부산대학교 도서관

The bonding in the X 1Σ+g state of Mg2 is investigated using near-complete valence one-particle Slater and Gaussian basis sets containing up to h functions. Full configuration interaction (FCI) calculations are used to calibrate four-electron correlation treatments. We show that the four-electron complete CI limit can be approached using a sequence of either second-order CI (SOCI) or interacting correlated fragment (ICF) calculations. At the valence level, our best estimate of the dissociation energy (De) is 464 cm-1. We show that this is a lower limit and probably within 5 cm-1 of the complete basis value. The inclusion of core–valence correlation using a model operator approach decreases De by about 35 cm-1 and increases the bond length by 0.03 a0, thereby yielding spectroscopic constants in good agreement with experiment. Attempts to compute the core–valence effect accurately by expanding the CI treatment were unsuccessful. [ABSTRACT FROM AUTHOR]