Optical and nonlinear optical properties of Ln(Tp)2, where Ln = La,…,Lu and Tp = tris(pyrazolyl)borate: a DFT+TD-DFT study

The molecular structure of Ln(Tp)2 (where Ln = La to Lu rare earths and Tp = ring-unsubstituted tris(pyrazolyl)borate) complexes is determined by DFT calculations at B3LYP/CEP-121G and PBE/TZP levels. Electronic, structural, and thermodynamic properties, magnetic moment, and static and dynamic polarizability (α and Δα) and hyperpolarizability (β, γ) of the title compounds are determined by using B3LYP/CEP-121G in gas phase. The effect of solvent on nonlinear optical (NLO) response has been studied using the DFT-CPCM model. Time dependent density functional theory (TD-DFT) and Slater's transition state (TS) have also been used to calculate the optical absorption spectrum of the lanthanide complexes in gas phase. For the first time such a panel of properties has been calculated for the whole series of rare earths. The role of 4f electrons vs. 5d electrons is discussed for all studied properties.