Quantum Theory of Harmonic Crystals

Introduction
Classical situation we have shown that classical coordinates, us(R), and momenta,
Ps(R), can be transformed to new set in which eqs. of motion are those of an
assembly of independent Simple Harmonic Oscillators (SHOs) of frequency s (k )
for each value of k .
Complex interacting many-body problem reduced to a set of simple independent
collective excitations; results from periodic lattice and identical cells
Quantum mechanically, allowed energies of a (1D) simple harmonic oscillator are
given by En = ( n + 12 ) , where is the frequency of the oscillator (more later).
Now we use general QM result for energy density
Ei e Ei
1
u = i
V

Ei , =
k BT
i e

Here Ei is energy of ith stationary state of the crystal,

at temperature T, and is over all stationary states.

e Ei

is the statistical weight of state Ei

Quantum Theory of Harmonic Crystals

Normal Modes vs. Phonons
We can describe energy of the system in terms of the excitation number nks of normal modes
of wave vector k in branch s. (Classical Picture)
An equivalent corpuscular picture is to designate the quanta of excitation (normal modes
above) by the term PHONONS and to treat the phonons as indistinguishable quantum particles
(bosons in this case). nks is the number of phonons of wave vector k and type s.
(Quantum Mechanical Picture)
To calculate u, introduce the Partition Function
1
f = ln( e Ei ).
V
i

Easy to show that

f
u =

Evaluate f:
Rewrite as

"
$
1 '
"
$
f = ln & exp #!! E"#n ! $% %(
ks
V '#"#nks! $%
(%

! # represents a configuration, i.e., the excitation number of the normal modes at k.

Here !"nks
$

For each k

E!"n ! #$
ks

!
= % (n + )"! s (k )
!
ks

!
ks

1
2

For a particular k energy can only take on values

Is the energy of this configuration.

!
!
!
!! s (k ) 3!! s (k ) 5!! s (k )
,
,
,..........
2
2
2

Quantum Theory of Harmonic Crystals

In Eq. 1

!"n ! #$ specifies particular SET of allowed values of n ! , e.g.,

ks
ks

nk!1s = 100, nk!2s = 75, nk!1s = 50,........... or nk!1s = 10, nk!2s = 1, nk!1s = 0,.......
So we can write in

1 as,

!
"!! ( n ! + 1 ) !! k $
exp
'&
s
2
ks
#
%
!

"#n ! $%
ks

()

ks

Can exchange order of and , provided is over just allowed values of nks (0,1,2,3..)

!
"
1
!
exp #!! ( nks + 2 ) !" s k $%
'
&
!

ks

()

!
nks

Students verify that every term occurring in

!
!
"
$
"
3
1
exp #!! ( 2 ) !" s k % + exp #!! ( 2 ) !" s k
&
!
ks

()

2 also occurs below (exactly once)

!
$ + exp "!! ( 5 ) !" k $ +........
s
2
%
#
%

()

()

! %
" !
But the series in ( ) above is a convergent geometric series of ratio exp $! !" s k '
# 2
&
! %
! %
" !
" !
So
exp $! !" s k '
exp $! !" s k '
1
# 2
&
# 2
&
=
and
thus
f
=
ln
!
!
3
(
(
!
!
"
%
"
%
V
1!
exp
!
!
!
"
k
ks
ks 1! exp ! ! !" s k
s
#
&
#
&

()

()
()

()
()

Quantum Theory of Harmonic Crystals

And

as ln = ln

!& .
*
# !
exp
!
!
!
k
%$ 2 s (' ,,
"f
1 "f ,,
u=!
=!
+) ln
! /
"!
V "! , ks! 1! exp #!! !! s k & ,
$
'
,,0

()
()

!
!
)
1&
1#
!
u = '% !! s (k )"ns (k ) + 2 $*
V ( ks!
+

Write out ln(quo6ent) and

take deriva6ve
Where

!
ns (k ) =

1
!
! !! s ( k )
e
!1

Therefore

is the Bose-Einstein distrib. function,

the mean excitation number of mode ks,
or the ave. # of phonons of type ks,
at temp. T

!
! 1
1 1
"! (k )
equil.
u=u
+ ! !! s (k ) + ! ! !! s( k! )
V ks! 2
V ks! e s "1
Indep. of T
-- Zero pt. energy

Approaches 0
as T 0

All T-dep,. (hence sp. ht.) comes

from 3rd term

Note: could start with nks, write ave. energy as U = ks Eksnks, etc.

Quantum Theory of Harmonic Crystals

General expression

!
#
1
! !! s ( k ) &
cV = ) % ! !! ( k! ) (
V ks! !T $ e s "1'

Depends on
details of s(k)

Limiting cases

!
1
>> !" s (k ) (arg. of exponent in 6 is small --- expand in series, and
High T:
!
then use binomial expansion.) Take der. after doing this.

3N
cV =
kB = 3nkB
V

Dulong and Petit

(classical result); additional terms in series
expansion give Quantum Corrections

!
k
T
<<
!
!
(
k
) First convert to integral (dense set of allowed k-values).
Low T: B
s

$1
'
lim V!" % # F(k)( =
& V k!
)
Then

cV =

!
$#
!T s

dk

( 2! )

!
!
dk !! s (k )
!
3 ! !! s ( k )
(2! ) e
"1

Comes from cyclic b.c.s and

determining volume in k-space
occ. by ONE allowed state
Integral is over first BZ (or
suitable equal vol. k-space equal

Quantum Theory of Harmonic Crystals

Comments (low T):
1) at low T phonons with kBT << s will contribute negligibly to cV (exp in
denominator becomes very large.)
2) Acoustic modes (s 0 as T 0) -- some modes always contribute
(cant satisfy kBT << s for those modes)
Simplifications:
1) Ignore opt. modes (bounded from below)
2) Acoustic modes
!replace s (k) for 3 acoustic branches by long
!
wavelength result ! s (k ) = cs (k )k (OK as long as kT << energies for which there are
appreciable deviations from linearity.)
3) Replace integral over first BZ by integral over all k.
(large k-contributions are negligible)
Replace this

!
! s (k )

!
! s (k )

L
T
T
L
T
T
ZB

Schema'c for p = 2

ZB

By this

!
k

ZB

Schema'c for p = 2

ZB

!
k

Quantum Theory of Harmonic Crystals

low T (cont.):
With previous simplifications at very low T:
7

dk cs (k )k

cV =

3 s ( k )

T s all k space (2 ) e
1

Solid angle
element

Use spherical polar coord. dk k2dkd ; and let x = cs(k)k

4

(k BT ) 3 x 3 dx
1 1 d 1
3
cV =
,
where
=

3
2 x
3
T (c ) 2 0 e 1
c
3 s 4 cs (k )

4
15

Then
8

3
4
(k BT ) 2 2 2 k BT
=
cV
k B

T (c )3 10
5

CV T3
Very important result

Quantum Theory of Harmonic Crystals - Debye

Intermediate T - Debye Interpolation Scheme:
1) Replace ALL branches of vibrational spectrum with three branches,

each with same disp. rel.

(k ) = ck
2) Replace Integral over 1st BZ with integral over sphere of radius kD chosen
to contain exactly N allowed values of k (N = # of ions in xtal). Leads to

(2 )3 N = 4 k 3
V

Vol. of
1st BZ

3 branches

k D3
or n = 2
6

Vol. of Debye
sphere

cV =
T

3c
2
2

And using 9 in 7

kD

k 3 dk
0 e ck 1

10

Now dene Debye Frequency : D = ck D

Debye Temperature : D =

D ck D
=
kB
kB

Used sin
d d = 4

Quantum Theory of Harmonic Crystals - Debye

With these deni'ons Eq. 10
becomes

3c
cV = 2
2

kD

k 3 dk 3k B
0 T e ck 1 = 2 2

kD e

ck
k BT

(e

c 2 4
) k dk
k BT
ck
k BT

1) 2

ck
kBD
=
x
,
and
writing
k
and
dk
in
terms
of
x
;
with
k
=
LeAng
D
k BT
c

The above can be wriEen
cV in terms of single
3
xD = D / T
4 x
3k B T 3
x e dx
empirical parameter, D,

c
=
k
11
V
0 (e x 1) 2
determined from Qng
2 2 D
experimental data.

Limits

Low T: T << D , and D ,

T


So

4 4
=
15

T
T
12 4
= 234nk B

cV =
nk B
5

D
D

As in general
case
3

12

Compare with Low-T limit of general formula6on (Eq. 8 )

4

T 2 2 k BT
12
c
2
3
=
cV =
nk B
k B
or, as D = k D , we recover 6 n = k D
5
5
kB
c
D

Quantum Theory of Harmonic Crystals - Debye

High T: T >> D , integrand (x << 1) - - ser. expansion for exp. and binomial expansion :
3

T 3
k
cV = 9nk B

D /T

D /T

T x 3
x 4 e x dx

9nk B
(e x 1) 2

D 3 0

= 3nk B

Classical Result

Physical Interpretation and comments:

1) kD measure of inverse interparticle spacing
2) D measure of maximum phonon frequency
3) D temperature above which ALL modes begin to be excited
thermally, and below which all modes begin to be frozen out . A Temperature that
VERY APPROXIMATELY separates classical from quantum regimes.
4) NOTE: D D = ckD, where c is sound velocity, the slope of(k) vs. k.
As we have seen, in long wavelength limit (k) = a[K/M]1/2. So D [K/M]1/2. This
means that hard materials (large K) like diamond have high Debye temperatures
(particularly if they have atoms with light masses like Carbon; while soft materials
like Pb and In have low Debye temperatures (particularly if they are comprised of
heavy mass atoms. This is directly reflected in the frequencies of optical modes.

D (2)

(k )

Large slope (2)

D (1)

kD

ZB

Small slope (1)

!
k

Quantum Theory of Harmonic Crystals - Einstein

Einstein Model:
Previous discussion for monatomic crystals. In Debye model of polyatomic xtals, optical
branches of the (k) spectra represented by high k-values of the same linear expression
(k) = ck , whose low k-values give acoustic branch. More realistic to apply Debye model only to
acoustic branches, and represent optical branches by single frequency (indep. of k). (Einstein )

Pictorial comparison: (Debye vs. Einstein 2D sq. diatomic latt. primitive cell
separation = a)
ky

Debye circle (area = BZ1+ BZ2)

kD

1st BZ

kx

2nd BZ

Pure Debye:
First 2 BZs
represented by
circle (radius kD)
having same area, 2
[2/a]2. Entire
spectrum replaced
by linear (k).

Op'cal Branch

/a

kD 2/a

Debye circle (area = BZ1)

ky
kDE

1st BZ

Op'cal Branch
E

Debye/Einstein:
First BZ replaced by
circle (radius kDE)
having same area,
kx
[2/a]2 ; linear (k)
within circle. Optical
branch replaced by
E (a const.) within
the circle.
Constitutes Debye
model for acoustic
branches and
Einstein model for
optical branches

/a kDE

Quantum Theory of Harmonic Crystals - Einstein

In Debye/Einstein Model density appearing in Debye formula must be taken
to be density of prim. unit cells, and then the strictly Debye result will give
contribution of acoustic branches to cV. (recall that acoustic modes correspond
to vibrations of unit cells).
n
In addition, each opt. Branch will contribute k TE
to the energy density
(e

1)

in the Einstein approx. (straightforward to show this).

Einstein Model Result:
2

cV ( Einstein) =

pnk B ( E / k BT ) e E / k BT

(e

E / k BT

p is # of
branches

Characteristics:
1) Well above E = ( E / k B ) each opt. mode contributes a const. (kB) to cV (Dulong and Petit).
2) At low T ( E / k BT ) >> 1 in denom. exponent is >> 1, so
2

cV ( Einstein) pnk B ( E / k BT ) e E / k BT ,
and this contribution is exponentially small at low T.
Note: Einstein proposed this model of sp. heats of solids to explain observed behavior of
sp. heats (T3). Doesnt work in general decreases far too rapidly. However, works
reasonably well for narrow bands of optical modes.

Quantum Theory of Harmonic Crystals Density of Normal Modes

Often have to deal with lattice properties that depend on summing over all k and s. (Also
in electronic properties), e.g.,

1
1
dk
Q s (k ) = V s (2 )3 Q s (k ) , 13
V k , s

(k
) is some function of frequency, which itself is a function of k. Convenient
Where
s

to transform to equivalent frequency interval and integrate over frequency.

Introduce density of normal modes - phonon density of states (DOS) g() defined such
that g ( )d is number of normal modes (phonons) in the infinitesimal range d between
and and + d, divided by volume of crystal.
Then integrals like 13 can be written

q = g ( )Q( )d.

14

Comparing 13 and 14 we can show

that
!
!
dk
g(! ) = # "
! " ! " s (k ) .
3
( 2! )
s

Much easier way of getting g() for isotropic situation.

1 dN 1 dN dk 1 dN
g ( ) =
=
=
V d V dk d V dk

Think of Q as funct.
of only here

15

Plug 15
into 14
;
interchange order of and
integral, and use prop. of
-funct

d , and (3D) dN = V d 4 k 3 = V k 2 ; so

dk (2 )3 dk 3
dk
2

What does this look like for long

wavelength modes ( = ck)?

k2
g ( ) =
2 d dk

Quantum Theory of Harmonic Crystals Density of Normal Modes

A&M provide another useful representation (for anisotropic mode dispersion);
Use g()d is just # of allowed modes (ks) in freq. range between and + d divided by vol.
of xtal. But this is just vol. of k-space cell (axes along prim. BL axes) with s(k) +d
divided by vol. of k-space per allowed k.
Defines shell in k-space. Convert to surface
integral and get
16

Integra6on is over that

surface in rst BZ on which
s(k) =

dS s
1
g ( ) =

3
(
)
2

s ( k )
s surface

Because s(k) periodic there are values of k (typically at BZ boundaries) for which the
denominator (group vel.) vanishes
Van Hove Singularities in DOS. -- also
happens in electronic case. Important in phonon and electronic properties (optical in
particular).
We can do everything weve done previously (total energy, specific heats, etc. in terms of
level density (usually called the density of states (DOS), e.g., Debye approx.
Take all three branches to have same dispersion, s(k) = ck, and all wave vectors
!
assumed to like within sphere of
dk " 4! k 2 dk
! radius kD
dk

3
gD (! ) = 3 "
!
"
!
ck
=
(
)
3
2! 2
k<kD ( 2 ! )

17

3 !2
, ! < ! D = ckD
g(! ) = 2" 2 c 3
0, ! < ! D

kD

"k
0

dk" (# ! ck )

gD()

Area = tot. # of
allowed states in
1st BZ

3 kD2
2! 2 c

Quantum Theory of Harmonic Crystals Quantizing normal modes

Now examine in more detail the concept of PHONONS (more than just
En = (n + ) ).
First examine the Hamiltonian for a 1D simple harmonic oscillator and consider
the OPERATOR APPROACH and commutation relations for obtaining the
allowed energies and eigenfunctions.
Then generalize this to 3D and a periodic lattice to consider how to apply the
simple 1D results to phonons.
+
This involves the CREATION and ANNIHILATION operators a and a .

Review: Simple Harmonic Oscillator

Hamiltonian

2
2

p
p
1
K
H =
+V (x) =
+ m! 2 x 2 , where ! =
,
2m
2m 2
m
with K the spring constant and ! the characteristic frequency.

Schroedinger Eq.

p 2
1
u + m! 2 x 2u = Eu
2m 2

Commutator Bracket [ p, x] = ( p x ! xp ) = !i!

Rewrite Hamiltonian
1

(m x ip ) (m x + ip ) 1
H =
(m x ip )(m x + ip ) +
=

+
2m
2
2
2m
2m

Define Annihilation and Creation Operators

(mx + ip )
(mx ip )
a =
; a + =
2m
2m
So

+ 1

H = a a +
2

Very simple form

Simple Harmonic Oscillator (Cont.)

Properties of Creation and Annihilation Operators

[a, a + ] = 1; [a + , a + ] = 0 = [a, a ]
And, using commutator identity
[ A , B C ] = B [ A , C ] + [ A , B ]C ,

can show that

[a , a + ] = 2a +
3
2
[a , a + ] = 3a +
:
n
n 1
[a , a + ] = na +

From properties of operators, and

H un = Enun ,

can show that

a + ]u + a + ( Hu
), and that [ H,
a + ] = !! a +
H (a +un ) = [ H,
n
n
thus
H (a +u ) = (E + !! )(a +u )
n

similarly

H (aun ) = ( En )(aun )

Shows that if un is e-f of H with e-val En, (a+un) is also e-f of H , but
with e-val En +

In General, (a+un) is e-f of H with e-val En +

of H with e-val En n .

n , and (aun) is e-f

Simple Harmonic Oscillator (Cont.)

Now assume that system has ground state, u0, with energy E0, and consider
Clearly

H (aun ) = ( En )(aun )
au0 = 0, and we can use this to generate u0 .
1 m 2
u0 ( x ) = N 0 exp(
x ) , where N 0 is normalization .
2

Use a + to to generate u1, u2, etc.

Can get e-values without knowledge of explicit e-fs.

= !! (a + a + 1 )u = 1 !! u , ! E = 1 !! .
Hu
0
0
0
0
2
2
2
Generate excited states with a + :
1
+

a
u
,
and
E
=

(
+ n).
nth excited state is
n
0
n
2
so e-vals are:
Can Generate the
normalized e-f s from

1
En = (n + ).
2
+

un = cn a u0 , and un *u n dx =1 :
+

m
1 +n
get u n =
a u0 , where u0 =

n!

1/ 2

exp(

1 m 2
x )
2

Simple Harmonic Oscillator and Phonons

Summary

SHO energy levels

H = (a + a + 12 )

[a, a ] = 1
+

H un = (n + 12 )un
1 +n
a u0
n!

( )

un =
*
n m

u u
u

dx = nm

n = 3
n = 2
n = 1
n = 0

=1

How do we apply this to phonons?

Normal modes
18

H =

1 2 1
P ( R) + 2
u
(
R
)
D
(
R
R)u ( R)

2M
RR

Define: 1) Phonon Creation operator

1
a k+ =
N

ik R

M (k )u ( R) iP( R)

(k )

2M (k )

2) Phonon Annihilation Operator

1
a k =
N

ik R

M (k )u ( R) + iP( R)

(k )

2M (k )

Take (k) and (k) to

be angular freq. and
pol. vector of
classical normal
modes

Simple Harmonic Oscillator and Phonons

Commutation Relations

[u ( R ), P ( R)] = i

RR

[u ( R ), u ( R)] = 0 = [P ( R ), P ( R)]

Can show that

ik R

Leads to

0, k not RLV
N , k is RLV

[a , a ] =

k k

[a , a ] = 0 = [a , a ]

Express P and u in terms of a and a+

Use

ik R

1

+
(k ) ( k ) =

u ( R) =
2M (k) (ak + ak ) (k )e
N

k

R eik R = 0

ik R

i
M (k )
+

P( R) =
2 (ak ak ) (k )e
(k ) = (k )
N k

(k ) = (k )

19

Simple Harmonic Oscillator and Phonons

Substitute Eqs. 19 for P and u in terms of a and a+ into Hamiltonian 18
1
2M

Kinetic Energy

1
R P ( R) = 4 (k ) ak a+k a +k ak
k

1
k + a +k a a k+

(
k
)
a

k
4 k

)(

Potential Energy
Add these to get H (use

(a )(a

)(

)= (a )(a ) )

k ak+ + a k+ a
H=

(
k
)
a
k
2 k

+
Now use [ak , ak ]= 1 , and include branches (s)

+
1
ks a +
H =

(
k
)
a

ks
2

ks

20

Sum of 3N indep. Harmonic osc. (N values of k and 3 branches)

Eigenvalues are sum of individual eigenvals. and e-functions are products. Therefore
specify eigenstates of system by set of 3N quantum numbers, nks, one for each of 3N
independent harmonic osc. Hamiltonians

E=

(
k
)
n
+
ks

ks

Quantum Harmonic Crystals Measuring Phonon Frequencies and

Dispersion
Two primary Probes used: 1) neutrons; 2) photons (inelastic scattering processes)
LO

Typical Frequencies:

Width depends
on material

TO

Note: opt. modes can be

observed directly in the IR
(reec6on, transmission)

Different freq. of longitudinal

and transverse modes at k 0.

ZB

Examples: Optical modes

KBr 5 x 1012 Hz 170 cm-1 21 meV
III-V semiconductors -- range from about 200 400 cm
25 50 meV
Acoustic modes
k 0 at long wavelengths
Zone Boundary typically < optical mode freq. (7 20 meV)

Now examine dispersion relationships for Neutrons and Photons:

Neutrons: En = p2/2Mn (quadratic) Mn = 1836me
Photons: E = cp (linear) c = 3 x 1010 cm/s = 3 x 108 m/s
Drama6cally dierent over range of k-val. appropriate to rst BZ of typical crystals
(/a - 2/a, with a = 2 x 10-8 cm = 0.2 nm)

Quantum Harmonic Crystals Measuring Phonon Frequencies and

Dispersion
Log10E (E in eV)

6
4
2

0
- 2
- 4
- 6
- 8
-10
-12
-14
-16
-18

Typical op6cal
phonon
energies

En

0 2 4 6 8 10

Typical
ZB wave
vector

Will refer to this later

Points:
1) For a given momentum about 8
orders of magnitude dierence
in energy
2) For a given energy about 6 7
orders of mag. dierence in
momentum

Log10k (k in cm-1)

Crystal Momentum
For phonon of wave vector k, due to a symmetry of the ion-external field /particle interaction,
so-called CRYSTAL MOMENTUM = K + k is conserved (K is a RLV). Weve seen special
Case of this for static situation ( u = 0). X-ray diffraction ,von Laue, where q q = - K. Here
Xtal as a whole takes up mom. K (recoils). (estimate order of mag. of recoil -- < 10-19 cm/s)

Quantum Harmonic Crystals Crystal momentum

Can show explicitly for Neutron scaEering the symmetry that leads to mom. conserva6on law.
Note: Total mom. (par6cles + crystal ignoring periodic pot.) conserva6on comes from invariance of
tot. Ham under transla6ons . This is transla'onal invariance. Real system NOT COMPLETELY
TRANSLATIONALLY INVARIANT PERIODIC. Only when r0 = R0 with R0 a BL vector is it invariant.

So we assert that if ri ri + R0 (n = 1,2,3,4,.....) (particles)


u ( R) u ( R R 0 );

u(R)

P( R) P( R R0 ) for all R

u ( R) = r R; r r + R0


so u ( R) r + R0 R = r ( R R0 )

So for ionic coord. This

amounts to simple
permuta6on of ionic
variables

Also, the very short ranged interac6on term in e.g., neutron-ion interact.
is invariant.

Here w is very short-ranged pot.
H
=
w
(
r

u
(
R
))

n i
A
between neutron and ion.
R

Neutron coord.

Ion coord. (R + u(R))

Make transforma6on: r r + R0 ; so rIon rIon + R0 , where rIon = R + u ( R); u ( R) u ( R R0 )

H n i
w(r + R0 R u ( R R0 )) =
w(r ( R R0 ) u ( R R0 )

As sum is over all BL vectors, B

= A
.

Quantum Harmonic Crystals Measuring Phonon Frequencies and

Dispersion
Fundamental physics -- symmetries of Hamiltonian imply conservation laws
(this symmetry (invariance of Ham under translations by BL vector --- k + K is
conserved. Write as

p p =
k nks + K

ks

par6cle

# of phonons excited

In words: incident
momentum = scal.
mom. + Crystal mom. +
RLV (x )

Crystal momentum defined as times its wave vector k; crystal mom.

conserved to within an additive constant K . This is weaker than usual mom.
Conservation (symm. is LESS that than of empty space).
Now combine crystal momentum conservation with energy conservation.
And represent scattering events pictorially.
Electron, neutron, .. any particle
Photon
Phonon
p p
Look at neutron scattering
Momentum p
Energy E = p2/2Mn

k s + K

Incident on xtal; interacts

strongly only with nuclei; will
pass thru xtal and emerge with
mom. p and energy
E = p2/2Mn

Quantum Harmonic Crystals Measuring Phonon Frequencies and

Dispersion
Ini0al state
Crystal in some state with set of phonon occ. #s.
[nks]; neutron with initial mom. p, energy E = p2/2Mn.
Final state
Crystal in state characterized by [nks]; neutron with p and energy E = p 2/2Mn.
Conservation of Energy

Assume harmonic approx. for xtal

s (k )nks + E = E + s (k )nks
ks

ks

or E E =
s (k )nks ; nks = nkx nks

ks

Conservation of Crystal Momentum

p+
k nks = p +
k nks K

ks

ks

or p p =
k nks + K

ks

Quantum Harmonic Crystals Measuring Phonon Frequencies and

Dispersion
Some specific cases:
Case 1): Zero-phonon scattering (final state = initial state -- for crystal)

Write for particle: p = q; p = q

Precisely the von Laue condi6on. Elas6cally scalered

neutrons are found only in direc6ons that sa6sfy Bragg
condi6on. Same structural informa6on as X-rays in this case

Then E = E ( p = p ); and q = q + K

Case 2): One-phonon scattering (very important)

Absorp'on of one phonon

Ini0al state

E, q

(1)phonon s (k ), k

ks

Final state

neutron

neutron

E , q

phonon no added or subtracted phonons

Energy cons. E = E + s (k )

p
=
p
+

k
+

K
Mom. cons.

n = 1

ks

Emission of one phonon

q q
ks

Very similar
students do this

Equilibrium
phonon number
assumed to be
unchanged

Quantum Harmonic Crystals Measuring Phonon Frequencies and

Dispersion
Notes:
When we subst. for k in energy expression, we can ignore K, because s(k) is periodic
function in reciprocal space, with period = shortest RLV (K) in direction of interest.
So, procedure is to solve momentum eqs. For k K (equiv. to k), and subst. in energy eq.
for s(k) gives s((p p)/ ))
single eq. for abs. and single eq. for emission.
Absorption

p2
p2
p p
=
+ s

2M n 2M n

Emission

p2
p2
p p
=
s

2M n 2M n

We know p and p2/2Mn; measure 3 components of final neutron momentum and final
neutron energy. In general, three components and energy define 3D surface, and by
specifying a direction (detector angle) determine point on this surface. See neutrons
scattered by one-phonon processes at a few discrete energies, E. Use spectrometer to
measure as function of neutron wavelength ( = 2/q); Determines |p |; knowing direction,
can construct E - E, and p - p = k . ( = (p 2 - p2)/2Mn -- plot this vs. k = (p - p)/ .
(homework problems on graphical solutions for simple cases). Determine k and s(k ) from
whole series of angles, orientation of crystal and neutron energies.

Quantum Harmonic Crystals Phonon Frequencies from Inelastic

Light Scattering
Photon Scattering: (Inelastic Light Scattering)
Usually Visible Light. 1) Raman Scattering (Optical Phonons); 2) Brillouin Scattering
(acoustic phonons). Can only measure phonons at very small wave vectors (near k = 0)
What is k for a visible photon (wavelength 500 nm)? Wave vectors for photons inside media
(solids) differ from those in vacuum (index of refraction, n; qin = nqout ).
Raman Scattering
Absorp'on of one phonon

nq

nq

!
!! + !! s (k ) = "! !
" " "
"
!nq + !k + !K = !nq!

Emission of one phonon

nq
q photon wave vector in vacuum
k phonon wave vector in vacuum

nq

!
!! ! = !! " !! s (k )
!
! ! !
"nq! = "nq " "k + "K

Freq.
shised
UP

Freq.
shised
DOWN

As q, q are very small, xtal mom. conserv. only sa6sed for K = 0.

In this case:
Max. energy of OPT phonon
nq
! ! $ ! 2n" $ ! ! $
k
100 meV; Photon energy about
k = 2nqsin # & = #
& sin # &
/2
nq

2 eV, ( ; |q| |q|) ;so

triangle is approx, isoceles.

The tricky part

"2% " c %

"2%

Dir. of k det. from triangle, and

(k ) from measured (small)
change in photon frequency

Quantum Harmonic Crystals Phonon Frequencies from Inelastic

Light Scattering
Brillouin Scattering (Acoustic Phonons)

Frequency shis

!
!
! " ! = ! s (k ) = #!
absorp6on
!
#!
cs (k )k = #!; or k = !
cs (k )

Speed of sound

! !! " c % " " %

c
(
k
$ ' csc $ '
Equate C
and D
s ) =
2! # n & # 2 &
Laser Frequency

Frequency shi^ very small; n 3, cs(k) 5 x 105 cm/s; = 2c/ ( 500 nm)
! " n % "! %
" 3 %
!! !"
=
= 2cs (k ) $ ' sin $ ' ( 2x5x10 5 x $
(1) ( 10 )4
10 '
#c& #2&
# 3x10 &
!
"
2" x3x1010
!=
; so # = 6x1014 Hz, and "# # 60GHz
!5
5x10

Very small shis;

requires Fabry-
Perot
spectrometer