Two-dimensional correlation spectroscopy: Effect of normalization of the dynamic spectra

Simulation studies have demonstrated that linear nonselective intensity var iations coupled with nonlinear selective intensity changes may develop new features in two-dimensional (2D) correlation spectra. Some types of linear nonselective intensity changes are hardly seen in the normal and synchronou s 2D correlation spectrum. In contrast, they may develop quite strong featu res in the companion asynchronous spectrum, especially if the selective int ensity variations for different bands have similar response functions. The simplest way of removing this effect is normalization of the dynamic spectr a prior to 2D correlation analysis. This operation can be easily performed if we know the relationship between the perturbation and the nonspecific in tensity variations. Otherwise, one has to employ an "internal reference" fo r normalization of the experimental spectra. The "internal reference" means the band that does not selectively change in its intensity under given per turbation. Fourier transform near-infrared (FT-NIR) measurements of octan-1 -ol in CCl4 revealed a strong correlation between the concentration and the integrated intensity of the second overtone of the v(C-H) band. Also a str ong correlation was found between the integrated intensity of the same band and the temperature-induced density changes of pure octan-1-ol. Thus, in t he NIR region the second overtone of the v(C-H) band can be successfully ap plied for normalization of both the concentration and temperature-perturbed spectra of numerous organic samples. The most complicated situation appear s For a rheo-optical experiment involving pronounced deformation, where any simple normalization of the experimental spectra cannot be applied. In thi s instance, knowledge of the exact relationship between the strain and the sample thickness is required.