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Mercury under Pressure acts as a Transition Metal: Calculated from First Principles
Author(s) -
Botana Jorge,
Wang Xiaoli,
Hou Chunju,
Yan Dadong,
Lin Haiqing,
Ma Yanming,
Miao Maosheng
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201503870
Subject(s) - chemistry , transition metal , oxidizing agent , molecule , metal , mercury (programming language) , atomic orbital , chemical physics , electronic structure , computational chemistry , crystallography , organic chemistry , physics , quantum mechanics , computer science , electron , programming language , catalysis
The inclusion of Hg among the transition metals is readily debated. Recently, molecular HgF 4 was synthesized in a low‐temperature noble gas but the potential of Hg to form compounds beyond a +2 oxidation state in a stable solid remains unresolved. We propose high‐pressure techniques to prepare unusual oxidation states of Hg‐based compounds. Using an advanced structure search algorithm and first‐principles electronic structure calculations, we find that under high pressure Hg in HgF compounds transfers charge from the d orbitals to the F, thus behaving as a transition metal. Oxidizing Hg to +4 and +3 yielded the thermodynamically stable compounds HgF 4 and HgF 3 . The former consists of HgF 4 planar molecules, a typical geometry for d 8 metal centers. HgF 3 is metallic and ferromagnetic owing to the d 9 configuration of Hg, with a large gap between its partially occupied and unoccupied bands under high pressure.