Statistical Mechanics Notes UKM

Mohd Hafizudin Kamal
Statistical Mechanics
UKM
STATISTICAL MECHANICS
(SESSION 2018/2019)
WEDNESDAY 26th SEPTEMBER 2018
LECTURER: Prof. Dato. Dr. Roslan Abd Shukor

SUBJECT: Statistical Mechanics
Note 1: Statistical Mechanics Vs Thermodynamics

Statistical Mechanics Cases:
It contains 3 distributions which are:
1) Maxwell Boltzmann Distribution: - IDEAL gas
2) Fermi-Dirac Distribution:- Specific heat for electron, 𝑃𝑉 = 𝑛𝑅𝑇
3) Bose-Einstein Condensation :- specific heat for phonon, photon (Black Body
Radiation by comparing with experiment)
Thermodynamics Cases:
Compressing Particle in the box: IDEAL GAS LAW

𝑃𝑉 = 𝑛𝑅𝑇
Differentiate between Classical Statistic and Quantum Statistics.
Classical Statistics Quantum Statistics

𝑝2 1
Energy: 𝐸 = 2𝑚 + 𝑉 Energy: 𝐸 = (𝑛 + ) ℏ𝜔
2
Where, 𝑛 = 0,1,2,3, …
Example: Maxwell Boltzmann Examples: Fermi-Dirac and BEC
Distribution Distribution
STATISTICAL MECHANICS 1
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Law of Thermodynamics:
1) 0th Law
2) 1st Law
3) 2nd Law
4) 3rd Law
0th Law stated that the system is undergo equilibrium to each other.
For example:
1 2
Equilibrium System
3
1st law stated that at equilibrium microstates of a system can be characterized by a quantity
of internal energy which has property that for an isolated system, 𝐸 = constant. If the
system is allowed to be interact, that means the ∆𝐸 = −𝑊 + 𝑄 where the 𝑊 is a work done
by the system and 𝑄 is the heat absorbed by the system.
2nd Law stated that: Entropy, 𝑆. The change of entropy, ∆𝑆 ≥ 0 for the case of isolated
system. If the system is not isolated and undergoes a quasi-static process and it will
absorbed heat, 𝑑𝑄. From the equation below, we can define the Entropy,
𝑑𝑄
𝑑𝑆 =
𝑇
Where the 𝑇 is the absolute temperature and 𝑑𝑄 is the heat absorbed. When the cases where
∆𝑆 = 0, that’s mean the process is reversible process. Instead of that, it also can be written
as
𝑆 = 𝑘 ln(𝛺)
Where the 𝛺 is the number of possible state.
3rd Law stated that the entropy of a system lies a limiting property (isolated)
𝑆𝑇→0𝐾 → 𝑆0 where the 𝑆0 is constant.
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How to connect the Thermodynamics and Statistical Mechanics?

By applying the Partition Function, 𝑍
Given the equation of partition function in the form of entropy, 𝑆 = 𝑘 ln(𝑍)
Where the)
𝐸
− 𝑟
𝑍 = ∑𝑒 𝑘𝐵 𝑇
And
𝑆 = 𝑘 ln(𝑍)
𝐸
− 𝑟
= 𝑘 ln (∑ 𝑒 𝑘𝐵 𝑇 )
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TUESDAY 02 OKTOBER 2018
Note 1: Internal Energy in Thermodynamic Equations

Given that:
𝑑𝑄 = 𝑑𝐸 + 𝑝𝑑𝑉
𝑑𝐸 = 𝑇𝑑𝑆 − 𝑝𝑑𝑉
Then we define that,
𝐸 = 𝐸 (𝑆, 𝑉 ) … (1)
Equation (1) so called Internal energy.
𝜕𝐸 𝜕𝐸
𝑑𝐸 = | 𝑑𝑆 + 𝑑𝐸 = | 𝑑𝑉 … (2)
𝜕𝑆 𝑉 𝜕𝑉 𝑆
And
By comparing equation (1) and (2), then:
𝜕𝐸 𝜕𝐸
𝑇= | 𝑎𝑛𝑑 𝑝 = − |
𝜕𝑆 𝑉 𝜕𝑉 𝑆
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From
𝜕 𝜕 𝜕2𝐸 𝜕𝑇
| = =
𝜕𝑉 𝜕𝑆 𝑉 𝜕𝑉𝜕𝑆 𝜕𝑉
And
𝜕 𝜕 𝜕2𝐸 𝜕𝑝
| = =−
𝜕𝑆 𝜕𝑉 𝑆 𝜕𝑆𝜕𝑉 𝜕𝑆
Note 2: Enthalpy, 𝐻
𝑝𝑑𝑉 = 𝑑 (𝑝𝑉 ) − 𝑉𝑑𝑝
𝑑𝐸 = 𝑇𝑑𝑆 − 𝑝𝑑𝑉 = 𝑇𝑑𝑆 − 𝑑 (𝑝𝑉 ) + 𝑉𝑑𝑝
Thus,
𝐻 = 𝐸 + 𝑝𝑑𝑉
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑣𝑑𝑝
It gives the relation of:
𝐻 = 𝐻(𝑆, 𝑝)
Therefore:
𝜕𝐻 𝜕𝐻
𝑑𝐻 = | 𝑑𝑆 + | 𝑑𝑝
𝜕𝑆 𝑝 𝜕𝑝 𝑆
By comparing that equation:

𝜕𝐻
𝑇= |
𝜕𝑆 𝑝
𝜕 𝜕𝐻
= |
𝜕𝑝 𝜕𝑆 𝑝
𝜕2𝐻
= |
𝜕𝑝𝜕𝑆 𝑝
𝜕𝑇
=
𝜕𝑝
Note 3: Helmholtz Free Energy, 𝐹
𝑑𝐸 = 𝑇𝑑𝑆 − 𝑝𝑑𝑉 = 𝑑(𝑇𝑆) − 𝑆𝑑𝑇 − 𝑝𝑑𝑉
𝑑(𝐸 − 𝑇𝑆) = −𝑆𝑑𝑇 − 𝑝𝑑𝑉 + 𝐹
𝐹 = 𝐸 − 𝑇𝑆
𝑑𝐹 = −𝑆𝑑𝑇 − 𝑝𝑑𝑉
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From the relation there,

𝐹 = 𝐹(𝑇, 𝑉)
𝜕𝐹
| =𝑆
𝜕𝑇 𝑆
And
𝜕𝐹
| =𝑝
𝜕𝑉 𝑝
Thus:
𝜕𝑆 𝜕𝑝
| = |
𝜕𝑉 𝑇 𝜕𝑇 𝑉
Note 4: Gibbs Free Energy, 𝐺
𝑑𝐸 = 𝑇𝑑𝑆 − 𝑝𝑑𝑉 = 𝑑(𝑇𝑆) − 𝑆𝑑𝑇 − 𝑑(𝑝𝑉 ) + 𝑉𝑑𝑝
𝑑 (𝐸 − 𝑇𝑆 + 𝑝𝑉 ) = −𝑆𝑑𝑇 + 𝑉𝑑𝑝
𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑝
Give the relation to:
𝐺 = 𝐺(𝑇, 𝑝)
𝜕𝑆 𝜕𝑉
=
𝜕𝑝 𝜕𝑇
𝜕𝑇 𝜕𝑝
| =− |
𝜕𝑉 𝑆 𝜕𝑆 𝑉
𝜕𝑇 𝜕𝑉
| = |
𝜕𝑝 𝑆 𝜕𝑆 𝑝
𝜕𝑆 𝜕𝑝
| = |
𝜕𝑉 𝑇 𝜕𝑇 𝑉
𝜕𝑆 𝜕𝑉
− | = |
𝜕𝑝 𝑇 𝜕𝑇 𝑝
Note 5: Wave function for Bose-Einstein Condensation and Fermi-Dirac

Given the 2 particle,
𝜓𝐴 (1) 𝑎𝑛𝑑 𝜓𝐵 (2)
A and B are quantum number defining single state. 1,2 are the space and spin coordinate
for each particle. For the composite of 𝜓𝐴𝐵 (1,2) = 𝜓𝐴 (1)𝜓𝐵 (2)
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For many particle, the composite wave function is given below:

𝑁
∏ 𝜓𝑖 = 𝜓𝐴 𝜓𝐵
𝑖=1
For the cases of:

𝜓 = 𝜓𝐴𝐵 + 𝜓𝐵𝐴
Then after normalize it, it will become:
1
𝜓= (𝜓𝐴𝐵 + 𝜓𝐵𝐴 )
√2
1
𝜓= (𝜓𝐴𝐵 + 𝜓𝐵𝐴 ) … (𝑆𝑦𝑚𝑚𝑒𝑡𝑟𝑦)
√2
1
𝜓= (𝜓𝐴𝐵 − 𝜓𝐵𝐴 ) … (𝐴𝑛𝑡𝑖𝑠𝑦𝑚𝑚𝑒𝑡𝑟𝑦)
√2
If 2 electron in the same state, that’s mean: 𝐴 = 𝐵, therefore
1
𝜓𝐴 𝐴 = (𝜓𝐴𝐴 − 𝜓𝐴𝐴 ) = 0
√2
Note 6: Partition Function, 𝑍

Consider a system A in thermal contact with heat reservoir, the system is in an ensemble
and distributed in the allowed state in the canonical distribution.
By given the probability, 𝑃𝑟

𝐸𝑟
𝑒 −𝑘𝑇
𝑃𝑟 = 𝐸𝑟
∑𝑟 𝑒 −𝑘𝑇
𝑒 −𝛽𝐸𝑟
=
∑𝑟 𝑒 −𝛽𝐸𝑟
1
Where, 𝛽 = 𝑘𝑇
By looking at the average energy, 𝐸̅ ,

∑𝑟 𝐸𝑟 𝑒 −𝛽𝐸𝑟
𝐸̅ =
∑𝑟 𝑒 −𝛽𝐸𝑟
By letting that, the 𝑍 = ∑𝑟 𝑒 −𝛽𝐸𝑟
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Thus,
1 𝜕𝑍 𝜕 ln 𝑍
𝐸̅ = − =−
𝑍 𝜕𝛽 𝜕𝛽
𝜕𝑍 𝜕𝑍 𝜕𝑇
= ∙
𝜕𝛽 𝜕𝑇 𝜕𝛽
𝜕𝑍
𝐸̅ = −𝑘𝑇 2
𝜕𝑇
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TUESDAY 09th OCTOBER 2018
Note 1: Recall back Partition Function 𝑍.

From the Partition Function,
𝑍 = ∑ 𝑒 −𝛽𝐸𝑟
𝑟
1
Where, 𝛽 = 𝑘𝑇 .
Equation 1: To get the average energy 𝐸̅ of the system:

𝜕 ln 𝑍 1 𝜕𝑍
𝐸̅ = 𝑘𝑇 2 = 𝑘𝑇 2
𝜕𝑇 𝑍 𝜕𝑇
Equation 2: To get the heat capacity 𝐶𝑣 of the system:
𝜕𝐸 𝜕 𝜕 ln 𝑍
𝐶𝑣 = | = {𝑘𝑇 2 }
𝜕𝑇 𝑣 𝜕𝑇 𝜕𝑇
𝜕 ln 𝑍 2
𝜕 2 ln 𝑍
= 2𝑘𝑇 + 𝑘𝑇
𝜕𝑇 𝜕𝑇 2
Equation 3: To get the pressure 𝑝 of the system:
𝜕 ln 𝑍
𝑝̅ = 𝑘𝑇
𝜕𝑉
Equation 4: To get the entropy 𝑆 of the system:
𝜕 ln 𝑍
𝑆̅ = 𝑘 ln 𝑍 + 𝑘𝑇
𝜕𝑇
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Equation 4: To get the Helmholtz Free Energy 𝐹of the system:
𝐹̅ = 𝐸̅ − 𝑇𝑆̅
= −𝑘𝑇 ln 𝑍
Note 2: System that being consider to used.

 Ideal Gas
 Harmonic Oscillator (Einstein Solid Model)
 Two Level System
 Specific Heat of Glass
Note 3: Ideal Gas System

Equation of Ideal Gas system is given by:
𝑝𝑉 = 𝑁𝑘𝑇 … (1)
Proved equation (1):
From:
𝑝2
𝐸= +𝑈
2𝑚
Where 𝑝 is the momentum continuous of the system and 𝑈 is the potential energy.
From the PF:
𝑟
𝑝2
−𝛽( +𝑈)
= ∑𝑒 2𝑚 … (2)
𝑟
To generalize equation (2): Then it become

𝑝 2
1 −𝛽( +𝑈) 3
3𝑁 ∫ 𝑒
2𝑚 𝑑 𝑝𝑑 3 𝑟
ℎ0
𝑝 2 𝑃2 𝑝2 𝑝2
1 −𝛽𝑝[( 1 + 2 + 3 +.. 𝑁 )+𝑈(𝑟1,𝑟2 ,𝑟3 …𝑟𝑁 )]
2𝑚 2𝑚 2𝑚 2𝑚
∫𝑒 𝑑 3 𝑝1 𝑑 3 𝑝2 … 𝑑 3 𝑝𝑁 𝑑 3 𝑟1 𝑑 3 𝑟2 … 𝑑 3 𝑟𝑁
ℎ03𝑁
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𝑝 2 𝑃2 𝑝2 𝑝2
𝑉𝑁 −𝛽𝑝[( 1 + 2 + 3 +.. 𝑁 )]
2𝑚 2𝑚 2𝑚 2𝑚
𝑍 = 3𝑁 ∫ 𝑒 𝑑 3 𝑝1 𝑑 3 𝑝2 𝑑 3 𝑝3 … (3)
ℎ0
Equation (3) tells us that the 𝑑 3 𝑟1 𝑑 3 𝑟2 𝑑 3 𝑟3 … 𝑑 3 𝑟𝑁 ≈ 𝑉 𝑁 and 𝑈 (𝑟1 , 𝑟2 , 𝑟3 … 𝑟𝑁 ) = 0

Therefore, by considering into one particle system:
𝑝 2
𝑉 −𝛽( 1 )
2𝑚
𝑍 = ∫𝑒 𝑑 3 𝑝1
ℎ0
𝑝 2
𝑉 −𝛽( 1 )
2𝑚
𝑍 = ∫𝑒 𝑑𝑝1𝑥 𝑑𝑝1𝑦 𝑑𝑝1𝑧
ℎ0
By integrating the equation above:
+∞
𝑝2
−𝛽( 1 )
2𝑚 2𝑚𝜋
∫ 𝑒 𝑑𝑝1𝑥 = √ = √2𝑚𝜋𝑘𝑇
𝛽
−∞
𝑉𝑁 3𝑁
𝑍= ( 2𝑚𝜋𝑘𝑇 ) 2 … (4)
ℎ03𝑁
By putting ln 𝑏𝑜𝑡ℎ 𝑠𝑖𝑑𝑒:

3𝑁
ln 𝑍 = ln [(𝑉 𝑁 )(2𝑚𝜋𝑘𝑇) 2 ] − ln(ℎ03𝑁 )
3𝑁
= ln(𝑉 𝑁 ) + ln(2𝑚𝜋𝑘𝑇) 2 − ln(ℎ03𝑁 )
3𝑁
= 𝑁 ln 𝑉 + ln(2𝑚𝜋𝑘𝑇) − 3𝑁 ln ℎ0
2
Note 4: From the equation of pressure 𝑝, we can justify that
𝜕 3𝑁
𝑝̅ = 𝑘𝑇 [𝑁 ln 𝑉 + ln(2𝑚𝜋𝑘𝑇) − 3𝑁 ln ℎ0 ]
𝜕𝑉 2
𝜕 ln 𝑉
= 𝑁𝑘𝑇
𝜕𝑉
1
𝑝̅ = 𝑁𝑘𝑇
𝑉
Thus,
𝑝𝑉 = 𝑁𝑘𝑇. . 𝑄𝐸𝐷
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Note 5: How about the energy 𝐸̅ . From the equation below

𝜕 ln 𝑍
𝐸̅ = 𝑘𝑇 2
𝜕𝑇
𝜕 3𝑁
= 𝑘𝑇 2 [𝑁 ln 𝑉 + ln(2𝑚𝜋𝑘𝑇) − 3𝑁 ln ℎ0 ]
𝜕𝑇 2
𝜕 3𝑁
= 𝑘𝑇 2 ln(2𝑚𝜋𝑘𝑇)
𝜕𝑇 2
3𝑁𝑘𝑇 2 𝜕
= ln(2𝑚𝜋𝑘𝑇)
2 𝜕𝑇
3𝑁𝑘𝑇 2 1
= (2𝑚𝜋𝑘 )
2 2𝑚𝜋𝑘𝑇
3𝑁𝑘𝑇
𝐸̅ =
2
3𝑘𝑇
𝐸̅ = ,𝑁 = 1
2
Where, 𝑁 is the number of particle.
Note 6: How about finding the heat capacity 𝐶𝑣
𝜕𝐸 𝜕 3𝑘𝑇 3
𝐶𝑣 = = ( ) = 𝑘𝑇
𝜕𝑇 𝜕𝑇 2 2
Note 7: Get the entropy 𝑆 of the system:

𝜕 ln 𝑍
𝑆̅ = 𝑘 ln 𝑍 + 𝑘𝑇
𝜕𝑇
Given that:
3𝑁
ln 𝑍 = 𝑁 ln 𝑉 + ln(2𝑚𝜋𝑘𝑇) − 3𝑁 ln ℎ0
2
Substitute the equation above:
3𝑁
𝑆̅ = 𝑘 [𝑁 ln 𝑉 + ln(2𝑚𝜋𝑘𝑇) − 3𝑁 ln ℎ0 ]
2
𝜕 3𝑁
+ 𝑘𝑇 [𝑁 ln 𝑉 + ln(2𝑚𝜋𝑘𝑇) − 3𝑁 ln ℎ0 ]
𝜕𝑇 2
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3𝑘𝑁
= 𝑘𝑁 ln 𝑉 + ln(2𝑚𝜋𝑘𝑇)
2
𝜕 3𝑁 𝜕 𝜕
− 3𝑘𝑁 ln ℎ0 + 𝑘𝑇 𝑁 ln 𝑉 + ln(2𝑚𝜋𝑘𝑇) − 3𝑁 ln ℎ0
𝜕𝑇 2 𝜕𝑇 𝜕𝑇
3𝑘𝑁 3𝑁 1
= 𝑘𝑁 ln 𝑉 + ln(2𝑚𝜋𝑘𝑇) − 3𝑘𝑁 ln ℎ0 + 2𝑚𝜋𝑘
2 2 (2𝑚𝜋𝑘𝑇)
3𝑘𝑁 3𝑘𝑁
= 𝑘𝑁 ln 𝑉 + ln(2𝑚𝜋𝑘𝑇) − 3𝑘𝑁 ln ℎ0 +
2 2𝑇
3 3
= 𝑘𝑁 [ln 𝑉 + ln(2𝑚𝜋𝑘𝑇)2 − ln(ℎ0 )3 + ]
2𝑇
𝑆̅ = 𝑘𝑁 ln 𝑉 + 𝜎 … (5)
3
3
Where, 𝜎 = ln(2𝑚𝜋𝑘𝑇)2 − ln(ℎ0 )3 + 2𝑇
But we look at the theorem, when the entropy is double, means that the volume also
doubles. But in equation (5), its violated. So, its need something to solve it. This is what
we called as Gibbs Paradox.
Note 8: Gibbs Paradox’s

The entropy is not extensive. So we need to modified PF. We need to assume that the
particle is behave indistinguishable particle.
𝑍
𝑍′ =
𝑁!
3𝑁
𝑉 𝑁 (2𝜋𝑚𝑘𝑇) 2
𝑍 ′ = 3𝑁 … (6)
ℎ0 𝑁!
By putting log both site and gets:

ln 𝑍 ′ = ln 𝑍 − ln 𝑁!
= ln 𝑍 − 𝑁 ln 𝑁 + 𝑁
Therefore:
ln 𝑁! = 𝑁 ln 𝑁 − 𝑁. . (7)
Equation (7) we called as Sterling approximation
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Note 9: Einstein Model

From Einstein model (Harmonic Oscillator)
Solving for 𝐸̅ regarding to high and lower temperature condition

Given that:
𝑟
∞
1
= ∑ 𝑒 −𝛽(𝑛+2)ℏ𝜔
𝑛=0
∞
1
= 𝑒 −𝛽 2ℏ𝜔 ∑ 𝑒 −𝛽𝑛ℏ𝜔
𝑛=0
This can be done by using Taylor series:

1 1
𝑍 = 𝑒 −𝛽 2ℏ𝜔 [1 + 𝑥 + 𝑥 2 + 𝑥 3 ] =
1−𝑥
Thus:
𝑒 −𝛽ℏ𝜔
𝑍=
1 − 𝑒 −𝛽ℏ𝜔
𝜕 ln 𝑍
𝐸̅ = 𝑘𝑇 2
𝜕𝑇
Put both side with log and reduce to:
ℏ𝜔 ℏ𝜔𝑒 −𝛽ℏ𝜔 𝑒 𝛽ℏ𝜔

= − [− − ]∙
2 1 − 𝑒 𝛽ℏ𝜔 𝑒 𝛽ℏ𝜔
1 1
= ℏ𝜔 [ + 𝛽ℏ𝜔 ]
2 𝑒 −1
For high temperature 𝑇,
𝑒 𝛽ℏ𝜔 ≪ 1
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Thus,
1 1
𝐸̅ = ℏ𝜔 [ + ]
2 (𝛽ℏ𝜔)2
(1 + 𝛽ℏ𝜔 + 2! + ⋯ − 1)
1
= ℏ𝜔 = 𝑘𝑇
𝛽ℏ𝜔
Therefore,
𝐸̅ = 𝑘𝑇
How about 𝐶𝑣 at high temperature 𝑇,
𝜕𝐸
𝐶𝑣 = | =𝑘
𝜕𝑇 𝑉
At low temperature 𝑇,
𝛽ℏ𝜔 ≫ 1
1
𝐸̅ = ℏ𝜔 ( + 𝑒 −𝛽ℏ𝜔 )
2
The heat capacity 𝐶𝑣 is given by:
𝜕𝐸
𝐶𝑣 = |
𝜕𝑇 𝑉
𝜕 1
𝐶𝑣 = [ℏ𝜔 ( + 𝑒 −𝛽ℏ𝜔 )]
𝜕𝑇 2
𝜕 1 ℏ𝜔
𝐶𝑣 = [ℏ𝜔 ( + 𝑒 − 𝑘𝑇 )]
𝜕𝑇 2
________________________________________________________________________
UKM
WEDNESDAY 10th OCTOBER 2018

Note 1: Revised Einstein Model
From the equation of:
1 1
𝐸̅ = ℏ𝜔 [ + 𝛽ℏ𝜔 ]
2 𝑒 −1
To get the specific heat 𝐶𝑣 ,
𝜕𝐸
𝐶𝑣 = |
𝜕𝑇 𝑣
𝜕 1 1
= ℏ𝜔 [ + 𝛽ℏ𝜔 ]
𝜕𝑇 2 𝑒 −1
𝜕𝐸 𝜕𝛽
= ∙( )
𝜕𝛽 𝜕𝑇
3𝑁ℏ𝜔 ℏ𝜔𝑒 𝛽ℏ𝜔
= ( )
𝑘𝑇 2 (𝑒 𝛽ℏ𝜔 − 1)2
We noticed that:
𝜕𝛽 1
=
𝜕𝑇 𝑘𝑇 2
Thus, the specific heat 𝐶𝑣 is given by:
𝜃𝐸
𝜃𝐸 2 𝑒𝑇
𝐶𝑣 = 3𝑇 ( ) 2
𝑇 𝜃𝐸
(𝑒 𝑇 − 1)
We know that: 𝑅 = 𝑁𝑘
Therefore;
ℏ𝜔𝐸 𝑘𝐵 𝜃𝐸
𝜃𝐸 = , 𝜔𝐸 =
𝑘𝐵 ℏ
Note 2: What is the Higher temperature limit for the Einstein Model
When the higher temperature limit, the specific heat will be
𝐶𝑣 = 3𝑅
By taking:
𝜃𝐷
≪1
𝑇
UKM
𝜃𝐷 𝜃 21
2 (1 + + ( 𝐷) + ⋯)
𝜃𝐷 𝑇 𝑇 2!
𝐶𝑣 = 3𝑅 ( )
𝑇 𝜃 𝜃 21
(1 + 𝑇𝐷 + ( 𝑇𝐷 ) 2! + ⋯ − 1)
𝜃𝐷 2 1
𝐶𝑣 = 3𝑅 ( )
𝑇 𝜃 2
( 𝑇𝐷 )
Therefore:
𝐶𝑣 = 3𝑅. . 𝑄𝐸𝐷
Note 3: At lower temperature limit Cases

Given that:
𝜃𝐸
≫1
𝑇
And the specific heat 𝐶𝑣 is given by:
𝜃𝐸
𝜃𝐷 2 𝑒𝑇
𝐶𝑣 = 3𝑅 ( ) 2
𝑇 𝜃𝐸
(𝑒 𝑇 − 1)
𝜃𝐸
𝜃𝐷 2 𝑒 𝑇
= 3𝑅 ( ) 2𝜃𝐸
𝑇
𝑒 𝑇
𝜃𝐷 2 −𝜃𝐸
= 3𝑅 ( ) 𝑒 𝑇
𝑇
It’s strange! It must consider
𝐶𝑣 ≈ 𝑇 3
One good example is Diamond.
The 𝜃𝐸 = 1320𝐾
UKM
Note 4: Two Level System: Application glassy (Amorphous Materials)

From the picture below:
1
𝐸2 = ± ∆
2
∆
1
𝐸1 = ± ∆
2
So, the partition function 𝑍 is given by:
1 1
𝑍 = 𝑒 +2𝛽∆ + 𝑒 −2𝛽∆
1
𝑍 = 2 cosh ( 𝛽∆)
2
To get the energy 𝐸,
1 𝜕𝑍
𝐸=−
𝑍 𝜕𝛽
1
𝐸=− 2∆ 1
∙ 2 sinh ( 𝛽∆)
1 2
2 cosh (2 𝛽∆)
1 1
𝐸 = ∆ tanh ( 𝛽∆)
2 2
To get the specific heat 𝐶𝑣 ,
𝜕𝐸
𝐶𝑣 =
𝜕𝑇
1 𝜕𝐸
=−
𝑘𝑇 2 𝜕𝛽
1 𝜕 1 1
=− [ ∆ tanh ( 𝛽∆)]
𝑘𝑇 2 𝜕𝛽 2 2
∆ ∆ 1
= 2
sech ( 𝛽∆)
2𝑘𝑇 2 2
UKM
From:
2
2
2
sech 𝑥 = ( 𝑥 )
𝑒 + 𝑒 −𝑥
Therefore,
∆
∆2 1 𝑒 𝑘𝑇
𝐶𝑣 = 2 ∙ ( ∆
)
𝑘𝑇 2 1
𝛽∆
1
− 𝛽∆
(𝑒 2 + 𝑒 2 ) 𝑒 𝑘𝑇
∆
∆2 𝑒 𝑘𝑇
= 2
𝑘𝑇 2 ∆
(𝑒 𝑘𝑇 + 1) }
{
For 𝑁 particles,
∆
𝑁∆2 𝑒 𝑘𝑇
𝐶𝑣 = 2
𝑘𝑇 2 ∆
(𝑒 𝑘𝑇 + 1) }
{
Note 5: Specific Heat of Glassy

Glass can be considered to be made of cluster of atoms. Each cluster inside of the energy
band. Each cluster has different energy gap, ∆. The total specific heat up to the sum of all
two level system is given by:
𝜀0 ∆
∆2 𝑒 𝑘𝑇 𝑁
𝐶𝑣 = ∫ 2 ∙ 𝑑∆
𝑘𝑇 2 ∆ 𝜀0
{(𝑒 + 1) }
0 𝑘𝑇
By letting 𝑥 = 𝛽∆, then it became:

𝛽𝜀0
𝑁 1 𝑥 2𝑒 𝑥 𝑑𝑥
𝐶𝑣 = ∫
𝜀0 𝑘 𝑇 2 𝛽 2 ( 1 + 𝑒 𝑥 )2 𝛽
0
𝜀0
𝑁 𝑥 2𝑒 𝑥
= ∫ 𝑑𝑥
𝜀0 𝑘𝛽 3 𝑇 2 (1 + 𝑒 𝑥 )2
0
UKM
𝜀0
𝑁
= ∫ 𝐻 (𝑥 )𝑑𝑥
𝜀0 𝑘𝛽 2 𝑇 2
0
Given that:
𝑥 2𝑒 𝑥
𝐻(𝑥 )𝑑𝑥 =
(𝑒 𝑥 + 1)2
𝜀0
= ∫ 𝐻(𝑥 )𝑑𝑥 = 𝐻0
0
Thus,
𝐶𝑣 = 𝛼𝑇
𝑁 (𝑘𝑇)3
= [ ] 𝐻0
𝜀0 𝑘 𝑇 2
Where
𝑁𝑘 2
𝛼= 𝐻
𝜀0 0
________________________________________________________________________
TUESDAY 30th OCTOBER 2018

GRAND CANONICAL ENSEMBLE
(Energy and Particle Playing Together)
Note 1: Thermodynamics Approached

Given that:
𝑑𝐸 = 𝑇𝑑𝑆 − 𝑝𝑑𝑉 + 𝜇𝑑𝑁
= 𝑇𝑑𝑆 − 𝑝𝑑𝑉 + ∑ 𝜇𝑟 𝑑𝑁𝑟

𝑟
𝐸 = 𝑇𝑆 − 𝑝𝑉 + 𝜇𝑁
𝐹 = 𝐸 − 𝑇𝑆 = 𝜇𝑁 − 𝑝𝑉
UKM
𝐺 = 𝐸 − 𝑇𝑆 + 𝑝𝑉
𝐹 + 𝑝𝑉 = 𝜇𝑁
Given that:
𝑇𝑑𝑆 = 𝑑𝐸 + 𝑝𝑑𝑉 − 𝜇𝑑𝑁
𝑑𝐸 𝑑𝑉 𝜇
𝑑𝑆 = +𝑝 − 𝑑𝑁
𝑇 𝑇 𝑇
𝜕𝑆 1
| =
𝜕𝐸 𝑉,𝑁 𝑇
𝜕𝑆 𝑝
| =
𝜕𝑉 𝐸,𝑁 𝑇
𝜕𝑆 𝜇
| =−
𝜕𝑁 𝐸,𝑉 𝑇
From the definition of chemical potential 𝜇. Given that:

𝜕𝑆
𝜇𝑗 = −𝑇 |
𝜕𝑁𝑗 𝐸,𝑉,𝑁
𝜇𝑖
𝜇𝑖 𝜇𝑗
𝜇𝑗 Equilibrium State
The 𝜇𝑗 can be written in 3 cases:
 All parameter except 𝑁𝑖 are constant. Thus:
𝑑𝑉 = 𝑑𝑁𝑖 = 𝑑𝑆 = 0, 𝑖 ≠ 𝑗
𝜕𝐸
𝜇𝑗 = |
𝜕𝑁𝑗 𝑆,𝑉,𝑁
 Given that:
𝑑(𝐸 − 𝑇𝑆) = 𝑑𝐹 = −𝑑𝑆𝑇 − 𝑝𝑑𝑉 + ∑ 𝜇𝑖 𝑁𝑖

𝑖
UKM
𝜕𝐹
𝜇𝑗 = |
𝜕𝑁𝑗 𝑇,𝑉,𝑁
 Given that:
𝑑 (𝐸 − 𝑇𝑆 + 𝑝𝑉 ) = 𝑑𝑄
= −𝑆𝑑𝑇 + 𝑉𝑑𝑝 + ∑ 𝜇𝑖 𝑑𝑁𝑖

𝑖
𝜕𝐺
𝜇𝑗 = − |
𝜕𝑁𝑗 𝑇,𝑝,𝑁
When it equilibrium,
𝜇𝑖 = 𝜇𝑗
𝜕𝐺 𝜕𝐺
=
𝜕𝑁𝑖 𝜕𝑁𝑗
Note 2: Grand Partition Function

Given that the normal partition function
1
𝑍 = ∑ 𝑒 −𝛽𝐸𝑟 , 𝛽 =
𝑘𝑇
𝑟
𝑃𝑟 ∝ 𝑒 −𝛽𝐸𝑟 −𝛼𝑁𝑟
1
𝑃𝑟 ∝ 𝑒 −𝑘𝑇 (𝐸𝑟 −𝜇𝑁𝑟 )
𝑒 −𝛽(𝐸𝑟 −𝜇𝑁𝑟 )
𝑃𝑟 =
∑𝑟 𝑒 −𝛽(𝐸𝑟 −𝜇𝑁𝑟 )
Given that, grand partition function 𝛯
𝛯 = ∑ 𝑒 −𝛽(𝐸𝑟 −𝜇𝑁𝑟 )
𝑟
The average number of particles is given by:

∑𝑟 𝑁𝑟 𝑒 −𝛽(𝐸𝑟 −𝜇𝑁𝑟 )
̅=
𝑁
𝛯
UKM
The average energy is given by:

∑𝑟 𝐸𝑟 𝑒 −𝛽(𝐸𝑟 −𝜇𝑁𝑟 )
𝐸̅ =
𝛯
1 𝜕𝛯
=−
𝛯 𝜕𝛽
𝜕 ln 𝛯
=−
𝜕𝛽
𝜕𝛯
= 𝛽 ∑ 𝑁𝑟 𝑒 −𝛽(𝐸𝑟 −𝜇𝑁𝑟 )
𝜕𝜇
𝑟
𝜇 𝜕 ln 𝛯 𝜕 ln 𝛯
̅𝑟 − 𝐸̅ =
𝜇𝑁 −
𝛽 𝜕𝜇 𝜕𝛽
1 1 𝜕𝛯 1 𝜕 ln 𝛯
̅𝑟 =
𝑁 =
𝛽 𝛯 𝜕𝜇 𝛽 𝜕𝜇
1 𝜕𝛯 𝜕 ln 𝛯
̅̅̅̅̅̅̅̅̅̅
𝜇𝑁 − 𝐸 = 𝜇𝑁̅ − 𝐸̅ = =
𝛯 𝜕𝛽 𝜕𝛽
𝜕 ln 𝛯
𝐸̅ = 𝜇𝑁
̅−
𝜕𝛽
𝜇 𝜕 ln 𝛯
̅=
𝜇𝑁
𝛽 𝜕𝜇
𝜇 𝜕 𝜕
𝐸̅ = ( − ) ln 𝛯
𝛽 𝜕𝜇 𝜕𝛽
𝑑 (𝑝𝑉 ) = 𝑆𝑑𝑇 − 𝜇𝑑𝑁 + 𝑝𝑑𝑉
𝜕 ln 𝛯
𝑆 = 𝑘 ln 𝛯 + 𝑘𝑇
𝜕𝑇
𝜕 ln 𝛯
̅ = 𝑘𝑇
𝑁 | … (1)
𝜕𝜇 𝑉,𝑇
This equation (1) is used to derive the Fermi-Dirac Distribution and Bose-Einstein
Condensate
𝜕 ln 𝛯
𝑝̅ = 𝑘𝑇 |
𝜕𝑉 𝜇,𝑇
UKM
Thus,
𝜕 ln 𝛯
𝜇𝑗 = −𝑘𝑇 |
𝜕𝑁𝑗 𝑁,𝑉
In equilibrium where 𝜇𝑖 = 𝜇𝑗
Example like in Thin Film Using Laser Ablation
Ideal Gas in 3D
Laser
From the equation of 3D:
𝑝𝑥2 𝑝𝑦2 𝑝𝑧2
𝐸= + +
2𝑚 2𝑚 2𝑚
And for the equation of 2D:
𝑝𝑥2 𝑝𝑦2
𝐸= + − 𝜀0
2𝑚 2𝑚
𝜇3𝐷 = 𝜇2𝐷−𝜀0
We know that:
𝜕𝐺
𝜇=
𝜕𝑁
** Consider an ideal gas with 𝑁 particles, each with mass 𝑚 in a volume 𝑉 and temperature
𝑇. Use classical approximation for the partition function and assume that the particles
indistinguishable. Determine the chemical potential 𝜇.
𝜉 = ∑ 𝑒 −𝛽𝐸𝑟
𝑟
UKM
𝑝𝑥2 + 𝑝𝑦2 + 𝑝𝑧2 2 2

𝜉 = ∫ exp −𝛽 ( ) 𝑑 𝑟𝑑 𝑝
2𝑚
3𝑁
(2𝜋𝑚𝑘𝑇) 2
𝑁
𝜉𝑁 𝑉 ℏ2
𝑍= =
𝑁! 𝑁!
Given that:
𝐺 = 𝐹 + 𝑝𝑉
= 𝐸 − 𝑇𝑆 + 𝑝𝑉
𝐺 = −𝑘𝑇 ln 𝑍 + 𝑁𝑘𝑇
Given that,
3 2𝜋𝑚𝑘𝑇
ln 𝑍 = 𝑁 ln 𝑉 + 𝑁 ln ( ) − ln 𝑁!
2 ℏ2
By using Stirling approximations:
ln 𝑁! = 𝑁 ln 𝑁 − 𝑁
3 2𝜋𝑚𝑘𝑇
ln 𝑍 = 𝑁 ln 𝑉 + 𝑁 ln ( ) − 𝑁 ln 𝑁 + 𝑁
2 ℏ2
𝑉 3 2𝜋𝑚𝑘𝑇
= 𝑁 [ln + ln ( ) + 1]
𝑁 2 ℏ2
Therefore,
𝑉 3 2𝜋𝑚𝑘𝑇
𝐺 = −𝑁𝑘𝑇 [ln + ln ( ) + 1] + 𝑁𝑘𝑇
𝑁 2 ℏ2
Thus, to get the 𝜇(3𝐷) , we have:
𝜕𝐺 𝑉 3 2𝜋𝑚𝑘𝑇
𝜇3𝐷 = = −𝑘𝑇 [ln + ln ( )]
𝜕𝑁 𝑁 2 ℏ2
UKM
WEDNESDAY 31th OCTOBER 2018

Note 1: 2-D of Ideal Gas Formation
2D Ideal Gas Occupies

and Stick on The
Substrate
Binding
Energy, 𝜀0
Energy of the 2 dimensional structure is given by:

𝑝𝑥2 + 𝑝𝑦2
𝐸𝑟 = − 𝜀0
2𝑚
Thus,
𝜉 = ∑ 𝑒 −𝛽𝐸𝑟
𝑟
𝑝𝑥2 +𝑝𝑦
2
1 −𝛽(
2𝑚
−𝜀0)
= 2∫𝑒 𝑑 𝑝𝑑 2 𝑟
2
ℎ0
+∞ 2 𝑝2
𝑝 𝑦
1 𝛽𝜀 −𝛽( 𝑥 ) −𝛽(2𝑚 )
= 2𝑒 0 ∫ 𝑒 2𝑚 𝑒 𝑑𝑝𝑥 𝑑𝑝𝑦 𝑑𝑥𝑑𝑦
ℎ0
−∞
1 𝛽𝜀 2
= 2𝑒
0 𝐴(√2𝜋𝑚𝑘𝑇)
ℎ0
1 𝛽𝜀
= 𝑒 0 𝐴(2𝜋𝑚𝑘𝑇)
ℎ02
Thus:
𝐴 𝛽𝜀
𝜉= 𝑒 0 𝐴(2𝜋𝑚𝑘𝑇)
ℎ02
For N-particles:
𝑁 𝑁 𝛽𝑁𝜀0
2𝜋𝑚𝑘𝑇 𝑁
𝜉 =𝐴 𝑒 ( )
ℎ2
UKM
Then:
𝜉 𝑁 𝐴𝑁 𝛽𝑁𝜀 2𝜋𝑚𝑘𝑇 𝑁
𝑍= = 𝑒 0( )
𝑁! 𝑁! ℎ2
To get the Gibbs Free Energy:

𝐺 = 𝐹 + 𝑝′𝐴
Where 𝑝𝑉 = 𝑝′𝐴 and 𝑝′ is surface tension.
𝐺 = −𝑘𝑇 ln 𝑍 + 𝑝′𝐴
𝐴 2𝜋𝑚𝑘𝑇 𝜀0
ln 𝑍 = 𝑁 [ln + ln ( 2
)+ + 1]
𝑁 ℎ 𝑘𝑇
𝐺 = −𝑁𝑘𝑇 [ln + ln ( 2
)+ + 1] + 𝑝′𝐴
𝑁 ℎ 𝑘𝑇
= −𝑁𝑘𝑇 [ln + ln ( 2
)+ ]
𝑁 ℎ 𝑘𝑇
Thus:
𝜕𝐺 𝐴 2𝜋𝑚𝑘𝑇 𝜀0
𝜇2𝐷 = = −𝑘𝑇 [ln + ln ( 2
)+ ]
𝜕𝑁 𝑁 ℎ 𝑘𝑇
When it at equilibrium:
𝜇2𝐷 = 𝜇3𝐷
Use the distribution to determine the average number of particles per unit area and absorbed
when the pressure of 3D gas is 𝑃. and the total number of particle absorbed is 𝑁.
Thus:
𝐴 2𝜋𝑚𝑘𝑇 𝜀0 𝑉 3 2𝜋𝑚𝑘𝑇
−𝑘𝑇 [ln + ln ( 2
) + ] = −𝑘𝑇 [ln + ln ( )]
𝑁 ℎ 𝑘𝑇 𝑁 2 ℏ2
Just a short note:

𝑉 𝑘𝑇 𝐴 1 𝑘𝑇𝐴 𝑝𝑉 𝑝𝑉
In 3D: 𝑝𝑉 = 𝑁𝑘𝑇, 𝑁 = while in 2D: 𝑁 = 𝑛 = , 𝑁 = 𝑘𝑇 = 𝐴𝑛, 𝑛 = 𝑘𝑇𝐴
𝑝 𝑝𝑉
2𝜋𝑚𝑘𝑇 𝜀0 𝑘𝑇 3 2𝜋𝑚𝑘𝑇
−ln 𝑛 + ln ( ) + = ln + ln ( )
ℎ2 𝑘𝑇 𝑝 2 ℏ2
UKM
The, modified equation above and get 𝑛:

𝑘𝑇 1 2𝜋𝑚𝑘𝑇 𝜀0
ln 𝑛 = − ln − ln ( 2
)+
𝑝 2 ℏ 𝑘𝑇
Therefore:
1
𝑝 2𝜋𝑚𝑘𝑇 2 𝜀0
𝑛(𝑇, 𝑝) = ( ) 𝑒 𝑘𝑇
𝑘𝑇 ℏ2
Where:
Average number of particle absorbed
𝑛=
Area
Note 2: Derivation of Bose-Einstein Distribution from the partition function.

From:
∞
𝛯 = ∑ 𝑒 −𝛽(𝐸𝑟 −𝜇𝑁𝑟 )
𝑟=0
̅ is the occupancy (Average number of particles for particulate state)

Where 𝑁
1 𝜕 ln 𝛯
̅=
𝑁
𝛽 𝜕𝜇
For BEC condition:
̅ = 𝑓(𝜀 )𝐵𝐸
𝑁
Consider a system of BEC/boson which non-interacting in thermal contact with reservoir
that the energy is occupied by the particle and there are N-particles in state, 𝐸𝑟 = 𝑁𝜀
Let focus on one state only in their system or BE statistic any number of particles can be in
their state energy level.
∞
𝛯 = ∑ 𝑒 −𝛽(𝑁𝜀−𝜇𝑁𝑟 )
𝑛=0
∞
= ∑ 𝑋𝑁
𝑛=0
= 1 + 𝑥 + 𝑥2 + ⋯
UKM
1 1
𝛯= =
1 − 𝑋 1 − 𝑒 −𝛽(𝜀−𝜇)
Thus, to get the
̅ = 𝑓(𝜀 )𝐵𝐸
𝑁
1 𝜕 ln 𝛯
=
𝛽 𝜕𝜇
1 1 𝜕𝛯
=
𝛽 𝛯 𝜕𝜇
11 𝜕 1
= [ ]
𝛽 𝛯 𝜕𝜇 1 − 𝑒 −𝛽(𝜀−𝜇)
1 − 𝑒 −𝛽(𝜀−𝜇) 𝜕 1
= [ −𝛽(𝜀−𝜇)
]
𝛽 𝜕𝜇 1 − 𝑒
1 − 𝑒 −𝛽(𝜀−𝜇) 𝛽𝑒 −𝛽𝜀 𝑒 𝛽𝜀
= [ ]
1 − 𝑒 −𝛽(𝜀−𝜇) (1 − 𝑒 −𝛽(𝜀−𝜇) )2
𝑒 −𝛽(𝜀−𝜇) 𝑒 𝛽(𝜀−𝜇)
= ∙
1 − 𝑒 −𝛽(𝜀−𝜇) 𝑒 𝛽(𝜀−𝜇)
1
=
𝑒 𝛽(𝜀−𝜇) −1
Therefore:
1
𝑓 (𝜀 )𝐵𝐸 =
𝑒 𝛽(𝜀−𝜇) −1
Note 3: Derivation of Fermi-Dirac Distribution from the partition function.

Consider one state and we assume that the state is the system. Other state is considering as
reservoir. What is the occupancy of this state? Fermion obeys Pauli Exclusion Principle
which is each state can occupy by one 1 or 0 particle.
∞
𝛯 = ∑ 𝑒 −𝛽(𝑁𝜀−𝜇𝑁𝑟 )
𝑛=0
= ∑ 𝑒 −𝛽(𝑁𝜀−𝜇𝑁𝑟 )
𝑛
= 1 + 𝑒 −𝛽(𝜀−𝜇)
UKM
Thus,
1 1 𝜕𝛯
𝑓(𝜀 )𝐹𝐷 =
𝛽 𝛯 𝜕𝜇
1 1 𝜕
= −𝛽(𝜀−𝜇)
(1 + 𝑒 −𝛽(𝜀−𝜇) )
𝛽1+𝑒 𝜕𝜇
1 1
= (𝛽𝑒 −𝛽(𝜀−𝜇) )
𝛽 1 + 𝑒 −𝛽(𝜀−𝜇)
𝑒 −𝛽(𝜀−𝜇) 𝑒 𝛽(𝜀−𝜇)
= ∙
1 + 𝑒 −𝛽(𝜀−𝜇) 𝑒 𝛽(𝜀−𝜇)
1
=
𝑒 𝛽(𝜀−𝜇) +1
Therefore:
1
𝑓 (𝜀 )𝐹𝐷 =
𝑒 𝛽(𝜀−𝜇) +1

Statistical Mechanics Notes UKM

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Statistical Mechanics Notes UKM

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Mohd Hafizudin Kamal

LECTURER: Prof. Dato. Dr. Roslan Abd Shukor

Note 1: Statistical Mechanics Vs Thermodynamics

Compressing Particle in the box: IDEAL GAS LAW

Classical Statistics Quantum Statistics

How to connect the Thermodynamics and Statistical Mechanics?

TUESDAY 02 OKTOBER 2018

Note 1: Internal Energy in Thermodynamic Equations

By comparing that equation:

From the relation there,

Note 5: Wave function for Bose-Einstein Condensation and Fermi-Dirac

For many particle, the composite wave function is given below:

For the cases of:

Note 6: Partition Function, 𝑍

By given the probability, 𝑃𝑟

By looking at the average energy, 𝐸̅ ,

By letting that, the 𝑍 = ∑𝑟 𝑒 −𝛽𝐸𝑟

TUESDAY 09th OCTOBER 2018

Note 1: Recall back Partition Function 𝑍.

Equation 1: To get the average energy 𝐸̅ of the system:

Equation 4: To get the Helmholtz Free Energy 𝐹of the system:

Note 2: System that being consider to used.

Note 3: Ideal Gas System

To generalize equation (2): Then it become

Equation (3) tells us that the 𝑑 3 𝑟1 𝑑 3 𝑟2 𝑑 3 𝑟3 … 𝑑 3 𝑟𝑁 ≈ 𝑉 𝑁 and 𝑈 (𝑟1 , 𝑟2 , 𝑟3 … 𝑟𝑁 ) = 0

By putting ln 𝑏𝑜𝑡ℎ 𝑠𝑖𝑑𝑒:

Note 5: How about the energy 𝐸̅ . From the equation below

Note 7: Get the entropy 𝑆 of the system:

Note 8: Gibbs Paradox’s

By putting log both site and gets:

Note 9: Einstein Model

Solving for 𝐸̅ regarding to high and lower temperature condition

This can be done by using Taylor series:

ℏ𝜔 ℏ𝜔𝑒 −𝛽ℏ𝜔 𝑒 𝛽ℏ𝜔

WEDNESDAY 10th OCTOBER 2018

Note 3: At lower temperature limit Cases

Note 4: Two Level System: Application glassy (Amorphous Materials)

Note 5: Specific Heat of Glassy

By letting 𝑥 = 𝛽∆, then it became:

TUESDAY 30th OCTOBER 2018

Note 1: Thermodynamics Approached

= 𝑇𝑑𝑆 − 𝑝𝑑𝑉 + ∑ 𝜇𝑟 𝑑𝑁𝑟

From the definition of chemical potential 𝜇. Given that:

 All parameter except 𝑁𝑖 are constant. Thus:

𝑑(𝐸 − 𝑇𝑆) = 𝑑𝐹 = −𝑑𝑆𝑇 − 𝑝𝑑𝑉 + ∑ 𝜇𝑖 𝑁𝑖

= −𝑆𝑑𝑇 + 𝑉𝑑𝑝 + ∑ 𝜇𝑖 𝑑𝑁𝑖

Note 2: Grand Partition Function

The average number of particles is given by:

The average energy is given by:

Example like in Thin Film Using Laser Ablation

𝑝𝑥2 + 𝑝𝑦2 + 𝑝𝑧2 2 2

WEDNESDAY 31th OCTOBER 2018

2D Ideal Gas Occupies

Energy of the 2 dimensional structure is given by:

To get the Gibbs Free Energy:

Just a short note:

The, modified equation above and get 𝑛:

Note 2: Derivation of Bose-Einstein Distribution from the partition function.

̅ is the occupancy (Average number of particles for particulate state)

Note 3: Derivation of Fermi-Dirac Distribution from the partition function.

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