| CH$sb5sp+$ is used extensively as a proton transfer chemical ionization reagent, but it is energetically possible for CH$sb5sp+$ to undergo charge transfer with some molecule A. The enthalpy change for this process would be IP(A) - 7.91 eV assuming the charge transfer produces A$sp+$, CH$sb4$ and H. Thus species with low IP might undergo charge transfer with CH$sb5sp+$. Ferrocene (I.P. = 6.75 eV), for example, reacts mainly by charge transfer, but so does anisole (I.P. = 8.21 eV) unless the CH$sb5sp+$ has suffered thermalizing collisions subsequent to its formation. Thermalized CH$sb5sp+$ reacts with anisole only by proton transfer. Both kinetic and thermodynamic evidence suggests that it is excited CH$sb5sp+$ that reacts by charge transfer with anisole.;Ethoxylated alcohol CH$sb3$(CH2)$sb{rm x}$-(OC$sb2$H$sb4)sb{rm y}$OH, and polyethylene glycol (PEG), H-(OC$sb2$H$sb4)sb{rm n}$OH, self chemical ionization (Self CI) spectra show protonated parent ions. Proton transfer between the polymer molecules is observed. Clustering of the protonated polymers is observed for ethoxylated alcohols where y $le$ 3, but not for y $ge$ 4. It is suggested that this results from an internal strong hydrogen bond in the larger protonated species. Such an internal hydrogen bond is shown to have a strong effect on the proton affinity, the entropy of protonation and the CID of a typical ethoxylated alcohol (x = 14 and y = 7).;Reactions of proton donors with formamide and the potential energy hypersurface obtained by high level ab initio calculations show that the relative importance of the H$sb2$O loss and CO loss processes have comparable large energy barriers. |
