Optical transitions in excited alkali + rare gas collision molecules and related interatomic potentials:

Abstract

Theoretical and experimental collision induced spectra associated with the transitions as well as in are compared. By means of quantum mechanical simulations, using new ab initio (AI) and semiempirical (MP) potentials and transition moment functions, the contributions from free-free and bound-free transitions on the individual molecular channels to the spectra are analysed and the accuracy of the potentials is tested. In particular, from the excitation spectra measured with absolute intensity scaling, the experimental potential in the barrier region 8- is obtained by inversion. It is found that the barrier parameters of the AI method reproduce the experimental values within error limits, whereas the barrier height from the MP approach is off by about . Beyond the barrier maximum the theoretical energies decrease faster than the experimental ones. The experimental spectrum is well reproduced by the calculations with the AI data set, showing that the latter are accurate within their limits of confidence.