CHE 485: STATISTICAL MECHANICS AND THERMODYNAMICS ASSIGNMENT # 7 SOLUTIONS

TOPICS: (1) FLUCTUATIONS (2) ISING MODEL

1. (Chandler 3.15) For an open multicomponent system show that (

where

is the fluctuation from the average of number of

to particles of type i and is the chemical potential of type i. Similarly relate a thermodynamic quantity. Finally, for a one component system in the grand canonical and relate this quantity to the constant volume heat capacity ensemble evaluate and compressibility. Solution: Using the given definition of we get: ( ) Expanding, taking averages and canceling out terms we get ( ) ( )

Here the probability distribution is given by: where Now taking derivatives of ( ( ) )

with respect to

and

we get

Taking the mixed derivative we get Substituting these values in the above equation we get ( ) ( ( ) )

Similarly

( ) ( ) ( ) We only have to evaluate the first expression, which is given by:

So putting the other expressions we get the equation as:

For a one component system in the grand canonical ensemble the probability distribution is given by: and The fluctuation in energy is given by: ( Now Hence * + ) *

Taking the second derivative we get: Also * + * [ + ]

* +

+ * + * +

Here and temperature.

are the isothermal compressibility and co-efficient of volume expansion with

2. (Chandler 3.17a) x is a random variable with distribution p(x) in a<x<b and the average over the distribution of x is given by:

To prove that if and only if where is the Dirac delta function. Solution: For for all x in (a,b) this is trivially true, so we consider From the definition we get for the two sides of the equality: ( ) ( )

So the two sides will be equal only when Rearranging we get ( ) now as

) hence we have ( so we must have

(Chandler 3.17b) For two random variables x and y the joint probability distribution is given by only when p(x, y). Prove that where and are the distributions of x and y. Solution: Again, the equation is trivially true if sides of the equation are ( ) ( ) ) which gives or for all x or y. The two

Hence subtracting we get ( as before.

3. (Chandler 3.18) Consider a system of N distinguishable non-interacting spins in a magnetic field H. The energy of a particular state is given by Here is the magnetic moment in the direction of the field.

a) Determine the internal energy of this system as a function of , H and N by employing an ensemble of these variables Solution: A particular state of the system is completely characterized by values of the indices , so state . Only the energy of the system is fluctuating based on the directions of the spins so this ensemble is a canonical type ensemble with the probability distribution of a state given by: The Boltzmann factor is given by:

Hence the partition function is Now all possible states are generated by varying the indices of the molecules which can take 2 values -1 or 1. This will give 2N possible states of the system. The partition function Q: ( )

As we put we get the following terms: and : One of each N and : There are N ways of replacing a positive or negative sign from N of each. N(N-1)/2 and : There are N(N-1)/2 ways of replacing two positive or negative sign from N. and so on. So the summation can be written as (using the shorthand ( ) for replacing m signs from n) ( ) Which we recognize as the binomial expansion of ( ) ) So for the current system we have ( ) hence ( Using the relation for internal energy with the partition function Q given by: ( )

Also, energy can be obtained from using just the definition of average:

Putting the expression for energy we get ( ( ) )

In this case we can write the sum in the same way as explained above for the partition function but it is clear that same number of +1 and -1 in the sum will give rise to terms with equal and opposite coefficients and we can use the identity ( ) ( ): [ ( ) ] ( )

The above series is just what is obtained if we differentiate the series for Q with respect to , so we can write: This gives the same result as above. b) Determine the entropy of this system as a function of , H and N. Solution: Using the definition of the Helmholtz energy we get ( )

Now, ( ), for this system and from the previously derived expression. Hence we get: ( Again we can also derive S from the Gibbs formula: Separating terms we get: ( ( c) Determine system behavior as T->0 Solution: As ( ( ( ) ) ) or we get for the energy and entropy the limits as: ) ( ) as before. ) )

The last form is obtained by applying L Hopital rule for indeterminate limits (form 0/0). Problem 4. (Chandler 3.19 a) For the system mentioned above find the average total magnetization M

 as a function of , H and N

Solution: Using the definition of average we get: ( )

This can be written in expanded form as:

Again using the combination of +1 and -1 we get the different energy states as below:
( ( ) ( ) ( ) )

We recognize the series from previous problem as the derivative of Q which gives: b) Determine ( ) Solution: where Again using the combination of +1 and -1 we get the different energy states as below: ( ( ( )( ) Then the fluctuation is given by: ( ( ) ) ) ) and compare results with the susceptibility . We only need to find ( ) .

This is recognizable as just the second derivative of the partition function with respect to :

Now susceptibility is given by:

c) Determine system behavior as T->0 This is just using the previously shown limit of .

we see that Now based on the definition of when for all i, which is the state when all the spins are aligned with the magnetic field. This shows that there is not fluctuation for this ground state. Problem 5 (Chimowitz 7.3) The energy if interacting spins in a mean field model is given by: To show that for a single spin given by fluctuating in this field the mean field strength is

For a single spin we see that the energy is given by The fluctuation term is zero as there are no neighboring interactions. Then partition function is given by: For a single spin there are only two states with , so the partition function is given by:

Hence the expectation value will be given by: For we get the equation as We consider the function The derivative is given by The equation has real solution only when the slope of exceeds the slope of the later is just 1. So this only requires that

for which