Why is Q=q^{N} only valid for distinguishable particles?

In summary, the probability of finding a system in microscopic state i is determined by the partition function, which is the sum of all possible energy states. For distinguishable particles, the partition function is equal to the molecular partition function raised to the power of the number of particles. However, for indistinguishable particles, this is not true. The probability of finding a particle in a specific state is obtained by summing over all possible system-states, with the condition that the particle is in that state.
  • #1
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The probability of finding the system in microscopic state [itex]i[/itex] is:
[itex]p_{i}=\dfrac{1}{Q}e^{-\beta E_{i}}[/itex]

Where [itex]Q[/itex] is the partition function.

Assumption: molecule [itex]n[/itex] occupies the [itex]i_{n}[/itex]th molecular state (every molecule is a system).

The total energy becomes:
[itex]E_{i_{1},i_{2},...,i_{N}}=\epsilon_{i_{1}}+ \epsilon_{i_{2}}+...+\epsilon_{i_{N}}[/itex]

[itex]Q=\underset{i_{1},i_{2},...,i_{N}}{\sum}e^{-\beta\left(\epsilon_{i_{1}}+ \epsilon_{i_{2}}+...+\epsilon_{i_{N}}\right)}[/itex]

[itex]=\underset{q}{\underbrace{\left(\underset{i_{1}} {\sum} e^{-\beta e_{i_{1}}}\right)}}\times\left(\underset{i_{2}} {\sum} e^{-\beta\epsilon_{i_{2}}}\right)\times...\times\left(\underset{i_{N}}{\sum}e^{-\beta\epsilon_{i_{N}}}\right)[/itex]

Where [itex]q[/itex] is the molecular or particle partition function.

The partition function becomes [itex]Q=q^{N}[/itex] . This is valid for distinguishable particles only (why?).

The probability of finding molecule [itex]n[/itex] in molecular state [itex]i'_{n}[/itex] is obtained by summing over all system-states subject to the condition that [itex]n[/itex] is in [itex]i'_{n}[/itex]

[itex]p_{i'_{n}}=\dfrac{1}{Q}\underset{i_{1},i_{2},...,i_{N}}{\sum}\delta_{i_{n},i'_{n}}e^{-\beta\left(\epsilon_{i_{1}}+ \epsilon_{i_{2}}+...+ \epsilon_{i_{N}}\right)}=\dfrac{1}{Q}e^{-\beta\epsilon_{i'_{n}}}q^{N-1}=\dfrac{1}{q}e^{-\beta\epsilon_{i'_{n}}}[/itex]

So why is [itex]Q=q^{N}[/itex] only true when the particles are distinguishable and what does it mean when it is stated that "the probability of finding molecule [itex]n[/itex] in molecular state [itex]i'_{n}[/itex] is obtained by summing over all system-states subject to the condition that [itex]n[/itex] is in [itex]i'_{n}[/itex]"
 
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  • #2
Q = qN says that each particle occupies the available states independently of the others, thus the overall probability distribution is the product of the individual probability distributions. This is true for classical (distinguishable) particles but not for quantum (indistinguishable) particles.

For example consider how two particles 1, 2 would occupy two states A, B, and suppose that εA = εB so we may ignore the exponentials. For distinguishable particles the individual probabilities are 1/2, independently, so the probability of finding both particles in state A is 1/4. And likewise 1/4 for both in state B. But finding one in A and one in B can happen two ways, so the probability of that is 1/2. By contrast, boson states are counted by occupation number so there are three equally like cases: both in A, both in B or one in each. For fermions there is only one possibility: one in A and one in B.
 
  • #3
Thanks for clarifying. I now fully understand it.
 

1. What is the molecular partition function?

The molecular partition function is a mathematical concept used in statistical mechanics to describe the distribution of energy among the different possible states of a molecule. It takes into account the different energy levels and degeneracy of a molecule's internal states, and is used to calculate thermodynamic properties such as entropy and free energy.

2. How is the molecular partition function calculated?

The molecular partition function is calculated by summing over all possible energy states of a molecule, weighted by their respective Boltzmann factors. This involves taking into account the number of particles, the energy levels, and the degeneracy of each energy state.

3. What is the significance of the molecular partition function?

The molecular partition function is a fundamental concept in statistical mechanics, as it allows us to calculate thermodynamic properties and understand the behavior of molecules in different physical and chemical conditions. It also provides a link between the microscopic and macroscopic worlds, connecting the properties of individual molecules to bulk properties of matter.

4. How does temperature affect the molecular partition function?

Temperature has a direct effect on the molecular partition function, as it is used in the calculation of the Boltzmann factor. As temperature increases, the Boltzmann factor decreases, resulting in a larger contribution from higher energy states in the partition function. This can lead to changes in thermodynamic properties such as entropy and free energy.

5. Can the molecular partition function be applied to all types of molecules?

Yes, the molecular partition function can be applied to all types of molecules, as long as their internal energy levels and degeneracy are known. It is a general concept in statistical mechanics that is used to describe the behavior of molecules in different physical and chemical conditions, regardless of their chemical composition or structure.

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