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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

ℏ? = 0.1??

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

Einstein statistics.

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

or sound waves, inside a solid electromagnetic radiation

medium can 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

~a0 =10-10m

~10-6m

h

p phonon p photon

h

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 ?1ҧ , ?ҧ2 , … , ?ҧ? 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 xi2 21 mi2

i 1 i 1

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

Φ(?1 , ?2 , … , ?? )

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

positions:

?Φ 1 ?2Φ

Φ = Φ xത i xi − xത i + xi − xത i xj − xത j

?xi xi =തxi

2 ?xi ?xj xi =തx

i i i

**• 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)i and 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

1 ?2Φ

??,? = ?? − ?ҧ? ?? − ??ҧ

2 ??? ??? ?? =?ҧ

?,? ?

• Taking a normal coordinates (qi = (xi − xത i ))

?Φ 1

Φ = Φ ?ҧ? + ?? − ?ҧ? + ??,? ?? ??

??? ?? =?ҧ?

2

? ?,?

**• 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 ij

2

ij

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

st

1

q j qk st Ajk q j qk

2 j ,k q j qk 2 j ,k

when introducing q j q j m j

Ajk

A jk force constant matrix Ajk

m j mk

Since

2 2 Ajk Akj

A jk Akj and Ajk Akj

q j qk qk q j m j mk mk m j

real and symmetric

We can find an orthogonal matrix T which diagonalizes A

1

T

T

12 0 ... 0

0 2

2

1

such that AT T AT where

T

T

0 2

3 N

T

T AT jk

T jj Ajk Tk k j j ,k

j , k

2

**With normal coordinates q j q T
**

k

k kj

1

we diagonalize the quadratic form st

2 j ,k

Ajk q j qk

From q j q T

j

j j j qk Tk k q k

k

1 1

st

2 j , k

A q q

j k j k st

2 j , k

Ajk T jj q j Tk k q k

j k

1 1

st Ajk T jj q jTk k q k st j jk q j q k

2

2 j , k , j , k 2 j ,k

1

st j j

2 2

q

2 j

• We now introduce a linear transformation, from the

coordinates i to the so-called normal coordinates (qi = (xi −

xത i )) and

3N

i = 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

(

q2

i

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 i 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 r .

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 r .

r 1 2

3N

= N n r r .

r 1 20

1 3N

N 0 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 n11 n2 2 ...

n1, n 2

.

N

=e e n11

... e n3 N 3 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 ...

1 e 1 e

1

3N

• The logarithm form of the partition function is

1 e

1

ln Z N ln

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 1 ( ) d

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

E N ( )d

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

Cv k ( )d

2

0 e

1 2

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

kT

0

For ω > ωm

e 1 ...

Cv k ( )d 3Nk

0

Dulong and

Petit law

Cv 3Nk

• 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 3N

2 exp 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

2 k BT

e

Cv k B

B e

2 2

k T

kBT

1

2

eT

Let Einstein Cv k B

T e T 1

2

temperature

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， 1 x x

2

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

2

? −?ൗ?

?? ~3? ?

?

• 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

c v ∝ 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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