Evidence for sevenfold coordination in the first solvation shell of Hg(II) aqua ion

J Am Chem Soc. 2007 May 2;129(17):5430-6. doi: 10.1021/ja066943z. Epub 2007 Apr 6.

Abstract

A quite unexpected sevenfold coordination of the hydrated Hg(II) complex in aqueous solution is revealed by an extensive study combining X-ray absorption spectroscopy (XAS) and quantum mechanics/molecular dynamics (QM/MD) calculations. As a matter of fact, the generally accepted octahedral solvation of Hg(II) ion cannot be reconciled with XAS results. Next, refined QM computations point out the remarkable stability of a heptacoordinated structure with C2 symmetry, and long-time MD simulations by new interaction potentials including many-body effects reveal that the hydrated complex has a quite flexible structure, corresponding for most of the time to heptacoordinated species. This picture is fully consistent with X-ray absorption near-edge structure experimental data which unambiguously show the preference for a sevenfold instead of a sixfold coordination.

MeSH terms

  • Absorptiometry, Photon
  • Algorithms
  • Mercury / chemistry*
  • Quantum Theory
  • Solutions
  • Water / chemistry

Substances

  • Solutions
  • Water
  • Mercury