Exploring the Vibrational Degrees of Freedom for Diatomic Molecules

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Discussion Overview

The discussion revolves around the vibrational degrees of freedom for diatomic molecules, particularly addressing why some participants assert it to be two at high temperatures while others maintain it is one. The conversation includes theoretical considerations and interpretations of the Equipartition Principle, as well as references to additional degrees of freedom such as libration.

Discussion Character

  • Debate/contested
  • Technical explanation
  • Conceptual clarification

Main Points Raised

  • Some participants propose that the vibrational degree of freedom for diatomic molecules is two at high temperatures, suggesting that both potential and kinetic energy contribute to this count.
  • Others argue that diatomic molecules have only one vibrational degree of freedom, regardless of temperature, and challenge the interpretation of degrees of freedom in relation to temperature.
  • It is noted that the Equipartition Principle assigns two (1/2 kT) average energy to a single vibration, but this does not imply two degrees of freedom.
  • Some participants mention "libration" as a potential separate degree of freedom, describing it as a bending of the inter-atomic axis, while others clarify that libration does not apply to free diatomic molecules.
  • There is a discussion about the total degrees of freedom for a diatomic molecule, which is commonly stated as three translational, two rotational, and one vibrational, suggesting that any additional degrees of freedom would not be independent.

Areas of Agreement / Disagreement

Participants do not reach a consensus on the number of vibrational degrees of freedom for diatomic molecules, with multiple competing views remaining regarding the interpretation of vibrational and librational motions.

Contextual Notes

The discussion includes references to the Equipartition Principle and the definitions of degrees of freedom, which may depend on specific assumptions about the system being analyzed. The role of libration in the context of diatomic molecules is also debated, with varying interpretations of its applicability.

td21
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For diatomic molecule, why is the vibrational degree of freedom equal to two at high temperature?
Why not just one?
Thank you very much.
 
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The energy of the vibration is the sum of the potential energy and the kinetic energy. The first is determined by the change of the distance between the atoms, the other is determined by their speeds. Speed and distance are the two degrees of freedom.

ehild
 
td21 said:
For diatomic molecule, why is the vibrational degree of freedom equal to two at high temperature?

You are mistaken. Diatomic molecules have exactly one vibrational degree of freedom, regardless of temperature.

You may have mean something else, which is related to degrees of freedom and temperature, but but you will have to formulate your question correctly.
 
Are you referring to rotational and vibrational degrees of freedom?
 
Khashishi said:
Are you referring to rotational and vibrational degrees of freedom?
If you asked me, the answer is NO.

The diatomic molecule can perform only one kind of vibration: the interatomic distance change sinusoidally in time.

But the general SHM motion of angular frequency ω is of the form x=Asin(ωt+θ). Two data are needed to know the energy of the vibrating body : for example, the position and the velocity at the same time.
In Kinetic Theory, the Equipartition Principle assigns two (1/2 kT) average energy to a single vibration.ehild
 
ehild said:
the Equipartition Principle assigns two (1/2 kT) average energy to a single vibration.

But not two degrees of freedom, as stated in the original message.
 
td21 said:
For diatomic molecule, why is the vibrational degree of freedom equal to two at high temperature?
Why not just one?
Thank you very much.

A number of sources refer to "libration" as a separate degree of freedom. This is described as a flexing or bending of the inter-atomic axis. Other sources do not mention libration.
 
klimatos said:
A number of sources refer to "libration" as a separate degree of freedom. This is described as a flexing or bending of the inter-atomic axis. Other sources do not mention libration.
Libration is restricted rotation. It does not exist for free diatomic molecules. Libration can happen in some external force field, or a diatomic part of a molecule can librate with respect to the other part.
http://en.wikipedia.org/wiki/Libration_(molecule)
ehild
 
klimatos said:
A number of sources refer to "libration" as a separate degree of freedom.

The total number of degrees of freedom in a system of particles cannot be greater than the sum of the degrees of freedom of all the particles assumed unconstrained. The latter is 6 for a diatomic molecule. The nomenclature of the degrees of freedom commonly used in this case - 3 for the motion of CoM, two rotational and one vibrational - is thus maximal and any other degree freedom will not be independent.
 

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