First-order character of the displacive structural transition in BaWO₄

Nearly all displacive transitions have been considered to be continuous or second order, and the rigid unit mode (RUM) provides a natural candidate for the soft mode. However, in-situ X-ray diffraction and Raman measurements show clearly the first-order evidences for the scheelite-to-fergusonite displacive transition in BaWO₄: a 1.6% volume collapse, coexistence of phases and hysteresis on release of pressure. Such first-order signatures are found to be the same as the soft modes in BaWO₄, which indicates the scheelite-to-fergusonite displacive phase transition hides a deeper physical mechanism. By the refinement of atomic displacement parameters, we further show that the first-order character of this phase transition stems from a coupling of large compression of soft BaO₈ polyhedrons to the small displacive distortion of rigid WO₄ tetrahedrons. Such a coupling will lead to a deeper physical insight in the phase transition of the common scheelite-structured compounds.