Abstract
The resonance Raman (RR) and MCD spectra of a classical, strongly coupled intervalence (IV) system, tris(μ-halo)bis(triammineruthenium)(2+), have been re-examined. Raman spectra obtained in resonance with the strong absorption in the red, provide polarization ratios of 0.33±0.03. However MCD spectra show saturated C terms with ΔA/A>0.2, which are not possible for a pure z polarized transition. The apparent discrepancy is resolved by invoking an “interference” mechanism between two transition dipole mechanisms and substantial involvement of the eg orbitals on the metals. Furthermore the absorption and MCD data indicate that the red absorption is composed of at least three distinct transitions. This is consistent with the observation that photochemical degradation rate depends on the wavelength of excitation within the red band.
Keywords
Resonance Raman Resonance Raman Spectrum Dipole Strength Depolarization Ratio Intense Electronic TransitionPreview
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