Spin-orbit effects, electronic decay and breakdown phenomena in the photoelectron spectra of iodomethane

► We provide relativistic iodomethane single- and double ionization spectra over a large energy range. ► Outer valence photo-double ionization spectra could be theoretically reproduced. ► Pronounced breakdown phenomena in the iodomethane subvalence single ionization spectrum are described. ► The participating satellites could be adequately characterized.