Basis set and correlation effects on computed proton affinities of some oxygen and nitrogen bases

Abstract Basis set expansion and correlation effects on the computed proton affinities of the oxygen and nitrogen bases CH 3 OH, H 2 CO, CO, CH 3 NH 2 , CH 2 NH, and HCN have been evaluated. Basis set enhancements lead to systematic changes in computed proton affinities. These effects appear to be additive, and are greater for correlated proton affinities than for Hartree‐Fock energies. Inclusion of correlation decreases proton affinities, with fourth‐order Møller‐Plesset energies bracketed by second and third order energies.