10031-18-2Relevant articles and documents
A Flowing-Afterglow Study of the Quenching Reactions of Hg(3P2) and Hg(3P0) Atoms by Halogens, Interhalogens, and Polyatomic Halide Molecules
Zhang, Fu Min,Oba, D.,Setser, D. W.
, p. 1099 - 1114 (1987)
Mercury (3P2) and (3P0) metastable atoms were prepared in a flowing afterglow reactor by passing He, Ne, or Ar carrier gas containing Hg through a dc discharge.The interaction of Hg(3P2) with 30 halogen-containing molecules (325 K) was studied by observation of the HgCl, HgBr, and HgI(B2Σ+-X2Σ+) chemiluminescent spectra.Intramultiplet relaxation to Hg(3P1) also was monitored for some of these molecules plus NH3, CH4, and CF4 and five nonreactive diatomic molecules.The addition of N2 to the flow reactor removes the Hg(3P2) atoms and the reactions of Hg(3P0) can be isolated.The branching fraction for HgX(B) formation, X = Cl, Br, and I, is much lower for Hg(3P0) than for Hg(3P2) reactions.Computer simulation of the HgX(B-X) spectra provided nascent HgX(B) vibrational distributions.The reactions of Hg(3P2) with halogens, mixed halogens, and ICN resemble the analogous Xe(3P2) atom reactions with regard to product branching fractions and energy disposal.These data are discussed in terms of the covalent-ionic curve-crossing reactive quenching mechanism.Upper limits are set for the bond energies of CF3NCl-Cl, CF3NCl-Br, CF2ClNCl-Cl, CF2ClNF-Cl, CF2N-Cl, and CF2BrCF2-I from the HgX(B-X) spectra.The B- and X-state potentials of HgCl, HgBr, and HgI were improved relative to our prior work to better simulate the HgX(B-X) spectra.The excitation-transfer reaction between Hg(3P0,2) and CN was observed as a secondary reaction with BrCN and ICN.