Intermolecular acetaldehyde and dimethoxymethane formation mechanisms viaethenol and methoxymethylene precursors in reactions of atomic carbon with methanol: a computational study
文献信息
Yavuz Dede, Ilker Ozkan
Atomic carbon, a reactive intermediate abundant in the interstellar medium (ISM) can participate in various energetically demanding reactions in its extremely long living (69 min) first excited singlet state (1D). Several studies on reactions of oxygen containing species with carbon atoms have been reported, however mechanistic details of the title reaction remain obscure. We report here quantum chemical studies on reactions of methanol with 3P and 1D carbon atoms at the CCSD(T)/cc-pVTZ level of theory, with which experimentally well known facile CO production, intermolecular acetaldehyde formation, and intermolecular dimethoxymethane production mechanisms are explained. Energetics of the fragmentation, O–H insertion, C–H insertion, and O–C insertion channels on the triplet and singlet surfaces are studied. The CO production mechanism by C (1D) is identified as an oxygen abstraction and a triplet PES seems non-operative. Presenting novel features for the intermolecular reaction channels, current findings may be applicable to C + ROR reactions.
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来源期刊
Physical Chemistry Chemical Physics

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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