Correlating phosphorus core binding energies, phosphorus lone pair ionization potentials, and proton affinities of tervalent phosphorus compounds

Phosphorus core binding energies have been determined for a wide variety of tervalent phosphorus compounds. These values are compared with literature values of the corresponding lone pair ionization potentials and proton affinities. No single correlation is found between all the core binding energies and the corresponding lone pair ionization potentials or proton affinities, but the lone pair ionization potentials are linearly correlated with the proton affinities. It is concluded that the electronic relaxations accompanying lone-pair ionization and proton attachment are similar in character and energy, whereas the electronic relaxation accompanying core ionization is of a somewhat different type, in which atomic orbital rehybridization plays a relatively unimportant role.