Dynamic heterogeneities in glassy polymers

The photoinduced isomerization of molecules incorporated in a glassy polymer matrix exhibits a wide spectrum of quantum yields. The source of the spectrum is matrix heterogeneities. The kinetics of the photoisomerization of 1-naphthyl-p-azomethoxybenzene in poly(ethyl methacrylate) and poly(n-butyl methacrylate) films is first used to study the rearrangement of the environments of photochromic molecules. The nonequilibrium distribution of cis molecules over the spectrum is obtained via conversion of trans molecules with the highest quantum yield into the cis form with the use of 405-nm light. The kinetics of attainment of the photostationary ratio for concentrations of cis and trans isomers under the action of light with a wavelength of 546 nm is studied through variation in the pause between the conversion of molecules into the cis form and the beginning of the studied process. It is shown that reversible changes in the structure of polymer matrices occur at a high rate at temperatures much lower than the glasstransition temperature.