Characterization of the structure and dynamics of an aqueous Hg solution by an ab initio molecular dynamics study

Quantum mechanical charge field (QMCF) MD simulation has been performed to investigate the structure and dynamics of Hg²⁺ hydrate. The first-shell hexacoordinated Hg(H₂O)₆]²⁺ complex with an average Hg²⁺-O distance of 2.40 Å is dominantly found, which corresponds to the neutron diffraction and extended X-ray absorption fine structure (EXAFS) experiments. Other species, in particular the 7-fold coordinated complexes, can be formed transiently, according to the water exchange processes with an associative interchange (I_a) mechanism. The second hydration shell exhibits a Hg²⁺-O distance of 4.6 Å with a coordination number of ~ 14. The mean residence times (MRTs) of first- and second-shell waters clearly indicate a strong “structure-forming” ability of Hg²⁺ in aqueous solution.