Effect of TiO 2 particles on normal and resonance Raman spectra of coumarin 343: a theoretical investigation

It is well known that interfacial structures and charge transfer in dye-sensitized solar cells are extremely important for the enhancement of cell efficiency. Here, the normal Raman spectra (NRS) and resonance Raman spectra (RRS) of a C343-sensitized TiO 2 cluster (Ti 9 O 18 ) are theoretically predicted from combined electronic structure calculations and a vibrationally-resolved spectral method to reveal the relationship between interfacial geometries and excited-state dynamics. The results show that although the NRS of free C343 and the C343–TiO 2 cluster correspond to the vibrational motions of C343 in a high frequency domain, their mode frequencies show obvious differences due to the interaction of the TiO 2 cluster on C343, and several new Raman active fingerprint modes, such as bidentate chelating bonding modes, can be used to determine interfacial geometries. However, the resonance Raman activities of low-frequency modes are significantly enhanced and several modes from the TiO 2 cluster can be observed, consistent with experimental measurements. Furthermore, the RRS from a locally excited state and a charge transfer state of C343–TiO 2 are dramatically different, for instance, new Raman active modes with 1212 cm −1 , 1560 cm −1 and 1602 cm −1 , corresponding to the motions of CH 2 rocking, CC/C–N/CO stretching and CO/CC stretching, appear from the charge transfer state. The obtained information on mode-specific reorganization energies from these excited states is greatly helpful to understand and control interfacial electron transfer.