Vibrational population distributions from rare gas halide spectra: An inversion technique

An inversion technique, based on multiple linear régression, has been developed to extract vibrational population distributions from bound-free transitions in rare gas halide spectra. Some simple tests of the method are described and the technique is then applied to some experimental Xel B(½) spectra taken from the literature. For the Systems Xe(³P₂)/CF₃ and Xe(³P₂)/CH₂I₂ the vibrational distributions obtained in this way are in broad agreement with those obtained through simulation techniques by Setser et al. Analysis of the Xe(³P_2.0)/I₂ System, however, gave a distribution with only one maximum in contrast to the bimodal distribution determined earlier. The discrepancy is probably due to the neglect of the underlying C(3/2)→A(3/2) contribution to the main P(½) continuum.