Abstract
Ab initio calculations were performed to study the quantum chemistry reactions mechanisms among Hg0, elemental halogen and O3. The geometry of reactions, transition states (TS), intermediates (M) and products were optimized using the MP2 method at the SDD basis function level for Hg, and using 6-311++G (3df, 3pd) for other species. Molecular energies were calculated at QCISD (T) level with zero point energy. Activation energies were calculated along with pre-exponential factors . The reaction rate constants within 298–1800 K were calculated according to transition state theory (TST). The influences of O3 on the reaction of Hg0 with halogen are discussed. Hg0 can be oxidized to Hg1+ by halogen and O3, and halogen and O3 can be arranged in decreasing order as: Br2 > BrO > O3 > Br > Cl, BrCl > HBr > HCl, Br2 > Cl2 according to reaction rate constants. When O3 is presented, Br2, HBr, BrCl, Cl2 and HCl react with O3 and are initially converted to BrO and ClO. O3 is unfavorable for oxidation of Hg0 by Br2. The mixture of HBr and O3 has better oxidizing Hg0 performance than HBr and O3. Cl is less effective than Br for oxidation of Hg0.
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Gao, Z., Lv, S., Yang, W. et al. Quantum chemistry investigation on the reaction mechanism of the elemental mercury, chlorine, bromine and ozone system. J Mol Model 21, 160 (2015). https://doi.org/10.1007/s00894-015-2707-0
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DOI: https://doi.org/10.1007/s00894-015-2707-0