Classical Theory of Harmonic Crystals

Introduction
Relax rigid lattice assumption of all preceding discussion. Investigate motion of
lattice ions/atoms, etc. about equilibrium lattice sites.
Two Assumptions in what follows:
!
1) Mean equilibrium position of each ion is a BL site, and R denotes
this position.
2) Excursions of each ion away from its equil. pos. are SMALL
compared with interionic spacing. (define more precisely in what follows)
Leads to Harmonic approximation
to make life easier

!
!
Now: Denote position of ion whose mean position is R by r! ( R) .
! ! !
! !
! !
At any given time r ( R) = R + u( R) , where u( R) is deviation from equil. pos.
Internal Energy:

1) Initially, assume only pairwise interactions, i.e., pair of ions separated by r ,

!
contributes ! (r ) to P.E. of crystal.
2) Static approx. (like last chapter)

Classical Harmonic Crystal

Total P.E. is just sum of P.E.s of all distinct pairs.
! !
!
!
! ! P.E. at site R
1
1
U = # ! ( R ! R") = #! ( R") , where ! ( R!) = $ ! ( R " R!) due to all
! !
2 R,! R!"
2 R!"
R# R!
other ions

All BL vectors

!
!
But all BL sites are equivalent, so "! R! = N! R! and thus
!
R!

( )

( )

! !
!
N
N
R - R is also BL vector and we
U = $ ! R ! R" = $! R
are summing over all BL vectors.
! !
!
2 R#
2 R#0
R"
Now relax static approx.
!
! !
Atom whose average pos. is R will generally be found at r ( R)
Thus

( )

! ! ! ! ! !
! ! ! !
1
1
U = #! r ( R) ! r ( R") = #! R ! R" + u( R) ! u( R")
2 R!R!"
2 R!R!"
! !
P.E. now depends on dynamical variables u( R) .

Hamiltonian for dynamical system, H = T + U, given by

! ! 2
! P( R)#
"
$
H =%
+U
!
2M
R

!
R ! !
r ( R)

! !
u( R)

Classical Harmonic Crystal

Harmonic Approximation

! ! ! !
! !
1) Assume u( R) are small in sense that u( R) ! u( R") is small for all atom pairs
! !
that have appreciable interaction, ! R ! R" .

2) Expand P.E. in 3D Taylors series of the form

! !
! ! ! ! 1 ! ! 2 ! 1 ! ! 3 !
f (! + a) = f (! ) + a !f (! ) + (a !) f (! ) + (a !) f (! ) +....
2
3! !
! ! !
!
! !
!
Apply this to each term of 1
with R ! R" = ! , and u( R) ! u( R") = a :
! ! !
! !
! ! ! !
(! ( R ! R") + u(
, order
First
R) ! u( R") #! ( R ! R") +
*
1 *
U = /)
! 2 ! !
! ! !
!
!
1
!
!
3
$
&
2 RR" *
u( R) ! u( R") #' ! ( R ! R") + O(u ) +....*
%
+
. 2nd order
2

Zeroth
order

N
=
2

from previous static result

(
R
)

R 0

Rewriting on next pg

Classical Harmonic Crystal

U =

N
2

( R) +

R 0

1
1

) + O (u 3 ) + ...
u
(
R
)

u
(
R
)

(
R

R
)
+
u
(
R
)

u
(
R
)

(
R

2 RR
4 RR

[(

) ]

Linear in u ( R) u ( R) :

Coeff. of u (R) is

( R R) ; but this is just minus (F = grad P.E.), the force on atom at R

R

exerted by ALL other atoms when at their equil. positions;

Eval. at
this R
order

This 0 --- no net force in equil. -- Ditto for atom at R

Linear Term = zero

Lowest-order non-vanishing correct to equil. is quadratic! The harmonic approx.

retains only this term, U = Uequil. + Uharm., where
U

harm.

1
=
4

2 ( r )
u ( R ) u ( R) ( R R) uv ( R ) u ( R) , where ( r ) =
r r

RR
, = x , y , z

Frequently ignore Uequil. (constant, indep. of us and Ps), and then U = Uharm.
Starting point for essentially all theories of lattice dynamics. Further corrections u3 and u4
are known as anharmonic terms.
Harmonic P.E. usually written in more general form:

harm.

1
=
2

u ( R ) D ( R R)u ( R)

RR

, = x , y , z

Relaxes restriction
to only pairwise
interactions

Classical Harmonic Crystal

U harm . =

1
2

)
u
(
R
)
D
(
R

R
)
u
(
R

RR
, = x , y , z

This is equivalent to prev. expression for Uharm. (assuming pairwise interactions) if we take

D ( R R) = RR

(
R

R
)

(
R
R)

Not in sum over R

Demonstrating the equivalence is a

straightforward but tedious exercise

Eq. 2
represents general interaction (through D) between displaced ion at R
with displaced ion at R . It need not be simple, direct pairwise interaction. Could
take place via another mechanism, e.g., distortion of electronic arrangement around
ions (contributes to P.E. of xtal), with arrangement depending on ionic configuration.
Also Coulombic interaction among ions is not simply pairwise, e.g., displacement of
ion i directly affects ion j, but also affects ion j through interacting with ions k, l, m, .,
and their direct interaction with j.
Generally very complex.

Classical Harmonic Crystal

To simplify, make Adiabatic Approximation:
Electronic arrangement, and hence contrib. of valence electrons to total energy
depends in detail on arrangement of ion cores. When ions displaced from equilib.,
electronic wavefunction can be deformed --- hard to calculate so we make
adiabatic approx.
Note that electron velocities in atom/ion are typically much greater than the
Velocities of ions in solids: velec. 106 m/sec; vion 103 m/sec. So, we assume that
at any instant the electrons have adjusted to the slow motion of the ions and are in
Their ground state configuration they can follow the ionic motion.

Still a tough problem

Classical Harmonic Crystal

Specific Heat of Classical Crystal (want to calc. u(T) = U(T)/V)
Must average over all possible configurations, giving each a weight proportional to exp[-E/kBT),
Where E is the energy of a particular configuration of all ions.
From Classical Stat. Mech., energy density is
H
U 1 de H
u= =
, with = 1 / k BT
V V de H

Here H is the classical

Hamiltonian of the system

du ( R)dP( R)
du ( R)dP ( R) .
And d is the volume element in crystal Phase Space, d =

Write

in more compact form

1
u=
[ln de H ]
V

Now

H =

2
P( R)
+ U harm.
2M

Ignoring Uequil.

Make change of variables

1
3

2
u ( R) = u ( R) ; du ( R) = 2 du ( R)
3

P( R) = P ( R); dP( R) = 2 dP ( R)

1
2

R,

1 u ( x)
ln u ( x) =
x
u ( x) x

Be careful with
notation in the ! !
following: u and u( R)

1 1 1
(du represents du x du y du z = 2 2 2 du x du y du z )

Classical Harmonic Crystal

With some manipulations

de

P
( R) 2 1
3 N
=
du ( R)dP ( R) exp
u ( R) D u ( R)

2
M
2

Here N is # of
Bravais Lattice
points

Integral is indep. of T ()
u=

1
1
[ 3N ln + ln(const.)]
[ln 3 N term indep. of ] =
V
V

u=

[3N ] = 3nk
V

cV =

u
= 3nk B
T

n = # ions per
unit volume

Dulong-Petit Law

Does not agree at all with experiment (particularly at low T)

1) at low T, cV drops well below this value, 0 as T 0.
2) Even at higher T substantial discrepancies (largely because of Harm. Approx.)

Need for Quantum Theory

Classical Harmonic Crystal (cont.)

Need quantum theory, but must understand classical problem ---- Harm. crystal
represents special case of general class of problems concerning small oscillations.
(quadratic in P and u). General solution for N ions is represented as superposition
(or linear comb.) of 3N normal modes of vibration, each with its characteristic
frequency, .
Carry over to quantum mechanics solution of harmonic osc. So analysis of normal
mode problem for lattice ions is helpful.
Initially consider only 1D problems to get ideas across absent the
overwhelming notation.

Normal modes of 1D monatomic BL

Consider linear chain sketched below; BL vectors are just R = na, with n an integer.
Let u(na) be displacement along the line of the ion whose equil. position is na.
Dropping vector notation and considering only longitudinal oscillations.

(n-3)a

(n-2)a

u(n-2)a

(n-1)a

na

(n+1)a

(n+2)a

(n+3)a

static
dynamic

u(na)

Classical Harmonic Crystal (cont.)

For pairwise interactions
U harm. =

1
4

'

!!
RR"
,! =x, y,z

!
!
! !
!
!
#u ( R) ! u ( R")%! " ( R ! R")#u! ( R) ! u! ( R")%
$
&
$
&

e.g., R = (n+1)a,
R= na

Further assume only nn interactions, (R-R = a )

Therefore only non-zero terms are of the form u(na) u([n+1]a), and we
drop the subscripts since its 1D.
U

harm.

1
#2!
2
= K " [u(na) ! u([n +1]a)] , where K =
2
#x 2
n
!
R!

identical for nn interactions

Equations of motion
2,
"U harm.
" )K
$
&
!!
#
#
Mu(na) = !
=!
* (%u(n a) ! u ([ n +1]a )' "u(na)
"u(na) + 2 n#
.

$ "u(n#a) "u ([ n# +1]a ) &

= !K ($%u(n#a) ! u ([ n# +1]a )&'/
!
0
"u(na)
"u(na) '
%
n#

nn

x=a

(x) is P.E. of
two ions a
distance x
apart

Factor of 2 because ! and " are

!
R

= ! $$(a)

n,n+1

A = 0 unless
n=n (and then A=1)
B = 0 unless
n = n+1 (and then B = 1)

Classical Harmonic Crystal (cont.)

So

"U harm.
!
= !K #$u(na) ! u ([n +1]a )%& + K #$u([n !1]a) ! u ( na )%&, and
"u(na)
!!
Mu(na)
= !K #$2u(na) ! u ([n !1]a ) ! u ([n +1]a )%&
Same Eq. of motion as for linear
chain of masses connected by
perfectly mass spring of spring
const. K

Boundary Conditions

For finite # of ions N must specify how ions at ends are to be treated.
Assume very large N (end effects relatively unimportant) and use
Born-von Karmen (cyclic) boundary conditions.
a

Linear chain

Join ions at either end of chain by same spring that connects internal ions.
Assume osc. solns. of form

a
Na
Boundary

u(na, t) ! ei(kna"!t )
a

2a

u(Na, t) = u(0, t); eikNa = e 0 = 1

Boundary
cond.

so kNa = 2! m, and k =
Allowed values
of k

2! m
a N

Classical Harmonic Crystal (cont.)

Very Important Physics
If k is changed by 2 /a (i.e., k k 2/a) u(na,t) is unchanged .

ei ( kna ) ei ( kna ) e

2
i na
a

Example: ( = 4a)

= ei ( kna ) 1
= 4a; k =

k =

2
=
2a

2
2 5
2 4a
; so k = +
= , and =
=
a
2a a 2a
k
5

Amplitude at lattice sites is

the same in both cases

What does this mean??

We can change k by ANY RECIPROCAL LATTICE VECTOR (an integral multiple of
2 /a in this simple case) WITHOUT CHANGING THE PHYSICAL SOLUTION!!!!
(a displacement of the ion in this case)

Classical Harmonic Crystal (cont.)

Summary and Additional Comments
From the preceding, there are just N values of k that provide solutions to the
eq. of motion and satisfy the boundary conditions. Values of k span a range of 2/a
In reciprocal space. We pick them to lie between -/a and + /a to be consistent with
The usual definition of the first Brillouin zone in 1D (bisect nn. vectors of RL, which
have length 2/a.

Now
Substitute assumed solutions for u(na,t) into eq. of motion.
Mu(na, t ) = K [2u (na, t ) u ([n 1]a, t ) u ([n + 1]a, t )]

2K
(1 cos ka )
M

There are harmonic

solutions provided this is
satisfied

M 2 ei ( kna t ) = K 2ei ( kna t ) e ika ei ( kna t ) e +ika ei ( kna t )

or 2 =
1/ 2

1 cos ka
or, using

1
= sin ka
2

(k ) =

and taking the positive root

1
sin ka
2

2K
(1 cos ka ) = 2 K sin 1 ka
M
M
2

Solutions are periodic with period 2/a

k
2! / a

Classical Harmonic Crystal (cont.)

Actual displacements are given by real or imag. parts of u(na, t)

cos(kna t )
u (na, t )
sin(kna t )
Took positive root because is usually considered to be positive and because is an even
funct. of k; above solutions for k and -(k) are the same as those for -k and (k) .
K
1
K
1
sin ka t ) and cos(kna 2
sin ka t ) are the same
M
2
M
2
since cos(x) = cos(-x)
cos(+ kna + 2

Negative root
doesnt add
anything

.
Now there are N distinct values of k (between -/a and +/a, each with a unique frequency; so
There are 2N independent solutions (but only N normal modes) But sine solution is cosine
solution shifted in time by /2 -- can take linear combination of the two normal modes. Arbitrary
Motion of the chain is obtained by specifying N initial positions and N initial velocities so this
is a complete solution. These solutions are waves propagating along the chain with phase
velocity c = /k and group velocity v = /k.
(k)
K
1
(k ) = 2
sin ka
M
2

Long wavelength limit: >> a, or k << 2/a

4K
M

(k ) = 2

K 1
K
ka = a
k
M 2
M
K

k << 2/a
-/a

/a

Zone boundary, (k ) = 2 M sin( 2 ) = 2 M

Group velocity = 0. (standing wave)

Classical Harmonic Crystal Lattice with basis

Normal modes of 1D BL with a basis
One-D lattice with 2 atoms/prim cell. Equilibrium pos. na and na +d.
Assume identical ions (same mass M), but d a/2, so force between neighboring
ions depends on whether their separation is d or a d. Assume also only nn
interactions.
d

a-d
na

(n-1)a

(n+1)a

(n+2)a

(n+3)a

Denotes unit
cell; cells
separated by a

Now denote by u1(na) the displacement of ions that oscillate about equilibrium site
at na
, and by u2(na) the displacement of ions that oscillate about equilibrium site
at (na + d) .
Recall general form for P.E. (generalized a bit and specific to 1D no need for sum).
U

harm.

1
=
4

[
]
[
u ( R) u ( R ) ( R R ) u ( R) u ( R)]

RR
s =1, 2

Added sum over s (basis will yield 2 sums , one for u1s and one for u2s.)
Again a factor of two will arise from assumption of nn interactions and double sum over
R and R (sums are equivalent). As we assumed only nn interactions,

2u
2u
within
between
K>G
R R = d ,
or
( a d );
K =
; G=
2
2
a cell
cells
x d
x a d

( n 1) a + d ( n 1) a = d

na [( n 1) a + d ] = a d

Classical Harmonic Crystal Lattice with basis

d

a-d

(n-1)a
1) Single out ion

na

(n+1)a

(n+3)a

(n+2)a

in cell na, and examine interaction with ion

in same cell.
2

2) Single out ion

in cell na, and look at interaction with ion

in cell (n + 1)a.
2

So
U harm. =

K
2

G
[u2 (na) u1 ([n + 1]a))]2
4

G
2
2
[
]
u
(
na
)

u
(
na
)
+
1
[u2 (na) u1 ([n + 1)a)]
2
2

within a cell

between cells

Equations of Motion (2 sets)

K
U harm.

Mu1 (na ) =
=

u1 (na )
u1 (na ) 2

G
2
[u2 (na) u1 ([n + 1)a)]2
n [u1 (na) u2 (na)] + 2
n

= K [u1 (na ) u2 (na )] nn G [u2 (na ) u1 ([n + 1)a )] n ,n+1

n

K
[u1 (na) u2 (na)]2
4

u ( na )
= nn
u ( na )
u ([ n + 1]a )
= n , n+1
u ( na )

Mu1 (na ) = K [u1 (na ) u2 (na )] G[u1 (na ) u2 ([n 1)a )]

Singled out site at na; nn

interac. ( spring const. G)
with cell at n-1

Classical Harmonic Crystal Lattice with basis

U harm.
Mu2 (na ) =
= K [u2 (na ) u1 (na )] G[u2 (na ) u1 ([n + 1)a )]
u2 (na )
at site na

Solutions of form:

at site (n+1)a

1 and 2 are amplitude and

phase of u1 and u2 (to be
determined)

u1 (na, t ) = 1e i ( kna t )
u 2 (na, t ) = 2 e i ( kna t )

Apply B-vK b.c.

k=

2 m
a N

Now substitute us into Eqs. of Motion

1

[M

[M

2 =

[M

] [

[K + Ge ] + [M

(K + G ) 2 + K + Geika 1 = 0

K +G 1

M
M

Rewriting

This condition yields dispersion relation

3

m is an integer, N is number of unit

cells in chain (there are 2N ions)!

] [

(K + G ) 1 + K + Ge ika 2 = 0

K 2 + G 2 + 2 KG cos ka

] [

(K + G ) 1 + K + Ge ika 2 = 0
ika

(K + G ) 2 = 0

Pair of homogeneous linear eqs.- 2

unknowns (1 and 2 )
(Solutions if det. of coeff. vanishes)

Classical Harmonic Crystal Lattice with basis

Look at amplitudes of displacements:
From

and

2
K + Geika
K + Geika
=
=
, but K 2 + G 2 + 2 KG cos ka = K + Geika
2
1
M ( K + G )
K 2 + G 2 + 2 KG cos ka
2
K + Geika
thus
=
4
1
K + Geika

Consider two limiting cases:

1) k 0, so

2
(
ka )
cos ka 1

K +G 1

M
M

K 2 + G 2 + 2 KG 2 KG

(K + G)
2

Positive Root
+2 2

(ka )2
2

K +G K +G
KG
(ka )2

1
2
M
M
(K + G )

K + G K + G
KG

(ka) 2 + ....
1
2
M
M 2(K + G )

K + G KG
( K + G)

(ka) 2 + ....; so + = 2
O(ka) 2
M
M
M (K + G )

Negative Root
2

K +G K +G
KG
KG

+
(ka) 2 + ....; so
ka
M
M
2M (K + G )
2M ( K + G )

Long modes 2 = +1 for - ; and 2 = -1 for +

Use binomial
expansion on
radical

Binomial expansion
again; also note:
const. plus neg.
quadr. term. (ZB
value < Z. center
Linear in k, and
2 = + 1

2 = - 1

Classical Harmonic Crystal Lattice with basis

2) k = /a, (cos = - 1)
2

1
K +G 1 2
K +G K G

K + G 2 2 KG 2 =

M
M
M
M

Positive Root
K +G K G
K
2K

+
= 2 ; so + =
M
M
M
M

2 = - 1

K +G K G
G
2G

= 2 ; so =
M
M
M
M

2 = + 1

2
+

Negative Root

(k)

2( K + G )
M

KG
Slope =
ka
2M ( K + G )

1st BZ

2
K + Geika
=
1
K + Geika

For k = /a, eika = cos()+

i sin() = cos() = -1

K G
= 1 ( K > G )

So 2 =
1
K G

Motion at k = /a: (eikan = ein; =2a)

2K
M

+ optical modes
d

2G
M

a-d
Within cell ions are out-of-phase
- acoustic modes

-2/a

-/a

k = 2/

/a

2/a

In long limit (>>a) motion is the same cellto-cell

Note: for K = G, no GAP at BZ boundary; just
monatomic lattice with spacing 2a. (left as
exercise)

a-d

Within cell ions are in-phase

1 corresponds to

; 2 corresponds to

Classical Harmonic Crystal Lattice with basis

3) K >> G
1
K +G 1 2
K G K
G 2 2G
2
2
=

K + G 2 KG = 1 +
1+ 2 +
cos ka
M
M
M K M
K
K
K K G

2 1 + cos ka
M M K

For +ignore G/K term in bracket and take plus sign

+

2K
M

1
+
O
(
)

For - keep G/K term in bracket and take minus sign

K
G
K
(1 + )
M
K M
2

2G ka
G
G
1
+
cos
ka

(
1

cos
ka
)
=
sin , and
K
M
M
2

2G
ka
sin
M
2

Amplitudes
G ika
e
2
K
=
1
G ika
1
1+ e
K
1+

For +: 2 = - 1
For -: 2 = + 1

Classical Harmonic Crystal Lattice with basis

Discussion
Optical branch (+) has freq. indep. of k: freq. of single diatomic molecule composed
of 2 mass M ions connected by spring constant K. motions within cell are 180 degrees outOf-phase indep. Of wavelength of normal mode. (G/K 0. so ther eis a small spread

of frequencies over the first BZ.

Acoustic branch (-) is that for linear chain of atome of mass 2M and weak spring
constant G. (compare with monatomic result). Atoms move in-phase with a cell.

Suggests General Charactistics of Motion

Acoustic modes:
All ions within cell move in-phase as units -- dynamics dominated
by interaction between cells.
Optical Modes:
Ions within cell execute essentially molecular vibrations (internal to
cell)mbroadened out into a band by interaction between cells

Classical Harmonic Crystal 3D

Extension to 3D
Matrix/Tensor D

Monatomic BL first
U harm. =

! ! " ! ! ! !
1
u(
# R)D( R ! R")u( R")
2 R!R! "
D(R R) = D(R R)
D(R R) = D(R R)

Make use of symmetries to derive prop. of D(R R)

See A&M

R D( R) = 0

3N Eq. of Mot., one for each 3 components of displ. of N ions

U harm.
= D ( R R)u ( R)
Mu ( R ) =
u ( R ) R ,

Assume harm. Solutions:

Use B-vK b.c. s:

i ( k R t )

u ( R, t ) = e

is complex polarization vector

u ( R + ni ai ) = u ( R ), N = N1 N 2 N 3

Allowed values of k

n5
n1
n2
k =
b1 +
b2 +
b3
N1
N2
N3

Very large integers

Remember, only values of k lying in

primitive cell of RL give distinct
solutions

Next Page

Classical Harmonic Crystal 3D

Subst. assumed solutions into eqs. of motion:

ik R

M = D(k ) , where D(k ) =

D( R )e

D(k) is even function of k and a real,

symmetric matrix.(from above
symmetries)

From matrix algebra - real symm. matrix has 3 real e-vectors that satisfy

e-val. Eq. --- diagonalizes matrix D(k)); 1, 2, 3
D(k ) s (k ) = s (k ) s (k )

e-vectors can be made orthonormal s ( k ) s ( k ) = ss , s, s = 1,2,3

So e-val. Eq. becomes

M s = D(k ) s = s (k ) s
2

3 normal modes with wave vector k will have pol. vectors s(k)
and frequencies

s ( k )
s (k ) =
M

As in 1D case

; when k 0, s ( k ) c s ( k ) k , >> a

In general, in 3D must consider relationships among directions of pol. vectors, ,

and directions of propagation vectors, k.
Isotropic media
Choose one s parallel to k (longitudinal); other two are perpendicular to k (transverse)
Anisotropic media (not so simple)
For k along symmetry axes (3-fold, 4-fold, 6 fold) one pol. can be chosen along k, and
the other two perpendicular (common in cubic matls). Refer to long. And transverse
modes even for general direction where they are mixed not purely long. or transverse.

Classical Harmonic Crystal 3D

3D Lattice with a Basis

(Introduce index to refer to ions in the basis)

OPTICAL MODES

Cells vibrate
as a unit

For each k, 3p normal modes, where p is number of ions in basis

!
Frequencies ! s (k ) (s = 1, 2, .p) are all functions of k with periodicity of RL.
!
Three of 3p branches are acoustic -- ! s (k ) goes to 0 linearly as k
0.
!
Other 3(p-1) branches
are optical -- ! s (k ) ! const. as k
0.
!
Ions vibrate
! s (k )
relative to
Along symmetry directions in
one another
cubic crystals, 2 transverse
L
in cells
T modes are degenerate and lower
T in freq,. than long. mode
L
T
T

ZB

Schematic for p = 2

ZB

!
k

Why are freq. of L modes higher than T?

Additional contrib. to restoring force for L.
Optical due to long range Coulomb
interactions; acoustic due to elastic
restoring forces being smaller for T than for L.

Important points:
1)
2)
3)
4)

Original Eqs. of motion: p atoms/cell, N cells, 3pN equations

Reduce to set of eqs. in k-space; only 3p equations, (for each allowed k, N values of k.
Results in terms of set of independent
SHOs for each k (can always diagonalize matrix D(k))
!
Generate dispersion relations ! s (k ) .