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Excited-State Metal-to-Ligand Charge Transfer Dynamics of a Ruthenium(II) Dye in Solution and Adsorbed on TiO2 Nanoparticles from Resonance Raman Spectroscopy

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journal contribution
posted on 17.12.2003 by Lian C. T. Shoute, Glen R. Loppnow
The dynamics of metal-to-ligand charge transfer (MLCT) in a cis-bis(4,4‘-dicarboxy-2,2‘-bipyridine)-bis(isothiocyanato)ruthenium(II) dye (N3) are compared for the free dye in solution and the dye adsorbed on the surface of the TiO2 nanoparticles from resonance Raman spectroscopy. The 544-nm MLCT absorption band of N3 adsorbed on TiO2 is slightly blue-shifted from that of the free N3, indicating a weak electronic coupling between N3 and TiO2. The resonance Raman spectra of N3 and the N3|TiO2 complex obtained upon excitation within the lowest-lying MLCT singlet state of the dye are similar except for slight shifts in band positions. Resonance Raman cross sections have been obtained for the vibrational modes of both N3 and N3|TiO2 with excitation frequencies spanning the 544-nm MLCT band. Self-consistent analysis of the resulting resonance Raman excitation profiles and absorption spectrum using a time-dependent wave packet formalism over two electronic states yields mode-specific vibrational and solvent reorganization energies. Despite the weak electronic coupling between N3 and TiO2 in N3|TiO2, adsorption strongly affects the reorganization energies of N3 in the intramolecular MLCT state. Adsorption of N3 onto TiO2 increases the absolute Raman cross section of each mode by a factor of ca. 1.6 and decreases the vibrational and solvent reorganization energies by factors of 2 and 6, respectively. The excited-state dynamics of N3 adsorbed on the surface of TiO2 nanoparticles were observed to be independent of the number of N3 molecules adsorbed per TiO2 nanoparticle. The effect of TiO2 on the dynamics of the adsorbed N3 is primarily due to both mode-specific vibrational and electronic pure dephasing, with the dominant contribution from the latter process.