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The NIST atomic spectra database has atomic energy levels well documented. I understand that discrete energy levels in gases can be identified using emission and absorption spectroscopy, due to the presence of isolated atoms.

However, I'm curious about how we can experimentally identify the discrete energy levels in metals, and solids in general, in which the conduction and valence bands are generally known.

Are there sophisticated experimental techniques to vaporize a medal/solid and then use absorption or emission spectroscopy to identify the energy levels? What if you bring the metal to a liquid form, would that help (I'm thinking about the Mercury example for which the discrete energy levels are known)? Are the discrete levels somehow deduced theoretically from the conduction and valence band knowledge?

To summarize, are there specific (experimental) or other techniques designed for probing discrete energy levels in metals/solids and liquids?

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    $\begingroup$ Well, there generally are not discrete energy levels in metals - the electronic state of the solid is those bands. Now you can measure a lot about the characteristics of the bands. Some solids have discrete energy levels, say defect states in a band gap. $\endgroup$
    – Jon Custer
    Commented Feb 13 at 17:03
  • $\begingroup$ I see! I was hoping that maybe there are ways to probe the discrete levels of say Iron using some exotic technique. After all, I think we first observed discrete levels using Mercury (Franck-Hertz experiment). Forgive my ignorance, I'm a theorist! $\endgroup$
    – cconsta1
    Commented Mar 3 at 20:14

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