Quantum chemical study of the electronic properties of an Iridium-based photosensitizer bound to medium-sized silver clusters

•Interaction of silver clusters with Ir dye was studied by means of long-range TDDFT.•Optimal tuning of range-separation parameter in LC-BLYP was applied.•The internal redox process and intermolecular charge-transfer were analyzed.•Absorption spectra of joint systems are non-additive with respect to pure clusters and Ir dye spectra.

The equilibrium structures and electronic excitation spectra of the Ir(III) photosensitizer [Ir(ppy)2(bpy)]+ bound to medium-sized silver clusters Agn(n=19,20) are investigated using time-dependent density functional theory. The long-range corrected LC-BLYP approach is used with a system-specific range separation parameter. The weak physisorption of the hybrid complexes yields only small changes in the broadened absorption spectra of the hybrid system as compared with its constituents. However, the density of states as well as the fine structure of the spectra is strongly modified upon complexation. It is shown that the standard range separation parameter (0.47 bohr−1) cannot predict these properties correctly and the optimized value of 0.16 bohr−1 should be used instead.

Graphical abstractDownload high-res image (178KB)Download full-size image