Do large molecules ionize?

A possible mechanism for the ionization or lack thereof in large molecules is discussed. The experimental observation is that the ionization efficiency rapidly decreases with increasing weight, whether one uses electron impact, single-photon or multi-photon ionization. Possible mechanisms for this decline in the yield of ions are considered. It is suggested that in larger molecules ionization occurs through the intermediate formation of charge pairs which can ionize in a unimolecular-like fashion due to an energy fluctuation. A more probable route is however for the charge pairs to recombine. Possible experimental tests of the proposed mechanism are considered and a scaling law for the mass-dependence is derived and shown to fit the available data.