Abstract

A method of spectral analysis, phase angle description of perturbation correlation analysis, is proposed. This method is based on global phase angle description of generalized two-dimensional (2D) correlation spectroscopy, proposed by Shin-ichi Morita et al., and perturbation-correlation moving-window 2D (PCMW2D) correlation spectroscopy, proposed by Shigeaki Morita et al. For a spectral data set collected under an external perturbation, such as time-resolved infrared spectra, this method provides only one phase angle spectrum. A phase angle of the Fourier frequency domain correlation between a spectral intensity (e.g., absorbance) variation and a perturbation variation (e.g., scores of the first principle component) as a function of spectral variable (e.g., wavenumber) is plotted. Therefore, a degree of time lag of each band variation with respect to the perturbation variation is directly visualized in the phase angle spectrum. This method is applied to time-resolved infrared spectra in the O–H stretching region of the water sorption process into a poly(2-methoxyethyl acrylate) (PMEA) film. The time-resolved infrared (IR) spectra show three broad and overlapping bands in the region. Each band increases toward saturated water sorption with different relaxation times. In comparison to conventional methods of generalized 2D correlation spectroscopy and global phase angle mapping, the method proposed in the present study enables the easier visualization of the sequence as a degree of phase angle in the spectrum.

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