HF dimer:: Empirically refined analytical potential energy and dipole hypersurfaces from ab initio calculations

The interaction between two HF molecules as a function of all six internal coordinates is reported as calculated for 3284 selected points in configuration space at counterpoise-corrected explicitly correlated levels and fitted to an analytical expression, which is described in detail. The unweighted rms deviation for all 3284 points is 21 cm(-1). Empirical refinements are applied through mixing and scaling of the ab initio data, guided by the comparison of multidimensional nuclear quantum energy levels with experimental data. The resulting semiempirical pair potentials (labeled SC-2.9 and SO-3) contain 67 and 61 freely adjusted parameters and are combined with a four parameter monomer potential of generalized Poschl-Teller type. Various minimum energy paths and cuts are investigated. Major improvements over earlier HF dimer potentials are demonstrated via multidimensional solutions of the nuclear Schrodinger equation. Comparison with other high level ab initio calculations and with various experimental data reveals very good overall consistency. The new potential suggests strong Coriolis coupling in the librational degrees of freedom. Best estimates of stationary points, of the dimer dissociation energy (D(e)=19.1+/-0.2 kJ/mol), of the electronic barrier to hydrogen bond exchange (4.2+/-0.2 kJ/mol), of the electronic barrier to linearity (3.9+/-0.2 kJ/mol), and of the electronic barrier to hydrogen exchange (175+/-10 kJ/mol) are inferred. Based on accurate electric dipole functions for the monomer and distortion contributions calculated with a large basis at SCF level, a simple analytical six-dimensional electric dipole hypersurface is presented. (C) 1998 American Institute of Physics.