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Can anyone please explain me the concept of electronic, vibrational and rotational autoionization.

What I understood is, autoionization usually occurs when the ion core is rotationally or vibrationally excited so that the ion core excitation energy is larger than the binding energy of the Rydberg electron. When we think more physically, the electron might get a "kick" from the ion core which can cause it to escape from the coulomb field. Well, this is the case if the ion core is rotationally or vibrationally excited. But, what is then electronic autoionization? If the electron excitation cause the electron to escape the coulomb field, it is normal ionization, not autoionization right?

Please explain me.

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The Auger effect would be an example of electronic autoionisation. If a core electron is removed, an outer electron can fall into the empty core orbital and the energy release ejects one of the outer electrons leaving a positive ion.

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And indeed this can happen multiple times. Removing a K shell electron from neutral Fe (when isolated in interstellar space at least) will lead to an average of 4.7 additional Auger electrons lost as other electrons cascade down to fill the hole. – Chris White Apr 18 '13 at 15:51

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