The analysis of series of molecular fluorescence or absorption spectra forms an integral part of innumerable investigations on the physicochemical properties of chemical or biological systems.
In many typical complex applications, such as photochemical systems with multiple interconversion processes in the ground and in the excited states or biochemical ligand binding studies with several possible binding sites, the number of species contributing to the spectral variation is not known a priori. Moreover, in the frequent case of strongly overlapping spectra of the species, their number cannot be estimated by simple inspection of the experimental spectra.
Principal Component Global Analysis (PCGA) is reviewed as an efficient and reliable way to determine how many species contribute to the observed spectral variation, to set up the correct mechanism and to estimate the values of the corresponding model-parameters. PCGA is applied to examples of host-guest interactions with two and three components and to systems showing complex ground and excited-state proton-transfer reactions with corresponding one and two acid-base equilibria.
Principal Component Analysis Component Spectrum Residual Spectrum Double Proton Transfer Spurious Component
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We thank the Spanish Ministry of Education and Science, the European Union ERDF, and the Xunta de Galicia for financial support.
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