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

Abstract

AbstractSpecific 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.