Aqueous Microsolvation of Mercury Halide Species

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• 作者：Benjamin C. Shepler ; Ashby D. Wright ; Nikolai B. Balabanov ; Kirk A. Peterson
• 刊名：Journal of Physical Chemistry A
• 出版年：2007
• 出版时间：November 8, 2007
• 年：2007
• 卷：111
• 期：44
• 页码：11342 - 11349
• 全文大小：201K
• 年卷期：v.111,no.44(November 8, 2007)
• ISSN：1520-5215

文摘

The effects of aqueous solvation on the thermochemistry of reactions between mercury and small halogenmolecules has been investigated by the microsolvation approach using ab initio and density functional theory(DFT) calculations. The structures, vibrational frequencies, and binding energies of 1, 2, and 3 water moleculeswith mercury-halide (HgBr₂, HgBrCl, HgCl₂, HgBr, and HgCl) and related mercury and halogen species(Br₂, BrCl, Cl₂, Cl, Hg, and Br) have been computed with second order Mller-Plesset perturbation theory(MP2) and the B3LYP density functional method. Accurate incremental water binding energies have beenobtained at the complete basis set (CBS) limit using sequences of correlation consistent basis sets, includinghigher order correlation effects estimated from coupled cluster calculations. The resulting energetics wereused to calculate the influence of water molecules on the thermochemistry of a number of reactions betweenmercury and small halogen-containing molecules. In general, the presence of water favors the formation ofoxidized mercury halide species.