Related Experiment Video
Updated: Jul 15, 2026

Cooling Rate Dependent Ellipsometry Measurements to Determine the Dynamics of Thin Glassy Films
Published on: January 26, 2016
Dynamical heterogeneity in glassy o-terphenyl: manifestation of environment changes in photoisomerization kinetics of
S Yu Grebenkin1, B V Bol'shakov
1Institute of Chemical Kinetics and Combustion, Novosibirsk, Russian Federation.
Abstract:
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.
Related Concept Videos
Variables Affecting Phosphorescence and Fluorescence
Thermal and Photochemical Electrocyclic Reactions: Overview
UV–Vis Spectroscopy: Molecular Electronic Transitions
Photochemical Electrocyclic Reactions: Stereochemistry
Selection Rules: Photochemical Activation
IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration
According to Hooke's law, the vibrational frequency is directly proportional to the...
Thermal Electrocyclic Reactions: Stereochemistry
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.

