The aperiodic nature of incommensurately modulated structures

The discovery of aperiodic crystals is perhaps one of the most important event which has changed our vision on crystalline architectures since the discovery of diffraction 100years ago. It was the merit of a Dutch crystallographer, P.M. de Wolff, to interpret their diffraction pattern as a three dimensional projection of a higher dimensional reciprocal lattice, idea which led directly to the generalization of the concept of crystal. Aperiodic crystals are currently described as periodic objects in higher-dimensional space, i.e. the superspace and their structures can be described in terms of 3-d cuts. Incommensurate structures, composite structures and quasicrystals all belong to aperiodic structures. Many interesting properties of superspace have been discovered which are also directly applicable to crystals in the conventional sense, i.e. crystals with 3-d periodicity. In particular the concept of structure type can be extended for a better understanding of structure relations. The notion of solid solution has also benefited from superspace considerations. Moreover, superspace is a very powerful tool for a better understanding of structure-property relations in material science, e.g. luminescence properties could be directly associated to the description of structures in superspace. Recently, this concept has been used for the prediction of new structural modifications including polytypes and even polytypic modifications of a well-known pharmaceutical produc

Atomic clusters and phase transitions in the metastable beta-Ta phase between 4.2 and 293 K

Atomic clusters were identified in the ground state of the non-equilibrium Ta phase (Frank-Kasper sigma-structure type) at 15, 120 and 293K. The evolution of the clusters with temperature leads to two phase transformations at 65 and 150K which are related to the electrical and magnetic properties. The magnetic phase transition at 65 K is associated with the magnetic symmetry group transformation P4'(2) /mn'm ( 65 K). It is shown that beta-U is also a two-component composite containing similar clusters. The nature of the stabilisation of beta-Ta at the cathode is discussed

Optically switched magnetism in photovoltaic perovskite CH3_3NH3_3(Mn:Pb)I3_3

The demand for ever-increasing density of information storage and speed of manipulation boosts an intense search for new magnetic materials and novel ways of controlling the magnetic bit. Here, we report the synthesis of a ferromagnetic photovoltaic CH$_3$NH$_3$(Mn:Pb)I$_3$ material in which the photo-excited electrons rapidly melt the local magnetic order through the Ruderman-Kittel-Kasuya-Yosida interactions without heating up the spin system. Our finding offers an alternative, very simple and efficient way of optical spin control, and opens an avenue for applications in low power, light controlling magnetic devices

The aperiodic nature of incommensurately modulated structures

The discovery of aperiodic crystals is perhaps one of the most important event which has changed our vision on crystalline architectures since the discovery of diffraction 100 years ago. It was the merit of a Dutch crystallographer, P.M. de Wolff, to interpret their diffraction pattern as a three dimensional projection of a higher dimensional reciprocal lattice, idea which led directly to the generalization of the concept of crystal. Aperiodic crystals are currently described as periodic objects in higher-dimensional space, i.e. the superspace and their structures can be described in terms of 3-d cuts. Incommensurate structures, composite structures and quasicrystals all belong to aperiodic structures. Many interesting properties of superspace have been discovered which are also directly applicable to crystals in the conventional sense, i.e. crystals with 3-d periodicity. In particular the concept of structure type can be extended for a better understanding of structure relations. The notion of solid solution has also benefited from superspace considerations. Moreover, superspace is a very powerful tool for a better understanding of structure–property relations in materials science, e.g. luminescence properties could be directly associated to the description of structures in superspace

Cimetidine, C10H16N6S, formC: crystal structure and modelling of polytypes using suoperspace approach

An efficient method for modelling a polytypic family is presented with the example of cimetidine in the form C polymorph. The method exploits the (3 + 1)-dimensional superspace model, which is a powerful tool for the description, prediction and understanding of polytype modifications in small-molecule crystallography, as illustrated with this pharmaceutical example

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

The study of incommensurate structures as a probe to reveal atomic interactions in crystals

The structure of aperiodic crystals which includes incommensurate, quasi- and composite crystals is usually described in spaces of higher dimension, the so called superspace. The main advantage of the superspace formalism is that an aperiodic structure in three dimensions recovers its full periodicity in higher dimensions. The symmetry properties of aperiodic crystals are obviously more convenient to describe in superspace too. The origin of the incommensurate nature of structures can often be found in competing interatomic interactions. From molecular dynamics simulation of a simple three dimensional model with close-packed layers and a single degree of freedom for each particle, it is possible to find the existence conditions of commensurate and incommensurate phases. Incommensurate phases can already be predicted on the basis of nearest and next nearest neighbour particle interactions only. We illustrate this principle of interactions with two examples of structures, Na2CO3 and K3In(PO4)(2). These examples shows clearly the importance of non-oxygen interactions i.e. next nearest interactions for the formation of incommensurate structures

Getting more out of an incommensurately modulated structure: the example of K_5Yb(MoO_4)_4

A method based on the superspace approach is presented with the aim of generating a family of modular structures from a single incommensurately modulated structure. This approach based on the variation of the modulation vector q is applied to the generation of the K5Yb(MoO4)4, potassium ytterbium tetramolybdate, family of modular structures. The $\beta$ coefficient of the modulation vector q = $\beta b*$ is a temperature-dependent variable which determines the modification. Our method gives a unified frame to describe and explain the three temperature-dependent phases of K5Yb(MoO4)4. Phase can be represented as a polytypic modification with 1/2b*\le q\le 2/3b*; phases $\gamma$ (q = 1/2b*) and \alpha (q = 1b*) are the lowest and the highest temperature members of the K5Yb(MoO4)4 family, respectively

The self-hosting structure of beta-Ta

Using electrodeposition from a bath of molten fluorides, single crystals of tetragonal beta-tantalum have been obtained for the first time at normal pressure. The unit-cell parameters are a = 10.211 (3), c = 5.3064 (10) Angstrom, space group P (4) over bar2(1)m. The beta-Ta structure belongs to the sigma-type Frank-Kasper structures which are typical for binary intermetallic compounds and beta-U. In comparison to the sigma-type, additional intercalated Ta atoms (population factor similar to 0.01) have been detected between the atoms located in the channels of the structure. The shorter interatomic distances observed between the channel atoms in comparison with the atoms of the framework justify the 'self-hosting' characteristic. beta-Ta exhibits common features with the complex tetragonal structures of the high-pressure phases for the elements Rb, Ba, Sr, Bi and Sb. [References: 24] 2