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Issue 3, 2017
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First kinetic study of the atmospherically important reactions BrHg˙ + NO2 and BrHg˙ + HOO

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Abstract

We use computational chemistry to determine the rate constants and product yields for the reactions of BrHg˙ with the atmospherically abundant radicals NO2 and HOO. The reactants, products, and well-defined transition states are characterized using CCSD(T) with large basis sets. The potential energy profiles for the barrierless addition of HOO and NO2 to BrHg˙ are characterized using CASPT2 and RHF-CCSDT, and the rate constants are computed as a function of temperature and pressure using variational transition state theory and master equation simulations. The calculated rate constant for the addition of NO2 to BrHg˙ is larger than that for the addition of HOO by a factor of up to two under atmospheric conditions. For the reaction of HOO with BrHg˙ the addition reaction entirely dominates competing HOO + BrHg˙ reaction channels. The addition of NO2 to BrHg˙ initially produces both BrHgNO2 and BrHgONO, but after a few seconds under atmospheric conditions the sole product is syn-BrHgONO. A previously unsuspected reaction channel for BrHg˙ + NO2 competes with the addition to yield Hg + BrNO2. This reaction reduces the mercury oxidation state in BrHg˙ from Hg(I) to Hg(0) and slows the atmospheric oxidation of Hg(0). While the rate constant for this reduction channel is not well-constrained by the present calculations, it may be as much as 18% as large as the oxidation channel under some atmospheric conditions. As no experimental kinetic or product yield data are available for the reactions studied here, this work will provide guidance for atmospheric modelers and experimental kineticists.

Graphical abstract: First kinetic study of the atmospherically important reactions BrHg˙ + NO2 and BrHg˙ + HOO

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Publication details

The article was received on 12 Sep 2016, accepted on 30 Nov 2016 and first published on 06 Dec 2016


Article type: Paper
DOI: 10.1039/C6CP06276H
Citation: Phys. Chem. Chem. Phys., 2017,19, 1826-1838
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    First kinetic study of the atmospherically important reactions BrHg˙ + NO2 and BrHg˙ + HOO

    Y. Jiao and T. S. Dibble, Phys. Chem. Chem. Phys., 2017, 19, 1826
    DOI: 10.1039/C6CP06276H

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