SOLID STATE PHYSICS I (PHS- 316)

LECTURER: NGWA Engelbert AFUOTI.

( ngwaengelbert@yahoo.com)

ENSAB

CONTENTS
 1

1. Introduction…………………………………………………………...2
2.1 Classes of solids………………………………………………………4
2.2 Crystal structures……………………………………………………..5
2.2.1 Translational symmetry………………………………………………5
2.2.2 Bravais lattice…………………………………………………………6
3 Some Group Theory, Theory of Symmetry, Schoenflies Notations,
Non-Cubic Crystallographic Point Group…………………………… 8
3.1 Definition and Simple Properties of Groups………………………….8
3.2 Unitary Transformation………………………………………………10
3.3 Symmetry Transformation……………………………………………10
3.3.1 Point Group………………………………………………………… . 11
4. Periodic Function of Reciprocal Lattice, Miller Indices……………...23
4.1 Recesciprocal lattice…………………………………………………..26
4.2 Miller indices………………………………………………………… 26
5. Lattice Dynamics…………………………………………………….. 28
5.1 Vibrational Modes of a Monatomic Lattice………………………….. 28
5.1.1 Linear Monatomic Chain…………………………………………….. 28
5.1.2 Density of State………………………………………………………. 37
5.2 Vibrational Modes of a Diatomic Linear Chain……………………… 38
5.3 Vibrational Modes in Three-Dimensional Crystal…………………… 45
5.4 Normal Vibration of a Three-Dimensional Crystal………………….. 52
5.5 Second Quantization of the Phonon Field…………………………… 57
6. Electronic State in Ideal Crystal…………………………………….. 62
6.1 The zone theory……………………………………………………… 62
6.1.1 Bloch theorem………………………………………………………. 64
6.2 The Approximation of the Nearly Free Electron
Model (N.F.E)……………………………………………… ……… 70

6.3 The Tight-Binding Approximation (T.B.A)………………............... 75

1. INTRODUCTION
 2

Solid state Physics is that branch of physics that deals with the structure and
properties of solids. It is the largest branch of condensed matter physics, which
study rigid matter, or solids, through methods such as quantum mechanics,
crystallography, electromagnetism and metallurgy. Solid state physics
considers how the large-scale properties of solid materials result from their
atomic-scale properties. Solid-state physics thus forms the theoretical basis of
materials science, as well as having direct applications, for example in the
technology of transistors and semiconductors.
Solids consist of atoms or molecules packed closely together-frequently in a
very orderly way. Most of the physical properties of solids depend upon the way
in which the atoms or molecules are packed, or arranged; that is, on the internal
structure of the solid. For this reason the study of the structure of solids, called
crystallography, is of basic importance to all other investigations in solid state
physics.
The study of the attractive forces between atoms or molecules in solids is
another basic aspect; it has helped greatly in the understanding of many of the
properties of solids. For example, since the attractive forces are electrical in
nature, they play a very important role in determining such electrical properties of
solids as conductivity. These forces also determine to a large extent the optical
and thermal properties of solids, such as refractive power and the ability to
conduct heat.
Solids are rarely, if ever, pure. (A pure substance consists of one chemical
element or compound only; impurities are traces of other elements mixed in with
the main element or compound.) The study of the influence of impurities upon the
properties of solids is an important aspect of solid-state physics. For example,
devices such as the solar battery and the transistor were made possible only after
scientists had learned how to control impurities in silicon and similar substances.
Frequently an atom or molecule is unexpectedly absent in the packing
arrangement of a solid. The gap left in the structure is called a vacancy. Vacancies
may profoundly alter the mechanical properties of materials. For example, a piece
of cold-worked metal has many more vacancies than a comparable piece of
annealed metal, and is usually much harder and tougher. Thus the study of
vacancies by solid-state physicists is of considerable interest to metallurgists.
The atoms or molecules at the surface of a solid are not packed in the same way
as those in the interior; unlike interior atoms or molecules, they are not
completely surrounded by neighboring atoms or molecules. Thus the surface
behavior differs substantially from that of the rest of the solid. The study of solid
surfaces and of films (that is, very thin solids consisting mostly of surface) has led
to the use in electronics of thin films with unusual electrical properties and to
ways of increasing the resistance of metal surfaces to corrosion.
The crystal lattice can vibrate. These vibrations are found to be quantised, the
quantised vibrational modes are known as phonons. Phonons play a major role in
many of the physical properties of solids, such as the transmission of sound. In
insulating solids, phonons are also the primary mechanism by which heat
 3

conduction takes place. Phonons are also necessary for understanding the lattice
heat capacity of a solid, as in the Einstein model and the later Debye model.
One of the principal aims of solid-state physicists is to figure out how to exploit
properties of solids for something useful. For example, detailed study of band-
structure led to development of PN-junction, which led to the invention of the
transistor, of which there are now several varieties (bipolar-junction transistors,
junction FETs, Metal-Oxide Semiconducting FETs, Modulation-Doped FETs,
Pseudomorphic High-Electron Mobility Transistors, etc). Study of band structure
also led to the ability to create a population inversion in group III-V material for
the lasing process to be possible for the laser diode. Peltier coolers, often used on
CDs and microprocessors, have been invented by studying phonon interactions of
solids.
Over the past years this branch of physics has undergone a considerable evolution
with current research fields like:
- Quantum electronics
- Semiconductor device fabrication in the semiconductor industry
- Quasicrystals
- Spin glass
- Superconductivity and many others.

In these lectures we exclude the so-called amorphous solids (e.g. glass, some
times also called a supper cooled liquid) from consideration. We also exclude
from consideration systems known as liquid crystals. Concerned in these lectures
is to present a systematic study of the principles underlying solid state physics.
The general notion of crystalline structures, properties of solid such as –
mechanical, electrical, thermal, optical …, are therefore not left out. Concerned is
also on the microscopic description of the physical phenomena in solids. Quantum
mechanics is the basic tool for the adequate description of phenomena at the
atomic level. Thus a complete solid state theory must be quantum mechanically
examined. Physical phenomena are examined using models; for example, a simple
picture of a solid can be seen as an ensemble of point masses coupled to each
other by springs. Point masses may be made to oscillate by electromagnetic
radiations, sound and so on. The study based on this model result in
- The frequency spectrum of a mechanical oscillator ( we examine the
acoustic and optical branches of the spectrum)
- Understanding the variation of specific heat with temperature and so on.
 4

2.1 Classes of solids

Solids can be classified according to their properties (more profoundly by their

chemical binding) and their structures (symmetries). Based on their chemical
binding, there are basically four types of solid which we briefly present below
with the aim to give mere reasons why atoms combined to form solids:
- Molecular crystals - Examples of molecular crystals are nitrogen (N2)
and rare gas crystals such as argon (Ar). Molecular crystals consist of
chemically inert molecules (neutral molecules which have little or no
affinity for adding or sharing additional electrons). They are also referred
too as chemically saturated units. The interaction between chemically
saturated units is described by the Van der Waals forces. Quantum
mechanics describes these forces as being due to correlations in the
fluctuating distributions of charges in the chemically saturated units. The
appearance of virtual excited states causes transitory dipole moments to
appear on adjacent atoms, and if these dipole moments have the right
directions, then the atoms can be attracted to one another. The Van der
Waals forces are weak, short range forces, and hence molecular crystals
are characterised by low melting and boiling point. The forces in
molecular crystals are almost central forces (central forces act along the
line joining the atoms), and they make efficient use of their binding in
closed packed crystal structures. We should not forget to mention that
there is also a repulsive force which keeps the lattice from collapsing.
- Ionic crystals – Examples of ionic crystals are sodium chloride ( NaCl)
and lithium fluoride ( LiF). Ionic crystals also consist of chemically
saturated units (the ions which form their basic unit are in rare gas
configurations). The ionic bond is due mostly to the electrostatic attraction
between oppositely charged ions. However there is the core repulsion
between the ions due to an overlapping of electron clouds (as constrained
by the Pauli principle) to prevent the lattice from collapsing. Since the
Coulomb forces of attraction are strong, long range, nearly two body
central forces, ionic crystal are characterised by close packing and rather
tight binding. These crystals also show good ionic conductivity at high
temperatures, good cleavage, and strong infrared absorption.
- Metallic crystals – Examples of metals are sodium ( N a ) and copper
(Cu). A metal such as sodium is viewed as being composed of positive ion
cores ( N a ) immersed in a “sea” of free conduction electrons which
comes from the removal of the 3s electron from the atomic sodium Na.
One reason for the binding in metals is lowering of the kinetic energy of
the “free” electrons relative to their energy in the atomic 3s state. In a
metallic crystal the valence electrons are free (within the constrained of
the Pauli principle) to wander throughout the crystal causing them to have
a smoother wave function and less kinetic energy. Lowering of the kinetic
energy implies binding. Due to the important role of free electrons in
binding, metals are good electrical and thermal conductors. A more
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quantum mechanical description of metallic bonded crystals is given by

the Wigner-Seitz theory.
- Valence crystals – An example of valence crystal is carbon in diamond
form. Some insight into a covalent bond can be gained by considering
them as being caused by sharing electrons between atoms of unfilled
shells. Sharing electrons can lower the energy because the electrons can
get into lower energy states without violating the Pauli principle. Covalent
crystals are characterised by hardness, poor cleavage, poor electronic and
ionic conductivity. The forces in covalent bonds can be thought of as short
range, two-body, but not central forces. The covalent bond is very
directional, and the crystals tend to be loosely packed. The quantum
mechanical description of this bonding is given by the Heitler-London
theory.

We shall present a systematic study of bonding in crystals in our lectures in

solid physics II.

2.2 Crystal structures

Many properties of materials are affected by their crystal structure. This

structure can be investigated using a range of crystallographic techniques,
including X-ray crystallography, neutron diffraction and electron diffraction.
The chemical element position on the periodic table uniquely determines the
crystal properties. Each crystal structure differs from the other in atomic structure.
The regularity and symmetry of the given crystal structure makes it homogeneous
and isotropic. For a homogeneous structure, for all interior point, there exists a
point with identical properties to that of the first point located at a certain distance
from it. If the properties of a crystal structure are the same for all directions, then
we say the structure is isotropic. Below we give the definition of crystal structure
terms and some facts about crystal structure.

2.2.1 Translational symmetry

A crystal has periodic properties due to the regular array of atoms on it. The
symmetry of the space periodic field is that of the crystal lattice. The basis of the
space periodicity is defined by three fundamental period a1 , a 2 and a 3 such
that
an  n1 a1  n2 a2  n3 a3
2.2.1.1
Where ni are integers and any set of ni leaves the crystal invariable. The space
periodic field f  r   ;
  
f r  f r  an 2.2.1.2
Where r is a radius vector , vector a n is the principal translation or lattice
vector. It is also called crystal axis, lattice constant and or radius vector of the
n th lattice site.
 6

The characteristic feature of a crystal structure is the translational invariant

(2.2.1.2). For the most complete description of the translational invariant, we
select the shortest ai , i  1,2,3 that are not coplanar for which (2.2.1.2) is true.
A crystal structure that satisfies (2.2.1.2) possesses translational symmetry. Hence
a crystal is said to be translationally symmetric or periodic if there exist three
linearly indepent vectors a1 , a 2 and a such that a translation by a n brings
3

one back to an equivalent point in the crystal.

The set of operations that elements differ by the selection on ni is a
translational group. The geometrical array of points generated by a translation is
a lattice. Each point in the array is the lattice site. If one place at each point on
the lattice sites a collection or basis of atoms, the resulting structure is called a
crystal structure. Construct fundamental periods ai from the centre of the given
atom. The volume of the parallelepiped with sides ai is called an elementary
cell or unit cell. A primitive cell is an elementary cell with corners coinciding
with lattice points i.e. a cell with lattice sites only at the corners. For simplicity a
primitive cell is one with the shortest translation vectors a i . It is clear that a
crystal is made up of identical primitive cells. An elementary cell is simple if it
contains only one atom and otherwise compound.
There is also a type of translation operation that relates objects within a unit
cell so that the same objects are found at coordinates that are half multiples of unit
cell distances along two or three of the axes. These operation are for example
responsible for the face and body-centered lattices found in three dimensions as
seen in Bravais lattices which we see in the next section .
The ensemble of all symmetry elements (operations) in a crystal structure is a
space group. A symmetry operation lives the crystal environment invariable or
that operation which brings the crystal back onto itself. (2.2.1.2) satisfies this
requirement. In addition to translation operation, there are also rotation, reflection,
and inversion operations. A symmetry operation with no translation is a point
operation. Examples are rotation about an axis, reflection about a plane and
inversion about a point. Point operation applies to object and translation to lattice.

2.2.2 Bravais lattice

A crystal lattice has an infinite set of translational symmetry. Let ai and aj be
two fundamental periods:
a i'  
j
ij aj , j  1,2,3 2.
2.2.1
Also
ai    ij a 'j 2.2.2.2
j

where  ij  is the symmetric inverse to   ij  . As  ij and  ij are integers, then

 ij  1 . Construct on any lattice sites an elementary cell (parallelepiped) using
the fundamental period (2.2.2.2), some atoms are found at the vertices of the
elementary cell. The vertices overlap relative to the parallel translation by a
fundamental period. The totality of such equilibrium sites that overlap with
 7

each other relative to the fundamental period forms the Bravais lattice of the
crystal. It may be seen that for every lattice, we may find three primitive
translation ai such that any motion from one position in the crystal to another
with exactly the same physical environment, is given by
an   n j a j 2.2.2.3
j

The quantities a j are three smallest non zero lattice vectors. The vectors a n
given by equation (2.2.2.3) define a set of points; that is known as the Bravais
lattice of the crystal. The unit cell is the smallest volume for which translation
from the cell interior point through the vector a n enables all other points in the
crystal to be reached. The unit cell then contains just one Bravais lattice point and
we can construct a unit cell about each lattice point. The fundamental concept in
the description of any crystal structure is the Bravais lattice. Crystals have only 14
different possible parallelepiped network of points (i.e. the fourteen unit cell
represents the only possible ways space can be filled without gaps, that is
consonant with the restriction of translation and rotation symmetry ). These are
the 14 Bravais lattices corresponding to the 7 crystal system ( symmetries). The
list of the 7 crystal system and the 14 Bravais lattices is provided at the end of the
next chapter.

3 SOME GROUP THEORY

THEORY OF SYMMETRY
SCHOENFLIES NOTATION
NON-CUBIC CRYSTALLOGRAPHIC POINT GROUP
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To discuss the symmetry properties of solids, one needs an appropriate

formalism. The most concise formalism for this is an abstract mathematical theory
called group theory. Group theory was developed long before it found
application in physics. With the development of Quantum Mechanics in the first
quarter of the twentieth century, it was realised that this abstract mathematical
theory can be of considerable use in analysing the eigen states of energy of a
physical system. However, we shall be interested at this stage it use in describing
crystal symmetry. To use the crystal symmetry operation as examples of groups,
we start by introducing some group theory notations and defining various terms
which helps in organizing in one’s mind the various sorts of symmetries that are
presented to us by crystals.

3.1 Definition and Simple Properties of Groups

A group G is a collection of elements with a rule to combine two elements

given. This process of combination is called group multiplication which must
satisfy the following properties:
- Closure. If g and h are any two elements of the group G , then gh is
an element of G
- Associative law. If g, h, x are arbitrary elements of G , then
g  hx    gh  x
- Existence of the identity element. There is an element, e in G such that
ge  g , where g is any element in G, e is called the identity element.
- Existence of inverse. For every element g there exist another element
(denoted by g 1 ) in G, such that gg 1  e . g 1 is called the inverse of
the element g.
From the above axioms we can prove that eg  g and g 1 g  e . By definition
ee  e . Now multiply the relation gg 1  e from the left by e, we obtain
egg 1  ee or  eg  g 1  e . Thus eg  g . Similarly, multiply gg 1  e by g from
the right, one obtains gg 1 g  eg or g  g 1 g   g . Thus g 1 g  e
In general group multiplication is not commutative (i.e. gh  hg ). A
commutative group is known as an Abelian group (i.e. gh  hg ).
For a finite group, the number n of elements is called the order of the group.
We now consider an example of a group to fix our ideas.
Example 1. The four numbers 1, i,  i , -1, where i   1 form a group under
ordinary multiplication. If we multiply any two elements the result is one of the
four elements. Thus closure is satisfied. The multiplication is associative. The
element 1 is obviously the identity element. Also, i  i   1 and   1  1  1 ,
showing that  i is the inverse of the element i and verse versa and -1 is it own
inverse.
If we denote the element i by x , the elements of the group can be specified
as x , x 2 , x 3 , x 4  e . Such a group in which all the element are powers of a
single element is called a cyclic group. For a cyclic group of order n, with
generator x , x n  e . This group constitute a particular case of the abelian group.
 9

A subgroup H of G is a subset of elements of G which form a group under

the same rule of group multiplication as in G . For every group there are two
trivial sub groups: (i) the identity element, e, by itself forms a sub group, (ii) also
the whole group G can be considered a sub group of itself. A subgroup H of
G is called a proper subgroup if H  G . In example 1, the numbers (1.-1) forms
a subgroup of the original group.
If g , h , x are some basis elements of a group G such that ; h  xgx 1 . It
can be seen that g  x 1 hx . In h  xgx 1 , h is conjugate relative to g and in
g  x 1 hx , g is conjugate relative to h . It therefore follows that g and h are
conjugate relative to each other. If xi , y i  G , and
1
hi  xi gxi , i  1,2,..., n
3.1.1
then the set of elements hi and g form a class with the basis xi . This follows
that two elements hi and g form a class if there exist an element xi in the
group such that (3.1.3) is satisfied. Suppose xi is an operator denoting the
change of the coordinate system, then if   hi we must have
1
xi  gxi or   xi1 gx i ie hi  xi gxi
3.1.1'
Equation (3.1.3) constitutes a general definition: a set of members of a group that
are obtained by similarity transformation of the form ( 3.1.1' ) with the operator
x i also being a member of the group constitute a class. It is easy to show that the
elements of a class are conjugate elements.
1 1 1
It is obvious that hi  xi gxi , hk  x k gx k then it follows that, g  xi hi xi ,
1 1

hk  x k xi hi xi x k or hk  xi 1 x k  h x
1
i i
1

x k . We have use the fact that
1
 1
 1 1 1
x k xi  xi x k . Since xi x k  z  G and, then hk  z hi z is the definition
of the conjugate. It follows that hi and hk are conjugate to one another. In
example 1, let us consider the elements conjugate to i :
 i,   i  i   i   i ,   1 i   1  i
1 1 1
i
Thus i is conjugate only to itself and forms a class of one element. The same is
true for all the other elements. This is a general characteristic of all abelian
groups. Also in every group the identity element forms a class by it self. This is
1 1
because the only element conjugate to e is e: e  xi exi  xi xi  e

3.2 Unitary Transformation

Let’s introduce the notion of the vector space. For this we construct the system
of basis
e1 , e 2 ,..., e n
3.2.1
 10

having the property ei ek   ik . The system in (3.2.1) is called basis of the vector
space. The vector of a point in space in define as
x ex
i i i

3.2.2
This is the element of vector space. The set of all unitary transformation in an n-
dimensional vector space forms a group. This group is isomorphic to the group of
all unitary matrices which forms a group under unitary transformation. Two
groups G and G ' are said to be isomorphic to each other if there is a one to one
correspondence between their elements i.e. Gi  Gi ' .

3.3 Symmetry Transformation

We talk of a symmetry operation of a function as the operation of rotation,

reflection and translation of the function which leaves the system of coordinate
unchanged. Thus a symmetry transformation overlaps a body onto itself. Suppose
we have a function f  x  ; Ta f  x   f  x  a  . Then the operation displaces the
function f  x  by a. The conversion is called the active point of view. For the
passive point of view, we imagine the function remaining fixed and we rotate or
translate the coordinate system. We take the active point of view in these lectures.
The set of all symmetry transformations which leaves a physical system
invariant forms a group. Group multiplication in this case is the application of two
transformations successively. If each transformation leaves the system invariant,
the product will also leave the system invariant. The product is thus a symmetry
transformation. The successive application of three transformations obeys
associativity. The identity element is the transformation that leaves the system
undisturbed. Finally, for every symmetry transformation there is the inverse

operation. (for example, the inverse of the operation “rotation by in the anti-
2

clockwise direction about the z-axis” will be “rotation by about the same axis
2
in the clockwise direction”). The inverse operation will leave the physical
quantity invariant and is thus a symmetry operation.
A crystalline solid may also contain symmetry operations which are not
group product of its rotation, inversion, and translational symmetry elements.
There are two possible types of symmetry of this type:
- Screw axis symmetry. A screw axis is the combination of a rotation about an
axis with a displacement parallel to the axis.
- Glide plane symmetry. A glide plane is a reflection with a displacement
parallel to the glide plane axis.

3.3.1 Point Group

A complete set of symmetry operations in a crystal is it space group. Point

groups are collections of crystal symmetry operations which form a group and
also leave one point fixed. The point group controls the external morphology of a
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crystal. There are 32 such crystallographic point groups with 7 crystal system
which is specified by the types of symmetry of the 14 Bravais lattices. In general
associating bases of atoms to the 14 Bravais lattices gives a total of 230 periodic
patterns ie there are 230 space groups. Of these space groups, 73 are simple group
product of point groups and translational groups. These are the so called
symmorphic space groups. The rest of the space groups have screw or glide
symmetries. Point groups denoted in the Scheonflies notation are:
C n , C nv , C nh , S n , Dn , Dnh , Dnd . Where the denotation C- cyclic, D- dihedral, S-
spiegel (mirror), h, v and d are horizontal, vertical and diagonal respectively.

3.3.2. C n group
2
The rotation through an integral multiple about some axis is called an n-fold
n
rotation axis denoted by C n ; n  1,2... . n  1 correspond to rotation 2 and
0 o . The structure is mapped back onto itself in this case. Any real crystal
exhibits both translational and rotational symmetry. The mere fact the crystal
must have translational symmetry places restriction on the type of rotational
symmetry that one can have. This may be stated in the theorem; a crystal can
have only one-, two-, three-, four- and six-fold axis of symmetry. The proof of
this may be facilitated by the geometrical construction below:

pa
 
R rr
a a a
r
R 
R RR1 1R 1

x
Fig. 3.1
In fig. 3.1 R is a vector drawn to a lattice point (one of the points defined by
a n ), and R1 is another lattice point. R1 is chosen so as to be the closest lattice
point to R in the direction of one of the primitive translations; thus a  R  R 1

is the minimum separation distance between lattice points in that direction. The
coordinate system is chosen so that the y-axis is parallel to a . It will be assumed
that a line parallel to the x-axis and passing through the lattice point defined by
R is an n-fold axis of symmetry. Since all lattice points are equivalent, there
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2
must be a similar axis through the tip of R1 . If   , then a counter-
n
clockwise rotation of a about R by  produces a new lattice vector R r .
Similaly a clockwise rotation by the same angle of a about R1 produces a new
lattice point R1 r . From fig 3.1, R r  R1 r is parallel to the y-axis and
 
. Further, p a  a  2 a sin    a 1  2 cos   . Therefore
r
R r  R1  pa
2
p  1  2 cos  or cos    p  1 2  1 . This equation can be satisfied only for
p  3,2,1,0,1 or     2 1, 2 2, 2 3, 2 4, 2 6  . This is the result that
was to be proved.
It may be shown that if there exists C 3 , C 4 , C 6 then obviously , they lie on
vertical planes; ie C 3v , C 4 v and C 6 v that we see further. Do the operation C n
twice, thrice, …, k – times then we have the following:

Twice  2  C n2
2 
 n 
Thrice  2  C n3
3 
 n 
………. ………. ……..
k-times  2  C nk
k 
 n 

k n
If n is a multiple of k then C n  C n k . If k=n , then C n  e ; The structure
overlaps or is brought back onto itself. e denotes an identity element under
multiplication.
k  2 
 Cn are rotation through k   k= 0, 1, …, n-1 about an axis through
 n 
the centre and perpendicular to the structure plane. Elements of the given
k

1 2
group are : C n , k= 0, 1, …, n-1 or e, C n , C n ,..., C n
n 1

1
 The order of C n is n, generated by the element C n . Generated implies
1
each element of the given group may be obtain by multiplication of C n
by itself an appropriate number of times. The group C n is abelian as
C n  C n  C n  C n  C n ; C n has q  n classes. It should be noted
k l k l l k

that each C n has only one symmetry element of the n-fold rotation axis;
C1 has no symmetry element.

3.3.2.1 REFLECTION

A reflection maps every point onto it mirror image about a plane. Denote  a
reflection about a plane; a two-fold reflection about that plane is:  2  e
 13

3.3.2.2 ROTATION-REFLECTION

The operation C n followed by  in a plane perpendicular to that rotation axis

is an n-fold rotation–reflection S n (the group order is the number element in
that set ). S n  C n h   h C n
 h is the operation of reflection about the plane perpendicular to the given axis.

A
AB- rotation axis, u1 u 2 -
planes
 - solid angle between plane
u1 and u 2
M- observable point
u1  u2
M

B
Fig. 3.2

C AB  2  denotes rotation about AB: points A and B are invariant under

C AB  2  : A  A, B  B . Consider fig 3.3

2

1  2
 

Fig. 3.3

 1 and  2 denote mirror reflection about planes u1 and u 2 respectively. 

is the mirror reflection of  1 relative to  2 . Rotation through the solid angle
2 ;
 2 1  C  2  3.3.2.2.1
Thus, the product of two reflections about an axis perpendicular to two planes u1
and u 2 is equivalent to twice the angle between the two planes . (3.3.2.2.1) is a
reflection from the plane  2 to  1 . Rotation  2 1 is in the reverse direction
to  1 2 . Multiply (3.3.2.2.1) by  1 :
 2 1   1C  2  ; but  1  e ,  2   1C  2 
2 2
3.3.2.2.2
 14

Thus the product of rotation and reflection about a plane passing through the
rotational axis is equivalent to the reflection in another plane intersecting with the
first through half the angle of rotation.
Denote inversion operator by I :
I  S 2  C 2 3.3.2.2.3
Multiple (3.3.2.2.3) by  then we have I  C 2  C 2 or I  C 2 . Also
2

IC 2   .
The S 2 group has two elements: i.e. e and I and denoted as C i   e, I  . Thus,
the S 2 group has only a center of symmetry.

3.3.2.3 Dn group
It is the group of all axis of symmetry of a regular prism . Dn has the subset
of elements e, C n
1 2
, C n ,..., C n
n 1
 corresponding to the set of planes
 u1 , u 2 ,..., u n  . The Dn group has 2n elements. The order of the group is 2n.
The group is not abelian. E.g. :
1) n-odd, rotation through 120 0 and 240 0 fall into one and the same class.
k
Thus the set of elements C n , C n
n k
. Cn 
k

may be taken as rotation in the
k
reverse direction to Cn . Subtract from n , unity due to unit element; then (n-1)-
even. Thus the set of elements  e and C n , C n
k k
  fall into two classes .
n 1
Among rotations n-1 are pair-wise conjugate. They form classes each
2

with two elements C n , C n
k n k
 , k  1,2,..., n 2 1 . C    e n
n
form a class. All
two-fold axis C 2 form one class. Hence the number of classes q:
n 1 n3
q 11  . Here all axes are equivalent.
2 2
n2 nn 2 n n 2
2) n- even, we have C n  Cn , C n  e and Cn = C 2 constitute a class.
n2
The rest of the n-2 rotations pair-wise conjugate gives again classes of
2
n 2 nn 2
two elements each. It should be noted that C n  Cn  C 2 . Thus the classes

   
 e , C n k , C n n  k , C n n 2 ; k  1,2,..., n . Thus the number of classes with two
2
n2
elements is . It should be seen that the number of classes q:
2
n2 n
q  2 2  3.
2 2
Consider the group D3 . Examine the equilateral triangle in fig 3.4

u2 u1
 15

u3
Fig. 3.4

D3 group contains C 3 group with elements e, C 3

1
, C3
2
 . Consider rotation
through  rad about u1 , u 2 , u 3 planes. These are two-fold rotations that
correspond to two-fold axes and ui  e
Examine also in fig 3.5

u1
u4

u3

u2

Fig. 3.5

In addition to the four-fold rotations axis ,the group contains the two-fold axis
perpendicular to the four-fold axis plus additional two-fold axis ad required by the
existence of the four-fold axis. The order of the group is 8 with the elements
 1 2 3

e, C 4 , C 4 , C 4 , u1 , u 2 , u 3 , u 4 .

3.3.2.4 T. Group (regular tetrahedron group)

The system of axis of the T. group is the symmetry axis of a regular tetrahedron.
The three-fold axis passes through each vertices of the tetrahedron. Three-fold
1 2
axis corresponds to two rotations C3 and C3 . There are two-fold axes at the
1
opposite faces of a tetrahedron. The two-fold axis correspond to one rotation C 2
The above rotation correspond to an identical element e . The two-fold axes are
mutually perpendicular. The three-fold axis forms with each other the tetrahedron
angle   109 0 28' .
C3
C2 The T group has:
 16

an ide - an identity element e ;

N1  1
1
 - three rotation C 2 ;
 N 2  3 1  3
1 2
 - four rotation of C3 and C 3
 each;
N3  4  2  8

Thus the group has N elements: N  1  3  1  4  2  12 . The order of the group

is thus 12 . The T group as seen has four classes:  e , C 21   , C 
3
i 1
1 4
3 i 1
,

C  3
2 4
i 1
; here i indicates the axis. The number of classes q = 4 .

3.3.2.5 O. Group ( octahedral group)

It is a cubic group. It is a group of all symmetry operation of a cub in which

1 2 3
there are three four-fold axis C 4 , C 4 , C 4 through the centre of opposite
1 2
axis ; four three-fold axis C3 and C3 through opposite vertices ; six two-fold
axis C 2 through the middle of opposite sides. The elements of the group are:  e
1

   
3 3
  4
  6
, C 41 , C 4 3 i 1 , C n 2 i 1 , C31 , C3 3 i 1 , C 21 i 1 . The class number is, q  5
and number of elements N  1  2  3  1  3  2  4  1 6  24 .

C3
C4
C4

C2

GROUPS OF THE SECOND KIND

3.3.2.6 S 2 n Group
S 2 n is the simplest group of the second kind. It is a cyclic group. Thus the
entire group is obtained from the elements of the first kind. S 2 n is group rotation
 17

about a 2n-fold rotation-reflection axis. The group has 2n elements:

 2 2m 1 2

C 2 n , C 2 n ,..., C 2 n ,  h C 2 n ,  h C 2 n ,...,  h C 2 n .
1 2m

The operation S 2 n is equivalent to a rotation-reflection about a horizontal plane:

S 21n   h C 21n ,  2 m  e as two reflections is equal to an identity element.
Consider S 21 : S 21   h C 21  I . Thus the S 2 group has two elements e and I and
denoted as Ci   e, I 
Consequently the group has 2n elements.
Consider n  2k  1 ; then:  S 2 2 k 1 
2 k 1
 S 21   h C 21  I , then for n  2k  1 , the
group has an inversion I. Denote such a group by S nk  2  C 2 k 1,i  C 2 k 1  Ci .
1

The S 2 n is abelian; As each element form a class in the group, then the class
number is q  2n .

3.3.2.7 C nh Group

In addition to the n-fold axis of Cn , it contains a single mirror plane  h

perpendicular to the axis. The C nh has 2n element; i.e. n-rotation:
1 2 n 1
e, C n , C n ,..., C n and n rotation-reflection operations:
 h C n1 ,  h C n 2 ,...,  h C n n1 . Here C nn h   h . As each element in the group
forms a class there are q  2n classes. The group is Abelian.
If n  2k then the group has a centre of symmetry:
C 2kk  h  C 21 h  I
The simplest group C1h has two element e and  h denoted as C s ;
C s   e,  h  , C 2 n   e, C 2 ,  h , I  .

3.3.2.8 C nv Group

In addition to the n-fold rotation axis of C n the group C nv has a mirror plane
 v that contains the axis of rotation plus as many additional vertical mirror
planes as the existence of the n-fold axis requires. The C nv has 2n elements; i.e.
1 2 n 1
n-rotation about the n-fold axis: e, C n , C n ,..., C n and n-reflection in the
vertical planes:  v1 ,  v2 ,...,  vn . The group is not Abelian. The C nv group is
isomorphic to the Dn group:
1 2 n 1
e, C n , C n ,..., C n , u1 , u 2 ,..., u n : Dn
,  v ,  v ,...,  v : C nv
1 2 n 1
e, C n , C n ,..., C n 1 2 n

The distribution of element of C nv in terms of their classes depend on even and

odd n.
 18

n n
1) n-even. C nn  e , C 2  C n  2  C Constitutes a class each and the rest of
n n 2
n
n-2 rotation which are pair-wise conjugate gives again  1 classes of
2

  C n2 
n
two elements each. The classes are:  e , C k , C n k 2 ,  n  and
n n k 1  
n n
q  1  2  2   3 classes.
2 2
2) n-odd. All symmetry planes are equivalent. Reflections in them belong to
one and the same class . Amongst rotation about the axis , n-operation are
n 1
pair-wise conjugate with each other. They form classes each with
2


two elements: C k , C n k
n n 
n 1
2
k 1
   e form also a class.
. The set C n
n

n 1 n3
Thus q  11  classes.
2 2

3.3.2.9 Dnh Group

This is the most symmetric of the groups. It contains all elements of Dn plus a
mirror plane perpendicular to the n-fold axis of Cn . In addition to the n-fold
1 2 n 1
elements in Dn : e, C n , C n ,..., C n , u1 , u 2 ,..., u n , the group has n-
n 1
reflections  h and n rotation-reflections operations: e, S n , S n ,..., S n
1 2
. Thus
the group has 4n elements; the order of the group is 4n.The reflection commutes
with the rest of the elements of the group Dnh ; Dnh  Dn   e,  h   Dn  C s ,
where C s   e,  h  .
* If n-even, then an inversion of an element in the group: Dnh  Dn  Ci
Thus from the above , the number of classes in Dnh is doubled compared to the
Dn group
n3
1) n-odd ; q  2  n3
2
n 
2) n-even ; q  2  3   n  6
 2 
However the classes in Dnh coincides with those of Dn (rotation about the axis)
and the rest obtained due to multiplication by  h . If n-odd, then reflection in the
vertical plane  v belongs to the same class and if n-even, then they form two
classes. The reflection-rotation operation  h C nk and  h C nn  k are pair-wise
conjugate with each other.

2.3.2.10 Dnd Group

 19

Dnd contains elements of Dn plus planes containing the n-fold axis that bisect
the angles between the two-fold axis. Elements of this group are:
- The S 2 n group with the 2n-fold rotation–reflection about the horizontal
 1
axis with elements: e, S 2 n , S 2 n ,..., S 2 n
2 2 n 1
 ; it has 2n elements.
- The reflection in diagonal plane with elements:  d1 ,  d 2 ,...,  d n ; it  
has n elements
- The reflection about the two-fold axis with elements:  u1 , u 2 ,..., u n  ; it
has n elements
Thus the Dnd group has 4n elements. The number of classes is independent of
the parity of n.
Considering S 2 n group, then for even-n we have a two-fold rotation axis C 2
and for odd-n , an inversion I. It follows that the number of classes in Dnd is
2n  2
q  2  2  n  3 .The group is not Abelian. The elements of the group are:
2
e, S 1 2
, S 2 n ,..., S 2 n
2n
2 n 1

 2n elements
 d1 , d2 ,..., dn   n elements
 u1 , u 2 ,..., u n   n elements
The total number of element is 4n. The element  e and S 2 n coincide. It is
n
 
seen that for even-n we have C 2 and for odd-n, we have I. Thus for class
number, we have q  n  3
The Dnd group is a group of all symmetry elements of a figure that is made up
of two regular n-fold prism place on each other such that the side of one passes
through the centre of the other.

3.3.2.11 Td Group

The Td group is an n-fold symmetric group of a regular tetrahedron including

all improper operations. By improper operation any operation that takes a right
handed object onto a left handed one. The group has 3-fold axes C3 with
elements C31 and C32 giving a total N = 8 elements, and three 2-fold axes C 2
with element C 21 giving a total of N =3 elements, and then an identity element
e . It has the mirror planes:  d ,  d ,...,  d , making a total of six and three of
1 2 6

the elements: S and S , as S  C 2 making a total of six element. Thus in the

1
4
2
4
2
4
Td group, 24 elements are found:

Element Number of elements

4C 3 C31 , C32 8
4C 2 C 21 3
e 1
 20

 d ,  d ,...,  d
1 2 6
6
S 41 , S 42 ( 6
S 42  C 2 )

     
The classes are:  e , C3 ,C3 , C 21 , S 42 , S 42 ,  d  . It follows that the number
1 2

of classes is q  5 . The group is not abelian.

3.3.2.12 Th Group
Adding an inversion to T yields Th . Thus
Th  T   e, I   T  Ci
The Th group has N = 24 elements; 12 from T group and 12 due to inversion.
It has q  8 classes; 4 from T group and 4 due to inversion.

3.3.2.13 O h Group
The Oh group is an n-fold symmetric group of a cube (thus the O group)
including also improper operations that the horizontal reflection ( h ) admit;
Oh  O   e, I   O  Ci It is obtained by adding an inversion to the O. group. The
O. group has:

Element Number of elements

4C 4 C 41 , C 42 , 9
C 43
4C 3 C31 , C32 8
4C 2 C 1
2
6
e 1
Total=24

Considering the fact that Oh  O   e, I   O  Ci , the group has N = 24 elements;

10 classes as compare to 5 classes of the O. group.

CRYSTALLOGRAPHIC POINT GROUP

SYSTEM NOTATION BRAVAIS CLASSES ELEMENTS

LATTICE
TRICLINIC t 1 C1 , Ci 1, 2

MONOCLINIC m 2 C 2 , C1h , C 2 h 2, 2, 4

RHOMBIC 0R o 4 C 2 v , D2 , D2 h 4, 4, 8
ORTHOROMBIC
 21

RHOMBOHEDRAL rh 2 C 3 , S 6 , C 3v , D3 , D2 d 3, 6, 6, 6, 12
OR TRIGONAL
TETRAGONAL q 1 C 4 , S 4 , C 4 h , C 4 v , D2 d , , D4 , D44,4,8,8,8,8,12
h

HEXAGONAL h 1 C 6 , C3h , C 4 h , C 6 v , D3h , , D6 , D6,6,12,12,12,12,2

6h
4

CUBIC c 3 T6 , Th , Td , O, Oh 12,24,24,24,48

The list of the 7 crystal system and the 14 Bravais lattices

PROBLEMS

1. Consider the symmetry group of transformation of an equilateral triangle

(i.e. the dihedral group D3 ).
a) Write down the symmetry operations and work out the group
multiplication table.
b) Identify all the subgroups
c) Identify the classes.
 22

2. Show that an element of a group G constitutes a class by itself, if and

only if it commutes with all the elements of G .
3. Show that the set of elements which are the inverses of the elements of a
class of a group also forms a class.
4. Consider a class C of a group. Each element of C is use to generate a
cyclic group. Prove that the order is the same for each element of the class.
5. Prove that a crystal can have only one-, two-, three-, four-, and six-fold
axis of symmetry.

4. PERIODIC FUNCTION OF RECIPROCAL LATTICE

MILLER INDICES

4.1 RECIPROCAL LATTICE

We introduce a second Bravais lattice namely the reciprocal lattice with the
primitive translation that is shown further in the lecture. We select the Cartesian
system of coordinate  1 ,  2 ,  3 for a primitive cell. The vectors ai , i  1, 2,
 23

3 are dependent on the crystal symmetry. The vectors ai and  i are in the same
direction as in figure 4.1.1. 1

a1 2

a2
3
a3
Fig. 4.1.1

For the example of the use of the reciprocal lattice, we consider the microscopic
physical space value (said V  r  ) in the crystal to be periodic. Periodicity implies
that

 
V r  an  V r 
4.1.1

When we wish to deal with crystals of finite size, the question on boundary
condition usually arises: suppose the crystal is very large, and then we expect the
precise form of this not to affect the physical description of properties over the
broad crystal. We call this the cyclic or periodic boundary condition. Here the
value of any wave function is the same at equivalent points on opposite sites of
the crystal. This periodicity is represented mathematically by (4.4.1) or


V r  a n  Tˆa V r  n
 4.1.1'
Let N be the number of primitive cells counting from the direction of each
primitive translation Na j , j = 1, 2, 3. Suppose this brings us to a point not only
physically identical but mathematically identical to the original point. Thus we
may have Tˆa   r   t a   r  . This follows that t a  1 so that every eigen value
N N N
n n n

t aN  1 of TˆaN is root of unity of the form e ik . As the translation operator

n n

TˆaN commutes amongst themselves and with the Hamiltonian Ĥ , then for all
n

vectors an it may be found that

  Tˆ  Tˆ 
TˆaN  Tˆa
n 1
n1

a2
n2

a3
n3
  exp i   1  n 2  m 3  
We expand (4.1.1) in Fourier series:

     

V r   Vk1k 2 k3 exp2i 1 k1  2 k 2  3 k 3 
k1 , k 2 , k3     a1 a2 a 3 
4.1.2

Here k i , i  1, 2, 3 are some integers. Let`s do the transformations

 i   ik x k , i, k = 1, 2, 3
4.1.3
 24

Where  ik is the transformation matrix, then

   

V r   v   1 2 3
exp 2i   1 x1   2 x 2   3 x3   V b
exp 2i b, r
  
1, 2, 3 b

4.1.4
is the desired expansion using the reciprocal lattice: here r  r  x1 , x 2 , x3  ,
b  b  1 ,  2 ,  3  . In order to find b we use property (4.1.1):

V r  an   V b
  
exp 2i b, r exp 2i b, a n   
b

4.1.4 '
In order that it should be identical to (4.1.4), then exp 2i b, a n  1 or   

2i b, a n  2ik 
4.1.5
where k is some integer and:
G , a   n b , a   n  b , a   n b , a 
n 1 1 1 2 2 2 3 3 3

4.1.6

n1 b1 , a1  g 1   ;   
n 2 b2 , a 2  g 2  ; 
n3 b3 , a 3  g 3 
4.1.7
a1 , a 2 , a3 are not coplanar vectors. It’s a necessary and sufficient condition
to define vector b . From (4.1.7) it is obvious that b has the dimensions of
inverse length. Thus it is a reciprocal vector to vector a and a is a direct
vector, then:
b1 
a , a   ;
2 3
b2 
a , a   ;
3 1
b3 
a , a 
1 2

0 0 0
4.1.8
  
Here,  0  a1 , a 2 , a3 is the volume of elementary cell of the direct lattice and
b i , i  1, 2, 3 is the vector of the reciprocal lattice with primitive translation
b g  g 1 b1  g 2 b2  g 3 b3 4.1.9
It is obvious that
 bm , a n    mn 4.1.10
Take scale product of (4.1.8) by either vector a1 , a 2 or a3 then
1
 4.1.11
0
where  is the volume of the elementary cell of the reciprocal lattice. We may
obtain (4.1.11) in another manner. Let’s represent the expansion (4.1.2) in the
form


Vb   01  V r exp 2i b, r dr     
0

where  0 is the volume of the unit cell of the direct lattice. Suppose b i and bi`
be any two vectors. Consider first the Fourier representation of the Dirac delta
function:
 25

1 
  b  bi'    exp2i b  b
'
, r 
d r 4.1.12
   2  3 0
i

This is qualitatively obvious as completely localized functions must have the
Fourier component. Consider equation (4.1.1`), then we may be able to reduce
equation (4.1.12) to sum of integration over the unit cell namely
  exp2i  b  b , r  a  d r
1
  b  bi'   '
   2  3 an  0
i n

This follows that

 
 exp2i b  b , r d r     b, b ' 
'
i 0
  4.1.13
Here the generalized Kronical symbol is defined

1; if b  b '
 
 b, b ' 
  
  
0; otherwise

4.1.14
Equation (4.1.13) implies the result ( 4.1.4 ' ). When use in 4.1.4, suppose q

and q are two distinct direct lattice vectors; then the analogous equation
!

  d     q, q ' 
 exp2i q  q ,   2  4.1.15
'


3
 
where  is the volume of the unit cell of the reciprocal lattice which is called
the Brillouin zone (BZ). It is the basic region inside which the dispersion relation
of electron waves is discussed.
Let’s consider two expansions that are formally true:

 0   r  an    exp2i b, r 
an b

4.1.16
and
   b  bi'  
   exp2i b, a n 
b an

4.1.17

From equation (4.1.12), we may write:


 0   r  an     exp2i b, r  a n d b   exp2ib, r  exp2ib, a d b n
an an  0 an

 exp2i b, r    b  b d b    exp

  '   ' 
 2i b , r   b  b d b
'

b
 b
     

  exp  ' 
2i b , r     0   r  a n
  
  4.1.18
b an

This yield  0   1 .
The reciprocal lattice has all symmetries as the direct lattice. In reciprocal space is
set of reciprocal lattice. Its sites are specified by the radius vector bg related to
the translation vector a n of the direct lattice through (4.1.6). In real space, each
site may be surrounded by a polyhedron with properties: All points within it are
near to the given site than any other one. Such a construction is the Wigner-Seitz
 26

cell. The first BZ is the analogue in reciprocal space. Dispersion laws,

calculations in the band theory are carried out in the the BZ .

4.2 MILLER INDICES

Differentiate atomic planes in crystal. This may be done using Miller indices.
The coordinate of three atoms lying on the plane defined the position and
orientation of crystal plane. Select any atomic plane with three atoms as in fig.
4.2.1

 1

a1

 2

a2

a3  3

Fig. 4.2.1

Here  1 ,  2 ,  3 are coordinates where the given plane intersects with the main
coordinate axes (in unit of the lattice constant). Examine the ratio
1 1 1
; ; h; k ; 
1 2 3
4.2.1
Here h , k ,  are called Miller indices denoted as  hk . h , k ,  are
whole numbers. If the plane intersects the given coordinate axes at infinity, then
zero is the corresponding Miller indices. The selection of the indices implies a
separate plane or a family of parallel planes. The Miller indices is negative if the
plane intersect the given coordinate axes in the domain where it is negative. The
minus sign is put over the number not in front. For example we write  hk  and
not  h  k ,  .

Problems
1. Draw the plane of the faces of a cubic crystal with the following Miller
Indices: (100), (010), (001),  1 00 ,  0 1 0,  00 1  .
2. Show that a space lattice of a face centered cubic can be body centered
cubic and vice-versa in a reciprocal space.
3. Show that in a cubic system, the angles between normal to the planes

 h1 , k1 , 1  and  h2 , k 2 ,  2  is defined by the formula

 27

h1 h2  k1 k 2  1 2
cos  
h
1
2
 
 k12  12  h22  k 22  22 

5. LATTICE DYNAMICS

5.1 VIBRATIONAL MODES OF A MONOATOMIC LATTICE

5.1.1 LINEAR MONOATOMIC CHAIN

The atoms in a solid are always in constant thermal induced motion. Models in
which we discuss this motion are required. We may conveniently illustrate many
of the critical concepts in one dimension. This heading examines in details the
dynamics of a linear chain of atoms. For the sake of convenience, we assume only
one atom per unit cell for the given crystalline solid. Here we consider only
classical motion of the chain with no reference to quantization:
1-We assume atomic arrangement with minimum energy to be a periodic array of
atoms. In order to avoid surface effects, we consider the familiar periodic
 28

boundary condition: The crystal with it N lattice vector is part of an infinite

Bravais lattice; then the potential energy of the system is expanded in powers of
atomic displacements from the equilibrium position. The harmonic
approximation is used in the expansion of the potential energy where orders
higher than the quadratic are ignored. The approximation is good for mere solids
at room temperature. This can be further defined using the perturbation method.
The harmonic approximation leads to a classical equation of motion that is
conveniently solvable by introducing special linear combination of atomic
displacement called the normal coordinates. Express the potential and kinetic
energy of the system in terms of the normal coordinate. This contain no cross
terms. In it, we have only quadratic terms. This reduces the equation of motion
into a set of independent harmonic oscillator equations that are easily solvable.
The solutions of the system are called normal modes.
2-Despite large size and apparent complexity of the system, the ideal crystal
perfect periodicity enables us to define required normal modes frequency of the
system. This we assume periodic boundary conditions. Generally, crystal motion
is examined as a linear superposition of normal modes. These normal modes
correspond to the solution of traveling plane waves.
Apply some of the properties of these solutions to the case of a one dimensional
chain. Examine properties of a finite chain of N atoms with interatomic distances
a (lattice constant) as in fig 5.1.1

I
a

II

u n 1 un
u n 1
Fig. 5.1.1
To find normal modes, we impose further, boundary conditions at the end of the
finite chain. Neighboring atoms are coupled by a spring with force constant  .
In fig. 5.1.1 I, we have equilibrium position, and in 5.1.1 II, the atoms are
displaced out of their equilibrium position with displacement u k of the k th atom
. For the above system each atom has a degree of freedom, and for the entire
system, N degrees of freedom. The above model is well described by a linear
elementary Bravais lattice cell where the positions of the atom are determined by
the translation vector Tˆa  n a n where n is an integer showing the equilibrium
n

position of the atom in the given chain.

The atoms are linked among themselves in the chain by coupling force such that
the excitations are propagated in the chain in the form of waves in compression,
and all the atoms are displaced from their equilibrium position. We assumed that
 29

the coupling between near neighbors is much stronger than that between distance
neighbors.
If we consider the transmission of plane waves along the ox-axis of the chain,
then the displacement u : u  u  x, t  where x is the position and t , the time
moment of the wave. Considering the linear array of atoms with the interatomic
spacing a , then the equation u  u  x, t  can only be described at each atomic
site, and u have no value for intermediate values of x , and as a consequence,
the given equation is made more precised in the form u n  u  na, t  , where u n
is considered as the displacement of the n th atomic site at the time moment, t .
If we assume that the displacement of the atoms from their equilibrium position is
small, then the displacement function W  u n  (the potential energy) is small such
that we expand the function W  u n  in atomic displacement u n

 W  1   2W 
W  un  W  0   
 u 
 un  2    u
 u n u ' 
n  n 0 n  n 0
1   3W 
 
 u
 u n u ' u "  ...

n u n ' u n "
n n
6 n ' n"  0
5.1.1
The subscript zero means that the derivatives are evaluated at equilibrium. The
ground state configuration W  0   W0 is the equilibrium value and thus may be
the reference point (origin). We neglect W0 as it will not affect our answer. As
the potential has a minimum at the equilibrium position; then it follows that
 W 
   0  . This is because, in the equilibrium configuration, there is no net
 u n 0
force acting on the nucleus. The dynamic problem which (5.1.1) gives rise to is
only solvable in closed form if the anharmonic terms are neglected. For small
oscillations their effect is presumably much smaller than the harmornic terms. The
cubic and higher order terms are responsible for certain effects which completely
vanishes if they are left out. Whether or not one can neglect them depends on
what one wants to describe. We need anharmonic terms to explain thermal
expansion, a small correction (linear in temperature) to the specific heat of an
insulator at high temperatures, and the thermal resistivity of insulators at high
temperatures. The effect of the anharmonic terms is to introduce interactions
between the various normal modes of the lattice vibration. This shall not be our
point of concern in this heading, so we neglect their effects. At equilibrium, W is
minimum, thus the remaining term in (5.1.1) is quadratic in displacement and
describes the harmonic oscillations of the atomic lattice:
1   2W 
W  un     unu ' 5.1.2
2 n'  u n u n ' 
0
n

Such an approximation is called harmonic approximation. Here u n and u n '

corresponds to the displacement of two neighboring atoms. Further to avoid

surface effects, we take the periodic boundary conditions: the crystal with N
 30

lattice vector a n is part of an infinite crystal that is made of crystal vibrating

with identically atoms.
In order that the chain should have the property of translational invariance, it is
necessary that
  2W   
   W  
2
   P n  n' 5.1.3
 u n u '   
 n  0  u n ' u n 0
where 
P n  n'  is a tensor. The kinetic energy of the lattice is
1
E kin   M u .
2

n 2
Let’s find the equation of motion of the system. For that we write the Lagrangian
of the system as follows
1
L   M u n
2

1

 P n  n ' u n u n' 
n 2 2 nn'
and the equation of motion
d L L
  0.
dt u n u n
Considering the fact that
  2W   
 unu '  1    W  
2
1  u ' un  1  P n  n' unu ' ,
 
2 nn '  u n u n'  n
2 nn '  u n ' u n  n 2 nn ' n then
0 0

Mun   P n  n ' u n ² 
n'

5.2.4
The solution of this equation then proceeds in the usual way. In order to avoid
surface effect, we consider the familiar boundary conditions. The translational
symmetry of the lattice guarantee’s that the tensor P  n  n  depends only on the
'

difference n  n ' . For crystals with more than one atom per primitive cell will
require separate equations for each of the atoms per primitive cell.
Equation (5.1.4) is a large number of couple differential equations. It has no
direct solution. If we suppose that the wave length  a , then we have a
continuous distribution of the given wave as is the waves in a string. We consider
interaction constant representing coupling between pairs of atoms. We assume
coupling between near neighbors to be large as to that between distant neighbors.
Hence if (5.1.4) represents point particles coupled by springs, then we expect the
spring constant to be larger for nearer neighbors. Hence we are concerned with
short range interactions.
Let’s find the normal modes of vibration, i.e. type of movement such that all the
atoms oscillates with time with the same procession according to the law e it .
We find the solution of (5.1.4) in the form of progressive wave
u n  t   u n0 e it
5.1.5
Then considering (5.1.4)
Mu n0 2   P n  n ' u n0   ²
5.1.6
n'
 31

The tensor P has the property of translational symmetry. If we do the translation

n  n  1 and n '  n '  1 , then the difference n  n ' is invariant relative to this
translation and consequently u n0 and u n01 should describe a given defined state.
Thus the quantity u n0 and u n01 are connected through the relation
u n01  u n0 and  1

5.1.7
This follows that  is a complex value function and may be represented
  e iqa , where q has the dimension of inverse length and u n 1  u n  ...
0 0

and implies that

u n0  ae i q a ; a n  n a
n
5.1.8
where a n is lattice vector and q has the sense of wave vector. Considering
(5.1.5) and (5.1.8), it follows that
u n  t   ae i  q an t 
5.1.9
2
Here q  , where  is the wave length of the wave. If we substitute (5.5.9)

into (5.1.6), then it follows that
 
M 2   P n  n ² e i q  n  n 
'

n'

5.1.10
if we let   n  n ' then

M 2  P  0   2 P    cos qa   5.1.11
1

(5.1.11) is a dispersion relation. In the simplification, the sine function counsel’s

out as they are odd function with respect to  and the cosine function remains as
they are even functions. (5.1.11) shows that the frequency of the the distribution
of the wave in the crystal for different q are different. This phenomenon is
called dispersion. It follows that    q     q  , which implies the system has a
certain centre of inversion. Considering (5.1.11), the frequency of vibration of the
crystal does not depend on n . This implies that all atoms in the chain vibrate
with the same frequency.
2g
Let’s examine how q changes. Let q '  q  then
a
2g
u 'n  t   un  t e
ian
a

5.1.12
from where it follows that u n'  t   u n  t   . So q ' and q are physically equivalent
quantities. This of course is true since the crystal is translationally invariant. Let’s
find the domain of change of q . Let’s find the domain of change of q . For the

minimum value, it follows that 0  q   ; since  2   q    2  q  then it follows
a
  q is called the first Brillouin zone (BZ);
that   q  . This range of
a a
 32

which is defined in physics as the zone for different q . The centre of the BZ
corresponds to q   , where  is an infinitesimal value of q . This implies, we
may expand  2  q  in the sense that
 2  q    2  0    2  q  0 q   2  q 0 q 2  ...
' "

5.1.13
We consider (5.1.11) and we take the limits q  0 , then it follows that
  0   P  n  n   0 . This expresses the fact that the forces on any atom are the
2 '

same if each atom is displaced from the equilibrium position by the same amount.
Also since  2  q  is an even function of q and hence  2  q 0  0 , thus for
'

sufficiently small q ,
 2  q    const  q 2 or   q    const  q , 5.1.14
Equation (5.1.14) is a dispersion expression for waves propagating without
d
dissipation; i.e. their group velocity v g = dq equals their phase velocity

v ph  v ph ;
q
vg= v ph  const.
This is the type of vibrations in a continuum. The small q approximation is a
low frequency or long wavelength approximation; hence the discrete nature of the
lattice is unimportant. The significance of the phase velocity should be questioned
if we consider that many q may be use to describe the same lattice wave. If we
consider a periodic medium, say a crystal in contact with a homogeneous region,
then the phase velocity is not a uniquely defined concept; which follows that
2 
q max   , here min is the minimum wave length of the distribution of
 min a
the wave in the chain. This follows that the entire chain is made of two sublattice
where all the even atoms vibrate out of phase with respect to the odd ones. The
wavelength less than  min  2a cannot propagate down the linear chain lattice.
We know that the wave motion are periodic occurring time and space. If
min  2a the adjacent atoms are always 180 0 out of phase and for  min 2a
the adjacent atoms should be in phase. In this case, is not a wave motion but a
translation of the entire chain. Suppose we have a chain of N atoms as in fig. 5.12

1 2 3 ….. N

a
We enclose this chain so that the distance between the first and the N th is a.
The enclosed chain has N intervals. In order that the translational symmetry of the
crystal should not be disturbed, they should satisfy the condition
u n N  u n 5.1.15
 33

Condition (5.1.15) also known as the Born Von Karman condition implies that the
numbers n  N concerns one and the same atom. This implies that e iqaN  1
or qaN  2g , g  0,1,2... and
2g
q
aN
5.1.16
This implies that q is quantified. This follows that q is quantified and is found
only in expression of the type e  iqaN for which qan  2g . Then there is no
2
change in adding multiple to the wave vector q . Considering the inequality
a
 
 q and (5.1.16), then we have
a a
N N
 g 5.1.17
2 2
Thus the allowable quasi parameter q takes countable even values and N the
number of elementary cells in the chain. It is seen that the same cell of the atomic
2g
displacement may be represented by any one of the vectors q '  q  . It
a
2
should be noted that is the vector of the reciprocal lattice for the one
a
dimensional crystal. The redundancy is often expressed as periodicity in
reciprocal space of certain physical quantities is a consequence of the periodicity
in real space of the physical system. It should be noted q values of magnitude
greater than  gives no new solution to the equation of motion and thus gives
no new information and should be of no interest.
Consider a particular case, let from (5.1.8), we consider three values n '  n  1 ,
n , n  1 that correspond to P1 ; P 0  ; P 1  1  respectively. If we

consider the fact that  P n  n  0 then
'

n'
1
P  0   2 P 1  0 then P  0    P 1  
2
5.1.18
Considering (5.1.4) and (5.1.18) then we have
Mun     u n  u n 1    u n  u n1   5.1.19
or
Mun    2u n  u n 1  u n 1 
5.1.19 '
One the right hand side of (5.1.19`) of the square bracket, we may see a
displacement to the left and to the right of the given atom. Equation (5.1.19 `)
resembles the force in classical mechanics  F  x  . From the general law of
dispersion (5.1.11) we have: M 2  P  0   2 P  cos qa and considering
(5.1.18)
 qa 
M 2  P  0  2 P 1 cos qa   2 1  cos qa    4 sin 2   5.1.20
 2 
 34

4  qa 
and    sin   or
M  2 
 qa 
   max sin  
 2 
5.1.21
The (+) or (-) sign in equation (5.1.21) represents waves traveling either to the
right or to the left. The negative sign in (5.1.21) also correspond to the domain of
negative q . The frequency and wave vector may not independently be chosen.
Specifying one, the others are determined from the dispersion relation (5.1.21) for
the chain. From the dispersion relation (5.1.21), it follows that, what ever the
choice of the wave vector q or wave length  , the angular frequency  may
never be greater than unity. This is contrary to an ideal string that will propagate
the wave in any frequency. We may see from (5.1.21) that the vibration of the
atoms is independent of n . This implies that all the atoms in the chain oscillate
with one frequency.
 q

d

dq

 0 
 q
a a
Fig. 5.1.3

  
We may see that in fig 5.13 within the interval  ,  the dispersion curve
 a a
flattens at the edge of the BZ. This flattening is thought of as reflected waves

(waves in the opposite direction) that gradually increases until at q  and the
a
amplitude is equal to the incident component.
It may be seen that the graph is symmetric between q and  q . This implies
2
that waves to the left and right are identical. There is a repetition at each q   
a
 2g 
;  q    q   where g is an integer. This identical set of atomic
 a 
displacement may be represented by any of the set of the wave vector
 35

2g
q'  q  . Note that at long wave length  the frequency is linear in wave
a
number q . At large wave number, the dispersion curve approaches the BZ and
phase horizontal.

Consider N atoms and the periodic boundary condition; it follows that we have
N allowed values of q as the given wave. Considering N atoms, we have N
degrees of freedom and thus as a consequence, we may say all the modes are
found. Considering (5.1.21) it can be seen that, we have only one branch to the
vibration spectrum. Formula (5.1.21) is the dispersion law and its graph is shown
in fig 5.13. From the figure it is seen that the maximum frequency that the wave
may have in the lattice is  max . This frequency corresponds to the value

q max   . The values outside the given limit do not give us any new
a
information.
 qa  qa
In the case of long wave, i.e. for q small; sin    , in this case (5.1.21)
 2  2
takes the form
qa
   max
2
5.1.22
which is a linear dependence of   q  . The phase velocity v ph (wave velocity)
takes the form
 qa 
v ph    max a 5.1.23
q 2 M
and the group velocity
 
vg  a 5.1.24
q M
This implies that v g  v ph . That should have been expected as waves of long
wave length will not be sensitive to the discreteness of the structure. In other
words a large number of the atoms will participate like on a homogeneous line.
Thus long waves correspond to the propagation of sound wave. There is the

puzzling result that the group velocity goes to zero at q max   . This confirms
a
the fact that in the chain, the modes of vibration characterized stationary waves. If
2g
we consider that q ²  q 
a
 
then we expand  q ' in Taylor series:
d 1 ' 2 d 
 q '    q  q '  q  q  q
2
 ... .
dq 2 dq 2
If we consider only the first two terms of the expansion considering that powers
higher than q '  q are infinitesimally small then,
d
q '    q  q'  q
dq
 36

d
This shows formerly that the group velocity of the wave packet is dq . As we

have seen this velocity is zero at the boundary of the BZ q . This is energy
a
associated with the wave packet and located within it. The group velocity is the

velocity with which energy is carried and that velocity goes to zero for q   .
a
E
If we consider v ac  , the velocity of an acoustic wave where E is the

Young’s modulus and  the density, then
 qa  qa E 2
   max sin     max  q  v ac q and  max  v ac .
 2  q 0 2  a
Thus the phase velocity
 qa 
  qa  sin  
v ph    max sin   q hence  2  5.1.26
q  2  v ph  v ac
qa 2
and
  qa 
vg   v ac cos  5.1.27
q  2 
It is seen that for small q (see fig 5.1.4) we have v ph  vac  vac
v
v ph
E
v ac 

2
v ac

vg

0
 q
a
Fig. 5.1.4

5.1.2 DENSITY OF STATE

Consider q restricted to the first BZ for convenience. The notion of normal

modes with q chosen outside the first BZ is physically indistinguishable from
the one association with q ' within the first zone with q  q ' being the reciprocal
lattice vector. We evaluate how many modes have frequency in the range
    d . Defined the number of modes     d and call the distribution
function     the density of mode. The density of mode refers to the number of
 37

d£
modes d£ per unit frequency interval d :      . In the quantum picture
d
the given mode correspond to the different possible states of phonons. The modal
frequency  corresponds to an allowed phonon state of energy E   . This
follows that the density of modes may be referred too as density of state of
phonons. We already know that the condition for the allowed wave vector for the
2g 2
wave in a chain of N atoms is q  and then dq  dg and from (5.1.1)
Na Na
we have:
a a 2
d   max cos qa a  dq   max cos qa a  dg
2 2 Na
a 2 d£
 d£  2dg   max cos qa a 
2 Na 2
5.1.2.1
d£ 2N 1 2 1
and d  q  cos qa 2       N or
max  2
max 2
2 1
    ; 0   max 5.1.2.2
N  2
max 2
It should be noted that,     is finite at the point of frequency  max . The
divergence at    max is not physically unrealistic. Since it is an integral, this
singularity points no problem. It may be shown that the total number of modes is
N;

2 max d
    d  N 0  2   2  N
max

5.2 VIBRATIONAL MODES OF A DIATOMIC LINEAR CHAIN

We generalize discussion by considering the propagation of lattice vibration in

crystal with more than one atom per unit cell. We may do this such that the mass
of nearest neighbors differs from the mass of next nearest neighbor. The manner
of sodium chloride structure makes a simpler generalization by modifying masses
at alternate points as in fig 5.2.1.

u n! 1 u !n! 1 u !n u !n!

a
!
m m !!
Fig. 5.2.1
The propagation of waves remains one dimensional. Our analyses are carried out
in analogy with those in heading (5.1.1). In the case of two atoms per primitive
cell, there arises a new phenomenon. In the dispersion law, there arises two
 38

branches called the acoustic and optical branch. The optical mode appears in the
infra-red frequencies and can be excited by infra-red radiations.
Consider for convenience a linear Bravais lattice for which the elementary cell
of parameter 2a has two atoms. Such a system has 2N degrees of freedom. In
fig 5.1.1 is a linear chain with two types of atoms arranged alternately. A distance
a separate two neighboring atoms. Suppose we have light and heavy m '' atoms
with masses m ' and m '' respectively (i.e. m ' m '' ). We consider the force of
interaction between atoms to be short range. This implies that the atoms interact
only with their neighbors and as a result the equation of motion takes the form:
 
m ' un'   2u n'  u n''  u n'' 1
5.2.1

m "u ''
 n     2u ''
n  u '
n 
Where  is a force constant related with the elasticity. If we take into
consideration the fact that the interaction of the atoms with different masses has
different amplitudes, then we find the solution of equation (5.2.1) in the form of
progressive wave in the crystal:
u n'  a ' exp i  qan  t  ,
''
un  a " exp i  qan  t   5.2.2
It can be seen in u and u that we assume the same  and q for the motion
' ''
n n

of two types of atoms. This is from the fact that, we assume a simple wave motion
for which both types of atoms participate. It should be noted that though the
displacement of both types of atoms are different, they both contribute to one and
the same wave disturbance. If we substitute (5.2.2) into (5.2.1), then we have:


 m  ' 2
 2  a '
  e  iqa



 m  " 2
 2  a "
  e iq a

5.2.3

This system of homogeneous equation has a solution only if their determinant is

equal to zero:

2
 2

m'
 1  e iqa 
"
m

m
1  e iqa 
=0 5.2.4
2
  ''
2

The determinant gives immediately the dispersion law:

 39

 1 1  4 2  qa 
    2  '  ''   ' '' sin 2    0
4 2
5.2.5
m m  mm  2 
' ''
 1 1  4m m
0 2  2  '  ''  ,   '
2
'' 2 ,   1
2
Let 5.2.6
 m m  m  m 
Then
0 2  2  qa 

2  1  1   sin   
2
5.2.7
2   2  
The negative values of  have no physical sense and as consequence, we are
interested only on the positive values.
If we consider the case of (5.1.3), then each value of q correspond to each value
of  (univalent dependence of  on q ) and for the case of (5.2.7), each value
of q corresponds to two values of  ( bivalent dependence of  on q as a
result of  sign) and as consequence, we have two modes of vibration of the

type (5.2.2) which repeat for every . It should be expected as unit cell in this
a
 
case has a size of 2a and the first zone runs from  to . We have N
2a 2a
values of q in the given interval and thus, for the two complete branches, are
required 2N normal modes corresponding to 2N degrees of freedom of 2N atoms
that are confined to a line.
Examine what differentiate the two branches in (5.2.7):

0 2  2  qa 

ac 2  12  1  1   sin   
2
5.2.8
2   2  
called acoustic branch and
0 2  2  qa 

op  2 
2 2
1  1   sin   
2
5.2.9
2   2  
called optical branch. The splitting into acoustic and optic branches occurs for
any crystal with two atoms per primitive cell. It occurs also for the transverse as
well as longitudinal modes. For a general crystal with two atoms per primitive
cell, there are six modes.
Our structure chosen for treatment is selected for mathematical convenience.
The typical crystal with two atoms per primitive cell is NaCl structure. Let’s
 
investigate the two branches. Examine the Brillouin’s zone   q  , if we
a a
consider the fact that ac and op are even functions , then we limit ourselves to

the domain 0  q  .
a
For q = 0, we have
ac (0)=0, op (0)= 0 5.2.10
 40


For q = , we have
a
 2   2
ac ( )= , op ( )= m"  m ' 5.2.11
a m ''
a m'
For an infinitely increasing wave length (    and q  0 ), we expand (5.2.8)
and (5.2.9) in MacLaurin’s series limiting ourselves only to the first term of the
series:

ac  0  aq 5.2.12
4
and for the optical
2  qa     q 2 a 2  0 2   2q 2a 2 
2
op 2  0 1  1   2 sin 2     0 1  1   2  1  1 
2   2   2  4  2  8 

  2q2a2 
 0  1 
2

 16 
then

  2q2a 2 
op  0  1   5.2.13
 32 
It is seen that the dispersion of the optical branch is weak at the neighbourhood of
q = 0. Relations (5.2.12) and (5.2.13) are shown in figures 5.2 2. It is seen that
the optical branch decreases in a parabolic form.

 q

 op
2
m'

forbiden zone m ''  m '

2
m ''
 ac

  q
 0
a a
Fig. 5.2.2
 41

Consider the group velocity for the acoustic and optical branches
dac 0 2 2 a sin  qa  dop  2 2 a sin  qa 
  0
dq 16ac  qa   ; dq 16op  qa 
1   2 sin 2   1   2 sin 2  
 2   2 
 dac d op
 For q = , if m '  m" then   0 . It follows that  1 ,
a dq dq
d ac  02 a d op  02 a
if m  m (i.e.   1 ) then
' "  ; 
dq 8 ac dq 8 op

dac d
Thus for m'  m" ,  0, op  0
dq dq
dac 0 a
* For q = 0, considering (5.2.12), we have   0 and from (5.2.13),
dq 4
d op  02 a 2  2 q
we have  . Examine the case where m'  m"  m (see figure
dq 16
5.2.2).
It can be seen that the transition from the compound to a simple lattice will take
the lattice constant a twice less than the same, it follows that the Brillouin’s

0q
zone should be increases twice for the compound lattice a or
2
2
0q and for m'  m"  m , it follows   1 and we have figure 5.2.3 and fig
a
5.2.4. If in (5.2.6) and (5.2.7) we let m'  m"  m , then
 qa
ac  2 sin( ) 5.2.14
m 4
and
 qa
op  2 cos( ) 5.2.15
m 4

 q

m"  m '  m

Fig. 5.2.3

  q
 0
a a
 42

 q

2
m ''

2   2
  0
a a a a
q
Fig.5.2.4

 qa
In the previous heading (see 5.1.2) we had   2 sin( ) and if we
m 2
a  qa
substitute in place of a the quantity , then we have   2 sin( ) . It
2 m 4
follows that in the compound lattice, the acoustic branch satisfies the limiting
 
case. If from the part of the branch (  , ), we try to do the change of q , q ' =
a a
q  2 g , g = 1 then for q  q '  q  2 , the optical branch is the prolongation
a a
of the acoustic branch ‘(see figure 5.2.4). Then, we may see that the cosine
solution should be the duplication of the sine solution .This implies that, each
point on the cosine curve represents already a mode. This is an extended zone
representation .We examine the physical sense of the difference between the
acoustic and optical mode of vibration of atoms in the chain. In this connection,
we compare the amplitude of vibration and the phase of this vibration of
neighbouring atoms of each of the branches. It should be noted from (5.2.2)
u n'  a ' e i  qan t  , u n"  a" e i  qan t  from where we have
'
un a '
"

un a"
5.2.16
We examine the system of equation 5.2.3 from where we have
un '

a'


 e  iqa  1 
un "
a" 2  m ' 2
5.2.17
It follows that the amplitude are complex values. However, the physical sense

belongs to the real part and at the point q = 0 and q = (limiting vibration)
a
 43

they are real. Examine the case q = 0, that is the case of long waves length , in
this case , we have
u n' 2
 1 5.2.18
u n ac 2  m '  0
''

It implies that for the case of long wave vibration, the displacement of light and
heavy atoms coincide. The elementary cell vibrates as a whole. The vibrations of
neighbouring atoms are in phase. This follows that, both type of atoms move
together in a long wave length; pressure wave. We thus have a vibration of a
density and as the vibration of a density is sound vibration hence, the name
acoustic vibration. Consider (5.2.7), (5.2.6),
and (5.2.9), then for q = 0, we have

u n'   e iqa  1 2 m '' m ''

    '  e  i '
u n'' 2  m ' op 2
 1 1  m m
op q 0 2  m ' 2  '  '' 
m m 
This implies that one vibration lacks the other in the cell i.e. the atoms vibrate in
opposite direction ( in opposite phase). The two atoms in the cells are out of phase
by  . The centre of mass of each cell that has two types of atom is at rest; we
have
u n' m '  u n'' m ''  0 5.2.20
Dividing (5.2.20) by m  m :
'' '

m ' OG1  m " OG2 u n' m '  u n'' m ''

OG   =0
m ' m " m ''  m '
we have the displacement of the centre of mass. The heavy and light atoms have
zero displacement for long wave length. If there is a charge difference of the two
atoms, this causes a polarization wave with wave vector q . Such a system may
either absorbs or emits light from where the name optical vibration. For mere
solids, this frequency is similar to that of infrared light and thus the name optical
vibration. Thus, optical modes occur at infra-red frequencies. They can be
excited with infra-red radiations.

Consider the case of the limiting value q  for the Brillouin zone
a
u n' 0 0
 
u n'' 2 0 5.2.21
ac 2  m ' '
m
This follows that in the limit of short acoustic wave, the light atoms are at rest and
the heavy ones displace and as consequence the density changes as the atoms are
heavy. Let’s consider the case of the optical branch,
un'


 1  e  i  
0
un op 2  m' 2 0
'' 5.2.22
'
m
 44

 2  2
It is known from (5.2.11) that ac ( )  , op ( )  . Let’s remove the
a m' a m"

indeterminacy in (5.2.22). Suppose q =    :
a
un'
 1  e 
 i
 5.2.23
u n op 2  m ' 2
''

0 2  2 a    0 
2
2  a 

op 2   1  1   2
sin       1  1   cos    .
2

2  2 a  2   2 
u n'  1
We expand this taking that  is very small then :     . This
u n'' op
2 
implies that the heavy atoms are at rest and the light atoms are vibrating.

5.3 VIBRATIONAL MODES IN THREE- DIMENSIONNAL

CRYSTAL

We consider the lattice dynamics in the crystal base on the harmonic interaction
potential. The force constant on the nearest neighbour interaction is considered
stronger. We consider a crystal in which every atom undergoes small oscillation
around their equilibrium position. Considering a harmonic potential, we find
solution to the equations of motion of atoms in the form of plane wave (sinusoidal
or cosinusoidal). Sinusoidal or cosinusoidal time dependant is determined by the
phonon frequency  that is a function of the phonon wave vector q . We
consider an elementary cell with s atoms that have masses mk , k  1,..., s . The
crystal with volume V= N0 has N  G 3 elementary cells with  0 being the
volume of an elementary cell has a total of Ns atoms. Each atom in the crystal has
three degrees of freedom, then for Ns atoms, 3Ns degrees of freedom. Consider a
crystal to be a parallelepiped with edges of length Gai , i  1, 2,3 that are parallel

to the corresponding lattice vector. Taking as basis vectors ai , we denote the

equilibrium position by an  :
   
an  n1 a1  n2 a2  n3 a3 5.3.1
where n1 , n2 , n3 are integers. The displacement of the k th atom from the
k k
equilibrium position is denoted by un so that the position vector rn of the k th
  k
atom is : rnk  an  u n where un has  cartesian components un ,   ( x, y, z ) .
k k

We proceed classically then the total kinetic energy may be written:

1
Ekin   mk u nk u nk 5.3.3
2 nk
where mk is the mass of the k th atom. Since the vibration of the lattice involves,
small execution from the equilibrium position, then we may expand the many
k
body potential in powers of atomic displacement un  :
 45

 W  1 k'   2W 
W  W0    k  unk   n n ' '  u k u k '   .....
u k
u
nk  un  0 2 nk n ' k ' '  n n ' '  0
Here, the subscript zero implies that the derivatives are evaluated at the
equilibrium configuration. The ground state potential energy W0 , may always
be said equal to zero and there by makes a reference point. This will not affect our
answer. We assume that the electrons in the crystal always have time to adjust it
selves to the configuration with lowest energy even during crystal vibration. In
fact at the equilibrium configuration, there is no net force on the nuclei. If we
limit ourselves to the harmonic approximation in which terms in the expansion of
the order higher than quadratic are ignored, then W becomes:
1  k k ' k k'
W  W '   un un ' ' 5.3.5
2 nk n ' k ' '  n n '

  2W   k k '
where  k k '   W '   5.3.6
 un un ' '  0  n n '
The quantity 5.3.6 depends on the atomic arrangement of the crystal and the
interatomic potential. It is seen that the harmonic potential W of the 3-
dimensional crystal is written in terms of the displacement vector of each atom
from its equilibrium position as in (5.3.5). The sum externs over all pairs of atoms
located at n and n’.
At low temperatures ( T  0 ), it is not too unreasonable to go by the harmonic
approximation. The separation between atoms is of the order of one Armstrong
and at some temperature; vibration has amplitude of the order of 0.1 Armstrong.
Experiments will show our idealisation to be false. In our case, the general
approach is to make idealisation then find corrections to this approach to give
better results. It should be noted that the harmonic approximation is a good
approximation; a classical mechanical theorem is used to have exact solution to
the equation of motion. This can be done by first finding special linear
combinations called normal coordinates of the atomic displacement coordinates.
The potential and the kinetic energy of the system contain no cross terms if
express in the normal coordinates, they contain only quadratic terms. We then
find equations of motion that reduce to set of independent harmonic oscillation
equations that are easily solvable. The solutions are called normal modes of the
system. Write the Lagrangian L of the system; L  E kin  W , and then the equation
of motion becomes:
d  L  L
 k   k  0 or mk un   n
 k W '  nn '  un ' '
kk ' k'
5.3.7
dt  u n  un ' k ' '

This gives a system of 3Ns equations. These equations are true for each 
k
Cartesian component of displacement un . This shows that (5.3.7) forms a large
number of coupled differential equations and thus may not be solved directly.
Consider the properties of (5.3.6):
 46

1) W '  nn '   W '  nn '  . It is invariant relative to all indices .This is as a result of
kk ' kk '

the independence of the order of differential equation in (5.3.6).

2) W ' 
kk '
nn '  W 
 '
k 'k
n'  n  . The expression in (5.3.5) is invariant under translation
by the lattice vector (5.3.1).
3) We suppose that at the initial moment, the crystal is at the temperature T=0.
This follows there is no vibration and consequently, the displacement is a
0
constant. If all atoms in the crystal have the same displacement say u ' from the
equality: u '  u ' then the entire system is simply displaced without interval
k' 0

distortions. Then the right hand side of (5.3.7) will have the same value as when
the displacement vanishes:
 u0 ' W '  kknn''   0
' n 'k '
5.3.8
from where is followed that
W '  kknn''   0
n'k '
5.3.9
0
which is the condition that (5.3.8) vanishes for arbitrary u ' . Equation (5.3.9)
expresses the fact that the forces on any atom is zero if each atom is displaced
0
from the equilibrium position by the same amount say u ' .
Expression (5.3.5) is invariant relative to the translation by the lattice vector
(5.3.1). Then it satisfies Bloch’s theorem:
  
uk n  ak ei ( q .an t )  ei q.an uk 0  t  5.3.10


where  is the phonon frequency associated with the wave vector q . Substitute
this in (5.3.7)
 2 mk ak   W '  kknn ''  ei ( q an ' an ) ak '' .
  

5.3.11
n ' k ' '

Let’s call
' ( q )   W '  e
  
kk '  kk ' i ( q , an '  an )
B nn ' 5.3.12
n'

the dynamic matrix. Thus the phonon properties can be determined from the
kk '
dynamic matrix B ' . If we move from the sum with respect to n’ to the sum with
respect to   n  n ' , then we see that the right hand side (5.3.11) is independent of
n. We expect that as the left hand side is independent of n, then it follows that:
kk '  k '
 2 mk ak   B ' ( q )a '   5.3.13
k ' '

Introducing the Kroneker dalta symbol, the left hand side of (5.3.13) can be
written in the form
 2 mk ak    2 mk ' ak '' kk ' '
k ' '
then
 (B
k ' '
kk '
 '   2 mk ' kk ' ' )ak ''  0 5.3.14
 47

k'
It is a system of homogeneous equation for the quantity a ' . This system has non
trivial solution if the determinant is zero. This is a condition for which the phonon
frequency  (q ) may be obtained. Thus
'   mk ' kk '  0
kk ' 2
B 5.3.15
It is a determinant of the type 3s  3s with 3s independent eigen values and there
are (3s-3) optical modes. The number of equations in (5.3.14) is obtained from the
number of possible polarization direction (three of them). That is two transverse
and one longitudinal times the number of atoms in the unit cell.
Considering the fact that the production is a factor N smaller than the number of
equations in (5.3.7), then the solution of (5.3.14) is quite possible. In principle, the
system should be solvable for all possible value of q for which we have N of
them. Practically, it is sufficient to solve for a reasonable number of q. Other
solution are obtained from interpolation, thus the equation of the determinant
(5.3.15) gives the phonon spectral of the crystal. This gives us information about
the rule of electron-electron, electron-ion and electron-phonon interaction. It
explains phonon characteristic responsible for atomic properties.

kk '
PROPERTIES OF THE DYNAMIC MATRIX B '
If we consider (5.3.12), we see that the dynamic matrix is hermitian. That is it
takes real values
 kk ' * 
Bkk'' (q )  B ' (q ) 5.3.16
The characteristic equation has a real spectrum. This implies that  is real. 2

Physically, it is obvious that  2 may not be less than zero as considering (5.3.10),
there appears the term e 0t which implies the instability of the lattice. If we solve
2  2  2 
(5.3.15), then we have 3s different values: 1 (q ),...,  j (q ),..., 3 s (q ) , j =1,2,
 2 
…,3s ; q is a 3-dim vector and thus, the surface  (q ) is a 4-dimensional hyper
 
surface. If we do the change q  q then it is easy to see that 

' (  q )   B ' ( q )  B ' ( q )

kk '  k 'k  * k 'k 
B 5.3.17
and if we substitute in (5.3.15), we see that the determinant changes rows for
columns and vice-versa and thus
 
 2j (q )   2j (q ) 5.3.18
Since  j  0 , it implies
2

 
 j ( q )   j ( q ) 5.3.19
 
If in (5.3.11), we let q  q then
 
a kj (q )  (a kj )* (q ) 5.3.20
Let    
q  q '  q  2 b j 5.3.21

where b j is the vector of the reciprocal lattice. If we substitute (5.3.21) into
(5.3.10), then:
 48

   

k i ( q .an t ) i 2 ( bg , an ) k i 2 ( bg , an )
(u )  a e
k '
n  e u e
n uk nei 2 l
  
Here l  (bg , an ) is an integer and ei 2 l =1. The minimum of bg in order to have
    
the minimum value of q is the inverse value of an  n1 a1  n2 a2  n3 a3 . If
            
a1  a2  0 or a1  a3  0 or a2  a3  0 then we either have a1 or a2 or a3  0
   
from where it follows that an  ai , i =1,2,3. Similarly, bg  bi , i =1,2,3 . This
follows that
         
(q ', an )  (q ', ai )  (q , ai )  2 (bi , ai )  (q , ai )  2 5.3.22
It is obvious that with the result, there is no appearance of the new wave and thus
 
  (q , ai )   , i =1,2,3 5.3.23
which is the domain of  physically non differentiable value  of q. For the cubic
crystal, we have   q   ,   ( x, y, z ) , where q is the   cartesian

component of q for the  axis. Thus, the physical non differentiable domain of q
2 
is the Brillouin zone (BZ); for the dispersion law in place of the graph of  j (q ) ,

we have  j (q )  const . There are points in the BZ where the dynamic matrix is
  
real. That is when ei ( q , an  an ') disappears, that is when:
 
1) q  0
 
2) ( q , a )  
3) If in the lattice, there is a centre of inversion, then the sum with respect to n’
 
may be divided into two for which at the end the ei ( q ,a n  a n ' ) tends to a cosine
function that is real.
We examine the case when q = 0, this is the limiting case for long wave vectors.
If we consider (5.3.11), then:
 2j (0)a kj (0)   W '  nn '  a j ' (0)
kk ' k'
5.3.24
n ' k ' '

For   0 , then the right hand side of (5.3.24) is equal to zero. This is a
2
j

particular case of the one-dimensional lattice for q = 0 for which ac  0 . If we

consider (5.3.9), then the right hand side of (5.3.24) is equal to zero and for that
ak '' (0)  a0 ' 5.3.25
There exists three directions which  j  0 independent of the symmetry of the
2

crystal. This is because q = 0 corresponds to identical displacement (see 5.3.25) of

all atoms of the crystal and cannot cause any change. Hence,
 
 2j (q  0)  0 5.3.26
This is in accordance with Bohm-Staver for longitudinal wave at q = 0.
Not withstanding, there is more than one type of atom in the case where atoms
occupy physically equivalent site. The different type of atoms may vibrate out of
phase with one another. Thus (5.3.26) may not hold for all modes. However it
must hold for three modes; these three modes are called acoustic modes. This is
 49

due to the fact that at low q, there are frequencies of the order of those of sound.
The remaining mode that equation (5.3.26) does not hold has frequencies in the
infrared region of the spectrum. They are called optical modes. From (5.3.25), it
follows that the amplitude is independent of the type of atom and from (5.3.10),
0  it
we have un  a .e ; which follows that the entire elementary cell vibrate as a
k

total whole with different phases. If we assume    , then such a wave does
not fill the discreteness of the structure in an elastic medium. If the crystal is
isotropic, then for the given waves, we have one longitudinal and two transverse
waves. In an anisotropic crystal, it is not possible to see longitudinal and
transverse wave. A crystal as a whole is anisotropic. We examine a cubic crystal
for longitudinal and transverse waves simply for convenience. We know that j
=1,2,…..,3s and for the case of j =1,2,3, we have  j (0)  0 and for the case of
(3s-3), we have  j (0)  0 (3s-3 optical modes). Then from (5.3.24), we have:
 2 (0) mk ak (0)   ak '' (0) W '  nn '
kk '
5.3.27
k k ' ' n'k

As W ' is symmetric with respect to indices n and n’ then from (5.3.27),
W    W    0
n 'k
 '
kk '
nn '
nk
 '
kk '
nn '

and as  j (0)  0 then

m a
k
k
k  (0)  0 5.3.28
 
i ( q .an t )
If we multiply (5.3.28) by a factor considering e then

m U
k
k
k
n (0)
 
0 5.3.29
q 0

This gives us a character of the vibration for (3s-3) cases, in particular, for the
elementary cell, the centre of mass remains at rest .Such a vibrationis called
 
optical. The centre of gravity is constant. From  (q )   (q ) , for q  0 , we

expand  (q ) in the series:

 (q )   (0)   C 'q q ' 5.3.30 
 '

We may bring the sum  C ' q q ' , to the diagonal form C q 2
that leads us  
 ' 
2
 
to Cq . All the acoustic frequencies are equal to zero for q  0 . Here, we have
 
degeneracy. The dependence for q  0 , implies
 
 (q )  c ( q ) 5.3.31
that for which we have the acoustic vibration. In the crystal of N a Cl type, we
have s = 2 and j =1  6. This follows that there exists 3 branches which are

obviously acoustic; see figure 5.3.1. The inferior branches are small for small q
and linearly tend to zero which we call acoustic and the rest of the (3s-3) branches
are optical and have branches with longitudinal and transverse vibrations. The
 50

velocity of propagation of longitudinal waves is greater than those of transverse

wave as the frequencies of vibration of longitudinal waves are greater than those
of transverse waves ( L T2 T1 ). Here L and T stand for longitudinal and
transverse modes respectively.

 q

Lop

T2 OP

T1op

Lac

T2 ac

T1ac

  q
 0
a a

Fig. 5.3.1

CYCLIC BOUNDARY CONDITION FOR THREE-DIMENSIONNAL

CASES (BORN-VON KARMAN CYCLIC CONDITION)

Let’s be given a cell as illustrated in figure 5.3.2:

 51

G2 a2

G3 a 3

G1 a1
Fig. 5.3.2
  
We have the cyclic condition if for an  an  Gai , j =1,2,3 then in (5.3.10) i.e. in
 
unk  ak .ei ( q .an t ) , the displacement un is invariant since
k

 
ei ( q.ai )G  1 5.3.32
 
where G ( q, ai )  2 gi and gi whole numbers from where
  2 gi
( q , ai )  5.3.33
G
It can be shown that
 2 
q bg 5.3.34
G
 
where bg is a vector of reciprocal lattice and q is now quasi discrete. It can be
shown that the variation of q may be bounded by the limits of the BZ (Wigner-
Seitz cell ) and may be found from
 
  (q , ai )   5.3.35
and from here, considering (5.3.34), we have
G G
  gi  5.3.36
2 2
where gi takes G/2 values , G 3  N the number of elementary cells in the

principal domain of the crystal . If G1  G2  G3 then q is equal to G1G2G3  N
values and Gi is a whole number. We know that the volume of the BZ is equal to
(2 )3
. We may calculate the number of different vibrations per unit volume of
0
the given crystal which is equal to the density of vibration; thus
N N 0 V
 
(2 ) 3
(2 ) 3
(2 )3
0
where V is the volume of the given crystal.
 52

5.4. NORMAL VIBRATION OF A THREE DIMENSIONAL

CRYSTAL

The kinetic energy of the lattice is

1
Ekin   mk (u nk ) 2 5.4.1
nk 2
and the potential energy is
1
W  W '  kk nn '  un u n ' '
' k k'
5.4.2
2 nk n ' k ' '
It is convenient for us to transform to normal modes. This implies that instead of
the system of vibrating atoms, we deal with the set of wave (modes). The
amplitude of these are called normal  coordinates. It may be seen further that, they
are dependant on the wave vector q  :
1   i ( q, 
unk 
N qj

a j ( q , t ) a k
j ( q )e an ) 5.4.3
   k
where a kj (q )ei ( q ,an ) are plane waves in the crystal and a j is the amplitude of the
wave with polarization j . If
 
a j (q )  a*j (q ) 5.4.4

then a j (q) is complex value and we can show that the expression on the right
hand side of (5.4.3) is real:
1    i ( q,an )
unk*  
N qj
a j (  q , t ) a k
j ( q )e  unk 5.4.5

We introduce the following normalization condition that we prove:

nk
 
    *

 mk a kj (q )ei ( q,a n ) a kj ' (q )ei ( q ',a n )  Nm qq' jj ' 5.4.6
s
where m represents the mass of all atoms in the system ; that is m   mk . Let’s
k 1

define
 
   ei ( q  q ', an ) 5.4.7
n
  
If q  q ' as e 0  1, implies   N , which is the number of the lattice vector an .
     2 
If q  q ' then q and q '  q  b g are physically equivalent. If we consider the
G
   
lattice vector a m , then we can do the transformation a n  a n  a m in (5.4.7). The
crystal is a closure of the entire space then  is invariant relative to such a
transformation and thus
         
   ei ( q  q ', an )   ei ( q  q ', an  am )  ei ( q  q ', am ) 
n n

and
  
 1  ei ( q  q ', am )   0
 
 53

  
Since a m is a vector of the direct lattice and since q  q ' , then it follows that
only  = 0, thus
  

n ei (q  q ',a n )  N qq ' . 5.4.8

 
The quantity  is called lattice sum. Here q  q ' is a lattice vector of a reciprocal
  2 
lattice. It is obvious that q '  q  b g . Let’s get equation for the amplitude of
G
the wave i.e.
mk  2j a kj   B kk ' k '
' a j ' 5.4.9a
k ' '

 a    B  a
* kk ' * k '
mk  2
j'
k
j '  ' j ' ' . 5.4.9b
k ' '

Let’s multiply (5.4.9a) and (5.4.9b) by  a kj  and a j ' respectively and we take
k *

the sum with respect to the indices k and  after which we subtract the second
from the first and we have :
( 2j   2j ' ) mk a kj a kj '    B
kk ' k ' *k *kk ' * k k

' a j ' a j ' '  B ' a j ' a j '  '   0 5.4.10
k kk ' '

We do the change of indices k   k

'
and    
'
if j  j ' and there is no
degeneracy, then the different branches do not intersect and thus  j   j ' and the
2 2

right hand side of (5.4.10) is zero. If j  j ' , then  j   j ' and the right hand side
2 2

of (5.4.10) may be equal to zero. Then to what should be the sum m a

k
k
*k
j a kj '

for j  j' . If we examine a particular case, then the lattice is simple for k=1:
 mk a*kj a kj '  m  a* j a j '
k k 1,

If the amplitude is taken in such a way that there are a unit polarization vector i.e.
unk  1 , then it follows that
m a
k
k
*k
j a kj '  m jj ' 5.4.11
1
But from definition Ekin   mk u n (t ) . If we substitute (5.4.3) into (5.4.1),
k 2

nk 2

then we have:
1   
   *
Ekin  
2 N nk
mk  a j (q , t ) a kj ei ( q , an )  a *j ' (q , t )  a kj ' (q )ei ( q , a n )  =

q, j

q ', j '

1  m  2
 
2 N q, jq', j '
a j (q , t )a*j (q, t ) Nm qq ' jj '   a j (q , t )
2 q ', j
Thus
m  2
Ekin   a j (q,t ) 5.4.12
2 q, j
Let’s examine the expression for the potential energy:
 54

1 1
W '  kk
nn '  un un ' '  W '    j  j )e  
*   i ( q,a n ) *
W 
2 nk n ' k ' '
' k k'

2N

nk n ' k ' '
kk '
nn ' a
q, j
( q , t )  a k
( q
  i ( q,a n )


k'
a j ' (q , t )a j ' (q ')e 
q, j '

1     
 
=
2N
   
nk n ' k ' ' q , j , q ', j '
W 'ei ( q , a n '  a n ) ei ( q '  q , a n ) a*j (q, t )a kj ' (q ).a*jk (q ) a j  q, t  '

1 kk '   *k  i ( q' q,a n ) 

=
2N

nk n ' k ' '
B ' ( q ') a k'
j ' ( q )a j (q )e a j ' (q, t )a*j (q , t )

From (5.4.9), mk  j a j   B ' .a j ' then,

2 k kk ' k'

k ' '

1   
 
W
2N

nk jj ' qq '
mk  2j ' a kj a*j ei ( q '  q ,an ) a j ' (q , t )a *j ' (q , t )

and from (5.4.11) m a

k
k
*k
j a kj '  m jj ' then

 jj ' e i  q  q ,qn  a j '  q, t  a *j  q, t 

1
 m
'
W  2
j
2N njj ' q ' q
  

and considering (5.4.8)  e  N  qq ' , then we have

i ( q '  q , an )

m 2   2

2 q j
 j ( q ) aW
j ( q , t) 5.4.13

The total energy of vibration of the crystal is:

 
m 
E 
2 2
 j ( q, t )   2j ( q) a j ( q, t )
a 5.4.14
2 q j
This expression is the energy of the system of independent harmonic oscillation
with frequencies  j . In order to represent the energy of the system in the form of
independent harmonic oscillator, we have to express the complex valued function
a j (q, t ) through real normal coordinate such that the condition (5.4.4) i.e.
a j (q )  a*j ( q) should be automatically satisfied. Let’s be given the Lagrangian :

L  Ekin  W
then the equation of motion for the normal coordinate is obtained from
d  L  L
  0
dt  a j  a j
from where we have
a j   2j a j  0 , j  1, 2,3,... 5.4.15

Vector q has Ns values and the system (5.4.15) has 3Ns equations. The normal

coordinate a j are complex values. We moved from complex valued normal
coordinate to real valued normal coordinate. The wave in the crystal should be a
 55

moving wave and not a standing wave and thus, the real normal coordinate should
be canonical. Thus, the canonical transformation:
  1  
a j (q )  Q j (q )   Q (q ) 5.4.16
 j (q ) j
 * 
There is difficulties here; considering (5.4.4), then we have a j (q , t )  a j (q , t ) .
 *  3Ns
As Q j (q )  Q j (q ) then we have equations and not 3Ns as expected. Thus
2

we select a j (q) such that 
 1    i   
a j (q )  Q j (q )  Q j (q )   Q j (q )  Q j (q )   5.4.17
2   j (q ) 
Let
 1  i 
 j ( q )  Q j ( q )   Q (q )  5.4.18
2   j (q ) 
then :
1 
 
 j  q   *j q   
Q j  q 
i
 

 q
Q 5.4.19
j
2  q
 j 
Thus from (5.4.17), (5.4.18), (5.4.19), we have:
  
a j (q )   j (q )   *j (q ) 5.4.20

We show that Q j (q) are normal coordinate. For this, we classify the dependence
of  j on time t . Let’s derivate  j with respect to time:
1 

 j q 
2

Q j q 
i
j q  
 q 
Q j


It is necessary to obtain
 (q)   2 ( q)Q (q)  0
Q 5.4.21
j j j

from where:
1 

 j q  Q j q  i
    
  2j q Q j q    j q    q 
2
 j q  

j 5.4.22

It follows from here that

 i j t i j t
j e ,  j  e
5.4.23 
for a given q and j, from (5.4.3) considering (5.4.20), we have
1    1  
 

unk   j (q )a kj (q )ei ( q ,an )   *j (q )a kj (q )e i (q ,an )
N q, j N q, j
and from
   
a kj (q )  a*jk (q ) , unk  A cos  (q, an )   j t   
which shows that in the crystal we have a moving wave. If now, we substitute
(5.4.20) into (5.4.14); then it follows that
 56

E
m

2 q, j
 2
 j   *j   2j  j   *j
2

Then from condition (5.4.22), we have:
m
E    2j  ( *j (q )   j ( q )( j ( q )   *j ( q )  ( j (q )   *j ( q )( *j ( q)   j ( q )) =
       
2 q, j
m 
  2
 2  2j (q )  j (q )   j ( q ) .
2 q, j 
 2

As the Brillouin zone has a centre of inversion, then
 2
E  2m  j (q )  2j (q )

q, j
 
5.4.24

And from here considering (5.4.18), for  j (q ) , we have:
m
  
E   Q 2j (q )   2j (q )Q 2j (q )
2 q, j
 2
 5.4.25

Here Q j are normal coordinates. Let’s find the Hamilton function of the crystal
vibration. The general momentum is given by:
 E
Pj ( q )    mQ j 5.4.26
Q j
Thus
  
 Pj2 (q ) m 2j (q )Q 2j (q ) 
H ( P, Q )      5.4.27
q, j 

 2m 2 

5.5 SECOND QUANTIZATION OF THE PHONON FIELD

For higher temperatures T in a crystal, the kinetic energy is must higher than the
potential energy. In this case, we may renormalize the potential energy. If the
temperatures are lower, then the potential energy is much higher than the kinetic
energy. When we examine the interaction of the electron with the crystal lattice
vibrations then the above notions are very convenient to take note of. In the
coordinate representation, the Hamiltonian of the system has the form
  
 Pj2 (q ) m 2j (q )Q 2j (q ) 
H ( P, Q )      5.5.1
q, j 

 2 m 2 
and
 Pˆj2 (q) m 2j (q)Qˆ 2j (q) 
H ( p, q )   
ˆ   5.5.2
q, j 

 2 m 2 

where in the coordinate representation, we have
 
Pj ( q )  i  5.5.3
Q j (q )
Let’s solve the Schrödinger equation
 57

Ĥ  E 5.5.4
We find the eigen value E and the eigen states  of the operator (5.5.2). The
eigen states  describe the small vibrations of the crystal lattice and E is the
eigen value of the energy. As the Hamiltonian (5.5.2) represents the sum of
independent identical summands then the solution of (5.5.4) may be found in the
form

   qj Nqj (Q j (q )) 5.5.5
where  Nqj is a wave function of single oscillator for which (5.5.4) becomes
Hˆ   E  Nqj Nqj Nqj 5.5.6
and
E   ENqj 5.5.7
q, j

where
 1
ENqj   j (q )( N qj  )
2
The equation (5.5.6) for the squarable and integrable function  Nqj represents a
standard problem in quantum mechanics for a harmonic oscillator .The solution of
this problem is well known. Let’s introduce the dimensionless quantity:
 12
  m ( q ) 
 q , j   j (q )   j
 Q j (q ) 5.5.8
  
then
 1 
 m j (q )  4 2 j
 Nqj ( j )    e H Nqj ( j ) 5.5.9
  
where H Nqj ( j ) is the Hermite polynomial:
N
(1) Nqj  2j d qj  2j
H Nqj ( j )  e N
e 5.5.10
N qj !2 Nqj.  d  j qj
We know that:
 1  1 
   m j (q )  2   ( m ( q )) 2 i
Pˆj ( q )  i   i    = j
 qj
Q j (q )     qj
Thus
1

Pj ( q )  ( m j ) 2 Pˆ qj
ˆ 5.5.11

Here we have a dimensionless value Pˆ qj  i  .
 qj
Dirac was the first person who introduced that in the case of non interacting
electrons, it is convenient to use the method of the second field quantization to
describe the particles. This follows that, the field is represented as a quasi
classical particles. This method is used to investigate the field with variable
number of particles. Introduce the second quantization for harmonic oscillator:
 58

  1 ˆ ˆ
 aˆqj  2 ( qj  iP qj )


 5.5.12
 aˆ    1 (ˆ  iPˆ  )
 qj
 qj 2
qj

Thus
1 1

   
1   2  2
ˆ q j
2
 
 Q j q 

i
   
q
 q   1
Q j

  ˆ  iP
2  m j q  qj
ˆ
qj
    aˆ
 2m q  qj
 
 j     j 

1
 2
  a

or ˆ q j 5.5.13
 
ˆ
 2m q  qj
 j 
In the same manner, we find
1
 2
  a

ˆ q j
ˆ 5.5.14
 2m q 
 j   
qj

We examine the rule of commutation of these operators. Hence, we act them on

the wave function of the oscillator. From the property of the Hermite polynomial;
it follows that:
 N N 1
 N   N 1   N 1
 2 2
 5.5.15
  N  N   N  1
  2
N 1
2
N 1

Then from here and (5.5.12), we have:

ˆ 
a  N qj 
qj Nqj N q j 1

ˆ
a  N  1 Nqj 1
qj Nqj qj

5.5.16
It follows from here that when aˆqj (aˆqj ) acts on the state N qj    Nqj of the given


oscillator, it reduces (increases) the phonon number N qj by one quantum number

of oscillator. The energy of the oscillator is:
 1
ENqj   j (q )  N qj  
 2
The state of the oscillator for which N qj =0 is a state with no phonons. The

expression  j ( q ) N qj gives the excitation energy of the system. This energy
depends on N and increases with an increase in N. The excitation energy has a
form of the total energy of an ideal gas. The particle of this gas i.e. the quanta of
the energy of excitation, are called phonons. From Dirac’s notation:
 aˆqj N qj   N qj N qj  1

  5.5.17
 aˆqj N qj   N qj  1 N qj  1
 59


Here aˆqj ( aˆqj ) is called annihalation (creation) operator. It follows that
 aˆqj aˆqj N qj   ( N qj  1) N qj 
  5.5.18
 aˆqj aˆqj N qj   N qj N qj 
Thus from (5.5.18), we have: 
 aˆqj , aˆq ' j '   0 5.5.19
or
 aˆqj , aˆqj   1 5.5.19’
also
 aˆqj , aˆq' j '   0  ;  aˆqj , aˆq' j '    qq
   ˆ  ˆ  
' jj '  ;  aqj , aq ' j '   0

The commutation in (5.5.19) is true for base particles. In the quantum state, there
may exist an arbitrary number of bosons (phonons). The wave function is
symmetric relative to the change of position of two phonons. Let’s find the
Hamiltonian of the vibrating crystal in the representation of the second field
quantization. Considering (5.5.2) and (5.5.11), the dimensionless Hamiltonian of
the system has the form
 
Hˆ   qj ( Pˆ2qj  ˆqj2 ) 5.5.21

q, j 2
Where
 ˆ 1
 qj  2 (aˆqj  aˆqj )

 

 5.5.23
 Pˆ  i (aˆ   aˆ  )

qj qj qj
2
We evaluate Ĥ , thus:
  1
Hˆ   q , j (aˆqj aˆqj  aˆqj aˆqj )   q, j (aˆqj aˆqj  ) 5.5.24

q, j 2 
q, j 2
Thus the eigen states of (5.5.24) are those of aˆ  aˆ since this operator has a sense
of N qj and does not change the state  Nqj then it is referred to as the phonon
 q j
operator. The value E 0  describes the ground state ( zero point) called
2
vacuum state energy with no phonon i.e. O . This energy implies that at the
qj

temperature of zero Kelvin, the atoms in the crystal are in state of oscillatory
motion. The additional energy is a considerable quantity, it shows also that the
localization of the atoms in their exact position of equilibrium leads to the
indeterminacy of their velocity according to Heisenberg relation. The excited state
to just one phonon:
ˆ O
a  1q j 1q j
qj qj

5.5.25
and if
 60

aˆ 

qj
N
qj
Oq j  Nqj Nqj

5.5.26
and
ˆ
a qj
Oq j  Oq j

5.5.27
then it follows that;
 1
E   q j  q j  N q j  
 2
5.5.28
This is the energy of the normal vibration of the oscillators. It is an approximate
solution (from the expansion of the potential energy). Phonons as quanta of
elementary excitation are fictitious transformation. Phonon may be called quanta
of sound vibration. Phonons in the process of interaction with others may
disappear and new ones arise. The question is on the mean value of the phonon
number per normal vibration. Plank solved this problem and this number is equal
to:
1
N  
qj Bohr-Einstein distribution.
e T 1
In the formula E q j  N q j  q j , the quantity N q j is the phonon number. It
should be noted that at any finite temperature, a crystal is completely full of
phonons. They contribute significantly to the warming (heating) of the crystal
only at low temperatures or high intensity. If optical branch are excited, the
resultant is optical phonon. If the temperature is raised phonon are created order
wise they are destroyed. There is the point of conservation of energy in the
process of creation and annihilation as energy flow into or out of the crystal
through heat conduction as expected.
 61

6. ELECTRONIC STATE IN IDEAL CRYSTALS

6.1 THE ZONE THEORY
All solids are made of atoms i.e. they represent a totality of nuclei and
electrons. In crystalline solids, the nuclei of atoms are situated at sites of
crystalline lattice and has a space periodicity .The stationary state of the particles
in the crystal is described by the Schrödinger equation
ˆ   E
H 6.1.1

where Ĥ is the Hamiltonian of the totality of the particles, i.e. the Hamiltonian of
the solid  is the eigen function and E the eigen value. Let ri  , i  1,2,..., N
be the radius vector of the electron and Ri  , i  1,2,..., N be the radius vector of
the nuclei. Let M k be the mass of the nuclei of the k th family and m that of
the electron. The kinetic energy of the system is that due to the motion of the
electrons and that due the motion of the nuclei

Pˆ 2 Pˆ 2
Kˆ   i   k
i 2m k 2M k
6.1.2
and the potential energy of the totality is that due to the interaction between the
electrons and the nuclei and amongst electrons
1 e2 1 Z k Zie2 1 Zk e2
Uˆ      
2 i j r  r 2
2 k i R  R 2
2 k ,i r  R 2 6.1.3
i j k i i k

Thus the Hamiltonian

Hˆ  Kˆ  Uˆ 6.1.4
The movement of the electrons in the field of the nuclei at rest

 2m   U  r   2 
ˆ2
P 1 e2
ˆ 
H i
i 2
i i i j ri  r j

6.1.5
Thus in this case we neglect thermal motion and

 
U ri  
1

Z k e2
2 k ,i r  R 2
i k

6.1.6
The wave function (6.1.4) depends on the coordinate of all particles:
 62


   r1 , r2 ,...; R1 , R2 ,... 
To solve the equation (6.1.1) till the present moment is very difficult and we
move to certain approximations. We suppose that M k m which follows that
the nuclei perform their motion about a certain equilibrium position while those
of the electron are progressive and their velocities are much higher than those of
the nuclei. In this case we may suppose that the nuclei are practically at rest
compare with the motion of the electron. This is called the adiabatic
approximation or the Born-Oppenheimer approximation. In this case we may
consider the radius vector of the nuclei as not variable but constant. In this
connection the Schrödinger equation becomes more and more simple. If nuclei
are at rest then their kinetic energy is zero and their interactions become a
constant;
1 Z k Zie2

2 k i R  R 2
 const.
k i

6.1.7
This may be neglected considering choice of the origin of the energy. Considering
adiabatic approximation, the variables are not separable and thus, we sole
equation (7.1.1) approximately. First approximation stem from the fact, the
principal role is played by the kinetic energy and the interactions are neglected.
Thus

2
   i  E
2m i 6.1.8
Here the variables are separable

   
   r1 , r2 ,...rN   i i ri
7.1.9

 
where  i ri is the wave function for the free particle


 i ri 
1
3
e i ki ri
L 2
6.1.10
and

 2 k i2
E 6.1.11
i 2m

(7.1.10) is not true wave function (It does not respect the Pauli exclusion
Principle). It should be noted that the physical situation of the atomic system that
contains two or more electrons is always such that, the corresponding wave
function should be anti-symmetric with respect to the interchange of the position
 63

of the electrons. The wave function is dependent on the spatial and spin
coordinate of the electrons and the nuclei and the time. According to the Pauli
exclusion principle it is only two electrons with opposite spins that can be found
in the same quantum state. The total wave function of the system which satisfy
this principle should be anti-symmetric i.e. the wave function changes sign for the
interchange of the position of any two electrons. The function  i i does not
satisfy this condition. The anti-symmetric wave function is written in the form of
Slater determinant;

  
 1 r1 , 1 r2 ,..., 1 rN    
 r 1 , r2 ,...rN  
1  
...................................... 
N! 
 N r 1 , 
N r2 
,..., 
N rN 
  
6.1.12
1
The factor assumes the normalization of 
N!

If we denote by V  r  the potential energy of an electron in the crystal, then it

follows to solve the Schrödinger equation:

 2
 

 
  V r  r  E r 
 2m  6.1.13
In a crystal the arrangement of atoms in space are strictly periodic and as a
consequence, the total potential V  r  of the crystal should posses a three-
dimensional periodicity.
7.1.1 BLOCH THEOREM
Considering (7.1.13), then the potential acting on an electron in the crystal
obeys the property of periodicity

 
V r  an  V r 
6.1.1.1

where a n  n1 a1  n 2 a 2  n3 a3 . Consider the translational vector Tˆa n


Tˆa  r   r  a n
n
  6.1.1.2
This translation is called translational symmetry. If for that translation the
Hamiltonian is invariant i.e.

Tˆa Hˆ  Hˆ
n
6.1.1.3
It can be shown that all translational symmetry of a given system form a cyclic
group. This follows from group theory. If is true (7.1.1.3) then it follows that
 64

Tˆa 
commutes with Ĥ  : Tˆa Hˆ  r  Tˆa Hˆ Tˆa  r  Hˆ Tˆa  r
n
       . We can
also proceed as follows: let Hˆ   r   F  r  then :
n n n n

      
Tˆa Hˆ  r  Tˆa F r  F r  a n  Hˆ r  a n  r  a n  Tˆa Hˆ  r  a n  Hˆ  r  a n 
n n
    n
   

 Hˆ  r  a n  Hˆ Tˆa  r   n
 
from here if follows that

n

Tˆa Hˆ  r  Hˆ Tˆa  r  Tˆa H
ˆ  Hˆ Tˆ  r  Tˆ H
a n a
 
ˆ r 0
n n
   n
 
this follows the commutation of Tˆa and Ĥ . It follows from the theory of n

commutation that if two operators commute then they have one and the same
eigen function i.e. operator Tˆa and Ĥ have one and the same eigen function.
n

Let us find the form of Tˆa . If we consider (7.1.1.2), then

n

       
  r  e  an ,  r 

1
Tˆa  r   r  a n   r  a n ,  r  ... 
n
 !a
 0

n

Thus the explicit form of the translational operator Tˆa ; n

Tˆa  e  an , 
n
6.1.1.4
This operator commutes with the Hamiltonian. Let us find the eigen value of this
operator. This can be obtain from the eigen value equation


Tˆa  r  t a  r
n n

6.1.1.5

Where t a is the eigen value of Tˆa then

n n


 r  an  t a  r  n
 7.1.1.6
and as the translation does not change the normalization of the wave function of
the electronic system, then we have
2
ta 1
n

6.1.1.7

Let show again that Tˆa and Ĥ commute. The operator Ĥ  ;

n

Hˆ  Kˆ  Vˆ
 65

where K̂ and Vˆ operator of the kinetic and potential energy respectively.

Consider Vˆ , then select an arbitrary wave function   :

    
Tˆa V r  r  V r  a n  r  a n  V r  r  a n  V r Tˆa  r
n
     n

Thus

Tˆ ,Vˆ   0
an

6.1.1.8

Hence Tˆa and n

Vˆ commute. It should be noted that  
Vˆ r  a n  Vˆ r . 
Consider the case of the kinetic energy operator:

2 2  1    
1  2 
Kˆ Tˆa  
2m
   an ,   
 0 !   ! a 
n ,    
 2m
 2   Tˆa Kˆ

n n
 0
'
6.1.1.8

If we consider (6.1.1.7) and ( 6.1.1.8 ' ) then Tˆa commutes with n

Ĥ . Consequently Tˆa is a constant of motion and

n

d ˆ
Ta 
dt n
1 ˆ ˆ

T H  Hˆ Tˆa  r  Tˆa Hˆ  0
i a n n n
   
Suppose we are given two translation operators Tˆa and Tˆa then from (6.1.1.6)
 t  
1 2

we have  r  an  an ta  r  ta  r . From here it follows that

a n1 n  an 2
1 2
n2

ta ta  ta  an 2 . It means that our eigen value takes the form

n1 n2 n

t a  e i  q , an  6.1.1.9
n

This is the Bloch’s theorem. If we consider the eigen value (6.1.1.9), then

 e i  q , an   cos 2  qa   sin  qa   1
2 2
 cos qa n   i sin  qa n 
2 2
ta
n

In relation (6.1.1.9), q represents the wave vector characteristic of the quantum

state of an electron in the crystal . Its physical sense is the number of wave length
in the interval  0,2  ;
2
q q

6.1.1.10
The relation 6.1.1.10 characterizes the properties of the translation of the wave
function. This is an indication that when an electron is displaced in a periodic
field, the eigen function of the Hamiltonian satisfy the condition of translation i.e
 66

in 6.1.1.10. In this wise we may write   r     r  and Hˆ   r   E r  and

q q q

we show that E  E  q  . The establishment of this relation is a crucial problem in

solid state physics. For any wave function satisfying the Schrödinger equation
with the periodic potential, there always exists such a vector q that the
translation with respect to the lattice vector a n result in the product e i  q ,an 
(plane waves) on   r  having the periodicity of the Bravais lattice.

Theorem 6.1.1.10 also satisfies plane waves i.e.  q  r   e i q ,r which is also

 

solution of the Schrödinger equation with potential equals to zero. Bloch gave
some specific form to the wave function in 6.1.1.9 and in particular

 q r  e i  q , r U q r  
6.1.1.12

This is the plane modulated wave. It is a Bloch wave and Uq r   is the Bloch’s
amplitude. There exist some supplementary condition to Uq  r  . If we carry the
translation (6.1.1.10), then we have:

   
 q r  a n  e i  q , r  e i  q , a U q r  a n  e i  q , r  e i  q , a U q r
n n

6.1.1.13
From here it follows that
 
U q r  an  U q r  6.1.1.14
' 2
From here follows the condition for the domain of periodicity: q  q  q  bg
G

As q and an are scalarly multiplied, then q and q belong to one and the
same eigen value. It follows from here that, quasi wave vector of an electron in a
crystal has the same properties as the wave vector q . We have seen this earlier in
our previous heading; this corresponds to the Brillouin zone


   q,a i   . 
6.1.1.15
Here, ai , i =1,2,3 are the primitive vectors. For the finite crystal to have a
periodic property, it is necessary to introduce the cyclic boundary condition,
 q
(r  G ai )   (r )
q

6.1.1.15
Here, the wave vector most be real. Apply Bloch’s theorem to the boundary
condition (6.1.1.15) then we have
 q
( r  G ai )  e
i ( q , G ai )
 q
(r )
 67

from here, it requires that: e

i ( q , G ai )
 1 and q, G a   2g or
i i

q, a   2G g
i i

6.1.1.17 Here g i is an integer. It follows that q, a

i   is quasi discrete. If we
substitute (6.1.1.17) into (6.1.1.15) then we have
G G
  gi 
2 2
6.1.1.18
It follows from here that q takes G 3  N values; then from (6.1.1.17)
2
q b
G g

6.1.1.19
Let’s examine the order of the Bloch’s amplitude; we normalize the wave
function to unity  Uq r  2
d  1 where  0 is the volume of elementary cell
0 N

and N 0 , the volume of the crystal lattice, Thus

 Uq r  2
d  N  
Uq r
2
d 0  1
0 N 1st cell

The last integral is taken with respect to the first elementary cell and
1
U q  r  

. Though, it is difficult to give the exact solution to (6.1.1.13). It is
N
necessary to have an idea to the energy spectrum. Let’s substitute (6.1.1.11) in
(6.1.1.13), then we have:

2
2m
 2
   
  iq U q r  V r U q r  E q U q r   6.1.1.20
from here, we may find the property for Uq r   ; let’s take the complex conjugate
of (6.1.1.20):

2
2m
 2
   
  i q U q* r  V r U q* r  E q U q* r  
6.1.1.21
Suppose in (6.1.1.21), we do the change q  q ,

E q  E q   
6.1.1.22
and U r   U r  *
q q
*
6.1.1.23
Condition (6.1.1.22) shows that the energy E is an even function of q .
Considering the property of periodicity then V  r  may be represented in the
Fourier series and also U  r  q


V r  V
g
g e

2i bg , r 

6.1.1.24
 68


U q r   Ch e
h

2i bg , r 

6.1.1.25
Here bg and bh are vector of the reciprocal lattice. V g and Ch are the Fourier
coefficients since. V  r  is a periodic function, then it follows that Vg  Vg .
*

Let’s substitute (6.1.1.25) and (6.1.1.24) into (6.1.1.20) then we have

  i q  2
e

2i bg , r  
   i q'   i q e  
2i bg , r  
 i 2 bg  q   i q e  
2i bg , r  


 i 2 2 bg  q e  2 
2i bg , r 

 
V r U q r  Vg C h e
h, g

2i bg  bg , r    V0 C h e
h

2i bg , r 
V
h, g 0
g Ch e

2i bg  bg , r 

and
2

2m h

2 2i  bg , r  2i  bg , r 

C h 2 b g  q e     V0 C h e     V g C h e 
h h, g 0
2i  bg  b g , r 



Eq   C e h
h

2i bh , r 

6.1.1.26 The solution (6.1.1.26) is based on the fact that all terms are
function of r . As r is an arbitrary vector, then it follows from (6.1.1.26) that

 E q  
2
2m
2 bg  q   2 
 V0  C h   V g C h  g  0 6.1.1.27
  g 0

This is a system of homogeneous equations relative to the coefficient C h . In

order that (6.1.1.27) should be solvable, it is necessary that it determinant should
be equal to zero. The diagonal elements are:
Eq   2
2m

2 bg  q  2
 V0

And the non-diagonal elements V g is unknown. This follows that the equation
cannot be solvable but we can have a representation of energy spectrum. The
N  N determinant has N roots: E1 E 2 ,..., E N which are the eigen values. It
should again be noted that E   q   E  q  i.e. energy has no centre of inversion
and Ei  q  2 bg   Ei  q  then we may have the sketch of the energy spectrum.
We take for convenience the one dim case.

E2

Forbiden zone

E1
 69

3 2   2
   0
a a a a a
3 q
a

Fig. 6.1.1.1

The correct form of Ei is unknown fig 6.1.1.1 is drown from intuition as

Ei  q  2 bg   Ei  q  .

6.2 THE APPROXIMATION OF THE NEARLY FREE ELECTRON

MODEL (N.F.E)

In the N.F.E model, a crystal is considered as a special lattice of ions immersed

in an electron gas. The perturbation in the eigen value problem is the departure of
the true potential from zero. If we consider a vacuum, then for a zero potential, an
iqr
electron wave function is a plane wave normalize in the entire space    0 e
. In the crystal, the normalization integral is conveniently represented as a sum of
the contribution from all the lattice site, and as the contributions are the same,
then they may be taken out of the sum and what is left is the total number of the
sites. On introducing the volume of the Weigner Seitz cell where  is the
volume of the given crystal it is found that the plane wave may just as well be
normalized to the Weigner Seitz cell. Let’s solve 6.1.1.27:
2
2m
 2

2 bg  q C h  V0 C h   V g C h  g  EC h
g 0

6.2.1
The periodic potential V g is assume to be small and is a perturbation; from
(6.2.1) we have

E 
2
2m
2 bg  q   2 
 V0 C h   V g C h  g  0
  g 0

6.2.1'
Considering the perturbation theory, we have: E  E  E  E  ... from
0 1 2

V0  0 , it follows that
 2q 2
E  E0  6.2.2
2m
This shows that we have a free wave in the crystal. If we substitute (6.2.2) in
(6.2.1’) for V0  0 then
 2q2
 
2
  2
2 bh  q C h  0  6.2.3
 2m 2m 
 70

for h  0 , we have C 0  0 ; for h  0 , C 0  0 , Ch  0 , and

0


U q r   C h e 2i bh ,r   C 0
h

6.2.4
and also
  
 q r  U q r e i  q , r   C 0 e i  q ,r  6.2.5

for the first order perturbation theory, if we substitute E  E0  E1 in (6.2.1’)

then,

 E 0  E 
2
2m

2 bg  q  2 
 V0 C h   V g C h  g
  g 0

if h  0 , then
  2q2 
 E 0  E1   V0  C 0  0
 2m 
2 2
 q
and as E 0  then E1  V0 . If h  0 , then
2m

 E 0  E1 
2
2
m
 2 

2 bg  q  V0 C h  0  Vh C 0
 
and
mC0 Vh
C h 0  
nd

2 b h , q   b h
2

6.2.6 We find the energy for the 2 order perturbation, if we consider
E  E0  E1  E 2 and we take h  0 , then
 2q2 
E
 0  E1  E 2   V0 C 0   V g*C g 6.2.7
 2m  g 0

from here, we have

2
m Vh
E2  
2 2
 b
g 0 , q   bh  This
h

is the energy for the 2nd order perturbation. Thus the energy for the system


2
2q2 m Vh
Eq 
2m
 V0 
2 2
 b 
g 0 g ,q   bg

6.2.8
However, it is entirely very possible that if we take the correct reciprocal lattice
bg , we may always find q such that


bg ,q  bg  0  6.2.9
This is the condition of discontinuity of the energy and
 2q2
2m

2
2m

2 bg  q  2
6.2.10
Let’s find out the geometrical physical sense of (6.2.9). This shows that bg and
q   b g are orthogonal. Consider fig 6.2.1
P
 71

q   bg

P! 2 b g
Fig. 6.2.1
The plane pp’ is perpendicular to the vector 2 bg . All the vectors in the plane pp’
will either be perpendicular to 2 bg or bg . All vectors on pp’ may be obtained
through the sum of  bg and q on condition that the head of q should be on pp’
plane. Thus all the vectors with their heads on the pp’ plane satisfy expression
(6.2.9). This is the equation of the plane perpendicular to b g . The totality of the
planes passing through the middle of 2 bg which are perpendicular to them
determine all the vectors q satisfying the condition E  2 bg  q   E  q  or
bg , q   bg   0 . The equation (6.2.9) may be used to construct the Brillouin zone
of all crystalline solids from their reciprocal lattice.
We may see from above that the given perturbation theory is not physical as
E 2 appear to be greater than E0 . This is connected with the destruction of the
N.F.E. .As there exist q that satisfies (6.2.10) then there exist a plane on which
there is a scattering of the free moving electrons. This correspond to the forbidden
zones in the energy band diagram.
Consider now an amended variant of the perturbation theory; i.e. we consider
C g for the direction of q not satisfying (6.2.9). Let’s consider (6.2.1’)
If h  0 , then
 2q2 
E   V0  C 0  V g C  g 6.2.11
 2 m 
If h  g , then

 E 
2
2m

2 bg  q  2 
 V0  C g  V g C 0 6.2.12
 
For the solution of the above equation, the determinant of the system should be
equal to zero:
2 2
E q  V0  V g*
2m 0
 Vg E
2
2m
2
q  2 bg  V 0  
From where we have
   
2
2  2  2
 E  V0   E  V0   q  2 bg  q   
2 2
2
 2
 q q  2 bg  V g 0
2m    2m 
6.2.13
or
 72

      
2
1 2  2 2 1  2   2 2 2
2
E  V0  q  q  2 b g   q  q  2 b g  Vg
2 2m  4  2m   6.2.14
If we consider (6.2.9) and (6.2.10) then it follows that:
2 2
E  V0  q  Vg 6.2.15
2m
2 2
or E q  V g  V0
2m
6.2.16
The two solutions in (6.2.16) correspond to the minimum E min and maximum
E max ; E min and E max are separated by a forbidden gap of which
E g  2 V g

6.2.17
The Brillouin zone is the zone for space and the energy-zone is the zone for
which
b g , q   b g   0 6.2.18
and it is an equation in -space. The energy is discontinuous in N  G planes
q 3

that are intersecting.

We show that between E min and E max , there exist a forbidden zone. Suppose
q  q1  q 2  q3 6.2.19
where q1 is parallel to bg . If we substitute (6.2.19) in (6.2.16), then we have:
b , q   b   b , q
g g g 1 
  bg  0
and as bg is arbitrary, then
q1   bg  0 6.2.20
Equation (6.2.13) is the resonance condition and follows that q1  0 . Consider
 q  2 b  g
2
q 2

 4 q   b g , b g  q  2
 4 
 b g , q1' 


 6.2.21
and from (6.2.21), we have
2

q '  2 bg  2

 2q 2  4 bg , q   bg  
6.2.22
 2 b , q    b
 2 2 2   2 2 2 2

 2q1'  q 2  q3   2 q1  q 2  q3   bg 
2 2 2
g 1 g

If we substitute this in (6.2.14), then we have;

  
2
 2 ' 2 2 2  1  2   2 2
E  V0  q1  q 2  q3   2 bb2  q  2 bg    16 2 bg q1'  V g
2m 4  2m 
2
Although we are constructing the theory of V g at the neighborhood of q1'
which is again smaller than V g , we have:
  2 
 2 ' 2 2 2
    8 2 bg2 q1'
 2
1
  
E  V0  q1  q 2  q3   2 bb2 Vg   1 6.2.23
2m  4  2m  V 2 
 g 
 73

And as the 2nd summand at the right hand side of (6.2.23) is greater than zero, then
it follows that lower part of the energy is less than E min and upper part, greater
than E max . From here, it is obvious that between E max and E min , we have a

forbidden zone. For the exact resonance, q2'  0 ; the energies 

Eq 
2 2
2m
q

and E  2bg  q  coincide and we have a degeneracy (there is a coincidence at



zero approximation). It follows the degeneracy of two known perturbed states. At

the point of resonance, we have a mixture of two wave functions. If we consider
g
the one dimensional case, in place of bg , we put , then in place of q  bg ,
a
g
we have q   . This follows that:
a
g g
q    0 6.2.24
a a
This follows that
 3  2    2 3
q  ..., , , ,0, , , ,...
a a a a a a
since  
E 2bg  q  E q    , then follows fig 6.2.1

E  q   V0

forbidden zone

second allowable zone

2V

first allowable zone

3 2   2 3
   0
a a a a a a
q
 74

Fig. 6.2.1

7.2 THE TIGHT-BINDING APPROXIMATION (TBA)

In the previous headings, emphases were put on the plane wave part of the
Bloch function neglecting the atomic part. We may take an alternative approach
with emphasis of the atomic function at the neighborhood of the nuclei. The
T.B.A is connected with the overlap of the atomic wave function enough to
require some correction to the picture of the isolated atoms. It should be noted
that this correction is not much as to render atomic descriptions completely
irrelevant. The T.B.A is much suitable for electrons that are tightly bound to
their atoms as for the case of the band built for inner electrons or d-electrons
whose orbits may have relatively small radii.
When developing the tight-Binding-approximation we should consider that at
the neighborhood of each lattice site, a complete Hamiltonian of the crystal
should be approximated with the Hamiltonian of the single atom located at a
lattice site; it is also assume that, the boundaries of the atomic Hamiltonian are
well localized.
Let’s consider the valence electron for which the periodic potential strongly
changes at the neighborhood of the nucleus. If we consider the model of the
Tight-Binding electron, then it follows that in the first approximation, the electron
is tightly bound to the atomic nucleus and the interaction with the rest of the atom
is examined as a perturbation. Considering the theory of the tight Binding
approximation, we may take the wave function of the zero approximation to be
  r  a  . This is the atomic wave function. This implies that the wave
a n

function of the electron interact only with the nucleus where it is seated. In the
wave function r and a n are coordinate of the electron and nucleus
respectively. This wave function may also be written as:

 a r  an    r 
n

6.3.1
and satisfy the Schrödinger equation:


2
2m
  
 n r  U n r  n r  E 0 n r 
6.3.2
  
Un r  U r  a 
6.3.3
In a crystal, an electron with energy E0 may be localized in any atom. Let
N  G 3 be the number of elementary cells. It should follows from above that
different states correspond to the first energy ; this follows, quantum degeneracy;
it follows in such a case to construct the eigen function of the zero approximation
applying quantum mechanics and in particular
 75

 
 r   C n a r  a n   C n n r
n
 n

6.3.4
If   r  is the wave function of the zero approximation in the crystal, then it may
be represented in the form  
 r  U q r e i  q ,r   and Uq r   has a property of
periodicity. It follows that,

 r e i  q ,r    C n e i  q , r  r
n

6.3.5
Here,
C n  e i  q , an 
6.3.6
Then considering (6.3.5), we have

 r  e  i  q , r 
   e
n
 i  q , r  a n 
 n r   e  n
 i  q , r  a n 
  a  r  an   r  r  an 
 

 e
n
 i  q , r   a n  a m  
  a  r  a  a   a  a  a   e 


n m 
 
n m l


i q, r  a 



 a  r  a 





This follows that (6.3.5) is a periodic function with respect to coordinate thus the
selection of Cn is correct. It therefore follows that (6.3.4) has the form

 r   e i  q , a  a r  a n
n
n
 
6.3.7
This is the zero approximation correction to the wave function since the
function   r  a  is normalized to unity then we may find the normalization
a n

factor for the wave function  r   :


*
r  r d   e  m
i q , an  am  *
 a  r  a   r  a d
m a n

6.3.3
We may reduce the double sum to a single one through a change of variables:
r   r  a m r  r ;  a m , d  d ' , thus
 
   r *
 a   r  a d      r  a  a   d
 
r   * ; ; '
a m a
  
n

a a n m

 
*
a  r  a
 r '  a  d


 

'

The integrant is the product of the function  a*  r  and   r  a  and is a
'


dependent not only on the position of the nuclear but also on the distance that
separate them. Suppose
   r
* ;
 a 
 ' 
 r  a   d
'
 S
a
  
* If a  0 then S   0
 76

* If the distance between two nuclei is large, then the corresponding wave
function does not overlap and S   0 will practically be equals to zero that is
S  0
Thus S   0 for only small values of a . Supposes am is fixed then an  am  0

and a have the same values. Hence, the summation relative to n will be
equivalent to summation relative to  :

n

  
 e i  q,a    a* r  am  a r  an d   e i  q,a  S   


2
It should be noted that the quasi wave vector q is such that q  bg . It will be
G
quite enough to use the first order perturbation theory. It follows that we may use
the wave function (6.3.7) and from where follows the Schrödinger equation:

2
2m
 q  V r  q  E q  q 
6.3.9
Where V r   is an intrinsic periodic potential of an electron. Consider all
interactions, then we substitute (6.3.4) into (6.3.9) and we have

2
 C n  n  V r
2m n
  C 
n
n n 
 E q  C n n
n

6.3.10
which is the first order of the perturbation theory. If we have the wave function in
the zero approximation of the perturbation theory, then we have:

2
 C n  n  
2m n n
C nU n r  n  E 0  C n n
n

6.3.11
Let’s take the difference (6.3.10) and (6.3.11), then we have:
 E  q   E  C 
0
n
n n  C
n
n V r   U  r  a  n n

6.3.12
Multiply this relation by  m* and integrate the resultant with respect to the
configuration coordinate. Considering the fact that:

*
m  n d  
*
a  r  a   r  a d  
m a n mn

from here, we have:

 E  q   E  C 
0
n
n mn  C
n
n 
A an  am  or
 E q   E C 0 m 
  Cn A an  am
n

6.3.14 The quantity A a  is the exchange energy which result from


the fact that any electron may be found about any nucleus with a certain
probability; this peculiarity takes into consideration the fact that for the formation
of A a  we have the wave function of two atoms at the distance of a . This


implies that two nuclei at the separation of a can exchange electrons. This
exchange is done with the help of the field of all the nuclei excluding that of the
 77

two nuclei in question. The exchange is also done with the help of the component
of the periodic self- consistent field of the crystal. It should be noted that A a  

is only considerable for small distances. If A a   0 , then a is large. That is



to say, the exchange is only for close neighboring atoms.

It should be noted that A a  is considerable at the neighborhood of two


neighboring nuclei. Consider (6.3.14), then

 E q   E C
0 m  
  C n A a n  a m  n  n '  m   C n'  m A a n;
n n'
 
 C
n
n m  
A an

Considering (6.3.6), then

  
E q  E 0   e i  q ,an  A a n  E 0   e i  q ,an  An
n n

 E 0  A0   e
i q , an A
n
n 0

6.3.15
Considering (6.3.15), we may already obtain some information about the
spectrum. A0 gives a shift of the energy level upwards or downwards. When the
atoms are brought closer together, there arises an interaction that leads to the
splitting of the energy level. Consider a crystal that is made up of atoms that are
distant from each other. Let’s examine fig. 6.3.1.

0 r
U

V
U V
Fig. 6.3.1

Let’s investigate
An  
*
a  r  a V r   U r  r d
n a

At the neighborhood of zero, a n  0 and V  r   U  r  and already for the

neighboring sites U  V . Thus, in order to evaluate E  q  , it is necessary to
consider the neighboring sites; thus

E q  E0  A0  A e i  q ,an 
n0

6.3.16
It follows that for a cubic crystal, we have:
 78


E q  E 0  A0  2 A cos q x a  cos q y a  cos q z a  6.3.17
Let’s examine the bottom of the permissible zone, here q  0 and cos q a  0
then
E min  E0  A0  6 A
This is evaluated at the center of the Brillouin zone. Let’s examine the ends of the

first Brillouin zone, here q   ; this follows that
a
E max  E0  A0  6 A

This should be the ceiling of the zone. Then E g  12 A . Considering the value
of and , we may see that the width of the forbidden zone is defined by the
parameter A. The value of this is E g  12 A for the cubic crystal. Let’s
examine the center of the Brillouin zone. We examine the value of the relation
(6.3.17) as q  0
 
E q  E 0  A0  2 A 3 
a2 2
2

q x  q y2  q z2    E min  Aa 2 q 2 6.3.18
 
This follows that at the neighborhood of the bottom of the zone the dispersion is
quadratic in q and

E q  E min  Aa 2 q 2 
 2q 2
2
where  
2
6.3.11
2Aa 2
is the effective mass of the hole. Let’s examine the neighborhood of the ceiling.

Consider q'   q , from (6.3.17), we have
a

   
E q  E 0  A0  2 A cos  q   
 a 
   
 E0  A0  2 Acos cos q  sin sin q   E 0  A0  2 A cos q a
 a a 


as q  0 ; E q  E0  A0  2 A1 
 q2 a 2 
2

 

E q  E max   Aa 2 q 2

At the ceiling again, we have the quadratic dispersion relation and

2
 0 6.3.20
2 Aa 2
which is the effective mass of the electron.
 79

PROBLEMS
1. In the general case, in the problem an the chemical bonding in molecules and
solid state , it is necessary to solve the Schrödinger equation for system of N
nuclei and n electrons amongst which act Coulomb forces. Let’s neglect
relativistic effect that may arise due to the dependence of the spins of
terms. Write this equation using the denotation below
Coordinates Mass Charge
Nucleus Ra  X a , Ya , Z a  Ma Zae
 a  1,2,..., N 
Electrons Rk  X k , Yk , Z k 
m -e
( k  1,2,...n)

2. In order to describe the motion of electrons in a system, consisting of N nuclei

and n electrons, it is necessary to make a very good approximation. Here, we
assume that the nuclei are at rest because their mass is greater than that of the
electron. Write the Schrödinger equation for a system of N fixed nuclei and n
electrons. Use the atomic units, that is assume the electronic charge e, electronic
h
mass m and the Planck constant   to be the equal to unity.
2
 80

3. Not withstanding that the eigen value E e in the Schrödinger equation for the
Z a Zbe2
electron include the inter-nuclei repulsion  a ,b
a b
 
Rb  R b it is often called the
electronic energy. In it, is found as a parameter, the inter-nuclei distance, it plays
the role of the potential energy in the Schrödinger equation for the motion in the
field of the nuclei. If we assume that the center of mass of diatomic molecule is
fixed, then the Schrödinger equation describes the motion of two of its nuclei A
and B and has the form
 2  MaMb
   E e  R    E 
 2  where Ma  Mb
is the reduce mass and R  R  R . Find  and E considering that the
 
a b

k
potential has the form E e  R   R  R0  2 . Such a potential correspond to a
2
force acting between atoms and proportional to the displacement of the inter-
nuclei distance R from its equilibrium value R0 (here k is a force constant). For
convenience, let its potential energy be given by its value R  R0 . Hint: The
problem is similar to that of a particle of mass  in a centre potential field
E e  R  . Consequently, in spherical system of coordinate R,  ,  , the wave
f  R
function  has the form         
R .

ADMINISTRATIVE

These lectures are basically the lectures taught by Prof. LUKONG Cornelius
FAI in the University of Dschang. All errors associated with typing and
failures to transmit information are mind. I shall be happy to welcome
questions and critics in and out of class or through e-mail.
The grading policy of this course is as follows:
o Class participation, 10 %
o Homework, 10 %
o Quiz, 10 %
o Final exams 70 %