TY - JOUR A1 - Gorfman, Semen A1 - Tsirelson, Vladimir A1 - Pucher, Andreas A1 - Morgenroth, Wolfgang A1 - Pietsch, Ullrich T1 - X-ray diffraction by a crystal in a permanent external electric field : electric-field-induced structural response in alpha-GaPO4 N2 - For the first time, site-selective distortion has been investigated for two different structural units in the ternary compound alpha-GaPO4 under the influence of a permanent external electric field. Based on 54 measured reflection intensities, the electric-field-induced distortion of PO4 and GaO4 tetrahedra in alpha-GaPO4 crystals is evaluated using a model of pseudoatomic displacements introduced recently [Gorfman, Tsirelson & Pietsch (2005). Acta Cryst. A61, 387- 396]. A stronger variation of the P-O bond lengths in the PO4 tetrahedron was found compared to the bonds in the GaO4 tetrahedron. The different distortions of the tetrahedra owing to the electric field were analysed in terms of the valence charge density of alpha-GaPO4 and its topological characteristics. The larger charge of the P pseudoatom compared to the Ga atom was recognized as the main reason for the higher sensitivity of the PO4 tetrahedron to a permanent external electric field Y1 - 2006 UR - http://onlinelibrary.wiley.com/journal/10.1111/(ISSN)1600-5724 U6 - https://doi.org/10.1107/S0108767305036111 SN - 0108-7673 ER - TY - JOUR A1 - Porȩba, Tomasz A1 - Racioppi, Stefano A1 - Garbarino, Gaston A1 - Morgenroth, Wolfgang A1 - Mezouar, Mohamed T1 - Investigating the structural symmetrization of CsI3 at high pressures through combined X-ray diffraction experiments and theoretical analysis JF - Inorganic chemistry N2 - ABSTRACT: Structural evolution of cesium triiodide at high pressures has been revealed by synchrotron single-crystal X-ray diffraction. Cesium triiodide undergoes a first-order phase transition above 1.24(3) GPa from an orthorhombic to a trigonal system. This transition is coupled with severe reorganization of the polyiodide network from a layered to three-dimensional architecture. Quantum chemical calculations show that even though the two polymorphic phases are nearly isoenergetic under ambient conditions, the PV term is decisive in stabilizing the trigonal polymorph above the transition point. Phonon calculations using a non-local correlation functional that accounts for dispersion interactions confirm that this polymorph is dynamically unstable under ambient conditions. The high-pressure behavior of crystalline CsI3 can be correlated with other alkali metal trihalides, which undergo a similar sequence of structural changes upon load. Y1 - 2022 U6 - https://doi.org/10.1021/acs.inorgchem.2c01690 SN - 0020-1669 SN - 1520-510X VL - 61 IS - 28 SP - 10977 EP - 10985 PB - American Chemical Society CY - Washington ER - TY - GEN A1 - Spiekermann, Georg A1 - Harder, M. A1 - Gilmore, Keith A1 - Zalden, Peter A1 - Sahle, Christoph J. A1 - Petitgirard, Sylvain A1 - Wilke, Max A1 - Biedermann, Nicole A1 - Weis, Thomas A1 - Morgenroth, Wolfgang A1 - Tse, John S. A1 - Kulik, E. A1 - Nishiyama, Norimasa A1 - Yavaş, Hasan A1 - Sternemann, Christian T1 - Persistent Octahedral Coordination in Amorphous GeO₂ Up to 100 GPa by Kβ'' X-Ray Emission Spectroscopy T2 - Postprints der Universität Potsdam Mathematisch-Naturwissenschaftliche Reihe N2 - We measure valence-to-core x-ray emission spectra of compressed crystalline GeO₂ up to 56 GPa and of amorphous GeO₂ up to 100 GPa. In a novel approach, we extract the Ge coordination number and mean Ge-O distances from the emission energy and the intensity of the Kβ'' emission line. The spectra of high-pressure polymorphs are calculated using the Bethe-Salpeter equation. Trends observed in the experimental and calculated spectra are found to match only when utilizing an octahedral model. The results reveal persistent octahedral Ge coordination with increasing distortion, similar to the compaction mechanism in the sequence of octahedrally coordinated crystalline GeO₂ high-pressure polymorphs. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 699 KW - rutile-type KW - glass KW - crystalline KW - pressures KW - complexes KW - silicon KW - oxygen KW - SIO₂ KW - MO KW - CU Y1 - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-427755 SN - 1866-8372 IS - 699 ER - TY - JOUR A1 - Spiekermann, Georg A1 - Harder, M. A1 - Gilmore, Keith A1 - Zalden, Peter A1 - Sahle, Christoph J. A1 - Petitgirard, Sylvain A1 - Wilke, Max A1 - Biedermann, Nicole A1 - Weis, Thomas A1 - Morgenroth, Wolfgang A1 - Tse, John S. A1 - Kulik, E. A1 - Nishiyama, Norimasa A1 - Yavaş, Hasan A1 - Sternemann, Christian T1 - Persistent Octahedral Coordination in Amorphous GeO₂ Up to 100 GPa by Kβ'' X-Ray Emission Spectroscopy JF - Physical Review X N2 - We measure valence-to-core x-ray emission spectra of compressed crystalline GeO₂ up to 56 GPa and of amorphous GeO₂ up to 100 GPa. In a novel approach, we extract the Ge coordination number and mean Ge-O distances from the emission energy and the intensity of the Kβ'' emission line. The spectra of high-pressure polymorphs are calculated using the Bethe-Salpeter equation. Trends observed in the experimental and calculated spectra are found to match only when utilizing an octahedral model. The results reveal persistent octahedral Ge coordination with increasing distortion, similar to the compaction mechanism in the sequence of octahedrally coordinated crystalline GeO₂ high-pressure polymorphs. KW - rutile-type KW - glass KW - crystalline KW - pressures KW - complexes KW - silicon KW - oxygen KW - SIO₂ KW - MO KW - CU Y1 - 2019 U6 - https://doi.org/10.1103/PhysRevX.9.011025 SN - 2469-9926 SN - 0556-2791 SN - 1050-2947 SN - 1094-1622 VL - 9 IS - 1 PB - American Physical Society by the American Institute of Physics CY - Melville, NY ER - TY - JOUR A1 - Dey, Somnath A1 - Schönleber, Andreas A1 - Smaalen, Sander van A1 - Morgenroth, Wolfgang A1 - Larsen, Finn Krebs T1 - Incommensurate phase in Λ-cobalt (III) sepulchrate trinitrate governed by highly competitive N-H...O and C-H...O hydrogen bond networks JF - Chemistry - a European journal N2 - Phase transitions in molecular crystals are often determined by intermolecular interactions. The cage complex of [Co(C12H30N8)](3+) . 3 NO3- is reported to undergo a disorder-order phase transition at T-c1 approximate to 133 K upon cooling. Temperature-dependent neutron and synchrotron diffraction experiments revealed satellite reflections in addition to main reflections in the diffraction patterns below T-c1. The modulation wave vector varies as function of temperature and locks in at T-c3 approximate to 98 K. Here, we demonstrate that the crystal symmetry lowers from hexagonal to monoclinic in the incommensurately modulated phases in T-c1