Chiroptical spectroscopy usually requires theoretically computed spectra to assist in the elucidation of absolute configuration of samples for which experimental spectra have been recorded. Due to the inherently different nature of these two types of spectra, perfect agreement is quasi impossible. Several methods exist to quantify the degree of similarity between the two spectra but rather limited work has been done to evaluate the robustness of the similarity between theory and experiment. In this work, a novel method is described to determine the statistical significance of the numerical degree of similarity between experimental and calculated vibrational circular dichroism spectra and to offer a valuable support for performing absolute configuration assignments. The approach is successfully applied to a number of quinolizidine alkaloids
