Density functional theory study of substitution effects on the second-order nonlinear optical properties of lindquist-type organo-imido polyoxometalates

Density functional theory and time-dependent density functional theory have been enacted to investigate the effects of donor and acceptor on the first hyperpolarizability of Lindquist-type organo-imido polyoxometalates (POMs). These calculations employ a range-separated hybrid exchange-correlation functional (ωB97X-D), account for solvent effects using the implicit polarizable continuum model, and analyze the first hyperpolarizabilities by using the two-state approximation. They highlight the beneficial role of strong donors as well as of π-conjugated spacers (CH=CH rather than C≡C) on the first hyperpolarizabilities. Analysis based on the unit sphere representation confirms the one-dimensional push-pull π-conjugated character of the POMs substituted by donor groups and the corresponding value of the depolarization ratios close to 5. Furthermore, the use of the two-state approximation is demonstrated to be suitable for explaining the origin of the variations of the first hyperpolarizabilities as a function of the characteristics of a unique low-energy charge-transfer excited state and to attribute most of the first hyperpolarizability changes to the difference of dipole moment between the ground and that charge-transfer excited state.