ME 697R: Computational Methods for

Nanoscale Energy Transport

Chapter 1: Lattice ynamics
!ection 1"1: Lattice !tructure
Reading: #ittel$ pp" 1%&6
'iulin Ruan
!chool of Mechanical Engineering
(urdue )ni*ersity
The +uilding +loc,s of
these t-o are identical$
+ut different crystal
faces are de*eloped
Kittel, Introduction
to Solid State Physics,
p. 2
Crystal Structure
http://ultimate-luxury-
community.com/the-111-facet-las-
vegas-cut-diamond
A crystal is constructed by the infinite repetition of identical
structural units in space.
Bravais lattice: an infinite array of discrete points whose
position vectors can be described as
: primitive translation vectors (lattice vectors) and
n
i
: integers.
,
3 3 2 2 1 1
a n a n a n R

+ + =
i
a

(oint
Translation
.ectors
a
1
a
/
a
&
a
1$
a
&
$a
/
Crystal Lattice
Primitive unit cell is a volume of space that, when translated
through all possible s, just fills all space, without overlap or
voids. This cell contains ONE lattice point.
Smallest building block for the crystal structure, primitive.
The choice of primitive unit cell is not unique
R

S
S S
S
example in 2D
Primitive Unit Cell
The choice of primitive cell is not unique
Wigner-Seitz cell is a special primitive cell and is unique.
Lattice point is always in the center of the cell.
Procedure:
(1) Draw lines to connect a given
lattice point to all nearby
lattice points
(2) At the midpoint and normal to
these lines, draw new lines of
planes
(3) The smallest volume
enclosed in this way is the
Wigner-Seitz primitive cell
Wigner-Seitz Primitive Cell
Lattice with a Basis
Often, we need to
describe a
crystalline materials
structure by placing
a primary atom at
each lattice point
and one or more
basis atoms relative
to it
For compound
materials (eg CuO
2
),
this is an obvious
requirement
Also applies to some
monoatomic crystals
(eg Si)
There are 14 lattice types in 3D
Most common types (Kittel Table 3):
Cubic:
Li, Na, Al, K, Cr, Fe, Ir, Pt, Au etc.
Hexagonal Closed Pack (HCP):
Mg, Co, Zn, Y, Zr, etc.
Diamond:
C, Si, Ge, Sn (only four)
Lattice Types
a
1
a
/
a
&
a
1
0a
&
0a
/
a
1
a
&
a
/
1" !imple Cu+ic 1!C2
3dd one atom at the
center of the cu+ic
&" 4ody%Centered Cu+ic 14CC2
3dd one atom
at the center of
each face
/" 5ace%Centered Cu+ic 15CC2
Con*entional Cell0 (rimiti*e Cell
Con*entional Cell (rimiti*e Cell
Cubic Lattices
SC: One lattice point per conventional cell
(0, 0, 0): fractional coordinate, means (0*a
1
, 0*a
2
, 0*a
3
)
BCC: Two lattice points per conventional cell
(0, 0, 0), (0.5, 0.5, 0.5)
FCC: Four lattice points per conventional cell
(0, 0, 0), (0.5, 0.5, 0), (0.5, 0, 0.5), (0, 0.5, 0.5)
Replicate the unit cell to form a crystal. FCC for example:
(0, 0, 0), (0.5, 0.5, 0), (0.5, 0, 0.5), (0, 0.5, 0.5)
(1, 0, 0), (1.5, 0.5, 0), (1.5, 0, 0.5), (1, 0.5, 0.5): translate a along x
(0, 1, 0), (0.5, 1.5, 0), (0.5, 1, 0.5), (0, 1.5, 0.5): translate a along y
(0, 0, 1), (0.5, 0.5, 1), (0.5, 0, 1.5), (0, 0.5, 1.5): translate a along z
Lattice Points per Conventional Cell
Primitive Cell of BCC
6 Rhom+ohedron primiti*e cell
179
o
&8
6 (rimiti*e Translation .ectors:
Kittel, Introduction to Solid
State Physics
Primitive Cell of FCC
63ngle +et-een a
1
$ a
&
$ a
/
: 67
o
Kittel, Introduction to Solid
State Physics
Kittel p. 12
Diamond Structure
C, Si, Ge, a-Sn
FCC structure, 2 atoms per basis, 8 atoms per conventional
cell
Tetrahedral bond arrangement
Each atom has 4 nearest neighbors and 12 second nearest
neighbors
1) Find the intercepts on the axes in terms of the lattice constants a
1
, a
2,
a
3
. The
axes may be those of a primitive or nonprimitive unit cell.
2) Take the reciprocals of these numbers and then reduce to three integers
having the same ratio, usually the smallest three integers. The result enclosed in
parethesis (hkl) is called the index of the plane.
Index System for Crystal Planes (Miller Indices)
Crystal Planes
ME 697R: Computational Methods for
Nanoscale Energy Transport
Chapter 1: Lattice ynamics
!ection 1"&: Reciprocal Lattice
Reading: #ittel$ pp" &8%97
'iulin Ruan
!chool of Mechanical Engineering
(urdue )ni*ersity
Fourier Transform of the Lattice
Consider the mass density (x) of a 1D atomic lattice. The primitive
translation vector is
Lattice periodicity dictates
The Fourier series of density is
We claim that G
n
is a point in the reciprocal lattice of the crystal. The
primitive lattice vector for the reciprocal lattice is:
a
x
( ) ( ) x ma x + =
{ }
{ } { } { }
( ) exp
( ) exp ( ) exp exp
n n
n
n n n n n
n n
x iG x
x ma iG x ma iG x iG ma
=
+ = + =

{ }
2
exp 1 (given that is an integer)
n n
n
iG ma G m
a

= =
2

= g x

a = a x
a
4rillouin :ones are ;eigner%!eit: primiti*e cell in the
reciprocal lattice
5or 1 lattice$ the first 4rillouin :one is <%=a$ =a>
Real lattice
Reciprocal lattice
0 2/a
4/a
-2/a -4/a -6/a
x
-/a /a
First Brillouin zone
Reciprocal Lattice in 1D and Brillouin Zone
Generalization to 3D
Lattice periodicity dictates
The Fourier series of density is
Therefore
1 1 2 2 3 3
( ) ( )
where
m
m
m m m
+ =
= + +
r R r
R a a a
{ }
{ } { } { }
{ }
( ) exp
( ) exp ( ) exp exp
exp 1 (given that is an integer)
n n
n
m n n m n n n m
n n
n m
i
i i i
i m
=
+ = + =
=

r G r
r R G r R G r G R
G R
2 integer
n m
= G R
Reciprocal Lattice in 3D
Note
Then
The simplest choice of the gs are
where
1 1 2 2 3 3 n
n n n = + + G g g g
( ) ( )
1 1 2 2 3 3 1 1 2 2 3 3
2 integer
n m
n n n m m m = + + + +
=
G R g g g a a a
2
j i ij
= g a
1 for
0 for
ij
i j
i j
=

Reciprocal Lattice in 3D
The solution for gs are
A plane oblique lattice and its corresonding
reciprocal lattice
2 3 3 1 1 2
1 2 3
1 2 3 1 2 3 1 2 3
2 ; 2 ; 2 ;

= = =

a a a a a a
g g g
a a a a a a a a a
1 2 2 1
; ; g a g a
Reciprocal Lattice to Simple Cubic Lattice
The primitive translation vectors of the simple cubic lattice
are:
The primitive translation vectors of the reciprocal lattice are
The reciprocal lattice of a simple cubic lattice is still a simple
cubic lattice.
1 2 3

; ; a a a = = = a x a y a z
1 2 3

(2 / ) ; (2 / ) ; (2 / ) a a a = = = g x g y g z
The primitive translation vectors of the
lattice are:
The primitive translation vectors of the
reciprocal lattice are
The reciprocal lattice of a BCC lattice is an
FCC lattice.
The first Brillouin zone is a rhombic
dodecahedron.
Reciprocal Lattice to BCC Lattice
1
2
3
1

( );
2
1
( );
2
1

( )
2
a
a
a
= + +
= +
= +
a x y z
a x y z
a x y z
1 2
3

(2 / )( ); (2 / )( );

(2 / )( )
a a
a
= + = +
= +
g y z g x z
g x y
The first Brillouin zone
The BCC Lattice
Reciprocal Lattice to FCC Lattice
The primitive translation vectors of
the lattice are:
The primitive translation vectors of
the reciprocal lattice are
The reciprocal lattice of an FCC
lattice is a BCC lattice.
1 2
3
1 1

( ); ( );
2 2
1
( )
2
a a
a
= + = +
= +
a y z a x z
a x y
1
2
3
(2 / )( );

(2 / )( );

(2 / )( )
a
a
a
= + +
= +
= +
g x y z
g x y z
g x y z
The first Brillouin zone
The FCC lattice
ME 697R: Computational Methods for
Nanoscale Energy Transport
Chapter 1: Lattice ynamics
!ection 1"/: Crystal 4inding and ?nteratomic
(otentials
Reading: #ittel$ pp" 9@%79
'iulin Ruan
!chool of Mechanical Engineering
(urdue )ni*ersity
Chemical bonds are responsible for the
formation of a crystal structure.
Interaction exists for any atom pairs. It
can be bonding interaction (such as
ionic bonds, covalent bonds) or non-
bonding interaction (such as van der
Waals interaction and Coulomb
interaction).
The bond energy U is the energy
released by the atomic pair when
separating to infinite distance. Usually,
U is equally shared between the two
atoms.
R
1 2
1 2
( )
1
2
( ) 0
U U R
U U U
U R
=
= =
= =
( ) 0 U R = =
Chemical Bond in a Crystal
van der Waals Interaction
Ar
+ Ar - + Ar -
Ar
R
Kittel, Page 63
Attraction
Repulsion
Examples: inert gases, molecular crystals
Attraction: dipole-dipole interaction; act at long distance
Repulsion: Pauli exclusion principle; act at short distance
Lennard-Jones (L-J) potential model:

Bond energy: ~ 0.01 eV (weak): low melting point

12 6
( ) 4 U R
R R

(
| | | |
=
(
| |
\ \
(

Attractive Repulsive
where and are constants
for argon, = 3.4 , = 0.01042 eV
min
( ) 0 when
( ) 0 when
( ) at 1.12
U R R
U R R
U R R

< >
> <
= =
Kittel, Page 64
Lennard-Jones (L-J) potential model
The cohesive energy is the total potential energy
of all atoms in a crystal.
Consider an FCC argon lattice with N (very large)
atoms, the potential energy of atom i is:
12 6
1 ,
1
(4 ) ,
2
i
j N j i
ij ij
U
p R p R

=

(
| | | |

(
=
| |
`
| |
(
\ \

)

12 6
1 ,
1
(4 ) ,
2
tot
j N j i
ij ij
U N
p R p R

=

(
| | | |

(
=
| |
`
| |
(
\ \

)

Cohesive Energy of the Lattice

p
ij
R: the distance between atom i and atom j, expressed in terms of
the nearest neighbor distance R. p
ij
= 1 for nearest neighbors, and p
ij
> 1 for second nearest and further neighbors.
The cohesive energy of this N-atom crystal is
For fcc crystal (12 nearest neighbors and 6 second nearest neighbors)
Evidently the lattice cohesive energy is a function of R. For the lattice to
be at equilibrium, the cohesive energy should be at its minimum.
Now you start to see nano size effect on R
0
!
The process of minimizing the lattice energy to find the equilibrium lattice
configuration is called energy minimization or geometry optimization.
12 6
13 7
0
,min 0
0 2 (12)(12.13) 6(14.45)
1.09
( ) (2.15)(4 )
tot
tot tot
dU
N
dR R R
R
U U R N

(
= =
(

=

= =

for fcc crystal

( )
( )
12
12 12
1 ,
6
6 6
1 ,
12 1 6 2 ... 12.13188
12 1 6 2 ... 14.45392
ij
j N j i
ij
j N j i
p
p

=
= + + =
= + + =

Equilibrium Lattice Constant

Potential model for short-range interaction :
One electron of the Na atom is removed and
absorbed to the Cl atom
Short-range interaction: Pauli exclusion principle;
repulsive
Long-range interaction: Coulomb force; attractive
or repulsive
Bonding energy: 1-10 eV (strong): high melting
point
Na
+
Cl
-
Cl
-
Cl
-
Cl
-
Cl
-
Na
+
Na
+
Na
+
,
exp
ij
ij sh
r
U A

| |
=
|
\
where A and are constants, and r
ij
is the distance between the two
atoms.
Ionic Bond and Short Range Interaction
Coulomb Interaction and Potential Model
Coulomb interaction is important when
atoms are charged
Coulomb potential model:
q
i
and q
j
: atomic charges for atoms i and j,
including the sign

0
: dielectric function
Coulomb interaction is very long range
since it decays as 1/r.
Na
+
Cl
-
Cl
-
Cl
-
Cl
-
Cl
-
Na
+
Na
+
Na
+
,
0
4
i j
ij Coulomb
ij
q q
U
r
=
0
4
i j
ij
q q
r
exp
ij
r
A

| |
|
\
ij
U
Kittel, Page 72
Total Potential Energy for an Ionic Bond
The total potential
energy for a pair:
, ,
0
exp
4
ij ij sh ij Coulomb
ij i j
ij
U U U
r q q
A
r
= +

| |
= +
|
\
Consider an ionic lattice with 2N atoms, where R is the nearest neighbor
distance
The potential energy of atom i is
The lattice energy is
0
0
exp (nearest neighbors)
4
(otherwise)
4
i j
ij
i j
ij
q q
R
A
R
U
q q
p R

| |
+
|
\
=

nearest neighbors second neighbors

0 0
1
exp ...
2 4 4
i j i j
i
j j
ij
q q q q
R
U A
R p R
= =

(
(
| |

= + + +
( `
( |
\ (


)

nearest neighbors second neighbors
0 0
(2 )
exp ...
4 4
tot i
i j i j
j j
ij
U N U
q q q q
R
N A
R p R
= =
=

(
(
| |

= + + +
( `
( |
\ (


)

Lattice Energy
The lattice will be equilibrium if the lattice energy is at its minimum.
The evaluation of the electrostatic terms is tricky. Take NaCl as an
example, q
Na
= +e, q
Cl
= -e.
z: number of nearest neighbors
: Madelung constant defined as
( )
j
ij
p

0 ,min
0 and
tot
tot
dU
R U
dR
=
nearest neighbors second neighbors
0 0
2
0
( )( ) ( )( )
exp ...
4 4
exp
4
tot
j j
ij
R e e e e
U N A
R p R
R e
N zA
R

= =

(
(
| | + + +
= + + +
( `
( |
\ (


)
(
| |
=
( |
\


Equilibrium Lattice Constant
For 1D
1 1 1 1 1 1 1
2 2 2 2 ... 2 1 ... 2ln 2
1 2 3 4 2 3 4

| |
= + + = + + =
|
\
Madelung Constant
For NaCl
Other materials
Electrostatic interaction is a long-range interaction.
1 1 1
6 12 8 ... 1.747565
1
2 3
= + =
Material
CsCl 1.762675
ZnS 1.6381
Buckingham form:
Compared to the original form, the term is added to
account for the van der Waals attraction.
,
6
exp
ij ij
ij sh
ij
r C
U A
r

| |
=
|
\
Buckingham Potential for Short-Range Interaction
6
ij
ij
C
r

Covalent Bond
Two atoms share a pair of electrons
Bonding energy: ~1-10 eV (strong)
Examples: C, Ge, Si, H
2
C
C C
C
C
A
A B A A
pair angular torsional
Multi-body Potentials for Covalent Bonds
Since electrons pairs are shared, the
changes in bond angles and plane angles
will result in potential energy change.
Typically multi-body interactions need to
be considered.
Born harmonic model
k: spring (force) constant
r
0:
reference length or equilibrium bond length
Expanded harmonic model
k
3
and k
4
are optional
It is actually a Taylor series of a more complicated function
Pair Potentials
2
0
1
( ) ( )
2
U r k r r =
2 3 4
2 0 3 0 4 0
1 1 1
( ) ( ) ( ) ( ) ...
2 6 24
U r k r r k r r k r r = + + +
r
Morse model:
D
e
: the depth of potential
well
a = , where ke is
the force constant at the
minimum of the well
r
e:
equilibrium bond length
Morse potential can take
into account the
anharmonic effect when r
is much larger than r
e
.
Morse Potentials
2
( )
( ) 1
e
a r r
e
U r D e

(
=

/ 2
e e
k D
A convenient model for the potential energy of a diatomic
molecule.
It is a better approximation for the vibrational structure of the
molecule than the quantum harmonic oscillator
It explicitly includes the effects of bond breaking, such as the
existence of unbound states.
It also accounts for the anharmonicity of real bonds.
Features of Morse Potential
Angular (Three-Body) Potentials
Expanded harmonic model:
k
2
, k
3
and k
4
: angular spring constant
k
3
and k
4
are optional

0
: equilibrium bond angle
Cosine model
angular
2 3
2 0 3 0
4
4 0
1 1
( ) ( ) ( )
2 6
1
( ) ...
24
U k k
k


= +
+ +

2
0
( ) (cos cos ) U A =
Torsional (Four-Body) Potentials
Harmonic model:

1234
: angle between planes 123 and 234

1234,0
: equilibrium angle
Plane 123 defined
by atoms 1, 2, and 3
1234 1234,0
( ) 1 cos( ) U A n ( = +

Plane 234 defined by
atoms 2, 3, and 4
Stillinger Weber Potential
One of the first attempts to model a semiconductor.
Includes two- and three-body terms.
Two-body term:
where A, B, p, q, a are positive.
1
2
( ) exp ( ) ,
( )
0,
p q
A Br r r a r a
f r
r a

(
<

Stillinger Weber Potential

Three-body term:
where
i, j, k: labels of atoms
r
ij
: Length of the bond between atoms i & j

ijk
: Bond angle between bonds ij & ik
The parameters for silicon:
A = 7.049556277, B = 0.6022245584
p = 4, q = 0, a = 1.80, = 21.0, = 1.2
3
( , , ) ( , , ) ( , , ) ( , , ) i j k ij ik jik ji jk ijk ij ik jik r r r h r r h r r h r r f = + +
( ) ( )
2
1 1 1
( , , ) exp * cos
3
ij ik jik ij ik jik h r r r a r a

| |
(
= + +
|

\
Tersoff Potential
Originally developed to the Group IV elements (e.g. carbon,
silicon, germanium). Later extended to other metallic
bonding.
Form
ij
1
, ( )[ ( ) ( )] ;
2
i ij c ij R ij ij A ij
i i j
E E V V f r f r b f r

= = = +

( ) exp( ), ( ) exp( );
1,
1 1
( ) cos[ ( ) ( )], ,
2 2
0,
R ij ij A ij ij ij ij ij ij
ij ij
c ij ij ij ij ij ij ij ij
ij ij
f r A r f r B r
r R
f r r R S R R r S
r S

= =
<

= + < <

>

Tersoff Potential
i,j,k: labels of atoms
r
ij
: length of the bond between atoms i & j

ijk
: bond angle between bonds ij & ik
f
A
: pair wise attraction term
f
R
: pair wise repulsion term
f
c
: cutoff function
b
ij
: bond order
( )
( )
( )
1
,
2
2 2 2 2
1 2
1 , ( ) ( )
( ) 1 [ ];
cos
2, ,
, , , ,
n
i
k i
ijk
ij ij ij c ij ij ijk
ijk
i i i i
ij i
ij
i j
n n
i i
b f r g
i ij
g
c d c d h
i
X X Xj for X
X for X A B R S
XX

=
| |
= +

|
\
= + +
= + =
= =

Tersoff Potential Parameters

C Si Ge
A(ev) 1.396X10
3
1.8308X10
3
1.769X10
3
B(ev) 3.4674X10
2
4.7118X10
2
4.1923X10
2
(Ang
-1
) 3.4879
2.4799 2.4451
(Ang
-1
) 2.2119
1.7322 1.7047
1.5724X10
-7
1.1X10
-6
9.0166X10
-7
n 7.2751X10
-1
7.8734X10
-1
7.5627X10
-1
c 3.8049X10
4
1.0039X10
5
1.0643X10
5
d 4.384
1.6217X10
1
1.5652X10
1
h -5.7058X10
-1
-5.9824X10
-1
-4.3884X10
-1
R(Ang) 1.8
2.7 2.8
S (Ang) 2.1
3.0 3.1
REBO Potential
Reactive Empirical Bond Order (REBO) potential
where A, Q, B
1
, B
2
, B
3
,
1
,
2
,
3
are fitting parameters.
The values of the parameters for Carbon are:
3
1
1
( ) 1 .
2
i j n i j
r r
c ij ij n
b
i j n
Q
E f r A e b B e
r

=
| |
| |
= +
| |
\
\

B
1
=12388.79197798 ev
1
=4.7204523127Ang
-1
Q=0.313460296
B
2
=17.56740646509 ev
2
=1.43320132499Ang
-1
A=10953.54416217 ev
B
3
=30.71493208065 ev
3
=1.3826912506Ang
-1
=4.7465390606595 Ang
-1
D
min
=1.7 D
max
=2.0
Metallic Bonds
Metallic bonding is the type of bonding
found in metal elements. This is the
electrostatic force of attraction between
positively charged ions and delocalized
outer electrons.
The metallic bond is weaker than the
ionic and the covalent bonds.
A metallic bond result from the sharing
of a variable number of electrons by a
variable number of atoms. A metal may
be described as a cloud of free
electrons.
+
+
+
+
+
+
+
+
+
Embedded Atom Model (EAM)
The potential energy for an atom i is:
F

: embedding function that represents the energy required to

place atom i of type into the electron cloud

: contribution to the electron charge density from atom j at the

location of atom i

: pair-wise potential function

Tabulated functions
F

: as a function of

: as a function of r
ij

: as a function of r
ij
1
( ) ( )
2
i ij ij
i j i j
E F r r



(
= +
(


#a*iany$
Aeat
Transfer
(hysics$
Cam+ridge
)ni*ersity
(ress$ &778"
Available Interatomic Potentials in GULP
#a*iany$
Aeat
Transfer
(hysics$
Cam+ridge
)ni*ersity
(ress$ &778"
Available Interatomic Potentials in GULP
http://projects.ivec.org/gulp/help/gulp_30_manual/gulpnode8.html
ME 697R: Computational Methods for
Nanoscale Energy Transport
Chapter 1: Lattice ynamics
!ection 1"@: ynamical MatriC and (honon ispersion
Reading: #ittel$ pp" 98%177
'iulin Ruan
!chool of Mechanical Engineering
(urdue )ni*ersity
Harmonic Approximation
Harmonic approximation:
near the potential well
minimum. This
approximation works
especially well for low
temperature (is exact at 0
K).
Chemical bonds can be
assumed as elastic
springs.
Energy
Distance
r
o
Parabolic Potential of
Harmonic Oscillator
E
b
Equilibrium and deformed positions
Force and Equation of motion for the s
th
atom
Crystal Vibration for Monatomic Chain
a
Spring constant, g Mass, m
x
n
x
n+1
x
n-1
Equilibrium
Position
Deformed
Position
u
s
: displacement of the s
th
atom from its equilibrium position
u
s-1
u
s
u
s+1
( )
( )
1 1
2
1 1
2
( ) ( ) 1
( 2 ) 2
s s s s s
s
s s s
F C u u C u u
d u
M C u u u
dt
+
+
= +
= +
equilibrium coordinates
displacements
Assume a wave solution in the form
Then
The equation of motion (2) becomes
Note
Solution of the Wave Equation
( )
( )
1
0
exp
exp( ) exp
s s
s
u u iKa
u u i t iKsa

=
=
0
( , ) exp( ) u x t u i t iKx = +
2
2
2
s
s
d u
u
dt
=
( )
2
1 1
( 2 ) 3
s s s s
M u C u u u
+
= +
The Equation (3) becomes
Identity
The -K relation is called the dispersion relation
Solution of the Wave Equation
( )
[ ] [ ] ( ) { }
( ) ( )
2
0
0
2
exp
exp ( 1) exp ( 1) 2exp
exp exp 2
Mu iKsa
Cu i s Ka i s Ka iKsa
M C iKa iKa

=
+ +
= + (

( )
1/ 2
2
2 4 1
1 cos sin
2
C C
Ka or Ka
M M

| |
= =
|
\
( ) ( )
2cos exp exp Ka iKa iKa = +
Phonon Dispersion Relation
The dispersion relation has a period of 2/a, so the range of
independent K values is [- /a, /a]. This is the first Brillouin
zone of 1-D lattice.
-/a<K< /a
K
max
= /a
K = 2/

min
= 2a
Polarization and Group Velocity
Group Velocity:
Speed of Sound:
Zone edge
(boundary):
Standing wave
F
r
e
q
u
e
n
c
y
,

Wave vector, K
0 /a
dK
d
v
g

=
dK
d
v
K
s

0
lim

=
/
lim 0
g
K a
d
v K
a dK

| |
= = =
|
\
Longitudinal Acoustic Phonons
Long wavelength
Zone edge
Standing wave
Two Atoms per Basis
Equation of motion:
Lattice Constant, a
x
s
y
s
y
s-1
x
s+1
M
2
M
1
u
s
v
s
v
s-1
u
s+1
equilibrium coordinates:
displacements:
( )
( )
2
1 1
2
2
2 1
2
( 2 ); 1
( 2 ); 2
s
s s s
s
s s s
d u
M C v v u
dt
d v
M C u u v
dt

+
= +
= +
Assume a wave solution in the form
Then the equations of motion becomes
The homogeneous linear equations have a solution only if
Solution of the Wave Equation
0
0
exp( ) exp( )
exp( ) exp( )
s
s
u u isKa i t
v v isKa i t

=
=
[ ]
[ ]
2
1 0 0 0
2
2 0 0 0
1 exp( ) 2
exp( ) 1 2
M u Cv iKa Cu
M v Cu iKa Cv

= +
= +
[ ]
[ ]
2
1
2
2
2 1 exp( )
0
1 exp( ) 2
C M C iKa
C iKa C M

+
=
+
The solution is
Limiting cases:
K 0,
K /a,
Dispersion Relation
1/ 2
2
2
1 2 1 2 1 2
1/ 2
1/ 2
2
1 2 1 2 1 2
1 1 1 1 4
sin
2
1 1 1 1 4
sin (3)
2
Ka
C C
M M M M M M
Ka
C C
M M M M M M

(
| | | |
( = + +
| |
(
\ \


(
| | | |

( = + +
` | |
(
\ \


)
1/ 2
LA
1 2
,
2( )
C
Ka
M M

(
=
(
+

1/ 2
LO 0
1 2
1 1
2C
M M

(
| |
= = +
( |
\

1/ 2
LA
1
2
,
C
M

| |
=
|
\
1/ 2
LO
2
2C
M

| |
=
|
\
Dispersion Relation Profiles
Kittel, Figure
7, page 105
Eq. (3)
Dispersion relation for Ge.
At K = 0
For acoustic mode, , vibrations of neighboring atoms are in
phase
For optical mode, , vibrations of neighboring atoms are out
of phase
0
0
1
u
v
=
Acoustic and Optical Phonons
0 2
0 1
u M
v M
=
Kittel, Figure
10, page 107
Standing
wave
Traveling
wave
Consider the diatomic linear chain case. The homogeneous
linear equations have a solution only if
or
Define
So
Dynamical Matrix Approach
[ ]
[ ]
2
1
2
2
2 1 exp( )
det 0
1 exp( ) 2
C M C iKa
C iKa C M

( +
=
(
+
(

( )
( )
1
1 2
2
2
1 2
2
1 exp
1 0
det 0
2 0 1
1 exp
C C
iKa
M
M M
C C
iKa
M
M M

(
( +
(
(

(
=
`
(
(

( +
(


(

)
( )
( )
1
1 2
2
1 2
2
1 exp
( )
2
1 exp
C C
iKa
M
M M
D K
C C
iKa
M
M M

(
( +
(
(
=
(

( +
(

(

Dynamical
Matrix
2
det ( ) 0 D K I ( =

Atomic Position Nomenclature in 3D
An atom in unit cell n and at basis
position has an equilibrium
position r
n
Subscripts i and j denote direction
Subscripts m and denote the
position of a different atom in the
lattice (analogous to n and )
Perturbed expression for the
potential (like a Taylor series
expansion)
0 because assumed zero potential and first
derivative at the equilibrium position
Note: expressions such as
this use implied summation
of repeated super/subscripts
Force Constant Matrix
We define a matrix
that serves the function
of a normalized spring
constant
Lattice invariance tells
us that this spring
constant depends only
on the distance
between positions n
and m
Mathematically, this
means that
Equations of Motion
The force on the atom at position n can be expressed in
terms of the spatial derivative of potential energy
Atomic displacement s can be expressed as a Fourier wave
The wave vector K is an important parameter (inversely proportional
to wavelength)
Wave frequency gives the rate of vibration of the wave
Substituting into the equation of motion, we find
( )
m j
n i n i
n i n i m j n i
n i
F M

+
= = =

r s
s s
s

[ ]
2
1
( ) exp ( ) ( )
m j
i n i m n j
u i u
M M

= K K r r K
( )
1
( ) exp
n i i n
u i t i
M

= + s r
Dynamical Matrix and Dispersion Relation
The dynamical matrix contains each spring constant
Second equality from translational invariance, and r
p
is defined as r
m
r
n
The euqation of motion becomes
Where is the Kronecker delta (identity matrix).
The dispersion relation defines the relationship between the
wave vector K and frequency and emerges from the
secular equation,
det[D(K) -
2
I] = 0
( )
2
( ) 0
j j
i i j
D u


= K
[ ]
0
1 1
exp ( ) exp
j m j p j
i n i m n i p
D i i
M M M M



( = =

K r r K r
Phonon Dispersion of Silicon
Phonon dispersion is typically
plot along high symmetry lines in
the first Brillouin zone.
X