Theoretical Study of the Monohydration of Mercury Compounds of Atmospheric Interest.

The structures, vibrational frequencies, and model IR spectra of the monohydrates of oxygenated mercury compounds (BrHgO, BrHgOH, BrHgOOH, BrHgNO2, BrHgONO, and HgOH) have been theoretically studied using the ωB97X-D/aug-cc-pVTZ level of theory. The ground state potential energy surface exhibits several stable structures of these monohydrates. The thermodynamic properties of the hydration reactions have been calculated at different levels of theory including DFT and coupled-cluster calculations DK-CCSD(T) with the ANO-RCC-Large basis sets. Standard enthalpies and Gibbs free energies of hydration were computed. The temperature dependence of ΔrG°(T) was evaluated for the most stable complexes over the temperature range 200-400 K. Thermodynamic data revealed that the highest fraction hydrated at 298 K and 100% relative humidity will be BrHgNO2-H2O at ∼5%.