Preliminary observations of the interplay of radiation damage with spin crossover

Intense synchrotron radiation makes time-resolved structural experiments with increasingly finer time sampling possible. On the other hand, radiation heating, radiation-induced volume change and structural disorder become more frequent. Temperature, volume change and disorder are known to be coupled with equilibrium in molecular spin complexes, balancing between two or more spin state configurations. Combining single-crystal diffraction and synchrotron radiation it is illustrated how the radiation damage and associated effects can affect the spin crossover process and may serve as yet another tool to further manipulate the spin crossover properties.publishedVersio

LEGAL MEANS OF ENSURING PUBLIC SAFETY AS A BASIS FOR THE PROGRESSIVE DEVELOPMENT OF SOCIETY

Objective: The article investigates the key areas to improve the effectiveness of legal means for human rights protection in the conditions of spreading ideology that promotes the development of extremist and terrorist activities. Methods: Close attention is paid to the scale of spreading extremism and terrorism ideology at transnational, interstate and national levels. Results: The focus of activity in terrorist organizations is emphasized on destruction or disruption of transport infrastructure, life support facilities, intimidation of population and committing acts of nuclear terrorism. Conclusions: It is necessary to develop a legal policy that promotes the implementation of measures to protect human rights, regardless to the nature of the political and legal system in the state. The universality of measures for the protection of human rights implies their viability in various socially interactive legal systems. The necessity to develop new approaches to justify the formation of ideology of terrorism and extremism is determined. Attention is paid to the necessity to improve legal grounds for understanding terrorism and extremism

Crystal structures of cristobalite-type and coesite-type PON redetermined on the basis of single-crystal X-ray diffraction data

Hitherto, phosphorus oxonitride (PON) could not be obtained in the form of single crystals and only powder diffraction experiments were feasible for structure studies. In the present work we have synthesized two polymorphs of phosphorus oxonitride, cristobalite-type (cri-PON) and coesite-type (coe-PON), in the form of single crystals and reinvestigated their crystal structures by means of in house and synchrotron single-crystal X-ray diffraction. The crystal structures of cri-PON and coe-PON are built from PO2N2 tetrahedral units, each with a statistical distribution of oxygen and nitrogen atoms. The crystal structure of the coe-PON phase has the space group C2/c with seven atomic sites in the asymmetric unit [two P and three (N,O) sites on general positions, one (N,O) site on an inversion centre and one (N,O) site on a twofold rotation axis], while the cri-PON phase possesses tetragonal I-42d symmetry with two independent atoms in the asymmetric unit [the P atom on a fourfold inversion axis and the (N,O) site on a twofold rotation axis]. In comparison with previous structure determinations from powder data, all atoms were refined with anisotropic displacement parameters, leading to higher precision in terms of bond lengths and angles

Chiral criticality in doped Mn1−y_{1-y}Fey_ySi compounds

The critical spin fluctuations in doped compounds Mn$_{1-y}$Fe$_y$Si have been studied by means of ac-susceptibility measurements, polarized neutron small angle scattering and spin echo spectroscopy. It is shown that these compounds undergo the transition from the paramagnetic to helimagnetic phase through continuous, yet well distinguishable crossovers: (i) from paramagnetic to partially chiral, (ii) from partially chiral to highly chiral fluctuating state. The crossover points are identified on the basis of combined analysis of the temperature dependence of ac-susceptibility and polarized SANS data. The whole transition is marked by two inflection point of the temperature dependence of ac-susceptibility: the upper one corresponds to the crossover to partially chiral state at $T^*$, where the inverse correlation length $\kappa \approx 2 k$, the lower one corresponds to the transition to the spin helix structure. The intermediate crossover to the highly chiral phase is observed at the inflection point $T_k$ of the first derivative of ac-susceptibility, where $\kappa \approx k$. The temperature crossovers to the highly chiral fluctuating state is associated with the enhancing influence of the Dzyaloshinskii-Moria interaction close to $T_c$.Comment: 5 pages, 5 figures, 1 table, 13 cite

Lithium distribution and transfer in high-power 18650-type Li-ion cells at multiple length scales

The distribution of lithium inside electrodes of a commercial Li-ion battery of 18650-type with LiFePO$_{4}$ cathode and graphite anode is investigated on different length scales using neutron diffraction, X-ray (synchrotron-based) diffraction and X-ray computed tomography. Evolution of 2D (in-plane) lithium distribution in lithiated graphite is monitored during charge/discharge using millimeter-sized spatial resolution. Micrometer-sized details of cell organization and lithiation of both the positive and negative electrodes are obtained from diffraction-based tomography applying synchrotron radiation. In-situ lithiation of the cathode over its thickness and development of the lithium concentration front during cell charge/discharge is traced by diffraction-based profiling with a micrometer-sized synchrotron beam in a single-layer electrochemical cell

Chirok: a post-refinement tool to analyse absolute structure

Chirok is software for a post-refinement test of the absolute structure. The software allows a user to calculate a distribution of the measure of chirality based on intensity quotients and linked to the Flack parameter. The distribution is fitted by a set of peak functions, the refined centre of which gives an estimate of the Flack parameter with the same or better precision compared with the usual refinement schemes. The use of this software is illustrated with a collection of published data for chiral structures

Principal Component Analysis (PCA) for Powder Diffraction Data: Towards Unblinded Applications

We analyze the application of Principal Component Analysis (PCA) for untangling the main contributions to changing diffracted intensities upon variation of site occupancy and lattice dimensions induced by external stimuli. The information content of the PCA output consists of certain functions of Bragg angles (loadings) and their evolution characteristics that depend on external variables like pressure or temperature (scores). The physical meaning of the PCA output is to date not well understood. Therefore, in this paper, the intensity contributions are first derived analytically, then compared with the PCA components for model data; finally PCA is applied for the real data on isothermal gas uptake by nanoporous framework γ –Mg(BH 4 ) 2 . We show that, in close agreement with previous analysis of modulation diffraction, the variation of intensity of Bragg lines and the displacements of their positions results in a series of PCA components. Every PCA extracted component may be a mixture of terms carrying information on the average structure, active sub-structure, and their cross-term. The rotational ambiguities, that are an inherently part of PCA extraction, are at the origin of the mixing. For the experimental case considered in the paper, the extraction of the physically meaningful loadings and scores can only be achieved with a rotational correction. Finally, practical recommendations for non-blind applications, i.e., what boundary conditions to apply for the the rotational correction, of PCA for diffraction data are given