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The crystal structure of CO 3 -cancrinite was analyzed by applying a generalized structure factor expression of the Gram -Charlier expansion to the least -squares refinement performed by using the X -ray intensities measured on single crystals at 173, 293, 473, and 673 K. No satellite reflection or diffuse scattering was observed. The space group is P6 3 with unit cell a = 1.2604(3) and c = 0.51144(8) nm at 173 K, and a = 1.2709(4) and c = 0.5202(6) nm at 823 K. The temperature behavior for the dehydration and the unit cell dimensions were considerably different from those previously reported for CO 3 -cancrinite, which shows superstructure reflections. Two position vectors were assigned to each of the framework atom sites or the CO 3 site for examining its asymmetric probability density function-one for the free energy minimum and another for the potential energy minimum. Two polarization vectors were obtained for a unit cell from those position vectors and ion charges. The rigid ion contributions to the pyroelectric coefficients p (σ) (measured under a constant stress σ) and the secondary coefficient p (2) were finally estimated from the temperature dependences of the polarization vectors.Keywords: Cancrinite, Asymmetric thermal vibrations, Pyroelectricity, Spontaneous polarization INTRODUCTIONCancrinite is a tectosilicate mineral belonging to a polar space group P6 3 (Grundy and Hassan, 1982), which allows the crystal to polarize electrically along the hexagonal c -axis. Figure 1 illustrates the structure of cancrinite in projections along [001] and [210]. Symmetrically independent atom sites obtained from the split -site refinement in the present study are shown in Figure 1a; the z -coordinates are rounded off and given in parentheses. Some measurements of the pyroelectric coefficients have been reported for CO 3 -cancrinite at temperatures 4.2 -500 K by Drozhdin et al. (1975) and Kozlov et al. (1989). These authors found that the temperature dependence of the pyroelectric coefficient p (σ) , which was measured under a constant mechanical stress σ, is non -monotonic, including sign changes below 100 K, and has some polarization relaxations. Most of these studies have pointed out the importance of water molecules in the absolute values of p (σ) , although the interpretation of temperature behaviors is not unique. Drozhdin et al. (1975) considered two cases, wherein the primary and secondary (the piezoelectric effect due to thermal expansions) effects are predominant, whereas Kozlov et al. (1989) considered the temperature dependence of the primary effect as the reason for the sign change. In a more general interpretation, another possibility has been pointed out on the basis of the compensation between the two values of the changes in polarization-one value for the aluminosilicate framework and another for one or more mobile structural elements possessing nonzero intrinsic dipole moments (Galitskii, 1981). Many compounds contain molecules or complexes in channels or voids in their structures, which ar...

Dopant Fe 3 t ions in tetrahedral and octahedral positions of Ge 4 I in the crystal Li,GePI5 were studied using EPR. Fe H substitutes for Gc 4 + with a local charge compensation. The octahedral site and the tetrahedral sites significantly differ by the value of the invariant sum S(B 4 ) of the B 4 tensor of the spin Hamiltonian of Fe H . The irreducible tensor products {V 4®V4 } 4 and {V 4®V4 } , of the V 4 tensor of the crystal field calculated using the point-charge model for octahedral and tetrahedral complexes provide the predominant contribution of the crystal field to the B 4 and B, tensors of the spin Hamiltonian of Fe H , respectively. A comparison of the fourth-rank tensors B 4 of the spin Hamiltonian and {V 4 ® V 4 } 4 of the crystal field determined at 300 K with those determined at 77 K supports the conclusion that the phase transition is accompanied by combined rotations of the [Ge0 41 tetrahedra with the [Ge(l)061 octahedron almost unaltered. The spectrum lines are narrow and the variety of point defects in the vicinity of the paramagnetic impurity ions Fe H , Cr 3 + and Cu" is not detected. These facts are inconsistent with the statistically distributed model for the Li(2) atom. In specific cases at 300 K, when the wings of the two spectrum lines of the M -M+ I and the M+ 2 -M+ 3 transitions of Fe H ions belonging to one system of translationally equivalent positions overlap an extra line appears in the center between these lines. It is suggested that this effect is due to the soft phonon mode above the phase transition temperature.

Electron paramagnetic resonance has been used to study the hole and electron paramagnetic centers formed in X-irradiated RbTiOPO4, the crystals of the KTP family. X-irradiation of RbTiOPO4 crystals at 77 K produced an oxygen hole center and four different trivalent titanium electron centers I" II, III and IV. The g-tensors, their principal values and axes for the defects were calculated and compared with those for KTiOPO4 centers. X-irradiation at 300 K produced another two oxygen hole centers and three electron centers I" 1 2 and II. EPR spectra of the center II revealed dissymmetrization, i.e., irregular distribution of growth defects, between the physically equivalent sites lowering the point group symmetry of the local environment of paramagnetic centers Ti'+

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An electron paramagnetic resonance study of a synthetic single crystal of Cr-doped LiScGeO4 was carried out at the X- and Q-bands at 300 K and at the broad band (70-370 GHz) at 4.2 K. It was established that the EPR spectra with the magnetic multiplicity KM = 2 observed in all the frequency bands are due to the Cr3+ substituted for Sc3+ at the mirror symmetry octahedral site. The angular dependences of the two symmetry-related spectra of Cr3+ in the three crystallographic planes were fitted with the spin Hamiltonian (S = 3/2) of monoclinic symmetry. The zero-field splitting of the ground state energy levels was determined as 1.309(5) cm-1 which compares well with that for Cr3+ in forsterite and alexandrite crystals with similar olivine-like structure. Additional weak lines due to Mn2+ and Fe3+ at the mirror symmetry sites were also identified in the X- and Q-band spectra.