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An Insight into Sequential Order in Two-Dimensional Correlation Spectroscopy
Volume 63, Number 3 (March 2009) Page 344-353
Jia, Qi; Wang, Nan-Nan; Yu, Zhi-Wu
Determination of the sequential order of events is a very important feature of generalized two-dimensional correlation spectroscopy (2D-COS). Recently, queries have been put forward on the actual effectiveness of this method when changes are non-periodic, particularly in the presence of local sequential order. Consequently, it brings an urgent necessity to understand the true connotation of the sequential order parameter derived from 2D-COS analysis. This article presents an attempt to address these questions based on the analysis of simulated spectra by assuming the band intensity changes in a logarithmic, exponential, hyperbolic, or polynomial manner. It is concluded that for two events changing monotonically and without local sequential orders, one event occurring prior to the other as determined using 2D-COS means in most cases that the former has both a shorter half-time and a greater half-intensity. As a rule of thumb, intensity versus the perturbation factor should be plotted before performing the 2D-COS analysis to determine the sequential order of the involved events. In the presence of obvious local sequential order, 2D-COS analysis is unnecessary. Otherwise, sequential order can be determined quite reliably based on 2D-COS analysis.