Gateway To Condensed Matter Physics and Molecular Biophysics: Concepts and Theoretical Perspectives 1st Edition Chaudhury

Full download ebooks at ebookmeta.
com
Gateway to Condensed Matter Physics and Molecular

Biophysics: Concepts and Theoretical Perspectives
1st Edition Chaudhury
https://ebookmeta.com/product/gateway-to-condensed-matter-
physics-and-molecular-biophysics-concepts-and-theoretical-
perspectives-1st-edition-chaudhury/
OR CLICK BUTTON
DOWLOAD NOW
Download more ebook from https://ebookmeta.com

More products digital (pdf, epub, mobi) instant
download maybe you interests ...
Condensed Matter Physics A Very Short Introduction 1st

Edition Ross H. Mckenzie
https://ebookmeta.com/product/condensed-matter-physics-a-very-
short-introduction-1st-edition-ross-h-mckenzie/
Theoretical Concepts in Physics An Alternative View of

Theoretical Reasoning in Physics 3rd Edition Malcolm S.
Longair
https://ebookmeta.com/product/theoretical-concepts-in-physics-an-
alternative-view-of-theoretical-reasoning-in-physics-3rd-edition-
malcolm-s-longair/
Condensed Matter Field Theory (3rd Edition) Alexander

Altland
https://ebookmeta.com/product/condensed-matter-field-theory-3rd-
edition-alexander-altland/
Condensed Phase Molecular Spectroscopy and Photophysics

2nd Edition Anne Myers Kelley
https://ebookmeta.com/product/condensed-phase-molecular-
spectroscopy-and-photophysics-2nd-edition-anne-myers-kelley/
Condensed Matter Field Theory 2nd Edition Alexander
Altland Ben D Simons
https://ebookmeta.com/product/condensed-matter-field-theory-2nd-
edition-alexander-altland-ben-d-simons/
Theoretical Cybersecurity: Principles and Advanced

Concepts 1st Edition Jacob G. Oakley
https://ebookmeta.com/product/theoretical-cybersecurity-
principles-and-advanced-concepts-1st-edition-jacob-g-oakley/
Communicating Fashion Brands Theoretical and Practical

Perspectives 1st Edition Emily Huggard
https://ebookmeta.com/product/communicating-fashion-brands-
theoretical-and-practical-perspectives-1st-edition-emily-huggard/
Magneto Optics An introduction Graduate Texts in

Condensed Matter 2019th Edition Fumagalli Paul Schoenes
Joachim
https://ebookmeta.com/product/magneto-optics-an-introduction-
graduate-texts-in-condensed-matter-2019th-edition-fumagalli-paul-
schoenes-joachim/
Chemistry The Molecular Nature of Matter and Change 9th

Edition Martin S. Silberberg
https://ebookmeta.com/product/chemistry-the-molecular-nature-of-
matter-and-change-9th-edition-martin-s-silberberg/
GATEWAY TO CONDENSED
MATTER PHYSICS AND
MOLECULAR BIOPHYSICS
Concepts and Theoretical Perspectives
GATEWAY TO CONDENSED
MATTER PHYSICS AND
MOLECULAR BIOPHYSICS
Concepts and Theoretical Perspectives
by
Ranjan Chaudhury, PhD
First edition published 2022
Apple Academic Press Inc. CRC Press
1265 Goldenrod Circle, NE, 6000 Broken Sound Parkway NW,
Palm Bay, FL 32905 USA Suite 300, Boca Raton, FL 33487-2742 USA
4164 Lakeshore Road, Burlington, 2 Park Square, Milton Park,
ON, L7L 1A4 Canada Abingdon, Oxon, OX14 4RN UK
© 2022 Apple Academic Press, Inc.

Apple Academic Press exclusively co-publishes with CRC Press, an imprint of Taylor & Francis Group, LLC
Reasonable efforts have been made to publish reliable data and information, but the authors, editors, and publisher cannot assume
responsibility for the validity of all materials or the consequences of their use. The authors, editors, and publishers have attempted to
trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in
this form has not been obtained. If any copyright material has not been acknowledged, please write and let us know so we may rectify
in any future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form
by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording,
or in any information storage or retrieval system, without written permission from the publishers.
For permission to photocopy or use material electronically from this work, access www.copyright.com or contact the Copyright Clearance
Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. For works that are not available on CCC please contact
[email protected]
Trademark notice: Product or corporate names may be trademarks or registered trademarks and are used only for identification and
explanation without intent to infringe.
Library and Archives Canada Cataloguing in Publication
Title: Gateway to condensed matter physics and molecular biophysics : concepts and theoretical perspectives / by
Ranjan Chaudhury, PhD.
Names: Chaudhury, Ranjan, author.
Description: First edition. | Includes bibliographical references and index.
Identifiers: Canadiana (print) 20210188766 | Canadiana (ebook) 20210188812 | ISBN 9781771889131 (hardcover) |
ISBN 9781774638057 (softcover) | ISBN 9781003057840 (ebook)
Subjects: LCSH: Condensed matter. | LCSH: Physics. | LCSH: Molecular biology.
Classification: LCC QC173.454 .C53 2021 | DDC 530.4/1—dc23
Library of Congress Cataloging‑in‑Publication Data
Names: Chaudhury, Ranjan, author.
Title: Gateway to condensed matter physics and molecular biophysics : concepts and theoretical perspectives / by Ranjan Chaudhury.
Description: First edition. | Palm Bay, FL : Apple Academic Press, 2021. | Includes bibliographical references and index. | Summary:
"This new book, Gateway to Condensed Matter Physics and Molecular Biophysics: Concepts and Theoretical Perspectives,
provides the necessary background material and brings into focus the fundamental concepts essential for advanced research in
theoretical condensed matter physics and its interface with molecular biophysics. It is the outcome of the author's long teaching
and research career in theoretical condensed matter physics and related interdisciplinary fields. The author aims to motivate
students to take up research in condensed matter physics and march toward new frontiers. He writes: "My long understanding of
students' attitude and orientation brings me to the conclusion that many of them are quite excited about the developments in the
frontier research areas at the beginning of their career; however, a sizable fraction of them start losing interest gradually as they
are often unable to connect these developments with the basic physics they have studied. I have tried to fill this gap in this book."
To this end special care has been taken to balance the physical concepts and mathematical expressions as well as proper mixing
of theoretical and experimental aspects. He starts with the very well known elementary ideas or basic concepts and goes forward
so as to remove the apparent conceptual and technical gap between the known laws and various interesting, challenging, and
novel experimental results and effects, some of which are amongst the latest discoveries. Key features: Introduces a new way
of looking at various important and fundamental phenomena in condensed matter from the perspective of microscopic theory
Explores a new interface of quantum condensed matter physics and molecular biophysics, highlighting research potentialities
Addresses the crucial questions surrounding these phenomena when they are mutually coexisting or competing in real condensed
matter systems or materials, from both theoretical and experimental angles Deals with biological molecules and some of their
properties and processes and discusses the modeling of these with the help of condensed matter physics and statistical physics
Emphasizes fundamental concepts, particularly in condensed matter physics and making proper use of them The book is unique
because it provides an insight into the microscopics of some of the fundamental phenomena in condensed matter physics and
their interrelations. It also attempts to bridge the apparently unconnected fields of molecular biophysics and condensed matter
physics. Gateway to Condensed Matter Physics and Molecular Biophysics: Concepts and Theoretical Perspectives will be an
invaluable advanced reference book for master's students (in physics) and PhD students (in condensed matter physics) in their
early years of research, and will also be helpful to faculty and researchers"-- Provided by publisher.
Identifiers: LCCN 2021016789 (print) | LCCN 2021016790 (ebook) | ISBN 9781771889131 (hardcover) | ISBN 9781774638057
(paperback) | ISBN 9781003057840 (ebook)
Subjects: LCSH: Condensed matter. | Molecular biology.
Classification: LCC QC173.454 .C498 2021 (print) | LCC QC173.454 (ebook) | DDC 530.4/1--dc23
LC record available at https://lccn.loc.gov/2021016789
LC ebook record available at https://lccn.loc.gov/2021016790
ISBN: 978-1-77188-913-1 (hbk)
ISBN: 978-1-77463-805-7 (pbk)
ISBN: 978-1-00305-784-0 (ebk)
Dedication
Dedicated to the Memory of

My Beloved Father.
About the Author
Ranjan Chaudhury, PhD

Superannuated Full Professor, Department of Condensed Matter Physics
and Material Sciences, S.N. Bose National Centre For Basic Sciences,
India; Full Professor Ramakrishna Mission Vivekananda Educational
and Research Institute, India (till 31.01.21)
Ranjan Chaudhury, PhD, has been a professor at S.N.

Bose National Centre, Kolkata, India, since 1994
and is at present attached there as a Superannuated
Full Professor in the Condensed Matter Physics
and Material Sciences Department. He was also an
Adjunct Professor in the Physics Department at the
Ramakrishna Mission Vivekananda Educational and
Research Institute (Belur) during 2017–2018 and later
was a Full Professor in the department there as well.
Professor Chaudhury has done extensive theoretical work in the areas
of superconductivity and magnetism in low-dimensional systems and
also in the few areas of theoretical molecular biophysics. He has about 80
publications to date, which include publications in international journals
as well as research reports and international conference papers. He has
been teaching regularly for last more than 20 years and has supervised
PhD and master’s students for their theses and major projects. He also
delivered invited talks at some of the well-known international and
national conferences, both abroad and in India. He has been the recipient
of several awards both at the national and international levels.
Prof. Chaudhury has been a member of a number of international
scientific societies and organizations such, as the American Chemical
Society (New York), MSI (Minneapolis), and ATINER (Athems Institute
for Education & Research). He has been a recipient of several awards both
at the national and at the international levels.
Dr. Chaudhury completed his Master’s in Physics at IIT Kharagpur
and obtained his PhD from TIFR (Mumbai). During his PhD, he did theo
retical work in the areas of superconductivity and magnetism. He was a
viii About the Author
postdoctoral fellow/collaborating visiting scientist at various institutions

abroad including, International Centre for Theoretical Physics (ICTP,
(Trieste, Italy); McMaster University (Hamilton, Ontario, Canada);
University of Minnesota (Minneapolis); LEPES, CNRS (Grenoble,
France); and BLTP, JINR (Dubna, Russia) during 1988–2000 and was
involved with theoretical research in various areas of condensed matter
physics. In addition, he was a Visiting Professor at African University of
Science and Technology (AUST) (Nigeria) during 2009–2010 and taught
there in the Theoretical Physics Department as well.
Contents
Abbreviations....................................................................................................... xi
Preface...............................................................................................................xiii
1. Introduction to Electronic Properties of Solids:

Band Theory and Consequences................................................................ 1
2. Magnetism ................................................................................................. 25
3. Lattice Dynamics, Phonons, and Some Applications for
Optical Properties of Solids...................................................................... 81
4. Electrons in Solids and Surface States .................................................. 101
5. Superconductivity ................................................................................... 121
6. Interface of Molecular Biophysics with Condensed
Matter Physics............................................................................................151
Index ................................................................................................................. 171

Abbreviations
AFM atomic force microscopy

BCS Bardeen-Cooper-Schrieffer
BEC Bose-Einstein Condensation
BKT Berezinskii, Kosterlitz, and Thouless
BPR base-pairing rule
BV Bogoliubov-Velatin
CDW charge density wave
CP Clauxius-Pearson
CR complementarity restoration
DM Dzyaloshinskii-Moriya
DNA deoxyribonucleic acid
DOS density of states
e.m. electromagnetic
EDOS electronic density of states
ESR electron spin resonance
GC Gorter-Casimir
GFP green fluorescent protein
GL Ginzburg-Landau
GMR giant magneto-resistance
GPB De Gennes, Peyrard-Bishop
HPT Holstein-Primakoff transformations
JSDC Jensen-Shannon divergence criterion
JSDF Jensen-Shannon divergence function
LFL Landau Fermi liquid
LP London-Pippard’s
MCMD Monte Carlo-molecular dynamics
MFL marginal Fermi liquid
MHI Mott-Hubbard insulator
MOKE magneto-optic Kerr effect
MW microwave
NMR nuclear magnetic resonance
PAC perturbed angular correlation
QHE quantum hall effect
xii Abbreviations
RE repairing efficiency
RKKY Rudolf-Kittel-Kasua-Yoshida
RPA random phase approximation
RWM random walk model
SBB Scafroth-Blatt-Butler
SDW spin density wave
SN superconductor-normal metal
SQUID superconducting quantum interference device
SSS statistical scoring scheme
STM scanning tunneling microscopy
SWCNT single-walled carbon nanotube
SWT Schrieffer-Wolf transformation
TBH tight-binding Hamiltonian
TLL Tomonaga-Luttinger liquid
TM tautomeric mutation
TMR tunneling magneto-resistance
VSM vibrating sample magnetometer
WS Wigner solid
Preface
This is an advanced reference book in theoretical condensed matter physics

and related interdisciplinary problems. Its target readers are post-graduate
(in Physics) and research students (in Condensed Matter Physics) in their
early years of research.
This book is an outcome of my long teaching experiences (at S.N. Bose
Center, AUST, and RKMVERI) of nearly 20 years at the master’s and
post-MSc level, combined with my research career (at TIFR, S.N. Bose
Center, and various institutions abroad) spanning about 35 years.
The principal aim of this book is to motivate students to take up basic
research in condensed matter physics and march towards the frontiers;
these frontier areas may not always be fashionable though. Conceptual
clarification with clear directions to the relevant textbooks and research
papers for details have been attempted systematically and with strong
emphasis. Special care has also been taken to balance the physical
concepts and mathematical expressions and as well as the proper mixing
of theoretical and experimental aspects.
A sincere attempt has been made to start from the very well-known
elementary ideas or basic concepts and go forward so as to remove the
apparent conceptual and technical gap between the known laws and various
interesting, challenging, and novel experimental results and effects, some
of which are amongst the latest discoveries.
My long understanding of students’ attitude and orientation brings me
to the conclusion that many of them are quite excited about the devel
opments in the frontier research areas at the beginning of their careers.
However, a sizeable fraction of them start losing interest gradually as they
are often unable to connect these developments with the basic physics that
they have studied. I have tried to fill this gap sincerely as much as possible
in this book.
My other strong feeling developed over years is that teaching and
research can actually supplement and strengthen each other very effec
tively. I have kept it especially in my mind when planning and writing this
book.
xiv Preface
I very genuinely and sincerely owe the motivation of this book writing
to my late beloved father, Prof. Tapas Kumar Chaudhury, who always
inspired me and helped me to concentrate and focus on this difficult but
noble assignment.
I would also like to express my deep gratitude to all my teachers,
PhD thesis supervisors, all my mentors, and research collaborators for
drawing my attention to various challenging problems in various areas of
condensed matter physics and quantum biology and help me tackling them
through collaborations. The list is very long but I would like to specially
mention the following names: Prof. S. K. Ghatak, Prof. S. S. Jha, Prof. B.
S. Shastry, Prof. M. Barma, Prof. A. K. Grover, Prof. D. Dhar, Prof. C. K.
Majumdar, Prof. J. P Carbotte, Prof. J. W. Halley, Prof. B. K. Chakraverty,
Prof. T. V. Ramakrishnan, Prof. M. Avignon, Prof. D. Feinberg, Prof. N.
Plakida, Prof. M. P. Das, Prof. G. Baskaran, Prof. T. Chatterjee, Prof.
V. Golo, Prof. D. Gangopadhyay, Prof. J. Chakrabarti, Prof. S. K. Paul,
and Prof. A. Parola, for enriching my knowledge and understanding and
sharing exciting science with me.
It would also be quite incomplete and unfair if I don’t acknowledge the
hidden contributions of my students (past and present). Through teaching
and supervision, my own understanding of the intricacies in various scien
tific concepts has acquired clarity and totality.
Special thanks are due to Suraka Bhattacharjee, one of my PhD
students, for helping me with the figures in this book.
Finally, I would like to thank my family members, relatives, and
friends who have stood by my side and supported me during the period of
my personal tragedies and have helped me to complete the preparation of
the manuscript.
It is indeed a pleasure for me to express my gratitude to Ms. Sandra Jones
Sickels, Vice President, Apple Academic Press, for her invitation to me to
write this book. I also would like to thank Mr. Ashish Kumar, President,
Apple Academic Press, and his team members for various technical
suggestions regarding the manuscript and cooperation.
Last but not the least, I would also like to gratefully acknowledge all
the infrastructural facilities provided by the S.N. Bose Center during the
writing of this book.
—Ranjan Chaudhury, PhD
CHAPTER 1
Introduction to Electronic Properties of

Solids: Band Theory and Consequences
1.1 GENERAL INTRODUCTION
Condensed matter physics is a branch of physics, which deals with

the properties of solids and liquids. This branch is further subdivided
into ‘hard-core condensed matter physics’ and ‘soft condensed matter
physics.’ The hard-core condensed matter studies and analyses the truly
microscopic properties of solids and liquids including both conventional
and non-conventional types. This contains both ordered and disordered
solids, as well as classical and quantum liquids. On the other hand, the
soft condensed matter generally looks at the nearly classical modeling
of semi-microscopic and even macroscopic aspects of a special class of
“soft materials” like granular materials, colloids, spongy materials, etc.
In Chapters 1–5, we will only introduce a few key areas falling within the
purview of the hard-core condensed matter physics. In these chapters, we
will mostly confine our discussions only to crystalline solids. In Chapter 6,
we will discuss a few problems at the interface of molecular biophysics
and condensed matter physics mostly involving DNA.
This book attempts to address concepts and problems at the level of both
foundations and frontiers in condensed matter physics, which are funda
mental and stimulating but may not necessarily be fashionable always.
The approach followed is based on a theoretical one but supplemented
with results from experimental and computational studies. Last but not
least, each chapter contains some of the advanced research results in the
respective fields as well as the development of the conceptual foundation.
The book is divided into six chapters. In the first chapter, a general
introduction to electronic band theory is presented. Moreover, various
experimental techniques and phenomena associated with the studies of
2 Gateway to Condensed Matter Physics and Molecular Biophysics
energy bands are also briefly dealt with. In the second chapter, we cover
various aspects of magnetism in solids, and we include both microscopic
theories as well as the experimental techniques along with some of the
effects observed. Applications to some new techniques and devices are also
discussed. The third chapter is devoted to lattice dynamics and the origin of
phonons. It also contains some manifestations of various types of phonons
to different kinds of phenomena and effects. The fourth chapter contains a
detailed analysis of the electrons in real solids. It introduces various many-
body techniques and effective theories, which are semi-phenomenological
in nature. Besides, a bit of surface physics is also included. Here again,
some connections to exotic phenomena and new devices are brought out.
The fifth chapter deals exclusively with superconductivity. It carries out a
fairly detailed analysis of the microscopic and phenomenological theories
of superconductivity, for both conventional materials as well as the exotic
materials. Moreover, it covers special topics such as magnetic superconduc
tors and high-temperature superconductivity. It also includes various forms
of experimental techniques and their applications. The very last chapter
deals with the theoretical attempts from a viewpoint of a quantum condensed
matter physicist to understand certain important biophysical properties of
DNA, a very crucial ingredient of all living systems.
Almost all the physical properties of solids can be linked to the
following three types of very fundamental and important characteristics:
(a) electrical transport, (b) magnetic, and (c) electrical polarization. Again
based on these three characteristics, the solids may broadly be classified
in the following ways:
1. Electrical transport:
i. insulator;
ii. semiconductor;
iii. metal; and
iv. superconductor.
2. Magnetic:
i. diamagnet;
ii. paramagnet;
iii. ferromagnet; and
iv. antiferromagnet.
Introduction to Electronic Properties of Solids 3
3. Electrical polarization:
i. paraelectric;
ii. ferroelectric; and
iii. anti-ferroelectric.
Under group (a) classification, an insulator is defined as a material,

which does not conduct electricity at all at room temperature or below. A
semiconductor is one, which behaves as an insulator at zero temperature
but becomes a moderate conductor at finite temperature. A metal is a
very good conductor at any temperature. A superconductor is a special
kind of metal, metallic alloy, or even a doped insulator which becomes
a perfect conductor, i.e., loses all electrical resistance below a certain
finite temperature. Besides these four types, there is a special variety of
semiconductors called “semi-metal,” which behaves like a semiconductor
at zero temperature but becomes metallic as soon as the temperature is
raised. Typically, in a semiconductor, the electrical conductivity increases
with temperature. A metal exhibits the opposite character viz. the elec
trical conductivity falls as temperature rises. Thus, a semiconductor is an
insulator at zero temperature. A very pure metal is a perfect conductor
only at zero temperature. In contrast, a superconductor becomes a perfect
conductor at a temperature above absolute zero and remains in that
state down to zero temperature. Some of the examples of the materials
belonging to these classes are the various metallic oxides like NiO, various
organic polymers like polythene, alkali halides like NaCl (insulator); Si,
Ge (semiconductors); Bi (semimetal); Na, K, Fe, Cu, etc. (metal); Hg, Pb,
Al, Sn, Nb3Sn, Nb3Ge, etc., (superconductor). It should also be remarked
however that the insulators belonging to the alkali halide subgroup, exhibit
a very feeble conductivity at room temperature due to the ionic migration.
Within the group (b) characterization, in a diamagnet and externally
applied magnetic field is opposed by an induced orbital current. Moreover,
there are no net intrinsic magnetic moments on the constituent atoms. In a
paramagnet even though the individual atoms have magnetic moments, they
are randomly oriented in the absence of any external magnetic field—leading
to the non-existence of any overall spontaneous moment in the system.
However, in both ferromagnet and anti-ferromagnet, there are the existence
of well-ordered structures of spontaneous magnetic moments. In a ferro
magnet, the magnetic moments on the neighboring lattice sites are oriented
parallel; whereas in an antiferromagnetic system, they are anti-aligned.
The group (c) classification is exactly analogous to that of the group

(b), with the quantity “magnetic moment” being replaced with “electrical
dipole moment.”
The comparison between dia-electric (so called !), i.e., both metallic
systems and some electrolytic substances with dielectric constant (micro
scopic dielectric function at finite q) becoming –ve and diamagnetic, i.e.,
both superconducting and insulating systems with magnetic (orbital)
susceptibility at very small q becoming –ve, is very important. Interest
ingly both of these can occur for a superconductor almost simultaneously;
however, one should also distinguish between a microscopic dia-electric
function and a macroscopic one.
It is quite interesting to note that there is a general pattern connecting
members of these three groups. The insulators are generally diamagnetic
or in some cases may show ferromagnetism or anti-ferromagnetism. The
metals are paramagnetic mostly; however, some of them show ferro
magnetism or even antiferromagnetism/spin density wave (SDW). The
superconductors are diamagnets and in fact, exhibit super-diamagnetism.
Most of the ferroelectric and anti-ferroelectric substances are insulators;
however, some of the metals may also exhibit spontaneous electric polar
ization under certain conditions. Again, there exist non-superconducting
super-diamagnets which are in fact insulators like AgI, CuCl, etc. More
over very interestingly, sometimes approaching a magnetic ordering or a
ferro/anti-ferroelectric ordering (involving charge ordering or structural
transition as well), a metal may turn favorably into a superconductor
without undergoing the long-range ordering which it was originally
heading towards (Chaudhury and Jha, 1984). A magnetic superconductor
binary alloy Y9Co7 showed this interesting feature. Some of the very novel
superconductors with substantial magnetic correlations, in particular the
high-temperature Cuprate superconductors and the Fe-based pnictide
superconductors, too quite often exhibit this trend (Chaudhury, 2009). On
the other hand, the alloys like Nb3Sn and Nb3Ge turn into superconductors
(the conventional high-temperature ones) at the threshold of a possible
structural transition (Ginzburg and Kirzhnits, 1982).
Besides, there are systems known as magnetic superconductors which
are mostly alloys of rare earth and transition metal components, which
display very rich interplay and sometimes coexistence between super
conductivity and long-range magnetic ordering. We will discuss them
elaborately in Chapter 2.
The theoretical understanding of these very interesting interplay

phenomena described above is often attempted schematically through a
simplistic jellium model-based approach. To make it truly relevant to the
real condensed matter systems and materials for quantitative comparison
and analysis, it is however crucial to bring in the lattice and include the
band structure effects in the theoretical treatments. Unfortunately, this is
often not done.
It turns out, as we will see later, that the properties (a) and (b) owe
their origin to the “electrons” present in the solid. The property (c), on the
contrary, mostly arises from the vibrations of the “ionic lattice” belonging
to the solid. In certain cases, in metallic/semi-metallic systems electron or
hole occupation in multiple electronic bands with a very small energy gap,
the electrons may also contribute to the spatial ordering of spontaneous
electrical polarization. The property (a) based classification is essentially
decided by the electronic energy or excitation spectrum of the system.
Furthermore, excepting the case of superconductor, the other three catego
ries within the group (a) can all be discussed within the approximation of
the “one-electron theory.” For superconductors and for some special kind
of insulators (viz. Mott-Hubbard insulator (MHI) and charge transfer insu
lator) “many-electron theory” is needed explicitly. In property (b)-based
categorization, all the types excepting diamagnet, require both “one-
electron” as well as “many-electron” treatments for complete theoretical
understanding. Diamagnetism is a “universal property” which can always
be discussed within the one-electron picture for a solid.
The theoretical understanding of these properties of solids enlisted
above is all based on full quantum treatments and often needs the use of
statistical mechanics of interacting particles at finite temperature.
In this first chapter, we present introductory but fairly detailed discus
sions on these electronic properties of solids.
1.2 ORIGIN OF BAND THEORY
In view of the tremendous applicability of the simple one-electron theory,

as brought out in the previous section, we first take up the problem of an
electron moving through a periodic crystal lattice in a solid. Just now,
we are not worried about the nature of the symmetry of the lattice or in
other words the type of the Bravis lattice to which the crystal belongs. Our
treatment is very general to start with. Since the property of electrons is

governed by the laws of quantum mechanics, we will have to make use of
Schrodinger’s equation to tackle this problem. It is well understood now
that a microscopic particle like an electron is described by the De Broglie
waves which are quantum waves describing the probability amplitude for
the location of the particle, obeying the time-dependent Schrodinger equa
tion. The Hamiltonian appropriate to this problem is given by, neglecting
the Coulomb interaction between the electrons for the time being:
h2 2
H= 2
V r (1.1)
2 2m
where, the first operator on the right-hand side is the kinetic energy
operator corresponding to an electron and the second quantity is the peri
odic potential experienced by an electron from the positively charged ion
cores situated on the lattice sites. Because of the perfect periodic nature
of the lattice, we have the translational symmetry property of the potential
experienced by the moving electron due to the ions on the lattice:
V (r) = V (r+R) (1.2)
where, R is any lattice translation vector.

In fact, in general, the full Hamiltonian obeys this translational
symmetry as well, as can be seen easily. Thus, we can write:
[H, T̂ ] = 0 (1.3)
where, T̂ is the ‘lattice translational operator’ defined by its action on any

function, as given below:
̂ (r) = ϕ((r +R))

Tϕ (1.4)
Now the operators T̂ and H being mutually commuting may have

simultaneous eigenstates, provided they are non-degenerate. This leads to
the following form for the eigenfunctions of the Hamiltonian:
l k ( r ) = uk ( r ) exp ( ik · r ) (1.5)
where, ψk(r) is an eigenfunction and uk(r) is a periodic function on the

lattice satisfying:
uk (r) = uk (r + R) (1.6)
The subscript k denotes the wave vector of the traveling wave described
by the eigenfunction ψ and it also represents a band state. It can be seen
very easily from the above form of ψk(r) that it satisfies the following
equation as well:
ψk (r + R) = exp (ik . R) ψk (r) (1.7)
Thus for a wave vector G satisfying:
G . R = 2nπ (1.8)
where, n is an integer, the eigenfunctions ψk(r) and ψk+G(r) are indistin

guishable. The vector G is called a “reciprocal lattice vector” or “Umklapp
vector.” It may be recalled that a reciprocal lattice is dual to the usual
crystal lattice in the real space, i.e., the basis vectors of the two lattices are
related by the equations:
a2 Xa3
b1 = 2n (1.9)
V
where, a1, a2, and a3 are the basis vectors of the crystal lattice or Bravis
lattice and b1, b2, and b3 are the corresponding basis vectors of the recip
rocal lattice; V is the volume of the unit cell in the crystal lattice.
This result bringing out the very definite functional form and properties
for the eigenfunctions for a single electron moving through a periodic lattice
is known as Bloch’s Theorem—named after the celebrated physicist Felix
Bloch who first showed this. The eigenfunctions ψk(r) are called Bloch’s
functions. They represent the propagating solutions for the electron waves
(De-Broglie waves corresponding to the electrons). These Bloch functions
are also the ‘electronic energy band states.’ The corresponding eigenvalues
εk are the ‘electronic band energies.’ They form band spectra of energy
eigenvalues, in contrast to the discrete energy eigenvalues exhibited by the
individual atoms. We will throw more light on this aspect later.
It is important at this stage, to get a feeling for the mathematical

viz. analytical form of these band state wave functions and also of the
k-dependence of the band energies. These can be achieved by choosing
a simple model for the periodic potential V (r). One such model is
the ‘Kronig-Penney model.’ In this model, V (r) is approximated as
Dirac-delta functions centered about the lattice sites. This leads to the
following form for the Schrodinger equation in the simplest case of a
one-dimensional lattice:
2
W x xi k2 k x 0 (1.10)
i
where, the periodic potential has been chosen as:
h2
V ( x) 2
W x xi (1.11)
2 2m i
2m ( 2n ) Ek
2
and k2 being equal to .

h2
The consequences of this equation are striking! They show the exis
tence of ‘allowed energy values’ and the ‘forbidden energy values’ within
the k space. Furthermore, these sets of energy values form distinct band
spectra of energy, viz. allowed band and forbidden band. In the language of
wave mechanics, the electron eigenfunction corresponding to an allowed
band is a propagating wave categorized as a Bloch wave; whereas the
eigenfunction corresponding to a forbidden band is a damped wave. This
result can easily be generalized to higher dimensions including three-
dimension. In this case, the allowed k space is defined as the region with
n n
all the three components kx, ky, and kz lying within - to + , because
a a
of the existence of G. This minimum unit of k space region is known as
the Brillouin Zone. The allowed energy bands may be fully occupied or
partially occupied by electrons; or may be completely empty. We will see
later that the partially occupied energy band with the highest energy is
very important for the electronic transport properties of a material. It plays
the most important role in deciding whether the material is metallic or
insulating. This particular band is called the “conduction band.” All the
completely occupied (filled) allowed bands with energies below that of the
conduction band are known as “valence bands.”
The degree of occupancy of an energy band depends upon the number
of electrons per each atom, belonging to the atomic orbital which forms
that particular band. For example, take the case of solid Sodium. A Sodium
atom has 1 lone electron in its outermost 3s orbital. Thus when a large
number of Sodium atoms are brought very close to each other to form
a solid Sodium, the discrete 3s orbitals of the atoms overlap and split
the degeneracy of these atomic states to form a 3s band which becomes
half-filled. The lower orbitals viz. 1s and 2s form the corresponding bands
which are completely filled. Thus for solid Sodium, the 3s band forms
the conduction band and the two lower bands become the valence bands.
This half-filled (and half-empty) conduction band of Sodium has sufficient
volume in the ε–k space for the electrons to get accelerated under the
application of an external electric field. This leads to an excellent electrical
conductivity for Sodium and its observed metallic properties. In general,
it can be shown that metals always have an unfilled conduction band.
Moreover, the metals with exactly half-filled conduction band are the best
conductors. The metals formed from Group I elements of the Periodic
Table belong to this class. The solids formed from Group II elements also
behave like metals, even though according to the Kronig-Penney model
they should not. The reason behind this is that the periodic potential V(r)
in a real solid deviates from the idealized Kronig-Penney potential. As a
result, real metal shows overlapping bands. This facilitates the creation
of unfilled conduction bands for various solids made out of even some
of the Group II and III elements and leads to metallic behaviors of these
solids. The solids formed from other remaining elements are insulators,
semiconductors, or semimetals.
One of the simplest approximations to the band Hamiltonian is that of
the nearest neighbor “tight-binding approximation.” In this approxima
tion, the Hamiltonian, known as the tight-binding Hamiltonian is given by:
0 ci , ci , tci , cj, (1.12)

i, i, j ,
Then the ε(k) dispersion relation takes the following form for a three-
dimensional semi-cubic lattice:
є(k) = є0 – 2t(coskx a + cosky b + coskz c) (1.13)

where, t is the electron hopping matrix element involving nearest-

neighbor lattice sites; a, b, and c are the lattice parameters along with
the 3 crystallographic directions. The parameter ε0 is the electron energy
corresponding to an atomic site. The quantities t and ε0 are determined by
evaluating the matrix elements of the original 1st quantized Hamiltonian
as used in Bloch’s theorem (see Eqn. (1.1)), between the atomic orbital
wave functions corresponding to the nearest neighbor sites and the same
site respectively. The dispersion relation is given by Eqn. (1.9) shows that
the process of hopping removes the degeneracy of the electronic energy
spectrum of isolated atoms and causes the formation of an energy band
with energies lying between ε0–6t to ε0+ 6t in a three-dimensional solid.
The energy width of 12t between the bottoms of the band to the top of the
band is known as the energy bandwidth.
In this most common version of the tight-binding model, the electron
hopping is considered only within the nearest neighbor lattice sites. In the
more general version, the hopping is considered even between the next
nearest neighbor sites as well. This model works very well for Group II
and III metals, semiconductors, and insulators.
The calculation of the dispersion relation or the band structure is
computationally quite involved for a real material. To make the compu
tational part simplified yet yielding accurate results, one takes recourse to
the introduction of a quantity known as “pseudo-potential.” The pseudo-
potential, as determined by a proper choice of the electronic basis states,
approximates the actual lattice periodic potential V(r) for a real condensed
matter system; however, it ensures that the band structure obtained is
genuine and correct, particularly for the higher valence and the conduc
tion bands. This method neglects the low-lying bands of the core electrons
completely (Madelung, 1995).
From a very generalized band dispersion, as described earlier, it is
possible to introduce the concept of “effective mass” or “band mass” of
an electron. This represents the effective inertial mass of a band electron.
This is defined as the 2nd derivative of the band energy with respect to
the wave-vector, in the vicinity of a band edge, i.e., near the minimum or
the maximum of the conduction band. More precisely, the effective mass
tensor is given by:
h2
m* (1.14)
g
2
2
where,
2
g k
(1.15)
k k k0
where, k0 gives the position of the band edge in the allowed k-space and α
and β are the Cartesian components.
From the above expression, we see that the effective mass becomes
a k-dependent anisotropic function and a tensor quantity. For a simple
tight-binding model corresponding to a simple cubic crystalline solid,
however, the effective mass becomes a scalar and similar to that of a free
particle. We may call this mass as mquasi– free(mqf). This is given by (from
Eqn. (1.13)):
h2
mquasi - free = (1.16)
( 21 )
2
2ta 2
Thus, we see that mqf is inversely proportional to the hopping parameter

t. This is what is expected on the physical grounds; as larger, the hopping
parameter is, the lighter the electron would appear to be and vice versa.
This mqf is generally larger than the real free-electron bare mass even for
good metal. An interesting feature of m* corresponding to any general
dispersion is that near the upper extremity of a band, it becomes –ve. This
leads to a well-known Bragg reflection occurring near the zone boundary.
The idea of the effective mass or band mass is also very useful in some
of the semi-classical descriptions for the motion of a band carrier. A band
electron is best represented by a “Bloch wave packet,” constructed out of
a suitable superposition of the extended Bloch wave functions around a
particular wave vector. The quantum mechanical equation of motion of
such a wave packet can be cast in the form of Newton’s Second Law, by
making use of the band mass and the group velocity – to be determined
2n d E ( k )
from the band dispersion by evaluating – of the wave packet.
hdk
This interesting result is known as “Bloch’s acceleration theorem.” This
helps to understand the transport process involving the carriers in a band.
A very important function used extensively in band theory to represent
electronic states, is the “Wannier function.” This is obtained from Bloch’s
function by a mathematical transformation similar to Fourier transforma
tion, viz.
a(Rn,r) 1
exp ik Rn k,r (1.17)
N 1/ 2 k
where, Rn is the position vector of the nth atomic/ionic site in the lattice. The
Wannier function a(Rn, r) represents a wave function strongly peaked at the
nth lattice site, in contrast to the Bloch function ψ(k, r) which is completely
delocalized in coordinate space. The Wannier functions also show oscilla
tions and resemble the atomic wave functions to a very great extent; however,
their added advantage is that they form an orthonormal complete set just like
the Bloch functions. Thus for rigorous and very accurate calculations of the
band structure, the various parameters occurring in the electronic Hamilto
nians for the solid, like the tight-binding Hamiltonian, are in fact the matrix
elements to be evaluated using the corresponding Wannier functions rather
than the atomic orbital wave functions.
The various possible filling fractions of the bands also lead to an impor
tant concept viz. that of a “fictitious” but very useful particle called “hole.”
A hole in a band state k is visualized as a particle representing the absence
of an electron in the k-state. Its effective mass and charge turn out to be
exactly opposite to those of an electron. It can be shown rigorously that all
the properties of a solid based on band theory, can be described in terms
of electron or hole picture equivalently for both qualitative and quantita
tive understanding. Besides, in semiconductors, the electrical transport is
governed by the concentration and the mobility of both electrons and holes
from the conduction band and the valence band respectively. This proves
the real and physical existence of the holes in band theory.
From the ε–k dispersion relation, whether from the tight-binding model
or a general one, it is lead to the idea of a constant energy surface for the band
electrons (and holes). This surface constructed in the k space is known as the
Fermi Surface. The shapes of the Fermi surfaces vary widely from mate
rial to material. They may be closed surfaces or open surfaces. The exact
shapes of the electron or hole Fermi surfaces of a crystalline solid depends
on the detailed band structure of the material involving the magnitudes of
the various material parameters occurring in the dispersion relation and also
the valency of the parental element. For a genuine free-electron system, the
Bloch function reduces to a plane wave with uk(r) becoming a constant and
the Fermi surface is a sphere. For the monovalent alkali metals like Li, Na, K,
etc., the Fermi Surfaces are approximately spherical, justifying the validity
of nearly free electron approximation for these materials. For band electrons
(and holes) in general, however, the topology of the Fermi surfaces can be
very complicated and interesting. This is most clearly seen for some of the
heavier alkali metals, polyvalent metals, and also the transition metals. The
equation defining a Fermi surface can be written as:
∈k = Constant (1.18)
The solution to the above equation, even for a simple tight-binding

model in general, will have to be obtained numerically. The detailed
investigation would lead to the various shapes and topologies of the Fermi
surfaces, as discussed earlier. The Fermi surface corresponding to special
characteristic energy called the Fermi energy is very important for metal,
as this determines most of the electronic properties of the metal at least at
low temperatures. The Fermi energy of a metallic system is defined as the
highest energy level occupied in the conduction band at zero temperature.
For a semiconductor and insulator, however, the Fermi energy falls well
within the forbidden gap region. In fact, for an intrinsic semiconductor
like pure Si and pure Ge, the Fermi level is situated exactly at the mid gap
position. All these properties follow from the Fermi distribution function
obeyed by the non-interacting band electrons and holes (Kittel, 1953).
A related quantity is often used in condensed matter physics to under
stand various phenomena and processes of electronic origin is the “elec
tronic density of states (EDOS).” It is defined as the number of band states
within an energy interval of ε to ε + dε. More precisely, mathematically it
is defined as:
N( ) k (1.19)
k
In particular, the density of states (DOS) evaluated at the Fermi energy

of a metal, characterized by N(0), is a very important parameter occur
ring in the expressions for various electronic properties of a solid, as we
will see later. Within a free electron-like approximation (corresponding
to jellium model which is a simplification of the lattice structure to a
continuous jelly and is a fairly good approximation for the alkali metals),
for a three-dimensional system N(0) can be shown to be proportional to m*.
1
In general for a 3d lattice under this approximation, N(ε) goes as ∈2
.
For a 1-dimensional lattice, the jellium model approximation gives N(ε)
proportional to -
1
and for a two-dimensional system it is a constant.
E2
Again in general for an electronic band, N(ε) can be quite a complicated
function of s depending upon the band dispersion. Moreover, in such a
case, N(ε) will have to be evaluated numerically. For a nearest-neighbor
tight-binding model, however, it is possible to obtain an exact analytical
form for N(ε) in 1d and 2d. They deviate quite strongly from those obtained
with the free-electron model. In particular, for a 2d square lattice with
symmetric nearest-neighbor hopping along with the ‘a’ and ‘b’ directions,
the DOS takes the form of an elliptic integral and exhibits a singularity at
some special value of ε. Inclusion of the hopping contributions for higher
neighbors leads to more complicated expressions. This has tremendous
consequences for various condensed matter phenomena particularly at low
temperatures (Roy Chowdhury and Chaudhury, 2016, 2018).
So far, we have confined our discussions only to a perfectly crystalline
solid. In reality, there are always random impurities and defects present
in a lattice. This causes the translational invariance of the electron-lattice
potential V (r) to be broken inside the solid. Thus, this amounts to a viola
tion of Bloch’s theorem. Moreover, a finite-sized solid also suffers from
the discontinuity of the potential V (r) at the boundary, leading to the emer
gence of new eigenstates different from the Bloch states. All these spatial
disorders related effects give rise to the existence of a number of stable
electronic states even within the forbidden region or the bandgap region of
the usual band theory corresponding to the ideal lattice. This aspect will be
taken up in greater detail in Chapter 4 in the section on “Surface States.”
The understanding of the effect of Coulomb interactions between
electrons is extremely important in the conduction band to explain various
properties of solids observed experimentally. This is however quite non-
trivial in terms of theoretical treatment. Before we come to this, let us
have a look at the interacting electron gas problem. It is well known from
the perturbative treatment of high-density electron gas that the Coulomb
interaction amongst electrons essentially leads to Fermi-liquid theory
where the basic properties of free electron gas remain intact with electron
mass scaled from m to m*. With the band electrons, this analysis becomes
much more complex.
We introduce and devote some clarifying discussions on some of the
concepts like Hartree-Fock, correlation energy involving perturbation
treatment in high density and metallic density electron gas, Wigner solid
(WS) formation in low-density electron gas and its melting, etc., taking
care of many-body effects in electron gas and in band structure calcula
tions; Fermi liquid theory, Tomonaga-Luttinger liquid (TLL) theory;
DFT with Kohn-Sham approach for exchange-correlation contributions;
Karr-Perinnello scheme for the electron-ion system; topological insula
tors (with bulk insulating and surface metallic), graphene, carbon nano
tubes, tunneling in the topological insulator-superconductor junction
(involving a junction of the topological insulator and a superconductor
in two-dimensions with the emergence of so-called “Majorana fermions”
in Chapter 4 in some details (Pines, 1999; Mahan, 1981; Atland and
Simons, 2006).
1.3 EXPERIMENTAL VERIFICATION OF BAND THEORY AND

DETERMINATION OF FERMI SURFACE
The experimental determination of the shapes of the Fermi surfaces is most

commonly done by making use of the De Haas-van Alphen effect, arising
from the diamagnetic response of the band carriers (electrons or holes). This
method involves tracking the motion of band electrons (or holes) in a static
uniform magnetic field. As an electron (or hole) experiences the Lorentz
force qvXB, its motion always takes place on a surface of constant energy.
Thus by this method, one can scan the Fermi surface easily. The detailed
discussion regarding the De Haas-van Alphen effect will be carried out in
the section on “magnetism.” For the time being, it is sufficient to say that in
this effect, the diamagnetic susceptibility of the band electrons (or holes) in
the high magnetic field and at low temperature, shows an oscillation with
reciprocal of the magnetic field. The origin of such oscillation lies in the
progressive shifting of the Fermi energy level as well as the alternate popu
lating and de-populating of the discrete energy levels (known as Landau
levels and generated by the external magnetic field) by the electrons/holes,
as the magnetic field increases. The period of this oscillation depends upon
the shape and other parameters of the Fermi surface.
Another phenomenon closely related to De Haas-van Alphen effect is
that of “cyclotron resonance.” The carriers in the band, when subjected
simultaneously to a static uniform magnetic field and also to an electro
magnetic (e.m.) field, exhibits a resonance absorption of the electromag
netic energy at a particular frequency of the e.m. wave. This frequency is
known as the cyclotron frequency. The cyclotron frequency turns out to

be inversely proportional to the effective mass (m*) of the band carrier.
Thus from the measurement of cyclotron frequency, one can determine m*.
This in turn provides valuable information about the dispersion relation of
the energy bands. The detailed discussions regarding this will be carried
out in Chapter 3, dealing with the interaction between the electron and
electromagnetic waves.
Besides the above two experimental techniques, “photoemission
spectroscopy” along with a more powerful angle-resolved photo-emission
spectroscopy and spin-resolved photo-emission spectroscopy, are also
used to determine the detailed shape and nature of the Fermi surface
with spin correlations present, in various materials. It can also in general
provide information regarding the energy dispersion of various bands. The
absorption spectroscopies of different kinds also prove the experimental
existence of the electronic energy bands with the band gaps (Kittel, 1953;
Madelung, 1995).
The effects of a uniform static magnetic field on the transport proper
ties of band carriers in a metal or semiconductor can be quite diverse!
Two notable phenomena related to this are: (i) magneto-resistance and (ii)
quantum Hall effect (QHE). The magneto-resistance in a paramagnetic
metal is primarily due to the loss of the conduction electrons participating
in the drift current, due to the Lorentz force exerted by the magnetic field
on these electrons. Thus in an experiment involving a combination of a dc
electric field and a magnetic field along the perpendicular direction, the
current along the direction of the electric field decreases with the increase
in the strength of the magnetic field. This tantamounts to an electrical
resistance induced by the applied magnetic field and are known as the
magneto-resistance. Moreover, the accumulation of the deflected electrons
leads to the formation of a potential difference, known as the Hall voltage,
along a direction perpendicular to both the direction of the electric field
and that of the magnetic field.
The other related effects are Hall effect, both classical and quantum. In
the classical Hall effect seen in a three-dimensional conductor (metal or
semiconductor), the sign of Hall voltage developed is an indicator of the
nature of the charge carriers viz. electron or hole. This is due to the fact
that the Lorentz force is the same for both these two types of carriers when
contributing to the current and as a result, the Hall voltage developed
between the two electrodes placed will be of opposite sign for these two
types of carriers. While in a metal, the charge carrier is always an electron,

in a semiconductor it can be either an electron or a hole. Moreover, the
Hall coefficient (derived from the ratio of Hall voltage to Hall current)
gives the carrier concentration also.
In QHE, seen in a conductor of highly two-dimensional geometry, the
transverse Hall conductance (defined as the ratio of usual transport current
to Hall voltage) plotted as a function of the magnetic field shows a series of
plateau. Because of this plateau structure, Hall’s conductance is quantized
in units (integer or fraction) of the fundamental conductance

( e ) 2n .
2
h
This is a purely quantum-mechanical effect originating from the existence
of discrete electronic energy levels viz. Landau levels and also from the
presence of disorder and sometimes even many body effects. The experi
mental discovery of integer QHE (integer multiple of the fundamental
conductance) was made by Alexander Von Klitzing at IBM (Zurich) and
was awarded Nobel Prize in 1985 for this. The experimental system was
a highly pure two-dimensional electron gas confined in a hetero-junction
involving GaAs –GaAlAs with parts per million (ppm) level of impurity
concentration. Theoretical understanding of these phenomena has been
quite successful (Pruisken, 1987; Laughlin, 1981; Jain, 1989).
In recent times, there has also been a lot of interest in a phenomenon
known as the “spin Hall effect.” This is related to the generation of spin
current in the presence of an applied electric field (or electric current) in
some of the materials which exhibit strong spin-orbit coupling of the form
of Dzyaloshinskii-Moriya (DM) interaction (Dyakonov and Perel, 1971;
Sinova et al., 2015) (Figure 1.1).
FIGURE 1.1 The spin Hall effect. An electrical current induces spin accumulation at the
lateral boundaries of a sample.
Source: Reprinted with permission from Dyakonov (2009, 2012).
1.4 VARIOUS NOVEL PHENOMENA ASSOCIATED WITH FERMI

SURFACE
There are several other important phenomena and effects associated with
the Fermi surface. Some of these are: Pauli paramagnetism, Stoner para
magnetism, spins density wave, charge density wave (CDW), and super
conductivity. Since all these phenomena occur or originate in metals, here
the Fermi surface with energy equal to the Fermi energy is only relevant.
The phenomenon of Pauli paramagnetism is a temperature-independent
paramagnetic susceptibility exhibited by metals at low temperature. The
magnitude of the spin susceptibility is proportional to the carrier density
of states at the Fermi energy (N(0)). Stoner paramagnetism is an enhanced
form of Pauli paramagnetism, the enhancement arising from the presence of
the many-body, i.e., Coulomb interaction between the electrons. An elabo
rate analysis of both Pauli and Stoner paramagnetism will be presented in
Chapter 2 dealing exclusively with magnetism. Many of these phenomena
can be discussed qualitatively and sometimes semi-quantitatively even
within the jellium model approximation, without taking recourse to the
detailed band structure.
The SDW occurs when a metal because of “many-body effects” arising
predominantly from Coulomb interactions amongst the band electrons,
develops an energy gap at the Fermi surface. The metal becomes a semi-
conductor and instead of Pauli or Stoner paramagnetism, one observes a
magnetically ordered state with an oscillatory spatial distribution of magnetic
moments. Sometimes the SDW may occur also because of competition
between different possible magnetic orderings involving the band electrons/
carriers, due to the complexities of interactions at the Fermi surface. In an
analogous way, the CDW also develops in a metal undergoing a transition
to a semiconductor, due to the energy gap developing at the Fermi surface
from electron-lattice interaction. It should be remarked however that the
occurrences of both the SDW and the CDW need the Fermi surface to
possess certain symmetry known as “nesting.” This is found to be satisfied
generally in the low-dimensional metals. The detailed analysis of these two
phenomena can be found in Chapter 2 and Chapter 3, respectively.
In comparison with the phenomena described above, the phenomenon of
superconductivity is a very different one. Although originating from insta
bility at the metallic Fermi surface leading to the formation of an energy gap,
the DC electrical resistivity vanishes completely when the metal is cooled
below a certain temperature. It should be emphasized here that the nature

of the energy gap developed here is drastically different from that seen in a
semiconductor. The energy gap in a superconductor arises from an effective
electron-electron (carrier-carrier) attraction brought about generally by the
electron-lattice interaction in a metal. As a result, two electrons near the
Fermi surface pair up to form an apparent bound state, and the normal metal
goes over to a superconductor. This pair of electrons known as a Cooper
pair moves as a whole coherently in the superconducting phase. Thus, this
transport process avoids Ohmic dissipation and the system exhibits an
infinite d c electrical conductivity. The temperature, at which the transition
from a normal metal to a superconductor takes place, depends upon the
range and the strength of the attractive interaction between the electrons
as well as on N(0). The detailed analysis of the origin and the properties of
superconductors will be dealt with in Chapters 3 and 5.
Very recently there have been a lot of experimental and theoretical
activities related to a certain new type of ferromagnetic materials known
as “Heusler alloys, discovered in 1903 by Heusler (Webster, 1969). In
many of these materials, amongst the band carriers, the majority spin sub-
band has a finite EDOS at the Fermi energy and hence exhibits a metallic
character; whereas the minority spin sub-band develops an energy gap
in the electronic excitation spectrum at the Fermi level, displaying an
insulator-like behavior. Therefore, they are also known as “half-metals,”
like for example NiMnSb. As a consequence, both the magnetic and trans
port properties of half-metals are very unusual and fascinating. The most
notable aspect of the Heusler alloys is that these alloys mostly ternary,
are ferromagnetic whereas the primary components of these alloys are
non-magnetic, like for example Cu2MnAl. These would be taken up again
in Chapter 2. The newly emerging applied field of “spintronics” makes
quite heavy use of such half-metallic behavior. An allied phenomenon is
known as tunneling magneto-resistance (TMR) which shows the existence
of very different magnitudes of electrical resistance for inter-layer charge
transport corresponding to the parallel and anti-parallel spin relative orien
tations for the carriers in the two layers is an active field of research for the
experimentalists and technologists.
Before concluding this chapter, it may be worthwhile to draw attention
to two more closely related issues viz. that of (i) heavy fermion metals and
superconductors and (ii) strongly correlated electronic systems, which are
exotic systems.
In the heavy-fermion materials, the effective mass of the conduction

electrons is found to be gigantic. The ratio of the observed m* to the usual
band mass sometimes exceeds even 1000. As a result, the Fermi energy is
very low and the EDOS at the Fermi surface is very high compared to the
usual metals. These systems also show a unique crossover from localized
magnetism (arising from the localized atomic-like electrons) to itinerant
magnetism (due to the truly de-localized band electrons) as temperature
goes down and at very low temperature; some of them even become super
conductors. Moreover, some amongst the non-superconducting metals
also exhibit enhanced paramagnetism of Stoner type. In these systems,
which are Lanthanides and Actinides and are made up of rare earth and
transition metal elements, the detailed analysis shows a very high degree
of hybridization between the s or d energy bands from the transition metals
and the f atomic state s of the rare earth elements. The many body effects
viz. the direct Coulomb interaction as well as that mediated through the
lattice, between these electrons, also play quite important roles in the
properties of these systems. In particular, the mechanism and the nature of
superconductivity in these materials are still not understood completely.
We will have a more elaborate discussion on these aspects in Chapter 2.
The strongly correlated electronic systems are those systems where
the conventional band theory breaks down. The transition metal oxides
and the cuprates exhibiting high-temperature superconductivity belong
to this class of systems. In these materials, the one-electron treatment
based band theory fails. This is because the strong Coulomb interaction
matrix element involving two electrons with opposite spins belonging
to the same lattice site, known as Mott-Hubbard repulsion, is much
larger than the single electron hopping matrix element connecting two
nearest-neighbor sites. This makes the electronic conduction energeti
cally unfavorable. As a consequence, a transition metal oxide like NiO
having 1 electron per site (equivalent to a half-filled band in normal
band theory), turns out to be an insulator rather than a metal. Again the
underdoped rare earth-based cuprates like La2–xSrxCuO4 for x below 0.1,
behave as very unconventional strongly correlated metals (conductors),
exhibiting properties not expected from standard band theory with minor
corrections from weak inter-electron interactions. These anomalous
conducting systems are derived from the parental systems like CuO
which are insulators (for reasons similar to those corresponding to NiO
and probably also due to some other many-body processes), by the
creation of vacancies and thereby facilitating some amount of electronic

conduction. In these unconventional conductors, however, even the
Fermi surfaces are not well defined sometimes. As a result, the known
phenomenological models describing the conventional metals cannot be
applied here. Consequently, the theory of superconductivity for these
materials is very complex. This is analogs to Wigner Crystal and its
melting, as discussed in the context of the jellium model. We will take
up some of these issues in Chapters 4 and 5.
Lastly, even the characterization of the materials on the basis of
electrical polarization properties need not be dependent on the behavior
of the ionic components only. The processes which are responsible
for the formation of CDWs and SDWs, may also lead to ferro or anti-
ferroelectricity of electronic origin (Ginzburg and Kirzhnits, 1982). The
detailed theory often involves a scenario of two electronic energy bands
with different levels of filling corresponding to a semi-conductor or
semi-metal. In this context, it is also interesting to comment that quite
recently another new class of materials known as “bi-ferroics” have been
prepared in laboratory (Manfred and Lei). They are mostly insulating
however, some of them can be of metallic character as well. They exhibit
coexistence or a crossover between ferromagnetic and ferroelectric
phases. More generalized systems known as “multi-ferroics” have also
been synthesized (Khomskii, 2004, 2006; Cheong and Mostovoy, 2007;
Ray and Waghmare, 2008). They display very rich interplay involving
magnetism, ferro (or antiferro)-electricity, and ferro-elasticity via
Piezo-electric effect and magnetostriction. These features can occur on
both microscopic as well as macroscopic scales. Again, the spin-orbit
coupling in the form of DM interaction or Rashba coupling plays a very
important role in the origin of the complex combined spin and charge
responses of these classes of systems. Some of these materials with
layered structures and with very high spin polarization of the conduc
tion electrons, like Manganite-Titanate composites, can also find a lot
of promising technological applications in various novel devices based
on “spintronics” and “spin valve” (Dorr and Thiele, 2006). The field of
spintronics deals with spin transport electronics as opposed to charge
transport in various solid-state devices (Yuassa et al., 2004; Parkin et al.,
2004). In particular, this involves exotic phenomena such as TMR and
GMR (Giant magneto-resistance) which are found to occur in sandwich
structures comprising of alternate ferromagnetic and non-magnetic
metal layers in experiments. The above effects have turned out to be very
useful for applications in the memory devices. Besides, another general
class of ‘novel’ or ‘smart’ materials called “shape memory alloys”
(ordinary or magnetic) have gained considerable interest amongst the
condensed matter physicists and technologists. These systems display
the memory effects related to the physical shape or magnetization with
the application and withdrawal of mechanical stress or magnetic field
under the thermal cooling and heating cycle. The understanding of these
phenomena requires a detailed analysis of lattice structure with defects
or distortions, the magnetic domains, and coupling between the two as
well. An example of such material is Ni2MnGa (Wayman, 2013).
Finally, the recent experimental and technological advances in
the areas of nano and mesoscopic sciences with the development and
investigation of single-walled carbon nanotube (SWCNT), graphene, and
quantum dots have contributed a lot in enriching the fields of materials
sciences as well as condensed matter physics, particularly in the areas of
theory and computation of electronic structures. The graphene sheet is a
single layer of graphite, which possesses a narrow band of π-orbital states.
This can be modeled by a tight-binding Hamiltonian (TBH) of electronic
band theory as a first approximation. A striking feature of the resulting
electronic structure is that the half-filled system is characterized by a point
like the Fermi surface. Furthermore, when slightly doped to move away
from the half-filling, the system exhibits two Dirac-like electron spectra
with a linear ε–k dispersion. The major practical utility of graphene lies
in the fact that it is a very light, i.e., low-density material although very
strong (Greim and Kim, 2008; Atland and Simons, 2006). A SWCNT
is a one-dimensional structure involving a graphene sheet rolled into a
cylinder. Again, electronic structure calculations based on TBH show
the presence of two nodal points in SWCNT and the electronic spectrum
shows approximately linear dispersion in the vicinity of one of these nodal
points (Atland and Simons, 2006). Technological advancements have
enabled the manufacturing of mesoscopic devices (of sizes of the order
of 10–4 centimeter) of metallic or semi-conducting character. A quantum
dot is one such device. Charging of a quantum dot is a very interesting
process which exhibits vanishing of EDOS at the Fermi surface due to the
Coulomb Blockade effect, arising from inter-electron interaction. This
has a tremendous application towards the tunneling characteristics for a
2D electron gas formed at the interface between GaAs and AlGaAs layers,
behaving as a quantum dot. Again, the realistic systems belonging to the

above class all contain spatial disorder weak or strong, and further are
non-self-averaging due to the mesoscopic sizes. These aspects are mani
fested in various novel phenomena like Anderson’s localization, different
types of anomalous transport behavior involving zero-bias anomalies,
both cooperon and diffusion contributions to charge current, etc., (Efetov
et al., 1982; Kamenev, 2004; Edwards and Anderson, 1975; Altshuler et
al., 1982). In many of these systems, the combined effect of disorder and
many-body interactions produce unexpected outcomes and both perturba
tive, as well as non-perturbative treatments, become essential for the clear
understanding (Altshuler et al., 1982). A quantum mechanical equation
for charge transport in mesoscopic systems was originally developed by
Landauer and Buttiker, although it had several limitations like the neglect
of dissipation at the junctions or leads (Leonhard, 2010). A statistical
mechanical treatment leading to Kubo-like formula for linear response,
in this case, was derived later with the help of Keldysh Green functions
and with the inclusion of dissipation (Das, 2010). Some of these issues
will be taken up briefly in Chapter 4 again.
All these are glaring examples of the confluence of material science,
technology, and condensed matter physics with involvement and applica
tion of both band theory, many-body physics, and statistical mechanics.
KEYWORDS
• density of states
• electronic density of states
• giant magneto-resistance
• quantum hall effect
• single-walled carbon nanotube
• tunneling magneto-resistance
REFERENCES
Altshuler, B. L., Aronov, A. G., Khmelnitskii, D. E., & Larkin, A. I., (1982). Chapter 3. In:
I. Lifshits, M., (ed.), Quantum Theory of Solids. MIR Publishers, Moscow.
Ashcroft, N. W., & Mermin, N. D., (2017). Solid State Physics. Brooks/Cengage Learning
India.
Atland, A., & Simons, B., (2006). Condensed Matter Field Theory. Cambridge University
Press, Cambridge.
Capra, F., (1982). The Tao of Physics. Flamingo (Harper Collins Publishers), London,
Chapter 11.
Casper, F., Graf, T., Chadov, S., Balke, B., & Felser C., (2012). Semiconductor Science and
Technology, 27, 6.
Chaudhury, R., & Jha, S. S., (1984). Pramana Journal of Physics 22(5), 431.
Chaudhury, R. (2009). Cond-mat arXiv.
Cheong, S. W., & Mostovoy, M., (2007). Nature Materials, 6, 13.
Das, M. P., & Green, F., (2003). arXiv: Cond-mat/0304573.
Das, M. P., (2010). IOP Science. iop.org/article/10.1088/2043-6262/1/4/043001/.
Dorr, K., & Thiele, C., (2006). https://doi.org/10.1002/pssb.200562441.
Dyakonov, M. I., &Perel, V. I., (1971). Sov. Phys. JETP Lett., 13, 467; Phys. Lett. A., 35(6),
459 (1971).
Dyakonov, M. I., (2009). arXiv: 1210.3200 [cond-mat.mes-hall] (2012) (Vols. 2–5, p.
656). Google Scholar.
Economou, E. N., (1990). Green’s Functions in Quantum Physics. Springer Verlag,
Heidelberg.
Edwards, S. F., & Anderson, P. W., (1975). J. Phys. F5.
Efetov K. B., et al., (1982). Sov. Phys. JETP, 55, 514.
Geim, A., K., & Kim, P., (2008). Scientific American, 298(4), 90.
Ginzburg, V. L., & Kirzhnits, D. A., (1982). High Temperature Superconductivity. New
York Consultants Bureau, New York.
Jain, J. K., (1989). Phys. Rev. Lett., 63, 199.
Kamenev, (2004). Cond-Mat/0412296.
Khomskii, D. I., (2006). Journal of Magnetism and Magnetic Materials-2004. https://
arXiv.org/pdf/Condmat/0601696 (accessed on 7 July 2020).
Kittel, C., (1953). Introduction to Solid State Physics. Wiley, New York.
Laughlin, R. B., (1981). Phys. Rev. B, 23, 5632.
Leonhard, N., (2010). Conductance Quantization and Landauer Formula, SS.
Madelung, O., (1995). Introduction to Solid State Theory. Springer, Heidelberg.
Mahan, G. D., (1981). Quantum Theory of Many-Particle Systems. Plenum Press.
Manfred, W., & Lei, Z. Cobaltferrite-Bariumtitanate Sol-Gel Biferroics. Digital Repository
at University of Maryland.
Pines, D., (1999). Elementary Excitations in Solids. Advanced books classics, Perseus
Books Publishing, Massachusetts.
Pruisken, A. M. M., (1987). Field theory, scaling, and the localization problem. In: Prange,
R. E., & Girvin, S. M., (eds.), The Quantum Hall Effect. Springer-Verlag.
Ray, N., & Waghmare, U. V., (2008). Phys. Rev. B., 77, 134112.
Sinova, J., Valenzuela, S. O., Wunderlich, J., Back, C. H., & Jungwirth, T., (2015). Rev.
Mod. Phys., 87, 1213.
Wayman, C. M., (2013). MRS Bulletin. doi.org/10.1557/S0883769400037350.
Webster, P. J., (1969). Contemporary Physics, 10(6), 559.
Yamada, K., (2004). Electron Correlation in Metals. Cambridge University Press,
Cambridge.
CHAPTER 2
Magnetism
2.1 INTRODUCTION
The phenomenon of “magnetism” is one of the oldest phenomena discovered

in the field of condensed matter physics. Besides the discovery of magnetic
stone (loadstone) by Magnes (2000 BC) and Gilbert (17th Century), it was
also known since long back that the earth itself also acts as a magnet. The
discovery of magnetic materials, more precisely ferromagnetic materials
such as Fe, Ni, Co, etc., has contributed a lot to the progress of material
science and technology. Besides the application aspects, the study of the
phenomenon of magnetism has also enriched the basic sciences. To start with,
the so-called “microscopic theory” for paramagnetism was attempted by the
classical electromagnetic theory involving the magnetic dipoles representing
the moments. The randomly oriented dipoles at a high temperature tend to
get oriented by the application of an external magnetic field and thereby
produce an induced magnetization. Langevin was the proponent of this idea.
However, very soon this theory ran into problems. Later with the development
of quantum ideas, there was an attempt to introduce “spins” to represent the
moments by Brillouin. This was fairly successful. The theoretical prediction
of the functional dependence of the induced magnetization with the applied
magnetic field and temperature was found to be in quite good agreement with
the experimental observations for various paramagnets.
After the successful treatment of the ordinary paramagnets, the efforts
began for the understanding of the transition from a paramagnet to a ferro
magnet, seen in a large class of materials. It was realized very soon that
the interaction between the magnetic moments plays a crucial role in this
case. Thus, initially, the classical electromagnetic interaction between the
magnetic dipoles was included in the model. However, the calculated transi
tion temperature turned out to be very small, viz. of the order of 4 degrees
Kelvin. This is below the experimental values seen in most of the well-known
systems. Furthermore, this model did not even ensure a parallel alignment of
the moments always. Therefore, it was concluded that this classical dipole
based model is not adequate to account for the ferromagnetic transition.
Later it was shown mathematically by Van-Leeween from the considerations
of equilibrium statistical mechanics that no form of magnetism, including
diamagnetism, can be accounted for in a macroscopic system, by a truly
microscopic theory within the purview of classical physics (White, 2007).
Werner Heisenberg with Paul M. Dirac, two of the founders of Quantum
Mechanics, independently proposed in 1926 an alternative and purely
quantum model for ferromagnetism, based on the electrostatic interaction
between the electrons belonging to the atoms in a solid and the symmetry of
the wave-function corresponding to these electronic systems. This model,
known as the Heisenberg model, was somewhat along the lines of the
theory for the formation of H2 molecule by the Heitler-London approach.
The Heisenberg model has been used to explain the origin of ferromagne
tism in insulators. Later when the phenomenon of antiferromagnetism was
discovered, the true quantum nature of magnetism was manifested more
clearly. Subsequently, different quantum models were suggested corre
sponding to various types of magnetism observed in different materials.
These models have been more or less successful both from the theorists’
as well as experimentalists’ viewpoints. Furthermore, these models are
derived from very basic condensed matter physics Hamiltonians.
The plan of this chapter is as follows: In the first section, to start with
we state and prove Van-Leewen’s theorem. Then we discuss diamagnetism.
In the second section, we present a theory for magnetism in insulators and
semiconductors. We cover different types of magnetism viz. paramagnetism,
ferromagnetism, antiferromagnetism, ferrimagnetism, etc. Then in the next
section, we turn to itinerant magnetism, i.e., the magnetism of metals and
metallic alloys. Here again, we attempt different types of observed viz.
paramagnetism, ferromagnetism, antiferromagnetism, spin density wave
(SDW), etc. In the fourth section, we present discussions for the magnetism
of exotic types and in novel materials. This includes spin glass, magnetic
superconductor, heavy fermion superconductor, doped cuprates, manganites,
etc., in some of which one sees a cross over between localized magnetism
and itinerant magnetism and also the interplay between magnetism and
superconductivity. Moreover, in many of the above systems, both spin and
orbital degrees of freedom contribute to magnetism in a very non-trivial
way. We also touch upon the exciting problem of magnetism in the low
Magnetism 27
dimensional systems, which are of paramount importance in both basic and

applied sciences. In the final section, i.e., the fifth section we briefly discuss
various experimental techniques used in the studies of magnetism. This
covers neutron diffraction, inelastic neutron scattering, nuclear magnetic
resonance (NMR), electron spin resonance (ESR), etc.
2.2 ORIGIN OF THE THEORY FOR MAGNETISM AND ANALYSIS

OF DIAMAGNETISM
We start out with the theorem showing the impossibility of the occurrence
of any form of magnetism in the classical theory. As stated before, this is
Van-Leewen’s theorem. The proof goes as follows: the truly microscopic
theory involving elementary particles with electrical charges similar to
those of electrons, is considered classically. The partition function for a
thermodynamic system of such free particles is given by:
z π i dpi dq i exp pi2

2m i
(2.1)
where, pi and qi are the momenta and the position vectors of these particles.
In the presence of an external vector potential A, however, the momenta
( eA )
get transformed to Pi - . Let us denote these transformed momenta
c
by pi' and the partition function in the presence of this external potential
as Z'. Then making use of Eqn. (2.1), one can easily see that Z' is iden
tical to Z. Therefore, in the classical theory, the free energy of a system
remains invariant when an external electromagnetic field is applied.
Again, magnetization induced is proportional to the derivative of the
free energy with respect to the external magnetic field. Thus, our simple
calculation presented above shows that no magnetization is induced in
a classical system even in the presence of an external magnetic field, in
thermodynamic equilibrium.
The above analysis clearly implies that magnetism of materials, as observed,
will have to be essentially a quantum phenomenon. Therefore, we will have
to deal explicitly with the quantum mechanical Hamiltonians for describing
all types of magnetism. To clarify this point, for example, even though the
phenomenon of diamagnetism is a universal one and is based on the property

of classical electromagnetic induction, the finite diamagnetic response is only
obtainable in a fully quantum mechanical treatment of the material system
which is coupled to the electromagnetic field. For the other forms of magne
tism, however, the microscopic origin itself is quantum mechanical besides
the necessity of using quantum variables in the Hamiltonian.
The phenomenon of diamagnetism or more precisely, orbital diamag
netism is a universal one, as stated before. Every system in this universe
exhibits diamagnetic response, i.e., negative magnetic susceptibility. Its
magnitude, i.e., the absolute magnitude of the diamagnetic susceptibility,
however, is generally quite small and is very often masked by the higher
magnitude of the spin response (positive magnetic susceptibility) from the
other forms of magnetism like paramagnetism. The only exceptions are
superconductors and some of the band insulators. These above-mentioned
systems behave as “super-diamagnets,” where the diamagnetic suscepti
-1
bility attains the highest value possible viz. . Moreover, these systems
4n
have vanishingly small spin susceptibilities. As a result, the overall
magnetic response of these systems is very prominently diamagnetic.
The origin of orbital diamagnetism is electromagnetic induction, as
has been pointed out before. The applied magnetic field is opposed by the
induced orbital screening current, governed by Faraday’s Law or Lenz’s
Law. The simplest quantum mechanical model incorporating this effect
was suggested by Landau among many others. The model essentially
describes a collection of non-interacting electrons in the presence of an
external electromagnetic field. It should be emphasized that the system of
electrons is treated quantum mechanically but the electromagnetic (e.m.)
field is regarded as classical. The Hamiltonian of such a system is given
by, as used earlier in Eqn. (2.1):
eA )
2
1 (
H= 2
2m i
pi -
c
(2.2)
h
Here, the variable pi is an operator denoted by -i \ . A is the e.m.
2n
vector potential experienced by the electrons. Simplifying the expression
above, one can show that the term proportional to A2 leads to the orbital
Magnetism 29
diamagnetism. It should also be pointed out that the term proportional to

operator pi corresponds to the orbital paramagnetism and this issue will be
taken up later in the next section. For electrons in an atom, the diamagnetic
susceptibility calculated using the term proportional to A2, can be shown
to be proportional to the square of the average radius of the electronic
orbital. The absolute magnitude of this susceptibility per unit volume is
found to be extremely tiny viz. of the order of 10–6 in CGS units. Again,
this diamagnetism generating a term occurring in Eqn. (2.2), can be recast
in a very standard form as given below:
1
H coupl j(r) A(r,t)dr (2.3)
c
where, the left-hand side represents the e.m. coupling between the elec
tronic system and the external vector potential field and j(r) is the orbital
current density operator (for simplicity we have dropped the hat symbol
on the operator). This form is the most common and widely used form
of the perturbation term for calculating the electromagnetic response in a
condensed matter system. This term can then be treated in linear response
theory to extract the diamagnetic response function or the diamagnetic
susceptibility for various condensed matter systems. For this, only the
diamagnetic contribution to the orbital current density operator will have
to be used.
The operator corresponding to this is given as:
N
e2
Jdia ( r) A(r) π i dri (ri r) (2.4)
i 1 mc
where, ψ(r1, rN ) is the field operator corresponding to the system. The

detailed treatment brings out the role of the excitation spectrum of the
condensed matter system. It can be shown explicitly that for systems
possessing an energy gap between the ground state and the lowest excited
state, like superconductors and some of the insulators/semiconductors,
the absolute magnitude of the diamagnetic susceptibility per unit volume,
-1
reaches the maximum possible value viz. . in the CGS units, as stated
4n
before. Moreover, the orbital and the spin paramagnetic susceptibility can
be shown to be vanishingly small for them, as we will discuss later. Thus,

they are the giant or super-diamagnets. The normal metallic systems,
possessing well-defined Fermi surfaces and having gapless excitations,
are however moderate diamagnets. Moreover, they also have finite spin
susceptibility, as will be shown in later sections.
In the previous chapter, we have discussed briefly de-Hass-van Alphen
effect and quantum hall effect (QHE). Both of these phenomena arise from
the diamagnetic response. In addition, the spatial dimensionality of the
system also plays an important role.
2.3 MAGNETISM IN INSULATORS
The magnetism in insulators owes its origin to the magnetism in the

constituent atoms. A magnetic solid must have atoms or ions with the
net magnetic moment, i.e., with an unfilled electronic shell having a net
non-zero ml (azimuthal quantum number) or ms (spin quantum number).
In other words, the solid must have paramagnetic atoms or ions. The
existence or non-existence of the net moment on the atoms is essentially
governed by the celebrated Hund’s Rule of atomic physics. Of course,
the situation is much more complicated in a solid compared to that in an
isolated atom, as the electrons belonging to an atom experience the elec
trostatic fields from the nuclei and the electrons from other atoms. To be
more precise, even the electrons which are essentially localized within the
atoms in a solid, experience the so-called “crystal field.” These changes
the electronic energy diagram from that expected in an individual atom.
Therefore, Hund’s Rule will have to be applied on this modified energy
level diagram to ascertain whether the condensed matter system will
have magnetic atoms or not. The next question is whether the magnetic
atoms are interacting among themselves or they are non-interacting. If
they are non-interacting, the system exhibits paramagnetism, i.e., the
absence of any spontaneous magnetization in the system. If they are
interacting, however, then they may order magnetically below a certain
temperature. The ordering can be of various patterns like ferromagnetic,
antiferromagnetic, or little uncommon like ferrimagnetic, spin glass, etc.
Nevertheless, all of these different phases show the appearance of an
average non-zero moment per atomic site in the absence of any external
magnetic field. The type of the magnetic order occurring will depend
Other documents randomly have
different content
BOOK IV
BOOK IV
Charles leaves Saxony—Pursues the Czar—Advances into Ukrania
—His losses and wounds, and the battle of Pultowa—The
consequences of the battle—Charles forced to escape into
Turkey—His reception in Bessarabia.
AT last Charles left Saxony in September 1707, with an army of

43,000 men, formerly steel-clad, but now shining resplendent in gold
and silver, and enriched with the spoils of Poland and Saxony. Every
soldier had with him fifty crowns ready money; not only, too, were all
the regiments complete, but there were several supernumeraries to
each company. Besides this army Count Levenhaupt, one of his best
generals, was waiting for him in Poland with 20,000 men; he had,
too, another army of 15,000 in Finland, and recruits were on their
way from Sweden. With all these forces it was not doubted that he
would dethrone the Czar.
The Emperor was then in Russia, trying to keep up the spirits of a
party which King Augustus seemed to have deserted. His troops,
divided into several corps, fled in all directions on the first report of
the approach of the King of Sweden. He had advised his generals
never to wait for the arrival of the conqueror with a superior force,
and he was well obeyed.
The King of Sweden, in the midst of his march, received an
embassy from the Turks. The ambassador was received in Piper’s
quarters; he kept up his master’s dignity by a certain display of
magnificence, and the King, who was worse lodged, worse served,
and more plainly clad than the humblest officer in his army, would
often say that Count Piper’s quarters were his palace. The Turkish
ambassador presented Charles with 100 Swedish soldiers, who had
been taken by the Calmouks and sold in Turkey, redeemed by the
Grand Master, and sent by him to the King as the most agreeable
present he could make him. Not that the proud Ottoman meant to
pay homage to the glory of Charles, but because the Sultan, the
natural enemy of the Emperors of Russia and Germany, wished to
strengthen himself against them by the friendship of the King of
Sweden and alliance with Poland.
The ambassador complimented Stanislas on his accession; so
that he had been owned as King, in a short time, by Germany,
France, England, Spain and Turkey. But the Pope deferred
acknowledging him till time had confirmed him in a kingship of which
a sudden fall might deprive him.
Scarcely had Charles interviewed the ambassador of the
Ottoman Porte than he went in search of the Russians. The Czar’s
troops had left and returned to Poland more than twenty times during
the war; as the country lay open on all sides, without strongholds to
cut the retreat of an enemy, the Russians were often able to return to
the very spot where they had suffered defeat, and could even
penetrate as far into the country as the conqueror. During Charles’s
stay in Saxony, the Czar had advanced to Leopold, on the southern
frontier of Poland. He was at that time in the north, at Grodno, in
Lithuania, about 100 leagues from Leopold.
Charles left Stanislas in Poland with about 1,000 Swedes and his
new subjects to help him preserve his kingdom against his enemies
at home and abroad; he himself, at the head of his horse, marched
through ice and snow to Grodno, in January 1708. He had already
passed the Niemen, within two leagues of the town, before the Czar
knew anything of his march. Directly the news came that the Swedes
were upon them, the Czar left the town by the north gate, while
Charles entered by the south. The King had only six hundred of his
guards with him, the rest being unable to follow him. The Czar,
imagining that a whole army was entering Crodno, fled with 2,000
men; but he heard that very day from a Polish deserter that he had
abandoned the place to not more than six hundred men, the body of
the enemy’s army being still more than five leagues away. He did not
lose time, but sent a detachment of 15,000 cavalry in the evening to
surprise the King of Sweden in the town. The 15,000 Russians,
helped by the darkness of the night, advanced as far as the first
Swedish guard without recognition. This guard consisted of thirty
men, and they alone supported the charge of the 15,000 for seven
minutes. The King, who was at the other end of the town, came up
presently with his six hundred guards, and the Russians fled in
haste. In a short time his army joined him, and he pursued the
enemy. All the Russians dispersed throughout Lithuania, retiring
hastily into the Palatinate of Minski, where they had a rendezvous.
The Swedes, whom the King also divided into several corps,
continued to pursue them for about thirty leagues of their way. The
fleers and the pursuers made forced marches almost every day,
though it was mid-winter.
The soldiers of Charles and the Czar had long become indifferent
to the seasons: it was only the terror inspired by the name of Charles
which made the difference between the Russians and the Swedes.
From Grodno eastward to the Borysthenes there is nothing but
marshes, deserts, mountains and immense forests. Even where the
ground is cultivated no provision was to be found; the country folk
hid all their grain and other dry goods underground. In order to find
these subterranean magazines, they had to sound the earth with
long poles tipped with iron. The Russians and the Swedes used
these provisions by turns, but they were not always discovered, nor
were they always sufficient when they were.
The King of Sweden, who had foreseen these difficulties, had
provided biscuit for his army, so that nothing hindered his march.
After he had crossed the forest of Minski, where his men were
obliged every moment to cut down trees to make way for the troops
and baggage, he found himself, on the 25th of June, 1708, near
Borislou, in front of the river Berezine.
The Czar had assembled the best part of his troops in this spot
and had entrenched himself to advantage; his aim was to hinder the
Swedes from crossing the river. Charles placed some of his regiment
on the banks of the Berezine, close to Borislou, as though he
intended to attempt the crossing in face of the enemy. At the same
time he led his army about three leagues up the river, threw a bridge
across it, cut his way through a body of 3,000 men who defended
that post, and marched straight against the enemy without a halt.
The Russians did not wait for his arrival, but immediately decamped
and withdrew towards Borysthenes, spoiling all the roads, and
destroying all on their line of march, so that they might at least delay
the Swedes’ advance.
Charles surmounted all difficulties, continually advancing towards
Borysthenes. On his way he met 20,000 Russians, entrenched at a
spot called Hollosin, behind a marsh, which could not be reached
without crossing a river. Charles did not wait till the rest of his
infantry had arrived to make the attack, but threw himself into the
water at the head of his foot-guards, and crossed the river and the
morass, though the water was sometimes above his shoulders.
While he thus attacked the enemy, he ordered his cavalry to pass
round the morass and take them in the flank.
The Russians, amazed that no barrier could defend them, were
simultaneously routed by the King on foot, and by the Swedish
horse. The horse, having made their way through the enemy, joined
the King in the midst of the fray. He then mounted, but some time
after, finding a young Swedish noble named Gyllenstein, for whom
he had great affection, wounded in the fray and unable to walk, he
insisted on his taking his horse, and continued to command on foot
at the head of his infantry. Of all the battles he had ever fought, this
was in all probability the most glorious—that in which he was
exposed to the greatest risks, and in which he showed the greatest
ability. The memory of it is kept by a medal with the inscription,
“Silvæ, paludes, aggeres, hostes, victi” on one side and “Victrices
copias alium laturus in orbem” on the other.
The Russians, driven out everywhere, recrossed the
Borysthenes, which separates Poland from their own country.
Charles lost no time in following them; he crossed the great river
after them at Mohilou, the last town in Poland, which is sometimes in
the hands of the Poles, sometimes in those of the Czar, after the
usual fate of frontier places.
The Czar, seeing his empire, into which he was introducing arts
and commerce, becoming a prey to a war which might in a short time
ruin his plans, and perhaps lose him his throne, was thinking of
peace, and even made proposals by a Polish nobleman whom he
sent to the Swedish army. Charles, who had been unaccustomed to
granting peace to his enemy except in their capitals, only replied, “I
will treat with the Czar at Moscow.”
When the Czar heard this haughty answer, “My brother Charles,”
he said, “would still pose as Alexander, but I flatter myself he will find
me no Darius.”
From Mohilou, where the King crossed the Borysthenes, turning
north along the river, upon the frontiers of Poland and Russia, is
situated the country of Smolensko, through which lies the main road
from Poland to Moscow. The Czar fled by this road, and the King
followed by forced marches. Part of the Russian rearguard was more
than once engaged with the dragoons of the Swedish vanguard.
Generally the latter got the advantage, but they weakened
themselves by these skirmishes, which were never decisive, and
always meant the loss of some of their men.
On the 22nd of September this year, 1708, the King attacked a
body of ten thousand horse and six thousand Calmouks near
Smolensko.
These Calmouks are Tartars, living between Astrakan, which is
part of the Czar’s dominions, and Samarcande, the country of the
Usbeck Tartars. The Calmouks’ country stretches from the east to
the mountains which separate the Mogul from the western part of
Asia. Those who dwell near Astrakan are tributary to the Czar. He
pretends to absolute dominion over them, but their wandering life
hinders him from subduing them, and forces him to treat them as the
Grand-Seignior treats the Arabs, sometimes bearing with their
robberies, and at others punishing them.
There are always some of the Calmouks in the Russian army,
and the Czar had even succeeded in reducing them to discipline like
the rest of his soldiers.
The King fell on this army with only six regiments of horse and
four thousand infantry; he broke the Russian ranks at the head of his
Ostrogothic regiment and forced the enemy to retreat. The King
advanced upon them by rough and hollow ways where the Calmouks
lay hid; they then appeared and threw themselves between the
regiment where the King was fighting and the rest of the Swedish
army. In an instant both Russians and Calmouks had surrounded
this regiment and made their way close up to his Majesty. They killed
two aides-de-camp who were fighting near him. The King’s horse
was killed under him, and as one of the equerries was offering him
another, both equerry and horse were struck dead on the spot.
Charles fought on foot, surrounded by some of his officers who
immediately hastened to rally round him.
Several were taken, wounded or slain, or swept off to a distance
from the King by the crowd which attacked them; so that there were
only five men left near him. By that extraordinary good luck which till
then had never deserted him, and on which he always relied, he had
killed more than a dozen of the enemy with his own hand without
one wound. At last Colonel Dardoff forced his way, with only one
company of his regiment, through the Calmouks, and came up just in
time to save the King. The rest of the Swedes put the Tartars to the
sword. The army reformed, Charles mounted, and, fatigued as he
was, pursued the Russians two leagues.
The conqueror was still on the main road to the capital of Russia.
The distance from Smolensko, where this battle was fought, to
Moscow, is about 100 French leagues; the army had scarcely any
provisions. The King was pressed to wait till General Levenhaupt,
who was to bring up reinforcements of 15,000 men, came to join
him. Charles, who rarely listened to advice, not only refused to listen
to this wise counsel, but, to the great amazement of the whole army,
left the Moscow road, and marched south towards Ukrania into the
country of the Cossacks, between lesser Tartary, Poland and Russia.
This country is about 100 French leagues from north to south,
and about the same from east to west. It is divided into two nearly
equal parts by the Borysthenes, which crosses from north-west to
south-west; the chief town is Baturin, on the little river Sem. The
northernmost part of Ukrania is under cultivation, and rich; the
southernmost part, in the forty-eighth degree, is one of the most
fertile and at the same time the most deserted districts in the world;
bad management quite counteracts its natural advantages.
The inhabitants of those parts, which border on lesser Tartary,
neither plant nor sow lest the Tartars of Budziac, Precop and
Moldavia, who are all brigands, should carry off their harvests.
Ukrania has always aspired to freedom; but being hedged in by
Russia, the dominions of the Grand-Seignior, and Poland, it has
been obliged to seek for a protector (who is, of course, a master) in
one of those States. First it put itself under the protection of Poland,
who treated it too much as a subject-state; then they appealed to the
Russians, who did their best to reduce them to serfdom. At first the
Ukranians had the privilege of choosing a prince, called general, but
soon they were deprived of this privilege, and their general was
nominated by the Russian Court.
The office was then filled by a Pole called Mazeppa; he had been
brought up as page to King John Casimir, and had got a little
learning at his Court. On the discovery of an intrigue with the wife of
a Polish nobleman, the latter had him tied, stark naked, to a wild
horse, and set him free in that state. The horse, which had been
brought from Ukrania, returned to its own country, carrying Mazeppa
with him half dead from hunger and fatigue. Some of the peasants
gave him relief, and he stayed a long time among them, and
distinguished himself in several attempts against the Tartars. The
superiority of his intelligence made him a person of consideration in
the eyes of the Cossacks, and as his reputation daily increased the
Czar was forced to make him Prince of Ukrania.
One day, as he was sitting at table with the Czar at Moscow, the
Emperor proposed to him to drill the Cossacks and make them more
independent. Mazeppa pointed out the situation of Ukrania and the
nature of the people as insurmountable obstacles. The Czar, who
was over-heated with wine, and had not always sufficient self-
control, called him a traitor, and threatened to have him impaled. On
his return into Ukrania Mazeppa planned a revolt. The Swedish army
appearing shortly after on the frontier facilitated matters for him, and
he resolved to gain independence, and to form for himself a powerful
kingdom from Ukrania and the ruins of the Russian Empire. He was
a man of great courage, of considerable enterprise, and most
painstaking, though he was advanced in years.
He made a secret league with the King of Sweden, to hasten the
Czar’s downfall and gain something himself out of it. He gave him a
rendezvous near the river Desna; Mazeppa promised to meet him
there with 30,000 men, ammunition and provisions, and all his
treasure, which was immense. The Swedish army was therefore
ordered to march towards that part of the country, to the great regret
of the officers, who knew nothing of the King’s treaty with the
Cossacks.
Charles sent orders to Levenhaupt to bring his troops and
provisions with all haste to Ukrania, where he intended passing the
winter, that, having subdued that country, he might conquer Russia
the following spring; meanwhile he advanced towards the river
Desna, which flows into the Borysthenes at Kiouw.
The obstacles they had hitherto encountered on their march were
trifles to those they met on this new route; they had to cross a forest
fifty leagues broad, which was full of marshes. General Lagercron,
who led the van with 5,000 men and pioneers, led the army thirty
leagues too far to the east. They had marched four days before the
King discovered their mistake. They regained the right road with
some difficulty, but almost all the artillery and wagons were stuck fast
or sunk in the mud.
They then marched for twelve days in this painful and laborious
fashion till they had eaten the little biscuit they had left, and so they
arrived, spent with hunger and fatigue, on the banks of the Desna,
where Mazeppa was to meet them. Instead of the Prince, however,
they found a body of Russians advancing towards them on the other
side of the river. The King was much astonished, and decided to
cross the Desna and attack the enemy. The banks of this river were
so steep that they were obliged to let the soldiers down by cords;
then they crossed in their usual manner, some by swimming, some
on hastily constructed rafts.
The band of Russians, which arrived at the same time, were only
8,000, so that their resistance was feeble, and this obstacle was also
overcome.
Charles advanced further into this desolate country, uncertain of
his route and of Mazeppa’s fidelity; at last the latter appeared, but
rather as a fugitive than as a strong ally. The Russians had
discovered and prevented his plan: they had fallen upon the
Cossacks and cut them in pieces; his chief friends were taken red-
handed, and thirty of them had been broken on the wheel. His towns
were reduced to ashes, his treasures plundered, and the provisions
he was preparing for the King of Sweden seized. He himself
escaped with difficulty, accompanied by 6,000 men, and some
horses laden with gold and silver. But he held out to the King the
hope that he would be of some service from his knowledge of this
unknown country, and by the affection of the natives, who, enraged
with the Russians, came in troops to the camp, and brought
provisions.
Charles hoped that at least General Levenhaupt would come to
repair this ill fortune; he was to bring about 15,000 Swedes (of more
use than 100,000 Cossacks), with stores and ammunition. He
arrived at last, but almost in the same condition as Mazeppa. He had
already passed the Borysthenes above Mohilou, and advanced
about twenty leagues further on the road to Ukrania. He brought the
King a convoy of 8,000 wagons, with the money he had raised in
Lithuania and on march. On reaching Lesno, near the spot where the
rivers Pronia and Sossa unite to flow into the Borysthenes far below,
the Czar appeared at the head of 50,000 men.
The Swedish general, who had not quite 16,000, decided not to
entrench. Their many victories had given the Swedes so much
confidence that they never inquired as to the enemy’s numbers, but
only their position. Levenhaupt marched against them on the 7th of
October, 1708, in the afternoon. At the first attack they killed 15,000
Russians; the Czar’s army took panic and fled in all directions, and
the Emperor of Russia thought he would be entirely defeated. He
saw that the safety of his dominions depended upon the action of the
day, and that he could be ruined if Levenhaupt joined the King of
Sweden with a victorious army.
As soon as he saw his troops fall back he ran to the rear, where
the Cossacks and Calmouks were posted, and said, “I order you to
fire on every man who runs away, and even to shoot me, should I be
so cowardly as to turn my back.” Then he returned to the van and
rallied the troops in person, assisted by the Prince Menzikoff and
Prince Gallitsin. Levenhaupt, who had pressing orders to join his
master, chose to continue his march rather than to renew the battle,
thinking that he had done enough to discourage the enemy from
pursuit.
No later than eleven the next morning the Czar attacked him on
the entrance to a morass, and spread his lines to surround him. The
Swedes faced about, and the fight lasted two hours with equal
resolution on both sides. The Russians lost three times as many
men, but still held their position, and the victory was undecided. At
four General Bayer brought the Czar reinforcements. The battle was
then renewed for the third time with greater fury than before, and
lasted till nightfall. Then the force of numbers carried the day; the
Swedes were broken, routed, and driven back on their baggage.
Levenhaupt rallied his men behind his chariots, and though they
were conquered they did not flee.
Not one from an army of about 9,000 men took to flight. The
general formed them up as easily as if they had not been beaten.
The Czar, on the other hand, passed the night under arms, and
ordered his soldiers on pain of death, and his officers on pain of
dismissal, to abstain from plunder.
Next morning at daybreak he ordered a fresh attack. Levenhaupt
had retired to a strong position some miles distant, after having
spiked some of his cannon and fired some of his wagons. The
Russians came up just in time to hinder the whole convoy from being
burned, and seized six thousand wagons which they saved. The
Czar, who wished to utterly crush the Swedes, sent one of his
generals, called Phulg, to attack them for the fifth time, and he
offered them honourable terms if they would capitulate. Levenhaupt
refused, and the fifth battle was as bloody as any of the former ones.
Of the 9,000 soldiers he had left he lost half, the other half not
breaking line. At last night came on, and Levenhaupt, after having
fought five battles against 50,000 men, crossed the Sossa by
swimming, followed by the 5,000 men remaining to him. The
wounded were carried over on rafts. The Czar lost about 20,000
Russians in these engagements, in which he had the glory of
conquering the Swedes, and Levenhaupt the credit of disputing the
victory for three days, and of retreating without being forced from his
last position. So that he came to his master’s camp with the honour
of having made so good a defence, but without ammunition or
forces. The King of Sweden, therefore, without provisions, and cut
off from communication with Poland, was surrounded by enemies in
the midst of a country where he had scarcely any resource but his
own courage.
In this extremity the memorable winter of 1709, which was still
more severe in those frontiers of Europe than it was in France,
destroyed a part of his army. Charles resolved to defy the season as
he had his enemies; he ventured on long marches with his troops
during the bitter cold. It was on one of these marches that 2,000 of
his men died of cold before his very eyes. The cavalry had no boots,
and the foot no shoes, and hardly any clothes. They were forced to
make footgear of the skins of beasts as best they could, and they
often went hungry. They had even been obliged to throw the best
part of their cannon into quagmires and rivers for want of horses to
draw them; so that this once flourishing army was reduced to 24,000
men at the point of starvation. They neither got news from Sweden,
nor were they able to send there. In this state of affairs one officer
only complained. “What,” said the King to him, “are you miserable at
being so far from your wife? If you are really a soldier I will lead you
to such a distance that you will not hear from Sweden once in three
years.”
The Marquis of Brancas, now Swedish ambassador, told me that
a soldier ventured to present the King, before the whole army, with a
piece of bread that was black and mouldy. It was made from barley
and oats, and was the only food they then had, and that in scanty
quantities. The King received the piece of bread unmoved, ate it all,
and then said coolly to the soldier, “It is not good, but one can eat it.”
This characteristic touch, insignificant as it is (if, indeed, that should
be called insignificant which increases respect and confidence), did
more than all the rest to help the Swedish army to bear hardships
which would have been insupportable under any other general.
In these circumstances he at last received news from Stockholm,
but only that his sister the Duchess of Holstein, aged 27, had been
carried off by small-pox. She was as gentle and pitiful as her brother
was imperious and implacable in revenge. He had always been very
fond of her; he felt her loss the more as, now that the tide of his
fortune had turned, he was more susceptible. He learned also that
they had carried out his orders and raised troops and money, but
could not send them to his camp; for there lay between him and
Stockholm nearly five hundred leagues and an enemy with a
superior force to encounter.
The Czar, who was as energetic as the King, after having sent
fresh forces into Poland to assist the confederates, united under
General Siniawski against Stanislas, and soon advanced into
Ukrania, in the middle of this severe winter, to oppose the King of
Sweden. He stayed there with the object of weakening the enemy by
small engagements, for by this means he thought the Swedish army
must be quite wrecked at last, as he was able to draw fresh forces
every moment from his dominions, while they could not get recruits.
The cold there must have been excessive, since it forced the two
enemies to suspend hostilities. But on the first of February, amid ice
and snow, they began to fight again.
After several small skirmishes and some reverses, the King’s
army was reduced in April to 18,000 men. Mazeppa alone, the
Prince of the Cossacks, supplied them with the necessaries of life;
without his assistance the army must have perished from hunger and
destitution.
At this moment, the Czar, to attract Mazeppa to his service again,
offered him terms; but the Cossack stood by his new ally, either from
fear of the terrible punishment of the wheel, by which his friends had
perished, or because he sought revenge.
Charles, with his 18,000 Swedes and as many Cossacks, had not
abandoned his plan of reaching Russia. Towards the end of May he
went to siege Pultawa, on the river Vorskla, on the extreme eastern
frontier of Ukrania, about thirteen full leagues from the Borysthenes,
where the Czar had a magazine. This country is that of the
Zaporavians, the strangest people in the world. They are a collection
of former Russians, Poles, Tartars, and all make profession of a kind
of Christianity, and of a kind of freebooting brigandage. They elect a
chief, whom they depose or assassinate; they allow no women to
live among them, but they kidnap all the children for twenty or thirty
leagues round, and train them in their ways. During summer they are
always in the field, during winter they sleep in vast barns, containing
400 or 500 men. They fear nothing, and live at liberty; they risk death
for the smallest booty, with the same boldness with which Charles
XII faced it to bestow crowns. The Czar sent them 60,000 florins in
the hope that they would side with him; they took the money and
then, through the exertions of Mazeppa, declared for Charles: but
they proved of very little use, for they think it ridiculous to fight for
anything but booty. It was a great point gained that they did no harm:
there were about 2,000 of them at most who did regular duty. Ten of
their chiefs were one day presented to Charles, but they had great
difficulty in finding those who were not intoxicated, for they always
began the day in that condition. They were taken into the trenches,
and showed their skill in shooting with long rifles, for they could pick
off the enemies they singled out at 600 paces away. Charles added
to these bandits some 1,000 Valaques; then he laid siege to
Pultawa, with an army of about 30,000 men, in a wretched condition
and wanting all necessaries. The Czar had made Pultawa a
magazine: if the King took it it would open the road to Moscow for
him, and he could await, well supplied, the recruits he expected from
Sweden, Livonia, Pomerania and Poland. As, then, his sole resource
lay in the taking of Pultawa, he carried on the siege with vigour.
Mazeppa, who had informants in the town, assured him that he
would soon master it, and hope began to reanimate the army. His
soldiers regarded the taking of Pultawa as the end of all their
miseries.
From the beginning of the siege the King realized that he had
given his enemies some useful lessons in the art of war. Prince
Menzikoff, in spite of all his precautions, threw reinforcements into
the town, and the garrison then amounted to almost 10,000 men.
They made sorties, sometimes successfully; but what made the town
impregnable was the approach of the Czar, who was advancing with
10,000 combatants. Charles XII went to meet him on the 27th of
May, his birthday, and beat one of their corps; but as he was
returning from his camp he got a musket-shot, which pierced his
boot and shattered his heel-bone. There was not the least sign on
his face that he had been shot; he continued calmly to give his
orders, and remained mounted nearly six hours after the accident.
One of his servants at last noticing that the sole of his boot was
covered with blood, ran for the doctor; then the King’s pain was so
acute that they had to take him off his horse and carry him to his
tent. The surgeons examined the wound and saw that it had already
begun to mortify, and thought that the leg must be cut off. The
consternation in the army was great. But one of the surgeons, called
Newman, better skilled and braver than the rest, was certain that he
could save the leg by means of a deep incision.
“Begin at once, then,” said the King; “cut boldly, fear nothing.” He
held his leg with his own hands, looking at the incisions made as if
they were in the leg of another.
As they were putting on the dressing he gave orders for an
assault next morning, but scarcely had he given the order than they
brought him word that the whole army of the enemy was upon him.
He was therefore obliged to alter his plan. Wounded and incapable
of action, he found himself shut in between the river Borysthenes
and the river which runs to Pultawa, in a desert district, with no forts
or ammunition, and opposed to an army which cut him off from
retreat or provisions. In this terrible position he did not, as might
have been expected, assemble a council of war, but on the night of
7th July he sent for Marshal Renschild, and ordered him, without
deliberation, but without uneasiness, to prepare to attack the Czar
next morning. Renschild did not argue, but went to carry out his
orders.
At the door of the King’s tent he met Count Piper, with whom, as
often happens between the minister and the general, he had long
been on bad terms. Piper asked him if there were anything new.
“No,” said the General coldly, and passed on to give his orders. As
soon as Piper entered the royal tent the King asked if Renschild had
told him anything. “Nothing,” answered Piper. “Well, then,” answered
the King, “I tell you that to-morrow we shall give battle.” Count Piper
was astonished at so desperate a resolve, but he knew that his
master could never be made to change his opinion; he only
expressed his astonishment by his silence, and left the King to sleep
till dawn.
The battle of Pultawa was fought on the 8th of July, 1709,
between the two most famous monarchs in the world: Charles XII,
distinguished by a course of nine years’ victories, and Peter
Alexiowitz by nine years of painstaking training of his troops to an
equality with the Swedes; the one famed for having given away the
dominions of others, the other for having civilized his own; Charles
loving danger and fighting only for the sake of glory, Alexiowitz not
running away from difficulties, and making war from interested
motives only; the Swedish King liberal from a generous
temperament, the Russian never generous but with some object in
view; the former sober and temperate in an extraordinary degree,
naturally brave and only once showing cruelty, the latter not having
thrown off the roughness of his education or his race, as terrible to
his subjects as he was wonderful to strangers, and addicted to
excess which, as a matter of fact, shortened his days. Charles bore
the title “Invincible,” which he might lose at any moment; the nations
had already given Peter the title “Great,” which he could not lose by
any defeat, as he did not owe it to his victories.
To get a clear idea of this battle and the place where it was
fought, one must imagine Pultawa to the north, the King of Sweden’s
camp to the south, slightly to the east; his baggage about a mile
behind him, and the river Pultawa on the north side of the town,
running from east to west. The Czar had passed the river about a
league from Pultawa, towards the west, and was beginning to form
his camp. At daybreak the Swedes appeared above their trenches
with four cannon for their artillery; the rest were left in the camp with
about 3,000 men, and 4,000 remained with the baggage. So that the
Swedish army marching against the enemy consisted of about
25,000 men, of whom not more than 12,000 were regulars. Generals
Renschild, Roos, Levenhaupt, Slipenbak, Hoorn, Sparre, Hamilton,
the Prince of Wirtemburg, a relation of the King, and some others,
most of whom had been at the battle of Narva, reminded the
subalterns of that day, when 8,000 Swedes had destroyed an army
of 100,000 Russians in entrenchments. The officers remarked it to
the soldiers, and all encouraged one another on the march.
The King conducted the march, carried in a litter at the head of
his infantry. By his order a party of horse advanced to attack that of
the enemy; the battle began with this engagement. At half-past four
in the morning the enemy’s cavalry lay to the west, on the right of the
Russian camp: Prince Menzikoff and Count Golowin had placed
them at intervals between redoubts fortified with cannon. General
Slipenbak, at the head of the Swedes, fell upon them. All who have
served with the Swedes know that it is almost impossible to resist
their first onset. The Russian squadrons were broken and put to
flight. The Czar himself ran to rally them, and his hat was pierced by
a musket shot. Menzikoff had three horses killed under him, and the
Swedes shouted victory.
Charles was sure that the battle was gained; he had sent General
Creuts about midnight with five thousand horse to attack the
enemy’s rear while he attacked their front, but, as ill-luck would have
it, Creuts lost his way and did not appear.
The Czar, who had thought that all was lost, had time to rally his
cavalry, and fell on the King’s horse in his turn; unsupported by
Creuts’ detachment it was broken, and Slipenbak taken prisoner. At
the same time seventy-two cannon from the camp played on the
Swedish horse, and the Russian foot, issuing from their lines,
advanced to attack Charles.
The Czar then detached Menzikoff and sent him to take up a
position between Pultawa and the Swedes. He carried out his
master’s orders dexterously and promptly: not only did he cut the
communication between the Swedish army and the troops remaining
in the camp at Pultawa, but meeting a body of 3,000 reserves he cut
them to pieces. Meanwhile, the Russian foot issued from their lines
and advanced in order into the plain on the other side; the Swedish
horse rallied within a quarter of a league of the enemy’s army, and
the King, assisted by General Renschild, gave orders for a general
engagement.
He ranged his remaining troops in two lines, his foot in the centre,
his horse on the two wings. The Czar arranged his forces in the
same way; he had the advantage in numbers and also seventy-two
cannon, while the Swedes had only four, and were running out of
powder.
The Czar was in the centre of his army, and at that time bore the
title of Major-General, and was apparently in the service of General
Czeremetoff; but as Emperor he went from rank to rank, mounted on
a Turkish horse, a present from the Grand-Seignior, exhorting his
officers and soldiers and promising them all rewards. At nine in the
morning the battle began again. One of the first discharges of the
Russian cannon carried off the two horses of the King’s litter; he had
two others harnessed in, and a second volley shattered the litter and
threw the King out. The troops who were fighting near him believed
he was killed; in the consternation the Swedes lost ground, and, their
powder failing and the enemy’s cannon keeping up fire, the first line
fell back on the second, and the second fled. In this last action of the
Swedish army they were routed by a single line of 10,000 Russian
infantry; so much had matters changed. Prince Wirtemburg, General
Renschild and several leading officers were already prisoners; the
camp before Pultawa was forced, and all in utterly hopeless
confusion. Count Piper and other officers had left the camp and did
not know what to do, nor what had become of their King. They ran
from one side of the field to the other; Major Bere offered to lead
them to the baggage, but the clouds of dust and smoke which
covered the field, and their own confusion, carried them to the other
side of the town, where they were taken prisoners by the garrison.
The King was unwilling to flee, and would not defend himself.
General Poniatowski chanced to be with him at that moment. He was
a colonel of King Stanislas’ Swedish guards, and a person of
remarkable merit, who was so attached to Charles XII that he had
accompanied him as a volunteer to Ukrania. He was a man who in
all the chances of life, and in danger, where others would at most
have only shown courage, always made his plans at once and met
with success; he signed to two soldiers, who took the King under the
arms and put him on horseback in spite of the great pain of his
wound.
Poniatowski, though he had no command in the army, being
made general by necessity on this occasion, rallied 500 horse round
the King’s person: some were dragoons, some ordinary troopers,
some officers. This band, inspired by the misfortune of their Prince,
made their way through more than ten regiments of Russians and
took Charles through the midst of the enemy, the distance of a
league, to the baggage of the Swedish army.
This amazing retreat was an achievement in such a disastrous
situation, but it was necessary for the King to flee further.
Though the King had never had a coach since he left Stockholm,
they found Count Piper’s among the baggage. They put him into it
and started for the Borysthenes with all haste. The King, who had
not spoken a single word from the time he was put on horseback till
he came to the baggage, then asked what had become of Count
Piper. “He has been taken prisoner with all his chancery officers,”
they told him. “And General Renschild and the Duke of Wirtemburg?”
he asked. “They too are prisoners,” said Poniatowski. “Prisoners of
the Russians!” exclaimed Charles, with a shrug; “let us rather escape
to Turkey.” His expression did not change, however, and whoever
had seen him and been ignorant of his position would never have
suspected that he had been either conquered or wounded.
While he was escaping the Russians seized his artillery in the
camp before Pultawa, his baggage and his military chest, containing

Gateway To Condensed Matter Physics and Molecular Biophysics: Concepts and Theoretical Perspectives 1st Edition Chaudhury

Uploaded by

Copyright:

Available Formats

Gateway To Condensed Matter Physics and Molecular Biophysics: Concepts and Theoretical Perspectives 1st Edition Chaudhury

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Gateway To Condensed Matter Physics and Molecular Biophysics: Concepts and Theoretical Perspectives 1st Edition Chaudhury

Uploaded by

Copyright:

Available Formats

Full download ebooks at ebookmeta.

Gateway to Condensed Matter Physics and Molecular

Download more ebook from https://ebookmeta.com

Condensed Matter Physics A Very Short Introduction 1st

Theoretical Concepts in Physics An Alternative View of

Condensed Matter Field Theory (3rd Edition) Alexander

Condensed Phase Molecular Spectroscopy and Photophysics

Theoretical Cybersecurity: Principles and Advanced

Communicating Fashion Brands Theoretical and Practical

Magneto Optics An introduction Graduate Texts in

Chemistry The Molecular Nature of Matter and Change 9th

© 2022 Apple Academic Press, Inc.

Dedicated to the Memory of

Ranjan Chaudhury, PhD

Ranjan Chaudhury, PhD, has been a professor at S.N.

postdoctoral fellow/collaborating visiting scientist at various institutions

1. Introduction to Electronic Properties of Solids:

Index ................................................................................................................. 171

AFM atomic force microscopy

This is an advanced reference book in theoretical condensed matter physics

Introduction to Electronic Properties of

1.1 GENERAL INTRODUCTION

Condensed matter physics is a branch of physics, which deals with

Under group (a) classification, an insulator is defined as a material,

The group (c) classification is exactly analogous to that of the group

The theoretical understanding of these very interesting interplay

1.2 ORIGIN OF BAND THEORY

In view of the tremendous applicability of the simple one-electron theory,

treatment is very general to start with. Since the property of electrons is

V (r) = V (r+R) (1.2)

where, R is any lattice translation vector.

where, T̂ is the ‘lattice translational operator’ defined by its action on any

̂ (r) = ϕ((r +R))

Now the operators T̂ and H being mutually commuting may have

where, ψk(r) is an eigenfunction and uk(r) is a periodic function on the

ψk (r + R) = exp (ik . R) ψk (r) (1.7)

Thus for a wave vector G satisfying:

where, n is an integer, the eigenfunctions ψk(r) and ψk+G(r) are indistin­

It is important at this stage, to get a feeling for the mathematical

where, the periodic potential has been chosen as:

and k2 being equal to .

0 ci , ci , tci , cj, (1.12)

є(k) = є0 – 2t(coskx a + cosky b + coskz c) (1.13)

where, t is the electron hopping matrix element involving nearest-

Thus, we see that mqf is inversely proportional to the hopping parameter

The solution to the above equation, even for a simple tight-binding

In particular, the density of states (DOS) evaluated at the Fermi energy

1.3 EXPERIMENTAL VERIFICATION OF BAND THEORY AND

The experimental determination of the shapes of the Fermi surfaces is most

known as the cyclotron frequency. The cyclotron frequency turns out to

types of carriers. While in a metal, the charge carrier is always an electron,

in units (integer or fraction) of the fundamental conductance

1.4 VARIOUS NOVEL PHENOMENA ASSOCIATED WITH FERMI

below a certain temperature. It should be emphasized here that the nature

In the heavy-fermion materials, the effective mass of the conduction

creation of vacancies and thereby facilitating some amount of electronic

behaving as a quantum dot. Again, the realistic systems belonging to the

The phenomenon of “magnetism” is one of the oldest phenomena discovered

dimensional systems, which are of paramount importance in both basic and

where, n is an integer, the eigenfunctions ψk(r) and ψk+G(r) are indistin