Exploring the electronic structure and stability of HgF6: Exact 2-Component (X2C) relativistic DFT and NEVPT2 studies

As a group 12 element, mercury locating at the sixth row with a valent electronic configuration of 5 d 10 6 s 2 has been treated as a main group element featuring +I and +II oxidation states for a long time. C. K. Jorgensen conjectured the existences of HgF4 and HgF6 molecules in early 1960s, where HgF4 was first synthesized in 2007, but HgF6 as the Hg(+VI) compound was less known. In this paper we explored the electronic structure and decomposition paths of HgF6 by scalar (X1C) and 2-component relativistic (X2C) density functional calculations and more accurate multi-reference NEVPT2 calculations. It is found that the HgF6 molecule, where the mercury atom presents an extraordinary high oxidation state of +VI, is protected by a considerable barrier height of about 22 kcal/mol for the decomposition into HgF4 and two isolated fluorine atoms. The results propose that HgF6 is kinetically stable and may exist under exorbitant conditions.