Accurate ab initio potential energy curves for the classic Li-F ionic-covalent interaction by extrapolation to the complete basis set limit and modeling of the radial nonadiabatic coupling.
Multireference configuration interaction calculations using large correlation consistent basis sets and full configuration interaction calculations with the smallest of such basis are utilized to describe the ionic-neutral curve crossing for the title system. The results of the former calculations have then been extrapolated to the complete basis set limit using the uniform singlet- and triplet-pair extrapolation scheme. A recent suggestion for locating the nonadiabatic matrix terms at the point where the dynamical correlation split vanishes has also been tested. Additionally, a consistent formalism is suggested to model the radial dependence of the nonadiabatic matrix terms that warrants an overlap dependence away from the crossing. When applied to LiF, the overall approach yields results in excellent agreement with the commonly accepted values for the geometric and energetic attributes at both the equilibrium and diabatic crossing regions.
Departamento de Química, Universidade de Coimbra, 3004-535 Coimbra, Portugal. varandas@qtvs1.qui.uc.pt
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Varandas