This paper demonstrates the potential of generalized two-dimensional (2D) Fourier transform (FT) infrared (IR) and near-infrared (NIR) correlation spectroscopy in the studies of temperature-dependent spectral variations of self-associated molecules. Three examples of the 2D correlation analysis are discussed in this paper. The first two are concerned with the temperature-dependent IR and NIR spectral changes of N -methylacetamide (NMA) in the pure liquid state. The 2D IR correlation approach revealed that almost all the peaks of NMA in the 3400-1100-cm-1 region consist of two to four separate bands. For example, the amide I band contains contributions from at least four distinct bands at 1685, 1665, 1650, and 1635 cm-1. The analysis of the asynchronous 2D IR spectrum in the amide I region showed that the sequence of spectral intensity change in the ascending order of temperature was given by 1635 < 1650 < 1665 < 1685 cm-1. These bands at 1635, 1650, 1665, and 1685 cm-1 were assigned to the amide I modes of chain oligomers of various sizes and dimer of NMA; the longer the chain, the lower the frequency. The closeup view of 2D NIR correlation spectra of NMA obtained at narrow spectral and temperature windows enabled us to propose not only band assignments in the 6800-6050-cm-1 region but also a detailed mechanistic picture of the thermally induced dissociation of NMA for each temperature range. We also applied the generalized 2D correlation approach to the analysis of a set of FT NIR spectra of oleyl alcohol under temperature variations. The 2D NIR analysis enhanced the spectral resolution and simplified the spectra with overlapped bands. For example, it was found that a band at 7090 cm-1 arising from the first overtone of an OH stretching mode of the monomeric alcohol consists of two bands due to the rotational isomerism of the free OH group. An intriguing possibility of correlating various overtone and fundamental bands to establish unambiguous assignments was also suggested from the 2D NIR study on oleyl alcohol.

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