Vibrational population distributions from rare gas halide spectra

Abstract

An inversion technique, based on multiple linear regression, 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 XeI B(½)→X(½) spectra taken from the literature.

For the systems Xe(³ P ₂)/CF₃I and Xe(³ P ₂)/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(³ P _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 B(½)→X(½) continuum.