Alla Arakcheeva

The modulated structure of Ba0.39Sr0.61Nb2O6. I. Harmonic solution

The structure of a crystal of Sr(0.61)Ba(0.39)Nb(2)O(6) has been solved and refined as an incommensurate structure in five-dimensional superspace. The structure is tetragonal, superspace group P4bm(pp1/2,p - p1/2), unit-cell parameters a = 12.4566 (9), c = 7.8698 (6) A, modulation vectors q(1) = 0.3075 (6) (a* + b*), q(2) = 0.3075 (6) (a* - b*). The data collection was performed on a KUMA-CCD diffractometer and allowed the integration of weak first-order satellite reflections. The structure was refined from 2569 reflections to a final value of R = 0.0479. The modulation affects mainly the positions of the O atoms, which are displaced by as much as 0.5 A, and the site 4c that is occupied by Sr and Ba atoms. Only a simplified model, in which this atomic position is occupied by an effective atom Sr/Ba, could be refined from the data set. The modulation of displacement parameters has been used to account for the modulated distribution of Sr and Ba. The whole refinement uses only first-order modulation waves, but there are strong indications that for a complete solution the use of higher-order satellites and a more complicated model is necessary.

The luminescence of NaxEu3+(2−x)/3MoO4 scheelites depends on the number of Eu-clusters occurring in their incommensurately modulated structure

Scheelite related compounds with general formula Mn(XO4)m are the subject of hefty interest owing to their optical properties, stability and relatively simple preparation. Eu3+-containing scheelites are considered as red-emitting phosphors and the main factors affecting their luminescence are thought to be chemical composition and particle size while the influence of their structure is generally ignored. Here we report eight compounds from the NaxEu(2−x)/3MoO4 series prepared by conventional solid-state reaction and present a detailed analysis of their crystal structures. Six of them have modulated structures, a common feature of SRCs, in which dopant Eu3+ ions are orderly distributed. Moreover, different amounts of Eu3+ dimers are detected in the modulated structures, characterized by weak satellite reflections appearing in the lower angle part of the XRD patterns. These reflections are indexed and incorporated into Rietvelds refinement using superspace (3 + 1)-dimension symmetry. The remarkable feature of the compounds is that the characteristic luminescence parameters, overall (QEuL) and intrinsic (QEuEu) quantum yields, Eu(5D0) lifetimes, and sensitization efficiencies (ηsens), correlate with the number of Eu3+ aggregates, but not directly with the composition x of the materials. This provides an efficient tool for understanding and controlling the luminescence properties of scheelite related compounds.

KSm(MoO4)2, an incommensurately modulated and partially disordered scheelite-like structure

The incommensurately modulated scheelite-like KSm(MoO(4))(2) structure has been refined in the monoclinic superspace group I2/b(alphabeta0)00 by the Rietveld method on the basis of synchrotron radiation powder diffraction data. The systematic broadening of satellite reflections has been accounted for by applying anisotropic microstrain line-broadening. The microstructure has been studied by transmission electron microscopy (TEM). The partial disorder of the K and Sm cations in the A position is best approximated by a combination of harmonic and complex crenel functions with (0.952Sm + 0.048K) and (0.952K + 0.048Sm) atomic domains. This combination yields a compositional wave distribution from {KMoO(4)} to {SmMoO(4)} observed in the ab structure projection along q. The specific features of KSm(MoO(4))(2) and degree of the A-cation ordering are discussed in comparison with the previously reported structure of KNd(MoO(4))(2).

The role of silver on the stabilization of the incommensurately modulated structure in calaverite, AuTe2

Abstract Structural investigations of several minerals belonging to the calaverite group with composition Au1-xAgxTe2 (x = 0.00, 0.02, 0.05, 0.09, 0.19, and 0.33) indicate that Ag is randomly distributed on the Au sites. This suppresses the valence fluctuation of Au and, therefore, the structure modulations. The results are compared with the previously published incommensurately modulated structure of calaverite, Au0.9Ag0.1Te2, which is characterized by valence fluctuations of Au reinforced by an ordered distribution of Ag. The (3+1)-dimensional calaverite structure type is able to reproduce both (3+1)D and 3D related structures with the general formula AB2(A = Au, Ag, Cu, Nb, Ta; B = Te).

Capabilities and limitations of a (3 + d)-dimensional incommensurately modulated structure as a model for the derivation of an extended family of compounds: example of the scheelite-like structures.

The previously reported incommensurately modulated scheelite-like structure KNd(MoO(4))(2) has been exploited as a natural (3 + 1)-dimensional superspace model to generate the scheelite-like three-dimensional structure family. Although each member differs in its space-group symmetry, unit-cell parameters and compositions, in (3 + 1)-dimensional space, they share a common superspace group, a common number of building units in the basic unit cell occupying Wyckoff sites with specific coordinates (x, y, z) and specific basic unit-cell axial ratios (c/a, a/b, b/c) and angles. Variations of the modulation vector q, occupation functions and t(0) are exploited for the derivation. Eight topologically and compositionally different known structures are compared with their models derived from the KNd(MoO(4))(2) structure in order to evaluate the capabilities and limitations of the incommensurately modulated structure to act as a superspace generating model. Applications of the KNd(MoO(4))(2) structure as a starting model for the refinement and prediction of some other modulated members of the family is also illustrated. The (3 + 1)-dimensional presentation of the scheelite-like structures reveals new structural relations, which remain hidden if only conventional three-dimensional structure descriptions are applied.

A reinterpretation of the phase transitions in Na2CO3

Based on the structural data of phases alpha (hexagonal; 756-972 K), beta (monoclinic; 605-751 K), gamma (incommensurate, monoclinic; 295 K) and delta (lock-in, monoclinic; 110 K) of sodium carbonate, Na2CO3, we could draw a parallel between the phase transitions and the evolution of the second coordination sphere of the C atoms. The temperature-dependent structures observed in the beta phase are reproduced in the incommensurate gamma phase as a modulation wave, which relates to the content of the symmetrically equivalent {110} lattice planes in the alpha phase. By decreasing the temperature, the phase transitions are associated with a stepwise increase in the number of Na ions participating in the second coordination sphere of the C atoms. Over the full temperature range, this number increases from 3 to 7. The C-O distances and the mobility of the O atoms depends on the number of Na ions in the vicinity of the C atoms.

Hexagonal ferrites: a unified model of the (TS)nT series in superspace

Hexagonal ferrites represent an extensive family of mixed-layer magnetic materials with periods up to 1500 A along the stacking direction, probably constituting the largest unit cells in the inorganic realm. The (TS)(n)T subfamily includes P3m1 and R3m structures that can be derived from Y ferrite Ba(2)M(2)Fe(12)O(22) (M = Zn, Fe, Co, Mg, Mn) by introducing stacking faults. A unified (3 + 1)-dimensional superspace model is proposed for all members of the (TS)(n)T family. The model belongs to the superspace group X3m1(00gamma) with X = {(1/3, 2/3, 0, 1/3), (2/3, 1/3, 0, 2/3)}, has a unit cell of the basic structure with a = 5.88, c = 4.84 A and modulation vector q = 4n+3/9n+6 c*, where n is rational for periodic structures and irrational for the aperiodic ones. The model was tested on calculated data of one of the principal members of the (TS)(n)T family, the Y ferrite (n = infinity). The fit obtained with the superspace model was excellent. The model allowed a reduction of refinable parameters by 19% with respect to the ordinary refinement without a significant increase of the refinement R values.

CH3NH3PbI3: precise structural consequences of water absorption at ambient conditions

The crystal structure of the pristine (I) and aged (II) crystals of CH3NH3PbI3 (hereafter MAPbI3) hybrid organic-inorganic lead iodide has been studied at 293 K with high-precision single-crystal X-ray diffraction using a synchrotron light source. We show that (I) and (II) are characterized by an identical tetragonal unit cell but different space groups: I422 for (I) and P42212 for (II). Both space groups are subgroups of I4/mcm, which is widely used for MAPbI3. The main difference between (I) and (II) comes from the difference in hydrogen bonds between the MA+ cation and the PbI3 framework which is the direct consequence of H2O insertion in the aged crystal (II).

Synthesis, growth and characterization of 4-bromo-4′-nitrobenzylidene aniline (BNBA): a novel nonlinear optical material with a (3+1)-dimensional incommensurately modulated structure

The organic nonlinear optical material of 4-bromo-4′-nitrobenzylidene aniline (BNBA, C13H9BrN2O2), a new derivative of benzylideneaniline family, was synthesized and purified by repeated recrystallization. Single crystals of BNBA were grown in acetone solvent by slow evaporation at room temperature. Its (3+1)-dimensional incommensurately modulated structure was elucidated from single crystal X-ray diffraction data obtained at 173 K. The non-centrosymmetric structure was solved and refined in the monoclinic superspace group A2(α0γ)0; the unit cell parameters are a = 10.5217(10) A, b = 16.2535(16) A, c = 7.4403(7) A, β = 110.709(7)°, modulation vector q = 0.0658(1)a*–0.2658(1)c*. At 290 K, the structure is partially disordered, however, the local structure of domains is identical to that at 173 K. The 1H and 13C NMR and Fourier Transform Infrared and FT-Raman spectroscopic studies confirmed the molecular structure. The Kurtz powder second-harmonic generation (SHG) test reveals that the SHG efficiency of BNBA is about 9.4 times higher than that of potassium dihydrogen phosphate. According to the thermogravimetric, differential thermal and differential scanning calorimetric analyses, BNBA is a stable phase starting from room temperature and up to the melting point, 436 K. The optical nonlinearity of BNBA was investigated at 532 nm using 5 ns laser pulses, employing the open aperture Z-scan technique.

The incommensurately modulated structures of natural natrite at 120 and 293 K from synchrotron X-ray data

Abstract The incommensurately modulated structure of the mineral natrite has been refined for the first time. Two single-crystal grains, Lv and Kh, from two different occurrences [Mt. Karnasurt, Lovozero massif (Lv), Kola peninsula, Russia, and the pegmatite of Mt. Koashva, Khibiny massif (Kh)], have been investigated at 293 and 120 K using synchrotron X-ray data. The average structures of both minerals are identical and the basic features of the structural modulations are similar to the synthetic γ-Na2CO3 phase previously published. The γ (incommensurate) → δ (lock-in) phase transition reported at low temperature for the synthetic compound was not observed down to 120 K in natural natrite. Crystalchemical aspects, especially about the second coordination sphere for the carbon atoms, are examined to explain the different structural behaviors observed at low temperature. The possible role played by the minor isomorphous substitutions in natural natrite specimens is also discussed.