PNNL

Abstract

The electron affinities (EAs) of aluminum through chlorine have been calculated with multireference single and double excitation configuration interaction calculations (MRSD-CI) with the augmented correlation consistent basis sets of Woon and Dunning [J. Chem. Phys. 98, 1358 (1993)]. The orbital space for the complete active space (CAS) wave functions is systematically expanded beyond the Hartree–Fock wave function by inclusion of additional s, p, and d orbitals. This approach provides a well balanced treatment of the neutral and ionic charge states and led to accurate EAs for hydrogen and the first row atoms [R. A. Kendall, T. H. Dunning, Jr., and R. J. Harrison, J. Chem. Phys. 96, 6796 (1992)]. The best MRSD-CI values for the EAs (in eV) of the second row atoms are Al, 0.440; Si, 1.413; P, 0.689; S, 2.023; and Cl, 3.606. Inclusion of spin–orbit effects in the calculated EAs yields (experimental values in parentheses): Al, 0.437 (0.441); Si, 1.395 (1.385); P, 0.700 (0.746); S, 2.019 (2.077); and Cl, 3.570 (3.613). The amenability of the correlation consistent basis sets for extrapolating to the complete basis set limit has also been exploited in this work. The neutral and anion energies are extrapolated separately in order to account for the different convergence rates in the energies of the two species. The extrapolated values of the EAs, including an empirical spin–orbit correction, are Al, 0.438; Si, 1.395; P, 0.713; S, 2.047; and Cl, 3.596. Additional calculations suggest that the remaining error is a measure of the residual imbalance in the MRSD-CI treatments of the neutral and anion. Extrapolated EAs for the first row atoms are also reported.