Water Catalysis of the Reaction of Methanol with OH Radical in the Atmosphere is Negligible

Junjun Wu, Lu Gem Gao, Zoltan Varga, Xuefei Xu, Wei Ren, Donald G. Truhlar

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

Faced with the contradictory results of two recent experimental studies [Jara-Toro et al., Angew. Chem. Int. Ed. 2017, 56, 2166 and Chao et al., Angew. Chem. Int. Ed. 2019, 58, 5013] of the possible catalytic effect of water vapor on CH3OH + OH reaction, we report calculations that corroborate the conclusion made by Chao et al. and extend the rate constant evaluation down to 200 K. The rate constants of the CH3OH + OH reaction catalyzed by a water molecule are computed as functions of temperature and relative humidity using high-level electronic structure and kinetics calculations. The Wuhan–Minnesota Scaling (WMS) method is used to provide accurate energetics to benchmark a density functional for direct dynamics. Both high-frequency and low-frequency anharmonicities are included. Variational and tunneling effects are treated by canonical variational transition state theory with multidimensional small-curvature tunneling. And, most significantly, we include multistructural effects in the rate constant calculations. Our calculations show that the catalytic effect of water vapor is not observable at 200–400 K.

Original languageEnglish (US)
Pages (from-to)10826-10830
Number of pages5
JournalAngewandte Chemie - International Edition
Volume59
Issue number27
DOIs
StatePublished - Jun 26 2020

Bibliographical note

Funding Information:
This work is supported the National Natural Science Foundation of China (51776179 and 21973053), by Research Grants Council of the Hong Kong SAR, China (14234116), and by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE‐SC0015997. J.W. is also supported by the Overseas Research Attachment Program from The Chinese University of Hong Kong.

Funding Information:
This work is supported the National Natural Science Foundation of China (51776179 and 21973053), by Research Grants Council of the Hong Kong SAR, China (14234116), and by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0015997. J.W. is also supported by the Overseas Research Attachment Program from The Chinese University of Hong Kong.

Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

  • anharmonicity
  • atmospheric chemistry
  • quantum chemistry
  • reaction kinetics
  • water catalysis

PubMed: MeSH publication types

  • Journal Article

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