Solvation model effects on the static first hyperpolarizability of a push–pull π‐conjugated molecule

Abstract

AbstractIn this work, we presented the results of density functional theory calculations for the static first hyperpolarizability for one representative push–pull π‐conjugated molecule, 2‐dimethylamino‐7‐nitrofluorene, in six organic solvents (p‐dioxane, chloroform, tetrahydrofuran, acetone, acetonitrile, and dimethylsulfoxide) spanning a large range of dielectric constant. The finite‐field formalism was used to calculate the longitudinal component of the static first hyperpolarizability. The solvent effect was calculated using two distinct polarizable continuum solvation models: the linear response and the state‐specific polarizable continuum models. The calculations demonstrated the existence of solvation model effects on the property of interest, which warranted further analysis. The two‐level model was then employed to illustrate the impact of solvation model. Our findings suggested that the state‐specific polarizable continuum model gave a decrease of the dipole moment of the excited state in high polarity solvent for a bathochromic molecule whose excited state should have a larger polarization than its ground state.