Thomson - Rayleigh Scattering: Rotational & Vibrational Energy Levels

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Discussion Overview

The discussion centers on the mechanisms of Rayleigh and Thomson scattering, particularly in relation to molecular energy levels, including rotational and vibrational states. Participants explore the implications of these scattering processes on energy changes in molecules and the nature of elastic scattering.

Discussion Character

  • Exploratory
  • Debate/contested
  • Technical explanation

Main Points Raised

  • Some participants note that Rayleigh scattering does not excite electrons to higher electronic levels but causes oscillation, while Thomson scattering involves free or quasi-free electrons that also oscillate and accelerate.
  • It is proposed that Thomson scattering cannot cause rotational energy changes due to its nature involving free electrons, raising questions about its effect on vibrational energy levels.
  • Participants discuss the elastic nature of both Rayleigh and Thomson scattering, suggesting that this implies no change in energy levels of the scatterers.
  • There is a question about how Thomson scattering can be elastic if it causes electrons to accelerate, with some suggesting this acceleration relates to oscillation or vibration.
  • One participant seeks clarification on the behavior of target mass during Rayleigh scattering, questioning whether it involves all electrons, the entire atom, or multiple molecules.
  • Another participant introduces the concept of thermal motion affecting Rayleigh scattering, suggesting that it could lead to both redshift and blueshift in scattered light.
  • A simple estimate of thermal velocities of free electrons at 300 K is provided, discussing the implications for scattering broadening and the differences between Thomson/Rayleigh and Compton scattering.
  • It is noted that scattering involving changes in vibrational or rotational energy is termed Raman scattering, distinguishing it from Rayleigh and Thomson scattering.

Areas of Agreement / Disagreement

Participants express differing views on the effects of Rayleigh and Thomson scattering on energy levels, with no consensus reached regarding the specifics of how these processes interact with molecular energy states.

Contextual Notes

Participants highlight the complexities of defining the target mass in scattering processes and the implications of thermal motion on scattering outcomes. The discussion remains open regarding the exact nature of energy changes during scattering.

cemtu
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TL;DR
Thomson Scattering can not cause rotational spectra or energy build-up, which requires the whole molecule to rotate since Thomson Scattering is about free and quasi-free electrons. But what about vibrational energy spectra, or energy build-up on such a free electron?

Rayleigh Scattering happens on the atomic level so it begs the question, "can it cause both rotational and vibrational energy level changes in atoms or molecules?."
We know from molecular spectroscopy that incoming light on a molecule can change a molecule's rotational, vibrational and electronic energy levels.

If the incoming light is,

  • on the far-infrared and microwave region the molecule gets rotational energy.(microwave spectra)
  • on the near-infrared region the molecule gets both rotational and vibrational energy.(infrared spectra)
  • on the ultraviolet & visible light region, the molecule gets all energy levels rotational, vibrational, and electronic energy (electronic band spectra)
We also know that,

  • Rayleigh Scatter does not excite electrons of atoms to another electronic level but only causes them to oscillate.
  • Thomson Scatter happens when an electron is free or quasi-free and it also makes the electron oscillate and more, accelerate.
Taking into account that both Rayleigh and Thomson most probably happen at low energies and vibrational and rotational energy changes of molecules happen at microwave and infrared spectra:

QUESTION:
It is clear that,
  • Thomson Scattering can not cause rotational spectra or energy build-up, which requires the whole molecule to rotate since Thomson Scattering is about free and quasi-free electrons. But what about vibrational energy spectra, or energy build-up on such a free electron?
  • Rayleigh Scattering happens on the atomic level so it begs the question, "can it cause both rotational and vibrational energy level changes in atoms or molecules?."
 
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Both Rayleigh and Thomson scattering are elastic, so they can't lead to a change in the energy levels of the scatterer.
 
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DrClaude said:
Both Rayleigh and Thomson scattering are elastic, so they can't lead to a change in the energy levels of the scatterer.
But Thomson Scattering causes electron to accelerate. What about it? How is it elastic then? Is it an acceleration in the sense of oscillation/vibration?
 
cemtu said:
But Thomson Scattering causes electron to accelerate. What about it? How is it elastic then? Is it an acceleration in the sense of oscillation/vibration?
The charged particles doing the scattering accelerate in the sense that the direction of motion changes, but the kinetic energy stays the same. See https://en.wikipedia.org/wiki/Thomson_scattering
 
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DrClaude said:
The charged particles doing the scattering accelerate in the sense that the direction of motion changes, but the kinetic energy stays the same. See https://en.wikipedia.org/wiki/Thomson_scattering
Oh I get it, you are talking only about Thomson and Rayleigh cuz they are elastic scattering, I get it now, I got confused for a moment thinking about Compton...
 
cemtu said:
I didn't quite understand this. Could you elaborate on it, please?
Consider a light speed photon scattering from a stationary target of a fixed mass.
The energy of the photon after Compton scattering is E=Eγ/(1+2Eγ/mc2)
On the limit of Eγ<<mc2, the momentum delivered on the target decreases linearly with the original photon momentum. But since the target is massive, the energy lost to the target is proportional to square of the energy of incoming photon. The redshift of the photon thus is proportional to its energy, diminishing at low energies - the limit of Thomson/Rayleigh scattering.
But the redshift never actually goes to zero if the photon energy is nonzero and target mass finite.
How does the target mass behave for Rayleigh scattering?
 
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snorkack said:
Consider a light speed photon scattering from a stationary target of a fixed mass.
The energy of the photon after Compton scattering is E=Eγ/(1+2Eγ/mc2)
On the limit of Eγ<<mc2, the momentum delivered on the target decreases linearly with the original photon momentum. But since the target is massive, the energy lost to the target is proportional to square of the energy of incoming photon. The redshift of the photon thus is proportional to its energy, diminishing at low energies - the limit of Thomson/Rayleigh scattering.
But the redshift never actually goes to zero if the photon energy is nonzero and target mass finite.
How does the target mass behave for Rayleigh scattering?
Target mass oscillates as the elastic scattering happens due to the wave nature of light, which happens because the electrons interact with the Electrical Field and this field causes the electrons to accelerate -> vibrate -> Change in direction(???) only not the value of velocity itself.

I don't even know how to vibrate or oscillate without changing the absolute value of velocity. How can you both oscillate and only change the direction of motion at the same time but not the absolute value of it?
 
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Target mass necessarily ends up changing momentum because the momentum of the incoming proton changes. But what is the target mass for Rayleigh scattering?
 
snorkack said:
Target mass necessarily ends up changing momentum because the momentum of the incoming proton changes. But what is the target mass for Rayleigh scattering?
All electrons of an atom or molecule?
 
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cemtu said:
All electrons of an atom or molecule?
And that´s the question.
One electron? All electrons? The whole atom including the nucleus? The whole molecule? A fluctuation of gas density spanning multiple molecules? Or the whole piece of solid?
Mind you, of course Rayleigh scattering from nonstationary targets must have both redshift and blueshift - according to thermal motion of the target molecules. Does the line shape of the Rayleigh scattered light match the Boltzmann distribution of the target?
 
  • #11
snorkack said:
And that´s the question.
One electron? All electrons? The whole atom including the nucleus? The whole molecule? A fluctuation of gas density spanning multiple molecules? Or the whole piece of solid?
Mind you, of course Rayleigh scattering from nonstationary targets must have both redshift and blueshift - according to thermal motion of the target molecules. Does the line shape of the Rayleigh scattered light match the Boltzmann distribution of the target?
I dont know... :(
 
  • #12
A simple order of magnitude estimate:
At 300 K, free electrons should have average thermal velocities of around 60 km/s. Which is about 1/5000 the speed of light. Thus Thomson scattered light should have broadening in the order of magnitude of 1/5000 (or maybe twice as much?).
Whereas the redshift of Compton scattered radiation is in the magnitude of 2Eγ/mc2,
so the Compton scattering redshift should match thermal broadening around 50 eV, or 25 nm. Vacuum UV. Strongly absorbed, nuisance to work with. Is this the reason Thomson/Rayleigh and Compton scattering are seen as different things? That the transition region is hard to explore?
 
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  • #13
If visible light scattering off a molecule causes a change in vibrational or rotational energy, it is termed Raman scattering rather than Rayleigh or Thomson scattering.
 

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