Ordering in the pyrochlore antiferromagnet due to Dzyaloshinsky-Moriya interactions

The Heisenberg nearest neighbour antiferromagnet on the pyrochlore (3D) lattice is highly frustrated and does not order at low temperature where spin-spin correlations remain short ranged. Dzyaloshinsky-Moriya interactions (DMI) may be present in pyrochlore compounds as is shown, and the consequences of such interactions on the magnetic properties are investigated through mean field approximation and monte carlo simulations. It is found that DMI (if present) tremendously change the low temperature behaviour of the system. At a temperature of the order of the DMI a phase transition to a long range ordered state takes place. The ordered magnetic structures are explicited for the different possible DMI which are introduced on the basis of symmetry arguments. The relevance of such a scenario for pyrochlore compounds in which an ordered magnetic structure is observed experimentally is dicussed

Magnetic frustration in the spinel compounds Ge Co_2 O_4 and Ge Ni_2 O_4

In both spinel compounds GeCo$_2$O$_4$ and GeNi$_2$O$_4$ which order antiferromagnetically (at $T_N = 23.5 K$ and $T_{N_1} = 12.13 K$, $T_{N_2} = 11.46 K$) with different Curie Weiss temperatures ($T_{CW}$=80.5 K and -15 K), the usual magnetic frustration criterion $f=|T_{CW}|/T_N>>1$ is not fulfilled. Using neutron powder diffraction and magnetization measurements up to 55 T, both compounds are found with a close magnetic ground state at low temperature and a similar magnetic behavior (but with a different energy scale), even though spin anisotropy and first neighbor exchange interactions are quite different. This magnetic behavior can be understood when considering the main four magnetic exchange interactions. Frustration mechanisms are then enlightened.Comment: submitted to Phys.Rev.B (2006

10 simple rules to create a serious game, illustrated with examples from structural biology

Serious scientific games are games whose purpose is not only fun. In the field of science, the serious goals include crucial activities for scientists: outreach, teaching and research. The number of serious games is increasing rapidly, in particular citizen science games, games that allow people to produce and/or analyze scientific data. Interestingly, it is possible to build a set of rules providing a guideline to create or improve serious games. We present arguments gathered from our own experience ( Phylo , DocMolecules , HiRE-RNA contest and Pangu) as well as examples from the growing literature on scientific serious games

One-dimensional metal-organic framework photonic crystals used as platforms for vapor sorption.

We present the fabrication of one-dimensional photonic crystals (Bragg stacks) based on a microporous metal–organic framework material and mesoporous titanium dioxide. The Bragg stack heterostructures were obtained using two complementary synthesis approaches utilizing the bottom-up assembly of heterogeneous, i.e. two-component photonic crystal multilayer structures. Zeolitic imidazolate framework ZIF-8 and mesoporous titanium dioxide were chosen as functional components with different refractive indices. While ZIF-8 is intended to impart molecular selectivity, mesoporous TiO2 is used to ensure high refractive index contrast and to guarantee molecular diffusion within the Bragg stack. The combination of micro- and mesoporosity within one scaffold endows the 1D-MOF PC with characteristic adsorption properties upon exposure to various organic vapors. In this context, the sorption behavior of the photonic material was studied as a function of partial pressure of organic vapors. The results show that the multilayered photonic heterostructures are sensitive and selective towards a series of chemically similar solvent vapors. It is thus anticipated that the concept of multilayer heterogeneous photonic structures will provide a versatile platform for future selective, label-free optical sensors

Annulation of phenols with methylbutenol over MOFs: The role of catalyst structure and acid strength in producing 2,2-dimethylbenzopyran derivatives

The catalytic behavior of metal-organic frameworks of different structures (Fe(BTC), MIL-100(Fe), MIL-100(Cr) and Cu-3(BTC)(2)) was investigated in annulation reaction between 2-methyl-3-buten-2-ol and phenols differing in size (phenol, 2-naphthol). MIL-100(Fe) possessing intermediate Lewis acidity, perfect crystalline structure, and the highest S-BET surface area showed the highest activity (TOF = 0.7 and 1.4h(-1) for phenol and 2-naphthol, respectively) and selectivities to target benzopyran (45% and 65% at 16% of phenol and 2-naphthol conversion, respectively). The increasing strength of Lewis acid centers for MIL-100(Cr) was found to result in the dramatically decreased activity of the catalyst, while negligible conversion of phenols was found over Fe(BTC), characterized by a less ordered framework.M.O. and J.C. acknowledge the Czech Science Foundation for the support (14-07101S) and RNDr. Libor Brabec, CSc. for SEM images.Shamzhy, MV.; Opanasenko, MV.; García Gómez, H.; Cejka, J. (2015). Annulation of phenols with methylbutenol over MOFs: The role of catalyst structure and acid strength in producing 2,2-dimethylbenzopyran derivatives. Microporous and Mesoporous Materials. 202:297-302. doi:10.1016/j.micromeso.2014.10.003S29730220

Modeling adsorption in metal-organic frameworks with open metal sites : propane/propylene separations

We present a new approach for modeling adsorption in metal-organic frameworks (MOFs) with unsaturated metal centers and apply it to the challenging propane/propylene separation in copper(II) benzene-1,3,5-tricarboxylate (CuBTC). We obtain information about the specific interactions between olefins and the open metal sites of the MOP using quantum mechanical density functional theory. A proper consideration of all the relevant contributions to the adsorption energy enables us to extract the component that is due to specific attractive interactions between the pi-orbitals of the alkene and the coordinatively unsaturated metal. This component is fitted using a combination of a Morse potential and a power law function and is then included into classical grand canonical Monte Carlo simulations of adsorption. Using this modified potential model, together with a standard Lennard-Jones model, we are able to predict the adsorption of not only propane (where no specific interactions are present), but also of propylene (where specific interactions are dominant). Binary adsorption isotherms for this mixture are in reasonable agreement with ideal adsorbed solution theory predictions. We compare our approach with previous attempts to predict adsorption in MOFs with open metal sites and suggest possible future routes for improving our model

Stability and Hydrolyzation of Metal Organic Frameworks with Paddle-Wheel SBUs upon Hydration

Instability of most prototypical metal organic frameworks (MOFs) in the presence of moisture is always a limita- tion for industrial scale development. In this work, we examine the dissociation mechanism of microporous paddle wheel frameworks M(bdc)(ted)0.5 [M=Cu, Zn, Ni, Co; bdc= 1,4-benzenedicarboxylate; ted= triethylenediamine] in controlled humidity environments. Combined in-situ IR spectroscopy, Raman, and Powder x-ray diffraction measurements show that the stability and modification of isostructual M(bdc)(ted)0.5 compounds upon exposure to water vapor critically depend on the central metal ion. A hydrolysis reaction of water molecules with Cu-O-C is observed in the case of Cu(bdc)(ted)0.5. Displacement reactions of ted linkers by water molecules are identified with Zn(bdc)(ted)0.5 and Co(bdc)(ted)0.5. In contrast,. Ni(bdc)(ted)0.5 is less suscept- ible to reaction with water vapors than the other three compounds. In addition, the condensation of water vapors into the framework is necessary to initiate the dissociation reaction. These findings, supported by supported by first principles theoretical van der Waals density functional (vdW-DF) calculations of overall reaction enthalpies, provide the necessary information for de- termining operation conditions of this class of MOFs with paddle wheel secondary building units and guidance for developing more robust units

XY antiferromagnetic ground state in the effective S= 12 pyrochlore Yb2Ge2 O7

We report neutron scattering and muon spin relaxation measurements (muSR) on the pyrochlore antiferromagnet Yb2Ge2O7. Inelastic neutron scattering was used to probe the transitions between crystal electric field levels, allowing us to determine the eigenvalues and eigenvectors appropriate to the J=7/2 Yb3+ ion in this environment. The crystal electric field ground state doublet in Yb2Ge2O7 corresponds primarily to m_J = +/- 1/2 with local XY anisotropy, consistent with an S_eff = 1/2 description for the Yb moments. muSR measurements reveal the presence of an ordering transition at T_N = 0.57 K with persistent weak dynamics in the ordered state. Finally, we present neutron diffraction measurements that reveal a clear phase transition to the k = (000) Gamma_5 ground state with an ordered magnetic moment of 0.3(1) mu_B per Yb ion. We compare and contrast this phenomenology with the low temperature behavior of Yb2Ti2O7 and Er2Ti2O7, the prototypical S_eff = 1/2 XY pyrochlore magnets.Comment: 10 pages, 6 figures, accepted in Phys. Rev.