Brunner and Pritchard (Brunner and Pritchard) have elegantly compared and contrasted "photon" spectroscopy and "collisional" spectroscopy. They point out that both spectroscopies are characterized (in principle) by massive amounts of data (mostly redundant) that should be calculable from a relatively small number of "spectroscopic" constants. However, the nature of "collisional" spectroscopy is such that it is much more difficult to invert the problem, so that fundamental parameters (in principle describable by multipole expansions of an intermolecular potential) can be recovered from the experimental results. Even if these parameters are given, it is usually a formidable computational task to compare experiment and theory because of the very large number of thermally accessible rotational states in each collision and because of the increased dynamics of the interplay between theory and experiment are further hindered by the nature of the available experimental data. Fundamental parameters are recoverable from most experimental data only via complex (and usually unrealizable) deconvolutions.
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