title: Quality Structures, Vibrational Frequencies, and Thermochemistry of the Products of Reaction of BrHg(•) with NO2, HO2, ClO, BrO, and IO.
abstract: Quantum chemical calculations have been carried out to investigate the structures, vibrational frequencies, and thermochemistry of the products of BrHg(•) reactions with atmospherically abundant radicals Y(•) (Y = NO2, HO2, ClO, BrO, or IO). The coupled cluster method with single and double excitations (CCSD), combined with relativistic effective core potentials, is used to determine the equilibrium geometries and harmonic vibrational frequencies of BrHgY species. The BrHg-Y bond energies are refined using CCSD with a noniterative estimate of the triple excitations (CCSD(T)) combined with core-valence correlation consistent basis sets. We also assess the performances of various DFT methods for calculating molecular structures and vibrational frequencies of BrHgY species. We attempted to estimate spin-orbit coupling effects on bond energies computed by comparing results from standard and two-component spin-orbit density functional theory (DFT) but obtained unphysical results. The results of the present work will provide guidance for future studies of the halogen-initiated chemistry of mercury.
authors.affiliation: Department of Chemistry, College of Environmental Science and Forestry, State University of New York , Syracuse, New York 13210, United States.
authors.forename: Yuge
authors.initials: Y
authors.lastname: Jiao
authors.affiliation: Department of Chemistry, College of Environmental Science and Forestry, State University of New York , Syracuse, New York 13210, United States.
authors.forename: Theodore S
authors.initials: TS
authors.lastname: Dibble
mesh_terms: D001959:Bromates / Q000737:chemistry; D001966:Bromine / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry*; D006997:Hypochlorous Acid / Q000737:chemistry; D017613:Iodine Compounds / Q000737:chemistry; D008628:Mercury / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009585:Nitrogen Dioxide / Q000737:chemistry; D010545:Peroxides / Q000737:chemistry; D011789:Quantum Theory; D013696:Temperature; D014732:Vibration
chemical_list: D001959:Bromates; D005609:Free Radicals; D017613:Iodine Compounds; D010545:Peroxides; C081961:hypoiodous acid; C049375:perhydroxyl radical; D006997:Hypochlorous Acid; D008628:Mercury; C027664:hypobromous acid; D009585:Nitrogen Dioxide; D001966:Bromine