Assessment of Gaussian-2 and density functional theories for the computation of ionization potentials and electron affinities

A set of 146 well-established ionization potentials and electron affinities is presented. This set, referred to as the G2 ion test set, includes the 63 atoms and molecules whose ionization potentials and electron affinities were used to test Gaussian-2 (G2) theory [J. Chem. Phys. 94, 7221 (1991)] and 83 new atoms and molecules. It is hoped that this new test set combined with the recently published test set of enthalpies of neutral molecules [J. Chem. Phys. 106, 1063 (1997)] will provide a means for assessing and improving theoretical models. From an assessment of G2 and density functional theories on this test set, it is found that G2 theory is the most reliable method. It has an average absolute deviation of 0.06 eV for both ionization potentials and electron affinities. The two modified versions of G2 theory, G2(MP2,SVP) and G2(MP2) theory, have average absolute deviations of 0.08–0.09 eV for both ionization potentials and electron affinities. The hybrid B3LYP density functional method has the smallest...

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