Dielectric dependence of the first molecular hyperpolarizability for electro-optic chromophores

Experimental and computational studies of the solvent dependence of the first molecular hyperpolarizability (β) for two donor-bridge-acceptor chromophores (CLD-1 and YLD156) are presented. Hyper-Rayleigh scattering (HRS) measurements are performed with 1907 nm excitation in a series of solvents with dielectric constants ranging from ~2 (toluene) to ~36 (acetonitrile). For both chromophores an approximately 2-fold increase in β is observed by HRS over this range of dielectric constants. Computational studies employing a polarized continuum model to represent the solvent are capable of reproducing this experimental result. The experimental and computational results are compared to the predictions of the widely employed two-state model (TSM) for β. Surprisingly, for the chromophores studied here the TSM predicts that β should decrease with increasing dielectric constant over the range investigated. The results presented here demonstrate that the TSM provides neither a quantitative nor qualitative description of the solvent dependence of β for CLD-1 and YLD156. The enhancement of β with increased dielectric constant suggests that modification of the dielectric surrounding the chromophore is one path by which the performance of nonlinear optical devices employing these chromophores may be significantly enhanced.