Two-dimensional cross-spectral correlation analysis and its application to time-resolved Fourier transform emission spectra of transient radicals.

A spectral analysis method, based on the generalized two-dimensional (2D) vibrational spectra correlation analysis, is developed for deciphering the correlation among the spectral peaks of two different spectra. This 2D cross-spectral correlation (2DCSC) analysis is aimed at revealing the vibrational features associated with a common species in two spectra, each obtained from a system containing multiple species with at least one common species. The cross-spectral correlation is based on the premise that the spectral features of the same species should have the same time and frequency responses toward similar perturbations. The effectiveness of the cross-spectral correlation analysis is first illustrated with model systems, with spectral peaks decaying linearly or exponentially with time, before being applied to analyzing time-resolved emission spectra obtained, by a Fourier transform IR spectrometer, for samples consisting of the vibrationally excited transient cyanooxomethyl radical (OCCN). 2DCSC among the three different sets of time-resolved spectra collected following the photodissociation of three different precursor molecules of OCCN, respectively, allows the identification of the CN and CO stretching modes of this radical.

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