Chapter 4

• Vibrations of Crystals with Monoatomic Basis

• Vibrations of Crystals with Diatomic Basis

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Real Crystal :

• Large of coupled atoms

• Form of coupling : Type of bonding

Atoms in the real crystal are not at rest indefinitely

Discrete Jump : Influence of a suitable field gradient

Internal energy of a solid : Increases by heat energy

(Increase in the vibration of atoms about their mean position)

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Lattice vibrations :
Series of superimposed sound waves (or) lattice waves with a
frequency spectrum (Elastic properties of the crystal)

Quantum of energy of an elastic wave : Phonon

Phonon : Quantum mechanical description of the vibrational motion

(Lattice uniformly oscillates at the same frequency)

Classical Mechanics : Normal modes

Phonons : Determining the Physical Properties of Solids

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Small vibrations of atoms in crystalline solids in terms of normal modes of motion

Vibrations of crystals with monoatomic basis

Force-Spring model, with masses m & spring constants K

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 The Monoatomic Chain

• Chain : Large number of atoms with identical masses m.

• Atoms move only in a direction parallel to the chain.

• Only nearest-neighbors interact with each other.

a a a a a a

Un-2 Un-1 Un Un+1 Un+2

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 a a

Un-1 Un Un+1

Equation of motion : l

..

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 Total Force (nth atom) = Force to the right - Force to the left
a a
Force to the right :

K (u n1  u n )

Force to the left : Un-1 Un Un+1

K (u n  u n1 )

..

Equation of Motion of each atom is of this form.

Only the value of ‘n’ changes.
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Harmonic solutions for the displacements un of the form :

un  A exp i  kxn0  t 

Travelling wave

Undisplaced Position : xn0  na

Displaced Position : xn  na  un

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 ..

un  A exp i  kxn0  t  dun

 i A exp i  kxn0  t 
.
un 
dt

d 2 un
u n  2   i   2 A exp i  kxn0  t 
.. ..
u n   2un
2

dt

Carry out some simple math manipulation

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 Equation of Motion for the nth Atom
..
mu n  K (un1  2un  un1 )

 m
2
Ae

i kxn0 t   K  Ae
i kxn10 t   2A e  i kxn0 t  Ae  i kxn10 t 

k ( n  1) a kna k ( n  1) a
kna
2 i kna t 
 m A e  K Ae 
i  kna  ka t 
 2A e
i  kna t 
 Ae
i  kna  ka t 

2
 m A e
i  kna t 
 K Ae  i  kna t 
e
ika
 2A e
i  kna t 
 Ae
i  kna t 
e
 ika

Cancel Common Terms & Get
m 2  K  eika  2  eika 
• Mathematical simplification finally gives

eix  eix  2cos x

4K ka
 sin
m 2

• Maximum allowed frequency is

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ω versus k relation for the monatomic chain

k
–л /a 0 л /a 2л /a

Dispersion curve : Periodic and symmetric about the origin

sinusoidal with period 2 л /a
Behavior of the lattice (Wave Propagation) : 0  k  /a

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 4K ka
 sin
m 2
For small k - values (or) long wavelength limit :
Lattice behaves as an elastic continuum 

 ma 
  k
 2 

 ma 
vs    Y
 2  

K  aY
k
–л /a 0 л /a 2л /a

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Group Velocity : More significant (physically)
(Energy and Momentum : Transmitted via pulse rather than by the waves)

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 4K ka
• Dispersion relation :  sin
m 2

• Group velocity :
vg  (dω/dk) = a(K/m)½cos(½ka)

vg = 0 at the BZ edge [k =  (π/a)]

– This tells us that a wave with λ corresponding to a zone edge

wavenumber k =  (π/a) will not propagate.

It must be a standing wave!

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Diatomic Chain

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 Diatomic Chain of Two Different Atom Types

M & m connected by identical springs of spring constant K

(n-2) (n-1) (n) (n+1) (n+2)

K K K K
M M m M
m
a

Un-2 Un-1 Un Un+1 Un+2

a is the repeat distance, so, the nearest-neighbor separation is (½)a

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• Model is complicated : Presence of 2 different atom types

M m M m M

Un-2 Un-1 Un Un+1 Un+2

• GOAL : Find the dispersion relation ω(k).

• 2 equations of motion : One for M & One for m.

..
M u n  K (un1  un )  K (un  un1 ) Equation of Motion
 K (un1  2un  un1 ) for M

..
mu n .. K (un  un1 )  K (un1  un2 )
-1 Equation of Motion
mu n  K (un  2un1  un2 )
-1
for m
• Harmonic (plane wave) solutions for the atomic displacements Un:

M m M m M

Un-2 Un-1 Un Un+1 Un+2

un  A exp i  kxn0  t   xn0  na / 2 Displacement for M

un   A exp i  kxn0  t   Displacement for m

α = Determines the relative amplitude and phase of the vibrational wave

u n   A exp i  kxn0  t  

..
2 Carry out some simple math
manipulation as follows
 Equation of Motion for the nth Atom (M)
..
M u n  K (un1  2un  un1 )
 k  n 1 a  k  n 1 a
 kna
i

t   i

t   kna
i

t  i t  


 2 MAe  2 
 K   Ae  
 2 Ae  2    Ae  
2 2

 
 
 kna
i

t    kna
i

t  i ka
 kna
i

t 
 kna
i t   i ka 


 2 MAe  2 
 K   Ae  2  e 2  2 Ae  2    Ae  2  e 2 
 
 
Cancel Common Terms
 i
ka
i
ka

 M  K   e  2   e 
2 2 2 eix  eix  2cos x
 
 ka 
 2 M  2 K 1   cos 
 2 
 Equation of Motion for the (n-1)th Atom (m)

..
mu n1  K (un  2un 1  un 2 )
 k  n 1 a  k  n 1 a  k  n  2 a
i

t   i kna t  i

t  i t  


 A 2 me  
 K  Ae  2   2 Ae  
 Ae  
2 2 2

 
 
 kna
i

t   i ka  i kna 
t 
 kna
i

t   i ka
 kna
i t   i 2 ka 


 2 mAe  2 
e 2
 K  Ae  2   2 Ae  2  e 2  Ae  2  e 2 
 
 
Cancel Common Terms
i 
ka
i
ka
 ika 
 me
2
 K 1  2 e  e 
2 2

 
 ka 
 i
ka
i
ka
  m  2 K  cos   
2
 m  K  e  2  e 
2 2 2
 2 
 
eix  eix  2cos x
• Equation for M becomes :

(1)
• Equation for m becomes :

(2)

• More algebra gives

2 K cos(ka / 2) 2K   2 M
 
2K   m
2
2 K cos(ka / 2)

• Combining (1) & (2) & manipulating:

• Cross multiplying & manipulating with (1) & (2) :

2 K cos(ka / 2) 2K   2 M
 
2K   m
2
2 K cos(ka / 2)

ka
4 K cos ( )  4 K 2  2 K 2 ( M  m)   4 Mm
2 2

2
ka
4 K (1  cos ( ))  2 K 2 (m  M )   4 Mm  0
2 2

4Mm - 2K2 (m+M) + 2K2 (1- coska) = 0

Solve this equation for 2

Examine the limiting cases

ka  1 and ka = 

4Mm - 2K2 (m+M) + 2K2 (1- coska) = 0

For Small ka

cos ka = 1 - 1/2k2a2

Two roots

(ω)2  2K(m + M)/(mM) : Optical Branch

or ω  constant

(ω)2  [(½) K/(M + m)]k2a2 : Acoustic Branch

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For k =  (π/a)

4Mm - 2K2 (m+M) + 2K2 (1- coska) = 0

(ω)2  2K/m : Optical Branch

(ω)2  2K/M : Acoustic Branch

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 

Optic

Acoustic

k
–π/ a 0 π/a 2π/a

Optical Branch :
Frequency is nearly constant in the limit k  0;
Dropping to 2K/m at the zone boundary

Salient features of the dispersion curve :

Observed two branches : Two different types of normal modes

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 Derive the state of atom motion : Two Branches

Optical Branch 2K(m  M)

 2
max op 
mM

2K   2 M
 k=0
2 K cos(ka / 2)

M
 
m
Two atoms are vibrating against each other
(Center of mass is fixed)
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Excite the motion of optical mode : Electric field of a light wave
(Optical Branch)

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 K(k 2 a 2 )
Acoustic Branch min
2

ac
2(m  M)

2K   2 M
 k=0
2 K cos(ka / 2)

=1

Two atoms : Same amplitude and phase

(long wavelength acoustic vibrations)

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All materials with 2 atoms per unit cell :

Two different kinds of vibrational normal modes

The Acoustic Branch & The Optic Branch

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Chapter 4 Ends

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The unit cell side of NaCl is 5.6A and the modulus of elasticity along [100] direction
is 5 x 1010 N/m2. Find the wavelength at which an electromagnetic radiation is
strongly reflected (optical range) by the crystal. [Atomic weight of Na = 23 and of Cl
= 35.5]

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Prove that the gradient of optical branch of a dispersion curve at the maximum
frequency is zero.

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Prove that in one dimensional diatomic lattice, the acoustic branch is given by
(k 0 ---------)

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Consider the normal modes of a linear diatomic chain in which the force
constants between nearest - neighbour atoms are alternatively C and 10C. Let
the masses be equal and let the nearest - neighbour separation be a/2. Derive the
dispersion relation and find (k) at k = 0 and k = /a.

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