Collect. Czech. Chem. Commun. 2007, 72, 197-222

Hartree-Fock Stability and Broken Symmetry Solutions of O2- and S2- Anions in External Confinement

Filip Holkaa, Pavel Neográdya, Miroslav Urbana,* and Josef Paldusb

a Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University, Mlynská dolina, Bratislava, SK-84215 Slovakia
b Max-Planck-Institut für Astrophysik, Karl-Schwarzschild-Strasse 1, D-85741 Garching, Germany


We study the effect of a confining potential on systems that exhibit Hartree-Fock (HF) instabilities, and thus admit broken symmetry (BS) HF solutions, by relying on the O2- and S2- doubly-charged anions as model systems. We find that with the increasing strength of the external harmonic confinement potential, W(r) = 1/2(ωr)2 (with 0.0 ≤ ω < 0.2), the BS solutions are systematically eliminated. We use extended, diffuse, doubly-augmented Gaussian basis sets up to and including d-aug-cc-pV6Z, and find that the number and the character of BS solutions exhibit significant basis set effects. These basis sets were further extended by additional ghost basis functions, located away from the atomic center. The role of the electron correlation effects for the BS HF solutions was examined by the CCSD(T) method. In addition to modelling the confinement by the harmonic-like potential W(r), we also examined a more realistic "confinement", realized by a grid of point charges modelling the crystal structure of MgO. Again, we find that the HF instabilities and the implied BS solutions disappear with the increasing magnitude of the model charges simulating the crystal environment. At the same time, the O2- anion is energetically stabilized with respect to both the O- anion and the neutral oxygen atom.

Keywords: Hartree-Fock stability; Broken symmetry solutions; Confined systems; Confining potential; Correlation effects; CCSD(T); O2- and S2- anions; MgO crystal; Ab initio calculations.

References: 61 live references.