The atmospheric oxidation of CH3OOH by the OH radical: the effect of water vapor

Literature Information

Publication Date 2017-04-13
DOI 10.1039/C7CP01976A
Impact Factor 3.676
Authors

Josep M. Anglada, Ramon Crehuet, Marilia Martins-Costa, Joseph S. Francisco, Manuel Ruiz-López


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Abstract

The atmospheric oxidation of methyl hydroperoxide by the hydroxyl radical has been investigated employing high level theoretical methods. This reaction is important in the chemistry of the troposphere because these species contribute to the oxidizing capacity of the atmosphere and therefore we have studied the bare reaction and the effect of the relative humidity as well. In both cases the reaction can proceed either by abstraction of the terminal hydrogen atom of the OH group, producing CH3O2 + H2O, or by abstraction of one hydrogen atom of the CH3 group, forming H2CO + OH + H2O. We have employed BH&HLYP, QCISD and CCSD(T) theoretical methods along with 6-311+G(2df,2p), aug-cc-pVTZ, aug-cc-pVQZ and CBS basis sets to investigate the reaction mechanism, and conventional and variational transition state theory to study the kinetics of the reaction. For the bare reaction we have computed at room temperature, a rate constant of 3.59 × 10−12 cm3 molecule−1 s−1 for the formation of CH3O2 + H2O and of 1.68 × 10−12 cm3 molecule−1 s−1 for the production of H2CO + OH + H2O, with branching ratios of 68% and 32% respectively. Water vapor enhances the rate constant for the formation of CH3O2 + H2O between 2 and 19%, depending on the temperature and relative humidity, whereas the rate constant for the production of H2CO + OH + H2O is enhanced between 0.3 and 5% by the effect of water vapor under the same conditions, which means that the branching ratio for the formation of CH3O2 + H2O is increased up to 2.5%.

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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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