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The electron would have to be in a bound system, such as an atom or a molecule, in order to have energy levels. Free electrons can only have momentum and intrinsic properties.
but in my answer I chose to stay away from the concepts of phase and group velocity, because they are not required to answer the original question as asked. As an experimental laser physicist, I prefer to give answers that can be explained with simple experiments.
It's actually because natural polarizers, such as certain crystals, and reflections at Brewster's angle, work on the electric field. So it is more than a convention, it is the natural way to formulate it in terms of experimental effects. Note that the measurement of polarization pre-dates electromagnetic field theory.
You would need to study the line profiles to see if the broadening is due to a series of close lines, or if it is dominated by Doppler shifts. The statistics are quire clear, and you will study this in a quantum optics class.