Computational Chemistry and Molecular Modeling
Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
Spin-orbit and dispersion energy contributions to the energy curves of XeF are examined. A rapid variation in the spin-orbit coupling with internuclear separation is found for both the ground and excited states. This result can explain the experimentally observed ordering of the ionic excited states when the spin-orbit perturbation couples 2σ and 2π energy curves obtained by both all-electron and effective core potential (ECP) calculations at the first-order configuration interaction (FOCI) level of accuracy. Damped dispersion energy contributions to the ground-state energy curve are shown to be comparable to the charge transfer contribution. The energy curve for XeF is in reasonable agreement with experimental results and a calculation of the analogous XeCl curve confirms the qualitative correctness of the calculation. The energy curves and transition moments were then applied to two problems related to the efficiency of the XeF laser. Photodissociation of the X state provides a means of removing a bottlenecked vibrational level but a calculation of the radiative transition probability between the X and A states finds the cross section is too small to yield rates competitive with collisional deactivation. The bottlenecked state may also be removed by electron dissociative attachment but the calculated energy curves for the X states of XeF and XeF- do not cross at a low energy indicating a small cross section.
Type of Medium: