Anisotropic intermolecular forces in rare gas-hydrogen halide systems
The thesis is concerned with the derivation of anisotropic intermolecular potentials from experimental data. For the rare gas - hydrogen halide systems the most useful experimental results are those from molecular beam rotational spectra of van der Waals complexes and from pressure broadening of hydrogen halide rotational spectra by rare gases. Intermolecular potentials for the Ar.HCl system had previously been obtained from each of these experiments separately, but none of the potentials proposed succeeded in reproducing all the available data. In the present work, improved theoretical methods are developed for the calculation of molecular beam spectra and line broadening cross sections from a proposed intermolecular potential. The methods developed are substantially faster than those previously available, allowing their use in a least squares procedure to determine potential parameters. Several possible parameterisations of the intermolecular potential are then considered for Ar.HCl, and least squares fits of potential parameters to experimental results are performed for this system. Measurements of total differential cross sections and second virial coefficients are included in the least squares fits, in addition to the experiments mentioned above. The experimental data demonstrate conclusively that the equilibrium geometry of Ar.HCl is linear, with the atomic arrangement as written. The equilibrium intermolecular distance is 400±3 pm, with an absolute well depth of 18andpm;10 cm-1 . The only feature of the potential which is not well determined by the experimental results is the behaviour around the linear Ar.Cl-H geometry. The results for Ar.HCl are then extended to the systems Ne.HCl, Kr.HCl and Xe.HCl, allowing the dependence of the intermolecular potential on the rare gas to be considered. The molecular beam spectra for Ne.HCl can be fitted only by a potential with a secondary minimum at the linear Ne.Cl-H geometry, in addition to the primary minimum at the linear Ne.H-Cl geometry. The experimental results for the other rare gas - HC1 systems are not very sensitive to this feature of the potential, and the potentials for these are constrained to be similar to that for Ne.HCl in this region. The potential surfaces for all the rare gas - HC1 systems have similar shapes, and appear to be nearly conformal. Finally, intermolecular potentials are obtained for the systems Ar.HF, Kr.HF and Xe.HF from molecular beam spectra. The experimental data for these systems are less extensive than for the HC1 systems, and the potentials obtained are reliable only in the region of the absolute minimum. The HF systems are considerably more anisotropic than the HC1 systems, and it is suggested that this is principally due to greater induction forces in the HF systems. Experiments are suggested which would provide further information on the intermolecular potentials for both HF and HC1 systems, and predictions of the results are made using the current best fit potentials.