Fulvenallene Decomposition Kinetics

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 115; no. 37; pp. 10281 - 10289
• Main Authors: Polino, Daniela, Cavallotti, Carlo
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 22-09-2011
• Subjects: A: Kinetics, Spectroscopy; Channels; Computer simulation; Decomposition; Decomposition reactions; Mathematical analysis; Radicals; Rate constants; Reaction kinetics
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp202756s

While the decomposition kinetics of the benzyl radical has been studied in depth both from the experimental and the theoretical standpoint, much less is known about the reactivity of what is likely to be its main decomposition product, fulvenallene. In this work the high temperature reactivity of fulvenallene was investigated on a Potential Energy Surface (PES) consisting of 10 wells interconnected through 11 transition states using a 1 D Master Equation (ME). Rate constants were calculated using RRKM theory and the ME was integrated using a stochastic kinetic Monte Carlo code. It was found that two main decomposition channels are possible, the first is active on the singlet PES and leads to the formation of the fulvenallenyl radical and atomic hydrogen. The second requires intersystem crossing to the triplet PES and leads to acetylene and cyclopentadienylidene. ME simulations were performed calculating the microcanonical intersystem crossing frequency using Landau–Zener theory convoluting the crossing probability with RRKM rates evaluated at the conical intersection. It was found that the reaction channel leading to the cyclopentadienylidene diradical is only slightly faster than that leading to the fulvenallenyl radical, so that it can be concluded that both reactions are likely to be active in the investigated temperature (1500–2000 K) and pressure (0.05–50 bar) ranges. However, the simulations show that intersystem crossing is rate limiting for the first reaction channel, as the removal of this barrier leads to an increase of the rate constant by a factor of 2–3. Channel specific rate constants are reported as a function of temperature and pressure.