Mechanism of Negative Thermal Expansion in Monoclinic Cu2P2O7 from First Principles

Negative thermal expansion (NTE) materials generally have high-symmetry space groups, large average atomic volumes, and corner-sharing octahedral and tetrahedral coordination structures. By contrast, monoclinic alpha-Cu2P2O7, which has a small average atomic volume and edge-sharing structure, has been reported to exhibit NTE, the detailed mechanism of which is unclear. In this study, we investigate the A(2)B(2)O(7) polymorphs and analyze the NTE behavior of alpha-Cu2P2O7 using first-principles lattice-dynamics calculations. From the polymorphism investigation in 20 A(2)B(2)O(7) compounds using 6 representative crystal structures, small A and B cationic radii are found to stabilize the alpha-Cu2P2O7-type structure. We then analyze the NTE behavior of alpha-Cu2P2O7 using quasi-harmonic approximation. Our calculated thermal expansion coefficients and anisotropic atomic displacement parameters were in good agreement with those of the experimental reports at low temperatures. From the mode-Gr & uuml;neisen parameter distribution plotted over the entire first-Brillouin zone, we found that the phonon contributing most significantly to NTE emerges not into the special points but between them. In this phonon mode, the O connecting two PO4 tetrahedra rotates, and the Cu and O vibrate perpendicular to the bottom of the CuO5 pyramidal unit, which folds the ac lattice plane. This vibration behavior can explain the experimentally reported anisotropic NTE behavior of alpha-Cu2P2O7. Our results demonstrate that the most negative mode-Gr & uuml;neisen parameter contributing to NTE behavior is not always located on high-symmetry special points, indicating the importance of lattice vibration analyses for the entire first-Brillouin zone.