title: Quantum chemistry guide to PTRMS studies of as-yet undetected products of the bromine-atom initiated oxidation of gaseous elemental mercury.
abstract: A series of BrHgY compounds (Y = NO2, ClO, BrO, HOO, etc.) are expected to be formed in the Br-initiated oxidation of Hg(0) to Hg(II) in the atmosphere. These BrHgY compounds have not yet been reported in any experiment. This article investigates the potential to use proton-transfer reaction mass spectrometry (PTRMS) to detect these atmospherically important species. We show that reaction of the standard PTRMS reagent (H3O(+)) with BrHgY leads to stable parent (M + 1) ions, BrHgYH(+), for most of these radicals, Y. Rate constants for the proton transfer reaction H3O(+) + BrHgY are computed using average dipole orientation theory. Calculations are also carried out on the commercially available compounds HgCl2, HgBr2, and HgI2 to enable tests of the present work.
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
authors.forename: Matthew J
authors.initials: MJ
authors.lastname: Zelie
authors.forename: Yuge
authors.initials: Y
authors.lastname: Jiao
mesh_terms: D000393:Air Pollutants / Q000032:analysis / Q000737:chemistry*; D001965:Bromides / Q000737:chemistry*; D004735:Energy Transfer; D013058:Mass Spectrometry / Q000379:methods*; D008628:Mercury / Q000032:analysis / Q000737:chemistry*; D017669:Mercury Compounds / Q000737:chemistry*; D008956:Models, Chemical; D010084:Oxidation-Reduction; D011522:Protons; D011789:Quantum Theory; D014835:Volatilization
chemical_list: D000393:Air Pollutants; D001965:Bromides; D017669:Mercury Compounds; D011522:Protons; D008628:Mercury; C042720:mercuric bromide