How Does the Equipartition Theorem Apply to Diatomic Molecules in a Box?

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In summary, Kerson Huang is discussing a classical system of N noninteracting diatomic molecules in a box and deriving the internal energy using the equipartition theorem. The Hamiltonian for a single molecule is used, and the author uses the formula for partition function and moves to the center of mass frame. The resulting energy is found to be consistent with the theorem, but the author is questioning the number of degrees of freedom and whether their approach is correct.
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[SOLVED] Equipartition Theorem

1. Kerson Huang, P 7.2:
Consider a classical system of N noninteracting diatomic molecules in a box of volume V at temperature T. The Hamiltonian for a single molecule is taken to be

[tex]H=\frac{1}{2m}(\vec{p_1}^2+\vec{p_2}^2) +\frac{K}{2}(|\vec{r_1}-\vec{r_2}|^2) [/tex].

Obtain the internal energy and show that it is consistent with equipartition theorem.

2. Homework Equations and attempt
I used the formulae for partition function

[tex]Q_N = \frac{1}{N!}Q_1[/tex]

where

[tex]Q_1 = \int d \omega e^{-\beta H}[/tex]

Further, I moved to the center of mass frame, and wrote the Hamiltonan in this form:

[tex]H= \frac{P_{cm}^2}{4m} + \frac{p^2}{4m} +\frac{Kr^2}{2}[/tex]

where now [tex]\vec{r}=\vec{r_1}-\vec{r_2}[/tex] and the mass of two atoms the same, while we all know what center of mass frame is (it is not too imprtant for my question to show all the way of derivations, I guess).

After all, using [tex]E =-\frac{\partial}{\partial \beta} \ln Q_N[/tex]

I found that [tex]E=\frac{9}{2}Nk_BT[/tex].

3. Question
According to equipartition theorem and using my last modified Hamiltonian looks I have 9 degrees of freedom and everything looks like being consistent. However, as far as I know, the diatomic molecule has 6 degrees of freedom (in case it is not rigid molecule). If I think, like that, then I am missing the factor (instead of 6 I have 9). Can you help me, where I am wrong?
 
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  • #2
Gravitino said:
1. Kerson Huang, P 7.2:
According to equipartition theorem and using my last modified Hamiltonian looks I have 9 degrees of freedom and everything looks like being consistent. However, as far as I know, the diatomic molecule has 6 degrees of freedom (in case it is not rigid molecule). If I think, like that, then I am missing the factor (instead of 6 I have 9). Can you help me, where I am wrong?
I am guessing that the quantum consideration gave wrong result, the fact that the relative distance actually does not vary from 0 to infinity in phase space in classical universe gave probably a weird result...
 

What is the Equipartition Theorem?

The Equipartition Theorem is a physical law that states that, in a system in thermal equilibrium, each degree of freedom will have an equal average energy of kT/2, where k is the Boltzmann constant and T is the temperature in Kelvin.

What is the significance of the Equipartition Theorem?

The Equipartition Theorem is important because it allows us to predict the average energy associated with each degree of freedom in a system at thermal equilibrium. This can be useful in understanding and calculating the behavior of gases, solids, and other systems.

What are the assumptions behind the Equipartition Theorem?

The Equipartition Theorem assumes that the system is in thermal equilibrium, meaning there is no net flow of heat within the system. It also assumes that the system is in classical equilibrium, meaning that it is not subject to quantum effects.

How is the Equipartition Theorem used in practice?

The Equipartition Theorem is used in statistical mechanics and thermodynamics to calculate the average energy of each degree of freedom in a system. This information can then be used to make predictions about the behavior of the system.

Are there any limitations to the Equipartition Theorem?

Yes, the Equipartition Theorem has limitations. It is not applicable to systems at very low temperatures, where quantum effects become important. It also does not account for interactions between particles in a system, which can affect the distribution of energy among degrees of freedom.

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