, which thus corresponds to the position of the maximum of |Y(x, 0)|. Since
the phase velocity increases with k [formula (C-26)], the maximum (3) of the
wave + 4) will gradually catch up with that of the wave (kq), which will
in turn eatch up with that of the wave(b - 4) After a certain time, we shall thus
have the situation shown in figure 6-0; it will be the maxima (3) which coincide and
2»thus determine the position of the maximum xy(/) of (x, 1)|. We clearly see
in the figure that xy(t) is not equal to 227, and a simple calculation again
Ko
yields (C-28).
jk
ko +f lo ly by ly ly le
ke ky le ley lo le ley
Ak
b- Thy le ley lo lo ley
es
1 fl
: 0) i” alt)
nouns 6
Positions of the maxima of the three waves of figure 4 at time 1 = 0 (fig. a) and at a subsequent 1
(ig. b). At time 1 = 0, ie isthe maxima (2), situated at x = 0, which interfere constructively : the
position of the center of the wave packet is xy( {At time 1, the three waves have advanced
‘with diferent phase velocities ¥,. It ts then the maxima (3) whleh interfere constructively and the
center of the wave packet is situated at x = xy(t), We thas see thatthe velocity ofthe center ofthe
‘wave packet (group velocity) is different frou the pise velocitis of the three waves.
The shift of the center of the wave packet (C-7) can be found in an analogous
fashion, by applying the “stationary phase” method. It can be seen from the
form (C-7) of the free wave packet that, in order to go from W(x, 0) to v(x, ) all
we need to do is change g(k) to g(k)e~". The reasoning of § C-2 thus remains
valid, on the condition that we replace the argument a(k) of g(k) by:
alk) = okt (C-29)
The condition (C-16) then gives :
éo-[42] «-[8] a
We are thus brought back to result (C-28) : the velocity of the maximum of
the wave packet is:
vats = [$2] (cn
Ve (ko) is called the group velocity of the wave packet. With the dispersion relation
given in (C-3), we obtain:
Velo) = To = 2g thy) (ca
30This result is important, for it enables us to retrieve the classical description of the
free particle, for the cases where this description is valid. For example, when one
is dealing with a macroscopic particle (and the example of the dust particle discussed
in complement B, shows how small it can be), the uncertainty relation does not
introduce an observable limit on the accuracy with which its position and momen-
tum are known. This means that we can construct, in order to describe such
a particle in a quantum mechanical way, a wave packet whose characteristic
widths 4x and dp are negligible. We would then speak, in classical terms, of the
position xy(t) and the momentum p, of the particle, But then its velocity must
be v = 22, This is indeed what is implied by formula (C-32), obtained in the
quantum description : in the cases where 4x and 4p can both be made negligible,
the maximum of the wave packet moves like a particle which obeys the laws of
classical mechanics.
COMMENT
We have stressed here the motion of the center of the free wave packet.
Ivis also possible to study the way in which its form evolves in time. TL is then
easy to show that, if the width 4p is a constant of the motion, 4x varies
over time and, for sufficiently long times, increases without limit (spreading
of the wave packet). The discussion of this phenomenon is given in
complement G,, where the special case of a Gaussian wave packet is treated,
D. PARTICLE IN A TIME-INDEPENDENT SCALAR POTENTIAL
We have seen, in § C, how the quantum mechanical description of a particle reduces
to the classical description when Planck's constant h can be considered to be
negligible. In the classical approximation, the wavelike character does not appear
because the wavelengih i =" assuciated with the particle is much smaller than
the characteristic lengths of its motion. This situation is analogous to the one encoun-
tered in optics. Geometrical optics, which ignores the wavelike properties of light,
constitutes a good approximation when the corresponding wavelength can be
neglected compared to the lengths with which one is concerned. Classical mechanics
thus plays, with respect to quantum mechanics, the same role played by geometrical
optics with respect to wave optics.
In this paragraph, we are going to be concerned with a particle in a time-
independent potential, What we have just said implies that typically quantum
effects (that is, those of wave origin) should arise when the potential varies
appreciably over distances shorter than the wavelength, which cannot then be
neglected. This is why we are going to study the behavior of a quantum particle
placed in various “square potentials”, that is, “step potentials”, as shown in
figure 7-a. Such a potential, which is discontinuous. clearly varies considerably over,
intervals of the order of the wavelength, however small it is: quantum effects must
therefore always appear. Before beginning this investigation, we shall discuss some
important properties of the Schrddinger equation when the potential is not time-
dependent.
3