Phase stability of stress-sensitive Ag2CO3 silver carbonate at high pressures and temperatures

Silver carbonate (Ag2CO3) is a material currently used for artificial carbon storage. In this work, we report synchrotron X-ray powder diffraction (XRD) experiments under high pressure and high temperature in combi-nation with density-functional theory (DFT) calculations on silver carbonate up to 13.3 GPa. Two pressure -induced phase transitions were observed at room temperature: at 2.9 GPa to a high-pressure (HP1) phase and at 10.5 GPa to a second high-pressure phase (HP2). The facts that a) the HP2 phase can be indexed with the initial P21/m structure, b) our DFT calculations predict the initial structure is stable in the entire pressure range, and c) the HP2 phase is stable under decompression suggest that the intermediate HP1 phase is a product of the appearance of non-hydrostatic stresses in the sample. The observed structural transformations are associated to a high sensitivity of this compound to non-hydrostatic conditions. The compressibility of Ag2CO3 has also been determined, showing the c axis is the most compressible and that the bulk modulus increases quickly with applied pressure. We attribute both observations to the weak nature of the closed-shell Ag-Ag interactions in this material. The behavior of Ag2CO3 under heating at approximately 3 GPa was also studied. No temperature -induced phase transitions were found at this pressure, and the thermal expansion was determined to be rela-tively high for a carbonate.

Automated summary

In this study, synchrotron X-ray powder diffraction experiments and density-functional theory calculations were used to investigate the phase transitions of silver carbonate under high pressure and high temperature. Two pressure-induced phase transitions were observed, and it was found that the intermediate phase transition was a result of non-hydrostatic conditions. The compound was found to be highly sensitive to non-hydrostatic conditions, and its compressibility and thermal expansion were determined to be relatively high.