High-pressure Crystal Structure Research Articles

A database of high-pressure crystal structures from hydrogen to lanthanum

This paper introduces the HEX (High-pressure Elemental Xstals) database, a complete database of the ground-state crystal structures of the first 57 elements of the periodic table, from H to La, at 0, 100, 200 and 300 GPa. HEX aims to provide a unified reference for high-pressure research, by compiling all available experimental information on elements at high pressure, and complementing it with the results of accurate evolutionary crystal structure prediction runs based on Density Functional Theory. Besides offering a much-needed reference, our work also serves as a benchmark of the accuracy of current ab-initio methods for crystal structure prediction. We find that, in 98% of the cases in which experimental information is available, ab-initio crystal structure prediction yields structures which either coincide or are degenerate in enthalpy to within 300 K with experimental ones. The main manuscript contains synthetic tables and figures, while the Crystallographic Information File (cif) for all structures can be downloaded from the related figshare online repository.

Evolution of structure and spectroscopic properties of a new 1,3-diacetylpyrene polymorph with temperature and pressure.

A new polymorph of 1,3-diacetylpyrene has been obtained from its melt and thoroughly characterized using single-crystal X-ray diffraction, steady-state UV-Vis spectroscopy and periodic density functional theory calculations. Experimental studies covered the temperature range from 90 to 390 K and the pressure range from atmospheric to 4.08 GPa. Optimal sample placement in a diamond anvil cell according to our previously presented methodology ensured over 80% data coverage up to 0.8 Å for a monoclinic sample. Unrestrained Hirshfeld atom refinement of the high-pressure crystal structures was successful and anharmonic behavior of carbonyl oxygen atoms was observed. Unlike the previously characterized polymorph, the structure of 2°AP-β is based on infinite π-stacks of antiparallel 2°AP molecules. 2°AP-β displays piezochromism and piezofluorochromism which are directly related to the variation in interplanar distances within the π-stacking. The importance of weak intermolecular interactions is reflected in the substantial negative thermal expansion coefficient of -55.8 (57) MK-1 in the direction of C-H...O interactions.

High-pressure crystal structure and properties of chlorine monofluoride

Chlorine Monofluoride (ClF) is a good fluoride that can react with tungsten, selenium, and other simple substances to generate fluoride and chlorine, but it is very unstable under environmental pressure. The pressure-induced structural phase transition of halogen compound ClF at high pressure was studied using the crystal structure AnaLYsis by Particle Swarm Optimization (CALYPSO) structure prediction method. The order of phase transition for ClF under high pressure was found as P1 → Cmc21 → P2/m → Imma, with corresponding phase transition pressures observed at 6 GPa, 54 GPa, and 130 GPa, respectively. The physical properties of each predicted phase were thoroughly studied, finding that the P1 phase is unstable at the Brillouin zone. Furthermore, the energy band structure and density of states showed that P2/m phase and Imma phase with a metal structure. The present studies provide a foundation and insight into the structural phase transition of other halogen compounds at high pressures.

Experimental observation of two-dimensional phase in compressed FeF2

Iron difluoride (FeF2) has attracted considerable attention for its physical characteristics and practical applications, and its compression behaviors usually play a key role in the in-depth understanding of this compound. Since its high-pressure crystal structure evolution determining a more profound comprehension remains disputable, we carried out extensive experiments to focus on the pressure-induced structural phase transitions of FeF2. Through in situ high-pressure synchrotron x-ray diffraction measurements, we not only confirmed a reported high-pressure orthorhombic Pbca phase at 11 GPa but also identified an interesting two-dimensional structure with hexagonal close packed symmetry (P-3m1) that appears above 25 GPa at room temperature. Furthermore, the spontaneous strain fitting and electronic transport measurements suggest that its ambient rutile-type structure (P42/mnm) evolves into an orthorhombic structure (Pnnm) through a second-order phase transition at 5 GPa. These experimental results elaborate on the pressure-induced phase transitions of FeF2 on the order of P42/mnm → Pnnm → Pbca → P-3m1, shedding light on a rare three-dimensional to two-dimensional configuration transition in difluorides.

High-Pressure Synthesis, Crystal Structure, and Physical Properties of a Spinel Compound Co0.7Al2S4.

In this paper, we report on the discovery of a spinel compound, Co0.7Al2S4, which was synthesized at high-pressure. The systematic characterizations were carried out by structural, magnetic, and heat capacity measurements. The compound crystallizes into a cubic structure with the space group Fd3̅m (no. 227) and the lattice constant a = 9.9580(1) Å. Magnetic susceptibility measurements suggest that Co0.7Al2S4 exhibits a spin glass ground state, freezing at Tf ∼ 7.2 K with a Weiss temperature Tθ ∼ -115.9 K, which is verified by ac magnetic susceptibility and heat capacity measurements. The frustration parameter f for Co0.7Al2S4 is calculated to be about 16.6, based on the formula f = | Tθ/Tf |, indicating that Co0.7Al2S4 is a high-frustration magnet. Specific heat data displays a T2 dependence below the freezing temperature, which is different from the linear dependence observed in a common spin glass system. Compared with the similar compound CoAl2O4, it is suggested that the vacancies in the Co sites should be responsible for the occurrence of the spin glass behavior of Co0.7Al2S4.

High-pressure syntheses, crystal structures, and magnetic properties of novel quadruple perovskite oxides LaMn3Ru2Mn2O12 and LaMn3Ru2Fe2O12

Quadruple perovskite oxides LaMn3Ru2M2O12 (M = Mn, Fe) have been synthesized under high-pressure and high-temperature conditions of 8 GPa and 1373 K. Synchrotron X-ray powder diffraction study demonstrates that both oxides crystallized in AA'3B4O12-type cubic quadruple perovskite structures, where the Ru and M ions did not form the special ordering at B-site. X-ray absorption spectroscopy reveals that the valence states are represented as LaMn3+3Ru3+2M3+2O12 (M = Mn, Fe) in the ionic models, indicating that the isovalent states of Ru3+ and M3+ ions disturb the B-site ordering. Magnetization, heat capacity, and neutron diffraction data prove that short-range magnetic orderings are predominant for both compounds instead of long-range magnetic orderings. We conclude that the competition between ferromagnetic and antiferromagnetic superexchange interactions between Ru3+ and M3+ ions at B-site prevent the long-range magnetic ordering Mn3+ ions at A′-site, although the A'- and B-site magnetic sublattices are expected to be intrinsically independent in A′-Mn quadruple perovskite system. This finding represents that the atomic ordering of the B-site is essential for the precise design of magnetic structures for the LaMn3M2M′2O12 quadruple perovskite series.

High-pressure crystal structures of organic radical molecules for applications in molecular electronics

High-pressure crystal structures of organic radical molecules for applications in molecular electronics

Low-temperature and high-pressure phase transitions in 1-decyl-3-methylimidazolium nitrate ionic liquid

The phase behavior of 1-decyl-3-methylimidazolium nitrate ([C10mim][NO3]) was investigated at a low temperature (LT) under ambient pressure and a high pressure (HP) under ambient temperature. [C10mim][NO3] is an ionic liquid (IL) possessing a long alkyl chain length. Detailed crystal structures of the IL at LT and HP were determined by synchrotron radiation experiments. The weak Bragg reflections in the low wavevector (Q) region were clearly observed. At LT, the Bragg reflection at the lowest Q was positioned differently than the prepeak in the liquid state. The 00ℓ Bragg reflections at Q00ℓ indicate a hybrid-layered structure with a lattice constant of 4.3 nm. In addition to the 00ℓ Bragg reflections, the double peak occurred in the region of Q002 at HP; thus new HP crystal structures were observed in [C10mim][NO3].

High-pressure synthesis, crystal structure, and characterization of the new non-centrosymmetric terbium borate Tb3B10O17(OH)5

Herein, the high-pressure/high-temperature synthesis (11 GPa, 650 °C) of Tb3B10O17(OH)5 in a modified Walker-type multianvil device is presented. The structure of this rare-earth borate was determined by single-crystal X-ray diffraction methods and was found to crystallize orthorhombically in the space group Pmn21 (no. 31) with the unit cell parameters a = 16.2527(4), b = 4.4373(1), and c = 8.8174(2) Å. The new compound was further characterized using infrared spectroscopy, energy-dispersive X-ray spectroscopy, second harmonic generation (SHG) measurements, and temperature-dependent X-ray powder diffraction. Tb3B10O17(OH)5 decomposes to β-Tb(BO2)3 at temperatures higher than 460 °C. With increasing temperatures, the formation of μ-TbBO3 was observed, which transforms to π-TbBO3 upon cooling.

A pressure-induced high-pressure metallic GeTe phase.

As an important phase-change material, GeTe has many high-pressure phases as well, but its phase transitions under pressure are still lack of clarity. It is challenging to identify high-pressure GeTe crystal structures owing to the phase coexistence in a wide pressure range and the reversibility of phase transitions. Hence, first-principles calculations are required to provide further information in addition to limited experimental characterizations. In this work, a new orthorhombic Cmca GeTe high-pressure phase has been predicted via the CALYPSO method as the most energetically favorable phase in the pressure range between ∼30 and ∼38.5GPa, which would update the GeTe high-pressure phase transition sequence. The crystal structure of the Cmca phase is composed of alternate stacking puckered layers of Ge six-membered rings and Te four-membered rings along the b direction. The high density of states near the Fermi level and delocalization of electrons from the two-dimensional electron localization function indicate a strong metallic property of the Cmca phase. Electron-phonon coupling calculations indicate that the Cmca phase is superconductive below ∼4.2K at 35GPa. The simulated x-ray diffraction pattern of the Cmca phase implies that this phase might coexist with the Pnma-boat phase under high pressure. These results offer further understanding on the high-pressure structural evolution and physical properties in GeTe and other IV-VI semiconductors.

The rich structural phase behaviour of 2,2,2-trifluoroethanol

A remarkable degree of polymorphism is exhibited in the high-pressure and low-temperature crystal structures of 2,2,2-trifluoroethanol, with the observation of four ordered phases (forms 1–4) and a cubic rotor phase (form 5).

High-pressure synthesis and crystal structures of molybdenum nitride Mo3N5 with anisotropic compressibility by a nitrogen dimer.

A novel high-pressure molybdenum nitride phase, Mo3N5, was synthesized at above 45 GPa via a nitridation reaction of molybdenum with nitrogen under high pressure using a laser-heated diamond anvil cell. Mo3N5, having an N-N dimer and 7-coordinated Mo sites, crystallizes in an orthorhombic structure with a space group of Cmcm (No. 63) without other prototype structures. The refined lattice parameters for Mo3N5 were a = 2.86201(2) Å, b = 7.07401(6) Å, and c = 14.59687(13) Å. The DFT enthalpy calculation suggested that Mo3N5 is a high-pressure stable phase, which is also consistent with an increasing coordination number compared to ambient- and low-pressure phases. The zero-pressure bulk modulus of Mo3N5 was determined to be K0 = 328(4) GPa with K'0 = 10.1(6) by the fitting for the compression curve, which is almost consistent with the theoretical E-V curve and elastic stiffness constants. The compressibility of Mo3N5 has axial anisotropy corresponding to the N-N dimer direction in the crystal structure.

Theoretical exploration of high-pressure crystal structures and valence states in the Li–Cl system

Chlorine plays an important role in the production of drinking water, disinfectants and textiles, but its valence states are seldom studied. Anionic chlorine of − 1 valence (Cl−) is the only negative valence state reported to date. This study considered stable structures and electronic properties of Li–Cl systems at pressures of 0–100 GPa. Among the predicted stable stoichiometries, Li2Cl, Li3Cl, Li4Cl, Li5Cl are electrides. Under extreme pressures, the calculated Bader charge of Cl indicates an unconventional negative valence state of − 2. Our results provide theoretical support for the further study of Li–Cl compounds and expansion of the valence states of Cl.

Reassigning the Pressure-Induced Phase Transitions of Methylammonium Lead Bromide Perovskite.

The high-pressure crystal structure evolution of CH3NH3PbBr3 (MAPbBr3) perovskite has been investigated by single-crystal X-ray diffraction and synchrotron-based powder X-ray diffraction. Single-crystal X-ray diffraction reveals that the crystal structure of MAPbBr3 undergoes two phase transitions following the space-group sequence: Pm3̅m → Im3̅ → Pmn21, unveiling the occurrence of a nonpolar/polar transition (Im3̅ → Pmn21). The transitions take place at around 0.8 and 1.8 GPa, respectively. This result contradicts the previously reported phase transition sequence: Pm3̅m → Im3̅ →Pnma. In this work, the crystal structures of each of the three phases are determined from single-crystal X-ray diffraction analysis, which is later supported by Rietveld refinement of powder X-ray diffraction patterns. The pressure dependence of the crystal lattice parameters and unit-cell volumes are determined from the two aforementioned techniques, as well as the bulk moduli for each phase. The bandgap behavior of MAPbBr3 has been studied up to around 4 GPa, by means of single-crystal optical absorption experiments. The evolution of the bandgap has been well explained using the pressure dependence of the Pb-Br bond distance and Pb-Br-Pb angles as determined from single-crystal X-ray diffraction experiments.

Competing dynamical and lattice instabilities in RVO4 rare-earth vanadium oxides under high pressure

Zircon-type ${R\mathrm{VO}}_{4}$ compounds (where R = rare-earth atom) constitute a family of ternary oxides which are abundant in both nature and the industrial field. Their structural systematics upon compression has been widely studied. According to the observed systematics, the high-pressure crystal structure is determined by the rare-earth cation size. Nonetheless, the mechanisms involved in the phase transitions remain relatively unexplored. Thus, we gathered the experimental data reported in the literature and compared it to our ab initio calculations, including not only enthalpy, but also the frequency of lattice modes and the value of elastic constants. Our study reveals systematic trends, where high-pressure phases appear only if they are thermodynamically stable and are always preceded by a mechanical or dynamical instability, which counteracts the effects of kinetic barriers in the zircon-to-monazite or -scheelite phase transition, respectively.

High-pressure crystal polymorphs and multiple pathways in 1-hexyl-3-methylimidazolium perfluorobutanesulfonate ionic liquid

• Crystal polymorphs and multiple pathways of fluorinated ionic liquid under high pressure. • Reentrant phase behavior with the layered structures. • Hybrid layered structure of [PFBS] − intermediate and gauche c onformers. 1-Hexyl-3-methylimidazolium perfluorobutanesulfonate ([C 6 mim][PFBS]), a fluorinated ionic liquid (fIL), exhibited complicated phase behaviors under high pressure (HP). The asymmetric [PFBS] − anion possesses conformational degrees of freedom. Using X-ray diffraction, HP crystal structures were determined upon compression and decompression. 00ℓ Bragg reflections at the small scattering angle representing the layered structures appeared reentrantly. The reentrant phase behavior is described by layering of [PFBS] − ( layering I) below 3.7 GPa ( P 1 ) and the hybrid layered structure of [PFBS] − ( layering II) above 7.6 GPa. The layering II caused irreversible crystal polymorph in the pressure cycle. Below P 1 , HP-phase transition changed to reversible crystal polymorph. The complicated HP-crystal polymorphs and multiple pathways were derived from the conformation-driven molecular packing states.

High-Pressure Synthesis of Transition-Metal Oxyhydrides with Double-Perovskite Structures.

We report on the high-pressure synthesis, crystal structure, and magnetic properties of four novel transition-metal oxyhydrides─Ba2NaVO3H3, Ba2NaVO2.4H3.6, Ba2NaCrO2.2H3.8, and Ba2NaTiO3H3─crystallizing in the double-perovskite structure. Notably, they have a higher hydride content in their anion sites (50%-63%) than known oxyhydrides with perovskite structures do (≤33%). Vanadium and chromium oxyhydrides exhibited Curie-Weiss magnetic susceptibilities with no magnetic ordering down to 2 K, which may be due to geometrical frustration in their face-centered lattices and weak magnetic interactions. Density functional theory calculations revealed that the transition metal-hydride bonding nature of the prepared oxyhydrides is more covalent than that observed for known perovskite oxyhydrides, as evidenced by the shorter bond lengths of the former. Remarkably, our double-perovskite oxyhydrides with a high hydride content may possess a bonding character intermediate between those of known oxyhydrides and hydrides.

High-pressure synthesis, crystal structure, and physical properties of NaAlB14 single crystals

Pure NaAlB14 single crystals were successfully synthesized directly from Na, Al, and B at high pressure and high temperature, different from the previously reported method, that is, synthesized from Na2B4O7, Al, and B. The growth of NaAlB14 single crystals was promoted by increasing the reaction temperature. The atomic structures of NaAlB14 single crystal along the [100], [010], [001], and [021] axes were characterized by using a scanning transmission electron microscope. The Raman spectra of NaAlB14 were investigated theoretically and experimentally, and they showed the expected oscillations of the covalent framework. In addition, photoluminescence spectra indicated that NaAlB14 is a semiconductor luminescence material with red (1.68 eV) and near-infrared (1.50 and 1.36 eV) emission characteristics. The band structure revealed that NaAlB14 is an indirect band gap semiconductor with a wide band gap of 2.22 eV.

High-pressure crystal structure and equation of state of ferromagnesian jeffbenite: implications for stability in the transition zone and uppermost lower mantle

Jeffbenite, ideally Mg3Al2Si3O12, has been identified as inclusions in super-deep diamonds originating from depths that exceed 300 km. Although Mg-end member jeffbenite has limited stability at upper-mantle conditions, iron-bearing jeffbenite may have broader P–T stability that extends to the transition zone or uppermost lower mantle, incorporating significant amounts of ferric iron. Using synchrotron-based, single-crystal X-ray diffraction (XRD) and synchrotron Mössbauer spectroscopy (SMS) at pressures up to 29 GPa, we report the crystal structure, compressibility, and likely spin transition of iron in ferromagnesian jeffbenite (Mg2.32Al0.03Fe2+1.28Fe3+1.77Si2.85O12). High-pressure structure refinements reveal that Fe3+ substitution for Si in the T2 site, which shares edges with the M2 octahedron, likely stabilizes jeffbenite at high pressure, because it increases the cation-to-cation distance between these sites. Although ferromagnesian jeffbenite does not undergo a structural phase transition below 30 GPa, SMS hyperfine parameters suggest the onset of an electronic spin transition of iron from high-spin (HS) to low-spin (LS) at around 22 GPa, which may increase its stability at high pressures. Pressure–volume data were fit to a third order Birch–Murnaghan equation of state, resulting in V0 = 816.54(9), KT0 = 181.54(1.39), and $${K}_{T0}^{\prime}$$ = 2.76(14). These equation of state parameters are applicable to evaluating the encapsulation pressures of super-deep diamonds. The density and bulk modulus of ferromagnesian jeffbenite are similar to or higher than pyrope–almandine, pyrope–majorite, and skiagite–majorite solid solution garnets, further suggesting that jeffbenite may be an important ferric–iron silicate in the deeper parts of the mantle transition zone and uppermost lower mantle. However, future studies on the influence of temperature and oxidation state on the stability and equations of state of iron-bearing jeffbennite are still needed to determine what role, if any, jeffbenite plays in transition-zone mineralogy.

High-pressure synthesis, crystal structure, and physical properties of NaB13C2 single crystals

A new boron-rich boride carbide of sodium, NaB13C2 single crystals have been successfully synthesized from the elements under high temperature and high pressure. The crystals are reddish black with a metallic luster and show a regular hexagonal prism shape. NaB13C2 crystallizes into an orthorhombic LiB13C2-type structure with a space group of Imma (No. 74) and the lattice constants are a = 10.9417 Å, b = 5.6756 Å, c = 8.0898 Å. The crystal structure is characterized by a covalent framework of B12 icosahedra connected by CBC chains and Na atoms located in the void of the framework. The measured and calculated Raman spectra of NaB13C2 are in good agreement and show expected oscillations of the covalent framework. The electronic band structures reveal that NaB13C2 is a wide band gap semiconductor with a band gap of 3.36 eV. As a novel wide band gap semiconductor, NaB13C2 may have potential applications in semiconductor field.