Computational Study of Polarizabilities and Second Hyperpolarizabilities of Inorganic Transition Metal Thiometalates and Metalates in Solution

A systematic study of nonlinear optical (NLO) properties of inorganic transition metal (TM) thiometalates and metalates is reported. Polarizabilities (α) and second hyperpolarizabilities (γ) are calculated in solution within the polarizable continuum model. It is found that NLO properties of anionic inorganic complexes can be successfully modeled in solution, when this cannot be done so in the gas phase. Solvent effects are found to significantly increase α and γ. The effects are stronger on γ (up to 80%) than on α (up to 40%) and stronger on TM thiometalates than on metalates. For α, solvent effects are found to be more important than electron correlation effects. For γ, the two effects are similarly important. Solvent effects on α and γ caused by subordinate factors other than the dominant electrostatic solute−solvent interactions were studied and assessed to be negligible. Upon solvation, large TM and ligand modification effects on α and γ are found. One oxo-to-sulfido substitution results in an increase in α by 38 au and γ by 10 000 au.