Hg+Br→HgBr recombination and collision-induced dissociation dynamics

Shepler, Benjamin C.; Balabanov, Nikolai B.; Peterson, Kirk A.
October 2007
Journal of Chemical Physics;10/28/2007, Vol. 127 Issue 16, p164304
Academic Journal
A global potential energy surface has been constructed for the system HgBr+Ar→Hg+Br+Ar to determine temperature dependent rate constants for the collision-induced dissociation (CID) and recombination of Hg and Br atoms. The surface was decomposed using a many-body expansion. Accurate two-body potentials for HgBr, HgAr, and ArBr were calculated using coupled cluster theory with single and double excitations and a perturbative treatment of triple excitations [CCSD(T)], as well as the multireference averaged coupled pair functional method. Correlation consistent basis sets were used to extrapolate to the complete basis set limit and corrections were included to account for scalar and spin-orbit relativistic effects, core-valence correlation, and the Lamb shift. The three-body potential was computed with the CCSD(T) method and triple-zeta quality basis sets. Quasiclassical trajectories using the final analytical potential surface were directly carried out on the CID of HgBr by Ar for a large sampling of initial rotational, vibrational, and collision energies. The recombination rate of Hg and Br atoms is a likely first step in mercury depletion events that have been observed in the Arctic troposphere during polar sunrise. The effective second order rate constant for this process was determined in this work from the calculated CID rate as a function of temperature using the principle of detailed balance, which resulted in k(T)=1.2×10-12 cm3 molecule-1 s-1 at 260 K and 1 bar pressure.


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