S. Huzinaga, M. Yoshimine
The Journal of Chemical Physics
Extensive configuration-interaction calculations have been carried out to determine electron affinities of the first-row atoms, B to F. Calculated electron affinities in eV with the observed values in parentheses are 0.15, 1.11(1.25), -0.52, 1.13(1.461), and 3.12(3.448), for B, C, N, O, and F, respectively. Our best estimates, based on an empirical extrapolation which makes use of the known C, O, and F affinities, for B and N electron affinities are 0.24 and -0.19 eV, respectively. Detailed analysis of the results in terms of contributions from various classes of configurations shows that the K-shell and K L-intershell correlation-energy contributions to these electron affinities are negligibly small, and that about 15% of the total correlation contribution comes from the triple and higher electron-excitation configurations. Symmetry-adapted pair-correlation calculations have been carried out for O, O-, F, and F- to study convergence patterns for the correlation energy and electron affinity with respect to the orbital basis used to construct the configurations. Such pair-correlation calculations are known to overcompute the correlation energy. The excess energies, which correspond to pair-pair interaction energies neglected in the pair-correlation calculations, were roughly constant over a range of orbital basis sizes, with magnitudes about twice the energy contributions from the configurations of triple and higher excitations omitted in the pair-correlation calculations. Accordingly, this approximation should overestimate the electron affinity if a complete orbital basis is used. © 1974 The American Physical Society.
S. Huzinaga, M. Yoshimine
The Journal of Chemical Physics
A.D. McLean, M. Yoshimine
The Journal of Chemical Physics
P.S. Bagus, A.J. Freeman, et al.
International Journal of Quantum Chemistry
J. Pacansky, M. Yoshimine
Journal of Physical Chemistry