Vibrational population distributions from rare gas halide spectra

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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.