Fyi

Malinowski, Teresa

doi:10.7771/2380-176x.2259

Cited by 1 publication

(1 citation statement)

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“…Once these uncorrelated vectors are removed, Q is reduced to the lowest dimensionality, Q , which preserves the correlation between time channels while removing uncorrelated time variation due to random noise. The decision regarding which vectors in Q result from noise can be facilitated through the use of an F-test on the reduced eigenvalues of Malinowski: [28][29][30] REV…”

Section: Self-m Odeling Curve Resolutio Nmentioning

confidence: 99%

Monitoring the Formation and Decay of Transient Photosensitized Intermediates Using Pump-Probe UV Resonance Raman Spectroscopy. I: Self-Modeling Curve Resolution

Kleimeyer

Harris

2003

Appl Spectrosc

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Resolution of transient excited-state Raman scattering from ground-state and solvent bands is a challenging spectroscopic measurement since excited-state spectral features are often of low intensity, overlapping the dominant ground-state and solvent bands. The Raman spectra of these intermediates can be resolved, however, by acquiring time-resolved data and using multidimensional data analysis methods. In the absence of a physical model describing the kinetic behavior of a reaction, resolution of the pure-component spectra from these data can be accomplished using self-modeling curve resolution, a factor analysis technique that relies on the correlation in the data along a changing composition dimension to resolve the component spectra. A two-laser UV pump-probe resonance-enhanced Raman instrument was utilized to monitor the kinetics of amine quenching of excited-triplet states of benzophenone. The formation and decay of transient intermediates were monitored over time, from 15 ns to 100 micros. Factor analysis of the time-resolved spectral data identified three significant components in the data. The time-resolved intensities at each Raman wavenumber shift were projected onto the three significant eigenvectors, and least-squares criteria were developed to find the common plane in the space of the eigenvectors that includes the observed data. Within that plane, the three pure-component spectra were resolved using geometric criteria of convex hull analysis. The resolved spectra were found to arise from benzophenone excited-triplet states, diphenylketyl radicals, and the solvent and ground-state benzophenone.

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Section: Self-m Odeling Curve Resolutio Nmentioning

confidence: 99%