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Question: Regarding the energy levels of an atom, when an electron becomes excited, assuming there is enough energy to move it up to the next level, does that first electron push away any pre-existing electrons that were previously on that level, or do they fit together somehow?
Answer: We certainly don't think of electrons as crowding into an energy level that is already full. If you have one atom, and you give your atom one photon of exactly the energy to move an electron from 2s to 3s, and the 3s is full, then the jump cannot happen. If you give your atom two photons, one for the 2s to 3s transition, and another to kick out one 3s electron, then the transition can happen. You see, if you want to push away the other electron, you need some more energy. But don't worry! Usually, you have a very large number of atoms, and in a situation of high-energy bombardment, least a few of those atoms will happen to have empty spots in energy levels for electrons to fill in whatever transition you want to excite. You can observe this by looking at spectra of stars and other space objects where atoms may be in high-energy environments, absorbing and emitting all sorts of wavelengths, revealing all the spectral fingerprints of all sorts of elements. Here is a related website from another university: http://stars.astro.illinois.edu/sow/spe ... absorption
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