The Equipartion principle for diatomic molecules

In summary, the classical treatment of the diatomic atom predicts a heat capacity of $7/2$ due to 7 degrees of freedom, but using a different Hamiltonian shows that there are actually 9 degrees of freedom that could contribute to the heat capacity. However, this is countered by the fact that k(r1-r2)^2 only has one degree of freedom due to symmetries of the Hamiltonian.
  • #1
enochnotsocool
2
0
It is taught that the classical treatment of the diatomic atom would give a heat capacity of $7/2$ due to 7 degrees of freedom, (three translational momentum, two rotational momentum, on vibration momentum and on vibration position).

This is based on the Hamiltonian looking like:
$$
H = \frac{\mathbf{P}^2}{2m} + \frac{L_1^2}{2I_1} + \frac{L_2^2}{2I_2} + \frac{p^2}{2m} + \frac{m\omega r^2} {2}
$$
To compute the partition function

But the original Hamiltonian could be written directly as
$$
H = \frac{\mathbf{P_1}^2}{2M_1} + \frac{\mathbf{P_2}^2}{2M_2} + k(\mathbf{r_1} - \mathbf{r_2})^2
$$
Using this there is clearly 9 degrees of freedom that could contribute to the heat capacity (two independent three dimensional momentums, and one three dimensional position).
Is there something I am missing?
 
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  • #2
Yes, you are missing the fact that k(r1−r2)2 has only one degree of freedom because of the symmetries of the Hamiltonian. Only the magnitude of the distance between the particles matter. The Hamiltonian is completely symmetric under rotations of one particle around the other.
 

What is the Equipartition principle for diatomic molecules?

The Equipartition principle for diatomic molecules is a physical law that states that the total energy of a molecule is equally distributed among all of its degrees of freedom. This means that each degree of freedom, such as translational, rotational, and vibrational, has an equal share of the total energy.

How does the Equipartition principle apply to diatomic molecules?

The Equipartition principle applies to diatomic molecules because they have three degrees of freedom: translational, rotational, and vibrational. This means that the total energy of a diatomic molecule is divided equally among these three degrees of freedom, according to the principle.

What is the significance of the Equipartition principle for diatomic molecules?

The Equipartition principle is significant because it allows us to predict the behavior and properties of diatomic molecules based on their energy distribution. It also helps us understand the relationship between temperature and the average kinetic energy of molecules.

Are there any exceptions to the Equipartition principle for diatomic molecules?

Yes, there are some exceptions to the Equipartition principle for diatomic molecules. For example, at low temperatures, some degrees of freedom may become frozen and not contribute to the total energy of the molecule. Additionally, for more complex molecules, the principle may not apply due to the presence of internal interactions or other factors.

How is the Equipartition principle for diatomic molecules used in scientific research?

The Equipartition principle is used in scientific research to understand and predict the behavior of diatomic molecules in various environments. It is also used in the development of new materials and technologies, as well as in the study of molecular dynamics and thermodynamics.

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