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Systems of interaction of particles

Aman Wassie,

Department of Applied Physics

University of Gondar

Contents

**• Thermodynamics of crystal lattice(Solid)
**

• Lattice vibration and norm, modes

• Phonons

• The Debye model., The Debye temperature.

• Specific heat of the solid in the Debye model.

• Non ideal classical gas

• Calculation of parti. Function for low densities

• Equation of state and virial coefficient

• Vander wals equation

Introduction

• The regular lattice of atoms in

a uniform solid material have

energy associated with the

vibrations of these atoms.

• The vibrations take the form

of collective modes which

propagate through the

material.

• Such propagating lattice

vibrations can be considered to

be sound waves. And their

propagation speed is the speed

of sound in the material.

•• The vibrational energies of molecules are quantized and

treated as quantum harmonic oscillators.

• Quantum harmonic oscillators have equally spaced energy

levels with separation ΔE = h.

• So the oscillators can accept or lose energy only in discrete

units of energy h.

• The collective vibrational modes can accept energy only in

discrete amounts, and these quanta of energy have been

labelled "phonons".

• Phonon corresponds to coherent motion of all the atoms in a

solid

– quantized lattice vibrations with typical energy scale of

• Like the photons of electromagnetic energy, they obey Bose-

Einstein statistics.

• The energy of the elastic waves, or • The energy of Quanta of

sound waves, inside a solid medium can electromagnetic radiation

be considered to be quantized in the form

of phonons. photon

• PHONONS • PHOTONS

• Quanta of lattice vibrations

• Energies of phonons are quantized • Energies of photons are

quantized as well

h s hc

E phonon = E photon =

l l

~a0=10-10m

~10-6m

h h

p phonon = p photon =

l l

Phonon

• Phonons are quantized lattice vibrations

– store and transport thermal energy

– primary energy carriers in insulators and semi-conductors

• Phonons are characterized by their

– Energy, wavelength (wave vector)

– polarization (direction)

– branch (optical/acoustic), acoustic phonons are the primary

thermal energy carriers

• Since the phonons have integral angular momentum, the assembly of

phonons in the solid may again treated as a boson gas.

• Its statistical occupation (Bose-Einstein), quantized (discrete)

energy, and only limited numbers at each energy level

– we can derive the specific heat!

• At finite temperatures, the

atoms in a crystal vibrate. If

the atoms only make small

displacements from their

equilibrium positions,

– the minima of the bond

potentials can be

approximated as parabolas

and

– the forces between the atoms

can be described by linear

springs.

• Any possible motion of a

mass-spring system can be

described in terms of its

normal modes.

• In a normal mode, all of

the atoms move with the

same frequency.

• There are as many normal

modes as there are degrees

of freedom in the problem.

• To illustrate this point, we

may consider the

Hamiltonian of a classical

solid composed of N atoms

whose positions in space

specified by the coordinates

(x1, x2,.…., x3N).

• In the state of the lowest

energy, the values of these

coordinates may be denoted

by

( xi xi )

• Denoting the displacements

of the atoms from their

equilibrium positions by the

variables

i (i=1,2,…3N),

• The kinetic energy of the

system in the configuration

(xi) is given by

3N 3N

K = 21 m x i2 = 21 m i2

i =1 i =1

•• Atoms interact with a potential (r=x) which )

**• Let’s perform a Taylor series expansion around the equilibrium
**

positions:

**• The main term in this expansion represents the (minimum) energy of
**

the solid when all the N atoms are at rest at their mean positions ;

**• This energy may be denoted by the symbol 0.
**

• The next set of terms in the expansion is identically equal to

zero,

– because the function (xi) has its minimum value at (xi)=( x) and

i

hence all its derivatives must vanish there.

**– The second-order terms of the expansion represent the harmonic
**

component of the atomic vibrations.

• If we assume that the overall amplitudes of the atomic

vibrations are not very large

j

1

xj

•• The second term

• Taking a normal coordinates (

**• we may retain only the harmonic terms of the expansion and
**

neglect all the successive ones; we are then working in the so-

called harmonic approximation.

• Note that the inharmonic components are important at phase

transition (from one crystal symmetry to another and solid-

liquid phases)

1

=

H

0

m

2

i

2

ij

i

j

i i

,j

**• This equation looks like as the potential energy associated of a
**

spring with a spring constant, Force constant matrix,

2

K = =

x x

i j x= x

The harmonic approximation

**Consider the interaction potential = ( q1 , ..., q3 N )
**

Let’s perform a Taylor series expansion around the equilibrium positions:

1 �2 1

= st � q j qk = st �A%jk q%%

j qk

2 j ,k �

q j� qk 2 j ,k

j = qj mj

when introducing q%

Ajk

Ajk = force constant matrix A%jk =

m j mk

Since

�2 �2 Ajk Akj

= Ajk = Akj and A%jk = = = A%

kj

�

q j� qk �qk �qj m j mk mk m j

real and symmetric

%

We can find an orthogonal matrix T which diagonalizes A

1 T

=T

�w1

2

0 ... 0 �

� �

�0 w2

2

�

A%T = T A%T = W

1 T

such that T where W=� �

�M O �

�0 2�

w3 N �

�

( T A%T

T

) jk

= �T j�j A%j �k �Tk �

j ��

,k

k = w

2

j d j ,k

**With normal coordinates q j = �q%T
**

k

k kj

1

we diagonalize the quadratic form = st � A%jk q%%

j qk

2 j ,k

From q j = �q%T j� j�

j k �= �

q% Tk �

k qk

j� k

1 %��q%% 1

= st � A q

j k j� k �= st � A%j�k ��T j�j q j �Tk �

k qk

2 j��

,k 2 j��

,k j k

1 %��T �q T �q = 1 w 2d q q

= st

2

� jk jj j kk k

j ��

,k , j ,k

A st � j jk j k

2 j ,k

1

= st �j j

2 j

w

2

q

2

•• We now introduce a linear transformation, from the

coordinates i to the so-called normal coordinates (and

3N

i = w i . j q r .

r =1

**• Choose the proper transformation matrix in such a way that
**

the new expression for the Hamiltonian does not contain the

cross terms, i.e.

H

= 1

m

2 (

q

2

i w

22

iq

i)

i

• where �i (i=1,2,..3N) are the characteristic frequencies of the

so-called normal modes of the system and are determined

essentially by the quantities �ij or, in turn by the nature of the

potential energy function (xi).

• The expression () suggests that the energy of the solid, over

and above the (minimum) value 0,

– may be considered as arising from a set of 3N one-

dimensional, non interacting, harmonic oscillators,

– whose characteristic frequencies wi are determined by the

nature of the interatomic interactions in the system.

• Classically, each of the 3N normal modes of vibration

corresponds to a wave of distortion of the lattice points, i.e a

sound wave.

• Quantum-mechanically, these modes give rise to quanta called

phonons, in very much the same way as the vibrational modes

of the electromagnetic field give rise to photons.

• However, there is one important difference, i.e.

– while the number of normal modes in the case of

electromagnetic field is indefinite,

– the number of normal modes (or the number of phonon

energy levels) in the case of a solid is fixed by the number

of lattice sites in it.

Taking in to account the quantum approach which a single

harmonic oscillator of quantum number nr is given by

1

r = nr wr .

2

** where ωr the energy of a particle called phonons and nr is the
**

total number of phonons with frequency ωr

we note that the quantum-mechanical eigenvalues of the Hamiltonian ()

Then the total energy is just the sum of all these,

3N

1

E n1 ...E n 3 N = 0 n r w r .

r =1 2

3N

= N ( n r ) w r .

r =1 20

1 3N

N = 0 w r

2 r =1

This expression gives the energy of the solid at absolute zero.

The term Φ is necessarily negative and larger in magnitude

than the total zero-point energy of the oscillators together they

determine the binding energy of the lattice

Then finally the partition function of the whole solid is simply

Z= e E R

n1, n 2

= e N n1w1 n2 w 2 ...

n1, n 2

.

n1w1

=e N

e ... e n3 N w3 N

n1 n3 N

• We note that each harmonic oscillator term is a geometric series, so the partition

• function becomes

N 1 1

Z =e w1 ... w3 N

1 e 1 e

• The logarithm form of the partition function is

( )

ln Z = N ln 1 e w1

n =0

• Clearly the sum depends on the dispersion of the crystal, then by introducing the

phonic density of states . Then convert the sum into integral and z of the system

becomes

(

ln Z = N ln 1 e w1 (w ) dw )

0

**• The relation connecting the frequency and wave number is known as the
**

dispersion relation.

The mean energy of the solid can now be studied from that

partition function, i.e

ln Z w

E = = N w (w ) dw

0

e 1

Its heat capacity at constant volume the system is then given

by

E E 2 E

Cv = = = k

T v T v

or

e w

Cv = k ( w ) 2

(w )dw

0 (e w

1 ) 2

**Let us take the high temp. limit where 23
**

w

w =

kT

(w ) = 0

For ω > ωm

e w = 1 w ...

Cv = k (w ) dw = 3 Nk

0

Dulong and

Petit law

Cv = 3 Nk

• To proceed further, we must have knowledge of the frequency

spectrum of the solid.

• To acquire this knowledge from first principles is not an easy task.

• Einstein, who was the first to apply quantum concept to the theory

of solids (1907), assumed, for simplicity, that the frequencies �i

are all equal in value!

• The crystal lattice structure of a solid comprising N atoms can be

treated as an assembly of 3N distinguishable one-dimensional

oscillators which oscillate with the same frequency,

• Denoting this (common) value by �, the specific heat of the solid

is given by

Einstein Model for Lattice Vibrations in a Solid

**• The Einstein Model was the first
**

quantum theory of lattice

vibrations in solids.

• He made the 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 3N times

• In this model, the atoms are

treated as independent

oscillators, but the energes of the

oscillators are the quantum

mechanical energies.

• The mean energy from partition function equation

1 1

E = 3 N w

2 exp ( w ) 1

• Hence the molar specific heat of the solid on the basis of this

simple Einstein model is given by

E E 1 E

C v = =

=

T v v T kT 2 v

hw

( hw )

2

e kBT

Cv = k B

( kBT ) e

( )

2 hw 2

2 q

kBT

1 �q � e T

Let Einstein hw Cv = k B � � q

q=

( )

2

temperature �T � e T 1

k

•• If the temperature is so high that kT >> ℏω or T >> θ, then θ/T < < 1

and Expanding of the exponentials in the above eq(), taking

1

when x �

1，<<

2

�1 x x

1 x

• Cv yields again the classical result. Simply for T >> θ

Cv = 3Nk=3R

• However, if the temperature is so low that kT << ℏω or T<< θ or

θ/T >>1, and the exponential factor becomes very large compared to

unity. The specific heat then becomes

• The Einstein model predicts much too low a heat capacity at

low temperatures!

• Thus the specific heat should approach zero exponentially as T

→0. Experimentally the specific heat approaches zero slowly

than this, indeed

cv ∝ T2

as T → 0

• The reason for this discrepancy is the crude assumption that all

atoms vibrate with the same characteristic frequency.

1.0

•good news: Einstein model

explains decrease of Cv for T->0

CV /3NkB

**0.5 •bad news: Experiments
**

show

C v T 3 for T->0

0.0

0 1 2 3

T/TE

• Assumption that all modes have the same frequency

refinement

• However, Einstein’s model ignores the fact that the atomic

vibrations are coupled together: the potential energy of an

atom in the crystal depends on the distance from its neighbors:

• This energy is not a sum of single-particle energies. Thus, the

calculation of the partition function may look rather difficult.

• But a system of N coupled three-dimensional oscillators is

equivalent to a system of 3N independent one-dimensional

oscillators. the price to be paid is that the independent

oscillators are not of the same frequency; the normal modes of

vibration of a solid have a wide range of frequencies.

• These modes are not related to the motion of single atoms, but

to the collective motion of all atoms in the crystal –

vibrational modes or sound waves.

• Debye’s model (1912) starts from the opposite point of

view, treating the solid as a continuum, i.e., the atomic

structure is ignored.

• A continuum has vibrational modes of arbitrary low

frequencies, and at sufficiently low T only these low

frequency modes are excited.

• These low frequency normal modes are simply standing

sound waves.

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