Reaction and complex formation between OH radical and acetone

Literature Information

Publication Date 2001-01-12
DOI 10.1039/B009601F
Impact Factor 3.676
Authors

Gábor Vasvári, István Szilágyi, Ákos Bencsura, Sándor Dóbé, Tibor Bérces, Eric Henon, Sebastien Canneaux, Frédéric Bohr


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Abstract

Kinetics and mechanism of the reaction of OH with CH3C(O)CH3 have been studied by discharge-flow experiments and CCSD(T) quantum chemical computations. In the experiments, the rate coefficient for the overall reaction, OH + CH3C(O)CH3 → products (1), and the branching ratio for the specific reaction channel OH + CH3C(O)CH3 → CH2C(O)CH3 + H2O (1a) have been determined to be k1 = (1.04 ± 0.03) × 1011 cm3 mol−1 s−1 and Γ1a = k1a/k1 = 0.50 ± 0.04, respectively (T = 298 K). Two different reaction pathways have been characterized by ab initio calculations. Both H atom abstraction and OH addition to the CO group have been found to occur through hydrogen bonded OH···CH3C(O)CH3 complexes. Most of our results support recent findings (M. Wollenhaupt, S. A. Carl, A. Horowitz and J. N. Crowley, J. Phys. Chem. A, 2000, 104, 2695; M. Wollenhaupt and J. N. Crowley, J. Phys. Chem. A, 2000, 104, 6429) but contradictions remain concerning the mechanism of this atmospherically important reaction.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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