Theoretical Study on the Gas Phase Reaction of Allyl Alcohol with Hydroxyl Radical

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 117; no. 30; pp. 6629 - 6640
• Main Authors: Zhang, Yunju, Chao, Kai, Sun, Jingyu, Su, Zhongmin, Pan, Xiumei, Zhang, Jingping, Wang, Rongshun
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 01.08.2013
• Subjects: Alcohols; Atmospheric Pressure; Atomic and molecular collision processes and interactions; Atomic and molecular physics; Barometric pressure; Chemistry; Computer Simulation; Exact sciences and technology; Gases - chemistry; Hydrogen - chemistry; Hydroxyl Radical - chemistry; Hydroxyl radicals; Interatomic and intermolecular potentials and forces, potential energy surfaces for collisions; Intermolecular and atom-molecule potentials and forces; Kinetics; Kinetics and mechanisms; Mathematical analysis; Models, Chemical; Organic chemistry; Physics; Potential energy; Propanols - chemistry; Rate constants; Reaction kinetics; Reactivity and mechanisms; Stabilization; Temperature; Thermodynamics; Inorganic compounds; Atmospheric pressure; Complex potential; Tunnel effect; Prediction; Theoretical study; Allylic compound; Alcohols; Hydrogen abstraction; Electron correlations; RRKM theory; Isotope effects; Transition state; Hydroxyl radicals; Potential energy surfaces; Kinetics; Gas phase; Rate constant; Triatomic molecule; Moller Plesset partition; Elimination reaction
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp402142b

The complex potential energy surface of allyl alcohol (CH2CHCH2OH) with hydroxyl radical (OH) has been investigated at the G3(MP2)//MP2/6-311++G(d,p) level. On the surface, two kinds of pathways are revealed, namely, direct hydrogen abstraction and addition/elimination. Rice-Ramsperger-Kassel-Marcus theory and transition state theory are carried out to calculate the total and individual rate constants over a wide temperature and pressure region with tunneling correction. It is predicted that CH2CHOHCH2OH (IM1) formed by collisional stabilization is dominate in the temperature range (200–440 K) at atmospheric pressure with N2 (200–315 K at 10 Torr Ar and 100 Torr He). The production of CH2CHCHOH + H2O via direct hydrogen abstraction becomes dominate at higher temperature. The kinetic isotope effect (KIE) has also been calculated for the title reaction. Moreover, the calculated rate constants and KIE are in good agreement with the experimental data.