Third-order resonant optical nonlinearity from trans–cis photoisomerization of an azo dye in a rigid matrix

 We investigated the trans–cis photoisomerization of an azo dye in a rigid matrix and the resulting third-order resonant optical nonlinearity by means of the simple theoretical prediction of a two-energy-level system, thin-layer chromatography and H-NMR studies. A methylorange (MO), a methylred (MR), congored (CR) or a Disperse Red 1 (DR1) doped polyvinyl alcohol (PVA) or silica film was used as nonlinear optical material. The existence of equi-absorbing points, or isosbestic points in the absorbance spectrum change and the remarkable stationary transmittance to be independent of the action beam intensity enabled us to confirm the photoisomerization even in a rigid matrix. Then, we measured the third-order resonant optical nonlinearity of dichroism through the polarization absorbance spectrum measurement and determined the characteristic optical parameters of the photoisomerization in the film such as the quantum yields φT, φC, the thermal reaction constant K and the photoisomerization time constant by fitting the theoretical curve of the two-energy-level system to the observed temporal transmittance change after the action beam exposure of the MO/PVA film. The quantum yields were φ¯T=0.36 and φ¯C=0.38, respectively. The photoisomerization time constant of MO embedded in the PVA film was a few seconds. The thermal reaction constant K depended on the excitation beam intensity.