Journal of Physical Chemistry B, Vol.106, No.37, 9528-9535, 2002
Distortions from the tetragonal HfCuSi2-type structures to the orthorhombic GdCuAs1.15P0.85-type structures in REMX2 (RE = rare earth; M = Cu, Ag; X = P, As, Sb): Mismatch between the sizes of the M and X atoms
The RECuAs2-xPx phases undergo symmetry-breaking transitions from tetragonal HfCuSi2-type structures (P4/nmm space group) to orthorhombic GdCuAs1.15P0.85-type structures (Pmmn space group) upon substitution of arsenic by phosphorus. According to Landau theory, the distortions correspond to the Big irreducible representation and can be continuous. The P4/nmm --> Pmmn transitions are not caused by a Peierls-like instability of the square As/P nets but result from a structural adaptation for the smaller P atoms. The stability of the tetragonal RECuAs2-xPx and other REMX2 structures with respect to the orthorhombic distortion can be characterized by a relative interatomic distance in the As/P or X layer. Although the tetragonal phases have small relative As/P-As/P or X-X interatomic distances, the orthorhombic phases have larger distances.