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Electronic transitions of the manganate(V) ion in aqueous solution: a resonance Raman study

✍ Scribed by L. K. Noda; M. C. C. Ribeiro; N. S. Gonçalves; A. H. Jubert; O. Sala

Publisher
John Wiley and Sons
Year
1999
Tongue
English
Weight
140 KB
Volume
30
Category
Article
ISSN
0377-0486

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✦ Synopsis

The resonance Raman spectra of manganate(V) ion in aqueous solution in the visible and near-UV regions were studied. The maximum in the Raman excitation profile (REP) of the totally symmetric vibrational mode (n 1 ) at ca 600 nm is assigned to a charge-transfer transition with appreciable d-d character. Owing to marked orbital mixing in such systems, the observed Raman enhancement could also be assigned to a d-d transition with a high charge-transfer character. The absence of overtones in the Raman spectrum indicates a small shift in the equilibrium Mn-O bond distances (d r ) between the excited and fundamental electronic states. This finding was confirmed by the calculation of the REP within the time formalism approach. The best fitted d r value is lower than the corresponding reported values for manganate(VII) and manganate(VI) ions. Two models were used in the calculations, in which whether a single or two electronic transitions were considered in the visible range of the absorption spectrum. Similar d r values were obtained with both models.

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