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Normal Modes of

Vibration
One-Dimensional
Model # 1:
The Monatomic
Chain
1- Dimensional Model # 1:
The Monatomic Chain
• Consider a
Monatomic Chain of
Identical Atoms
with nearest-neighbor, “Hooke’s Law”
type forces (F = - Kx) between the atoms.
• This is equivalent to a force-spring
model, with masses m & spring
constants K.
• Consider a typical interatomic potential as is
illustrated in the figure:
V(r)

Repulsive
a = lattice constant
0
a r1, r2 = “atomic radii”
Attractive
r2 r1
• Assume V(r) is known & expand it in a Taylor’s
series in displacements about the equilibrium
separation a, keeping only up through quadratic
terms in the displacements (r-a).
V(r)

Repulsive This potential is the same as


that associated with a spring
0 a with spring constant K:
Attractive Force  K (r  a)
r2 r1
 d 2V 
K   2 
 dr r a
One Dimensional Model # 1:
The Monatomic Chain
• This is the simplest possible solid. Assume that the chain
contains a large number (N  ) of atoms with identical
masses m. Let the atomic separation be a distance a.
• Assume that the atoms move only in a direction parallel
to the chain. Assume that only nearest-neighbors interact
with each other (the forces are short-ranged).
a a a a a a

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


The Monatomic Chain
•Consider the simple case of
a monatomic linear chain a a
with only nearest-neighbor
interactions. 0
•Expand the energy near
the equilibrium point for Un-1 Un Un+1

the nth atom. Then, the


Newton’s 2nd Law l
equation of motion is:
..
• This can be seen as follows. The total force on the
nth atom is the sum of 2 forces.
• The force to the right is: a a

K (u n1  u n )
• The force to the left is:
Un-1 Un Un+1

K (u n  u n1 )
Total Force = Force to right – Force to left
..

The Equation of Motion of each atom is of this


form.Only the value of ‘n’ changes.
• Assume that all atoms oscillate with the same amplitude
A & the same frequency ω. Assume harmonic solutions
for the displacements un of the form:
un  A exp i  kx  t   i A exp i  kxn0  t  
. dun
0
n
un 
dt
..
u n   un
2
u n  2   i   2 A exp i  kxn0  t  
.. d un 2 2

dt
Undisplaced 0 Displaced
Position: xn  na Position: xn  na  un
• Put all of this into the equation of motion:
..

• Now, carry out some simple math manipulation:


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 Manipulation finally gives:

• After more manipulation, this simplifies to

This is the solution to the normal


mode eigenvalue problem
for the monatomic chain.
• The maximum allowed frequency is:
This is the solution to the
normal mode eigenvalue
problem for the monatomic
chain.
• The physical significance of these results is: For
the monatomic chain, the only allowed vibrational
frequencies ω must be related to the wavenumber
k = (2π/λ) or the wavelength λ in this way.
• This result is often called the “Phonon Dispersion
Relation” for the chain, even though these are
classical lattice vibrations & there are no
(quantum mechanical) phonons in the classical
theory.
“Phonon Dispersion Relations” or Normal Mode
Frequencies or ω versus k relation for the monatomic chain.

K
max  2
m
Vs   / k
C B A

k
–л/a 0 л/a 2л/a

• Because of BZ periodicity with a period of 2π/a, only the


first BZ is needed. Points A, B & C correspond to the
same frequency. They all have the same instantaneous
atomic displacements.
Monatomic Chain
Dispersion Relation
Some Physics Discussion
• We started from the Newton’s 2nd Law equations of
motion for N COUPLED simple harmonic oscillators. If
one atom starts vibrating, it does not continue with
constant amplitude, but transfers energy to the others in a
complicated way. That is, the vibrations of individual
atoms are not simple harmonic because of this exchange
of energy among them.
• On the other hand, our solutions represent the
oscillations of N UNCOUPLED simple
harmonic oscillators.
Monatomic Chain 4K ka
 sin
Dispersion Relation m 2
• Our solutions represent the oscillations of
N UNCOUPLED simple harmonic oscillators.
• As we already said, these are called the Normal
Modes of the system. They are a collective property
of the system as a whole & not a property of any of
the individual atoms. Each mode represented by
ω(k) oscillates independently of the other
modes. Also, it can be shown that the number of
modes is the same as the original number of
equations N. Proof of this follows.
• To establish which wavenumbers are possible for the
one-dimensional chain, we can reason as follows: Not all
values are allowed because of periodicity. In particular,
the nth atom is equivalent to the (N+n)th atom. This\
means that the assumed solution for the displacements:
un  A exp i  kxn0  t  

must satisfy the periodic boundary condition: un  uN n


• This, in turn requires that there are an integer number
of wavelengths in the chain. So, in the first BZ, there are
only N allowed values of k. Na  p

Na 2 2
Na  p      Nk  p
p k a
• Physical significance of wave numbers k outside the
First Brillouin Zone [-(π/a)  k  (π/a)]?
•At the Brillouin Zone edge:

• This k value corresponds to the maximum frequency.


•A detailed analysis of the displacements shows
that, in that mode, every atom is oscillating π
radians out of phase with it’s 2 nearest
neighbors.
That is, a wave at this value of k is A
STANDING WAVE.
k

• At the Brillouin Zone edge:


l
• The maximum frequency occurs at this k. In that mode,
every atom is oscillating π radians out of phase with it’s
2 nearest neighbors. That is, a wave at this value of k is A
STANDING WAVE.  2m  4K sin2 ka
2
Black: k = π/a
or  = 2a
Note! This is also
the  for Bragg
reflection!

Green:
k = (0.85)π/a x

or  = 2.35 a
Dispersion  K
max  2
Relation: m
C B A Vs   / k
4K ka
 sin
m 2
-π/a 0 π/a 2π/a kk

• Points A & C are symmetrically equivalent. They have the


same frequency & the same atomic displacements.
• The group velocity vg = (dω/dk) at both of them is negative,
so that a wave at that ω & that k moves to the left. Point B in
the ω(k) diagram has the same frequency & displacement as
points A and C, but vg = (dω/dk) there is positive, so that a
wave at that ω & that k moves to the right.
• Adding a multiple of 2π/a to k does not change either ω or vg, so
point A contains no physical information that is different point B.
The Monatomic Chain
k = (/a) = (2/);  = 2a

k  0;   
For visualization purposes, it
is sometimes useful to
visualize a plane of atoms,
made up of a large number
of parallel chains like the
one we just analyzed.
See the next few slides:
• Lets briefly look in more detail at the group velocity, vg.
The dispersion relation is:
4K ka
 sin
m 2
So, the group velocity is:
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.
• That is, it must be a standing wave!
• At BZ edge, the displacements have the form (for site n):
Un= Uoeinka = Uo ei(nπ/a) = Uo(-1)n
Group Velocity, vg in the 1st BZ
vg  (dω/dk) = a(K/m)½cos(½ka)
At the 1st BZ Edge:
vg = 0
• This means that a wave
with λ corresponding to a
zone edge wavenumber
k =  (π/a)
Will Not Propagate!
• That is, it must be a
Standing Wave!
One-Dimensional Model # 2:
The Diatomic Chain
• Consider a Diatomic Chain of Two Different Atom Types
with nearest-neighbor, Hooke’s Law type forces (F = - kx)
between the atoms. This is equivalent to a force-spring
model with two different types of atoms of masses, 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 a)
m
a

b)

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

• This is the simplest possible model of a diatomic crystal. a is


the repeat distance, so, the nearest-neighbor separation is (½)a
• This model is complicated due to the presence of 2 different
atom types, which, in general, move in opposite directions.
M m M m M

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

• The GOAL is to find the dispersion relation ω(k) for this


model. There are 2 atom types, with masses M & m, so there
will be 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 ) for m
-1
• As before, assume 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  x  na / 2


0 Displacement
n
for M

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


for m
α = complex number which determines the relative amplitude & phase of
the vibrational wave. Put all of this into the 2 equations of motion.

u n   2 A exp i  kxn0  t  


..
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
 ka
i
ka
  ka 
 2 M  K   e 2  2   e 2   2 M  2 K 1   cos
i

   2 

eix  eix  2cos x


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

(1)

• The Equation for m becomes:

(2)
• (1) & (2) are two coupled, homogeneous, linear algebraic
equations in the 2 unknowns α & ω as functions of k.
• 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 2 (1  cos 2 ( ))  2 K 2 (m  M )   4 Mm  0
2
mM 2 2 sin ( ka / 2)
2
  2K (
4
)  4 K 0
mM mM
b  b 2  4ac
The 2 roots are: x1,2 
2a

K ( m  M ) m  M 4sin 2
(ka / 2) 1/ 2
 
2
K [( ) 
2
]
mM mM mM
• So, the resulting quadratic equation for ω2 is:

• The two solutions for ω2 are:

• Since the chain contains N unit cells, there


will be 2N normal modes of vibration,
because there are 2N atoms and 2N
equations of motion for masses M & m.
Solutions to the Normal Mode Eigenvalue Problem
ω(k) for the Diatomic Chain


A ω+ = “Optic” Modes
B
C

ω- = “Acoustic” Modes

–л/a 0 л/a 2л/a k

• There are two solutions for ω2 for each wavenumber k. That is


there are 2 branches to the “Phonon Dispersion Relation” for
each k. From an analysis of the displacements, it can be shown that, at
point A, the two atoms are oscillating 180º out of phase, with their
center of mass at rest. Also, at point B, the lighter mass m is oscillating &
M is at rest, while at point C, M is oscillating & m is at rest.
Diatomic Chain Model: Kittel’s Notation!
The solution is:
K K

Optic Modes (Optic Branch) Near BZ Center (qa << 1)


• The Optic Mode becomes:
(ω+)2  2K(M1 + M2)/(M1M2)
or ω+  constant
Gap
• The Acoustic Mode becomes:
(ω-)2  (½) Kq2/(M1 + M2)
qa
or ω-  vsq
vs  sound velocity in the
Acoustic Modes crystal. Just like an acoustic
(Acoustic Branch) wave in air!
The Diatomic Chain Solution:
K K

( = 2a)
Near BZ edge [q =  (π/a)]
Optic Modes (Optic Branch) (Assuming M1 > M2)
The Optic Mode becomes:
(ω+)2  2K/M2
Gap The Acoustic Mode becomes:
(ω-)2  2K/M1
So, at the BZ edge, the vibrations of
wavelength  = 2a for the 2 modes
behave as if there were 2 uncoupled
masses M1 & M2, vibrating
Acoustic Modes independently with identical springs
(Acoustic Branch) of constant K.
• Again briefly examine limiting solutions at points 0, A, B & C. In
the long wavelength region near k = 0 (ka«1), sin(ka/2) ≈ ½ka.

A
B
C

–л/a 0 л/a 2л/a k

A Taylor’s series expansion, using for, small x:

K (m  M ) m  M 2 4sin 2 (ka / 2) 1/ 2
1,2 2  K [( )  ]
mM mM mM
 The root with the minus sign gives
A
B
C
the minimum value of the
acoustic branch:

–л/a 0 л/a 2л/a k

The root with the positive sign gives the maximum value
of the optic branch:

Substituting these values of ω into the expression for the


relative amplitude α & using cos(ka/2) ≈1 for ka << 1
gives the corresponding value of α:

OR
Substituting min
2
ac
into the expression for the relative amplitude α:
2 2 2 K   2
M
min ac 
2 K(k a )   1
2(m  M) 2 K cos(ka / 2)
This solution corresponds to long-wavelength vibrations near
the center of the BZ at k = 0. In that region, M & m oscillate
with same amplitude & phase. Also in that region ω = vsk,
where vs is the velocity of sound & has the form:

A
1/ 2
 
B
w K
C vs   a  
k  2( m  M ) 

–л/a 0 л/a 2л/a k


Similarly, substituting max op
2
into the relative amplitude gives:
2K(m  M) 2K   2 M M
 2
max op    
mM 2 K cos(ka / 2) m
This solution corresponds to point A in the figure. This value of
α shows that, in that mode, the two atoms are oscillating
180º out of phase with their center of mass at rest.

A
B
C

–л/a 0 л/a 2л/a k


• The other limiting solutions 
A
for ω2 are for ka = π. In this B
C
case sin(ka/2) =1, so
1/ 2
K (m  M )  M  m 
2
4 
 2
max ac  K    
Mm   Mm  Mm  k
–л/a 0 л/a 2л/a

K ( m  M ) K ( M  m) 2K  2

2K
  2
max ac  OR minop m
Mm M
(C) (B)

• At point C in the plot, which is the maximum


acoustic branch point, M oscillates & m is at rest.
• By contrast, at point B, which is the minimum
optic branch point, m oscillates & M is at rest.
Eigenmodes of the chain at q = 0

Center of the unit cell is not moving!

Optical Mode: These atoms, if oppositely charged, would form an


oscillating dipole which would couple to optical fields with  < a
Acoustic & Optic Branches
• Despite the fact that diatomic chain model is one-
dimensional, it’s results for the vibrational normal modes ω
contain considerable qualitative physics that
carries over to the observed vibrational
frequencies for many real materials.
• So, much of the physics contained in the diatomic chain
results can teach us something about the physics
contained in the normal modes of many real materials.
• 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
The Acoustic Branch & The Optic Branch
The Acoustic Branch
• 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.
The Optic Branch
• 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.
A Longitudinal Optic Mode

The vibrational amplitude is highly exaggerated!


A Transverse Optic Mode
for the Diatomic Chain

The vibrational amplitude is highly exaggerated!


For the case in which
the lattice has some
ionic character, with
+ & - charges alternating:
A Long Wavelength Longitudinal
Acoustic Mode

The vibrational amplitude is highly exaggerated!


A Short Wavelength Longitudinal
Acoustic Mode

The vibrational amplitude is highly exaggerated!


A Transverse Acoustic Mode for the
Diatomic Chain

The vibrational amplitude is highly exaggerated!


For the case in which
the lattice has some
ionic character, with
+ & - charges alternating:
Acoustic vs. Optic Phonons
Which has lower energy? Why?
Acoustic Mode

Lower Energy, Less


Compression of Springs
Optic Mode