Simulation of the resonance Raman intensities of a ruthenium–palladium photocatalyst by time dependent density functional theory

Abstract

The absorption and resonance Raman (RR) properties of the [(tbbpy)(2)Ru(tpphz)PdCl(2)](2+) photocatalyst have been investigated by means of time-dependent density functional theory calculations. With the intention of evaluating the accuracy of the computations, three different exchange-correlation (XC) functionals, namely B3LYP, B3LYP-35 and CAM-B3LYP, have been considered and the effects of the solvent have been described within the polarizable continuum model. It is demonstrated that the inclusion of the solvent effects within the simulations is mandatory to obtain a correct description of the excited states contributing to the first absorption band. The RR spectra of the complex have been simulated for several excitation wavelengths and have allowed an assignment of all the intense experimental bands. The calculations succeed in reproducing several aspects of the experimental absorption and RR spectra, but it is also seen that the choice of the XC functional can lead to significant differences in the simulated spectra and that none of the considered functionals succeed in reproducing all the experimental features.