NDLI: First kinetic study of the atmospherically important reactions BrHg˙ + NO<sub>2</sub> and BrHg˙ + HOO

Content Provider	Royal Society of Chemistry (RSC)
Author	Dibble, Theodore S. Jiao, Yuge
Copyright Year	2017
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.
Starting Page	1826
Ending Page	1838
Page Count	13
File Format	HTM / HTML PDF
ISSN	14639076
Volume Number	19
Issue Number	3
Journal	Physical Chemistry Chemical Physics
DOI	10.1039/c6cp06276h
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Potential energy surface Computational chemistry Master equation Mercury-in-glass thermometer Addition reaction
Content Type	Text
Resource Type	Article
Subject	Physics and Astronomy Physical and Theoretical Chemistry

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