3b Lattice Vibrations PDF

3b.
Lattice Dynamics
Phonons
Thermal energy
Heat capacity
Einstein model
Density of states
Debye model
Anharmonic effects
Thermal expansion
Thermal conduction by phonons
Neutron scattering
G. Bracco-Material Science SERP CHEM 1
Phonons
So far we discussed a classical approach to the lattice vibrations.
Solving the problems of vibrations of atoms in lattice we have found that
coupled harmonic oscillations of atoms give rise to non coupled normal modes
of oscillation

Hamiltonian of a harmonic oscillator: =

+

As we know from quantum mechanics the energy levels of the harmonic

oscillator are quantized.
Similarly any normal mode of the lattice is quantized and the quantum of
vibration is called a phonon in analogy with the photon, which is the quantum
of the electromagnetic wave travelling wave of lattice vibrations
Similarly to photons, phonon number is not conserved: phonons can be

created and destroyed during processes

Phonons
Quantum harmonic oscillators have equally spaced
energy levels with separation =
oscillators can accept or lose energy only in discrete
units of energy and allowed energies for the

oscillator are n =(n+ )

n is the number of phonons and is the zero
point energy (for n=0)
A transition from states with different number 1 1
of phonons: if n2<n1 phonon annihilation = n2 + h n1 + h
if n2>n1 phonon creation 2 2

Since the phonon moves in the crystal its wave vector is k = but, although it

interacts with other particles (such as electrons) as it had a momentum ,
however a phonon does not carry physical momentum because the phonon
coordinates are relative coordinates of atoms
quasi-momentum or crystal momentum is conserved within

= +
Phonons
If Phonons are to be considered as particles (quasi-particle to study collisions
with other phonons or other particles), a mode with a well defined k is not
localized,
travelling waves of a single frequency and wavelength imply a vibration of
the whole lattice.
space
From the Heisenberg uncertainty principle, to localize a phonon the k must

be spread on a range k around k
The velocity of the wave packed (envelope) is

(in 3D is the gradient
)

the group velocity

Green point move with group velocity
Red point with the phase velocity

Phonons
Therefore, considering the dispersion relations we have found for a
diatomic chain, the phonon will not propagate at the BZ boundary and for
optical phonons at the center of the zone

=0

As observed, in these
points we have stationary
waves superposition of
two travelling waves with
opposite directions (+k and
k) due to Bragg reflection
Phonons
The lattice with s atoms in a unit cell is described by 3s independent
oscillators (3 acoustic modes and 3s-3 optical modes)
The frequencies of normal modes of these oscillators will be given by the
solution of 3s linear equations as we have discussed before.
Each mode has a frequency p(k), where p denotes a particular mode, i.e.
p=1,3s. The energy of this mode is given by
1
( = + ) ( )
2
the integer np(k) is the occupation number of the normal mode p,k.
The total energy of the lattice =

( + ) ( )


Thermal energy and lattice vibrations
Atoms vibrate about their equilibrium position.
The coupling produces vibrational waves.
This motion is increased as the temperature is raised
In a solid, the energy associated with these vibrations is the thermal energy of
the lattice and this concept is fundamental to understand many of the basic
properties of solids:
the vibrational energy changes with temperature a measure of the
heat energy which is necessary to raise the temperature of the material
(the specific heat or heat capacity is the thermal energy which is required
to raise the temperature of unit mass or 1 gmole by one Kelvin).
Scattering of a conduction electrons in a metal this scattering gives rise
to electrical resistance.
The energy related to lattice vibrations is the contribution to the heat capacity
present in all the solids.
It is the only contribution present in insulators, instead for metal there is also
a contribution from the conduction electrons.
Thermal energy and lattice vibrations

Classically, the thermal energy of an oscillator has one contribution from
the kinetic energy and one from the potential energy
average energy <K>= <V>=

Average energy for 1D oscillator

<E>=<K>+<V>=
For 3D oscillator <E>=<K>+<V>=3
Specific heat per atom =3 (or per

mol =3R about 25 J/mol K, R=gas
constant)
law of Dulong and Petit
This value is observed at room temperature
for most of the solids but, in general, for
T0 K where the harmonic approximation
should be a good approximation, 0.

Energy and heat capacity of a harmonic oscillator
Atomic vibrations leads to band of normal mode frequencies from zero up to

some maximum value.
Calculation of the lattice energy and heat capacity of a solid therefore
requires two steps:
i) the evaluation of the contribution of a single mode
ii) the summation over the frequency distribution of the modes.
At temperature T, each energy level of the oscillator is populated with a

probability given by the Boltzmann factor
Pn=exp(()) 1
n = n + h
2
E=

Total energy of the harmonic oscillator energy of the lattice
mode with angular frequency at temperature T

+ ( + / )
1 1
= 2 2

( + 2 / )
1
Lets introduce the partition function =

( + / )

whose

=
+ ( + / ) ( )

derivative

E=

Performing the calculation Z=
( + / ) =

( / )
( / )=

( / )
(/ ) since (/ )<1
n

the geometric series for x<1 converges to

=

( / )
= partition function of the oscillator
((/ ))

Performing the derivative =

+

E=

This is the mean energy of phonons. The first term in the above equation is the
zero-point energy, the minimum energy of the oscillator even at T=0 K.
Rearranging the result
= = <n()> + =

+

<n()>=
mean excitation number of phonon at frequency

The average number of phonons is given by the Planck distribution which is a

special form of the Bose-Einstein distribution.
Phonons are Bose-Einstein particles Phonons are bosons.
k BT Mean energy of a harmonic

E
oscillator as a function of T

1
h
=
+
2

T
low temperature limit Since exponential term gets

bigger = zero point energy

1 = 1 + + ! +

high temperature limit

retaining up to the linear term = +

the energy steps are now small compared with the energy of the
harmonic oscillatorclassical limit corrected by the zero point
energy (negligible at high temperatures).
Heat Capacity C
Heat capacity C can be found by differentiating the average energy of
phonons
= +

()
=
( )
= =
( )

E

E
=

E

1

Where E= has the dimensions of T and is the Einstein temperature.

Einstein model for the heat capacity of solids

The theory developed by Einstein is the first quantum theory of solids.
He made the simplifying assumption that all 3N vibrational modes of a 3D solid
of N atoms had the same frequency,
so that the whole solid had a heat capacity given by the previous results for 1D
oscillator multiplied by 3N (3 degrees of freedom for the N oscillators)
E

A. Einstein, Ann. Physik, vol.
E
= 3 = 3 22, p. 186 (1907)

E

1
In this model, the atoms are treated as identical independent oscillators

with energy .

Einstein model for the heat capacity of solids
E

E
= 3

E

1
This crude model gave the correct limit
at high temperatures heat capacity
given by Dulong-Petit law 3R (R is the
gas constant)
It tend to zero for T0 K, but its
exponential decreasing to zero is too Temperature dependence of
according to the Einstein model with
fast with respect values measured for E=1320 K in comparison with
solids. experimental values for diamond
atomic oscillators in a solid are not (A. Einstein, Ann. Physik, vol. 22, p.
186, 1907 )
isolated therefore they vibrate with frequencies distributed in optical and acoustic
branches.
For acoustic modes 0 therefore always exists a mode fulfilling

1 and the

decay to zero is not exponential.
Density of States (DOS)

The Einstein model correspond to the first step (contribution of a single mode),
for the second step we need to count how many energy level are present in a
interval EE+E N=g(E)E where g(E) is the function density of states
According to Quantum Mechanics if a particle is constrained

the energy of the particle can only have discrete energy values.
These energy differences can be so small depending on the system that the
energy can be considered as continuous This is the case of classical mechanics.
But on atomic scale the energy can only jump by a discrete amount from one
value to another.
Definite energy levels differences get small Almost a continuum
This discussion on DOS is valid also for electrons ( , boson E(k), fermion).
Density of States
In some cases, each particular energy level can be associated with more than one
different state (mode for phonons or wavefunction for electrons)
This energy level is said to be degenerate.
The density of states is the number of discrete states per unit energy interval, and
so that the number of states between and + is g() and

=N number of stated between and .

The dispersion relations ((k) or E(k)) provide the way to calculate g.
In 1D for monoatomic chain:

Both blue regions (stripes) contribute to
the counting of states (factor 2 because
(k ) they are equal)
(k ) The number of states in the red region
(=g((k ))d) is twice the number of
state between k and k
k k k k
Density of States (1D)

k
traveling waves: 4
2 0 2 4 6
L L L L L
Periodic boundary condition (Born-von Karman)
Distinct k wavevectors corresponding to traveling waves ( () )
all positive and negative values of n in the 1st BZ are allowed

Length of the 1D chain L=Na (N cells) k= n -N/2<nN/2

These allowed wavenumbers are uniformly distibuted in k,

any k occupy a volume and in this volume there is a single value dn=1

density in k between k and k+dk (k)= = = (constant density)

Number of states between (k)(k)+d g()d = 2 (k)dk= 2 dk=

dk g()d = dk

It is worth noting that the density of states is independent from the specific boundary
condition, in fact choosing the vanishing of the vibration at the boundaries to get
standing waves:
Distinct k wavevectors corresponding to standing waves (sin(kx-t))

only positive values of n in the 1st BZ are allowed

Length of the 1D chain L=Na (N cells) sin(kL)=0 k= n 0<nN

These allowed wavenumbers are uniformly distibuted in k,
any k occupy a volume and in this volume there is a single value dn=1

density in k between k and k+dk (k)= = = (constant density)

Number of states between (k)(k)+d g()d = (k)dk= dk

g()d = dk density equal to the case of Born-von Karman BC.


g() = or in term of the group velocity

g() =

The density of state is greater where the group

velocity is smaller and is divergent where =0

= 1 ( )

(k)= sin ( )

cos ( )

2

( )

Multiplying by 2 = 2 2

g()

= =


The energy of lattice vibrations will then be found by integrating the energy
of single oscillator over the distribution of vibration frequencies.
This has a typical structure: sum over all the states, each state at
populates in average by <n> phonons

1 h
= h + h / kT g ( ) d
Mean energy of a
0
2 e 1 harmonic oscillator
2N
( 2 )
2 1/ 2
for 1D g()=
max

For a 2D rectangular crystal, the Born-von Karman boundary conditions are
given by
ul,m(t) = ul+Nx,m(t) Lx=Nxax
ul,m(t) = ul,m+Ny(t) Ly=Nyay,

kx= nx -Nx/2<nxNx/2 ky= ny -Ny/2<nyNy/2
x y

any k occupy a volume = and in this volume there is a single
x y
point dn=1
for an isotropic oscillator (same dispersion along x and y) and a square

crystal (Lx=Ly=L)
density in k between k and k+dk (the annular region of area dA=2kdk)

2k
(k)dk=2kdk

= (k) = 2k and

g()= 2k
/
Density of States (2D) Isotropic
For anisotropic oscillators the curve at constant frequency
(energy) in the kx , ky plane is different from a circle
= ()
To calculate g() we have to sum all the modes between the Anisotropic
two lines
= and = +
as in the isotropic case, g() is the area between the two lines
divided by the density of k points in the kx , ky plane

=

g()= d 1st BZ

Simple square lattice
Curves =
but d=|| d=|vg | ( vg group velocity)
d
g()=

| v | dk
+d
g
d

This calculation has to be done for any dispersion curve and the
results summed up to get the total g().

For a 3D crystal, the Born-von Karman boundary conditions are given by
ul,m,n(t) = ul+Nx,m,n(t) Lx=Nxax
ul,m,n(t) = ul,m+Ny,n(t) Ly=Nyay,
ul,m,n(t) = ul,m,n+Nz(t) Lz=Nzaz

kx= nx -Nx/2<nxNx/2 ky= ny -Ny/2<nyNy/2
x y

k z = nz -Nz/2<nzN/2

any k occupy a volume = , in this volume dn=1
x y z z
for an isotropic oscillator (same dispersion along x, y and z) and a cubic

crystal (Lx=Ly=Lz=L)
density in k between k and k+dk (the spherical shell of volume dV=4k2dk)

4k2dk 4k2
(k)dk= = (k) = 4k 2 and

g()= 4k2

/

For anisotropic oscillators the surface at constant frequency
(energy) in the kx , ky , kz space is different from a sphere
= ()
To calculate g() we have to sum all the modes between the
two surfaces
= and = +
as in the isotropic case, g() is the area between the two surfaces divided by
the density of k points in the kx , ky , kz space
dk
+d
= S

g()=

d d

but d=|| d=|vg | ( vg group velocity)

d
g()= |vg|
Of course, the calculation is performed on any dispersion curve and the

results are summed up to get the total g() a non trivial task.

Ex. GaAs
Curves = () for a
section of 3D 1st BZ (FCC
lattice)
On the left: results of calculations.

On the right the curves determined
experimentally.
For 3D, the calculation of !() is a very heavy task and is performed
numerically.
To understand the thermal properties of a solid Debye proposed a model to

approximate the real dispersion curves.
In this model only the acoustic branches are considered and the true
dispersion curves are approximated by linear dispersion curves.
This model gives better results than the Einstein model.

The Debye model
Debye obtained a good approximation to the resulting heat capacity by
neglecting optical phonons and the dispersion of the acoustic waves, i.e.
assuming
=v (v the sound velocity) for arbitrary wavenumber v = = =v! .

In a one dimensional crystal this is equivalent to taking (k) as given by the

dotted lines rather than full curve. In 2D as the conical dispersion curves.
Einstein
approximation
=const. Debye
approximation
=v k
Density of state approximate by

The Debye model the Debye curve: both curves
enclose the same area
The DOS is g()= 4k2
k2 "
/vs= =

v 2 " " 2 vs
=
v3s
s
v
s
If the crystal of volume V contains N

cells, there is the following constraint on
the maximum frequency for each
dispersion curve (polarization)
$ this cutoff is the

g()
Debye frequency # $ 6&2 v3sN/V

and in turn also a cutoff in k space

Debye wave vector # $ v= 6&2 N/V

s
for a cubic

sample with periodicity
# $
$
radius of a sphere

in k space,
for the real crystal k within the 1st BZ

The Debye model
The thermal energy of the crystal can be calculated as
= ! + =
" 2
v3s
+

This for a single polarization
If we neglect differences between L and T modes the result must be multiplied by 3

(g() 3 g() since the degrees of freedom of the crystal are 3N
A better approximation is considering that there is a longitudinal mode and two
transverse modes = ( + ) ! / = ( + )
V V

# = 3
V V %&

g() = 3 ( + ) ( + )=
$
%&
! =

The Debye model

As we did for the Einstein model, for the Debye model it is useful to introduce the
D
Debye Temperature D=

a parameter that provides a way to say if the temperature is high (T>D ) or low
(T<D).
Neglecting the zero point energy which does not contribute to the heat capacity Cv

x3
= 9 ' x
D ex 1
and the dependence on T is outside
the integral and in # = D/T
For T>>D (high temperature limit)
x x = x3= (D/T)3 ,
2
ex1+x
3
Cv= 3 (Dulong-Petit law)
The Debye model
For T0 # (low temperature limit)
x3
e
x x= $
' ' D
The energy depends on the fourth power of T, therefore the heat capacity

Cv= =
' D
The heat capacity vanishes more

slowly than the exponential
behaviour of a single harmonic
oscillator because the vibration
spectrum extends down to zero
frequency.
The Debye model
The figure shows the excellent

agreement of this prediction with
experiment for an insulator: the
lattice heat capacity of solids thus
varies as at low temperatures: this
is referred to as the Debye law.

The heat capacity Cv= =
' D
is in agreement with experiments in both
high and low T limit.
Even for intermediate temperature the
heat capacity calculated by means of the
Debye model shows a good agreement
with experiments.

Debye interpolation scheme

The heat capacity Cv= =
' D
can be used as an interpolation formula for all temperatures even though
the actual phonon-density of states curve may differ appreciably from the
Debye assumption.
Debye frequency and Debye temperature scale with the velocity of sound in
the solid. So solids with low densities and large elastic moduli have high *# .
Debye energy # can be used to estimate the maximum phonon energy in
a solid.
Solid Ar Cs Pb
93 38 105
The Debye model Left panel, experimental results of

specific heats plotted as a function
of temperature very different.
Right panel, experimental results
scaled very similar and very
close to the Debye theory.
For metals there is another
contribution due to electrons
which is generally negligible and
the lattice heat capacity of
solids varies as for not too
low temperature.
At very low temperatures, the
lattice contribution vanishes
faster than the electron
contribution and the latter can
be measurable.
At high temperature the measured heat capacity can be also greater than the
Dulong-Petit value due to anharmonic effects.
Einstein & Debye models vs. real crystals
The two models can be applied to approximate
acoustic and optical dispersion curves as schematically
shown in the figure.
The different DOS are shown in the figure below.
For real crystals the DOS is given by
d)
gs()= | v | for any mode of polarization s
g
g()= * gs()
Density of state for Al.

Singular points where
the group velocity is zero
(van Hove singularities).
Anharmonic Effects
Up to now we have considered only vibrations with small amplitude and with
this assumption the interaction potential between atoms has been
approximated by an harmonic potential retaining only term up to second order.
The harmonic potential allows us to calculate crystal properties for T not too
high (below the melting point) to fulfill the requirements of small vibration
amplitude.
One could argue that anharmonic terms can added only to increase the
precision of the calculation.
Instead some of the phenomena cannot be explained even at low temperature

without anharmonicity
the specific heat should reach the Dulong-Petit value at high temperature,
but experimentally the value is not always reached and inclusion of
anharmonic terms is necessary.
Thermal expansion: A perfect harmonic crystal does not change size
increasing the temperature
Thermal conductivity: experimentally thermal conduction shows a complex
behavior, but in harmonic approximation is infinite.

Anharmonic Effects
The harmonic potential is symmetric but the real

potential is asymmetric. For large deformation, = +
2
any real crystal resists compression to a smaller
volume than its equilibrium value more strongly

than expansion due to a larger volume.
This asymmetric shape is an anharmonic effect
due to the higher order terms in potential which
are ignored in harmonic approximation.
Thermal expansion is an example of the anharmonic effect.

Increasing the energy of the oscillator in harmonic approximation the average
position is always centered around + . For the real potential the average
position R increases with temperature.
Anharmonic Effects: Thermal expansion

Considering the potential energy in terms of the displacement x between two
atoms from their equilibrium position:
, = ,+, + ,
+, = ! - with c, g, and f>0

Average displacement < > =
- ./0 1
=
- ./0 1
For small displacement |,

+, / | 1

exp (

)

exp
]exp [
]exp [

exp
][1 +
] [1 +

exp
][
+
+

.
!
2
exp .( ! - )
4
In a similar way the denominator
exp
]exp [
]exp [

exp
][1 +
] [1 +

exp
][1 +
+

exp

.

!
So <x> =
2
The thermal expansion does not involve the symmetric term but only the
asymmetric cubic term.
Anharmonic Effects: Thermal expansion
The linear expansion coefficient

= at constant pressure

generally depends on the crystal directions, for cubic crystal only a single value
Related to thermal expansion, there is the change in the phonon frequency
and this effect is described by the Grneisen parameter
(5)
sk=
for each mode and a total value where each sk is summed with a

weight given by the contribution of the mode to the specific heat
sk cvsk
= cvsk
In this way
thermodynamic
quantities depend on
the volume of the
crystal.
Anharmonic Effects: Thermal conductivity

In harmonic approximation, phonons do not interact with each other, in the
absence of boundaries, lattice defects and impurities (which also scatter the
phonons), the thermal conductivity is infinite.
In fact without collisions there will be no thermal equilibrium.
Treating high order term as perturbations, phonons interact (collide) with
each other and these collisions limit thermal conductivity which is due to the
flow of phonons. The most important terms are:
Phonon with wavevector k and
branch s decay in 2 phonons due to
3rd order term, or merging of two
phonons in one
Decay & Scattering

&merging involving 4
Phonons due to 4th
order term
All the processes fulfill , , ( ) = , , ( ) energy cons.
789, 8,
,

, = , , +G crystal momentum conservation
Consider a rod with the two ends maintained at different temperatures. Thermal
conductivity is defined as the energy j transmitted per unit time across unit
area per unit temperature gradient
/ = 0 in 1D 1 = 0

The thermal energy transfer is a random process involving scattering introduces
mean free path of phonons in the problem.
Kinetic theory: Lets assume that the energy contributed by a phonon at a point
depends on the position of its last collision with an average collision time
phonons coming from the high temperature end bring more energy than those
coming from the low temperature end, thus, although there is no net number
flux, there can be energy flux travelling from the high T end to the low T end.
Temperature at point x is T(x) and the energy at that point is E(T[x]).

Half of the phonons arriving at a point x from the high temperature side carry an

energy E(T[x- vx]) E(T[x]) vx, the other half are from the low-T side and

carry an energy E(T[x+vx]) E(T[x])+ v .
x
Number of phonons arriving at x per unit time per unit area of cross section is
1/2 n vx, where vx is the phonon speed in x direction.
Net energy flux: 1 = v {E(T[x- vx])-E(T[x+vx])} v 2 ( )

Averaging and assuming isotropy < v 2 >= < v: 2 >= < v; 2 >= < v2 >

=

1 = v2 = v

with the phonon mean free path.
In the Debye model the phonon velocity is constant (sound velocity) therefore
the temperature dependence of = 2 is that of and


For T>> 3< the Dulong-Petit law =3n Pure LiF
constant =732 K
And the average number of phonons

n()= but the scattering rate is

proportional to the number of phonons which
are present therefore the phonon mean free

path

The experiment is close to this results with
a dependence 1 4 2

For T<< 3< only phonon states with energies

up to are populated and for a crystal with
few defects, a phonon does not scatter
frequently with other phonons and defects.
The mean free path is limited mainly by the law intermediate T
boundary of the sample 5 (size effect)
and the dependence is that of .

In the intermediate region T 3< the conductivity
exceeds the trend giving a maximum before to
10
decrease as .
0
Energy is always conserved. Lets analyze the

wavevectors involved in the scattering process. 10-1 1
At low T, only phonons with low energy and in T
turn small k vectors are involved: in 3-phonon 5 10 20 50 100
T (K )
processes the final k3 vector is within the 1st BZ
and the crystal momentum is strictly conserved 3 =
2 + 1 (normal process)
The forward phonon motion is not disturbed.
In the intermediate region, phonon with energy

D (and kk D) are in number and for them
the crystal momentum is conserved within a G
vector 3 = 2 + 1 + 7 (umklapp process)

3 $ 2 8 1 8 7 (umklapp process) the forward motion is perturbed since
3 exceed the 1st BZ (3>&/9) and with a suitable choice of G it is folded back
in the zone the phonon velocity is backward.
The process due to anharmonicity provides a backward motion that allows the
phonon system to relax to equilibrium.
We have treated the collection of phonons as an ideal gas

but there are differences
Boundary-scattering limited thermal conductivity
Pure NaCl
=321 K
Worlock, Phys Rev 1966

Debye
temp
Melting
temp
Glassbrenner and Slack, Phys Rev 1964

Neutron scattering
Phonon dispersion curves can be determined by neutron scattering. A

beam of neutron is produced by a nuclear reactor and interacting with a
solid the beam may reemerge with a different energy (inelastic scattering).
X-ray are scattered by the electron density, instead neutrons are scattered
by the interaction with nuclei. The interaction is strong but is very localized
(nucleus size 10-15 m).
As in the case of X-ray, the interaction can be elastic (diffraction) and the Laue
relations must be fulfilled. The neutron momentum and energy are

= (neutron wavevector) and = energy conservation 8
=

|:8
| = |:8
| and the Laue condition :8
= :8
+ 7.
On the other hand the interaction with the solid can be inelastic and phonons
can be created or annihilated. In case of single phonon exchange
Energy cons. 8
=
( ) (+ for annihilation for creation)
Crystal momentum cons. :8
= :8
+ + 7.
In this way the dispersion curve ( ) can be measured.
Neutron scattering
The neutron beam produced by a
reactor has a very broad energy
distribution and the elastic
scattering with a crystal
(monochromator) can be employed
to select an energy in a small range
(quasi-monochromatic beam).
This energy selected beam can be
employed for inelastic scattering.
Neutrons have an energy similar to
phonon energies (10-100 meV)
therefore during an inelastic
scattering there is a relatively huge
energy exchange, that can easily be
measured.
The same technique can be used for
X-rays to get monochromatic beams
but the energy of phonons is in the
keV range and, for X-rays, phonon
energy exchange is negligible. G. Bracco-Material Science SERP CHEM 49
Neutron scattering
Typical experimental results of neutron inelastic

scattering for copper and for germanium.
The phonon peaks are broadened by anharmonic

effects that limit the lifetime of the measured
phonons
E=

3b Lattice Vibrations PDF

Hochgeladen von

Dokumentinformationen

Originaltitel

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

3b Lattice Vibrations PDF

Hochgeladen von

Copyright:

Verfügbare Formate

3b.

G. Bracco-Material Science SERP CHEM 1

As we know from quantum mechanics the energy levels of the harmonic

Similarly to photons, phonon number is not conserved: phonons can be

G. Bracco-Material Science SERP CHEM 2

quasi-momentum or crystal momentum  is conserved within 

G. Bracco-Material Science SERP CHEM 3

From the Heisenberg uncertainty principle, to localize a phonon the k must

The velocity of the wave packed (envelope) is

G. Bracco-Material Science SERP CHEM 4

G. Bracco-Material Science SERP CHEM 5

The total energy of the lattice  =

G. Bracco-Material Science SERP CHEM 6

Thermal energy and lattice vibrations

average energy <K>=   <V>=  

Average energy for 1D oscillator

Specific heat per atom  =3 (or per

G. Bracco-Material Science SERP CHEM 8

Atomic vibrations leads to band of normal mode frequencies from zero up to

At temperature T, each energy level of the oscillator is populated with a

G. Bracco-Material Science SERP CHEM 9

Lets introduce the partition function  =

the geometric series for x<1 converges to

G. Bracco-Material Science SERP CHEM 10

The average number of phonons is given by the Planck distribution which is a

G. Bracco-Material Science SERP CHEM 11

k BT Mean energy of a harmonic

low temperature limit  Since exponential term gets

retaining up to the linear term  =  +  

G. Bracco-Material Science SERP CHEM 13

Einstein model for the heat capacity of solids

In this model, the atoms are treated as identical independent oscillators

G. Bracco-Material Science SERP CHEM 14

Density of States (DOS)

According to Quantum Mechanics if a particle is constrained

Definite energy levels differences get small Almost a continuum

The dispersion relations ((k) or E(k)) provide the way to calculate g.

In 1D for monoatomic chain:

Density of States (1D)

These allowed wavenumbers are uniformly distibuted in k,

Distinct k wavevectors corresponding to standing waves (sin(kx-t))

These allowed wavenumbers are uniformly distibuted in k,

G. Bracco-Material Science SERP CHEM 19

Density of States (1D)

The density of state is greater where the group

G. Bracco-Material Science SERP CHEM 20

G. Bracco-Material Science SERP CHEM 21

Density of States (2D)

for an isotropic oscillator (same dispersion along x and y) and a square

Density of States (3D)

for an isotropic oscillator (same dispersion along x, y and z) and a cubic

but d=||  d=|vg | ( vg group velocity)

Of course, the calculation is performed on any dispersion curve and the

Density of States (3D)

On the left: results of calculations.

To understand the thermal properties of a solid Debye proposed a model to

G. Bracco-Material Science SERP CHEM 26

=v  (v the sound velocity) for arbitrary wavenumber v = = =v! .

In a one dimensional crystal this is equivalent to taking (k) as given by the

G. Bracco-Material Science SERP CHEM 27

Density of state approximate by

If the crystal of volume V contains N

$  this cutoff is the

quasi-momentum or crystal momentum is conserved within

The total energy of the lattice =

average energy <K>= <V>=

Specific heat per atom =3 (or per

Lets introduce the partition function =

low temperature limit Since exponential term gets

retaining up to the linear term = +

but d=|| d=|vg | ( vg group velocity)

=v (v the sound velocity) for arbitrary wavenumber v = = =v! .

$ this cutoff is the

For small displacement |,