Relativistic Configuration Interaction Study of the Electronic Spectrum of Thallium Chloride

✍ Scribed by Y. Li; H.P. Liebermann; G. Hirsch; R.J. Buenker

• Publisher: Elsevier Science
• Year: 1994
• Tongue: English
• Weight: 714 KB
• Volume: 165
• Category: Article
• ISSN: 0022-2852
• DOI: 10.1006/jmsp.1994.1124

✦ Synopsis

An ab initio configuration interaction study including spin-orbit coupling and employing relativistic effective core potentials for both constituent atoms is reported for the lowest lying states of thallium chloride. Good agreement is obtained with measured (T_{\mathrm{c}}) values (\left( \pm 1500 \mathrm{~cm}^{-1}\right)) for all known excited electronic states, as well as with the corresponding equilibrium bond distances and vibrational frequencies. A number of avoided crossings between various (\Omega=0^{+})states which are responsible for predissociation effects found by Lindner, Tiemann, and co-workers for this system are described. Details of the asymptotic behavior of the various potential curves leading to the (\left.\mathrm{Tl}\left({ }^{2} P_{u}\right)+\mathrm{Cl}^{2}{ }^{2} P_{u}\right)) atomic limits are faithfully reproduced in the calculations, and estimates of the radiative lifetimes of key vibrational states are also given. a: 1994 Academic Press. Inc.