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UNITEXT for Physics
Series Editors
Michele Cini, University of Rome Tor Vergata, Roma, Italy
Attilio Ferrari, University of Turin, Turin, Italy
Stefano Forte, University of Milan, Milan, Italy
Guido Montagna, University of Pavia, Pavia, Italy
Oreste Nicrosini, University of Pavia, Pavia, Italy
Luca Peliti, University of Napoli, Naples, Italy
Alberto Rotondi, Pavia, Italy
Paolo Biscari, Politecnico di Milano, Milan, Italy
Nicola Manini, University of Milan, Milan, Italy
Morten Hjorth-Jensen, University of Oslo, Oslo, Norway
UNITEXT for Physics series publishes textbooks in physics and astronomy,
characterized by a didactic style and comprehensiveness. The books are addressed
to upper-undergraduate and graduate students, but also to scientists and researchers
as important resources for their education, knowledge, and teaching.
Modern Physics
Introduction to Statistical Mechanics,
Relativity, and Quantum Physics
Luca Salasnich
Department of Physics and Astronomy
University of Padua
Padova, Italy
© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature
Switzerland AG 2022
This work is subject to copyright. All rights are solely and exclusively licensed by the Publisher, whether
the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse
of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and
transmission or information storage and retrieval, electronic adaptation, computer software, or by similar
or dissimilar methodology now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication
does not imply, even in the absence of a specific statement, that such names are exempt from the relevant
protective laws and regulations and therefore free for general use.
The publisher, the authors and the editors are safe to assume that the advice and information in this book
are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or
the editors give a warranty, expressed or implied, with respect to the material contained herein or for any
errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional
claims in published maps and institutional affiliations.
This Springer imprint is published by the registered company Springer Nature Switzerland AG
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
Preface
This book contains the lecture notes prepared for two one-semester courses at the
University of Padua: “Structure of Matter”, B.Sc. in Optics and Optometrics, and
“Quantum Physics”, B.Sc. in Materials Science. These courses give an introduction
to statistical mechanics, special and general relativity, and quantum physics.
Chapter 1 briefly reviews the ideas of classical statistical mechanics introduced
by James Clerk Maxwell, Ludwig Boltzmann, Willard Gibbs, and others. Chapter 2
is mainly devoted to the special relativity of Albert Einstein but we briefly consider
also the general relativity. In Chap. 3, the quantization of light due to Max Planck
and Albert Einstein is historically analyzed, while Chap. 4 discusses the Niels Bohr
quantization of the energy levels and the electromagnetic transitions. Chapter 5 inves-
tigates the Schrödinger equation, which was obtained by Erwin Schrödinger from
the idea of Louis De Broglie to associate with each particle a quantum wavelength.
Chapter 6 describes the basic axioms of quantum mechanics, which were formu-
lated in the seminal books of Paul Dirac and John von Neumann. In this chapter,
we also discuss the stationary perturbation theory, the time-dependent perturbation
theory, and the variational principle. In Chap. 7, there are several important appli-
cation of quantum mechanics: the quantum particle in a box, the quantum particle
in the harmonic potential, and the quantum tunneling. Chapter 8 is devoted to the
study of quantum atomic physics with special emphasis on the spin of the electron,
which needs the Dirac equation for a rigorous theoretical justification. In Chap. 9,
the quantum mechanics of many identical particles at zero temperature is explained,
while in Chap. 10 the discussion is extended at finite temperature by introducing
and using the quantum statistical mechanics. The appendices on Dirac delta func-
tion, complex numbers, Fourier transform, and differential equations are a useful
mathematical aid for the reader.
The author acknowledges Dr. Fabio Sattin, Dr. Andrea Tononi, and Prof. Flavio
Toigo for their critical reading of the manuscript and their useful comments and
suggestions.
v
Contents
vii
viii Contents
In this chapter we first discuss the kinetic theory of ideal gases and the Maxwell
distribution of velocities at thermal equilibrium. Then we consider the more general
Maxwell-Boltzmann distribution of non-interacting particles under the effect of an
external trapping potential. Finally, we analyze the statistical ensembles of Gibbs,
which are useful tools to connect the microscopic dynamics of interacting particles
to the macroscopic behavior of a thermodynamical system.
The kinetic theory of gases was formulated in the period between 1738 and 1871
with the contribution of several scientists, among them Daniel Bernoulli, Mikhail
Lomonosov, August Krönig, Rudolf Clausius, James Clerk Maxwell, and Ludwig
Boltzmann. This theory is the first historical example of statistical mechanics, where
the macroscopic thermodynamics is described in terms of many microscopic parti-
cles (atoms or molecules). Actually, it was the description of the stochastic Brow-
nian motion of a mesoscopic particle in a liquid, as due to the collisions with the
microscopic particles of the liquid (made by Albert Einstein in 1905), that provided
compelling proof that atoms and molecules exist. Jean Perrin confirmed this fact
experimentally in 1908. In 1926, Perrin received the Nobel Prize in Physics “for his
work on the discontinuous structure of matter”.
At thermal equilibrium a very dilute gas is well described by the equation of state
PV =nRT , (1.1)
where P is the pressure of the gas, V is the volume of the gas container, n is the
number of moles, R = 8.314 J/(mol×K) is the gas constant, and T is the absolute
© The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 1
L. Salasnich, Modern Physics, UNITEXT for Physics,
https://doi.org/10.1007/978-3-030-93743-0_1
2 1 Classical Statistical Mechanics
temperature (i.e. the temperature, usually measured in Kelvin, that is zero at the
absolute zero, where the pressure of the ideal gas becomes zero). Equation (1.1)
is known as the equation of state of ideal gases and it was formulated by Benoit
Clapeyron in 1834.
August Krönig in 1856 and Rudolf Clausius in 1857 found, independently, that
Eq. (1.1) can be derived from a microscopic kinetic theory. First of all, one observes
that the number n of moles is related to the total number N of identical particles by
the formula
N
n= , (1.2)
NA
where N A = 6.02 · 1023 is the Avogadro number. After introducing the Boltzmann
constant
R
kB = = 1.38 · 1023 J/K , (1.3)
NA
P V = N kB T . (1.4)
This equation clearly shows that the pressure P is proportional to the total number
N of identical particles and to the absolute temperature T . Thus, it is quite natural
to think that the pressure P exerted by the gas is due to the collisions of the particles
on the container walls.
Let us now consider a cubic container of side L and volume V = L 3 with N
identical particles of mass m inside. Let us choose the reference system with the
Cartesian axes (x, y, x) along the sides of the box. The force Fi,x that the i-th particle
exerts, along the x direction on the container wall that parallel to the plane (y, z), is
given by
(mvi,x ) 2 mvi,x
Fi,x = = , (1.5)
t t
where (mvi,x ) is the variation of the linear momentum in the elastic collision of
the i-th particle with the wall and t is the time interval. This time interval is not
arbitrary if the particles are only interacting with the walls of the container. In this
case
2L
t = , (1.6)
vi,x
that is the time interval between two collisions of the ith particle with the same wall.
It then follows that
2
mvi,x
Fi,x = (1.7)
L
and the pressure reads
1.1 Kinetic Theory of Gases 3
N
m 2
N
i=1 Fi,x m
P= = v = 3 N vx2 , (1.8)
L2 L 3 i=1 i,x L
mN 2
P= v . (1.11)
3V
Comparing Eq. (1.4) with Eq. (1.11) we obtain
1 3
mv 2 = k B T . (1.12)
2 2
This remarkable formula relates the statistical average of the kinetic energy of the
miscroscopic identical particles to the macroscopic absolute temperature T of the
gas.
In this treatment the gas is indeed ideal because its total internal energy E is
simply the sum of the kinetic energies (1/2)mvi2 of the single particles, i.e.
N
1 1 3 3
E= mvi2 = N mv 2 = N k B T = n RT . (1.13)
i=1
2 2 2 2
This is the correct formula for the internal energy of a monoatomic gas, where each
atom has only three traslational degrees of freedom. In this case the equipartition
theorem holds: at thermal equilibrium there is an associated thermal energy k B T /2
for each degree of freedom.
In 1860 James Clerk Maxwell considered the probability distribution f (v) of finding
a particle with velocity v in a volume d 3 v for the ideal gas at thermal equilibrium.
Because f (v) is a probability distribution it must satisfy the condition of normaliza-
4 1 Classical Statistical Mechanics
In particular, it follows that the statistical average of the square velocity v 2 reads
v =
2
v 2 f (v) d 3 v . (1.16)
R3
Taking into account Eqs. (1.12) and (1.16), it follows that f (v) must satisfy the
crucial condition
kB T
v 2 f (v) d 3 v = 3 . (1.17)
R 3 m
1 2 1
mv = m vx2 + v 2y + vz2 , (1.18)
2 2
and, due to the isotropy of the problem with respect to the velocity, it is quite natural
to assume that
where C is a constant fixed by the normalization to one, Eq. (1.14). The only function
f 0 (x) that satisfies the equation
Φ (v)
0.2
0.15
0.1
0.05
0
0 1 2 3 4 5
v
1
β= (1.25)
kB T
It is important to stress that, adopting spherical coordinates and taking into account
the spherical symmetry of the problem we have d 3 v = 4πv 2 dv, and we can also
introduce
mβ 3/2 2 −β mv2
(v) = 4πv f (|v|) = 4π
2
v e 2 (1.27)
2π
that is the probability distribution of the modulus v = |v| of the velocity v, and it is
such that (Fig. 1.1) +∞
(v) dv = 1 . (1.28)
0
We immediately find
+∞
8 kB T
v = v (v) dv = (1.29)
0 π m
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Had a bombshell exploded in their midst, it could not have produced
a severer or more painful shock.
Ralph Houston, after the first agonized start and shudder, drew
nearer to her, and paused, pale as death, to listen further, if,
perchance, he had heard aright.
All the others, after their first surprise, stood as if struck statue still.
Major Helmstedt remained nailed to the ground, a form of iron. Deep
and unearthly was the sound of his voice, as, lifting the head of his
daughter from his breast, he said:
“Miss Helmstedt, look me in the face!”
She raised her agonized eyes to his countenance.
All present looked and listened. No one thought by word or gesture
of interfering between the father and daughter.
“Miss Helmstedt,” he began, in the low, deep, stern tone of
concentrated passion, “what was that which you said just now?”
“I said, my father, in effect, that you must not fight; that your cause is
accurst; that the charges brought against me are—true!”
“You tell me that——”
“The charges brought against me are true!” she said, in a strange,
ringing voice, every tone of which was audible to all present.
Had the fabled head of the Medusa, with all its fell powers, arisen
before the assembled party, it could not have produced a more
appalling effect. Each stood as if turned to stone by her words.
The father and daughter remained confronted like beings charged
with the mortal and eternal destiny of each other. At length Margaret,
unable to bear the scrutiny of his fixed gaze, dropped her head upon
her bosom, buried her burning face in her hands, and turned away.
Then Major Helmstedt, keeping his eyes still fixed with a devouring
gaze upon her, slowly raised, extended and dropped his hand
heavily upon her shoulder, clutched, turned, and drew her up before
him.
“Again! let fall your hands; raise your head; look me in the face,
minion!”
She obeyed, dropping her hands, and lifting her face, crimsoned with
blushes, to his merciless gaze.
“Repeat—for I can scarce believe the evidence of my own senses!
The charges brought against you, by the Houstons, are——”
“True! They are true!” she replied, in a voice of utter despair.
“Then, for three years past, ever since your betrothal to Mr. Ralph
Houston, you have been in secret correspondence with a strange
young man, disapproved by your protectress?” asked Major
Helmstedt, in a sepulchral tone.
“I have—I have!”
“And you have met this young man more than once in private?”
“Yes, yes!” she gasped, with a suffocating sob.
“On the day of the festival, and of the landing of the British upon our
island, you passed several hours alone with this person in the
woods?”
A deprecating wave of the hand and another sob was her only reply.
“Once, at least, you received this man in your private apartment at
Buzzard’s Bluff?”
A gesture of affirmation and of utter despondency was her answer.
“The night of that same visit, you secretly left the room of your
protectors for an unexplained absence of several days, some of
which were passed in the company of this person?”
For all reply, she raised and clasped her hands and dropped them
down before her, and let her head fall upon her bosom with an action
full of irremediable despair.
Her father’s face was dark with anguish.
“Speak, minion!” he said, “these things must not be left to conjecture;
they must be clearly understood. Speak! answer!”
“I did,” she moaned, in an expiring voice, as her head sank lower
upon her breast, and her form cowered under the weight of an
overwhelming shame and sorrow.
And well she might. Here, in the presence of men, in the presence of
her father and her lover, she was making admissions, the lightest
one of which, unexplained, was sufficient to brand her woman’s brow
with ineffaceable and eternal dishonor!
Her lover’s head had sunk upon his breast, and he stood with folded
arms, set lips, downcast eyes and impassable brow, upon which
none could read his thoughts.
Her father’s face had grown darker and sterner, as he questioned
and she answered, until now it was terrible to look upon.
A pause had followed her last words, and was broken at length by
Major Helmstedt, who, in a voice, awful in the stillness and depth of
suppressed passion, said:
“Wretched girl! why do you linger here? Begone! and never let me
see you more!”
“Father, father! have mercy, have mercy on your poor child!” she
exclaimed, clasping her hands and dropping at his feet.
“Minion! never dare to desecrate my name, or pollute my sight again.
Begone!” he exclaimed, spurning her kneeling form and turning
away.
“Oh, father, father! for the sweet love of the Saviour!” she cried,
throwing her arms around his knees and clinging to him.
“Wretch! outcast! release me, avoid my presence, or I shall be driven
to destroy you, wanton!” he thundered, giving way to fury, and
shaking her as a viper from her clinging hold upon his feet; “wanton!
courtez——”
But ere that word of last reproach could be completed, swift as
lightning she flew to his bosom, clung about his neck, placed her
hand over his lips to arrest his further speech, and gazing intensely,
fiercely into his eyes—into his soul, exclaimed:
“Father, do not finish your sentence. Unless you wish me to drop
dead before you, do not. As you hope for salvation, never apply that
name to—her daughter.”
“Her daughter!” he retorted, violently, shaking her off, until she fell
collapsed and exhausted at his feet—“her daughter! Changeling, no
daughter of hers or of mine are you. She would disown and curse
you from her grave! and——”
“Oh, mother, mother! oh, mother, mother!” groaned the poor girl,
writhing and groveling like a crushed worm on the ground.
“And I,” he continued, heedless of her agony, as he stooped,
clutched her arm, jerked her with a spring upon her feet, and held
her tightly confronting him.
“I—there was a time when I was younger, that had any woman of my
name or blood made the shameful confessions that you have made
this day, I would have slain her on the instant with this, my right
hand. But age somewhat cools the head, and now I only spurn you—
thus!”
And tightening his grasp upon her shoulder, he whirled her off with
such violence that she fell at several yards distant, stunned and
insensible upon the ground.
Then, followed by his second, he strode haughtily from the place.
Dr. Hartley, who had remained standing in amazement through the
latter part of this scene, now hurried to the assistance of the
swooning girl.
But Ralph Houston, shaking off the dreadful apathy that had bound
his faculties, hastened to intercept him. Kneeling beside the
prostrate form, he lifted and placed it in an easier position. Then,
turning to arrest the doctor’s steps, he said:
“Before you come nearer to her, tell me this: What do you believe of
her?”
“That she is a fallen girl,” replied Dr. Hartley.
“Then, no nearer on your life and soul,” said Ralph, lifting his hand to
bar the doctor’s further approach.
“What do you mean, Captain Houston?”
“That she still wears the betrothal ring I placed upon her finger. That I
am, as yet, her affianced husband. And, by that name, I claim the
right to protect her in this, her bitter extremity; to defend her bruised
and broken heart from the wounds of unkind eyes! Had you had faith
in her, charity for her, I should have accepted, with thanks, your help.
As it is, you have none; do not let her awake to find a hostile
countenance bending over her!”
“As you please, sir. But, remember, that if the assistance of a
physician is absolutely required, my services, and my home also,
await the needs of Marguerite De Lancie’s daughter,” said Dr.
Hartley, turning to depart.
Frank also, at a sign from his brother, withdrew.
Ralph was alone with Margaret. He raised her light form, shuddering,
amid all his deeper distress, to feel how light it was, and bore her
down the wooded hill, to the great spreading oak, under which was
the green mound of her mother’s last sleeping place.
He laid her down so that her head rested on this mound as on a
pillow, and then went to a spring near by to bring water, with which,
kneeling, he bathed her face.
Long and assiduous efforts were required before she recovered from
that mortal swoon.
When at length, with a deep and shuddering sigh, and a tremor that
ran through all her frame, she opened her eyes, she found Ralph
Houston kneeling by her side, bending with solicitous interest over
her.
With only a dim and partial recollection of some great agony passed,
she raised her eyes and stretched forth her arms, murmuring, in
tender, pleading tones:
“Ralph, my friend, my savior, you do not believe me guilty? You know
me so thoroughly; you always trusted me; you are sure that I am
innocent?”
“Margaret,” he said, in a voice of the deepest pain, “I pillowed your
head here above your mother’s bosom; had I not believed you
guiltless of any deeper sin than inconstancy of affection, I should not
have laid you in this sacred place.”
“Inconstancy! Ralph?”
“Fear nothing, poor girl! it is not for me to judge or blame you. You
were but a child when our betrothal took place; you could not have
known your own heart; I was twelve years your senior, and I should
have had more wisdom, justice, and generosity than to have bound
the hand of a child of fourteen to that of a man of twenty-six. We
have been separated for three years. You are now but seventeen,
and I am in my thirtieth year. You have discovered your mistake, and
I suffer a just punishment. It is natural.”
“Oh, my God! my God! my cup overflows with bitterness!” moaned
the poor maiden, in a voice almost inaudible from anguish.
“Compose yourself, dear Margaret. I do not reproach you in the
least; I am here to serve you as I best may; to make you happy, if it
be possible. And the first step to be taken is to restore to you your
freedom.”
“Oh, no! Oh, Lord of mercy, no! no! no!” she exclaimed, in an agony
of prayer; and then, in sudden self-consciousness, she flushed all
over her face and neck with maiden shame, and became suddenly
silent.
“Dear Margaret,” said Ralph, in a tone of infinite tenderness and
compassion, “you have suffered so much that you are scarcely sane.
You hardly know what you would have. Our betrothal must, of
course, be annulled. You must be free to wed this lover of your
choice. I hope that he is, in some measure, worthy of you; nay, since
you love him, I must believe that he is so.”
“Oh, Ralph, Ralph! Oh, Ralph, Ralph!” she cried, wringing her hands.
“Margaret, what is the meaning of this?”
“I have no lover except you. I never wronged you in thought, or word,
or deed; never, never, never!”
“Dear Margaret, I have not charged you with wronging me.”
“But I have no lover; do you hear, Ralph? I never have had one! I
never should have so desecrated our sacred engagement.”
“Poor Margaret, you are distracted! Much grief has made you mad!
You no longer know what you say.”
“Oh, I do, I do! never believe but I know every word that I speak. And
I say that my heart has never wandered for an instant from its
allegiance to yourself! And listen farther, Ralph,” she said, sinking
upon her knees beside that grave, and raising her hands and eyes to
heaven with the most impressive solemnity, “listen while I swear this
by the heart of her who sleeps beneath this sod, and by my hopes of
meeting her in heaven! that he with whom my name has been so
wrongfully connected was no lover of mine—could be no lover of
mine!”
“Hold, Margaret! Do not forswear yourself even in a fit of partial
derangement. Rise, and recall to yourself some circumstances that
occurred immediately before you became insensible, and which,
consequently, may have escaped your memory. Recollect, poor girl,
the admissions you made to your father,” said Ralph, taking her hand
and gently constraining her to rise.
“Oh, Heaven! and you believe—you believe——”
“Your own confessions, Margaret, nothing more; for had an angel
from heaven told the things of you that you have stated of yourself, I
should not have believed him!”
“Oh, my mother! Oh, my God!” she cried, in a tone of such deep
misery, that, through all his own trouble, Ralph deeply pitied and
gently answered her.
“Be at ease. I do not reproach you, my child.”
“But you believe. Oh, you believe——”
“Your own statement concerning yourself, dear Margaret; no more
nor less.”
“Believe no more. Not a hair’s breadth more. Scarcely so much. And
draw from that no inferences. On your soul, draw no inferences
against me; for they would be most unjust. For I am yours; only
yours; wholly yours. I have never, never had any purpose, wish, or
thought at variance with your claims upon me.”
“You must pardon me, Margaret, if I cannot reconcile your present
statement with the admissions lately made to your father. Allow me
to bring them to your memory.”
“Oh, Heaven, have mercy on me!” she cried, covering her face.
“Remember, I do not reproach you with them; I only recall them to
your mind. You have been in secret correspondence with this young
man for three years past; you have given him private meetings; you
have passed hours alone in the woods with him; you have received
him in your chamber; you have been abroad for days in his
company; you have confessed the truth of all this; and yet you
declare that he is not, and cannot be a lover of yours. Margaret,
Margaret, how can you expect me, for a moment, to credit the
amazing inconsistency of your statements?”
While he spoke, she stood before him in an agony of confusion and
distress, her form cowering; her face sunk upon her breast; her eyes
shunning his gaze; her face, neck, and bosom crimsoned with fiery
blushes; her hands writhed together; her whole aspect one of
conscious guilt, convicted crime, and overwhelming shame.
The anguish stamped upon the brow of her lover was terrible to
behold. Yet he governed his emotions, and compelled his voice to be
steady in saying:
“Dear Margaret, if in any way you can reconcile these
inconsistencies—speak!”
Speak. Ay, she might have done so. One word from her lips would
have sufficed to lift the cloud of shame from her brow, and to crown
her with an aureola of glory; would have averted the storm of
calamity gathering darkly over her head, and restored her, a
cherished daughter, to the protecting arms of her father; an honored
maiden to the esteem of friends and companions; a beloved bride to
the sheltering bosom of her bridegroom. A word would have done
this; yet that word, which could have lifted the shadow from her own
heart and life, must have bid it settle, dark and heavy, upon the
grave of the dumb, defenseless dead beneath her feet. And the word
remained unspoken.
“I can die for her; but I cannot betray her. I can live dishonored for
her sake; but I cannot consign her memory to reproach,” said the
devoted daughter to her own bleeding and despairing heart.
“Margaret, can you explain the meaning of these letters, these
meetings in the woods, on the river, in your own chamber?”
“Alas! I cannot. I can only endure,” she moaned, in a voice replete
with misery, as her head sunk lower upon her breast, and her form
cowered nearer the ground, as if crushed by the insupportable
weight of humiliation.
It was not in erring human wisdom to look upon her thus, to listen to
her words, and not believe her a fallen angel!
And yet she was innocent. More than innocent. Devoted, heroic,
holy.
But, notwithstanding this, and her secret consciousness of this, how
could she—in her tender youth, with her maiden delicacy and
sensitiveness to reproach—how could she stand in this baleful
position, and not appear overwhelmed by guilt and shame?
There was a dread pause of some minutes, broken at length by
Ralph, who said:
“Margaret, will you return me that betrothal ring?”
She answered:
“You placed it on my finger, Ralph! Will you also take it off? I was
passive then; I will be passive now.”
Ralph raised the pale hand in his own and tried to draw off the ring.
But since, three years before, the token had been placed upon the
little hand of the child, that hand had grown, and it was found
impossible to draw the ring over the first joint.
Ralph Houston, unwilling to give her physical pain, resisted in his
efforts, saying quietly, as he bowed and left her:
“The betrothal ring refuses to leave your finger, Margaret. Well,
good-morning!”
A smile, holy with the light of faith, hope, and love, dawned within her
soul and irradiated her brow. In a voice, solemn, thrilling with
prophetic joy, she said:
“The ring remains with me! I hail it as the bow of promise! In this
black tempest, the one shining star!”
CHAPTER XV.
NIGHT AND ITS ONE STAR.
THE END.