auto-ionization

in mass spectrometry
This occurs when an internally supra-excited atom or molecular moiety loses an electron spontaneously without further interaction with an energy source. (The state of the atom or molecular moiety is known as a pre-ionization state.)
Source:
PAC, 1991, 63, 1541 (Recommendations for nomenclature and symbolism for mass spectroscopy (including an appendix of terms used in vacuum technology). (Recommendations 1991)) on page 1547
Orange Book, p. 206