title: Temperature-dependent neutron powder diffraction study of the Ba(OD)(2) polymorphs: a new low-temperature phase.
abstract: The structural behaviour of both low-temperature beta- and high-temperature alpha-Ba(OD)(2), barium dihydroxide-d, was investigated at temperatures between 10 and 552 K by neutron powder diffraction. While the beta phase (P2(1)/n) remains stable to the lowest temperature investigated, the quenchable alpha phase (Pnma) shows a reversible orthorhombic-to-monoclinic phase transition between 100 and 150 K. The structure of the new alpha(m) phase (P2(1)/n) is quite similar to that of the alpha phase. This behaviour is unusual as a metastable phase transforms to another metastable phase. The Pnma <--> P2(1)/n low-temperature phase transition is driven by an order-disorder mechanism, mainly caused by one of the D atoms, which is disordered on positions off the mirror plane, mimicking a special position on the mirror plane in the orthorhombic phase. Refinements of the alpha phase above the phase transition indicate this disorder across the mirror plane through a conspicuously high isotropic displacement parameter if compared to the other D atoms. At low temperature the energy of the vibration is lowered and the D atom is frozen at a general position in a correlated way, thus violating the mirror plane and reducing the space-group symmetry.
authors.affiliation: Laboratorium für Kristallographie, ETH Zentrum, Sonneggstrasse 5, CH-8092 Zürich, Switzerland. alexandra@kristall.erdw.ethz.ch
authors.forename: A
authors.initials: A
authors.lastname: Friedrich
authors.forename: M
authors.initials: M
authors.lastname: Kunz
authors.forename: E
authors.initials: E
authors.lastname: Suard