The Equipartion principle for diatomic molecules

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SUMMARY

The discussion centers on the Equipartition principle as it applies to diatomic molecules, specifically addressing the heat capacity derived from classical mechanics. It is established that the classical treatment yields a heat capacity of \( \frac{7}{2} \) due to 7 degrees of freedom: three translational, two rotational, and two vibrational (one for momentum and one for position). The Hamiltonian is presented in two forms, highlighting that while one suggests 9 degrees of freedom, the symmetry of the Hamiltonian indicates that only one degree of freedom is relevant for the vibrational component, confirming the heat capacity calculation.

PREREQUISITES
  • Understanding of classical mechanics and thermodynamics
  • Familiarity with Hamiltonian mechanics
  • Knowledge of degrees of freedom in molecular systems
  • Basic concepts of the Equipartition theorem
NEXT STEPS
  • Study the derivation of the Equipartition theorem in statistical mechanics
  • Explore Hamiltonian dynamics and its applications in molecular physics
  • Learn about the implications of molecular symmetry on physical properties
  • Investigate the role of vibrational modes in heat capacity calculations
USEFUL FOR

This discussion is beneficial for physicists, chemists, and students studying thermodynamics and statistical mechanics, particularly those focusing on molecular behavior and heat capacity in diatomic systems.

enochnotsocool
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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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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.
 

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