Centrosymmetric Positions Research Articles

Suppressed Lone Pair Electrons Explain Unconventional Rise of Lattice Thermal Conductivity in Defective Crystalline Solids.

Manipulating thermal properties of materials can be interpreted as the control of how vibrations of atoms (known as phonons) scatter in a crystal lattice. Compared to a perfect crystal, crystalline solids with defects are expected to have shorter phonon mean free paths caused by point defect scattering, leading to lower lattice thermal conductivities than those without defects. While this is true in many cases, alloying can increase the phonon mean free path in the Cd-doped AgSnSbSe3 system to increase the lattice thermal conductivity from 0.65 to 1.05Wm-1K-1 by replacing 18% of the Sb sites with Cd. It is found that the presence of lone pair electrons leads to the off-centering of cations from the centrosymmetric position of a cubic lattice. X-ray pair distribution function analysis reveals that this structural distortion is relieved when the electronic configuration of the dopant element cannot produce lone pair electrons. Furthermore, a decrease in the Grüneisen parameter with doping is experimentally confirmed, establishing a relationship between the stereochemical activity of lone pair electrons and the lattice anharmonicity. The observed "harmonic" behavior with doping suggests that lone pair electrons must be preserved to effectively suppress phonon transport in these systems.

Designing the antimicrobial peptide with centrosymmetric and amphipathic characterizations for improving antimicrobial activity.

Antibiotic-resistant bacterial infections are becoming a serious health issue and will cause 10 million deaths per year by 2050. As a result, the development of new antimicrobial agents is urgently needed. Antimicrobial peptides (AMPs) are found in the innate immune systems of various organisms to effectively fend off invading pathogens. In this study, we designed a series of AMPs (THL-2-1 to THL-2-9) with centrosymmetric and amphipathic properties, through substituting different amino acids on the hydrophobic side and at the centrosymmetric position to improve their antimicrobial activity. The results showed that leucine as a residue on the hydrophobic side of the peptide could enhance its antimicrobial activity and that glutamic acid as a centrosymmetric residue could increase the salt resistance of the peptide. Thus, the THL-2-3 peptide (KRLLRELKRLL-NH2 ) showed the greatest antimicrobial activity (MIC90 of 16 μM) against Gram-negative bacteria and had the highest salt resistance and cell selectivity among all the designed peptides. In summary, the results of this study provide useful references for the design of AMPs to enhance antimicrobial activity.

Orthorhombic and triclinic modifications of the arsenate Cu4O(AsO4)2 and isotypic phosphates Cu4O(PO4)2: strongly frustrated antiferromagnetics

A structural-magnetic models of the orthorhombic and triclinic modifications of the arsenates Cu4O(AsO4)2 and isotypic phosphates Cu4O(PO4)2 has been built and analyzed. Their base elements are the complicated ribbons composed of antiferromagnetic Cu4 tetrahedra. Structurally, these tetrahedra have no shared copper atoms; however, there are strong antiferromagnetic (AFM) and ferromagnetic (FM) couplings between them, both within the complicated ribbons and between them. It has been established that both modifications are strongly frustrated 3D antiferromagnetics due to competition between the nearest AFM interactions along the edges of the Cu4 tetrahedra and competition between interactions and a multiplicity of long-range secondary AFM and FM interactions. Additionally, a large number of weaker long-range interactions are competing among each other. However, there is a possibility of the ordering Dzyaloshinskii-Moriya (DM) interaction in the centrosymmetric orthorhombic modification (Pnma), because two of the three types of magnetic ions, Cu1 and Cu3, are in the partial position 4c, where the ions are not related by the inversion center. In the triclinic modification (P −1) of Cu4O(As(P)O4)2, all four copper ions are in the centrosymmetric equivalent position 2i, which prevents DM interactions. This centrosymmetry will allow magnetic interactions in the triclinic modification of Cu4O(As(P)O4)2 to be still frustrated at lower temperature. It is possible that the triclinic modification of these compounds is a quantum spin liquid.

Atomic‐Scale Observation of Off‐Centering Rattlers in Filled Skutterudites

AbstractAs one of the most fundamental order parameters, the coordinate order of atoms is a cornerstone in determining the physical and chemical properties of materials. Off‐centering shifts of atoms from their centrosymmetric positions, a phenomenon that is closely related to symmetry breaking and structural transitions in crystals, is of key importance in modifying a broad range of fundamental properties, such as ferroelectricity, antiferroelectricity, and piezoelectricity. In thermoelectric materials, which can be used to directly interconvert heat to electricity, off‐centering has been proposed in, e.g., lead tellurides, halide perovskites, type I and II clathrates, and filled skutterudites, to be the physical origin of the experimentally measured exceptionally low thermal conductivity, but only indirectly supported from structural refinements and experimental/theoretical vibration mode analyses. In this work, Yb partially filled and Ce fully filled skutterudite is taken as a model system for directly measuring the off‐centering shifts of filler atoms, i.e., rattlers, with picometer precision in real space, by means of atomic‐resolution negative spherical aberration imaging transmission electron microscopy. This finding allows an in‐depth understanding of the relationship between the off‐centering and the thermoelectric performance, and the presented methodology here is also applicable to investigate the off‐centering phenomena in other functional materials, e.g., ferroelectrics and solar cells.

Polarization-Resolved Extreme-Ultraviolet Second-Harmonic Generation from LiNbO3

Second harmonic generation (SHG) spectroscopy ubiquitously enables the investigation of surface chemistry, interfacial chemistry, as well as symmetry properties in solids. Polarization-resolved SHG spectroscopy in the visible to infrared regime is regularly used to investigate electronic and magnetic order through their angular anisotropies within the crystal structure. However, the increasing complexity of novel materials and emerging phenomena hampers the interpretation of experiments solely based on the investigation of hybridized valence states. Here, polarization-resolved SHG in the extreme ultraviolet (XUV-SHG) is demonstrated for the first time, enabling element-resolved angular anisotropy investigations. In noncentrosymmetric LiNbO_{3}, elemental contributions by lithium and niobium are clearly distinguished by energy dependent XUV-SHG measurements. This element-resolved and symmetry-sensitive experiment suggests that the displacement of Li ions in LiNbO_{3}, which is known to lead to ferroelectricity, is accompanied by distortions to the Nb ion environment that breaks the inversion symmetry of the NbO_{6} octahedron as well. Our simulations show that the measured second harmonic spectrum is consistent with Li ion displacements from the centrosymmetric position while the Nb─O bonds are elongated and contracted by displacements of the O atoms. In addition, the polarization-resolved measurement of XUV-SHG shows excellent agreement with numerical predictions based on dipole-induced SHG commonly used in the optical wavelengths. Our result constitutes the first verification of the dipole-based SHG model in the XUV regime. The findings of this work pave the way for future angle and time-resolved XUV-SHG studies with elemental specificity in condensed matter systems.

Structure and phase transitions in A -site ordered RBaMn2O6 ( R=Pr,Nd ) perovskites with a polar ground state

We report here a structural study of $R\mathrm{Ba}{\mathrm{Mn}}_{2}{\mathrm{O}}_{6}$ ($R=\mathrm{La}$, Pr, and Nd) compounds by means of synchrotron radiation x-ray powder diffraction and Raman spectroscopy. The three compounds are $A$-site ordered perovskites adopting the prototypical tetragonal structure at high temperature. A ferromagnetic transition is observed in the $\mathrm{LaBa}{\mathrm{Mn}}_{2}{\mathrm{O}}_{6}$ sample and the lattice parameters undergo anisotropic changes at ${T}_{C}$ related to the orientation of the magnetic moments. Both $\mathrm{PrBa}{\mathrm{Mn}}_{2}{\mathrm{O}}_{6}$ and $\mathrm{NdBa}{\mathrm{Mn}}_{2}{\mathrm{O}}_{6}$ have a structural transition coupled to an electronic localization and an antiferromagnetic transition. In both cases, the x-ray diffraction patterns reveal that the low-temperature phase is orthorhombic with lattice parameters $a+b,b\ensuremath{-}a$, and $c$ with respect to the tetragonal phase. Two possible solutions belonging to the space groups Pmam and $P{2}_{1}am$ can yield accurate refinements of the x-ray patterns. However, the active modes in the low-temperature phase disclosed by the Raman spectroscopy clearly point to the noncentrosymmetric space group, $P{2}_{1}am$. The symmetry analysis of this transition unveils that the primary modes belong to the irreducible representations M5\ensuremath{-} and GM5\ensuremath{-} and the main distortions correspond to rotations of the $\mathrm{Mn}{\mathrm{O}}_{6}$ octahedra and an asymmetric combination of stretching and scissoring modes of the basal oxygens in these octahedra. We conclude that the low-temperature phase is polar and the main contribution comes from the displacement of oxygen atoms from their centrosymmetric positions. However, negligible contribution from the asymmetric stretching associated with a Jahn-Teller distortion is found in this structural transition, suggesting the lack of ferroic orbital ordering of ${e}_{g}$ ($3{d}_{{x}^{2}\ensuremath{-}{y}^{2}}$) orbitals in the orthorhombic $ab$ plane. There is only one inequivalent site for the Mn atom in the low-temperature polar phase so charge ordering cannot account for the electronic localization having a structural origin.

The effect of non-centrosymmetricity on optical and electronic properties of BaHfO3 perovskite

This study is carried out using density functional theory within Gpaw code development. We considered a tetragonal structures of barium hafnate & have noticed a possession of spontaneous polarization. A GLLBSC approach for exchange-correlation treatment describes the bandgaps of the system more accurately. The Born effective charge calculation indicates that Hafnium and oxygen atoms are the main involved ones in a displacements from the centrosymmetric positions and hence resulting to the spontaneous polarization. To analyze the optical properties, two theories of dielectric function ε(ω) calculation are applied. It shows that the theories predict the nature of ε(ω) over a ranges of photon energies, and also indicate the exciton binding energy. Analysis of the results shows that the system has a potential of being suitable for a photovoltaic & thermophotovoltaic applications.

Local and electronic structure of Sr1-xGdxTiO3 probed by X-ray absorption spectroscopy

Gadolinium-doped strontium titanate (Sr1-xGdxTiO3) is a typical perovskite structure material which has been studied due their thermomechanical, termoelectrical and electrochemical properties. In this study, local and electronic structure of Sr1-xGdxTiO3 samples were analyzed through X-ray absorption spectroscopy measurements. The results obtained with the adjustment of extended X-ray absorption fine structure (EXAFS) spectra at Sr K-edge show that crystallographic model of Pm-3m space group is consistent with local structure around Sr atoms, as expected. This same analysis also reveals an increasing of the Debye-Waller as a function of the Gd content in some shells, which is associated with disorder induced by Sr vacancies due to the heterovalent Gd incorporation. EXAFS spectra at Gd LIII-edge for Sr1-xGdxTiO3 samples indicates regular GdO12 dodecahedra without displacement of Gd atoms from centrosymmetric position. A disorder was also identified in the shells beyond the first 12 O neighbors in which neither the crystallographic cubic structure of the SrTiO3 nor the orthorhombic structure of the GdTiO3 fits well. X-ray absorption near edge spectroscopy (XANES) spectrum at Ti LIII,II-edges shows an asymmetric peak because of the splitting between the eg orbitals of 3d band for SrTiO3 sample. The addition of Gd atoms to SrTiO3 structure cause an enlargement of this peak and this split is associated with a small displacement of Ti atoms from their centrosymmetric position. Several features of the XANES spectra at O K-edge for Sr1-xGdxTiO3 samples are affected by the increase of Gd concentration. According to our calculated projected density of states, these transitions are related to a reduction in the number of unoccupied O 2p - Ti 3d states caused by the split of Ti 3d band. Moreover, these XANES spectra also show a dependence of the increasing of the hybridization between O 2p and Gd 5d4f6s states.

Generalized L-Shaped Array Based on the Difference and Sum Coarray Concept

L-shaped array (LA) is traditionally used as two one-dimensional uniform linear arrays (ULAs) for two-dimensional direction of arrival (DOA) estimations. With elevation and azimuth angles estimated separately, the detectable source number is strictly limited by the number of elements in the ULAs. To increase the detection ability, in this paper, we propose to exploit the diff-sum co-array (DSCA) concept on the L-shaped array. As such, a virtual element in the quadrants of DSCA can be generated by only one pair of sensors in the LA. Therefore, it can acquire much higher number of degrees of freedom for DOA estimation. To further reduce the redundancy of elements on the horizontal and vertical axes of DSCA, an element moving strategy is proposed. It is proved that the DSCA can remain intact with any one or more physical sensors relocated to the centrosymmetric positions. Based on this strategy, a generalized L-shape array concept and a new configuration referred to as generalized L-shaped array with odd-even locations (GLA-OEL) are developed. For GLA-OEL, the number of sensor pairs with small spacing is as small as one, which dramatically reduces the mutual coupling of adjacent elements. Besides, with the same number of sensors, the GLA-OEL can generate much larger virtual uniform rectangular array in the DSCA. Simulations verify the superiorities of the proposed array in terms of detection performance and estimation accuracy.

Role of the Iodide–Methylammonium Interaction in the Ferroelectricity of CH3NH3PbI3

Excellent conversion efficiencies of over 20 % and facile cell production have placed hybrid perovskites at the forefront of novel solar cell materials, with CH3NH3PbI3 being an archetypal compound. The question why CH3NH3PbI3 has such extraordinary characteristics, particularly a very efficient power conversion from absorbed light to electrical power, is hotly debated, with ferroelectricity being a promising candidate. This does, however, require the crystal structure to be non‐centrosymmetric and we herein present crystallographic evidence as to how the symmetry breaking occurs on a crystallographic and, therefore, long‐range level. Although the molecular cation CH3NH3 + is intrinsically polar, it is heavily disordered and this cannot be the sole reason for the ferroelectricity. We show that it, nonetheless, plays an important role, as it distorts the neighboring iodide positions from their centrosymmetric positions.

Electron Paramagnetic Resonance in HoxLu1−xB12 Dodecaborides

The high-frequency (60 GHz) electron paramagnetic resonance is studied in HoxLu1−xB12 single crystals at low temperatures (2–80 K) in an applied magnetic field up to 7 T within a wide doping range, 0.01 ≤ x ≤ 1. These compounds are characterized by the presence of a low-temperature cage glass phase with random displacements of magnetic holmium ions from the centrosymmetric position in B12 boron cuboctahedra. For the samples with x ≥ 0.1, it is demonstrated that the electron paramagnetic resonance in the form of a single broad line with a g-factor of about 5 appears in the cage glass phase at T 0.3, the pronounced broadening of the resonance line and a steep decrease in the g-factor related to antiferromagnetic correlations is observed on cooling at T < 30 K. The performed simulation of the electron paramagnetic resonance spectra suggests the dominant role of the exchange interaction effects and positional disorder in determining the characteristic features of spin dynamics in HoxLu1−xB12.

Pressure-induced phase transitions and structural evolution across the insulator–metal transition in bulk and nanoscale BiFeO3

The pressure-induced phase-transition sequences and structural evolution across the insulator–metal transition (IMT) in multiferroic BiFeO3 still remain unclear. Here we use a combination of high-pressure XRD, XAFS experiment and first principle calculation to investigate the pressure-derived structural transformations and structure-related properties in bulk and nanoscale BiFeO3 up to 55 GPa. A new Imma structure of BiFeO3 has been discovered in the pressure range of 48–52 GPa, which presents ferromagnetic (FM) metallic properties and therefore plays a key role in the IMT. Local structure study reveals that the Bi3+ cation gradually shifts toward the centrosymmetric position in BiO12 cluster during IMT. Besides, the detailed structural information of post-perovskite Cmcm phase has also been determined and thus the complete phase sequence up to 60 GPa is obtained. Our research provides a structural origin of the IMT and a new way to understand the FM release in BiFeO3 system.

Structural dynamics in hybrid halide perovskites: Bulk Rashba splitting, spin texture, and carrier localization

The extended carrier lifetime in hybrid halide perovskites was attributed to a quasi-indirect band gap that arises due to Rashba splitting in both conduction and valence band edges. In this paper, we present results for an effective relativistic band structure of (CH3NH3)PbI3 with the focus on the dispersion of electronic states near the band edges of (CH3NH3)PbI3 affected by thermal structural fluctuations. We establish a relation between the magnitude of Rashba splitting and a deviation of Pb-atom from its centrosymmetric site position in the PbI6 octahedron. For the splitting energy to reach the thermal energy kT~26 meV (room temperature), the displacement should be of the order 0.3 Ang, which is far above the static displacements of Pb-atoms in the tetragonal phase of (CH3NH3)PbI3. The significant dynamic enhancement of the Rashba splitting observed at earlier simulation times (less than 2 ps) later weakens and becomes less than the thermal energy despite the average displacement of Pb-atoms remaining large (0.37 Ang). It is randomization of Pb-displacement vectors and associated cancelation of the net effective magnetic field acting on electrons at the conduction band edge is responsible for reduction of the Rashba splitting. The lattice dynamics also leads to deterioration of Bloch character for states in the valence band leading to subsequent localization of holes, which affects bipolar mobility of charge carriers in (CH3NH3)PbI3. These results call into question the quasi-indirect band gap as a reason for the long carrier lifetime observed in (CH3NH3)PbI3 at room temperature. An alternative mechanism involves dynamic localization of holes and their reduced overlap with electrons in reciprocal space.

Antiferromagnetic Resonance in GdB6

The electron spin resonance has been measured for the first time both in the paramagnetic phase of the metallic GdB6 antiferromagnet (TN = 15.5K) and in the antiferromagnetic state (T < TN). In the paramagnetic phase below T* ~ 70 K, the material is found to exhibit a pronounced increase in the resonance linewidth and a shift in the g-factor, which is proportional to the linewidth Δg(T) ~ ΔH(T). Such behavior is not characteristic of antiferromagnetic metals and seems to be due to the effects related to displacements of Gd3+ ions from the centrosymmetric positions in the boron cage. The transition to the antiferromagnetic phase is accompanied by an abrupt change in the position of resonance (from μ0H0 ≈ 1.9 T to μ0H0 ≈ 3.9 T at ν = 60 GHz), after which a smooth evolution of the spectrum occurs, resulting eventually in the formation of the spectrum consisting of four resonance lines. The magnetic field dependence of the frequency of the resonant modes ω0(H0) obtained in the range of 28–69 GHz is well interpreted within the model of ESR in an antiferromagnet with the easy anisotropy axis ω/γ = (H 0 2 +2HAHE)1/2, where HE is the exchange field and HA is the anisotropy field. This provides an estimate for the anisotropy field, HA ≈ 800 Oe. This value can result from the dipole−dipole interaction related to the mutual displacement of Gd3+ ions, which occurs at the antiferromagnetic transition.

Synthesis, crystal structure and characterization of new three-dimensional Cu(II) coordination polymer based on 1,3,5-tris(imidazol-1-ylmethyl)benzene

The title Cu(II) coordination polymer of 1,3,5-tris(imidazol-1-ylmethyl) benzene, namely {Cu(SO4)(C18H18N6)(C2H6O2)}n, was synthesized and characterized by elemental analysis, infrared spectra (IR), thermogravimetric analysis (TGA) and powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. Single crystal structure analysis shows that the title complex possesses a three-dimensional (3D) architecture with a very rare (3,4,6)-connected (4.62)2(42.68.83.102)(64.82) topology . There are two kinds of crystallographically independent CuII centres, each lying on a centrosymmetric position and having a similar six-coordinated octahedral structure. One is coordinated by four N atoms from four 1,3,5-tris(-imidazol-1-yl)methyl benzene (timb) ligands and two O atoms from two different bridging sulfate anions. The second is surrounded by two timb N atoms and four O atoms, two from sulfate anions and two from two ethane-1,2-diol ligands. The tripodal timb ligand bridges neighbouring CuII centres to generate a two-dimensional layered structure. Adjacent layers are further bridged by sulfate anions, resulting in a three-dimensional structure. X-ray powder diffraction studies of the title complex confirm that there is no impurity phase in the bulk material since experimental diffraction patterns match well with the simulated ones. In addition, their thermal stabilities have also been investigated.

Enhancement of tetragonal anisotropy and stabilisation of the tetragonal phase by Bi/Mn-double-doping in BaTiO3 ferroelectric ceramics

To stabilise ferroelectric-tetragonal phase of BaTiO3, the double-doping of Bi and Mn up to 0.5 mol% was studied. Upon increasing the Bi content in BaTiO3:Mn:Bi, the tetragonal crystal-lattice-constants a and c shrank and elongated, respectively, resulting in an enhancement of tetragonal anisotropy, and the temperature-range of the ferroelectric tetragonal phase expanded. X-ray absorption fine structure measurements confirmed that Bi and Mn were located at the A(Ba)-site and B(Ti)-site, respectively, and Bi was markedly displaced from the centrosymmetric position in the BiO12 cluster. This A-site substitution of Bi also caused fluctuations of B-site atoms. Magnetic susceptibility measurements revealed a change in the Mn valence from +4 to +3 upon addition of the same molar amount of Bi as Mn, probably resulting from a compensating behaviour of the Mn at Ti4+ sites for donor doping of Bi3+ into the Ba2+ site. Because addition of La3+ instead of Bi3+ showed neither the enhancement of the tetragonal anisotropy nor the stabilisation of the tetragonal phase, these phenomena in BaTiO3:Mn:Bi were not caused by the Jahn-Teller effect of Mn3+ in the MnO6 octahedron, but caused by the Bi-displacement, probably resulting from the effect of the 6 s lone-pair electrons in Bi3+.

A new three-dimensional manganese(II) coordination polymer based on the 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene ligand.

The self-assembly of coordination polymers and the crystal engineering of metal-organic coordination frameworks have attracted great interest, but it is still a challenge to predict and control the compositions and structures of the complexes. Employing multidentate organic ligands and suitable metal ions to construct inorganic-organic hybrid materials through metal-ligand coordination and hydrogen-bonding interactions has become a major strategy. Recently, imidazole-containing multidentate ligands that contain an aromatic core have received much attention. A new three-dimensional MnII coordination polymer based on 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene, namely poly[(ethane-1,2-diol-κO)(μ-sulfato-κ2O:O'){μ3-1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene-κ3N:N':N''}manganese(II)], [Mn(SO4)(C18H18N6)(C2H6O2)]n, was synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal structural analysis shows that there are two kinds of crystallographically independent MnII centres, each lying on a centrosymmetric position and having a similar six-coordinated octahedral structure. One is coordinated by four N atoms from four 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene (timb) ligands and two O atoms from two different bridging sulfate anions. The second is surrounded by two timb N atoms and four O atoms, two from sulfate anions and two from two ethane-1,2-diol ligands. The tripodal timb ligand bridges neighbouring MnII centres to generate a two-dimensional layered structure running parallel to the ab plane. Adjacent layers are further bridged by sulfate anions, resulting in a three-dimensional structure with 3,4,6-c topology. Thermogravimetric analysis of the title polymer shows that it is stable up to 533 K. The first weight loss between 533 and 573 K corresponds to the release of coordinated ethane-1,2-diol molecules, and further decomposition occurred at 648 K.

LiNbO3-Type InFeO3: Room-Temperature Polar Magnet without Second-Order Jahn–Teller Active Ions

Great effort has been devoted to developing single-phase magnetoelectric multiferroics, but room-temperature coexistence of large electric polarization and magnetic ordering still remains elusive. Our recent finding shows that such polar magnets can be synthesized in small-tolerance-factor perovskites AFeO3 with unusually small cations at the A-sites, which are regarded as having a LiNbO3-type structure (space group R3c). Herein, we experimentally reinforce this finding by preparing a novel room-temperature polar magnet, LiNbO3-type InFeO3. This compound is obtained as a metastable quench product from an orthorhombic perovskite phase stabilized at 15 GPa and an elevated temperature. The structure analyses reveal that the polar structure is characterized by displacements of In3+ (d10) and Fe3+ (d5) ions along the hexagonal c-axis (pseudocubic [111] axis) from their centrosymmetric positions, in contrast to well-known perovskite ferroelectrics (e.g., BaTiO3, PbTiO3, and BiFeO3) where d0 transition-metal ion...

High pressure single crystal x-ray and neutron powder diffraction study of the ferroelectric–paraelectric phase transition in PbTiO3

The results obtained by high pressure neutron powder diffraction and single-crystal x-ray diffraction for the P4mm–Pmm phase transition in the prototype ferroelectric perovskite lead titanate are shown. Neutron diffraction is found to be strongly sensitive to the dipolar moment in the PbTiO3 unit cell due to the gradual reduction of the displacement of the Ti and O atoms from centrosymmetric positions in the cubic perovskite structure which exhibits anti-phase scattering of Pb, Ti and O atoms. From applying both techniques, the anomalously high Debye–Waller factor for the lead atoms confirms the disordered character of the cubic phase. High pressure single crystal x-ray diffraction also perfectly describes the ferroelectric–paraelectric transition and will be the technique of choice to solve higher pressure structures for PbTiO3.

Two-dimensionally stacked heterometallic layers hosting a discrete chair dodecameric ring of water clusters: synthesis and structural study.

The stacked two-dimensional supramolecular compound catena-{Co(amp)3Cr(ox)3·6H2O} (amp = 2-picolylamine, ox = oxalate) has been synthesized from the bimolecular approach using hydrogen bonds. It is built from layers in which both Co(amp)(3+) (D) and Cr(ox)(3-) (A) ions are bonded in a repeating DADADA… pattern along the a and c axes by multiple hydrogen bonds. These layers host a well resolved R12 dodecameric discrete ring of water clusters built by six independent molecules located around the 2c centrosymmetric Wyckoff positions of the P21/n space group in which the compound crystallizes. These clusters are ranged along the [001] direction, occupy 733.5 Å(3) (22.0%) of the unit cell and have a chair conformation via 12 hydrogen bonds. The water molecules of the cluster are linked with stronger hydrogen bonds than those between the cluster and its host, which explains the single continuous step of the dehydration process of the compound.