Dynamical heterogeneity in glassy o-terphenyl: manifestation of environment changes in photoisomerization kinetics of probe molecules.
A new method for the investigation of dynamical heterogeneity in glassy matrixes is presented and illustrated by the example of o-terphenyl (OTP). UV-vis absorption spectroscopy has been used to monitor the cis-trans isomerization kinetics of probe molecules in glassy OTP. The dependence of isomerization quantum yield on light intensity has been established. This dependence is shown to be due to the change in the local environment of the probe molecules. The simple model is suggested to estimate the time required for the environment to change, tauex. The tauex values from 2.6 x 10(2) to 1.9 x 10(5) s have been obtained for environments of molecules of 1-naphthylazomethoxybenzene (NAMB) in OTP over a temperature range from 244 to 204 K (Tg+1 to Tg-39 K). The temperature dependence of exchange time has a non-Arrhenius character. As the temperature decreases, an increase in exchange time slows down. The activation energy of the relaxation process is 54 kJ/mol over the range of 224-239 K.
Grebenkin
S Yu
SY
Institute of Chemical Kinetics and Combustion, Novosibirsk, Russian Federation.
Bol'shakov
B V
BV
D001555:Benzene Derivatives / Q000737:chemistry* / Q000528:radiation effects; D007700:Kinetics; D008027:Light; D009281:Naphthalenes / Q000737:chemistry* / Q000528:radiation effects; D010777:Photochemistry; D013237:Stereoisomerism; D013696:Temperature; D013730:Terphenyl Compounds / Q000737:chemistry* / Q000528:radiation effects
C522072:1-naphthylazomethoxybenzene; D001555:Benzene Derivatives; D009281:Naphthalenes; D013730:Terphenyl Compounds