Determination of Constitution, Structure, and Bonding of Complex Ions in Solution by Raman Spectroscopy
Of the various methods employed for characterizing complex ions in solution, among the most direct is that of Raman spectroscopy. This method determines the vibrational spectrum of the complex species with a minimum of interference from the solvent and from other species present in the solution. By means of such studies in our laboratories, we have quantitatively characterized the complexes formed in the following aqueous systems: the cyanides of Cu(I), Ag(I), Zn(II), Cd(II), Hg(II), Fe(II), Co(III) (1,2); the bromides of Zn(II), Cd(II), and Ga(III) (3, 4). We have investigated the nitrates, sulfates, and perchlorates of a wide variety of cations and found Raman evidence for complexes with nitrate of Ca(II), Ce(III), Th(IV), Cu(II), Ag(I), Zn(II), Hg(II), Al(III), In(III) (5–7); evidence of inner-sphere sulfate complex formation was shown only by In(III) (5); no evidence was found for perchlorate complexes even from a careful study of Rarnan intensities and polarization ratios (in addition to the frequency measurements) (7); a Raman line characterizing the hydrated cation was found for Mg(II), Cu(II), Zn(II), Hg(II), Ga(III), and In(III) (7).
KeywordsRaman Spectroscopy Vibrational Spectrum Bond Order Molecular Polarizability Polarization Ratio
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