(593a) Mercury Oxidation Via Bromine

Understanding the fate and transport of mercury can aid in the development of more effective control strategies to prevent further release into the atmosphere. Specifically, determining the kinetic pathways of reactions involving mercury and tropospheric halogens will aid in a deeper understanding of mercuryfs role in regions of northern Canada and the Arctic. Scientific efforts have been directed toward the development of a kinetic model, which will be based upon ab initio calculations involving the following Hg oxidation reactions via bromine, from 298.15 to 2000K,

Hg + Br → HgBr

Hg + Br2 → HgBr + Br

HgBr + Br → HgBr2

HgBr + Br2 → HgBr2 + Br

The ab initio methods, QCISD and B3LYP were used in conjunction with relativistic pseudopotentials for mercury to predict the required energies for complete energetic surface plots. Energetic data was extracted from the potential energy surfaces to obtain theoretical rate constant expressions. Transition state theory was used for the bimolecular reactions and RRKM theory was employed for the unimolecular