One electron less or one proton more: how do they differ?

From the NIST website and the literature, we have collected the Ionisation Energies (IE) of 3,052 and the Proton Affinities (PA) of 1,670 compounds. For 614 of these, both the IE and PA are known; this enables a study of the relationships between these quantities for a wide variety of molecules. From the IE and PA values, the hydrogen atom affinities (HA) of molecular ions M^•+ may also be assessed. The PA may be equated to the heterolytic bond energy of [MH]⁺ and HA to the homolytic bond energy. Plots of PA versus IE for these substances show (in agreement with earlier studies) that, for many families of molecules, the slope of the ensuing line is less negative than -1, i.e. changes in the PA are significantly less than the concomitant opposite changes in IE. At one extreme (high PA, low IE) are the metals, their oxides and hydroxides, which show a slope of close to -1, at the other extreme (low PA, high IE) are the hydrogen halides, methyl halides and noble gases, which show a slope of ca. -0.3; other molecular categories show intermediate behaviour. One consequence of a slope less negative than -1 is that the changes in ionic enthalpies of the protonated species more closely follow the changes in the enthalpies of the neutral molecules compared with changes in the ion enthalpies of the corresponding radical cations. This is consistent with findings from ab initio calculations from the literature that the incoming proton, once attached to the molecule, may retain a significant amount of its charge. These collected data allow a comparison of the thermodynamic stability of protonated molecules in terms of their homolytic or heterolytic bond cleavages. Protonated nitriles are particularly stable by virtue of the very large hydrogen atom affinities of their radical cations.