Time-dependent and coupled-perturbed DFT and HF investigations on the absorption spectrum and non linear optical properties of push-pull M(II)-porphyrin complexes (M=Zn, Cu, Ni)

We report previous termtime-dependentnext term (TD) and previous termcoupled-perturbednext term (CP) previous termDFT/HF investigations,next term on the linear and non-linear optical properties of M(II)-complexes of [5-[(4′-dimethylaminophenyl)-ethynyl]-15-[(4″-nitrophenyl)ethynyl]-10,20-diphenylporphyrin], with M = Zn, Cu, Ni. The TD-previous termDFTnext term absorption spectrum is in good agreement with the experimental one, allowing us to identify the transitions mainly responsible of the NLO response. CP-previous termDFT/next termCP-previous termHFnext term calculations provide similar hyperpolarizability values for the three complexes, suggesting an irrelevant role of the metal center. A sharp hyperpolarizability increase is calculated at an incident laser wavelength of 1.064 μm compared to 1.907 μm, which seems to be responsible for the large differences between Zn, Cu and Ni complexes reported experimentally.