Frequency-resolved microscopic second-order hyperpolarizability of azochromophores: a study on nonlinear all-optical switching applications.
MOYSÉS, Renato Mafra; BARBANO, Emerson Cristiano; SILVA, Daniel Luiz da; VIVAS, Marcelo Gonçalves; MISOGUTI, Lino.
MOYSÉS, Renato Mafra; BARBANO, Emerson Cristiano; SILVA, Daniel Luiz da; VIVAS, Marcelo Gonçalves; MISOGUTI, Lino.
Abstract: 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(?)) and two-photon absorption spectra (a2PA(?)) of four azochromophores dissolved in methanol and acetone. The measurements ranging from B600 up to B1300 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(?), a2PA(?), and the second-order hyperpolarizability (?(?)) 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(?), a2PA(?), and ?(?) 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 figureof- merit for all-optical switching applications. Our results suggest that chromophores have the potential for applications in AOS based on Fabry-Perot filters.
@article={003126039,author = {MOYSÉS, Renato Mafra; BARBANO, Emerson Cristiano; SILVA, Daniel Luiz da; VIVAS, Marcelo Gonçalves; MISOGUTI, Lino.},title={Frequency-resolved microscopic second-order hyperpolarizability of azochromophores: a study on nonlinear all-optical switching applications},journal={Physical Chemistry Chemical Physics},note={v. 25, n. 7, p. 5582-5591 + supplementary information},year={2023}}