Master equation study of hydrogen abstraction from HCHO by OH via a chemically activated intermediate

Rui Ming Zhang, Wenqi Chen, Donald G. Truhlar, Xuefei Xu

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Abstract

The abstraction reaction of hydrogen from formaldehyde by OH radical plays an important role in formaldehyde oxidation. The reaction involves a bimolecular association to form a chemically activated hydrogen-bonded reaction complex followed by a unimolecular reaction of the complex to generate the products. The reaction rate is usually considered to be pressure-independent by assuming equilibrium between the reactants and the complex. However, our nonequilibrium calculations based on the chemically significant eigenmode of the master equation, carried out with our recently developed TUMME program, indicate that the reaction complex makes the rate constant dependent on pressure at low temperatures (T < 200 K). The calculations include anharmonicity, variational effects, and multi-dimensional tunneling. We find that the reaction rate constant reaches a low-pressure limit at pressures below 10 Torr over the whole investigated temperature range (20-1800 K), which explains why the available low-temperature experiments, which are for pressures below 2 Torr, did not observe the pressure dependence. A new extension of the TUMME master-equation program is used to explore the time evolutions of the concentrations of the OH radical and the complex under pseudo-first-order conditions. The time-dependent evolution of the concentrations of the complex at a low temperature provide direct evidence for the stabilization of the reaction complex at high pressures, and it shows the negligible role of the stabilized reaction complex at low pressures. The picture that emerges is qualitatively consistent with our previous study of the reaction of methanol with OH in that the tunneling in the unimolecular step from the complex to the products affects the phenomenological reaction rate constants differently at high and low pressures and leads to a significant pressure effect.

Original languageEnglish (US)
Pages (from-to)431-460
Number of pages30
JournalFaraday Discussions
Volume238
Issue number0
DOIs
StatePublished - Feb 8 2022

Bibliographical note

Funding Information:
This work was supported in part by the National Natural Science Foundation of China (awards 21973053 and 91841301) and by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0015997.

Publisher Copyright:
© 2022 The Royal Society of Chemistry

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