Fluorides of Silver Under Large Compression*

Abstract

The silver-fluorine phase diagram has been scrutinized as a function of external pressure using theoretical methods. Our results indicate that two novel stoichiometries containing Ag⁺ and Ag²⁺ cations (Ag₃ F₄ and Ag₂ F₃ ) are thermodynamically stable at ambient and low pressure. Both are computed to be magnetic semiconductors under ambient pressure conditions. For Ag₂ F₅ , containing both Ag²⁺ and Ag³⁺ , we find that strong 1D antiferromagnetic coupling is retained throughout the pressure-induced phase transition sequence up to 65 GPa. Our calculations show that throughout the entire pressure range of their stability the mixed-valence fluorides preserve a finite band gap at the Fermi level. We also confirm the possibility of synthesizing AgF₄ as a paramagnetic compound at high pressure. Our results indicate that this compound is metallic in its thermodynamic stability region. Finally, we present general considerations on the thermodynamic stability of mixed-valence compounds of silver at high pressure.

Keywords: fluorides; high pressure; magnetic superexchange; mixed-valent compounds; phase transitions.