Negative thermal expansion and local dynamics in Cu2O and Ag2O

Stringa bibliografica A. Sanson, F. Rocca, G. Dalba, P. Fornasini, R. Grisenti, M. Dapiaggi, G. Artioli, "Negative thermal expansion and local dynamics in Cu2O and Ag2O" in PHYSICAL REVIEW. B, CONDENSED MATTER AND MATERIALS PHYSICS, v. 73, (2006), p. 214305-1-214305-13. - DOI: 10.1103/PhysRevB.73.214305

Dettaglio

Breve descrizione dei contenuti: High-resolution x-ray powder diffraction and extended x-ray-absorption fine-structure EXAFS measurements have been performed on the iso-structural framework crystals Cu2O and Ag2O as a function of temperature. According to diffraction, both compounds exhibit a negative thermal expansion NTE of the lattice parameter over extended temperature intervals from 9 to 240 K for Cu2O, up to 470 K for Ag2O and anisotropic thermal displacements of M atoms M=Cu,Ag. EXAFS measures a positive expansion of the nearest-neighbors M-O pair distance and a perpendicular to parallel anisotropy of relative motion, much stronger than the anisotropy of the absolute M motion. The M-O bond is much stiffer against stretching than against bending. According to EXAFS, out of the 12 M-M next-nearest-neighbor pairs, the 6 connected via a bridging oxygen undergo negative expansion, while the 6 lacking the bridging oxygen undergo positive expansion. These results show a rather complex local behavior, which, while confirming the connection of NTE to strong perpendicular vibrations, is inconsistent with rigid unit modes models and suggests a more flexible model based on rigid M-O rods.