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Resonance Raman spectra excited at 458 and 476 nm are reported for [Ru(bipyridine)3]2+ in water, acetonitrile and their perdeuterated derivatives. Raman intensities of [Ru(bipyridine)3]2+ are about a factor of two greater in H2O than D2O for all vibrational modes, but are independent of solvent isotopomer in acetonitrile. Solvent dynamics apparently contribute more strongly to the dephasing dynamics in water than in acetonitrile. Mode‐specific dephasing rates seem to cause different depolarization ratios for different observed vibrations which can lead to a potentially misleading interpretation of the depolarization ratios. We speculate that a static complex between [Ru(bipyridine)3]2+ and water influences the excited‐state dynamics.
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Webb et al. (2001) studied this question.
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