WOLKITE UNIVERSITY

College of Natural science

Department of physics

Introduction to Condensed
Matter Physics
Year IV Sem. I
Stream BSc In Physics
PRESENTED BY GEBRU TESFAYE
(MSc in solid state physics)
 Introduction to
Condensed Matter Physics

CHAPTER ONE

Crystal Structure and X-ray Diffraction

 Introduction to Atomic model
 John Dalton atomic model
 Five main points of Dalton’s Atomic Theory
 All matter is composed of extremely small particles called atoms.
 All atoms of a given element are identical, having the same size, mass, and chemical properties.
 Atoms of a specific element are different from those of any other element.
 Atoms cannot be created, divided into smaller particles, or destroyed.
 Different atoms combine in simple whole-number ratios to form compounds.
 In a chemical reaction, atoms are separated, combined, or rearranged.
Weakness
 Atoms consist of even smaller particles called electrons, protons and neutrons.
Atoms can be created and destroyed in the nuclear reactions such as nuclear fusion and nuclear
fission..
Atoms of the same element can have different physical properties, for example, isotopes of hydrogen.
 J.J Thomson atomic model
 The electrons were positioned uniformly throughout the atom.

Ernest Rutherford
• the atom is mostly empty space,
 most of the atom’s mass concentrated in a tiny center, the nucleus and
electrons being held in orbit around it by electrostatic attraction.
 The nucleus was around meters in diameter, in the center of a metre
diameter atom.
Those alpha particles that had come into close proximity with the nucleus had
been strongly deflected whereas the majority had passed at a relatively great
distance to it.
 Neil's Bohr

 Electrons in an atom of an element are not randomly distributed around

the atomic nucleus.
 Electrons move around the nucleus in fixed orbits.
 Each orbit forms a circle and has a fixed distance from the nucleus.
 Modern Atomic Model
According to the modern atomic model,
Modern Atomic Model

•The central nucleus consists of protons and neutrons. It containing

almost all the mass of the atom.
•the nucleus of an atom is very small compared to the size of the atom
•the electrons are orbiting outside the nucleus in the electron shells
•the electrons are moving in electron shells at a very high speed and we
cannot determine the position of the electrons at a particular time
 Solid State Physics: definitions
 What is condensed matter physics?
 Why study condensed matter physics?
 What is solid state physics?
 Why study solid state physics?

 What is Condensed Matter Physics?

• Condensed matter physics is the field of physics that deals with the macroscopic and
microscopic physical properties of matter.
• In particular, it is concerned with the “condensed” phases that appear whenever the
number of constituents in a system is extremely large and the interactions between
the constituents are strong.
• The most familiar examples of condensed phases are solids and liquids, which arise
from the electromagnetic forces between atoms.
• The use of the term “Condensed Matter” being more general than just solid state
was coined and promoted by Nobel-Laureate Philip W. Anderson.
 Why study condensed matter physics?

1. Because it is the world around us

2. Because it is useful
3. Because it is deep
4. Because reductionism doesn’t work
5. Because it is a Laboratory

 What is solid state physics?

 Solid-state physics is the study of rigid matter, or solids, through methods such as
quantum mechanics, crystallography, electromagnetism, and metallurgy.
 It is the largest branch of condensed matter physics.
 Solid-state physics studies how the large-scale properties of solid materials result
from their atomic-scale properties.
Thus, solid-state physics forms a theoretical basis of materials science. It also has direct
applications, for example in the technology of transistors and semiconductors.
 A serious study of solid state physics (SSP) begin after the discovery of x-ray
diffraction by crystals and the publication of a series of simple calculations of the
properties of crystals and of electrons in crystals.
 Definitions cont.
 Solids are of two types
I. Crystalline solid:
♦ have definite repetition
pattern. have periodic
arrangement.
♦ have distinct melting point
♦ Example 𝑺𝒊 𝑶𝟐(quartz),
some metals and
semiconductors
 The periodicity of atoms in crystalline
solid can be described by a lattice.
Non-crystalline
II. solidsof(Amorphous
lattice is a network solids):
points in space
lattice
♦
(an infinite have
arrayno
of definite
points). repetition pattern
 A crystal ♦ischaracterized
formed by adding atomsarrangement
by random in a of atoms. E.g: 𝑆𝑖𝑂2 (glass).
constant environment, usually in a
solution. ♦ Have no clear shape or structure
 Well-defined crystal structure is an
♦ They do not have any determining melting point
arrangement of atoms in a lattice
Solid state Physics

Fig 1:Tree diagram of Solid State Physics

 Symmetry operations
 Four types of symmetry operations

⇨ Translations,

⇨ Reflections

⇨ Rotations &

⇨ Inversion.
 Lattice point and space lattice
 In perfect(ideal)crystal there is a regular arrangement of atoms.
 It is convenient to imagine points in space about which the atoms are
located such point in space are called lattice point.
 And the totality of such points forms crystal lattice or space lattice.
 If all atoms at the lattice points are identical the lattice is called Bravias
lattice.
 An ideal crystal is constructed by the infinite repetition of identical
groups of atoms .
 A group is called the basis.
 The set of mathematical points to which this basis is attached is called the
lattice.
 Lattice translation vectors
 The lattice in three dimensions may be defined by three translation vectors
𝑎1, 𝑎2, and 𝒂𝟑 such that the arrangement of atoms in the crystal looks the
same when viewed from the point r as when viewed from every point 𝑟
′ translated by an integral multiple of the a's:

𝒓 ′ = r + 𝒖 𝟏𝒂 𝟏+ 𝒖𝟐𝒂𝟐 +𝒖𝟑𝒂𝟑 (1)

where, 𝑢1, 𝑢2, and 𝑢3are integers.
 The set of points 𝑟 ′ defined by (1) for all 𝑢1, 𝑢2, 𝑢3 defines the lattice.
 The lattice is said to be-primitive if any two points from which the
atomic arrangement looks the same always satisfy (1) with a suitable
choice of the integers 𝑢1.
 Primitive translation vectors, 𝒂𝒊

 There is no cell of smaller volume than primitive cell,

𝑽𝟎 = 𝒂𝟏 ∙ 𝒂𝟐 × 𝒂𝟑

that can serve as a building block for the crystal structure.

 Primitive translation vectors define the crystal axes, which form three
adjacent edges of the primitive parallelepiped.
 No primitive axis are often used as crystal axes when they have a simple
relation to the symmetry of the structure.
 Basis and crystal structure
 A crystal is made by adding a basis to every lattice point.

 Lattice points themselves are mathematical constructions.

 Every basis in a given crystal is identical to every other in composition,

arrangement, and orientation.

The number of atoms in the basis may be one, or it may be more than
one.

The position of the center of an atom j of the basis relative to the

associated lattice point is

𝐫𝐣 = 𝐱𝐣𝐚𝟏 + 𝐲𝐣𝐚𝟐 + 𝐳𝐣𝐚𝟑

(2)

We may arrange the origin, which we .have called the associated lattice point,
 Primitive lattice cell
 The parallelepiped defined by primitive axes 𝒂𝟏, 𝒂𝟐 and 𝒂𝟑 is called a primitive cell (Fig.
3b). (Pag-5).
 A primitive cell is a type of cell or unit cell .
 A cell will fill all space by the repetition of suitable crystal translation operations.
 A primitive cell is a minimum volume cell.
Ways of choosing the primitive axes and primitive cell for a given lattice
The number of atoms in a primitive cell or primitive basis is always the same for a given
crystal structure.
There is always one lattice point per primitive cell.
If the primitive cell is a parallelepiped with lattice points at each of the eight corners, each
lattice point is shared among eight cells, so that the total number of lattice points in the cell

is one: 8× 81 = 1.

The volume of a parallelepiped with axes 𝑎1 ,𝑎2, 𝑎3 is;

𝑽𝒄 = 𝒂𝟏 ∙ 𝒂𝟐 × 𝒂𝟑 (3)
 The basis associated with a primitive cell is called a primitive basis.
 No basis contains fewer atoms than a primitive basis contains.
 Another way of choosing a primitive cell is known to physicists as a
Wigner-Seitz cell.
 FUNDAMENTAL TYPES OF LATTICES
 Crystal lattices can be carried or mapped into themselves by the lattice translations, T
and
by various other symmetry operations like translation, rotation, reflection and inversion.
 A typical symmetry operation is that of rotation about an axis that passes through a
lattice point.
 Based on the symmetry operation , five possible two dimensional Bravais lattice are
found. Two-Dimensional Lattice Types

Fig. Four special lattices in two dimensions.

 Three dimensional lattice types
 The point symmetry groups in three dimensions require the 14 different lattice types.

 The general lattice is triclinic, and there are 13 special lattices.

 These are grouped for convenience into systems classified according to seven types of
cells, which are triclinic, monoclinic, orthorhombic, tetragonal, cubic, trigonal, and
hexagonal.
 The division into systems is expressed in the table in terms of the axial relations that
describe the cells.
 The cells in Fig. are conventional cells: of these only the Sc is a primitive cell.

 Often a no primitive cell has a more obvious relation with the point symmetry
operations than has a primitive cell.
 There are three lattices in the cubic system: the cubic (Sc) lattice,
simple
cubic (fcc) lattice.
the body-centered cubic (bee) lattice, and the face-
centered
 3-D lattice types
Triclinic Monoclinic

Orthorhombic Simple Base-Centered

 Simple Cubic

• d

Hexagonal

Simple Body-Centered Face-Centered

cubic
3-D lattice types
 Cubic crystal systems

Sc

𝑺𝒄 𝑩𝒄𝒄 𝑭𝒄𝒄
 Coordination Number
 It is equal to the number of nearest neighbor that surrounds each
atom.
♦ Simple Cubic -6
♦ Body Centered Cubic – 8
♦ Face Centered Cubic - 12
 Cubic crystal structures
Sc Bcc Fcc
 Atomic packing factor
 The packing fraction is the maximum proportion of the available volume that can be
filled with hard spheres.

𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚 𝑖𝑛 𝑎 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

The atomic packing factor is given by = 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡h𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

For simple cubic crystal is given

𝟒𝝅 𝟑 𝟒𝝅 𝒂 𝟑
A.p.f = 1 𝟑𝒓
=1 𝟑 𝟐
=𝝅 = 0.524 (4)
𝒂𝟑 𝒂𝟑
𝟔

For body centered cubic

𝟑
𝟒𝝅 𝟑
𝟒𝝅 𝟑 𝟑 𝒂
𝟑𝒓 𝟒 𝟑𝝅
A.p.f = 2 𝒂𝟑
=2 𝒂𝟑
= 𝟖
= 0.680 (5)

For face centered cubic

𝟑
𝟒𝝅 𝟐
𝟒𝝅 𝟑 𝟑 𝒂
𝟑𝒓 𝟒 𝟐𝝅
A.p.f = 4 𝒂𝟑
=4 𝒂𝟑
= 𝟔
= 0.740 (6)
Figure 9 Body-centered cubic lattice,

showing a primitive cell.

 The primitive cell shown is

a rhombohedron of edge 12 3a, and

the angle between

adjacent edges
is 109°28.

Figure 10 Primitive translation vectors of the body centered cubic lattice; these vectors connect the
lattice point at the origin to lattice points at the body centers. The primitive cell is obtained
on completing the rhombohedron.
 In terms of the cube edge a, the primitive translation vectors are
𝒂𝟏 = 𝒂( 𝒙^ + 𝒚^ - 𝒛^ ) (7a)
𝟐

𝒂𝟐 = 𝒂𝟐(-𝒙^ + 𝒚^ + 𝒛^)
(7b)
𝒂𝟑 = 𝒂𝟐( 𝒙^ - 𝒚^ + 𝒛^ )
(7c)
Here 𝑥^, 𝑦^, and 𝑧 are the Cartesian unit
vectors.
 The characteristics of the three cubic lattices are summarized in Table 2.

 A primitive cell of the bee lattice is shown in Fig. 9, and the

primitive translation vectors are shown in Fig. 10.

 The primitive translation vectors of the fcc lattice are shown in Fig.
11.

 Primitive cells contain only one lattice point.

 However, the conventional bcc cell contains two lattice points, and
the fcc

cell contains four lattice points.

 Characteristics of cubic systems
№ Simple cubic Body centered Face centered

1 Volume of conventional 𝒂𝟑 𝒂𝟑 𝒂𝟑
cell
2 Lattice points per cell 1 2 4
3 Volume of primitive cell 𝒂𝟑 𝟏 𝟏
𝟐𝒂𝟑 𝟒𝒂𝟑
4 Lattice points per cell 𝟏 𝟐 𝟒
𝒂𝟑 𝒂𝟑 𝒂𝟑
5 Coordination number 6 8 12
𝒂
6 Nearest neighbor 𝒂 𝟑𝒂
= 0.866a = 0.707a
𝟐
distance 𝟐

7 № of next nearest 12 6 6
neighbor
8 Next neighbor distance 𝟐𝒂 𝒂 𝒂
𝟏
9 Packing fraction 𝝅 = 0.54 𝟑𝝅
= 0.68 𝟐
𝝅 = 0.74
𝟔 𝟖 𝟔
 The Nearest distance for Sc, Bcc &
Fcc
 For sc the nearest distance is a.

For bcc the nearest distance is

𝑎 2 𝑎 2 𝑎 2 3a
r= + + = = 0.866ɑ
2 2 22

 For Fcc, the nearest distance

is
2 2
𝑎 𝑎 2a
r= + + 0 2 = =
2 2 2
0.707a
𝑎1 = 21 a(𝑥^
+𝑎 𝑦^)
= 1 𝑎(𝑦^+
2 2
𝑧)
𝑎3 = 12a(𝑧 +
𝑥^)

The angles between the axes are 60ᵒ.

 The position of a point in a cell is specified by (2) in terms of the atomic coordinates x, y, z.

 Here each coordinate is a fraction of the axial length 𝑎1 > 𝑎2 > 𝑎3 in the direction of the
coordinate axis, with the origin taken at one corner of the cell.

111
 Thus the coordinates of the body center of a cell are 222
and the face centers include
1 1
0, 0 1 1
and 1 0 1 .
2 2 2 2 2 2

 In the hexagonal system the primitive cell is a right prism based on a rhombus with an
included angle of 120°.
 Figure 12 shows the relationship of the rhombic cell to a hexagonal prism.
 Index system for crystal planes
 The orientation of a crystal plane is determined by 3 - points in the
plane, which are not collinear.
 If each point lay on a different crystal axis, the plane could be specified

by giving the coordinates of the points in terms of the lattice constants 𝑎1,
𝑎2, 𝑎3.

 However, it turns out to be more useful for structure analysis to specify

the orientation of a plane by the indices determined by the following rules
(Fig. 13).

 Find the intercepts on the axes in terms of the lattice constants 𝑎1, 𝑎2, 𝑎3.

 The axes may be those of a primitive or non primitive cell.

 2

a3
a2
1 a1
1
2
2
3

 Take the reciprocal of these numbers and then

Figure 13. This plane intercepts
reduce to three integers having the same ratio,
the 𝑎1,𝑎2 ,𝑎3 axes at the 3𝑎1,2𝑎2, 2𝑎3. usually the three small integers, the result enclosed

1 1 1 in parenthesis, 𝒉𝒌𝒍 are the index of the plane.

The reciprocals of these numbers are 3 , 2, 2.

The smallest three integers having the same ratio are 2, 3, 3,

and
 For the plane whose intercepts are 4, l, 2, the reciprocals are 1, 1, and 1 .
4 2

 The smallest three integers having the same ratio are (142).
 For an intercepts at infinity, the corresponding index is zero.
 The indices of some important planes in a cubic crystal are illustrated
by Fig. 14.
 The indices (hkl) may denote a single plane or a set of parallel
planes.
 If a plane cuts an axis on the negative side of the origin, the corresponding index

is negative, indicated by placing a minus sign above the index: (h𝑘^ l).
 The cube faces of a cubic crystal are (100), (010), (001), (100), (010), and
(001).
 Planes equivalent by symmetry may be denoted by curly brackets (braces)
around
indices; the set of cube faces is {100}.
 When we speak of the (200) plane we mean a plane parallel to (100)

but cutting the 𝑎1 axis at 21a.

 The indices [uvw] of a direction in a crystal are the set of the

smallest integers that have the ratio of the components of a vector in
the desired direction, defined to the axes.
 The 𝑎1 axis is the [100] direction; the -𝑎2 axis is the [010] direction.

 In cubic crystals the direction [hkl] is perpendicular to a plane (hkl)

having the same indices, but this is not generally true in other crystal
systems.
 h, k, l are
Miller indices
 a, b, c are unit
cell distances
 , ,  are
angles between
the lattice
directions.

 Complexity of
calculations is
dependent on the
symmetry of the
crystal system.
 Miller Index
 Miller indices describes the directions & planes.

 The directions and planes could be in lattice or in crystals.

• In 1-D ; there is one index

• In 2-D; there are two indices
• In 3-D; there are three indices
 Note: In the case of miller- Bravaise indices for hexagonal a fourth
index is added to three redundant index (hkil).
 Where, i – is the redundant index.

 The redundant index is added to show the symmetry of the structure.

 Simple Crystal Structures
 We discuss simple crystal structures of general interest: the sodium chloride, cesium
chloride, hexagonal close-packed, diamond, and cubic zinc sulphide structures.

 𝑵𝒂+ ions form a face-centered cubic

lattice.
 𝑪𝒍; ions are located between each
two
neighboring 𝑵𝒂+ ions. Or,
 𝐶𝑙; ions form a face-centered cubic
lattice
 𝑵𝒂+ ions are located between each two
neighboring 𝑪𝒍; ions.
Cl: 000; 11
0,
1
0
1
0
11
111
Na: , 22
1
2
1
2
1
22
222 0 0 2; 0 2 0; 2
00
𝑁𝑎+

𝐶𝑙; NaCl structure

 Fig -16: Models of NaCl. The Na ions are smaller than chlorine ions. (Courtesy of A. N.
Holden and P. Singer.)
 NaCl primitive cell
•

Primitive
cell
 NaCl
NaCl
 The lattice is face-centered cubic; the basis consists of one 𝑁𝑎+ ions and one 𝑐𝑙;
ion separated by one-half the body diagonal of a unit cube.
 There are four units of NaCl in each unit cube, with atoms in the
positions. 11 1 1 1 1
Cl: 0 0 0, 22
0, 0 ,
2 2
02 2
1 1 1
0 12 0; 1
2
00
1
Na: 2 2 2
, 0 0 2;
 Each atom has as nearest neighbors six atoms of the opposite kind.

 Representative crystals having the NaCl arrangement those in the

include
following table.
 The cube edge a is given in angstrom; 1Å =10;8cm = 10;10𝑚 = 0.1nm.

(See for PbS)

 Cesium Chloride Structure
 The cesium chloride structure is shown in Fig. 18.

 There is one molecule per primitive cell, with atoms at the corners 000 and

body centered positions 21 1212of the simple cubic space lattice.

 Each atom may be viewed as at the center of a cube of atoms of the

opposite kind, so that the number of nearest neighbors or coordination
number is eight.
 CsCl structure

 Simple cubic lattice

𝑪𝒔+ions form a cubic lattice
𝑪𝒍−ions are located at the center of each
cube
 Equivalently, we can say that
𝑪𝒍− ions form a cubic lattice
𝑪𝒔+ ions are located at the center of each cube
Coordinates:
Cs: 000
111
Cl: 2 2 2
 Notice that this is a simple cubic lattice.

Fig:18
 Hexagonal close packed structure
 There are an infinite number of ways of arranging identical spheres in a
regular array that maximizes the packing fraction (Fig. 19) .
 One is the face centered cubic structure; another is the hexagonal close-packed
structure (Fig. 20).
 The fraction of the total volume occupied by the spheres is 0.74 for both
structures.
 No structure, regular or not, has denser packing.

⟐ There are an infinite number of ways of arranging identical spheres in a regular

array that maximizes the packing fraction.
 HCP structure

Hexagonal close packed structure

 HCP unit cell

Hexagonal close packed structure unit

cell
 The Diamond structure
 The diamond structure is the structure of the semiconductors silicon and
germanium and is related to the structure of several important semiconductor
binary compounds.
 The space lattice of diamond is face-centered cubic.

 The primitive basis of the diamond structure has two identical atoms at coordinates
000 and
1 1 1
, , associated with each point of the fcc lattice, as shown in Fig. 22.
4 4 4

 Because the conventional unit cube of the fcc lattice contains 4 lattice points, it follows
that the conventional unit cube of the diamond structure contains 2 x 4 = 8 atoms.
 There is no way to choose a primitive cell such that the basis of diamond contains only
one atom.
 Diamond structure: is non Bravaise lattice
 The diamond structure allows a center-at-inversion symmetry operation at
the
midpoint of every line between nearest-neighbor atoms.

 The inversion operation carries an atom at r into an atom at -r.

fig 23. Diamond structure

Each atom has 4 nearest neighbors and 12 next nearest neighbors.

The diamond structure is relatively empty: the maximum proportion of the

available volume which may be filled by hard spheres is only 0.34, which
is 46 percent of the filling factor for a closest-packed structure such as fcc
or hcp.

The diamond structure is an example of the directional covalent bonding

found in column IV of the periodic table of elements.

Carbon, silicon, germanium, and tin can crystallize in the diamond

structure, with lattice constants a = 3.567, 5.430, 5.6.5&, and 6.49 A,
respectively.

Here a is the edge of the conventional cubic cell.

 ZnS cubic structure
 The cubic ZnS structure does not have inversion symmetry.
 Examples of the cubic zinc sulfide structure are
Crystal ɑ Crystal ɑ
SiC 4.35Å ZnSe 5. 56Å
ZnS 5.41Å GaAs 5. 56Å
AlP 5.45Å AlAs 5.66Å
GaP 5.45Å InSb 6.46Å

 The close equality of the lattice constants of several pairs, notably (AI,
Ga)P and (AI, Ga)As, makes possible the construction of semiconductor
hetero-junctions (Chapter 19).
 ZnS structure

𝑪𝒐𝒐𝒓𝒅 №: 𝒁𝒏𝟐+𝟒 , 𝑺𝟐−:4 𝒔𝟐− at Fcc

Atomic unit cell 𝒁𝒏𝟐+at ½ Td holes
Zn:S= 4:4= 1:1 = ZnS
 Chapter
Wave diffraction2& reciprocal lattice vector
Bragg-law:
 Diffraction of wave depends on
⇨ Crystal structure &
⇨ Wavelength
 An optical wave length such as 5000Å, the superposition of waves scattered by
the individual atoms of a crystals results in ordinary optical refraction.
 Diffraction occurs when the wavelength is equal or smaller than the
lattice constant.
λ≤𝑎 (1)
 Bragg presented a simple explanations of the diffracted beams by the crystals.
 The Bragg deviations is simple & convincing only because it reproduce correct
result.
 Elastic scattering is treated b/ce in elastic scattering, energy of the x-ray is
not changed on reflection.
 We consider parallel lattice planes spaced ‘d’ apart.
 The path difference for rays reflected from the adjacent plane is 2dsinθ.
 The angle, θ – is measured from the plane.
 Constructive interference occur when the path difference is an
integral multiple of wave length.
2dsinθ = nλ (2)
,provided that λ ≤ 2d.
 The Bragg law in equ (2) is the consequence of the periodicity of the
lattice.
 The Bragg law does not depend on the composition of the
basis associated with the lattice point.
 Fourier analysis
 We have seen that a crystal is invariant under any translations of the form;

T = 𝒖𝟏𝒂𝟏 + 𝒖𝟐𝒂𝟐+ 𝒖𝟑𝒂𝟑 (3)

Where, 𝑢1, 𝑢2, & 𝑢3 are integers and 𝑎1, 𝑎2, & 𝑎3 are the
crystal axis
 Any local physical property of crystal such as
♦ Charge concentrations,

♦ Electron number density, &

♦ Magnetic moment density are invariant under translation, T.

 The most important quantity here is that the electron number density
is a periodic function of V, with periods; 𝑎1, 𝑎2 , & 𝑎3in the direction
of 3- crystal axis.
 n 𝑥 + 𝑎 = 𝑛 𝑜 + ∑ 𝑐𝑝𝑐𝑜𝑠
2𝜋𝑝𝑥
𝑎 + 2𝜋𝑝
+ 𝑠𝑝𝑠𝑖𝑛 2𝜋𝑝𝑥
𝑎 + 2𝜋𝑝

2𝜋𝑝𝑥 2𝜋𝑝𝑥
= 𝑛 𝑜 + ∑ 𝑐𝑝𝑐𝑜𝑠 𝑎
+ 𝑠𝑝𝑠𝑖𝑛 𝑎

=n 𝑥
(4)
 2𝜋𝑝𝑎 - is the point in the reciprocal lattice or Fourier space of the crystal.

 The reciprocal lattice points describes the allowed terms in the Fourier series.

 The term is allowed if it is constant with the periodicity of the

crystal.

 n r + T = n(r)
 Such periodicity creates an ideal situations for Fourier analysis.

 The most interesting properties of crystals are directly related to the Fourier
component of the electron number density
 We might expand n(x) in a Fourier series sine's & cosines.
2𝜋𝑝𝑥 2𝜋𝑝𝑥
n 𝑥 = 𝑛𝑜 + ∑𝑝>0 𝑐𝑝𝑐𝑜𝑠 𝑎
+ 𝑠𝑝𝑠𝑖𝑛 𝑎

 Where p’s are positive integers and 𝑐𝑝 & 𝑠𝑝 are real constants called the Fourier
coefficient of expansions.

 The factor 2𝜋 in the argument ensures that n(x) has the period 𝑎.
𝑎

 Other points in the reciprocal lattice are not allowed in the Fourier expansion of a
periodic functions.
 It is convenient to write the series (4) in the compact form as

𝑖2𝜋𝑝𝑥
n(x) = ∑𝑝 𝑛𝑝𝑒𝑥𝑝 (5)
𝑎
−𝒊𝟐𝝅𝒑𝒙
𝟏 𝒂
𝒏𝒑 = 𝒂∫ 𝟎𝒅𝒙𝒏 𝒙 𝒆𝒙𝒑 𝒂
 Where the sum is over all integers, p, positive, negative or zero. The coefficient 𝑛𝑝 are
complex numbers.
 To ensure that n(x) is a real function we require that

𝑛−𝑝 ∗ = 𝑛𝑝 (6)

 For the sum of the terms in p and –p to be real, equ(6) must be satisfied.

 The asterisk in 𝑛𝑝∗denotes the complex conjugate.

ϕ = 2𝜋𝑝𝑎 𝑥 , the sum in

𝑛𝑝 𝑐𝑜𝑠 ϕ + 𝑖𝑠𝑖𝑛 ϕ +𝑛−𝑝 𝑐𝑜𝑠 ϕ − 𝑖𝑠𝑖𝑛 ϕ = 𝑛𝑝 + 𝑛−𝑝 cosϕ+i 𝑛𝑝 − 𝑛−𝑝 sinϕ (7)

Which in turn is equal to the real function.

2Re 𝑛𝑝 cosϕ-2Im 𝑛𝑝 sinϕ (8)

 Here, Re 𝑛𝑝 & denotes the real and imaginary parts of the 𝑛𝑝 .

Im 𝑛𝑝
is extended to n 𝑟 , where r = 𝑥𝜄 + 𝑦j + 𝑧𝑘 .
 In three dimensions, n 𝑥
 We must find a set of vector G such that

(9)

Which is invariant under all crystal translations, T that leave the crystal
invariant.

Exercise
1. Discuss the difference between direct lattice and reciprocal lattice vectors.
 Inversion of Fourier series
 We now that the Fourier coefficient in equ (5) is given by

−𝒊𝟐𝝅𝒑𝒙
𝟏 𝒂 (10)
𝒏𝒑 = 𝒂∫ 𝟎𝒅𝒙𝒏 𝒙 𝒆𝒙𝒑 𝒂

 By substituting equ(5) in to equation (10) to obtain

𝒙
𝟏 𝒂 (11)
𝒏𝒑 = 𝒂∫ 𝟎𝒅𝒙𝒏 p 𝒆𝒙𝒑 𝒊𝟐𝝅 𝒑′ −𝒑 𝒂

 If p’≠ 𝑝 the value of the integers is

 For the term P’ = P, the integrand exp(0) =1 and the value of the integral is 𝑎. So,
that
𝑛𝑝 = 𝑎1 𝑛 𝑝 𝑎 = 𝑛𝑝.

 Which is an identity so that equ(10) is also an identity. As in (10) the inversion (9)
gives
𝑛𝐺 = 1 𝑑𝑣𝑛 𝑟 𝑒𝑥𝑝 −𝑖𝐺. 𝑟 (12)
𝑉𝑐 ∫𝑐𝑒𝑙𝑙

Where 𝑉𝑐 is the volume of the cell of the

 Reciprocal lattice vectors
 To describe more about Fourier analysis of the electron concentration, we need to

find a vector G of the Fourier sum, ∑ 𝑛𝐺 𝑒𝑥𝑝 𝑖𝐺. 𝑟 as in (9).

 The powerful tool to describe Fourier analysis is the use of the axis vectors, 𝑏1,

𝑏2, & 𝑏3 of the reciprocal lattice.

𝑎 𝑥𝑎
𝑏1 = 2𝜋 𝑎 𝑙 .𝑚𝑎𝑚𝑥 𝑛𝑎𝑛
𝑎𝑛 𝑥 𝑎 𝑙
𝑏2 = 2𝜋 𝑎 𝑙 . 𝑎𝑚 𝑥 𝑎𝑛 (13)
𝑎 𝑙 𝑥 𝑎𝑚
𝑏3 = 2𝜋 𝑎 𝑙 . 𝑎𝑚 𝑥 𝑎𝑛
 The factors 2𝛑 are not used by the crystallographer but is convenient in solid state
physics.

 𝑎1, 𝑎2 & 𝑎3 are the primitive vectors of the crystal(direct) lattice and 𝑏1, 𝑏2 & 𝑏3
are the primitive vectors of the reciprocal lattice.
 Each vectors defined by (13) is orthogonal to two axis vectors of the crystal
lattice.

 𝑏1, 𝑏2 & 𝑏3 have the prosperity that

𝑏𝑖. 𝑎𝑗= 2𝜋𝛿𝑖𝑗 (14)

 Where

𝛿𝑖𝑗 = 1, 𝑖𝑓 𝑖 = 𝑗
|
𝛿𝑖𝑗 = 0, 𝑖𝑓 𝑖 ≠ 𝑗

 Points in the reciprocal lattice are mapped by the set of the vectors, G such that

G = 𝑣1𝑏1 + 𝑣2𝑏2 + 𝑣3𝑏3

(15)

Where, 𝑣1, 𝑣2 & 𝑣3 are integers

 The vector G of this form is called the reciprocal lattice.

 In the Fourier series representations, electron number density is invariant under crystal
translations.

T= 𝑢1𝑎1+𝑢2𝑎2+𝑢3𝑎3
 Thus, the electron number density has the property;

n 𝑟 + 𝑇 = ∑𝐺 𝑛𝐺 𝑒𝑥𝑝 𝑖𝐺. 𝑟 𝑒𝑥𝑝 𝑖𝐺. 𝑇 (16)

But exp 𝑖𝐺. 𝑇 = exp 𝑖2𝜋𝑛
=1 Since,
exp(iG. T) = exp(i(𝑣1𝑏1 + 𝑣2𝑏2 + 𝑣3𝑏3)(𝑢1𝑎1+ 𝑢2𝑎2+ 𝑢3𝑎3)

= exp (𝑖2𝜋)𝑣1𝑢1 + 𝑣2𝑢2 + 𝑣3𝑢3

= exp 𝑖2𝜋𝑛 =1 (17)
 The argument of the exponential has the form 2𝜋I times an integer, n = (𝑣1𝑢1 + 𝑣2𝑢2 +
𝑣3𝑢3) .
 Thus, by equation (9) we have desired invariance.

n 𝑟 + 𝑇 = n(r) = ∑𝐺 𝑛𝐺 𝑒𝑥𝑝 𝑖𝐺. 𝑟

 Every crystal structure has two lattice associated with it.

1. Crystal(direct) lattice &

2. Reciprocal lattice.
 A diffraction pattern of a crystal is a map of the reciprocal lattice of the
crystal.
 A microscopic image if it could be resolved on a fine enough scale is a map of
crystal structure in real space.
 The two lattice are related by the equation (13).

 When we rotate a crystal, we rotate both the direct lattice & reciprocal lattice.

 Vectors in the crystal(direct) lattice has a dimension of 𝑙𝑒𝑛𝑔𝑡h .

1
 Vectors in the reciprocal lattice has a dimension of .
𝑙𝑒𝑛𝑔𝑡h

 A reciprocal lattice is a lattice in Fourier space associated with the

crystal.
 Diffraction conditions
 Theorem: The set of reciprocal lattice vectors G possible x-ray
determines diffractions.
 As shown in fig - 6 diffractions in the phase factors is exp 𝑖 𝑘 − 𝑘
′ .𝑟
 K & 𝑘’ are the wavevectors of incoming & out going beams of light.

Fig 6.
 The difference in the path length of the incident wave k
at point, O ,r is rsinφ.

2𝜋𝑟𝑠𝑖𝑛𝜑
 And the difference in phase angle is λ
which is equal
to k.r.
 For the diffracted wave the difference in phase angle is –k.r.

 The total difference in phase angle is 𝑘 − 𝑘′ .r

 The wave scattered from dv at r has the phase factor

exp 𝑖 𝑘 − 𝑘′ . 𝑟 relative to the wave scattered from
the volume element at the origin, O.
 𝐾′ ∆k = 𝐾 ′ - k

𝐾 ′ = k + ∆k
k

Fig 7: Definition of scattering vector ∆k such that k + ∆k = 𝑘′

 In elastic scattering the magnitude satisfies, 𝐾 ′ = k.

 Furthermore, in Bragg’s scattering from a periodic lattice any allowed ∆k

must equal some reciprocal lattice vectors, G.
 We suppose that the amplitude of the wave scattered from the volume
element is proportional to the local electron concentration, n(r).

𝑭~𝒏 𝒓
 The total amplitude of the scattered wave in the direction of k‫ ׳‬is proportional to integral

over the crystal of n(r)dv times the phase factor, exp 𝑖 𝑘‫ ׳‬− 𝑘 . 𝑟 .

 In other words the amplitude of the electric or magnetic vectors in the

scattered electromagnetic wave is proportional to the scattering amplitude, F.

F = ∫ 𝑑𝑣𝑛 𝑟 𝑒𝑥𝑝 𝑖 𝑘−𝑘‫ ׳‬. 𝑟

(18)
= ∫ 𝑑𝑣𝑛 𝑟 𝑒𝑥𝑝 −𝑖∆𝑘. 𝑟

Where, k – k‫ = ׳‬-∆k; or k + ∆k = k‫׳‬

 ∆k measures the change in the wave vector, and called the scattering
 vector.
In order to find the wave vector of the scattered beam , we add, ∆k to k‫׳‬.
 To find the scattering amplitude, we substitute equation (9) in to equ (18). The
resulting scattering amplitude is;

(19)
F = ∑𝐺 ∫ 𝑑𝑣𝑛𝐺 exp 𝑖 𝐺 − ∆𝑘 . 𝑟

 When the scattering amplitude is equal to a particular reciprocal lattice,

(20)
∆k = G
 The argument of the exponential vanishes and the scattering amplitude reduces to

F = VnG (21)

 It is simple exercise to show that F –is negligibly small when ∆k differs significantly from
any reciprocal lattice vectors.

 In elastic scattering of photons its energy ћω is conserved so that the frequency

ω = ck‫׳‬

)22(
 Of the emergent beam is equal to the frequency of the incident beam. Thus, the magnitude
k & k‫׳‬.

 Therefore, 𝑘 2 = 𝑘′2, a result that holds for elastic scattering of electrons and neutrons beams.
So that
∆kthe
=Gdiffraction
or k + Gcondition
= k‫׳‬ is obtained from

𝑘+𝐺 2 = 𝑘2

2kG + 𝐺 2 = 0 (23)
 This is the central result of the theory of elastic scattering of waves in a periodic
lattice.
 If G is a reciprocal lattice vectors so is -G and with this substitutions we can rewrite
equation

(23) as

2K.G = 𝐺2 (24)

 This particular expression is often used as the conditions for diffraction.

 Equ(23) is another statement of the Bragg’s diffractions conditions.

 The result of problem 1 is that the spacing 𝑑𝑕𝑘𝑙 between parallel planes that is normal to the
2𝜋
direction of G = h𝑏1+ k𝑏2+ l𝑏3 is 𝑑h = 𝐺
𝑘𝑙

2𝜋 2𝜋
Thus , the result 2k.G = 𝐺 2 might be written as λ
sinθ =
𝑑 ℎ𝑘𝑙
2

Or 2𝑑𝑕𝑘𝑙sinθ = λ
Θ is the angle between the incident beam and the crystal planes.

2dsinθ = nλ (25)

d - is the spacing between adjacent parallel planes with indices, 𝑛,h 𝑘𝑛, and 𝑙
𝑛.
 Brillouin zone
Brillouin zone: is defined as a Wigner Seitz primitive cell in the reciprocal lattice.
 It gives a statement of diffraction condition.
 It describe electron energy band theory & elementary excitations such as
photons,
phonons, Magnons, Plasmon's, etc.
 It gives vivid geometrical interpretation of diffraction condition

2𝐾. 𝐺 = 𝐺2 (26)
 are not an essential part of the X-ray diffraction in the analysis of
crystal structure, but it is part of the analysis of the electronic energy band
structure of the crystals.
 A reciprocal space is a space of k’s & G’s so that the diffracted beam is in the
direction of K-G.
 Reciprocal lattice to SC lattice
 The primitive translation vectors of sc lattice are

𝑎1 = 𝑎𝑥^

𝑎2 = 𝑎𝑦^ (27a)

𝑎3 = 𝑎𝑧

 Here, 𝑥^,𝑦^ & 𝑧 are orthogonal vectors of unit length. The volume of the cell 𝑣𝑐= 𝑎1. 𝑎2𝑥𝑎3 =
is

𝑎3 .
 The primitive translations vectors of the reciprocal lattice are found

2𝜋
𝑏1 = 𝑥
𝑎
^
2𝜋
𝑏2 = 𝑦 (27b)
𝑎
^
2𝜋
𝑏3 = 𝑧
𝑎

 Here, a reciprocal lattice is itself a simple cubic lattice with lattice constant 2𝜋
𝑎
.
 The boundaries of the FBZ are planes normal to the
six reciprocal lattice vectors, ±𝑏1, ±𝑏2 & ±𝑏3 at their mid
points. 𝜋
±𝑏1 = ± 𝑥
𝑎
^
𝜋
±𝑏2 = ± 𝑦 (28)
𝑎
^
𝜋
±𝑏3 = ± 𝑧
𝑎

3
2𝜋
 The six planes bound a cube of edge 2𝜋 & a volume of .
𝑎 𝑎

 This cube is the first Brillouin zone of the sc crystal lattice.

 Reciprocal lattice to bcc lattice
 The primitive translation vectors of the bcc lattice are

1
𝑎1 = −𝑥^ + 𝑦^
2𝑎
+𝑧
1
𝑎2 = 2𝑎 𝑥^ − 𝑦^ (29)
+𝑧
1
𝑎3 = 2𝑎 𝑥^ + 𝑦^
−𝑧
 Where ɑ - is the side of conventional cube and 𝑥^, 𝑦^ & 𝑧 are orthogonal unit vectors parallel to the
cubic

edges. The volume of the primitive cell is

𝑉𝑐 = 𝑎1. 𝑎2𝑥𝑎3 = 21 𝑎3 (30)

 The primitive translations of reciprocal lattice are defined by (13). Thus, we have

𝑏1 = 𝑎
2𝜋 𝑦^ +
𝑧

𝑏2 = 𝑎
2𝜋 𝑥^ (31)
+𝑧
2𝜋
𝑏3 = 𝑎 𝑥^
+ 𝑦^
 By comparison with fig -14 (p.37) these are just
the primitive vectors of an fcc lattice. So that an fcc lattice is
the reciprocal lattice of the bcc lattice.

 In general the reciprocal lattice vectors for integral 𝑣1, 𝑣2 &

𝑣3.

G = 𝑣1𝑏1+𝑣2𝑏2+𝑣3𝑏3
2𝜋
= 𝑣2 + 𝑣3 𝑥^ +𝑣1 + 𝑣3 𝑦^ +𝑣1 + 𝑣2 𝑧
𝑎

 The shortest G’s are the 12 vectors whose all choice of sign
are independent.
𝑏1 = 𝑎
2𝜋 ± 𝑦^ ± 𝑧

𝑏2 = 𝑎
2𝜋 ±𝑥^ (33)
±𝑧

𝑏3 = 𝑎 ±𝑥^
2𝜋
± 𝑦^
 One primitive cell of reciprocal lattice is the parallelepiped described by 𝑏1, 𝑏2 & 𝑏3. The volume of

this cell in the reciprocal lattice is

2𝜋 3
𝑉𝑐 = 𝑏1. 𝑏2𝑥𝑏3 = 2 (34)
𝑎

 The cell contains one reciprocal lattice point because each of the eight corners point is shared eight

parallelepiped.

 Each parallelepiped contains one eighth of each of the eight corners points.

 An other primitive cell the central (Wigner Seitz cell) of the reciprocal lattice which FBZ.

 Each cell contains one lattice point at the central point of a cell.

 This zone for bcc lattice is bounded by the plane normal to 12 vectors of equ(33) at their mid point.

 The zone is a regular 12-faced solid , a rhombo dodecadron.

 Reciprocal lattice to fcc
 The primitive translation vectors of fcc lattice are

𝑎1= 12𝑎 𝑦^
+𝑧
𝑎2= 12𝑎 𝑥^ (35)
+𝑧
𝑎3 = 12 𝑎 𝑥^
+ 𝑦^
 The volume of the primitive cell is

𝑉𝑐 = 𝑎1. 𝑎2𝑥𝑎3 = ¼𝑎3

(36)
 The primitive translation vectors of the lattice reciprocal to the fcc lattice are
𝑏1 = 𝑎 −𝑥^ + 𝑦^
2𝜋
+𝑧
2𝜋
𝑏2 = 𝑎 𝑥^ − 𝑦^ (37)
+𝑧
𝑥^ + 𝑦^
2𝜋
𝑏3 = 𝑎
−𝑧
 Equation (36) describes the primitive translation vectors of bcc lattice.
 Thus the bcc lattice is reciprocal to fcc lattice.

 The volume of the primitive cell of reciprocal lattice of fcc lattice is

3 3
2𝜋 𝜋
𝑉𝑐 = 4 = 32
𝑎 𝑎

 the shortest G’s are the eight lattice vectors

2𝜋
G= ±𝑥^ ± 𝑦^ ± 𝑧 (38)
𝑎

 The boundaries of the central cell are determined for the most part by eight planes normal to these
vectors at their mid point.
 The corner of the octahedral thus, formed are cut by the perpendicular bisector of six other reciprocal
lattice;

2𝜋
±2𝑥
𝑎
^
2𝜋
±2𝑦 (39)
𝑎
^
2𝜋
±2𝑧
𝑎
The 1st Brillouin zone is the smallest
bounded volume about the origin. (see fig 15)
4𝜋
 The six planes bound a cube of edge &
𝑎
volume 3
of 4𝜋 .
𝑎
 Chapter 3
Properties of Ionic crystals
 What holds a crystal together?
 The attractive electrostatic interaction between the negative of the
charges
electrons and the positive charges of the nuclei is entirely responsible for the
cohesion of solids.
 Magnetic forces have only a weak effect on cohesion and gravitational forces are
negligible.
 Specialized terms categorize distinctive situations: exchange énergies, vander
Waals forces, and covalent bonds.

 The observed differences between the forms of condensed matter are

caused in the final analysis by differences in the distribution of the
outermost electrons and the ion cores.
 3.1 Cohesive energy
 The cohesive energy of a crystal is the energy that must be added to the crystal to

separate its components into neutral free atoms at rest, at infinite separation, with

the same electronic configuration.

 Lattice energy the energy that must be added to the crystal to separate

its component ions into free ions at rest at infinite separation.

 It is used in the discussion of ionic crystals.

 The inert gas crystals are weakly bound, with cohesive energies less than a few

percent of the cohesive energies of the elements in the C, Si, Ge ... column.

 The alkali metal crystals have intermediate values of the cohesive energy.

 The transition element metals (in the middle columns) are quite strongly bound.
 The melting temperatures and bulk moduli vary roughly as the cohesive
energies.

CRYSTALS OF INERT GASES

 The inert gases form the simplest crystals.

 The electron distribution is very close to that of the free atoms.

Properties at absolute zero

 The crystals are;

♦ transparent insulators, weakly bound, with

♦ low melting temperatures.

♦ The atoms have very high ionization energies.

 The outermost electron shells of the atoms are completely filled, and the

distribution of electron charge in the free atom is spherically symmetric.

 Cohesive energy
 The crystal structures in (Fig. 2) are all cubic close-packed (fcc), except 𝐻𝑒3 and
𝐻𝑒4.
 What holds an inert gas crystal together? The electron distribution in the crystal is

not significantly distorted from the electron distribution around the free atoms
because not much energy is available to distort the free atom charge distributions.
 The cohesive energy of an atom in the crystal is only 1% or less of the ionization
energy of an atomic electron.
 Part of this distortion gives the Van der Waals interaction.

(Fig. 2) Cubic close-packed (fcc) crystal structure of the inert gases Ne, Ar, Kr, and Xe. The
lattice parameters of the cubic cells are 4.46, 5.31, 5.64, and 6.13 Å, respectively, at 4 K.
 Van der Waals - London interaction
 Consider two identical inert gas atoms at a separation R large in comparison
with the radii of the atoms.
 What interactions exist between the two neutral atoms?
 If the charge distributions on the atoms were rigid, the interaction between atoms
would be zero, because the electrostatic potential of a spherical distribution of
electronic charge is canceled outside a neutral atom by the electrostatic potential
of the charge on the nucleus.
 Then the inert gas atoms could show no cohesion and could not condense.
 But the atoms induce dipole moments in each other, and the induced
moments cause an attractive interaction between the atoms.
Exercise
1. What interactions exist between the two neutral atoms? (ans. attractive
interactions due to induced dipole moment).
 As a model, we consider two identical linear harmonic oscillators 1 and 2
Separated by R.
 Each oscillator bears charges ±e with separations 𝑥1 and 𝑥2 as in fig. 3.
 The particles oscillate along the x axis.
 Let 𝑝1 and 𝑝2 denotes the momenta .The force constant is C.
 Then the Hamiltonian of the unperturbed system is
𝒑𝟏 𝟐 𝟏 𝟐 𝒑𝟐
𝟐 𝟏
𝑯𝒐 = + 𝒄𝒙𝟏 + + 𝒄𝒙𝟐𝟐 (3.1)
𝟐𝒎 𝟐 𝟐𝒎 𝟐

 Each uncoupled oscillator is assumed to have a frequency of ω𝑜 of the

strong optical absorption line or the atom.
thus, C = m𝜔𝑜2
 Let 𝑯𝟏 be the coulomb interaction of the two oscillators, and
the internuclear coordinate is R.
 𝑯𝟏 = 𝑒2 +
𝑒2
- 𝑒2
- 𝑒2
(3.2)
𝑅 𝑅+𝑋1−𝑋2 𝑅+𝑥1 𝑅− 𝑥2

 In the limit, 𝑥1 , 𝑥2 ≪ R, we expand 3.2 in to obtain in

lowest order,
2𝑒2 𝑥1 𝑥2
𝐻1 ≅ - 3 (3.3)
𝑅
 The total Hamiltonian with approximate form in (3.3) for 𝐻1 can
be diagonalized by the normal mode transformations by the
normal mode transformation.
1
𝑥𝑠= 2
𝑥1 + 𝑥2
1
𝑥𝑎 = 𝑥1 − 𝑥2 (3.4)
2

On solving for 𝑥1 and 𝑥2

 1 1
𝑥1= 2
𝑥𝑠 + 𝑥𝑎 ; 𝑥2= 2
𝑥𝑠 − 𝑥𝑎
(3.5)
 The subscripts s and a denote symmetric and antisymmetric modes
of motion.
 The momenta 𝑝1 and 𝑝2 associated with the two modes are
1 1
𝑝1= 𝑝𝑠 + 𝑝𝑎 ; 𝑝2= 𝑝𝑠 − 𝑝𝑎 (3.6)
2 2

 The total Hamiltonian 𝐻𝑜 and 𝐻1after the transformations (5) and (6)
is
2
H= 𝑃 𝑠𝑚 1 𝑥
2𝑒𝑚
𝑠
2 + 𝑃𝑎𝑚 1 𝑎 (3.7)
2𝑚 + 2𝐶− 𝑛
𝑅
2𝑚 +2 𝐶 + 𝑛
𝑅
2𝑒𝑚 𝑥
 The two frequencies of the coupled oscillators are found
by inspection of (3.7) to be.
 The two frequencies of the coupled oscillators are found
by inspection of (7) to be
1/2 2
ω= 𝑐±
2𝑒𝑚 /𝑚 = 𝜔𝑜 [1 ± 1 2𝑒𝑚 1 2𝑒𝑚
- 8 𝐶𝑅𝑛 + …] (3.8)
𝑅𝑛
2 𝑐𝑅𝑛
𝐶 1/2
 With 𝜔𝑜
𝑚
given by
 The zero point energy of the system is 21 ℏ 𝜔𝑠 + 𝜔𝑎 ;because of the interactions,

the sum is reduced from uncoupled value 2. 𝟐𝟏 ℏ𝝎𝒐 by

∆𝑈 = 21 ℏ ∆𝜔 + 𝜔 = -ℏ𝜔 . 1 2𝑒2 2 −𝐴 (3.9)

𝑠 𝑎 𝑜 8 𝐶𝑅3 = 𝑅6

 This attractive interaction varies as the minus sixth power of the separation of
the two oscillators.
 This is called the van der Waals interaction, known also as the London in-
teraction or the induced dipole-dipole interaction.

It is the principal attractive interaction in crystals of inert gases and also in

crystals of many organic molecules.

The interaction is a quantum effect, in the sense that ∆U ~ 0 as ℏ ~ 0.

Thus, the zero point energy of the system is lowered by the dipole-dipole
coupling of Eq. (3).
 The van der Waals interaction does not depend for its existence on any
overlap of the charge densities of the two atoms.
 An approximate value of the constant A in (9) for identical atoms is given

by ℏ𝝎𝒐𝜶𝟐 where ℏ𝝎𝒐 is the energy of the strongest optical absorption line
and 𝛼 is the electronic polarizability.
 Repulsive interactions
As the two atoms are brought together, their charge distributions gradually decrease there

by changing the electrostatic energy.

As close separations, the overlap energy is repulsive in large part because of Pauli

exclusion principle.

Accordingly, two electrons can not have all their same quantum numbers equal.

The Pauli principle prevents multiple occupancy, and electron distributions of atoms with

closed shells can overlap only if accompanied by the partial promotion of electrons to

unoccupied high energy states of the atoms.

Thus the electron overlap increases the total energy of the system and gives a repulsive

contribution to the interaction.

Experimental data on the inert gases can be fitted well by an empirical repulsive
potential
of the form 𝐵 , where B is a positive constant, when used together with a long-range
𝑅12
attractive potential of the
 The constants A and B are empirical parameters determined from independent
measurements made in the gas phase; the data used include the virial coefficients and the
viscosity.
 It is usual to write the total potential energy of two atoms at separation R as

12
𝜎 𝜎 6
U(R)= 4𝜀 − (3.10)
𝑅 𝑅

 The 𝜎 and 𝜀 are the new parameters and are related through,

A = 4𝜀𝜎 6 and B = 4𝜀𝜎12

 The potential (3.10) is known as the Lennard - Jones potential.

 The force between the two atoms is given by, −𝑑𝑈

𝑑𝑅
.

 Values of 𝜀 and 𝜎 given in Table 4 can be obtained from gas-phase data, so that calculations
on properties of the solid do not involve disposable parameters.
 Other empirical forms for the repulsive interaction are widely used, in particular
the
exponential form λexp(−𝑅
𝜌
), where𝜌is a measure of the range of the interaction.
 Equilibrium lattice constants
 If we neglect the kinetic energy of the inert gas atoms, the cohesive energy of an inert gas
crystal is given by summing the Lennard -Jones potential (3.10) over all pairs of atoms in
the crystal.

 If there are N atoms in the crystal the total potential energy is 𝑝𝑖𝑗R

12 6
𝑈𝑡𝑜𝑡 = ½N(4ε) ∑′ 𝜎 ′ 𝜎
(3.11)
𝑗
𝑝𝑖 𝑗 𝑅 − ∑𝑗 𝑝𝑖 𝑗 𝑅

 Where, 𝑝 𝑖𝑗 R is the distance between the reference atom i & any other atom j expressed in
terms of the nearest neighbor distance, R.
 The factor ½ occurs with N compensate twice for counting of each atoms.

−12 −6
∑′𝑗 𝑝𝑖𝑗 = 12.13889 & ∑𝑗′ 𝑝𝑖𝑗 = 14.45392
 There are 12 nearest neighbor sites in the fcc structures; the series are rapidly converging
and is closer to 12.
 The nearest neighbors contribute most of the interaction energy of inert gas crystals.
 The corresponding sums for the hcp structure are 12.13229 and 14.45489.

 If we take 𝑈𝑡𝑜𝑡 in (11) as the total energy of the crystal, the equilibrium value 𝑅𝑜 is

given by requiring that 𝑈𝑡𝑜𝑙 be a minimum with respect to variations in the nearest-
neighbor distance R;
𝑑𝑈𝑡𝑜𝑙 6
= 0 = -2N𝜀 12 12.13 𝜎 12− 6(14.45) 𝜎 (3.13)
𝑑𝑅 𝑅13 𝑅7

𝑅𝑜
= 1.09 (3.14)
𝜎

, which is the same for all elements with an fcc structure.

 The observed values of 𝑅 𝑜 using independent determined values are given in table
𝜎
Ne Ar Kr Xe
𝑹𝒐 1.14 1.11 1.10 1.09
𝝈
𝑅𝑜
 The slight departure of lighter atoms from the universal value 1.09 predicted for inert
𝜎

gases can be explained by zero-point quantum

 Cohesive energy cont’
 The cohesive energy of inert gas crystals at absolute zero and at zero pressure is obtained
by substituting (12) and (14) in (11):

12 6

𝑈𝑡𝑜𝑡 (𝑅) =2N𝜀 12.13 𝜎 − (14.45) 𝜎 (3.15)

𝑅12
𝑅7
And at R = 𝑅𝑜

𝑈𝑡𝑜𝑡(𝑅) = - 2.15(4N𝜀) (3.16)

,Which is the same for inert gases.

 This is the calculated cohesive energy when atoms are at rest.

 Quantum-mechanical corrections act to reduce the binding by 28, 10, 6, and 4 percent of
Eq. (16) for Ne, Ar, Kr, and Xe, respectively.

 The heavier the atom, the smaller the quantum correction.

 We can understand the origin of the quantum correction by consideration of a simple

model in which an atom is confined by fixed boundaries.
If the particle has the quantum wavelength λ, where λ is determined by the
𝑝𝑚
boundaries, then the particle has kinetic energy with the de Broglie relation p = ℏ
2𝑚
λ

the connection between the momentum and the wavelength of a particle.

On this model the quantum zero-point correction to the energy is inversely pro-
portional to the mass.

One consequence of the quantum kinetic energy is that a crystal of the isotope 𝑁𝑒20 is
observed to have a larger lattice constant than a crystal of 𝑁𝑒22.

The higher quantum kinetic energy of the lighter isotope expands the lattice because
the kinetic energy is reduced by expansion.

The observed lattice constants (extrapolated to absolute zero from 2.5K) are

𝑁𝑒20 = 4.4644Å and

𝑁𝑒22 = 4.4559Å
 3.2 Ionic bonding
 Ionic crystals are made up of positive and negative ions.
 The ionic bond results from the electrostatic interaction of oppositely charged ions.
 Two common crystal structures found for ionic crystals, the NaCl and the CsCl
structures.
 The electronic configurations of all ions of a simple ionic crystal correspond to closed
electronic shells, as in the inert gas atoms.
 The electronic configuration of Lithium fluoride is
Li: 𝟏𝒔𝟐𝟐𝒔 and F:𝟏𝒔𝟐𝟐𝒔𝟐𝟐𝒑𝟓
 And the singly charged ions have of lithium fluoride has and electronic configurations
of
𝑳𝒊+: 𝟏𝒔𝟐and 𝑭−:𝟏𝒔𝟐𝟐𝒔𝟐𝟐𝒑𝟔
 As for helium and neon respectively.
 Inert gas atoms have closed shells, and the charge distributions are
spherically symmetric.
We expect that the charge distributions on each ion in an ionic crystal will
have approximately spherical symmetry, with some distortion near the
region of contact with neighboring atoms.

This picture is confirmed by x-ray studies of electron distributions (fig

3.7).

The distance between a positive ion and the nearest negative ion in
crystalline NaCl is 𝟐. 𝟖𝟏𝒙𝟏𝟎−𝟖cm, and

The attractive coulomb part of the potential energy of the two ions by
themselves is 5.1 eV.

This value may be compared (Fig. 8) with the experimental value of 7.9
eV per molecular unit for the lattice energy of crystalline NaCl with
respect to separated 𝑁𝑎+ and 𝐶𝑙− ions.
 Exercise
1. Ionic compounds are usually poor
conductors of electricity. Why?
 Electrostatic or Madelung Energy
 The long-range interaction between ions with charge ±q is the
electrostatic 2
interaction ±𝑞𝑟 attractive between ions of opposite charge and repulsive between
ions of the same charge.
 The ions arrange themselves in whatever crystal structure gives the strongest
attractive interaction compatible with the repulsive interaction at short distances
between ion cores.
 The repulsive interactions between ions with inert gas configurations are
similar to those between inert gas atoms.
 The van der Waals part of the attractive interaction in ionic crystals makes
a relatively small contribution to the cohesive energy in ionic crystals, of
the order of 1 or 2%.
 The main contribution to the binding energy of ionic crystals
is electrostatic and is called the Madelung energy.
 If 𝑈𝑖𝑗 is the is the energy between ions i & j we define a sum 𝑈𝑖
w/c
include all interactions involving, ions, i.
𝑈𝑖 = ∑ ′ 𝑢𝑖𝑗 (3.17)
𝑗

 the summation includes all ions except, i = j.

 𝑈𝑖𝑗 may be written

−𝑟
as the sum central field repulsive potential that as
the of λexp( 𝜌 ), where λ and 𝜌 are empirical parameter.
form

𝟐
 The electrostatic force, ±𝒒𝒓 .

 Thus,
−𝑟 𝑖𝑗 𝒒𝟐
𝑈𝑖𝑗 = λexp( )± (3.18)
𝜌
𝒓𝒊𝒋
In SI units the coulomb interaction is written as

±𝑞𝑚 ±𝒒𝟐
 𝐹𝑐 = and in CGS it is
4𝜋𝗌 𝑜 r 𝒓
 The repulsive part describes the fact that ions resist the overlap with the
electron distributions of neighboring atoms.
 The strength, λ and range ρ are constants to be determined from the observed
values of lattice constant & compressibility.
 we have used exponential form of the empirical repulsive potential instead
of
𝑅−12 for noble gases.
 The change is made because it may give better representations of the repulsive
potential.
 For the ions, we do don’t have gas phase data available to permit the independent
determinations of λ and ρ.
 ρ is the measure of the range of repulsive interaction.
 For r = ρ, the repulsive interaction is reduced to 𝒆𝟏 of the value at r = 0.

 In the NaCl, the value of 𝑈𝑖 does not depend on whether the reference
ion is positive or negative.
 We can neglect the surface effects and write the total lattice energy 𝑈𝑡𝑜𝑡 of crystal composed of N
molecules or 2N ions.
U = NUi
 Here, N rather than 2N occurs since we count each pairs of interactions or each bond only once.
 the total lattice energy 𝑈𝑡𝑜𝑡 is defined as the energy required to separate the crystal in to
individual ions at infinite distance apart.
 Here, we introduce the quantity, 𝜌𝑖𝑗 such that 𝑟𝑖𝑗= 𝜌𝑖𝑗R
 Where R is the nearest neighbor separations in the crystal.
 If we include the repulsive interactions to only nearest neighbors we have,

−𝑅
λ𝑒𝑥𝑝 𝜌 − 𝑅 𝑓𝑜𝑟 𝑛𝑒𝑎𝑟𝑠𝑡 𝑛𝑒𝑖𝑔𝑕𝑏𝑜𝑟
𝑞𝑚

𝑈𝑖𝑗 = { (3.19)
±1 𝑞𝑚
𝑜𝑡𝑕𝑒𝑟𝑤𝑖𝑠𝑒
𝜌𝑖 𝑗 𝑅

−𝑅
𝛼𝑞 𝑚
U = NUi = N 𝑧λ𝑒 𝜌 (3.20)
𝑅
−
Where z is the number of nearest neighbor of any atom.
 The madelung constant,𝛼 is given by

𝛼= ∑ ′𝑗 ±1 (3.21)
𝜌 𝑖𝑗

 The sum should include the nearest neighbor separation , z.

 The madelung constant if of central importance for the theory of ionic crystals.

 At the equilibrium separation, 𝑑𝑈𝑑𝑅𝑡 𝑜 𝑡 = 0, so that,

𝑑𝑈 𝑡 𝑜 𝑡
𝑑𝑅
𝑁𝑧λ
= 𝞀 𝑒𝑥𝑝
−𝑅
𝜌 +
𝑁𝛼𝑞𝑚
=0 (3.22)
𝑅𝑚

𝑅𝑜 2exp −𝑅
=
𝑁𝜌𝛼𝑞𝑚 (3.23)
𝜌 λ𝑧
 This determines the equilibrium separations, 𝑅𝑜 if the parameters,λ and 𝜌 of repulsive
interactions are known.
 Calculations from 3.19 through 3.23 are made in CGS systems.

 For SI systems 𝑞 2 is replaced by 𝑞𝑚 .

4𝜋𝗌 𝑜
 The total lattice energy of the crystal of 2N ion at their
equilibrium separation 𝑅𝑜is written using equations 3.20 and 3.23.

𝑈𝑡𝑜𝑡 = − 𝑁𝛼𝑞𝑚 1− 𝜌
𝑅𝑜 (3.24)
𝑅𝑜
𝑚
 The term − 𝑁𝛼𝑞 is the madelung energy.
𝑅 𝑜

 It is approximated that 𝜌 is of the order of 𝑅𝑜 so that the

repulsive interaction has very short range.

Fig-9 line of ions of alternating signs with distance r between ions

 Evaluation of Madelung constant, 𝜶
 The 1st calculation of the coulomb energy constant,𝛼 was made by madelung.

±
 It is given by 𝜶 = ∑ ′𝑗
𝑝 𝑖𝑗

 For equation (20) to be constant, 𝛼 should be positive.

 If we take the reference ion as negative charge, the plus sign we apply to

positive ions and the minus ions for negative ions.

 Equivalently, 𝛼 can be defined as

±
𝛼
= ∑ ′𝑗 (3.25)
𝑅 𝑟𝑗

Where, 𝑟𝑗 is the distance of the jth ion from the reference ion & R is the nearest

neighbor distance.
 The value of 𝛼 depends on nearest neighbor distance, R and
lattice parameter, 𝑎 or in terms of some other relevant length.
 Taking the negative ion as a reference, letting R the distance between
the adjacent ion;
𝛼 1 1 1 1
=2 − + − +⋯
𝑅 𝑅 2𝑅 3𝑅 4𝑅

α = 2 1 − 12 + 13 − 14 + ⋯
 The factor 2 occur because there are two ions, one to the right
and other to the left, at equal distance, 𝑟𝑗 .
 Summing this series by expansion,
𝑥𝑚 𝑥𝑛 𝑥𝑜
ln 1 + 𝑥 = x− + − +⋯
2 3 4
 Thus, the madelung constant for one - dimensional chain is
𝛼 = 2ln2
 In 3D, the series presents a greater difficulty.

 Thus, the series doesn’t converge unless the successive terms in

the series are arranged so that the contributions from positive to
negative ions cancel in the series.
 3.2 Covalent bonding
 The covalent bond is the classical electron pair or homopolar bond of
organic chemistry.

 It is a strong bond; the bond between the 2- carbon atoms in a diamond.

 The electrons forming the bond will tends to be partly localized in the
region between the two atoms joined by bonds.

 The spins of two electrons in the bond are antiparallel.

The covalent bond has a strong directional properties.

Properties:

 Formed by a system of continuous covalent bonds

 Non conductive LATTICES both in the solid and in the

molten state

 Diamond, boron nitride, quartz (𝑆𝑖𝑂2), graphite and

silicon carbide (SiC)

 Their arrangement thus, forms low filling factor, 0.34

The tetrahedral bond has 4-nearest neighbors where as hcp has 12 nearest
neighbors.
The binding of molecular hydrogen is a simple example of covalent
bonding.
The strong binding occurs when the spins of two electrons are antiparallel.
The binding depends on the relative spin orientations.
However, it doesn’t depends on the strong magnetic dipole force between
spins.
But Pauli principle modifies the distributions of charge according to the
spin orientations.
This spin dependent coulomb interaction is the exchange integrations.
 Fractional Ionic character of bonds in binary crystals
Crystal Fractional ionic Crystal Fractional ionic
character character
Si 0.00 GaAS 0.31
SiC 0.18 GaSb 0.26
Ge 0.00 AgCl 0.86
ZnO 0.62 AgBr 0.85
ZnS 0.62 AgI 0.77
ZnSe 0.63 MgO 0.84
ZnTe 0.61 MgS 0.79
CdO 0.79 MgSe 0.79
CdS 0.69 LiF 0.92
CdSe 0.70 NaCl 0.94
CdTe 0.67 RbF 0.96
InP 0.42
InAs 0.36
InSb 0.32
After, J.C Philips, bonds and bands in semiconductors
 3.4 Metallic bonding
 Metals are characterized by high electrical conductivity and; a large
number of electrons in a metals are free to move about.
 These free electrons are referred as conduction electrons.

 The valence electrons of the atom become the conduction electrons.

 In some metals the interactions of ionic cores with conduction electrons always
makes a large contributions to binding energy.
 The characteristic features of metallic binding;

⟹ Energy of the valence electrons is lower than energy of free atoms.

 The binding energy of alkali metals crystal is less than alkali metal
halides crystals.
 The bond formed by conduction electron is not very strong.
 The interatomic distances are relatively large in the
alkali
metals b/ce the kinetic energy of the conduction electron is
lower at large interatomic distance.

 This lead to weak binding.

 The strength of a metallic bond depends on three things:
i. The number of electrons that become delocalized from
the metal.
ii. The charge of the cation (metal).
iii. The size of the cation.
 In general, metallic bonding is due to delocalization of electrons.
 Metals tend to crystallize in relatively closed packed structures,
hcp, fcc, bcc but not in loosely packed structures such as
diamond.
 In the transition metals there is additional binding from inner
electron shells.

Fig. Hydrogen fluoride, 𝑯𝑭𝟐− 𝐻+

is stabilized by hydrogen bond.

 Transition metals and metals following these metals have large d-

electron shells and are characterized by high binding energy.
 3.5 Characteristics of Metallic crystals
 The delocalized electrons are free to move about the metallic lattice.

 This is sometimes described as "an array of positive ions in a sea of electrons".

 Each positive center in the diagram represents all the rest of the atom apart from the outer
electron, but that electron hasn't been lost.
 It may no longer have an attachment to a particular atom, but those electrons are still
there in the structure.
 Metals are generally ductile and malleable.

 They are conductive and not very hard.

They are highly symmetric because metallic

bonds are nondirectional.
 Exercise
1.Using the Lenard-Jones potential, calculate the ratio of the cohesive
energies of neon in the bcc and fcc structures. Use the lattice sums for
bcc structures be molecule as a sphere.
∑ ′ 𝑝𝑖𝑗 −12 = 9.11418 and ∑ ′ 𝑝 𝑖𝑗 −6 = 12.2533
𝑗 𝑗

(Ans. 0.958).

2.Using the values λ and ρ, and madelung constant calculate the

cohesive energy of KCl in the ZnS structure and compare the value
calculated for the KCl in the CsCl structure.

3. Explain how ion core interaction with conduction electron produce a

larger binding energy?
 Chapter 4
4.1 Vibrations of crystals
Vibrations of crystals with monoatomic
basis
 We consider the elastic vibrations of the crystal with one atom in the primitive cell.
 We want to find the frequency of an elastic wave in terms of the wave vector
that describe a wave and in terms of elastic constant.
 The mathematical solution is simple in [100], [110],and [111] propagation directions in
cubic crystal.
 These are the directions of cub edge, face diagonal, & body diagonal.
 When a wave propagate along one of these directions entire plane of atoms move in
a
phase with displacement either parallel or perpendicular to the direction of wavevector.
 We can describe with a single coordinate 𝑢𝑠, the displacement of a plane, s from its
equilibrium positions.
 The problem is now one dimensional.

 For each wave vector, there are three modes as a solutions for 𝑢𝑠; one longitudinal
polarizations & two transverse polarizations fig-2 & 3 respectively.
 We assume that the elastic response of a crystal is a linear function of force.

 This is equivalent to the assumption that elastic energy is quadratic function of relative
displacement of any two points in the crystal.
 Terms in the energy that are linear in displacement will vanishes in equilibrium.

♠ Moreover, cubic and higher terms may be neglected for sufficiently small
elastic deformations.

♠ we assume that the force on the plane, s caused by the displacement of the plane s +p
is

proportional to the difference , 𝑢𝑠+𝑝- 𝑢𝑠 of their displacement.

 For brevity, we consider only nearest-neighbor interactions with p= ±1

Fig 4.1 Spring Model

 Here n = s. The total force on plane s from
s±1 is
(1)
𝐹𝑠 = c 𝑢𝑠+1 − 𝑢𝑠 + c 𝑢𝑠−1 − 𝑢𝑠
 This expression is linear in displacement and is of the form of Hook’s
law.
 The constant, c is the force constant between nearest neighbor planes and
will differ for longitudinal and transverse waves.

 Here, c is defined for one atom & 𝐹𝑠 is the force on one atom in a plane s.
 The equation of motion of an atom in the plane s is

𝑑𝑚𝑢𝑠
M 𝑑𝑡𝑚 = c 𝑢𝑠+1 𝑠−1 − 2𝑢 𝑠 (2)
+𝑢
Where M-is the mass of an atom.
 We look for solutions with all displacements having the time dependency,

𝑒 −𝑖ω𝑡 .

𝑑 �𝑢 𝑠
Then � = -ω2 𝑢𝑠 .
𝑑𝑡𝑚

 Equation (2) becomes

-𝑀ω2𝑢𝑠= c 𝑢𝑠+1 + 𝑢𝑠−1 − 2𝑢𝑠 (3)

 This is a differential equations and have a solution of travelling wave

solution of as in (4).
 From the equations

𝑈𝑠±1= 𝑢0exp 𝑖𝑠𝑘𝑎 exp ±𝑖𝑘𝑎 (4)

where is the spacing between the planes and k is the wave vector.

 The choice of ɑ- depends on the direction of wave vector k. Using equations (4) and (3)

−𝝎𝟐𝒎𝒖exp 𝒊𝒔𝒌𝒂 = Cu 𝒆𝒙𝒑 𝒊 𝒔 + 𝟏 𝒌𝒂 + 𝒆𝒙𝒑 𝒊 𝒔 − 𝟏 𝒌𝒂 − 𝟐𝒆𝒙𝒑 𝒊𝒔𝒌𝒂

(5)

 We can cancel out uexp(iska) from both sides.

𝜔2 𝑚 = C 𝑒𝑥𝑝 𝑖𝑘𝑎 + 𝑒𝑥𝑝 −𝑖𝑘𝑎 − 2

𝜔2 𝑚 = -C 2𝑐𝑜𝑠𝑘𝑎 − 2
𝜔2 = 𝑀 1 − 𝑐𝑜𝑠𝑘𝑎 (6)
2𝑐

 The boundary of the first Brillouin zone lies in the region, ±𝜋

𝑎
.
 We show from (6) that the stop ω versus k is zero at the zone boundary.

2𝑐𝑎
𝑑𝜔𝑚 sinka = 0
𝑑𝑘 = (7)
𝑀

 At k = ±𝜋
𝑎
, for here sinka = sin ±𝜋 =0.

 The special significance of the phonon wave vector that lie on the zone
boundary is developed in (11) below.
 By trigonometric identity with equation (6) may be written as

4𝑐 1
𝜔2 = 𝑀
𝑠𝑖𝑛2 2
𝑘𝑎

𝑙
4𝑐 �
ω= 𝑀 � 𝑠𝑖𝑛 21 𝑘𝑎 (8)
Fig 4.2 Phonon dispersion relation
 Fig- 4 a plot of ω
versus K.
1
 The region of k or λ >> ɑ corresponds to the continuum
𝑎
<<
approximations.
 Here ω ~ 𝑘.
First Brillouin Zone
 What range of k is physically significant for elastic waves?
 From equation (4), the ratio of the displacements of two
successive planes is given by

𝑢𝑠+𝑙 𝑢 𝑒 𝑖 𝑠 + 𝑙 𝑘𝑎 (9)
𝑢𝑠 =
𝑢 𝑒 𝑖𝑠𝑘𝑎
= 𝑒 𝑖𝑘𝑎
 The range from -𝜋 to +𝜋 for the plane kɑ covers all independent values
of the exponential.
 The range of the independent values of k-is specified
by
−𝜋 < 𝑘𝑎 < 𝜋
Or
−𝜋 𝜋
𝑎
<𝑘< 𝑎

 The extreme values are 𝑘 𝑚𝑎𝑥 = ± 𝜋𝑎.

 The values of k- outside Brillouin zone (Fig - 5) merely reproduce

lattice motion
described by values with in the limit ±𝜋
𝑎.
of
 We may treat the value of k outside this limits by substituting the integral
2𝜋
multiple of 𝑎
that will give a value inside this limit.

 Suppose k lies outside the FBZ, but related wave vector, k’

defined
 K’ = k - 2𝑎𝜋𝑛 lies within the first Brillouin Zone, where n is an integer.
 The displacement ratio, (10) becomes

𝑢𝑠+𝑙 ′
= 𝑒 𝑖2𝜋𝑛 𝑒 𝑖(𝑘 𝑎−2𝜋𝑎)
𝑢𝑠

𝑢 𝑠+ 𝑙 𝑖𝑘′𝑎 = 𝑒 𝑖𝑘𝑎 (10)

𝑢𝑠 = 𝑒

Where,

𝑒 𝑖2𝜋𝑛 = 1
 Thus, the displacement can always be described by wave vector with in the first Brillouin
zone.

2𝜋𝑛 2𝜋
 We not that the is always a reciprocal lattice vector because is a reciprocal
lattice
𝑎 𝑎

vector.

 Thus, by subtracting an appropriate reciprocal lattice vector from k, we always obtain an

equivalent wave vector in the FBZ.
 At the boundaries, 𝐾𝑚𝑎𝑥 = ± 𝜋𝑎 of the Brillouin zone , the solution is 𝑢𝑠 = u𝑒𝑖𝑠𝑘𝑎,which does

not represent travelling wave but a standing wave.

 At the zone boundaries, s𝑘 𝑚 𝑎 𝑥 𝕚 = ±𝑠𝜋, when

𝑢𝑠= uexp ±𝑖𝑠𝜋 = u −1 𝑠 (11)

 This is a standing waves.

 Alternate atoms oscillates in opposite phase because 𝑢𝑠= ±1 according to whether s is an
even integer or an odd one.
 The wave moves neither to right nor to the left. This condition is equivalent to the
Braggs
– reflections of x-rays, when the Bragg condition is satisfied.
 A travelling waves can not propagates through the lattice but through the successive
reflections back and forth, a standing wave is set up.
 The critical value, 𝑘 𝑚𝑎𝑥 = ± 𝑎𝜋 found here satisfies the Bragg conditions, 2dsinθ = nλ.

Where, θ = 𝜋, n = 1, so that λ = 2ɑ.

2

d = ɑ , k = 2𝜋
𝕚
.
 Standing waves

Figure 3. The wave represented by solid curve conveys

no information given by the dashed line. Only
wavelengths longer than 2𝕚 are needed to represent the ,
motion.
Within X- rays we have n = other integers besides
unity because the amplitude of the EMW has
meaning in space between atoms but the
displacement amplitude of an elastic wave has
meaning only at the atoms themselves.
 Group
velocity
 Group velocity is a transmission velocity of a wave packet.

 It is the derivative of angular frequency,ω as a function of wave vector, k.

𝑑𝜔
𝑉𝐠 =
𝑑𝑘

𝑉𝐠 = 𝐠𝑟𝑎𝑑𝜔 𝑘

𝑉𝐠 = 𝛻𝑘𝜔 𝑘 12

 group velocity is the velocity of the energy in the medium of propagation.

 With particle dispersion relation, the group velocity is given by

𝑙
𝑐𝑎𝑚 𝑚
𝑉𝐠 = cos�𝑙𝑘𝑎 (13)
𝑀
�

 This is zero at the edge of the zone boundary where, k = 𝒂𝝅.

 Here, the wave is a standing wave as in equation(11) & expect zero net transmission

velocity for a standing wave.

 Now we might consider the long wavelength & short wavelength limit.

1. Long wave length limit:

1
when ka <<1, we expand, coska = 1- 𝑘𝑎 2 , so that the dispersion relation
2
(6)
becomes

𝐶
𝜔 2= 𝑀 𝑘 2𝑎 2

𝐶
𝜔= 𝑀
kɑ (14)

 This shows that angular frequency is directly proportional to the wave vector at long

wavelength limit.
 According to equation (15), the velocity of sound is independent of
frequency in long wave length limit.

 Thus, v = ω𝑘 , exactly in the continuum theory of elastic waves.

 In the continuum limit, kɑ << 1.

 Chapter
Phonon heat capacity
5
 By heat capacity we mean either heat capacity at constant pressure or heat capacity at
constant volume.
 However, heat capacity at constant volume is more fundamental one.

𝛛𝑈
𝐶𝑣 = 𝛛𝑇 𝑣
(1)

Where,

U – is the energy

T – is the temperature.

𝑐𝑣 -is the heat capacity at constant volume

 The contribution of phonon to the heat capacity of crystals is called lattice heat capacity

𝐶𝑙𝑎𝑡𝑡.
 The total energy of phonon at a temperature 𝜏 = 𝑘𝐵 𝑇 may be written as a
sum of the energies of all phonon modes, here indexed by the wave vector
k, and polarization index, p.
(2)
𝑈𝑙𝑎𝑡=∑𝑘 ∑ 𝑝 𝑛 𝑛𝑘 ћ𝜔𝑘,𝑝

Where,
- is the thermal equilibrium occupancy of phonons of wave vector k and
𝑛𝑘,𝑝
polarization, p.

 The form of 𝑛𝑘,𝑝 is given by the Planck distribution

function.
1
𝑛 = ћ𝜔
(3)
𝑒𝑥𝑝 −1
𝐾𝐵 𝑇

Here, … the average of thermal equilibrium.

 Planck distributions
We consider a set of harmonic oscillators in thermal equilibrium.

The ratio of number of oscillators in the 𝑛 + 1 𝑡𝑕 quantum state of excitations to the

number in the 𝑛𝑡𝑕quantum state is given by

𝑁𝑛+𝑙 −ћω
= exp τ
(4)
𝑁𝑛

Where τ = 𝐾𝐵𝑇
The fraction of the total number of oscillators in the 𝑛𝑡𝑕 quantum state is

𝑁𝑛 −𝑛ћω 𝜏
= 𝑒𝑥𝑝
(5)
∑𝑠=𝑘 𝑁𝑠 𝑠=𝑘 𝑒 𝑥 𝑝 −𝑠ћω
∑∞ 𝜏
∞

We see that the average excitations quantum number of an oscillator

is
−𝑠ћω
∑𝑠 𝑠𝑒𝑥𝑝
𝑛 = τ (6)
−𝑠ћω
∑𝑠 𝑒 𝑥 𝑝 τ
 The summations in 6
are
1
∑𝑠 𝑠 𝑠 = 1−𝑥
(7)

𝑥
𝑑
∑𝑠 𝑠𝑥 𝑠 = 𝑥 𝑑𝑥 ∑𝑠 𝑥 𝑠 = 1−𝑥 𝑚

Where

−ћω
X = exp τ

Thus, we may rewrite (6) as the Planck distributions.

𝑥 1
𝑛 = = (8)
1−𝑥 𝑒𝑥𝑝 τ −1 ћω
 Normal mode enumerations
 The energy of a collections of oscillators of frequency, 𝜔 𝑘,𝑝 , in thermal
equilibrium is found in (1) and (2).

ћω 𝑘,𝑝 (8)
U= ∑𝑘 ∑𝑝 ћ ω 𝑘,𝑝
−𝑙
𝑒 τ

 It is usually convenient to replace the summations over k by an integral.

 Suppose that the crystal has 𝐷𝑝 𝜔 𝑑𝜔 mode of a given polarization, p in the frequency ω
to ω + dω. Then, the energy is

ћω
(9)
U = ∑𝑝 ∫ 𝑑𝜔𝐷𝑝 𝜔 ћω
𝑒 𝜏 −1

 Thelattice heat capacity is found by differentiating lattice energy with

respect to
temperature.
 letting , x = ћω
τ
then

𝛛𝑈 𝑥 𝑚𝑒 𝑥 (10)
𝑣
𝐶 = 𝛛𝑇 = 𝐾𝐵 ∑𝑝 ∫ 𝑑𝜔𝐷𝑝
𝜔The central problem is to find D 𝜔 , the number of

𝑒 𝑥 −1 𝑚

modes per unit frequency range.

 This function is called the density of modes or more
often density of states.
 Consider the boundary value problem for vibrations
of a one dimensional line of length, L carrying N+1
particles of separations, ɑ.
 Density of States
Consider the boundary value problem for vibrations of a one dimensional line of
length, L carrying N+1 particles of separations, ɑ.
L
0 us
Fixed 𝑎 fixed

x=0 1 2 3 4 5 6 7 8 9 x = 10

Fig 2: Elastic line of N+1 atoms, with N = 0 for boundary conditions that the end of
atoms s = 0 and s =10 are fixed. The particle displacement in the normal modes for either
longitudinal or transverse displacement are of the form 𝑢𝑠~ sinska. This form is
automatically zero for atoms at the ends, s = 0 . We choose k - to make the displacement
zero at the ends, s = 10.

±2𝜋 ±4𝜋 ±6𝜋 𝑁𝜋

K = 0, , , ,… .
 𝜋 2𝜋 3𝜋 4𝜋 5𝜋 6𝜋 7𝜋 8𝜋 9𝜋 10𝜋
S=0 10𝑎 10𝑎 10𝑎 10𝑎 10𝑎 10𝑎 10𝑎 10𝑎 10𝑎 10𝑎

𝑾𝒂𝒗𝒆 𝒗𝒆𝒄𝒕𝒐𝒓, 𝒌 →
Figure 3. The boundary condition sinsKa = 0 for s = 10 can be satisfied by choosing
𝜋 2𝜋 3𝜋 4𝜋 7𝜋 8𝜋 9𝜋
values of S = 0, , , , , 5𝜋 6𝜋 , , where 10a is
10𝑎 10𝑎 10𝑎 10𝑎 10𝑎 , 10𝑎 , 10𝑎 10𝑎 10𝑎

the length L of the line. The present figure is in K space.

 The dots are not atoms but are the allowed values of K.
 Of the N + 1 particles on the line, only N – 1 are allowed to move, and their most
general motion car1 be expressed in terms of the N - 1 allowed values of K.
 This quantization of K has nothing to do with quantum mechanics but
follows
classically from the boundary conditions that the end atoms be fixed.
 Suppose that the particle at s = 0 and s = N, at the ends of the line are held fixed.

 Each normal vibration mode of polarizations ,p has the form of a standing wave where 𝑢𝑠 is the
displacement of the particle s.

𝒖𝒔 = 𝒖𝟎exp −𝝎𝒌,𝒑𝒕 sinskɑ (11)

𝝎𝑘,𝑝 - is related to the k by the dispersion relation. K is fixed by the end boundary conditions,

k= 𝝅
,
𝟐𝝅
,
𝟑𝝅
,…
𝑵−𝟏 𝝅 (12)
𝑳 𝑳 𝑳 𝑳
 The solution for k = 𝜋𝐿 has the solutions of

𝐬𝛑𝕚
𝐮𝐬 ~ 𝐬𝐢𝐧 𝐋
(13)

And vanishes for s = 0 and s = N as required.

𝑁𝜋 𝜋
 The solutions for K = = = 𝐾𝑚𝑎𝑥 has 𝑼𝒔 ~ 𝒔𝒊𝒏𝒔𝝅𝒂. This allows no motion of any
atom
𝐿 𝑎

because sins𝜋 vanishes at each atom.

 There are N-1 allowed independent values of K in (12). This number is equal to the № of
particles allowed to move.
 Each allowed value of K is associated with a standing wave.

 For the one dimensional line there is one mode for each interval;

𝑙
, 𝑓𝑜𝑟 𝑘 ≤ 𝑎𝜋
 ∆𝑘 = 𝜋𝐿 So, that the number of modes per unit a range of k is |𝜋
0, 𝑓𝑜𝑟 𝑘 > 𝑎𝜋

 There are three polarizations, p for each value of k.

 In 2-D two of these are transverse and one is the longitudinal.

 In three dimensions the polarizations are simple only for a wave vector in certain special
crystal direction.
 An other device for enumerating mode is equally valid. We consider the medium as
unbounded, but requires that the solutions be periodic over large distance, L so that
U 𝑠𝑎 = U 𝑠𝑎 + 𝐿 .
 The method of periodic boundary conditions does not change the physics of the problem
in any essential respect for large system.
 In the running wave solutions,

𝑢𝑠= U 𝑜 𝑒 𝑖 𝑠𝑘𝑎−𝜔 𝑘 𝑡
(14)

The allowed values of k are

±2𝜋 ±4𝜋 ±6𝜋 𝑁𝜋
K = 0, , , ,….
𝐿 𝐿 𝐿 𝐿

 This method of enumeration gives the same number of mode (one per mobile atom) as
in (12).
 The change in wavevector between successive values of k is, ∆𝑘 = 2𝜋 .
𝑙

𝐿
 For periodic boundary conditions, the number of modes per unit range of k is, for
2𝜋
−𝜋
≤ 𝑘 ≤ +𝜋 and 0 otherwise.
𝑎 𝑎

 We need to know the D 𝜔 the number of modes per unit frequency range for a
given polarizations.
Fig:4 For N atoms constrained to slid In a circular ring. s1

s2
 The particle oscillate if Connected by elastic spring. s8

In normal mode the displacement 𝑢𝑠 of the atom s

s3
will be of the form sin 𝑠𝑘𝑎 or 𝑐𝑜𝑠 𝑠𝑘𝑎 which are
s7
independent modes.
 By the geometrical periodicity of the ring
s4
 Boundary condition is 𝑢𝑠+1 = 𝑢𝑠for all s.
 a 
 So, 𝑁𝑘𝑎 must be an integral multiple of 2𝜋. us

2𝜋 4𝜋 6𝜋 8𝜋
 For N= 8, the allowed independent values of k are 0, 8𝑎 , 8𝑎, 8𝑎, 8𝑎
.

8𝜋
 The value k = 0 & the value k = 8𝑎
is meaning less for sine form and have meaning for cosine
term.
 The 3-other values of k are allowed for both sine & cosine term.
 Therefore, the periodic boundary conditions leads one mode of per particles exactly as for two
fixed end boundary conditions in fig-3.
 The number of modes D 𝜔 dω in dω at ω is given in one dimension
by
D 𝜔 dω = 𝜋𝐿 𝑑𝜔
𝑑𝑘
. 𝑑𝜔

𝐿 𝑑𝜔
=
𝜋 𝑑𝜔 / 𝑑𝑘

𝑑𝜔
With, 𝑑𝑘
= 𝑣𝐠

D(𝜔)dω = 𝐿𝑑𝜔 (15)

𝜋𝑣𝐠

𝑉𝐠 - is the group
velocity.
 We can also obtain the group velocity from the dispersion relation.
 There is a singularity in D 𝜔 when ever the dispersion relation ω 𝑘

is horizontal, at 𝑉𝐠 = 0.
 The Debye Model
 From dispersion relation the density of state g 𝜔 obtained by integrating over the
Brillion zone.
 The number allowed values are the number of unit cells (N) in the crystals.

 In the Debye model, define a cutoff 𝜔𝐷

𝜔𝐷
N=∫ g 𝜔 𝑑𝜔 (16)
0

Where, N is the number of unit cells in the crystal, and g(ω) is the density of states
in one phonon branch.
 For each mode the density of state is given by

𝑉 𝜔𝑚
g 𝜔 =
2𝜋𝑚 𝑣𝑛

𝑉 𝜔𝑚 𝑉 𝜔 𝑛
N = ∫0
𝜔𝐷
2𝜋𝑚 𝑣𝑛
𝑑𝜔 = 6𝜋 𝑚
𝐷

𝑣𝑛
 Hence, the Debye cutoff frequency is given by

𝜔𝐷 3 = 6𝑁𝜋𝑚 𝑣 3 (17)
𝑉

 Equivalently the Debye temperature, 𝜃𝐷 is given by

ℏ𝜔
𝜃𝐷= 𝐾 𝐵 𝑇 (18)

In the Debye model the specific heat capacity is

given by combining the Debye density of states with
the Bose-Einstein distribution.
Fig 5. Debye’s 𝑇 3 law for Argon
 The internal energy and the specific heat capacity's are given
by
𝑉 ℏ𝜔
U = ∑𝑛<3
𝜔𝐷 (19)
𝑖<1 2𝜋𝑚𝑣𝑚 ∫0 𝑑𝜔𝜔2 ℏ𝜔
𝑒 𝐾 𝐵 𝑇 −1−1

ℏ𝜔
with x = = 𝜃 , ω = 𝐾𝐵𝑇𝑥,and ω𝐷 = 𝐾 𝐵 𝜃 𝐷 𝑥
𝐾𝐵 𝑇 𝑇 ℏω
ℏω
4 𝑥𝐷 𝑛

3𝑉 ∫0 𝑑𝑥
U= 𝑥 𝑒 𝑥 −1

𝐾𝐵 𝑇 𝟑 𝒙𝑫
ℏ 𝑻 𝒙𝟑
U =𝑚9N𝑲 𝑩T ∫𝟎 (20)
2𝜋 𝑣
𝑚 ℏ 𝜽 𝒆𝒙−𝟏
𝒅𝒙

𝑥𝑛 𝑜
𝜋
Hence from table of integration, ∫
𝑥𝐷
𝑑𝑥0 𝑒 −1
𝑥 = 15
as T~0, 𝑥𝐷 ~∞

𝛛𝑈 12𝜋 𝑜 𝑇 3
𝐶𝑣 = 𝛛𝑇 = N𝐾𝐵 𝜃
5

𝑇 3
𝐶𝑣 = 234N𝐾𝐵 𝜃
(21)
 Einstein Model
According to Einstein’s Model the heat capacity of oscillator is given by

ℏ𝜔
𝛛𝑈 ℏ𝜔 2 𝑒 𝜏
𝐶𝑣 = 𝛛𝑇 𝑣
= N𝑘𝐵 𝜏 ℏ𝜔 � (22)
�
𝑒 𝜏 −1

This expresses the Einstein (1907) result for the contribution of N identical oscillators to

the heat capacity of a solid.

In three dimensions N is replaced by 3N, there being three modes per oscillator.

At high temperature limit, 𝐶𝑣 becomes 3𝑁𝐾𝐵, which is known as the Dulong and Petit law.

ℏ𝜔
At low temperatures (22) decreases as 𝑒 𝜏 , whereas the experimental form of the
phonon

contribution is known to be 𝑇3 as accounted for by the Debye model treated above.

The Einstein model, however, is often used to approximate the optical phonon part of the
 Heat capacities for different compounds

HeatCapacity drops zero

at low temperature
 At low T, Debye’s curve
drops slowly because long
wavelength vibration can
still be excited.

Fig -7 Heat capacity of silver at (𝜃𝐷= 215K)

 Einstein model: at low temperature, the heat capacity decrease as

−ћω
exp τ
.

 At high temperature, 𝐶𝑣 = 3N𝐾𝐵,the case of Dulong and Peteit

law.
3
𝑇
 Debye Model; at low temperature, 𝑣 𝐶 = 𝐵 .
𝜃
234N𝐾
 This means, 𝐶𝑣~𝑇3 and ,𝜃 = ћω is the characteristic temperature.
𝑘𝐵

 And at high temperature, 𝐶𝑣 =

3N𝐾𝐵.
 Thermal conductivity
 The thermal conductivity coefficient , K of solid is defined by

𝑗𝑣= -K𝑑𝑇𝑑𝑥
(23)
Where, 𝑗𝑣 is flux of thermal energy or energy transmitted across per unit area per time,
𝑑𝑇
and 𝑑𝑥
is temperature gradient.

 Thermal energy transfer is random. This random nature of conductivity

brings temperature gradient.
 From kinetic theory of gas, the thermal conductivity is given by

k = 1Cvℓ (24)
3

Where, C –is specific heat capacity, v – is the average particle velocity, and ℓ is the
mean free path of the particle.
 This result was first applied by Debye to describe the thermal
conductivity in dielectric solids.
 Exercis
1. Most e on a lattice do not carry
of the time Phonons
momentum. Why?
2. Show that the thermal conductivity coefficient, K is given by
k = 𝟑𝟏Cvℓ.
.

Good Luck!!!