Grand partition function

In summary, the conversation discusses the definition of the grand partition function and its application to finding the average occupancy of a point defect in a solid. The first method, using the total grand partition function, gives the correct answer, while the second method, using individual grand partition functions for each energy level, does not. The difference lies in not accounting for the factor of 2 in the second term of the individual grand partition functions. This leads to an incorrect answer and raises the question of why this is the case.
  • #1
jmz34
29
0
The example which I'll use to illustrate my problem is not a homework question but something I've found in a book and already know the answer to.

The grand partition function, G, is defined as SUM(over i)[exp(-B(Ei-yNi))] where B=1/kT, y is the chemical potential and Ei is the energy of the state i. I'm fine with this definition.

But the total grand partition of a system is also equal to the product of the individual grand partition functions of each energy level: G=G1*G2*...*GN . I thought I understood this as well until I came across the following example:

A point defect in a solid may be occupied by 0 ,1 (spin up or spin down) or 2 electrons, and the solid provides a reservoir of electrons at chemical potential y. The energy for occupation by a single electron is E, and that for 2 electrons is 2E+U, where U is the Coulomb repulsion energy between the two electrons. Obtain an expression for the average occupancy of the defect.

Now I tried doing this with the first definition to start with and that gave me the correct answer. So I said, G=1+exp(-B(E-y))+exp(-B(2E+U-2y)) and then used the grand potential etc.

However the second method didn't give me the correct answer. I identified the 4 independent energy levels as : 0, E, E, 2E+U. Then for each level I worked out the grand partition function:

G1=1
G2=1+exp(-B(E-y))
G3=G2
G4=1+exp(-B(2E+U-y))

since the energy level 4 can only exist if it's occupied by two electrons I grouped those two electrons together as effectively one particle with an associated energy of occupation 2E+U.

G=G1G2G3G4 does not give me the correct answer. Why is this?

Thanks.
 
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  • #2
So I said, G=1+exp(-B(E-y))+exp(-B(2E+U-2y)) and then used the grand potential etc.
Shouldn't the second term have a factor of 2?
 

1. What is the Grand Partition Function?

The Grand Partition Function is a statistical mechanical function that is used to describe the statistical behavior of a system with variable numbers of particles and energy. It is defined as the sum of all possible microstates of the system, weighted by the corresponding Boltzmann factor.

2. How is the Grand Partition Function different from the Partition Function?

The Partition Function describes the statistical behavior of a system with a fixed number of particles and energy. The Grand Partition Function, on the other hand, takes into account systems with variable numbers of particles and energy.

3. What are the applications of the Grand Partition Function?

The Grand Partition Function is commonly used in statistical mechanics to calculate thermodynamic properties of systems such as gases and liquids. It is also used in the study of phase transitions and critical phenomena.

4. How is the Grand Partition Function related to the chemical potential?

The chemical potential is defined as the change in free energy with respect to the number of particles. In terms of the Grand Partition Function, it can be expressed as the partial derivative of ln(Q) with respect to the number of particles at constant temperature and volume.

5. Can the Grand Partition Function be used for both classical and quantum systems?

Yes, the Grand Partition Function can be applied to both classical and quantum systems. In classical systems, the Boltzmann factor is used, while in quantum systems, the Fermi-Dirac or Bose-Einstein distribution is used depending on the type of particles in the system.

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