Anharmonicity and structural phase transition in the Mott insulator Cu2P2O7

Ab initio investigations of the structural, electronic, and dynamical properties of the high-temperature 0 phase of copper pyrophosphate were performed using density functional theory. The electronic band structure shows the Mott insulating state due to electron correlations in the copper ions. By calculating phonon dispersion relations, the soft mode at the A point of the Brillouin zone was revealed, showing the dynamical instability of the 0 phase at low temperatures. The double-well potential connected with the soft mode is derived and the mechanism of the structural phase transition to the & alpha; phase is discussed. The self-consistent phonon calculations based on the temperature-dependent effective potential show the stabilization of the 0 phase at high temperatures, due to the anharmonic effects. The pronounced temperature dependence and the large linewidth of the soft mode indicate an essential role of anharmonicity in the structural phase transition.