Abstract
The crystal structure of Gdz(MoO4)a has been investigated both at room temperature and at elevated temperatures below and above the ferroelectric-ferroelastic transition temperature (~ 160°C). Space group, unit-cell dimensions, and formula units per unit cell Pba2 (C8v), a= 103881 +00003, b= 104194+0.0004, c= 107007+0.0006/~,, Z = 4 at 25°C and PS421m (D~), a=7.393 +0.002, c= 10.670 + 0.004/~, Z= 2 at 183 °C. Full-matrix least-squares refinements have been carried out with anisotropic thermal parameters with two single-crystal diffractometer data sets measured at 25 and 183 °C, yielding conventional R values of 0.032 (3000 reflections) and 0-028 (880). The high-temperature structure comes close to the average structure of the two ferroelectric-ferroelastic orientations. The differences in interatomic distances between the two modifications are all less than 0.05 .~. Ferroelectric-ferroelastic switching can be accomplished through two macroscopically equivalent switching mechanisms. Changes in interatomic distances of nearest neighbors upon switching are all less than 0.05 ,~,. The main difference between the two ferroelectric-ferroelastic orientations results through movements of several oxygen atoms by as much as 0.7.~. The spontaneous polarization was calculated assuming point charges Gd 3+ and [MOO4]'from positional parameters: Ps = 0.175/tC.cm -2, in good agreement with experiment. Since most of the dipole moments cancel out within the unit cell, Gd2(MoO4)3 can be described as a canted antiferroelectric. The temperature dependence of intensities and peak widths of superstructure reflections has been monitored through the transition temperature. Below the transition temperature, temperature-dependent physical properties can be accounted for by gradual changes in positional parameters towards the high-temperature structure. The mechanism of the phase transition is discussed in terms of the 'positional order-disorder' and the 'soft mode' model. The results obtained in the refinement of the room-temperature structure are compared with results of an independent study of this structure by Keve, Abrahams & Bernstein.
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