Mercury under Pressure acts as a Transition Metal: Calculated from First Principles |
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| Authors: | Dr. Jorge Botana Dr. Xiaoli Wang Dr. Chunju Hou Prof. Dr. Dadong Yan Prof. Dr. Haiqing Lin Prof. Dr. Yanming Ma Prof. Dr. Mao‐sheng Miao |
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| Affiliation: | 1. Beijing Computational Science Research Center, Beijing 100094 (P.R. China);2. Institute of Condensed Matter Physics, Linyi University, Linyi 276005 (P.R. China);3. School of Science, JiangXi University of Science and Technology, Ganzhou 341000 (P.R. China);4. Department of Physics, Beijing Normal University, Beijing 100875 (P.R. China);5. State Key Lab of Superhard Materials, Jilin University, Changchun 130012 (P.R. China);6. Department of Chemistry and Biochemistry, California State University, Northridge, CA 91330 (USA);7. Materials Department and Materials Research Laboratory, University of California, Santa Barbara, CA 93106‐5050 (USA) |
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| Abstract: | The inclusion of Hg among the transition metals is readily debated. Recently, molecular HgF4 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 Hg? F 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 HgF4 and HgF3. The former consists of HgF4 planar molecules, a typical geometry for d8 metal centers. HgF3 is metallic and ferromagnetic owing to the d9 configuration of Hg, with a large gap between its partially occupied and unoccupied bands under high pressure. |
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| Keywords: | ab initio calculations crystal structure search high oxidation state high‐pressure chemistry mercury |
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