LATTICE VIBRATIONS PHONONS

Linear chain of identical particles

We first consider a linear chain of identical particles connected by springs of the
same strength so that only nearest neighbor atoms interact with each other; this is
shown schematically in Fig. 1. The separation of the particles in equilibrium is equal
to a, the lattice parameter.

u n-1

un

n-1

u n+1

u n+2

n+1

n+2

Fig.1. Linear chain of identical particles connected by springs.

The force acting on the atom n arising from the springs connecting this atom with
atoms n-1 and n+1 is

Fn = !(u n+1 " u n ) " !(u n " u n "1 ) = !(u n+1 + u n" 1 " 2u n )

(PH1)

where is the corresponding spring constant. The equation of motion of the nth atom
is then
d2 un
m 2 = !(u n +1 + u n "1 " 2u n )
dt
(PH2)
where m is the mass of the particles.
In the continuum limit, when the separation, a, between the particles decreases to
zero, lim(a ! 0)

un+1 + un"1 " 2un

a2

# 2u
= 2 , where x is the coordinate along the chain. If V is
#x

the volume per particle ( a = V ) then in this limit equation (PH2) becomes
1/3

m !2 u
!2 u
=" 2
V2 /3 !t 2
!x
This is the wave equation that can be written in the familiar form

(PH3.1)

2
!2 u
2! u
=c
!t 2
!x 2

!V 2/3
with c =
.
m

(PH3.2)

Solutions of (PH3.2) are harmonic waves

u = u k exp #%$ i(!t" kx)&(' + complex conjugate

(PH4)

where u is the amplitude of the vibrations with the frequency and the wave vector
k = ! c ; the wavelength, , is determined from the relation ! = 2" k . The
relationship between the wave vector k and the frequency is in this case linear and
thus the (group) velocity of the waves, defined as d! dk , is constant equal to
" ! %1/2
c = a$ ' ; such waves are called non-dispersive.
# m&
k

For the discrete system of particles, the vibrations of which are described by equation
(PH2), we seek, in analogy with (PH4), the solution in the form

u n = u k exp #%$ i(!k t "kna)&(' + complex conjugate

(PH5)

where the frequency of vibrations, ! k , is generally a function of k. It is obvious from

(PH5) that if k changes by 2/a then the displacement does not change since
exp(2!ni) = 1. Therefore, it is sufficient to consider ! " a < k < " a . This range of k
defines the first Brillouin zone of the wave vector. Inserting (PH5) into (PH2) yields

!" 2k m = #(exp [!ika ] + exp [ika ] ! 2)

and, therefore,

!k =
2

2"
4"
[1 # cos(ka)] = sin 2 (ka 2)
m
m

(PH6a)

The wavelength of the vibrations described by (PH5) is again ! = 2" k but the group
velocity of these vibrations is
1/2

#" &
d!
c = k = a %%% ((((
%$ m '
dk

cos(ka 2)

(PH6b)

and thus these vibrations are dispersive. In the long wavelength limit when k ! 0
# " &1/2
c ! a% ( as in the continuum case. The vibrational spectrum and/or dispersion
$ m'
2

relation is described by equation (PH6a) and in the present case it has the form shown
in Fig. 2.

-"/a

"/a

Fig, 2. Dispersion relation or vibrational spectrum for the linear chain of identical
particles connected by springs.
Definition of Phonons
The most general solution of equation (PH2) is a linear combination of waves with
various k vectors
(PH7)
u n = ( "$ a k exp (!ikna)+ a k exp(ikna)%'
k #

&

where a k = u k exp( i! k t) . The energy of the vibrating system of the particles is

2

2
m !# dun $&& (
E = ' ##
&& + ' (u n+1 )u n )
2 n #" dt &%
2 n

(PH8)

where the summation over n is over all the N particles of the chain. The first term is
the kinetic and the second term the potential energy. Inserting (PH7) into (PH8)
gives1
1

When evaluating the energy we use periodic boundary conditions for the chain containing N
N
0 for k " 0
2!
! , where ! is an integer and ! exp(ikna) =
atoms. In this case k =
Na
N for k = 0
n=1
3

E = 2mN" a k a k ! 2k = m" b k b k ! 2k
k

(PH9)

where we define b = 2Na .

k

The motion of a harmonic oscillator (single vibrating particle) is described by the

equation
m!!
u =!"u
The solution is u = Asin !t where A is the amplitude of vibrations and ! 2 = " m.
The energy of such harmonic oscillator is
1
1
1
E = m!u 2 + !u 2 = mA 2" 2 .
2
2
2
When the problem of the harmonic oscillator is solved quantum mechanically its
energy is
E = !!(n + 1 / 2) ,
where n=0,1,2,.... correspond to various quantum states.
Comparing the energy of the classical single particle harmonic oscillator with
equation (PH9), which gives the energy of the vibrating system of interacting
particles, it is seen that the latter can be formally regarded as the energy of noninteracting quasi-particles each vibrating as a harmonic oscillator with frequency
k k
k k
! k ; setting 2b b = A A is the amplitude of vibrations . Each of these quasiparticles, called phonons, is characterized by a value of the wave vector k. In the
quantum mechanical framework the total energy of the vibrating system, i.e. of the
phonons present in this system, is then

E = ! (N k + 1/ 2)!" k

(PH10)

where N k is the number of phonons in the state k.

Linear chain of two particles of different types

We now consider a linear chain composed of two types of particles that have different
masses m1 and m2 connected by different springs. The springs connecting different
particles are generally different but only nearest neighbor atoms are assumed to
interact with each other (see Fig. 3). The separation of like particles is a, and the
separation of unlike particles is a1 . The period of the system is equal to a.

a1
n 2- 1

n1- 1

n1

n2

n 1 +1

n 2+ 1

Fig. 3. . Linear chain of two types of particles connected by springs.

The force acting on the atom n 1 , arising from the springs connecting this atom with
atoms n 2 (spring constant ! 1 ) and n 2 ! 1 (spring constant ! 2 ), is
Fn = !1(u n "u n )+ !2 (u n "1 " un ) ; the force acting on the atom n 2 , arising from
1

the springs connecting this atom with atoms n 1 and n 1 + 1, is

Fn =!1(un "u n ) +! 2 (u n +1 "u n ) . Equations of motion for atoms n 1 and n 2 are
then

m1

d 2u n

dt2

= Fn

and m2

d 2u n
dt 2

= Fn

We again seek the solution in the form of plane waves analogous to (PH5)

u n1 = u1k exp $%i(!(k)" t # kna)&' + complex conjugate

u n2 = u k2 exp $%i(!(k)" t # kna)&' + complex conjugate

(PH11)

Again, as in the previous case, if k is changed by 2/a the displacement does not
change and, therefore, it is sufficient to consider ! " a < k < " a ; this again defines
the first Brillouin zone of the vector k. Inserting (PH11) into equations of motion
yields
$
$ # + # exp("ika) '
# +# '
)) = 0
u1k &&!2 " 1 2 )) + u k2 && 1 2
m
m
%
(
%
(
1
1
(PH12)
$ # + # exp(+ika) '
$
'
# + #2
)) + u k2 &&!2 " 1
)) = 0
u1k && 1 2
m
m
%
(
%
(
2
2
These equations determine frequencies ! k and amplitudes u kn . The former are
eigenvalues of the matrix

$ !1 + ! 2
! + ! 2 exp("ika) '
" #2
" 1
&
)
m
m
1
1
&
)
& !1 + ! 2 exp(+ika)
)
!1 + ! 2
2
"
"
#
&
)
m2
m2
%
(
and the latter are the corresponding eigenvectors. The equation for the eigenvalues is
the determinant of the above matrix equals zero and it is a simple quadratic equation
for !2 . The solutions are
'
1 $
!12 = ! 20 &&1" 1"# 2 sin2 (ka 2))))
(
2 %

'
1 $
! 22 = !02 &&1+ 1" #2 sin 2 (ka 2) ))) (PH13)
(
2 %

where

! 20 =

(" 1 + " 2 )(m1 + m2 )

m1 m2

and # 2 = 16

" 1" 2
(" 1 + " 2 )2

$ m1 m2 '
&
2)
% (m 1 + m2 ) (

For long wavelengths, when k ! 0, "1 ! 0 and " 2 ! " 0 . At the boundary of the
"
1 2
1 2
2
2
2
2
Brillouin zone, when k ! , # 1 ! # 0 1$ 1$ % and # 2 ! # 0 1+ 1 $ % .
a
2
2
The vibrational spectrum and/or dispersion relation has in the present case the form
shown in Fig. 4.

!0

OPTICAL

ACOUSTIC

"/a
-"/a
k
Fig. 4. Dispersion relation, or vibrational spectrum, for the linear chain of two types
of particles connected by springs.
6

It follows from equations (PH12) that the ratio of the amplitudes (eigenvectors) is

u1k !1 + ! 2 exp("ika) !1 + ! 2 " m 2 #2

=
=
u k2
!1 + ! 2 " m1#2
!1 + ! 2 exp(ika)

(PH14)

Considering first the frequency !1 . When k ! 0 (long wavelength) "1 ! 0 and

u1k
thus k ! 1 . This means that the amplitudes of the neighboring atoms are the same.
u2
This case is called acoustic and corresponding phonons are called acoustic phonons.
When considering the frequency !2 then when k ! 0 "2 ! "0 and thus

!1 +!2
m2
u1k
1
. This means that the amplitudes of
=
=
=
"
m1 + m 2
m1
u k2 !1 +!2 "m1#02
1"
m2

the neighboring atoms have opposite signs; this case is called optical and
corresponding phonons optical phonons.
It can be again shown that the energy of the system can be written as a sum of
energies of independent quasiparticles (phonons) and thus it is again given by
equation (PH10).

Three dimensional periodic structure

We now deal with a periodic system composed of N particles in the repeat cell
defined by three non-coplanar vectors a1 , a 2 and a 3 . The position vectors of the
particles within the repeat cell are ri (i=1,....,N) and the position vectors of the origins
3

of the cells are R n = ! N i ai where N i are integers. Let us assume that the potential
i=1

energy, U, of the system is a function of the positions of the atoms, ri + R n which we

shall mark R i,n . The atom at the position R i,n is displaced by u(R i,n ) and, assuming
that this displacement is small, we can expand the potential energy into the Taylor
series as follows
3

3
!U "
1
!2U
u
R
+
u" (R i,n )u $ R j,m
(
i,n ) 2 # #
"
"
$
"=1 !R i,n
i,n ",$=1 !R i,n !R j,m

U = U0 +# #
i,n

j,m

(PH15)

where R!i,n and u are coordinates of the vectors R i,n and u , respectively. In
!U
= 0 and thus the first order term in u vanishes. If particle at R i,n
equilibrium
!R"i,n
deviates by u! (R i,n ) from the equilibrium position, the force acting on this particle is
!
Fi,n
=

3
"U
!#
#
=
Fi,n;
$
$
j,m u R j,m
!
"u (R i,n ) j,m #=1

where

$2 U
=# !
$R i,n$R"j,m

!"
Fi,n;
j,m

(PH16)

is the force constant matrix. Equation of motion for the atom at R i,n is then

mi

d 2u! (R i,n )
dt

!"
"
= # # Fi,n;
j,m u R j,m
j,m "=1

(PH17)

The force constant matrix satisfies the following symmetry relations:

(a)
(b)

!"
!"
Fi,n;
j,m = Fj,m;i,n

i,n; j,m

!"
Fi,n;j,m
=0

The relationship (a) follows from the definition (PH16) and the relationship (b)
follows from the requirement of translational invariance that demands that if all
atoms are displaced identically (i. e. rigid body translation is imposed), the energy of
the system must not change. If the system considered possesses inversion symmetry
then
(c)

!"
"!
Fi,n;
j,m = Fi,n;j,m

We assume again that the displacements are plane waves of the type

u(R i,n ) = U i(k )exp $& i(k !R n "#(k )t)')

%

(PH18)

where k is the wave vector. If we add to the vector k a vector K such that
K !R n = 2"M , where M is an integer, then the displacement is not altered. Such
vector K is called a reciprocal vector and it is generally given as
3

K = ! ji bi

(PH19)

i=1

where ji are integers and

b1 = 2!

a2 " a3
a 3 " a1
a1 " a 2
, b2 = 2!
, b3 = 2!
a 1 # (a 2 " a 3 )
a 1 # (a 2 " a 3 )
a 1 # (a 2 " a 3 )

(PH20)

are the basis vectors of the reciprocal lattice. We can, therefore, limit k to a region
such that k ! K / 2 , where K is any reciprocal lattice vector, i. e. to the first Brillouin
zone.
By inserting (PH18) into (PH17) we obtain
3

"#
m i!2 (k)U"i (k) = , , Fi,n;
j,m exp
j,m #=1

{i &('k $(R m % R n ))+*} U#j (k)

(PH21)

and owing to the translation symmetry this equation is the same for any value of n.
We can choose, therefore, n=0 and R 0 = 0 . We now define the dynamic matrix for a
given vector k as follows
!"
D!"
i,j (k) = $ Fi;j,m exp{ik # R m }
m

(PH22)

where the summation extends over all repeat cells.

Equations of motion are now transformed into the system of 3N homogeneous linear
equations for U !i (k)

& & {D!"i,j # m i$ 2 (k)% !" % ij }U "j (k) = 0

3

(PH23)

j " =1

Corresponding eigenvalues are the squares of the frequencies, ! 2 (k) , and the
eigenvectors are the amplitudes U i (k) . For each value of k we obtain 3N solutions
and in the following we mark the frequencies and amplitudes corresponding to these
different solutions ! s (k) and U i,s (k) , respectively, where s=1,2,....,3N. The
subscript s numbers different branches (or bands) of the phonon spectrum.
Owing to the translational invariance, the potential energy U depends only on the
relative positions of the atoms forming the system, i. e. on the vectors

R k,p ! R!,q = R k,p;!,q ; this does not imply that U is only a function of the separation
of the atoms. Hence, the force constant matrix is

Fi;!"j,m = #

k,p;!,q

$2U
$R!i,0;k,p $R"j,m;!,q

(PH24.1)

For central forces, when U is only a function of the separation of atoms, i.e. of
R i,n;j,m , but not necessarily described by a pair potential,

Fi;!"j,m

%
R !i,0;k,p R "j,m;!,q
'
$2U
'
=#
'
k,p;!,q ' $R i,0;k,p$R j,m;!,q R i,0;k,p R j,m;!,q
&

(PH24.2)

0
*
R !i,0;k,p R "i,0;k,p -//2
$U ,,, )!"
//2
+ ()ij)m0)k!) pq #) jk)mp)i!)q0 )
#
,,
2
$R i,0;k,p ,+ R i,0;k,p
R i,0;k,p ///.22
1

Ideal body-centered-cubic lattice with first nearest neighbor interaction

!"

The force constant matrix elements that need to be evaluated are F1;1,m , where vectors
R m are

R1 =
R !1 =

1
2

[111]

R2 =

[1 1 1 ]

R !2 =

1
2

1
2

[1 11]

1
2

R3 =

[11 1 ]

1
2

R !3 =

!"

[11 1]
1
2

R4 =

[1 11 ]

1
2

[1 1 1]

R !4 =

1
2

[11 1]

!"

Owing to the inversion symmetry F1;1,m = F1;1,#m and the invariance with respect to
3

!"
= # % F1;1,k
. Since there is only one atom per unit

!"
F1;1,0

the translations requires that

k = #3
k$ 0

cell the dynamic matrix has only one element:

*

kx + k y + kz

,
+

!"
!"
D1,1
= , 2F1;1,1
& cos

!"
1;1,3 &

+ 2F

cos

kx # k y + kz
2

'

kx # k y # kz

!"
a # 1) + 2F1;1,2
& cos

'

a # 1)
(

'
$
'kx + k y # kz
!"
a # 1) + 2F1;1,4 & cos
a # 1) /
2
(
%
( /.

where k x , k y and k z are components of the k vector.

10

Using the trigonometric relation cos! " 1 = "2 sin 2 (! / 2)

$ !"
k #ky #kz
2 k x + ky + k z
!"
D !"
=
#
a + 2F1;1,2
sin 2 x
a
&2F1;1,1 sin
1,1
4
4
%
k # ky + k z
k + ky #kz '
!"
!"
+ 2F1;1,3
sin 2 x
a + 2F1;1,4
sin 2 x
a)
4
4
(

!"

In the following we write D 1,1 = D

and (PH23) then becomes

& {D!" # m$ 2 (k)% !" }U " (k) = 0

!"

(25)

" =1

There are three solutions for each

value of k. They corresponding to
three acoustic branches, as shown
schematically in the Fig. 5.

Brillouin
zone boundary

Fig. 5 Dispersion relation, or vibrational

spectrum, for BCC. lattice.

11

Phonons at interfaces and free surfaces

The calculation of lattice vibrations is made using so called slab method. In this case
the unit cell (often called supercell) contains either two interfaces or two free
surfaces. The repeat cell containing two interfaces, for example grain boundaries, is
shown schematically in Fig. 6a. The structure studied is then a periodic arrangement
of such repeat cells.

INTERFACE

Fig. 6a. Repeat cell (supercell) containing two interfaces.

The repeat cell containing two surfaces is shown schematically in Fig. 6b. The
structure studied is then a periodic arrangement of such repeat cells.

VACUUM

SURFACE

VACUUM

12

Fig. 6b. Repeat cell (supercell) containing two free surfaces.

! THz

! THz

For the case when the interface is the = 5 (12 0) /[001] symmetrical tilt boundary
and the repeat cell contains 120 atoms, the corresponding phonon dispersion curves
are shown in Fig. 7; a many-body central-force potential for gold was used in this
calculation.

0
0

0
X
-20

10

20

-10

"
0

Fig. 7. Phonon dispersion curves for the repeat cell contains 120 atoms and the S = 5 (12 0) /[001]
symmetrical tilt boundary. Peeled-off branches at low frequencies are acoustic interfacial waves and
branches peeled-off at high frequencies are optical branches associated with the interface.

The corresponding phonon dispersion curves for the ideal crystal, calculated using the
same type and size of the repeat cell as for the case of grain boundaries, are shown for
comparison in Fig. 8.

13

! THz

! THz

0
X
-20

0
0

10

20

-10

"
0

Fig. 8. Phonon dispersion curves for the ideal FCC. crystal when using the repeat cell containing 120 atoms.

Thermodynamic properties associated with phonons

In the quantum mechanical framework the total energy of the vibrating system, i.e. of
the phonons present in this system, is, similarly as in (PH10),

E = ! (N(k ,s)+1/ 2)!" s (k )

(PH25)

k ,s

where N(k,s) = 0,1,2,... is the number of phonons in the state (k, s). The summation
extends over both the branches (bands), marked by s, and the wave vectors k.
The partition function for the phonon system is, using (PH25),

14

"
N(k,s) +1/ 2 !) s (k) %'
"
$
"N(k,s) % %
E
$
$ k ,s
'
$
'& '
Z=
exp $! #
'=
exp $!
'=
$
'
$
'
k
T
k
T
B
B
N(k,s)
$#
'& N(k ,s)
$
'
$#
'&
" N(k ,s)+1/ 2 !) (k )%
" N(k, s)+1/ 2 !) (k) %
$
'
$
'
s
s
exp $!
exp $!
'=
'
$
' k ,s N(k,s)
$
'
kB T
kB T
N(k,s) k,s
$#
'&
$#
'&

(*

((

*(

(PH26)
where the summation extends over all possible occupation numbers
N(k,s) = 0,1,2,...and multiplication includes all states (k, s). The summation over
N(k,s) can be written as
#

# !" (k) &(

) N(k,s)!" (k) ,
%%
+
.
(
s
s
((
exp%%!
exp
!
+
.=
k
T
+
.
%$ 2k BT ((' N(k,s)
B
*
-

exp%%%%!
%$

!"s (k) &((

(
2k BT ((('

1!exp%%%%!
%$

!"s (k) &((

(
k BT ((('

# !" (k)&
since the last summation is a geometrical series with the quotient exp% ! s ( .
$ k BT '
Hence, the partition function is
#

!" s (k) &

(
$ 2k BT '
1
Z =)
=)
# !" (k) &
# !" (k) &
k,s
1! exp % ! s ( k,s 2sinh % ! s (
k BT '
$
$ 2k BT '
exp % !

(PH27)

Employing statistical physics:

Free energy
)
# !" (k) & ,
+
F = !k BTlnZ = k BT ln + 2sinh % s ( ..
%$ 2k BT ('
k ,s +*
.-

(PH28)

02
4
*
#
&(
#
&(-/ 22
2 !) (k)
# "F &(
,
%
!)
(k)
%
!)
(k)
2
2
S=!%%% ((( = kB 21 s coth%%% s ((((!ln ,,2sinh%%% s ((((// 25
%$"T ('
2
%$ 2kB T ('
%$ 2k BT ('/ 22
k,s 22 2kBT
V
,+
. 226
23

(PH29)

Entropy

15

Internal energy

)
,
+
.
+
.
.
!!s (k) ++
2
.
E= F +TS= k BT
+1+
.
"
%
.
$$ !!s (k) ''
k,s 2kB T ++
.
'
exp
(1
$$
''
+
.
k
T
'
$
#
B
&
+*
.202
242
22
22
22
22
1
1
2
2
E=
!!s (k) 12 +
52
"
%
222
$$ !!s (k) ''
2
k,s
exp$$
''(122
22
22
$# k BT ''&
22
26
3

(PH30)

Comparison with (PH25) reveals that the number of phonons in the state (k, s), at a
given temperature T, is

N(k,s)=

1
"
%
$$!!s (k) ''
exp$
'(1
$$ k T '''
#
B
&

(PH31)

i. e. it is given by the Bose-Einstein distribution since any state can be occupied by

any number of phonons.
Specific heat
2

" !E %
CV = $ '
# !T & V

* !( s ()) , 2k T /
+
B
.
= k B0
" !( ()) %
) ,s
sinh 2 $ s '
# 2k B T &

(PH32)

When the dispersion relation ! s (") , determined by solving equations (PH23), is

known, all the above-mentioned thermodynamical quantities associated with lattice
vibrations (phonons) can be evaluated.

16