A new concentration series is proposed for the construction of a
two-dimensional (2D) synchronous spectrum for orthogonal sample design analysis to
probe intermolecular interaction between solutes dissolved in the same solutions.
The obtained 2D synchronous spectrum possesses the following two properties: (1)
cross peaks in the 2D synchronous spectra can be used to reflect intermolecular
interaction reliably, since interference portions that have nothing to do with
intermolecular interaction are completely removed, and (2) the two-dimensional
synchronous spectrum produced can effectively avoid accidental collinearity. Hence,
the correct number of nonzero eigenvalues can be obtained so that the number of
chemical reactions can be estimated. In a real chemical system, noise present in
one-dimensional spectra may also produce nonzero eigenvalues. To get the correct
number of chemical reactions, we classified nonzero eigenvalues into significant
nonzero eigenvalues and insignificant nonzero eigenvalues. Significant nonzero
eigenvalues can be identified by inspecting the pattern of the corresponding
eigenvector with help of the Durbin-Watson statistic. As a result, the correct
number of chemical reactions can be obtained from significant nonzero eigenvalues.
This approach provides a solid basis to obtain insight into subtle spectral
variations caused by intermolecular interaction.
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