Abstract
Three-electron Auger decay is an exotic and elusive process, in which two outer-shell electrons simultaneously refill an inner-shell double vacancy with emission of a single Auger electron. Such transitions are forbidden by the many-electron selection rules, normally making their decay lifetimes orders of magnitude longer than the few-femtosecond lifetimes of normal (two-electron) Auger decay.
Here we present theoretical predictions and direct experimental evidence for a few-femtosecond three-electron Auger decay of a double inner-valence-hole state in CH3F. Our analysis shows that in contrast to double core holes, double inner-valence vacancies in molecules can decay exclusively by this ultrafast three-electron Auger process, and we predict that this phenomenon occurs widely.