Statistial spectroscopy: insight or nonsense?
Résumé
Stimulated Emission Pumping (SEP) spectra of acetylene, in an energy region intrinsically unassignable in terms of the usual vibrational quantum numbers, are uniquely suited to decoding by statistical methods such as: averaged square-modulus of the Fourier transform, autocorrelation, and cross-correlation. The key to the utility of statistical measures is that SEP spectra are nearly pure sequences, i.e., each spectrum contains features belonging to only one value of all rigorous quantum numbers. The short-time dynamical information quantum mechanically encoded in the vibrational spectrum is revealed directly by statistical reduction rather than indirectly via the traditional reduction to molecular constants.