7783-30-4Relevant articles and documents
Vibrational population dynamics of the HgI photofragment in ethanol solution
Pugliano, Nick,Szarka, Arpad Z.,Gnanakaran, S.,Triechel, Matt,Hochstrasser, Robin M.
, p. 6498 - 6511 (1995)
The vibrational population dynamics of HgI fragments in ethanol solution, resulting from the 320 nm photolysis of HgI2, are examined both experimentally and by a simulation.The experiments reveal an HgI population distribution which rapidly relaxes toward equilibrium.At the earliest times, the HgI exhibits vibrational coherent wave-packet motion that dephases with a time constant of ca. 1 ps.These data are used to gain insight into the character of the solvated potential energy curves.The population relaxation was adequately reproduced by master equations which were formulated to incorporate the HgI anharmonicity and a solvent frequency dependent friction.This treatment characterizes the spontaneous vibrational relaxation timescale for the n =1->0 transition to be ca. 3 ps, and is used to identify the relaxation rate constants for all other HgI level pairs.The simulations estimate that the initial excess energy of HgI is centered at n ca. 10 which corresponds to a total excess energy of ca. 1050 cm-1.
Vibrational distributions of HgBr(B2Σ) and HgI(B 2Σ) molecules formed by photodissociation of HgBr2 and HgI2
McGarvey, John A.,Cheung, Nai-Ho,Erlandson, Alvin C.,Cool, Terrill A.
, p. 5133 - 5142 (1981)
Reliable fluorescence spectra (+/- 3percent) of HgBr and HgI photofragments formed in the direct photodissociation of HgBr2 and HgI2 at 193 nm have been measured.The nascent vibrational distributions of HgBr(B2Σ) and HgI(B2Σ) have been determined.The distributions are revomable into the relative contributions from two process: (1) hν + HgX2 -> HgX(B2Σ) + X(2P3/2) and (2) hν + HgX2 -> HgX(B2Σ) + X(2P1/2).HgX(B2Σ) molecules formed with X(2P3/2) atoms exhibit vibrational population inversion and preferential energy disposal among the higher vibrational states.In contrast, the vibrational excitation of HgX(B2Σ) molecules formed with X(2P1/2) atoms produces a Boltzmann-like distribution which strongly favors the lowest vibrational states.
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 (2007/10/02)
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.
