Chapter 4

Vibration in Molecules and Crystals

4.1. Crystal vibration

4.2. Acoustic and optical modes
4.3. Thermodynamic properties
4.4. Long wave length limit and
elasticity theory

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 4.1. Crystal vibration
Monoatomic Chains
• We shall start by assuming that every atom’s
interactions with its neighbours may be
represented by a spring, so that the force in each
‘spring’ is proportional to the change in length of
the spring. This is called the harmonic
approximation.
• (Hook’s law) (1)
• Where k is spring constant.
• is displacement from equilibrium position.
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• Let us consider Longitudinal Waves on Linear
Chain:

• (2)
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• Lattice Vibration is the oscillations of atoms in
a solid about the equilibrium position.
• For a crystal, the equilibrium positions form a
regular lattice, due to the fact that the atoms
are bound to neighboring atoms.
• The vibration of these neighboring atoms is
not independent of each other.
 From the equation of motion we have;-

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 Cont…
• Then, by compering equations (2)&(3), we get;-
• (4)
• Since, atoms are periodically arranged in the crystalline
solid, is given in the form of plane wave. i.e.,

• Where: (6)
 (7)
 By combining equation 7 within (4), we will get:
 (8)
 Since,
 Equation (8), become;-
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 Cont…
• Then, the above equation become;
• }
}
 Again from trigonometric identity;

 Then, }
 After that, we get the dispersion relation
between and k as follows:

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• The chemical bonds that hold atoms together in solids
can be modeled very well by springs.
• Bonds can be stretched, compressed or bent and, for
small displacements of the atoms, the necessary force
is proportional to the displacement – that is, chemical
bonds obey Hooke’s law.
 There are some new features that appear in 3-D solids:
1. The number of atoms (N) in a macroscopic crystal is
very large – on the order of per .
This means that there are an enormous number of
modes, and their wavevector and frequency values are
very closely spaced.
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 Cont…

2) The “wave vector” k becomes a true, 3-D

vector, with components kx, ky and kz.
The Brillouin zone was a line segment in 1-D
on the k-axis.
In 3-D it becomes a polyhedron enclosing a
region of 3-D “k-space.”

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3) For waves propagating in any particular direction, we
now have to consider three “polarizations”:
(i) one longitudinal wave in which the atoms move in
the direction of wave propagation (similar to the
modes we have analyzed on chains);
(ii) two transverse waves in which the atoms move
perpendicularly to the direction of wave propagation.
 There are two transverse modes because there are two
orthogonal directions perpendicular to propagation. For
example, if a wave propagates in the z-direction,
transverse motion could occur in both the x- and y-
directions.
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• Lattice vibrations can explain sound velocity, thermal properties, elastic

properties and optical properties of materials.
 The normal mode vibrations of solids are referred to as phonons. They
plan an important role in determining many fundamental physical
properties of solids:
i. Conduction of sound. The long-wavelength propagating acoustic
modes of atomic displacements are, in fact, what we call “sound” in
solids.
ii. Elastic properties. Strain induced in a solid by external forces
(compression, tension, shear) requires motions of atoms relative to
their neighbors.
iii. Thermal properties. Phonons are usually the largest reservoir of
thermal energy in solids.
iv. Interactions with other excitations. Phonons are the most important
example of the “–ons,” the various fundamental carriers of energy a
solid.
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• A regular lattice with harmonic forces between atoms and
normal modes of vibrations are called lattice waves.
• Lattice waves range from low frequencies to high
frequencies on the order of Hz or even higher.
• However, the wavelengths at extremely high frequencies are
of the order of inter atomic spacing.
• Due to the shortness of these wavelengths, the motion of
the neighboring atoms is uncorrelated; with each atom
moving about its average position in three dimensions with
average vibrational energy, which is usually with ‘’
representing the Boltzmann constant and 'T' the absolute
temperature.
• Lattice vibrations can also interact with free electrons in a
conducting solid which gives rise to electrical resistance .
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 4.2. Acoustic and optical modes
• What is Phonons?
• The existence of the periodic crystal lattice in solid materials provides a
medium for characteristic vibrations.
• Between the lattice spacing, there are quantized vibrational modes called a
phonon.
• The study of phonon is an important part of solid state physics, as they play
an essential role in the physical properties of solids, the thermal and electrical
conductivity of the materials.
• The long wavelength property of phonon also gives attributes to sounds in
solids.
• Phonons are also a quantum mechanical version of a special type of
vibrational motion. This type of vibrational motion is called a normal mode
(elementary blocks of lattice vibration), which is a pattern of motion in which
all parts of the system move in a sinusoidal fashion, with the same frequency.
• An example of a normal mode is a standing wave, which is a continuous form
of normal mode and all space elements, (x, y and Z co-ordinates) are
oscillating at the same frequencies, and phase but different amplitude.
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Types of Phonons:
 In particular, ALL MATERIALS with 2 atoms per unit cell are observed to
have two very different kinds of vibrational normal modes. These are called
optical and acoustic modes (phonons)
1. Optical Phonons:
 This branch is always at much higher vibrational frequencies than the
acoustic branch. So, in real materials, a probe at optical frequencies is
needed to excite these modes.
 Historically, the term “Optic” came from how these modes were
discovered. Consider an ionic crystal in which atom 1 has a positive charge
& atom 2 has a negative charge. As we’ve seen, in those modes, these
atoms are moving in opposite directions. (So, each unit cell contains an
oscillating dipole.) These modes can be excited with optical frequency
range electromagnetic radiation.
 They are quantized modes of lattice vibrations when two or more charged
particles in a primitive cell move in opposite directions with the center of
mass at rest. This mode has highest energy for wavelength infinity or
k=0.,when the two lattices move in opposing direction of each other.
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2. Acoustic Phonons:
 This branch received it’s name because it contains long
wavelength vibrations of the form ω = vsk, where vs is the
velocity of sound. Thus, at long wavelengths, it’s ω vs. k
relationship is identical to that for ordinary acoustic (sound)
waves in a medium like air.

 They are phonons whose frequency which goes to zero in the

limit of small k.
 Let’s consider monatomic a linear chain of identical atoms of
mass ‘’ spaced at a distance ‘’, the lattice constant, connected by
invisible Hook's law springs and longitudinal deformations.
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 Group Velocity

• In physics, waves can be thought of as packets of

energy that travel through a medium.
• These packets can be made up of different individual
waves with varying frequencies and wavelengths.
• The way these waves combine together results in the
formation of a wave packet.
• Now, the group velocity represents the speed at which
the entire wave packet propagates through space or a
medium. It’s like measuring how fast the group of
waves, which constitute the wave packet, moves as a
single entity.
• or
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• The velocity of energy propagation in a medium is related to
the gradient of frequency w.r.t the wave vector (k).
• This gradient tells us how the frequency of the wave
changes concerning its direction of travel.
• Understanding this concept helps us gain insights into wave
behavior, design better communication systems, and explore
the properties of matter and energy in d/t environments.
• This group velocity with specific dispersion relation
represented as:-

• This is zero at the edge of the zone where Here the wave is a
standing wave and we expect zero net transmission velocity
for a standing wave.
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 4.3 Thermodynamic properties
• There are three types of thermodynamic properties: extensive, intensive, and
state.
 Extensive properties;- An extensive property depends on the amount of
mass present or upon the size or extent of a system. For example, the
following properties are extensive: Enthalpy, Entropy, Gibbs free energy, heat
capacity, internal energy, mass, volume.
• It depend on the amount of matter in a system.
 Intensive properties:- An intensive property is independent of the amount of
mass and may vary from place to place within the system at any moment. For
example, the following properties are extensive:- Compressibility, density,
specific Enthalpy, specific Entropy, specific heat capacity, pressure,
temperature, thermal Conductivity, thermal Expansion, vapor quality, specific
volume. They don’t change when the size of a system changes.
 State properties, like pressure and entropy, completely describe the
equilibrium state of a system.
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4.4 Long wave length limit and elasticity theory

• Long wavelength limit

• The long wavelength limit implies that when we
expand .so that the dispersion relation becomes:-
•
• The result that the frequency is directly proportional
to the wavevector in the long wavelength limit is
equivalent to the statement that the velocity of sound
is independent of frequency in this limit.
• Thus,as in the continuum theory of elastic waves- in
the continuum limit
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• All structure materials posses to a certain

extent the property of elasticity, i.e., if
external forces, producing deformation of a
structure, do not exceed a certain limit, the
deformation disappears with the removal of
the forces.

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 Thank you

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