Avoiding problems with hydrogen misplacement in reporting crystal structures

Intermolecular hydrogen bonding is an integral part of many crystal structures. Hydrogen bonding sometimes results in one‐, two‐ or three‐dimensional supramolecular assemblies, a common feature of which is positional disorder of H atoms related to space‐group symmetry. Yet some reported structures fail to include all possible donor–acceptor close contacts, or to seek H‐atom electron densities associated with apparent D—H...A trios, while some H‐atom positions violate principles of chemistry or crystal physics. Modern diffraction equipment and sophisticated computing systems provide high‐quality data; thus, failure to characterize and report fully an accurate, complete and physically correct hydrogen‐bonding model should not be acceptable. We illustrate the relevant issues with three published examples in the hope of slowing the proliferation of these problems, with the scientifically desirable goal of improving the accuracy of crystallographic models while also providing improved search keys for information retrieval.     

Mechanical and dynamic aspects of voice production as related to voice therapy and phonosurgery

Laryngeal framework surgery can change the position and tensionof the vocal folds safely without direct surgical intervention in the vocal fold proper. Some 23 years of experience with phonosurgery have proved its usefulness in treating dysphonia related to unilateral vocal fold paralysis, vocal fold atrophy, and pitch-related dysphonias. Meanwhile, much information about the mechanism of voice production has been obtained through intraoperative findings of voice and fiberscopic examination of the larynx . Based on such knowledge together with information obtained through model experiments, the human vocal organ was reconsidered mainly from the mechanical view point, and the roles of voice therapy and singing pedagogy were discussed in relation to phonosurgery. The vocal organ may not be an ideal musical organ and is rather vulnerable, but its potential is enormous.     

Unified description of nonclassical uniaxial ferroelectric materials in order–disorder phase transitions

An equation of state accounting for coupling of the primary order parameter (here the polarization) with a secondary order parameter (here a strain ?) is used to describe the temperature dependences of the spontaneous polarization and of the electric susceptibility on external biasing field. A new scaling invariant and its explicit expression are given. The theory is exemplified by the effective critical behavior of the molecular ferroelectric crystals (CH₃NH₃)₅Bi₂Cl₁₁ (MAPCB) and (CH₃NH₃)₅Bi₂Br₁₁ (MAPBB).     

Two Connections Between Random Systems and Non-Gibbsian Measures

In this contribution we discuss the role disordered (or random) systems have played in the study of non-Gibbsian measures. This role has two main aspects, the distinction between which has not always been fully clear: 1) From disordered systems: Disordered systems can be used as a tool; analogies with, as well as results and methods from the study of random systems can be employed to investigate non-Gibbsian properties of a variety of measures of physical and mathematical interest. 2) Of disordered systems: Non-Gibbsianness is a property of various (joint) measures describing quenched disordered systems. We discuss and review this distinction and a number of results related to these issues. Moreover, we discuss the mean-field version of the non-Gibbsian property, and present some ideas how a Kac limit approach might connect the finite-range and the mean-field non-Gibbsian properties.     

Coupled crystallographic order-disorder and spin state in a bistable molecule: multiple transition dynamics

A novel bispyrazolylpyridine ligand incorporating lateral phenol groups, H₄L, has led to an Fe^II spin‐crossover (SCO) complex, [Fe(H₄L)₂][ClO₄]₂ ? H₂O ? 2 (CH₃)₂CO ( 1 ), with an intricate network of intermolecular interactions. It exhibits a 40 K wide hysteresis of magnetization as a result of the spin transition (with T_0.5 of 133 and 173 K) and features an unsymmetrical and very rich structure. The latter is a consequence of the coupling between the SCO and the crystallographic transformations. The high‐spin state may also be thermally trapped, exhibiting a very large T_TIESST (≈104 K). The structure of 1 has been determined at various temperatures after submitting the crystal to different processes to recreate the key points of the hysteresis cycle and thermal trapping; 200 K, cooled to 150 K and trapped at 100 K (high spin, HS), slowly cooled to 100 K and warmed to 150 K (low spin, LS). In the HS state, the system always exhibits disorder for some components (one ClO₄^? and two acetone molecules) whereas the LS phases show a relative ≈9 % reduction in the Fe? N bond lengths and anisotropic contraction of the unit cell. Most importantly, in the LS state all the species are always found to be ordered. Therefore, the bistability of crystallographic order–disorder coupled to SCO is demonstrated here experimentally for the first time. The variation in the cell parameters in 1 also exhibits hysteresis. The structural and magnetic thermal variations in this compound are paralleled by changes in the heat capacity as measured by differential scanning calorimetry. Attempts to simulate the asymmetric SCO behaviour of 1 by using an Ising‐like model underscore the paramount role of dynamics in the coupling between the SCO and the crystallographic transitions.     

Correlation Functions by Cluster Variation Method for Ising Model with NN, NNN, and Plaquette Interactions

We consider a procedure for calculating the pair correlation function in the context of cluster variation methods (CVM). As specific cases, we study the pair correlation function in the paramagnetic phase of the Ising model with nearest neighbors, next to nearest neighbors, and plaquette interactions in two and three dimensions. In presence of competing interactions, the so-called disorder line separates in the paramagnetic phase a region where the correlation function has the usual exponential behavior from a region where the correlation has an oscillating, exponentially damped behavior. In two dimensions, using the plaquette as the maximal cluster of the CVM approximation, we calculate the phase diagram and the disorder line for a case where a comparison is possible with known results for the eight-vertex model. In three dimensions, in the CVM cube approximation, we calculate the phase diagram and the disorder line in some cases of particular interest. The relevance of our results for experimental systems like mixtures of oil, water, and surfactant is also discussed.     

Structural disorder, octahedral coordination and two-dimensional ferromagnetism in anhydrous alums

The crystal structures of the triangular lattice, layered anhydrous alums KCr(SO₄)₂, RbCr(SO₄)₂ and KAl(SO₄)₂ are characterized by X-ray and neutron powder diffraction (NPD) at temperatures between 1.4 and 773 K. The compounds all crystallize in the space group , with octahedral coordination of the trivalent cations. In all cases, small amounts of disorder in the stacking of the triangular layers of corner sharing MO₆ octahedra and SO₄ tetrahedra is seen, with the MO₆−SO₄ network rotated in opposite directions between layers. The electron diffraction study of KCr(SO₄)₂ supports this model, which on an average can be taken to imply trigonal prismatic coordination for the M³⁺ ions; as was previously reported for the prototype anhydrous alum, KAl(SO₄)₂. The temperature-dependent magnetic susceptibilities for ACr(SO₄)₂ (A=K, Rb, Cs) indicate the presence of predominantly ferromagnetic interactions. Low-temperature powder neutron diffraction reveals that the magnetic ordering is ferromagnetic in-plane, with antiferromagnetic ordering between planes below 3 K.     

Microstructure evolution and dielectric properties of Ba<Subscript>5-x</Subscript>Na<Subscript>2x</Subscript>Nb<Subscript>10</Subscript>O<Subscript>30</Subscript> ceramics with different Ba–Na Ratios

The tetragonal tungsten bronzes of Ba5−xNa_2x Nb₁₀O₃₀ (BNN, 0.5≤ x≤1.3) ceramics were synthesized using the solid state reaction method. The sintering behavior and dielectric characteristics of the BNN ceramics, as a function of the Ba-Na ratio, were examined. Densification of the samples with excess compositions of Ba and Na was higher than that of the stoichiometric BNN sample. The maximum dielectric constant and the Curie temperature showed highest values at the stoichiometric composition and decreased as the composition shifted away from the stoichiometry. in order to obtain a quantitative evaluation of the diffuse phase transition (DPT) behavior of the BNN ceramics, γ and C/κ_max were calculated. The weakest DPT behavior was observed in the stoichiometric composition. An increase in the DPT is in correlation with the increase in the number of ways of cation distribution by the disordered occupation of Ba and Na and the vacancies in the A1 and A2 sites of the tungsten bronze structure.