High-pressure experimental study on Rb2S: antifluorite to Ni2In-type phase transitions

• Published in: Acta crystallographica. Section B, Structural science Vol. 67; no. 2; pp. 109 - 115
• Main Authors: Santamaria-Perez, David, Vegas, Angel, Muehle, Claus, Jansen, Martin
• Format: Journal Article
• Language: English
• Published: 5 Abbey Square, Chester, Cheshire CH1 2HU, England International Union of Crystallography 01.04.2011; Blackwell Publishing Ltd
• Subjects: Chemical compounds; Crystal structure; Crystallography; high-pressure study; Phase transitions; powder diffraction; Pressure
• ISSN: 0108-7681; 2052-5192; 1600-5740; 2052-5206
• DOI: 10.1107/S010876811005370X

The high‐pressure behaviour of dirubidium sulfide, Rb2S, with antifluorite‐type structure under room conditions (space group ) has been studied up to 8 GPa at room temperature using angle‐dispersive X‐ray powder diffraction in a diamond–anvil cell (DAC). X‐ray measurements have allowed us to completely characterize two phase transitions upon compression: (i) to an anticotunnite‐type structure (Pnma) at some pressure between 1 bar and 0.7 GPa, and (ii) to a Ni2In‐type structure (P63/mmc) at 2.6 GPa. A gradual transition from the Pnma to the P63/mmc structures seems to occur between 2.6 and 4.5 GPa. These results are in excellent agreement with previous theoretical predictions. Strong luminescence is observed above 2.6 GPa (band maximum at 703 nm) when the transition to the Ni2In‐type phase starts to occur, the band maximum showing a non‐linear blue shift with pressure. The observed sequence of phase transitions in Rb2S is discussed in relation to the high‐pressure structural behaviour of isomorphic sulfides and the structures are compared with the cationic arrays of their corresponding oxides (e.g. rubidium sulfate, in which the sulfide has been oxidized).