Anomalous thermal expansion, negative linear compressibility, and high-pressure phase transition in ZnAu_2(CN)_4: Neutron inelastic scattering and lattice dynamics studies

摘要

We present temperature-dependent inelastic-neutron-scattering measurements, accompanied by ab initio calculations of the phonon spectra and elastic properties as a function of pressure to quantitatively explain an unusual combination of negative thermal expansion and negative linear compressibility behavior of ZnAu_2(CN)_4. Themechanism of the negative thermal expansion is identified in terms of specific anharmonic phonon modes that involve bending of the -Zn-NC-Au-CN-Zn- linkage. The soft phonon at the L point at the Brillouin zone boundary quantitatively relates to the high-pressure phase transition at about 2 GPa. The ambient pressure structure is also found to be close to an elastic instability that leads to a weakly first-order transition.