✍ Scribed by M. Krauss; W. J. Stevens; P. S. Julienne
No coin nor oath required. For personal study only.
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 ^2^σ and ^2^π 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.
📜 SIMILAR VOLUMES
The low-lying electronic states of PtH were studied by all-electron oneand two-component variational calculations on the multireference CI levels. The orbital optimization is performed within a one-component formalism, whereas the further refinement of the wave functions follows two different scheme