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

Basis set expansion and correlation effects on computed lithium cation affinities have been evaluated for the oxygen and nitrogen bases CH 3 OH, H 2 CO, CO, CH 3 NH 2 , CH 2 NH, and HCN. The presence of diffuse functions on nonhydrogen atoms is found to be the most important single enhancement of double‐ and triple‐split valence plus polarization basis sets. With the triple‐split basis, enhancement effects are nearly additive. Correlation usually decreases computed lithium ion affinities, with the second order Møller‐Plesset correlation term being the dominant term.