The origin of the reactivity of the Criegee intermediate: implications for atmospheric particle growth

Miliordos, Evangelos; Xantheas, Sotiris S.

doi:10.1002/anie.201509685

Title: The origin of the reactivity of the Criegee intermediate: implications for atmospheric particle growth

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Abstract

The electronic structure of the simplest Criegee intermediate (H₂COO) is practically that of a closed shell. On the biradical scale (β) from 0 (pure closed shell) to 1 (pure biradical) it registers a mere β=0.10, suggesting that a Lewis structure of a H₂C=O^δ+-O^δ- zwitterion best describes its ground electronic state. However, this picture of a nearly inert closed shell contradicts its rich atmospheric reactivity. It is the mixing of its ground with the first triplet excited state, which is a pure biradical state of the type H₂C•-O-O•, that is responsible for the formation of strongly bound products during reactions inducing atmospheric particle growth. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. This research also used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

Authors:: Miliordos, Evangelos; Xantheas, Sotiris S.

Publication Date:: Mon Jan 18 00:00:00 EST 2016

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1236303

Report Number(s):: PNNL-SA-108385
Journal ID: ISSN 1521-3773; KC0301050

DOE Contract Number:: AC05-76RL01830

Resource Type:: Journal Article

Journal Name:: Angewandte Chemie International Edition (Online)

Additional Journal Information:: Journal Volume: 55; Journal Issue: 3; Journal ID: ISSN 1521-3773

Publisher:: Gesselschaft Deutscher Chemiker

Country of Publication:: United States

Language:: English

Citation Formats


                    Miliordos, Evangelos, and Xantheas, Sotiris S. The origin of the reactivity of the Criegee intermediate: implications for atmospheric particle growth.  United States: N. p., 2016. 
        Web.  doi:10.1002/anie.201509685.

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                    Miliordos, Evangelos, & Xantheas, Sotiris S. The origin of the reactivity of the Criegee intermediate: implications for atmospheric particle growth.  United States.  https://doi.org/10.1002/anie.201509685

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                    Miliordos, Evangelos, and Xantheas, Sotiris S. 2016.  
        "The origin of the reactivity of the Criegee intermediate: implications for atmospheric particle growth".  United States.  https://doi.org/10.1002/anie.201509685.

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@article{osti_1236303,

  title        = {The origin of the reactivity of the Criegee intermediate: implications for atmospheric particle growth},

  author       = {Miliordos, Evangelos and Xantheas, Sotiris S.},

  abstractNote = {The electronic structure of the simplest Criegee intermediate (H₂COO) is practically that of a closed shell. On the biradical scale (β) from 0 (pure closed shell) to 1 (pure biradical) it registers a mere β=0.10, suggesting that a Lewis structure of a H₂C=Oδ+-Oδ- zwitterion best describes its ground electronic state. However, this picture of a nearly inert closed shell contradicts its rich atmospheric reactivity. It is the mixing of its ground with the first triplet excited state, which is a pure biradical state of the type H₂C•-O-O•, that is responsible for the formation of strongly bound products during reactions inducing atmospheric particle growth. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. This research also used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.},

  doi          = {10.1002/anie.201509685},

  url          = {https://www.osti.gov/biblio/1236303},
  journal      = {Angewandte Chemie International Edition (Online)},

  issn         = {1521-3773},

  number       = 3,

  volume       = 55,

  place        = {United States},

  year         = {Mon Jan 18 00:00:00 EST 2016},

  month        = {Mon Jan 18 00:00:00 EST 2016}

}

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