DFT/TD-DFT investigation of electronic structures and spectra properties of Cu-based dye sensitizers.

Molecular geometries, electronic structures, and optical absorption spectra were investigated using density functional theory (DFT) at the B3LYP/6-31G(d) and B3LYP/DZVP levels for [CuL(2)](+) and [CuL(2)][PF(6)] (L = 6,6'-dimethyl-2,2'-bipyridine-4,4'-dimethylformate), both in the gas phase and in methyl cyanide (MeCN) solution. The vertical excitation energies were calculated within the framework of the time-dependent DFT (TD-DFT) approach, whereas the solvent effects were taken into account using the polarizable continuum model (C-PCM). Our results show that the five highest occupied molecular orbitals (HOMOs) are composed of a set of distorted degenerate Cu 3d orbitals, whereas the four lowest unoccupied molecular orbitals (LUMOs) are the bipyridine ligand pi*(C horizontal lineN) orbitals. The spectra in the range of 400-600 nm were found to originate from metal-to-ligand charge-transfer (MLCT) transitions, whereas the spectra in the range of 350-400 nm are excitations mainly from the metal Cu 3d orbitals to the carboxyl pi* orbitals. The solvent effects lead to changes in both the geometries and the absorption spectra. The results of this work suggest that copper-based complexes might be effective sensitizers for next-generation dye-sensitized solar cells.