Abstract
Raman spectroscopy and multivariate curve resolution (Raman-MCR) are combined to yield a powerful spectroscopic method for identifying solute-induced perturbations of solvent molecules. The principles and applications of the resulting solvation-shell spectroscopy are described and illustrated using both numerical model spectra and experimental Raman spectra, including water in acetone and aqueous OH, as well as of both neutral and ionic acetic acid solutions. The results illustrate the quantitative capabilities of Raman-MCR as a solvation-shell spectroscopy, including fundamental limitations arising from ''intensity'' and ''rotational'' ambiguities. © 2012 Society for Applied Spectroscopy.