Solvent effects on the second harmonic responses of donor–acceptor Stenhouse adducts: from implicit to hybrid solvation models

Abstract

The effect of conformational dynamics and solvent interactions on the second-order nonlinear optical (NLO) responses of the open and closed forms of a donor–acceptor Stenhouse adduct (DASA) are investigated by a mixed quantum/classical computational approach, which couples molecular dynamics (MD) simulations and time-dependent density functional theory (TD-DFT) calculations. The latter are further combined with various solvation schemes, including polarizable continuum models, hybrid QM/MM approaches using either non polarizable or polarizable electrostatic embedding, and QM/QM′ schemes with explicit treatment of a few molecules of the first solvation shell. The performances of the different solvation models are discussed in the context of comparisons with experimental data obtained from hyper-Rayleigh scattering measurements.