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(

j

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_ _ _ _ _ _ _ _

c

j

Problem Set 5

Solutions - McQuarrie Problems

3.20 MIT

Dr. Anton Van Der Ven

Problem 3-4

Fall 2003

We have to derive the thermodynamic properties of an ideal monatomic gas from the following:

O = c

q

3

2

2¬:/T

` c

and ¡ \ = =

/

2

O is the partition function for the grand canonical ensemble, where T, \, j are ﬁxed. The characteristic potential

for the grand canonical ensemble is the ’’grand canonical potential’’

c = 1 T o j· = j\

(since 1 = T o j\ ÷ j· )

dc = odT jd\ ·dj

The thermodynamic properties for the grand canonical ensemble are:

∂c

o =

∂T

N,V

∂c

j =

∂\

T,

∂c

· =

∂j

T,V

The grand canonical potential is related to O according to

c = /T ln O (see table 3-1)

but O = c

q

so,

3 3

2¬:/T 2¬:

2 2

5

2

/T /T \ c = (/T ) \ oxp = ¡` =

2 2

/ / /T

Starting with ·,

3

2

2

2mkT

· =

∂

= \ oxp

kT ∂ h

T,V

((3-8-1))

and j

3

2

2

∂

_ _ _

_

j =

∂V

= /T

2mkT

oxp

kT h

T,

Putting those together we can get the ideal gas equation of state, namely

·

j = /T

\

Now o,

∂c ò 2¬: 2¬:

o = = / /T ) \ c ÷ (/T ) \ c

2 2

/T

2

∂T 2 / /

N,V

1

3

2

3

2

5

2

3

2

_ _

_ _ _ _

_

_ _ _ _

_

. ¸¸ .

_ _

_

_ _

_

_ _

_ _

__ _ _

_ _

_ _

__

_ _

_ _

_

_ _

_ _

_ _

_ _

^ =

j =

3

2

3

2

ò 2¬:/T j 2¬:/T

o / \ c \ c =

2 2

2 / T /

3

2

ò j 2¬:/T

o = / \ c

/

2

2 T

N

ò j

o = / · ((3-8-2))

2 T

But from (3-8-1) we can get

3

2

2¬:/T

c = ·\

1

/

2

2¬:/T

3

2

\

j = /T ln

/

2

·

Putting this into (3-8-2) we get

3 3

ò 2¬:/T \ 2¬:/T \

2 2

c

5

2

÷ ln o / ÷ ln · = ·/ ln / =

2 2

2 / · / ·

5

2

3

2

2

V

o = ·/ ln

2mkT

c

h N

This is the same expression as that obtained in the canonical ensemble (see Chapter 5). This is due to the

equivalence of ensembles when · is very large.

Problem 3-10

2

We are dealing with the isothermal-isobaric ensemble this time, with the partition function for an ideal monatomic

gas given to us in the problem as

(2¬:) (/T )

_

N 5 3

2

j/

3

The isothermal-isobaric is for ﬁxed ( ·, T, 1 ).

The characteristic potential for this ensemble is the Gibbs free energy

G = 1 T o ÷ j\

dG = odT ÷ \ d1 ÷ jd·

The thermodynamic properties are:

∂G

o =

∂T

p,N

∂G

\ =

∂j

T,N

∂G

∂·

p,T

G is related to the isothermal-isobaric partition function ^ according to (see Table 3-1):

(2¬:) (/T )

5 3

G = /T ln ^ = ·/T ln

j/

3

2

2 2

_ _

_ _

_ _

_ _

_ _

_ _

. ¸¸ .

_ _

_ _

_

_ _

_

_ _

_ _

_ _

_

_

_

_ _

ò

3

ln (2 ¬:)

3

2

÷ G = ·/T ln j ln ( /T ) ln /

2

Starting with \,

NkT

\ =

∂G

=

p ∂p

T,N

which is the ideal gas equation of state. Now for j :

(/T )

5

2

3

∂G (2¬:)

∂· j/

p,T

2

j = = /T ln

3

2¬:/T

j =/T ln /T ÷/T ln j

/

2

o

3

2

And now for o,

5

2

3

(/T ) ∂G

2

(2¬:)

∂T j/

ò

÷ ·/ o = = ·/ ln

3

2

p,N

3

2

\ 2¬:/T

2

5

o = ·/ ln ÷ ·/ ln c

/

2

·

5

2

3

2

2

V

o = ·/ ln

2mkT

c

h N

These are the same expressions as obtained in the grand canonical ensemble (Problem 3-8) and in the canonical

ensemble (see chapter 5). This is due to the equivalence of ensembles in the thermodynamic limit, i.e · is very large

such that ﬂuctuations are negligible.

Problem 3-12

When looking at ﬂuctuations, we derived

_

2

_

1 1 1

1 (^1) ≈ √ oxp

2

2¬/T C

v

2/T

2

C

v

For an ideal monatomic gas (derived explicitly in chapter 5)

8

1 = ·/T

2

∂1 8

C

v

= = ·/

∂T 2

4

We are now asked what is the probability that the ·-particle system will sample an energy that differs by 10 /

from the average energy, 1 =

3

·/T ? (We can let · = ·

A

= 6 022 10

23

`) .

2

_

10

4

_

_ _

8

1 10

6

^ = 1 = 10

6

1 = ·/T

100 2

2 2 2

(^1)

_

10

6

2

9

· / T

2

8

_

6

_

2

4

= = 10 ·

2 3

2/T C

v 2/T

2

·/ 4

2

So now we can go back to 1 (^1 , )

1 8

_

6

_

2

1 (^1) ≈ √ oxp 10 ·

/T 8¬·

4

3

_ ¸

_ _

_ _

_ _

_ _

_ _

_ _ _ _

_ _ _ _

_ _

_ _

_ _ _ _

_ _

_ _

1 (^1) ≈ √

1

oxp 4 ò 10 .

11

/T 8¬·

This is an extremely small probability which validates our earlier assumptions.

Problem 3-18

Derive an expression for the ﬂuctuation of the pressure in the canonical ensemble..

We know the pressure in state i is

∂1

i

j

i

=

∂\

and by deﬁnition

_ _ _ ¸

Ei

∂Ei

oxp

kT ∂V

i

j = _ ¸

Ei

oxp

kT

i

Fluctuation is deﬁned as o

2

= (j j)

2

= j

2 2

j .

p

Using the methods developed in class:

Step 1: Multiply both sides by the partition function

_ _

1

i

jQ = j

i

oxp

/T

i

Step 2: Get derivative with respect to mechanical variable’s conjugate.

∂ ∂

1

i

(jQ) = j

i

oxp

∂\ ∂\ /T

i

∂Q ∂j ∂

1

i

j ÷ Q = j

i

oxp

∂\ ∂\ ∂\ /T

i

∂

1

i

∂j ∂

1

i

j oxp ÷ Q = j

i

oxp

∂\ /T ∂\ ∂\ /T

i i

_ _ _ _ _ _ _ _ __ _ _ _ _ _ _

1

i

∂1

i

1 ∂j

∂j

i

1

i

1

i

∂1

i

1

j oxp ÷ Q = oxp ÷ j

i

oxp

/T ∂\ /T ∂\ ∂\ /T /T ∂\ /T

i i i

Step 3: Divide through by the partition function

_

oxp

_

Ei

¸

_

∂Ei

_ ¸

∂pi

_

Ei

¸ _ _ ¸ _ _ ¸

1

j

1

Q

∂V i

∂V

oxp j

i

oxp

Ei

∂Ei

i i

kT ∂V kT

∂p

kT kT ∂V kT

÷ = ÷

Q Q Q Q

j

2

_ _

j

2

∂j ∂j

i

÷ = ÷

/T ∂\ ∂\ /T

Rearranging a little...

∂j

o

2

= j

2

j

2

= /T

∂j

i

p

∂\ ∂\

Note:

∂pi

has no immediate macroscopic interpretation, it must be calculate in any speciﬁc case and depends

∂V

2

∂ Ei

on the particular spectrum of

∂V

2

. This conclusion holds for all generalized forces in the form ¹

i

=

∂Ei

, where

∂a

a is an extensive displacement conjugate to ¹. Hence, we cannot make an unqualiﬁed assertion that ﬂuctuations in all

kinds of external forces will be small.

4

_ _

_ _

_ _

Compare this with ﬂuctuations in extensive quantities such as 1, H, or · which can be expressed in terms of

thermodynamic response variables suchs as heat capacities or compressibilities.

Speciﬁc calculations of the ﬂuctuations in j of a perfect gas by Fowler is estimated as

2

) (j j

≈ ò 10

12

2

j

1

for a cubic centimeter of gas under standard conditions. This is approximately , where : is the number of

2

3 n

molecules in the gas.

(Source: The Principles of Statistical Mechanics, Richard C Tolman, Oxford University Press, ﬁrst edition

1938)

Problem 3-24

2

2

Show that H

2

H = /T C

p

in an ·, j, T ensemble.

·, 1, T ﬁxed means we are working in the isothermal-isobaric ensemble..

The partition function in this ensemble is

^ = c

Ej pV

V j

Where the 1

j

’s are the energies of the system when it has volume \. We also remember that H = 1 ÷ j\.

Using the methods developed in class:

Step 1: Multiply both sides by the partition function

÷j\ ) c

Ej pV

H^ = (1

j

V,j

Step 2: Get the temperature derivative at constant (·, 1 ) (The conjugate variable to H in this case)

_ _

∂H 1

÷ j\ ) c

Ej pV

^ ÷H

_

(1

j

_

=

1

(1

j

÷ j\ )

2

c

Ej pV

∂T /T

2

/T

2

N,P

V,j V,j

Step 3: Divide through by the partition function

∂H 1 V,j

(1

j

÷j\ ) c

Ej pV

1

V,j

(1

j

÷j\ )

2

c

Ej pV

÷ H =

∂T /T

2

^ /T

2

^

N,P . ¸¸ . . ¸¸ .

H H

or

2

2

2

_ _

=

N,P

H H /T

∂H

∂T

_ _

but we know

∂H

∂T

N,P

=

p

C . So,

2

2

2

=

p

H H /T C

2

5

=

=

=

=

_ _ _ _

_ _

_ _ _ _ _ _

_ _ _ _ _ _

_ _

_ _ _ _

_ _ _ _

_ _

_ _

Problem 3-26

2

2

∂p

∂V

∂ V

Show that ..

∂N N

V,T N,T

From Gibbs-Duhem we have

odT \ dj ÷ · dj = 0

At constant T , we then get

dj \

=

dj ·

We can use the chain rule and get:

dj dj d·

=

dj d·

V,T

dj

V,T

Using partial derivative manipulation

d· d· d\

dj

V,T

d\

P,T

dj

N,T

But for a single component system

dV

p,T

= the molar volume =

V

and we get

dN N

d· · d\

\ dj

N,T

dj

V,T

Putting this all together we get

dj \

2

dj

·

2

d· d\

V,T N,T

Problem 4-2

3

2

h

V 12mkT

2

6N

Show that given in table 4-1 is very large for electrons in metals at T = 800 1.

Take Na-metal having the following properties

10

. - stable in the bcc crystal structure with lattice constant a = 4 28 10 :

- two Na atoms per bcc unit cell

- number of valance electrons per Na atom = 1

- valance electrons in Na can be considered nearly free

So we can get the following values to substitute into the original equations:

· 2

=

\

(4 28 10

10

)

3

.

. / = 6 6262 10

34

J -

J

/ = 1 8807 10

23

.

1

:

e

= 0 100ò 10

31

/p .

Putting those all together we get

6· /

2

3

2

= 1ò24 1

¬\ 12:/T

Therefore Boltzmann statistics cannot be applied to electrons in metals. Must use Fermi-Dirac statistics.

6

Problem 4-6

∞

n n 2 1

o = a

1

a

2

N=0 {nj }

with :

1

and :

2

= 0 1 2 , , a:d . The means with the restriction that :

1

÷:

2

= ·.

1 {nj } n n2

n n 2 1

Let’s consider a a for several values of N.

1 2

{nj }

· = 0 → possible combinations of :

1

and :

2

are 0 and 0.

=⇒ = 1

{nj }

· = 1 → possible combinations of :

1

and :

2

are

:

2

· :

1

1 0 1

0 1 1

n n 2 1

=⇒ a a

2

= a

1

÷a

2

1

{nj }

· = 2 → possible combinations of :

1

and :

2

are

·

2

2

2

2 2

1

1 2

÷ a

1

=⇒ a a

2

= a

2

÷ a a

{nj }

· = 8 → possible combinations of :

1

and :

2

are

:

2

:

1

0 2

1 1

2 0

n n 2 1

:

2

· :

1

1 2 8

2 1 8

n n 2 2 2 1

=⇒ a a

2

= a a

2

÷a a

1

1 1 2

{nj }

· = 4 → possible combinations of :

1

and :

2

are

:

2

· :

1

2 2 4

n n 2 2 2 1

=⇒ a a

2

= a a

2 1 1

{nj }

n n 2 1

For · 4 → a

1

a = 0 because :

1

÷:

2

� 4

2

{nj }

Putting everything together we get

n n 2 2 2 2 2 2 1

2

1 2

÷ a

1

÷ a a

2

÷a a a

1

a = 1 ÷ a

1

÷a

2

÷a

2

÷a a

2

1 1 2

÷ a a

2 1

N {nj }

7

_ _

_ _ _ _

_ _

_ _

_ _ _ _

_ _ _ _

2

2

Now lets consider

k

o = 1 ÷ a

k

÷a

k=1

2

1

2

2

1

÷ a

2

÷ a

2

2

a

2

1

÷ a a

1

2

2

÷ a a

2

1

2

2

1

÷a a

2

2

o = 1 ÷ a

1

÷ a 1 ÷ a

2

÷ a = 1 ÷ a ÷

1 2

÷ a a

n n

This expression contains the exact same terms as that obtained with

1

a a

1

2

.

2 N

{nj }

Problem 4-8

We need to show this ( remember the upper (lower) signs is for Fermi-Dirac (Bose-Einstein)

:

o = / [:

j

ln :

j

(1 :

j

) ln(1 :

j

)[

j

Start with the partition function and go from there. Becuase of the equivalence of ensembles in the thermodynamic

limit, we can calculate the entropy using the ensemble that offers the most mathematical convenience. For Fermions

/

∂ ln

or Bosons, this is the grand canonical ensemble. o = ln O ÷ /T

∂T V,

_

� ε

j

_

kT

O = 1 ÷ `c

j

1

_

� ε

j

_

kT

ln O = ln 1 ÷ `c

j

� ε

j

∂ e kT

(

� ε

j

� ε

j

εj εj )

oxp

∂ lnO kT

2

kT

=

∂T

=

∂T

j

1 `c 1 `c kT

j

kT

_ _ __

_ _

� ε

j

_ `c

εj

εj

_

kT

o = / ln 1 `c

kT

÷

εj

_ _ 1 `c

j

To make this a little easier to manipulate we can write this shorthand by making the following substitutions. Let:

ε j

n = 1 `c

εj

and · = `c

n = 1 · and n · = 1

·

:

j

=

n

So we now have

o = / { ln n :

j

ln ·} = / { lnn :

j

ln :

j

:

j

ln n}

j j

1

o = / { 1 :

j

) ln n :

j

ln:

j

} = / 1 :

j

) ln :

j

ln:

j

( (

n

j j

Remembering that n · = 1

o = / { 1 :

j

) ln (1 :

j

) :

j

ln :

j

} (

j

o = / {:

j

ln :

j

(1 :

j

) ln (1 :

j

)}

j

8

_ _

_ _

_ _

_

_ _

!

Problem 4-12

N-distinguishable independent particles, each of which can be in state ÷ε

o

or -ε .

o

·

+

= number of particles with energy ÷ε

o

·

= number of particles with energy ε

o

with ·

+

÷ ·

= ·

The total energy is given as:

1 = ·

+

ε

o

·

ε

o

= 2 ·

+

ε

o

·ε

o

We now have to evaluate the partition function Q by summing oxp

E

over levels and compare it to the result

kT

Q = ¡

N

..

We know

1

j

Q = oxp

/T

j

where ¸ labels a state in which the system can reside.

Instead of summing over the states that the system can be in, we can also sum over the possible energy levels,

making sure we take account of the degeneracy of each energy level, i.e.

1

Q = \( 1) oxp

/T

E

where \(1) is the number of states with energy E.

For this system we have already stated the allowed energy levels are

1 = 2·

+

ε

o

·ε

o

where ·

+

can vary from 0 → ·.

For each allowed energy level 1, there are \(1) possible states compatible with this energy. Since the ·

particles are distinguishable,

·! ·!

\(1) = =

· ·

! ·

+

(· ·

+

)!

+

!

This represents the number of ways that ·

+

particles out of N can be in the ÷ state.

So now we can write

·!

(2

+

Q = \( 1) oxp ( a1 ) =⇒ oxp [ a · ε

o

·ε

o

)[

Since E is uniquely a function of N+ ·

+

(· ·

+

)!

E N+

This can be rewritten in a nicer form if we remember the binomial expansion

n

: a

n1

(1 ÷ a)

n

=

1

!( : : :

1

)!

n1 =0

So we have

_ _

2

Q = c

Nε o

_

·!

_

εo

_

N+

_

c

·

+

(· ·

+

)!

N+

2

if we let a = c

εo

and rewrite using the binomial expansion we have

1 ÷ c

2εo

_

N

Q = c

Nε o

or

Q = c

εo

÷ c

ε o

N

Now we need to compare this to Q = ¡

N

, where ¡ is the single particle partition function deﬁned as

9

_ _

_ _

_

_

_ _

εl

¡ = c

l

where | labels the single particle states. In this example there are two single particle states, with energy -ε

o

and + ε .

o

=⇒ ¡ = c

εo

÷ c

εo

and

ε o

Q = ¡

N

= c ÷ c

ε o

N

∂E

The last part of this problem asks us to calculate and plot the heat capacity for this system. We know C

v

=

∂T

and 1 is given as

εo

∂ ln Q

2

∂ ln c

εo

÷ c

1 = /T

2

= /T ·

∂T ∂T

εo

c

εo

εo εo

_

εo

c c

εo

2 kT

2

1 = /T ·

kT

2

εo

= ·ε

o

c

c

εo

÷ c

εo

c ÷ c

ε o

1 = ·ε

o

lanh ( aε

o

)

and C

v

is then

∂1

_

ε

o

_

C

v

= = ·/

ε

o

_

2

soch

2

∂T /T

2

/T

kT

Plotting

Cv

vs.

Nk εo

10

_

_ _

_

_ _

_ _

_ _

_ _

_ _

_ _

_ _

_ _

¯

¯

A =

2

2

Problem 5-4

Calculate the entropy of Ne at 8001 a:d 1 atm.

The entropy of an ideal gas (eqn 5-20):

5

3

2¬:/T \ c

o = ·/ ln

/

2

·

Note this is neglecting electronic excitations (see Chapter 5).

Some data:

: = 8 8ò1 10

26

/p .

/ = 1 8807 10

27

.

k

J

. / = 6 6262 10

34

J -

. j = 1 atm = 1 018 10

5

1 a

Putting that together we can get

\

=

/T

= 4 0880 10

26

.

· j

2¬:/T

3

2

= 8 8ò2 10

31

.

/

2

and

o = ·/ ln 4 41 10

7

.

N

o = / ln 4 41 10

7

.

where · = the number of Ne atoms.

We are now asked to estimate the translational degeneracy \

-From our study of ﬂuctuation theory, we found that the ﬂuctuation in energy of a thermodynamic system

(with · very large) is exceedingly small.

-Therefore, the energy of the gas is essentially always very close to 1 (see discussion on page 63 of

McQuarrie) and we can use the expression for the entropy in the microcanonical ensemble.

o = ln \ /

where \ is the degeneracy at ﬁxed energy 1. Compare this with

o = / ln 4 41 10

7

.

and we get

N

\ = 4 41 10

7

.

N

23

which makes sense since it should be large because · is on the order of 10

.

Problem 5-9

What is the DeBroglie wavelength of Arÿ at 2081´

/

2

2¬:/T

Use:

: = 6 684 10

26

/p .

1

2

/ = 1 8807 10

27

.

k

J

. / = 6 6262 10

34

J -

11

_ _

A

and we get A = 1 6 10

11

m .

Now compare this with the inter-atomic distance

The volume per Ar atom is

\ /T

=

· j

with j . = 1 018 10

5

Pa. So

V

N

. = 4 06 10

26 3

m . The interatomic distance ∼ . = 8 0 10

9

N

(See page 83 on the relevance of this result.)

1

3 V

12

Fall 2001

_ ¸

_ ¸

_ ¸

_ ¸ = _ ¸

_

_ ¸

_

Problem Set 5

Additional Problems Solutions

3.20 MIT

Dr. Anton Van Der Ven

Fall 2002

Problem 1

(a) A system of · non-interacting particles with two possible states either 0 or ε. A good rule is too assume

’’particles’’ (e.g. atoms, electrons, etc) are indistinguishable unless they are localized in a crystal or on a surface. The

number of atoms in the excited state can be determined using Boltzmann statistics under the assumption that we are

working at high temperature and/or low density::

·

ε

= ·¬

ε

where ¬

ε

is the probability an atom will be in state ε. This probability is determined using the single particle

partition function and can be written as

ε

oxp

kT

¬

ε

= _ ¸ (McQuarrie 4-14)

ε;

oxp

kT

i

But our system can be in only two states, so the sum in the denominator can be found explicitly:

ε

oxp

¬

ε

=

kT

_ ¸

ε

oxp [0[ ÷ oxp

kT

So ·

ε

can be written as

ε

oxp ·

·

ε

= ·¬

ε

= ·

kT

ε ε

1 ÷ oxp

kT

1 ÷ oxp

kT

·

ε

=

N

ε

1+exp[ [

kT

i i

(McQuarrie 4-12 and 4-13) (b) The total energy is simply l = ·ε = · ¬ ε

i

l = · ¬ ε

1 1

÷ ¬ ε

i i

= · (¬ ε

2 2

) = · [(1 ¬

2

) 0 ÷ ¬

2

ε[

i

ε

oxp

l = · ¬ ε ) = ·

kT

(

2

_ ¸ ε

ε

1 ÷ oxp

kT

l =

Nε

ε

1+exp[ [

kT

Note: Since many particles will occupy the same state (either 0 or ε) these particles must be Bosons. At lower

temperatures we would have to use Bose-Einstein statistics (McQuarrie 4-26) which would lead to a much more

complicated problem since we would have to determine the chemical potential j.

1

_ _

_ _

Problem 2

The magnetization is given as

N

` = : j

i o

i=1

This is basically saying that we have atoms localized in a crystal and the magnetic moment at each site can be

either up or down. The problem asks us to determine the thermodynamic properties as a function of T, ·, H. Let us

also assume for simplicity that we can work at constant volume. Therefore, our controlling variables are T, ·, \, H.

We need to make the appropriate Legendre transform to the entropy. Remember the entropy can be written

starting from 1:

1 = To j\ ÷ H` ÷j·

rearranging to get things in terms of o and a we get

o

= a1 ÷aj\ aH` aj·

/

Legendre transform such that our controlling variables are \, ·, T, H

o

( a1 ÷aH` = a To 1 ÷H` ) = ac = ln I

/

where c is the characteristic potential for this ensemble with \, ·, T, H constant and I is the partition

function. I can be written as

I = oxp[ a 1

state

`

state

H)[ (

states

where we sum over all possible energy states and magnetizations `

state.

Since the particles are non-interacting, the energy at ·, a = constant and H = 0 is constant. 1 is independent

of the number or arrangement of up versus down spins. Since the absolute scale of energy is not important for

thermodynamics, we can arbitrarily set the constant energy equal to zero giving us

N N

I = oxp[ a`

state

H[ = oxp a : j H = oxp [ a: j H [

i o i o

states n1 ,n 2,...nN i=1 n1,n 2 ,...nN i=1

N N +1

I = oxp[ a: j H [ = oxp[ a: j H [

i o i o

n1 ,n 2 ,...nN i=1 i=1 ni = 1

We can evaluate the sum since :

i

= 1 so,

I = (oxp[ aj H [ ÷ oxp[ aj H [)

N

o o

We know the characteristic potential of an ensemble is related to the partition function for that ensemble according

to

ac = ln I → c = /T ln I

Furthermore, we know from thermo that

dc = odT jd\ ÷ jd· `dH

which gives us the following relationships for the properties of the system:

∂c

o =

∂T

V,N,H

_ _

∂c

` =

∂H

V,N,T

2

_ _

_ _

_ _

_ _

_ _ _ _

_ _ _ _

j =

c

∂c

∂·

V,T,H

∂c

j =

∂\

T,N,H

and from stat mech we have from above

c = /T· ln [oxp [ aj H [ ÷ oxp [ aj H [[

o o

Lets get the entropy, o

∂c

o =

∂T

V,N,H

H

o

(oxp [ aj H [ oxp [ aj H [)

kT

2 o o

o = /· ln (oxp [ aj H [ ÷ oxp [ aj H [) ÷ /T·

o o

oxp [ aj H [ ÷ oxp [ aj H [

o o

o = /· {ln (oxp [ aj H [ ÷ oxp [ aj H [) aj lanh ( aj H )}

o o o o

Now for the magnetization

∂c oxp [ aj H [ oxp [ aj H [

o

` = = /T·aj

o

= ·j lanh ( aj H )

o o

∂H

o

oxp [ aj H [ ÷ oxp [ aj H [

V,N,T o o

` = ·j lanh ( aj H )

o o

The energy 1

c = 1 To H`

1 = ÷ To ÷ H` = 0

However if you deﬁne a quantity called the internal magnetic energy (which is a quantity analogous to the

enthalpy in the T, j, · ensemble)

1

H

= 1 H`

you can get

1

H

= ·j H lanh ( aj H )

o o

The last part of this problem asks you to determine the behavior of the energy and entropy as T → 0.

1

H

(T → 0) = ·j H

o

lim o = lim /· {ln (oxp [ aj H [ ÷ oxp [ aj H [) aj lanh ( aj H )} = 0

o o o o

→∞ →∞

( o T → 0) = 0 is in accordance with the third law of thermodynamics.

Problem 3

(a)

N

` = j :

i o

i=1

(see solution to Problem 2 - Method 1)

∂c oxp [ aj H [ oxp [ aj H [

o

` = = /T·aj

o

= ·j lanh ( aj H )

o o

∂H

o

oxp [ aj H [ ÷ oxp [ aj H [

V,N,T o o

` = ·j lanh ( aj H )

o o

3

_

_ _

_ _

(b) The partition function for the ·, \, H, T ﬁxed ensemble is

(

s

I = oxp [ a 1

s

` H )[

s

where - = -tatc-

We want to determine the ﬂuctuations in the extensive quantity `. Use the 3-step procedure developed in class.

Step 1: Multiply both sides by the partition function

`I = `

s

oxp [ a (1

s

` H )[

states

s

Because 1

s

is always constant (see comment in Problem 2) we can therefore arbitrarily set it to zero and write

_ __ _ _ ___

N N N

`I = j :

i

oxp aj H :

i o o

n1 ,n 2,...nN i=1 i=1

Step 2: Get derivative with respect to mechanical variable’s conjugate.

_ _ _ _ _ ___

2

N N N

∂` ∂I

I ÷ ` = a j

o

:

i

oxp aj H :

i

∂H ∂H

o

n1 ,n 2,...nN i=1 i=1

2

_ _ __ _ _ ____ _ _ _ _ _ ___

N N N N N N

∂`

I÷` a j :

i

oxp aj H :

i

= a j

o

:

i

oxp aj H :

i

∂H

o o o

n1 ,n 2 ,...nN i=1 i=1 n1 ,n 2 ,...nN i=1 i=1

Step 3: Divide through by the partition function

∂` 2

÷ a` = a`

2

∂H

or we can write it like this

(c`)

2

_

= `

2

`

2

=

1 ∂`

a ∂H

with:

∂`

_ _

= a·j

2

1 lanh

2

(ajH )

∂H

,N

(c) As a → ∞, lanh ( ajH ) → 1. Therefore `

T →0

= ·j and (c` )

2

= j

2

{1 1} = 0. In other

T →0

words, the ground state with all the spins aligned has no ﬂuctuations.

4

_ _

_ _ _ _

\ =

Problem 4

From the ﬁrst and second law we have

d1 = T do jd\ ÷ Hd` ÷ jd·

1 = T o j\ H` ÷ j· (Euler Form)

We are working with ﬁxed ·, T, \, ` in this problem. We need to make a Legendre transform because T is a

controlling variable instead of 1.

o

a1 = a1 = ln Q

/

Q = oxp [ a1

state

[

states

1 = /T ln Q

From the differential form of 1, namely

d1 = odT jd\ ÷ Hd` ÷ jd·

we get that

∂1

H =

∂`

T,V,N

We are working under constant magnetization so

N

` = j :

i

= j

o

(:

+

:

)

o

i=1

where :

+

= number of up spins and :

= number of down spins. That means that the sum in the expression

of Q must be performed over only those states with ﬁxed ` (i.e. ﬁxed :

+

and :

)

Also the atoms in the system do not interact, meaning that the energy is independent of the number and

arrangement of up/down spins and is therefore constant = 1

o.

Q = oxp [ a1

states

[ = oxp [ a1

o

[ = \ oxp [ a1

o

[

states with states with

magnetization M magnetization M

where \ is the number of states that are consistent with a magnetization ` = j (:

+

:

) .

o

·!

:

+

! (· :

+

)!

·!

Q = oxp [ a1

o

[

:

+

! (· :

+

)!

·! ·!

1 = /T ln oxp [ a1

o

[ = 1

o

/T ln

:

+

! (· :

+

)! :

+

! (· :

+

)!

using Stirling’s approximation,

1 = 1

o

/T {(· ln · ·) :

+

ln :

+

÷ :

+

(· :

+

) ln ( · :

+

) ÷ ( · :

+

)}

but we know from above that

` ÷ j ·

` = j (:

+

:

) = j (2 :

+

·) =⇒ :

+

=

o

o o

2j

o

we can substitute this back into our expression for 1 to get 1 as a function of `

_ _ _ _ _ _ __

` ÷ j · ` ÷ j · j · ` j · `

o

o

1 = 1

o

/T · ln ·

o

ln ln

o

2j 2j 2j 2j

o o o o

5

_ _

_ _

_ _

_

_ _

a

∂F

Remembering that H =

∂M T,V,N

_ _ _ _ _ _ _ _

∂1 1 ` ÷ j · 1 1 j · ` 1

H = = /T ln

o

÷ ln

o

÷

∂` 2j 2j 2j 2j 2j 2j

T,V,N o o o o o o

_ _ _ _ __

/T ` ÷ j · j · `

H = ln

o

ln

o

2j 2j 2j

o o o

` ÷ j ·

2j aH = ln

o

o

j · `

o

and it is easy to show that ` = j · lanh ( j aH ) which is the same result as in the other ensemble of Problems

o o

2 and 3. This is due to the equivalence of ensembles in the thermodynamic limit.

Problem 5

(a) Grand canonical ensemble:

∞ ∞

O =

j

oxp [ [ a1 oxp [ [ = aj· ( ) oxp [ [ Q ·, \, T aj·

=0 N j =0 N

. ¸¸ .

This sum extends

over allstates with

total # of particles = N

j

oxp [ a1 [ = ( ) = Q ·, \, T

N

¡

·!

j

for a one component gas of non-interacting particles. We can write ¡ in closed form as we have done before as

2¬:/T

3

2

¡ = \

/

2

So now O can be written as:

∞ ∞

_

¡

N

¡c

N

O = oxp [ aj· [ =

·! ·!

N=0 N=0

But if we let a = ¡c

then we can write this sum in a form for which the solution is know, namely

∞

N

a

a

= c

·!

N=0

If we now substitute in for ¡ we can write O as

O = c

zV

with . =

c 2¬:

/

2

(b) The characteristic potential for the grand canonical ensemble is

j\ = c = /T ln O

c = 1 T o j·

dc = odT jd\ ·dj

3

2

6

_ _ _ _

_ _ _ _

_ _

_ _

_ _

_ _

_ _

_ _

_ _ _ _

_

_

cj

( ∂c ∂ .\ )

j = = /T = /T .

∂\ ∂\

T,

∂c ∂.

· = = /T \ = .\

∂j ∂j

T,V

kT N

putting those two parts together and eliminating . gives us the familiar ideal gas equation j = .

V

(c)

2 2

( ) (c·)

= (because \ ﬁxed)

j

2

·

2

We need to get (c·)

2

= ·

2

·

2

. Follow the 3-step procedure.

Step 1: Multiply both sides by the partition function

∞

N

¡

·O = O = · c

N

·!

N=0

∞ ∞

N N

¡

· c

N

= ·

¡

c

N

·! ·!

N=0 N=0

Step 2: Get derivative with respect to mechanical variable’s conjugate.

_ _

∞ ∞

∂·

¡

N

¡

N

N

O ÷ · a· c

N

= a·

2

c

∂j ·! ·!

N=0 N=0

∂·

2

O O ÷ a· ·O = a·

∂j

Step 3: Divide through by the partition function

∂· 2

÷a· = a·

2

∂j

2 ∂·

·

2

· = /T

∂j

2

e

from (b) we have that · = .\ with . =

h

2m

3

2

.

∂· ∂.

= \ = a.\

∂j ∂j

2

·

2

· = .\

divide by \ to get the densities

j

2

j

2

=

.

=

·

\

2

\

j

2

j

2

·

=

j

2 2

·

j

2

j

2

1 /T

= √ =

j

·

j\

7

_ _

(d) To second order in c·

1

2

∂

2

ln1 · ( )

ln 1 · ( ) ÷ (c·) ( ) = ln1 ·

2 ∂·

2

N N =

_ _

2

assuming a Gaussian distribution around · with variance c· we get

( )

_

10

12

·

_

1 ·

10

= oxp = c

7

which is very unlikely.

1 · ( ) 2

8

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