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We report the finding of doubly charged molecular ions in a range of relatively large molecules including hydrocarbons upon their electron ionization as vibrationally cold molecules in supersonic molecular beams (SMB) (also named as Cold EI). Furthermore, we also report the detection by mass spectrometry of triply charged molecular ions in large PAHs such as decacyclene and ovalene upon their cooling in SMB. We found that the relative abundance of doubly charged molecular ions strongly depends on the internal vibrational cooling. While after some vibrational cooling the fragmentation pattern became cooling independent, the relative abundance of the doubly charged molecular ions was noticeably increased upon further cooling via increasing of the cooling make-up gas flow rate. In addition, the relative abundance of the doubly charged molecular ions was strongly increased with the compounds' size, and its electron energy threshold was lower than expected. These observations indicate a new mechanism that involves two separate electron ionization processes in the same compound, most likely with the same electron but at two separate atoms (places) in large molecules, to reduce Coulombic repulsion energy that can lead to fragmentation into two singly charged ions. These findings are shedding new light on electron ionization mass spectra. Accordingly, electron ionization mass spectra are the result of three separate mechanisms with relative magnitudes that depend on the compound size: (a) single electron ionization; (b) double electron ionization; and (c) single electron ionization with subsequent internal excitation by the same ionizing electron in another place.