Frequency-resolved microscopic second-order hyperpolarizability of azochromophores: a study on nonlinear all-optical...

Azochromophores present interesting optical properties for application in all-optical switches (AOSs), such as ultrafast photoisomerization and considerable nonlinear optical response. However, determining the frequency-resolved microscopic second-order hyperpolarizability (real and imaginary parts) related to the pure electronic effects of molecules in solution is a challenging task. In this context, we have used femtosecond-laser induced nonlinear ellipse rotation (NER) measurements to obtain the electronic nonlinear refraction (n₂(ω)) and two-photon absorption spectra (α_2PA(ω)) of four azochromophores dissolved in methanol and acetone. The measurements ranging from ∼600 up to ∼1300 nm were performed in Disperse Red 1 (DR1), Disperse Red 13 (DR13), Disperse Red 19 (DR19), and Disperse Orange 3 (DO3). Because we carried the solution in a silica cuvette and used a short focal length, we were able to measure the solution's nonlinearities with high precision, as the silica from the cuvette walls worked as a suitable reference medium. Consequently, we precisely determined n₂(ω), α_2PA(ω), and the second-order hyperpolarizability (γ(ω)) for all molecules and explained the different magnitudes based on the push-pull character. Furthermore, the solvation effect due to the change from methanol to acetone solvent on the n₂(ω), α_2PA(ω), and γ(ω) is also reported. The results were elucidated using the sum-over-states (SOS) approach within the few-energy-level model and the results were obtained via quantum-chemical calculations using the cubic response function formalism within the density functional theory framework. Finally, we used these results to determine the frequency-resolved figure-of-merit for all-optical switching applications. Our results suggest that chromophores have the potential for applications in AOS based on Fabry-Perot filters.