AuO: Evolving from Dis- to Comproportionation and Back Again

Inorg Chem. 2016 Feb 1;55(3):1278-86. doi: 10.1021/acs.inorgchem.5b02528. Epub 2016 Jan 21.

Abstract

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(II)O structures dominate, and metallization is predicted at 329 GPa.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.