Mercury is a contaminant of global concern that is transported throughout the atmosphere as elemental mercury Hg0 and its oxidized forms HgI and HgII . The efficient gas-phase photolysis of HgII and HgI has recently been reported. However, whether the photolysis of HgII leads to other stable HgII species, to HgI , or to Hg0 and its competition with thermal reactivity remain unknown. Herein, we show that all oxidized forms of mercury rapidly revert directly and indirectly to Hg0 by photolysis. Results are based on non-adiabatic dynamics simulations, in which the photoproduct ratios were determined with maximum errors of 3%. We construct for the first time a complete quantitative mechanism of the photochemical and thermal conversion between atmospheric HgII , HgI , and Hg0 compounds. These results reveal new fundamental chemistry that has broad implications for the global atmospheric Hg cycle. Thus, photoreduction clearly competes with thermal oxidation, with Hg0 being the main photoproduct of HgII photolysis in the atmosphere, which significantly increases the lifetime of this metal in the environment.
Keywords: atmospheric chemistry; mercury; multiconfigurational quantum chemistry; non-adiabatic dynamics; photodissociation.
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