Internal modes and the local symmetry of PO4 tetrahedra in K(H1−xDx)2PO4 by Raman scattering

The v₃ and v₄ internal modes of PO^3?₄ tetrahedra are observable in KH₂PO₄ even above the transition temperature in the scattering geometry x(zz)y contrary to the selection rule of the site symmetry S₄ in the D_2d space group. Tominaga et al. discussed that the origin of this broken selection rule is due to the momentary site symmetry C₂ of these tetrahedra, and that the mechanism of the phase transition is of the order-disorder type of these distorted tetrahedra. Parallel studies compatible with their results have been carried out on mixed crystals K(H_1?xD_x)₂PO₄ and the same conclusion has been obtained as to the momentary site symmetry. These internal modes increase in intensity with deuteration, and the origin of this increase is discussed.