Enhancing the information content of vibrational spectra through sample perturbation

Infrared and Raman band frequencies, intensities and line shapes are often sensitive to the local molecular environment determined by molecular conformation, surrounding matrix, temperature, pressure, etc. The variety of local environments experienced by a condensed-phase molecule can lead to vibrational spectra with broad bands containing many overlapped spectral features. The spectral resolution of these overlapped features can be enhanced by making perturbations to the sample environment. Examples of perturbations which can be applied to the sample to enhance the information content of infrared spectra are changes in temperature, concentration and mechanical strain. In each instance, the spectra obtained as a function of the perturbation can be cross-correlated to produce a two-dimensional correlation map defined by two independent wavenumber axes. in this representation, infrared bands which respond to the perturbation in a similar or different manner can be clearly identified. This information can be used to help resolve overlapped bands and make unambiguous band assignments.