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Altitude profile of the OH radical complex with water in Earth’s atmosphere: a quantum mechanical approach

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Abstract

The hydroxyl radical (OH) is important in both tropospheric and stratospheric chemical processes that occur in Earth’s atmosphere. The OH radical can also strongly hydrogen-bond to form complexes with other atmospheric constituents, like water molecules. Consequently, there is potential for altered reaction dynamics/kinetics as a result of this complexation. Without direct measurements of the abundances of such complexes in Earth’s atmosphere, we have adopted a theoretical approach to determine such abundances. Electronic structures, enthalpies and free Gibbs energies of formation of OH, H2O and H2O-HO were calculated at CCSD(T) and QCISD(T) levels of theory with either 6–311++G(2d,2p) or aug-cc-pVTZ basis. Statistical thermodynamic concepts were then used to assess the abundance of the complex as function of altitude.

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Notes

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Acknowledgements

We are thankful for the effective support of the Gaussian helpdesk, particularly from Dr. Fernando R. Clemente, when dealing with the low-lying excited structure of H2O-HO (Structure 2) at triple excitation level of theory.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, George Mason University, 4400 University Drive, Fairfax, VA, 22030, USA

    David Voglozin & Paul Cooper

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  1. David Voglozin
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  2. Paul Cooper
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Correspondence to David Voglozin.

Additional information

Supporting information QCISD(T) and CCSD(T) calculated geometries and normal modes frequencies of (H2O).OH, and Microsoft Excel table. This material is available free of charge upon request at: “voglozin11@gmail.com”

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Voglozin, D., Cooper, P. Altitude profile of the OH radical complex with water in Earth’s atmosphere: a quantum mechanical approach. J Atmos Chem 74, 475–489 (2017). https://doi.org/10.1007/s10874-016-9353-5

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  • DOI: https://doi.org/10.1007/s10874-016-9353-5

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