Falloff curves and mechanism of thermal decomposition of CF3I in shock waves. Issue 43 (25th October 2019)

• Record Type: Journal Article
• Authors: Cobos, C. J.; Sölter, L.; Tellbach, E.; Troe, J.
• Is Part Of: Physical chemistry chemical physics. Volume 21:Issue 43(2019)
• Page Start: 23893
• Page End: 23899
• Publication Date: 2019-10-25
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c9cp04771a
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : The falloff curves of the unimolecular dissociation CF3 I (+Ar) → CF3 + I (+Ar) are modelled by combining quantum-chemical characterization of the potential for the reaction, unimolecular rate theory, and experimental information on collisional energy transfer. Abstract : The falloff curves of the unimolecular dissociation CF3 I (+Ar) → CF3 + I (+Ar) are modelled by combining quantum-chemical characterizations of the potential energy surface for the reaction, standard unimolecular rate theory, and experimental information on the average energy transferred per collision between excited CF3 I and Ar. The (essentially) parameter-free theoretical modelling gives results in satisfactory agreement with data deduced from earlier shock wave experiments employing a variety of reactant concentrations (between a few ppm and a few percent in the bath gas Ar). New experiments recording absorption–time signals of CF3 I, I2, CF2 and (possibly) IF at 450–500 and 200–300 nm are reported. By analysing the decomposition mechanism, besides the unimolecular dissociation of CF3 I, these provide insight into the influence of secondary reactions on the experimental observations.