Influence of water on the CH3O˙ + O2 → CH2O + HO2˙ reaction

文献情報

出版日 2019-06-28

DOI 10.1039/C9CP00720B

インパクトファクター 3.676

著者

Subhasish Mallick, Amit Kumar, Brijesh Kumar Mishra, Pradeep Kumar

原文を見る

要旨

Electronic structure calculations employing density functional theory have been used to study the effect of a single water molecule on the CH3O˙ + O2 → CH2O + HO2˙ reaction. The investigation suggests that in the presence of water the reaction barrier reduces from 3.01 kcal mol−1 to −1.86 kcal mol−1. Consequently, when we consider the bimolecular rate constants for the water catalyzed channel, they were found to be 104 to 105 times higher than that of the uncatalyzed reaction. Interestingly, the Arrhenius plot indicates a negative temperature dependency of the catalyzed channel (anti-Arrhenius behavior); as a result of this the domination of the catalyzed channel over the bare reaction increases with the lowering of the temperature. But the effective bimolecular rate constant values for the catalyzed channel were found to be approximately four orders of magnitude lower than that of the uncatalyzed one, which implies that the contribution of the catalyzed channels to the overall rate of the reaction is very small.

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.