A theoretical study of the OH-initiated gas-phase oxidation mechanism of β-pinene (C10H16): first generation products

文献情報

出版日 2012-01-23

DOI 10.1039/C2CP23711C

インパクトファクター 3.676

著者

J. Peeters

原文を見る

要旨

An extensive mechanism for the OH-initiated oxidation of β-pinene up to the first-generation products was derived based on quantum chemical calculations, theoretical kinetics, and structure–activity relationships. The resulting mechanism deviates from earlier explicit mechanisms in several key areas, leading to a different product yield prediction. Under oxidative conditions, the inclusion of ring closure reactions of unsaturated alkoxy radicals brings the predicted nopinone and acetone yields to an agreement with the experimental data. Routes to the formation of other observed products, either speciated or observed as peaks in mass spectrometric studies, are also discussed. In pristine conditions, we predict significant acetone formation following ring closure reactions in alkylperoxy radicals; in addition, we predict some direct OH recycling in subsequent H-migration reactions in alkylperoxy radicals. The uncertainties on the key reactions are discussed. Overall, the OH-initiated oxidation of β-pinene is characterized by the formation of a few main products, and a very large number of products in minor to very small yields.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 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.