Resonance Raman spectrum of [Ru(bipyridine)(3)](2+) in water, acetonitrileand their deuterated derivatives: the possible role of solvent in excited-state charge localization

Resonance Raman spectra excited at 458 and 476 nm are reported for [Ru(bipy ridine)(3)](2+) in water, acetonitrile and their perdeuterated derivatives. Raman intensities of [Ru(bipyridine)(3)](2+) are about a factor of two gre ater in H2O than D2O for all vibrational modes, but are independent of solv ent isotopomer in acetonitrile. Solvent dynamics apparently contribute more strongly to the dephasing dynamics in water than in acetonitrile. Mode-spe cific dephasing rates seem to cause different depolarization ratios for dif ferent observed vibrations which can lead to a potentially misleading inter pretation of the depolarization ratios. We speculate that a static complex between [Ru(bipyridine)(3)](2+) and water influences the excited-state dyna mics. Copyright (C) 2001 John Wiley & Sons, Ltd.