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At a high enough KE, we would expect to obtain 1:1 signal ratios of ClO n- and Cl- (n=2-4), corresponding to the macroscopic stoichiometric proportions, given our assumption that the Cl 2p photoionization cross section is the same for all ionic species. While this assumption might not be fully accurate, e.g., due to small variations in the intensity of satellites which redistribute signal from the main PE line (Ref.) different cross sections for the ions are highly unlikely to explain the ClO n- / Cl- ratio of 1.2 at 900 eV KE. Rather, one must keep in mind that the photoemission signals are integrals of the total density distributions from the surface into the bulk, exponentially attenuated by the electron mean free path. In a recent photoemission study of aqueous NaI we have shown that the surface enhancement of iodide relative to sodium was observable only for electron KEs smaller than 600 eV; higher KEs primarily probe the bulk solution (Ref.). Probably, for the systems investigated here the preferential surface segregation is significantly stronger than for NaI solutions, and hence surface contributions to the total signal remain detectable at the highest KE achieved here. It would require considerably higher KEs for the surface contributions to become negligible.
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