[Physics] Is photon emission possible without electrons changing energy levels

electromagnetismmoleculesphotonsquantum mechanicsvibrations

Does molecular vibrational transition and consequent emission of infrared radiation involve electrons changing energy level? In wikipedia, about vibronic transitions it says "Most processes leading to the absorption and emission of visible light, are due to vibronic transitions. This may be contrasted to pure electronic transitions which occur in atoms and lead to sharp monochromatic lines (e.g. in a sodium vapor lamp) or pure vibrational transitions which only absorb or emit infrared light.". Does this mean infrared radiation is emitted without electrons playing a direct part?
What about changing in molecular rotational energies?
Also, I understand reflection is not a radiation absorption-emission phenomena, so can you explain what actually happens to the photons? Same thing for radiation scattering.

Best Answer

Regarding the general question posed in the title, yes, it is possible in general to have photon emission (or absorption) without electrons changing energy levels. For example, in nuclear magnetic resonance (NMR), EM radiation (photons) are absorbed and re-emitted with changes in nuclear spin state. NMR spectroscopy relies on splitting between nuclear spin states due to a large applied magnetic field. This splitting causes absorption and stimulated emission of EM radiation with energy equal to the splitting. So NMR is one example of photon emission without changes in electronic energy levels playing a direct role.

However, with regards to your specific examples, electrons are directly involved. In the vibrational modes, the resonant frequencies are determined by the stiffnesses of the molecular bonds. Those stiffnesses in turn depend on the electronic structure of the molecule. The question is, how much does the electronic energy change when the bond lengths and angles are changed by small amounts? This can be calculated using electronic structure packages like Gaussian and ABINIT. The nuclei are also involved; the masses of the nuclei also factor into the resonant frequencies. The picture is similar for (dihedral) rotation of chemical bonds.

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