Partition Function in Thermal Physics: Overcounting States?

In summary: The idea is that the partition function of a combined system is just the product of the partition functions of its subsystems. If the subsystems interact or are identical, then the partition function is not the same.
  • #1
ak416
122
0
This is a question about thermal physics. There's this partition function Z = sum over all states s of the system ( exp(-E_s/T)). And its just used to calculate the probability of any state by taking the Boltzman factor exp(-E_s/T) of that state and dividing over the partition function. Theres one question that asks to show that the partition function for a combined system, Z(1and2) = Z(1)*Z(2). I understand the way its proved, you just take a double sum and say that E(1and2) =E(1)+E(2), so you can separate the sums. But by using a double sum arent you possibly overcounting some states? For example if E_s1 + E_s2 = 1 + 3 and E_s1 + E_s2 = 3 + 1, also 2+2... Shouldnt this just count as one state of the system, call it E_s = 4. Or would it be better to just keep it this way and then whenever you want to count the probability of observing an E = 4 of the double system, you would have to add all the possible boltzman factors corresponding to E = 4. I think i just answered my question..., but I am just wondering what's the right way to think about it, because there's another part in the book about ideal gases talking about how when you have a system with distinct particles you can overcount, but when you have a system with identical particles, you have to multiply the partition function by 1/N! They also say at the end that in our argument we have assumed that all N occupied orbitals (i guess they mean energy levels) are always different orbitals. How does this change anything?
 
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  • #2
The assumptions here are independence and distinguishability. It isn't true that that the partition function of a composite system is simply the product of the partition functions of its subsystems if the subsystems interact or if they are identical. The [tex] 1/N! [/tex] in the classical partition function of an ideal gas is the classic example of this subtlety.
 
  • #3
ak : It sounds like your doubt is just another way of stating the Gibbs Paradox. You might want to look that up too.
 
  • #4
Do you suppose you could explain how you arrived at the answer in the first place?

Z = sum[exp(e/T)]

so Z(1+2) = Z(1)Z(2)

...

a double sum -- as in sum[ exp(e1/t) + exp(e2/t) ] = sum[exp(s1/t)*sum[sum[exp(s2/t)]
??

I understand the partition function idea - but I'm poor with sums :|
 

1. What is the partition function in thermal physics?

The partition function in thermal physics is a mathematical concept used to describe the distribution of energy among particles in a system. It takes into account the number of particles, their energy levels, and their interactions with each other.

2. How is the partition function related to entropy?

The partition function is related to entropy through the Boltzmann distribution, which states that the probability of a particle being in a certain energy state is proportional to the number of microstates (possible arrangements of the particles) associated with that energy state. The partition function is used to calculate the total number of microstates, which is then used to calculate the entropy of the system.

3. What is the significance of overcounting states in the partition function?

In some cases, the partition function may count certain energy states more than once, leading to an overcounting of states. This can occur when particles are indistinguishable or when the energy levels are degenerate. Overcounting states can affect the accuracy of thermodynamic calculations, and methods such as the Maxwell-Boltzmann distribution can be used to correct for this.

4. How does the partition function change with temperature?

The partition function is a function of temperature, as it takes into account the energy levels of particles and their interactions. As temperature increases, the partition function also increases, reflecting the fact that particles have a higher average energy and more microstates are available to them.

5. Can the partition function be used for both classical and quantum systems?

Yes, the partition function is a fundamental concept in both classical and quantum statistical mechanics. However, different formulations and assumptions are used for each type of system. Classical systems are typically assumed to have continuous energy levels, while quantum systems have discrete energy levels and require the use of quantum statistics.

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