MCSCF–CI calculations of the ground state potential curves of LiH, Li2, and F2

Abstract

The potential curves for LiH(X 1Σ+), Li2(X 1Σ+g), and F2(X 1Σ+g) have been calculated using a wave function comprising all single and double replacements from an MCSCF reference state. It is shown that in order to obtain satisfactory results, the reference function should describe properly not only the dissociation of the molecule, but also the united atom limit. This implies that for Li2, 1πu, and for F2,2πu orbitals should be included in the reference state. Calculated dissociation energies are 2.48 (2.52) eV for LiH, and 1.00 (1.05) eV for Li2 (experimental values within parentheses). For F2 only 1.31 (1.66) eV is obtained with 2πu excluded from the reference orbital space. A calculation including this orbital yields 1.40 eV even at the MCSCF level.