AuO: Evolving from Dis- to Comproportionation and Back Again

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• 作者：Andreas Hermann ; Mariana Derzsi ; Wojciech Grochala ; Roald Hoffmann
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：February 1, 2016
• 年：2016
• 卷：55
• 期：3
• 页码：1278-1286
• 全文大小：605K
• ISSN：1520-510X

文摘

The structural, electronic, and dynamic properties of hypothetical gold(II) oxide (AuO) are studied theoretically, at atmospheric and elevated pressures, with the use of hybrid density functional theory. At p = 1 atm, hypothetical AuO (metastable with respect to the elements) is predicted to crystallize in a new structure type, unique among the late-transition-metal monoxides, with disproportionation of the Au ions to Au^I/III and featuring aurophilic interactions. Under pressure, familiar structure types are stabilized: a semiconducting AgO-type structure at ～2.5 GPa and, with a further increase of the pressure up to ～80 GPa, an AuSO₄-type structure containing Au₂ pairs. Finally, above 105 GPa, distorted NaCl- and CsCl-type Au^IIO structures dominate, and metallization is predicted at 329 GPa.