Measurements of Specific Rate Constants for Dissociation of Substituted Aromatic Hydrocarbons. A Direct Acces to Thermal Dissociation Rate Constants

TLDR: In this article, specific rate constants for unimolecular bond fission reactions of substituted aromatic hydrocarbons were measured directly using excimer laser excitation at 193 nm followed by internal conversion.

Abstract: Specific rate constants for unimolecular bond fission reactions of substituted aromatic hydrocarbons were measured directly using excimer laser excitation at 193 nm followed by internal conversion. For methyl substituted benzenes C —H bond cleavage is the dominant process while C —C bond fission in the side chain is most important for α-methyl substituted toluenes. Calibration of statistial adiabatic channel modell (SACM) calculation with these experimental results allows for prediction of thermal decomposition rate constants which are difficult to measure directly.