Synthesis and characterization of the novel breathing pyrochlore compound Ba3⁢Tm2⁢Zn5⁢O11...

In this study, a novel material from the rare-earth based breathing pyrochlore family, Ba3⁢Tm2⁢Zn5⁢O11, was successfully synthesized. Powder x-ray diffraction and high-resolution powder neutron diffraction confirmed phase purity and the 𝐹⁡‾4⁢3⁢𝑚 breathing pyrochlore crystal structure, while thermogravimetric analysis revealed incongruent melting behavior compared to its counterpart, Ba3⁢Yb2⁢Zn5⁢O11. High-quality single crystals of Ba3⁢Tm2⁢Zn5⁢O11 were grown using the traveling solvent floating zone technique and assessed using Laue x-ray diffraction and single crystal x-ray diffraction. Thermodynamic characterization indicated paramagnetic behavior down to 0.05 K, and inelastic neutron scattering measurements identified distinct dispersionless crystal electric field energy bands, with the fitted crystal electric field model predicting a single-ion singlet ground state and an energy gap of ∼9meV separating it from the first excited (singlet) state. Additional low-energy excitation studies on single crystals revealed dispersionless bands at 0.8 and 1 meV. Computed phonon dispersions from first-principles calculations ruled out phonons as the origin of these modes, further illustrating the puzzling and unique properties of Ba3⁢Tm2⁢Zn5⁢O11.