Exploring the Electronic Structure and Stability of HgF6: Exact 2-Component (X2C) Relativistic DFT and NEVPT2 Studies

Publication date: Available online 25 May 2019Source: Computational and Theoretical ChemistryAuthor(s): Chun Gao, Shu-Xian Hu, Huixian Han, Guina Guo, Bingbing Suo, Wenli ZouAbstractAs a group 12 element, mercury locating at the sixth row with a valent electronic configuration of 5d106s2 has been treated as a main group element featuring +I and +II oxidation states for a long time. C. K. Jørgensen 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.Graphical abstract
Source: Computational and Theoretical Chemistry - Category: Chemistry Source Type: research
More News: Chemistry | Study