The entrapment of organic dyes into sol-gel matrix: Experimental results and modeling for photonic applications

To better understand the electronic absorption spectra in the UV-vis region of the methyl red (MR) dye in its anionic, isoelectronic and zwitterionic forms in aqueous solution, high level sequential-Monte Carlo/quantum mechanics (s-MC/QM) methodology was performed and compared to experimental measurements. The theoretical procedure consists in treating the solute-solvent system separately using classical MC simulations to build the MR aqueous solution and then, the MC structures are treated by quantum approaches. Thus, the solvent effects were investigated including on the INDO/CI-S calculations initially the micro and further the first hydration shells. As we excepted the absorption spectra are characterized by a strong band placed in the region of lowest energies. To the basic form we computed shoulders at 434.33 +/- 0.09 and 436.34 +/- 0.56 nm corresponding to the micro and first hydration shells, respectively. Our experimental measurements display this shoulder at 431 nm. Under acidic forms (isoelectronic and zwitterionic), we computed the red shift in relation to the basic compound. To the isoelectronic structure we found the absorption maximum located at 485.80 +/- 0.34 and 480.66 +/- 0.67 nm to the micro and first shells, respectively. The experimental prediction of 513 nm is in good agreement with theoretical result. Finally the zwitterionic form we did not obtain a micro layer, therefore we used only the first shell. Our theoretical results are converged to 502.13 +/- 0.79 nm in good concordance with the experimental confirmation of 511 nm. These samples were optically transparent, hard and resistant to dye leaching and to chemical attacks, being promising materials to be used in optical devices. (C) 2007 Elsevier B.V. All rights reserved.