Development of multivariate curve resolution and associated system identification tools for IR emission, chiroptical, and far-infrared and far-raman spectroscopies

Abstract

This thesis studies the system identification problems associated with IR emission spectroscopy, chiroptical spectroscopy, and Far-IR and Far-Raman spectroscopy. It focuses on solving the qualitative and quantitative analysis of multivariate data arrays with various chemometric methods. (1) IRES: Experimental measurements for solid and liquid phase samples and for organic synthesis in the liquid phase were carried out with an in-house designed cell. Emission mode BTEM was successfully applied to resolve the pure component emission spectra from the mixture data. (2) Chiroptical spectroscopy: Chiral-BTEM was developed and applied to chiroptical spectroscopic data from UV CD and ROA. An organometallic ligand substitution reaction was successfully studied with UV CD. ROA was combined with Chiral-BTEM and DFT to determine the absolute configurations and the enantiomeric purity of chiral system. (3) Far-IR and Far-Raman spectroscopy: M-C and M-M vibrations of some metal carbonyl complexes were successfully characterized by using these two spectroscopies and DFT.