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The excitonic insulator Ta$_2$NiSe$_5$ experiences a first-order structural transition under pressure from rippled to flat layer-structure at Ps = 3 GPa, which drives the system from an almost zero-gap semiconductor to a semimetal. The pressure-induced semimetal, with lowering temperature, experiences a transition to another semimetal with a partial-gap of 0.1-0.2 eV, accompanied with a monoclinic distortion analogous to that occurs at the excitonic transition below Ps. We argue that the partial-gap originates primarily from a symmetry-allowed hybridization of Ta-conduction and Ni-valence bands due to the lattice distortion, indicative of the importance of electron-lattice coupling. The transition is suppressed with increasing pressure to Pc = 8 GPa. Superconductivity with a maximum Tsc = 1.2 K emerges around Pc, likely mediated by strongly electron-coupled soft phonons. The electron-lattice coupling is as important ingredient as the excitonic instability in Ta2NiSe5., Comment: 6 pages, 4 figures

We report an alternative approach to the unnatural nucleobase fragment seen in remdesivir (Veklury). Remdesivir displays broad-spectrum antiviral activity and is currently being evaluated in Phase III clinical trials to treat patients with COVID-19. Our route relies on the formation of a cyanoamidine intermediate, which undergoes Lewis acid-mediated cyclization to yield the desired nucleobase. The approach is strategically distinct from prior routes and could further enable the synthesis of remdesivir and other small-molecule therapeutics.

The SARS-CoV-2 pandemic has prompted scientists from many disciplines to work collaboratively toward an effective response. As academic synthetic chemists, we examine how best to contribute to this ongoing effort.

Ta2NiSe5 has recently attracted interest as an excitonic insulator. In this paper, crystallographic parameters of three non-ambient phases are reported from across the P–T phase diagram. A reversible pressure-induced structural transition above 3 GPa is associated with the coherent sliding of weakly coupled layers., The crystal structure of the excitonic insulator Ta2NiSe5 has been investigated under a range of pressures, as determined by the complementary analysis of both single-crystal and powder synchrotron X-ray diffraction measurements. The monoclinic ambient-pressure excitonic insulator phase II transforms upon warming or under a modest pressure to give the semiconducting C-centred orthorhombic phase I. At higher pressures (i.e. >3 GPa), transformation to the primitive orthorhombic semimetal phase III occurs. This transformation from phase I to phase III is a pressure-induced first-order phase transition, which takes place through coherent sliding between weakly coupled layers. This structural phase transition is significantly influenced by Coulombic interactions in the geometric arrangement between interlayer Se ions. Furthermore, upon cooling, phase III transforms into the monoclinic phase IV, which is analogous to the excitonic insulator phase II. Finally, the excitonic interactions appear to be retained despite the observed layer sliding transition.

Stability and phase relations of coexisting enstatite and H2 fluid were investigated in the pressure and temperature regions of 3.1–13.9 GPa and 1500–2000 K using laser-heated diamond-anvil cells. XRD measurements showed decomposition of enstatite upon heating to form forsterite, periclase, and coesite/stishovite. In the recovered samples, SiO2 grains were found at the margin of the heating hot spot, suggesting that the SiO2 component dissolved in the H2 fluid during heating, then precipitated when its solubility decreased with decreasing temperature. Raman and infrared spectra of the coexisting fluid phase revealed that SiH4 and H2O molecules formed through the reaction between dissolved SiO2 and H2. In contrast, forsterite and periclase crystals were found within the hot spot, which were assumed to have replaced the initial orthoenstatite crystals without dissolution. Preferential dissolution of SiO2 components of enstatite in H2 fluid, as well as that observed in the forsterite H2 system and the quartz H2 system, implies that H2-rich fluid enhances Mg/Si fractionation between the fluid and solid phases of mantle minerals.

Species dissolved in H 2 fluid were investigated in a SiO 2 –H 2 system. Raman and infrared (IR) spectra were measured at high pressure and room temperature after heating experiments were conducted at two pressure and temperature conditions: 2.0 GPa, 1700 K and 3.0 GPa, 1500 K. With the dissolution of quartz, a SiH vibration mode assignable to SiH 4 was detected from Raman spectra of the fluid phase. Furthermore, an OH vibration mode was observed at 3260 cm −1 from the IR spectra at 3.0 GPa. With decreasing pressure, the OH vibration frequencies observed between 3.0 and 2.1 GPa correspond to that of ice VII, and those observed at 1.4 and 1.1 GPa correspond to that of ice VI. These results indicate that the chemical reaction between dissolved SiO 2 components and H 2 fluid caused the formation of H 2 O and SiH 4 , which was contrastive to that observed in SiO 2 –H 2 O fluid. Results imply that a part of H 2 is oxidized to form H 2 O when SiO 2 components of mantle minerals dissolve in H 2 fluid, even in an iron-free system.

Suppose that each arc in a digraph D = (V, A) has two costs of non-negative integers, called a spine cost and a leaf cost. A caterpillar is a directed tree consisting of a single directed path (of spine arcs) and leaf vertices each of which is incident to the directed path by exactly one incoming arc (leaf arc). For a given terminal set K ⊆ V, we study the problem of finding a caterpillar in D such that it contains all terminals in K and its total cost is minimized, where the cost of each arc in the caterpillar depends on whether it is used as a spine arc or a leaf arc. In this paper, we first study the complexity status of the problem with respect to the number of terminals: the problem is solvable in polynomial time for any digraph with two terminals, while it is NP-hard for three terminals. We then give a linear-time algorithm to solve the problem for digraphs with bounded treewidth, where the treewidth for a digraph D is defined as the one for the underlying graph of D. Our algorithm runs in linear time even if |K| = O(|V|).

High-pressure behaviors of Linde-type A (LTA) zeolite were investigated using a quasi-hydrostatic pressure medium of noble gases (helium or argon). High-pressure in situ X-ray diffraction measurements combined with the use of a diamond anvil cell did not observe any structural phase transition for LTA zeolites up to a pressure of approximately 12 GPa at room temperature. However, it was found that the compressibility strongly depended not only on the pressure medium but also on the pressurization process. LTA zeolites showed significant incompressible behaviors at pressures between 2 and ∼7 GPa when it was compressed in helium. Based on careful analyses of the data together with the results of previous high-pressure studies, the incompressibility of LTA zeolites was induced by the penetration of a large amount of noble gas atoms into the cages of LTA zeolites under high pressures. The present results offer interesting and important information on the atomic diffusion process for open-structured materials under high pressures and thus have great implications for the development of new noble-gas-atom filled materials, as well as geochemical implications.

High-pressure and high-temperature experiments were carried out in a Mg2SiO4-H2 system using laser-heated diamond-anvil cells to understand the influence of H2 fluid on the stability of forsterite. In situ X-ray diffraction experiments and Raman spectroscopic measurements showed the decomposition of forsterite, and formation of periclase (MgO) and stishovite/quartz (SiO2) in the presence of H2 after being heated in the range between 2.5 GPa, 1400 K and 15.0 GPa, 1500 K. Transmission electron microscopic observation of the samples recovered from 15.0 GPa and 1500 K showed that the granular to columnar periclase grains maintained the original grain shape of forsterite, indicating that the periclase crystals crystallized under high temperature. On the other hand, euhedral columnar stishovite crystals were found at the boundaries between residual forsterite grains and reacted periclase. This implies that the SiO2 component was dissolved in H2 fluid, and that stishovite was considered to have crystallized when the solubility of the SiO2 component became reduced with decreasing temperature. Additional experiment on a SiO2-H2 system clearly showed the dissolution of quartz in H2 fluid, while those on a MgO-H2 system, periclase was hardly dissolved. These lines of evidence indicate that forsterite was incongruently dissolved in H2 fluid to form periclase crystals in the Mg2SiO4-H2 system, which is different from what was observed in the Mg2SiO4-H2O system. The results indicate that the stability of forsterite is strongly affected by the composition of coexisting C-O-H fluid.

We have investigated the high-pressure behavior of cristobalite in helium by powder X-ray diffraction. Cristobalite transformed to a new phase at about 8 GPa. This phase is supposed to have a molar volume of about 30 % larger than cristobalite, suggesting the dissolution of helium atoms in its interstitial voids. On further compression, the new phase transformed to a different phase which showed an X-ray diffraction pattern similar to cristobalite X-I at about 21 GPa. On the other hand, when the new phase was decompressed, it transformed to another new phase at about 7 GPa, which is also supposed to have a molar volume of about 25 % larger than cristobalite. On further decompression, the second new phase transformed to cristobalite II at about 2 GPa. In contrast to cristobalite, quartz did not show anomalous behavior in helium. The behavior of cristobalite in helium was also consistent with that in other mediums up to about 8 GPa, where the volume of cristobalite became close to that of quartz. These results suggest that dissolution of helium may be controlled not only by the density (amount of voids) but also by the network structure of SiO4 tetrahedra (topology of voids).

X-ray diffraction measurements of distorted rutile-type oxyhydroxides β-GaOOH, InOOH, β-CrOOH, and β-CrOOD were taken at a maximum pressure of up to 35 GPa under quasi-hydrostatic conditions, at ambient temperature. Anomalies in the evolution of the relative lattice constants and the axial ratios of β-GaOOH, InOOH, and β-CrOOD suggest anisotropic stiffening along the a- and/or b-axes where the hydrogen bond is formed. The changes were observed at 15 GPa in β-GaOOH and InOOH and at 4 GPa in β-CrOOD. The pressures were higher in oxyhydroxides that have longer O…O distances of the hydrogen bond at ambient pressure. In contrast, such stiffening behavior was not observed in CrOOH, which has a significant short O…O distance and strong hydrogen bond. The stiffening behaviors observed in the present study can be attributed to the symmetrization of the hydrogen bonds in oxyhydroxides, as was previously found in δ-AlOOH(D).

Both Re2C and Re2N are ultra incompressible and have a bulk modulus of about 400 GPa. These materials are synthesized under high pressure and high temperature. The synthesis pressures are about 10 GPa or below for Re2C and 20–30 GPa for Re2N. If the synthesis pressure of Re2N was about 10 GPa or below, a large volume high-pressure cell like a multi-anvil apparatus can be used to synthesize Re2N. To realize this, a proper solid nitrogen source is needed instead of liquid or gas nitrogen. We used a precursor of a mixture of rhenium and home-made nanoscale amorphous two-dimensional carbon nitride as a solid nitrogen source. Consequently, the synthesis reaction produced Re2C but not Re2N. We characterized the synthesized Re2C by various techniques including high-pressure x-ray diffraction (XRD). The bulk modulus B0 of the synthesized Re2C under hydrostatic conditions was estimated to be 385.7 ± 18.0 GPa. This value is a little smaller than the previous data. When the pressure medium became non-hydrostatic, the peculiar compression behaviour occurred; the rate of broadening of XRD lines increased and the compression became negligible in the range of a few GPa. The reason for this peculiar behaviour is not known.

High pressure and temperature reactions of a mixture of forsterite and hydrogen molecules have been carried out using a laser heated diamond anvil cell at 9.8–13.2 GPa and ~1,000 K. In situ X-ray diffraction measurements showed no sign of decomposition or phase transitions of the forsterite under these experimental conditions, indicating that the olivine structure was maintained throughout all runs. However, a substantial expansion of the unit cell volume of the forsterite was observed for samples down to ~3 GPa upon quenching to ambient pressure at room temperature. The Raman spectroscopy measurements under pressure showed significant shifts of the Raman peaks of the Si–O vibration modes for forsterite and of the intramolecular vibration mode for H2 molecules toward a lower frequency after heating. Additionally, no OH vibration modes were observed by Raman and FT-IR spectroscopic measurements. These lines of evidence show that the observed volume expansion in forsterite is not explained by the incorporation of hydrogen atoms as hydroxyl, but suggest the presence of hydrogen as molecules in the forsterite structure under these high pressure and temperature conditions.

The rock salt (B1) structure of binary oxides or chalcogenides transforms to the CsCl (B2) structure under high pressure, with critical pressures P(s) depending on the cation to anion size ratio (R(c)/R(a)). We investigated structural changes of A(2)MO(3) (A = Sr, Ca; M = Cu, Pd) comprising alternate 7-fold B1 AO blocks and corner-shared MO(2) square-planar chains under pressure. All of the examined compounds exhibit a structural transition at P(s) = 29-41 GPa involving a change in the A-site geometry to an 8-fold B2 coordination. This observation demonstrates, together with the high pressure study on the structurally related Sr(3)Fe(2)O(5), that the B1-to-B2 transition generally occurs in these intergrowth structures. An empirical relation of P(s) and the R(c)/R(a) ratio for the binary system holds well for the intergrowth structure also, which means that P(s) is predominantly determined by the rock salt blocks. However, a large deviation from the relation is found in LaSrNiO(3.4), where oxygen atoms partially occupy the apical site of the MO(4) square plane. We predict furthermore the occurrence of the same structural transition for Ruddlesden-Popper-type layered perovskite oxides (AO)(AMO(3))(n), under higher pressures. For investigating the effect on the physical properties, an electrical resistivity of Sr(2)CuO(3) is studied.

The phase relations and compression behavior of MnTiO3 perovskite were examined using a laser-heated diamond-anvil cell, X-ray diffraction, and analytical transmission electron microscopy. The results show that MnTiO3 perovskite becomes unstable and decomposes into MnO and orthorhombic MnTi2O5 phases at above 38 GPa and high temperature. This is the first example of ABO3 perovskite decomposing into AO + AB2O5 phases at high pressure. The compression behavior of volume, axes, and the tilting angle of TiO6 octahedron of MnTiO3 perovskite are consistent with those of other A2+B4+O3 perovskites, although no such decomposition was observed in other perovskites. FeTiO3 is also known to decompose into two phases, instead of transforming into the CaIrO3-type post-perovskite phase and we argue that one of the reasons for the peculiar behavior of titanate is the weak covalency of the Ti–O chemical bonds.

A series of π-conjugated alternating copolymers consisting of Th-ITN-Th and p-C 6 H 2 (OR) 2 units were synthesized. XRD indicated that the copolymers assume an interdigitation packing mode, and UV-Vis spectra revealed a strong tendency for self-assembly. Upon molecular assembly of the copolymer, the UV-Vis absorption shifted by about 100 nm to a longer wavelength from that of the single molecule. The copolymers underwent electrochemical oxidation (or p-doping) and reduction (or n-doping) at 0.2 and -2.0 V versus Ag + /Ag, respectively. A p-doped copolymer film showed an electrical conductivity of 182 S · cm -1 , and the temperature dependence of electrical conductivity was measured. The copolymer showed piezochromism and served as a p-channel material for a field-effect transistor.

Lattice-preferred orientations (LPOs) of post-perovskite (PPv)-type MgGeO 3 formed by transformations from two different pre-phases, orthopyroxene (OPx) and perovskite (Pv), were studied using radial and axial X-ray diffraction techniques combined with a laser-heated diamond-anvil cell. When the PPv was made from Pv, strong LPO was formed in the PPv immediately after the transformation with an alignment of the (0 0 1) or (0 1 1) plane almost perpendicular to the compression axis. This present result contrasts markedly from that observed when the PPv was formed from OPx and those reported on MgGeO 3 -PPv and (Mg,Fe)SiO 3 -PPv transformed from OPx, in which the (1 0 0) or (1 1 0) plane was aligned to the compression axis. It was clarified that when the PPv-type MgGeO 3 is formed in diamond-anvil cells, it has strong transformation-induced LPO from the beginning even before plastic deformation occurs, and that its characteristics depend on the pre-phase before the transformation. The formed transformation-induced LPO of PPv did not change in spite of further compression using a conventional gasket because the sample became too thin to deform. However, by using a diamond gasket technique, we were able to deform the PPv at room temperature, resulting in significant variations of the relative intensities of several diffraction peaks. The change in the axial diffraction patterns can be explained only by assuming that the (0 0 1) plane aligns almost perpendicularly to the compression axis. The present results suggest that the (0 0 1) is a dominant slip plane in MgGeO 3 -PPv at room temperature. If one makes the assumption that the dominant slip system(s) of silicate PPv deformed in the D″ layer is or are identical to that of germanate PPv at room temperature, then a large S-wave polarization anisotropy in the Earth's D″ layer would be explained by the small degree of deformation-induced LPO of the PPv phase that is expected to exist in this layer.

Laser heating in diamond anvil cell (DAC) equipped with nano-polycrystalline diamond (NPD) anvils was tested for the first time using various types of lasers. An NPD-based DAC was found to provide better heating efficiency than a standard DAC with single-crystal anvils, probably due to the order of magnitude lower thermal conductivity of the NPD. We observed high-temperature generation exceeding 5000 and 3500 K during laser heating of hcp-Fe sample at pressures of ∼100 and ∼170 GPa, respectively. The results of the present study demonstrate promising potential of laser-heated nano-polycrystalline DAC for the generation of very high temperature under multi-megabar pressure conditions equivalent to those of the Earth's core.

The post-corundum phase transition has been investigated in Ti2O3 on the basis of synchrotron X-ray diffraction in a diamond anvil cell and transmission electron microscopy. The new polymorph of Ti2O3 was found at about 19 GPa and 1850 K, and this phase was stable even at about 40 GPa. A new polymorph of Ti2O3 can be indexed on a Pnma orthorhombic cell, and the unit-cell parameters are a=7.6965 (19) A, b=2.8009 (9) A, c=7.9300 (23) A, V=170.95 (15) A3 at 19 GPa, and a=7.8240 (2) A, b=2.8502 (1) A, c=8.1209 (3) A, V=181.10 (1) A3 at ambient conditions. The Birch–Murnaghan equation of state yields K 0=206 (3) GPa and K′0=4 (fixed) for corundum phase, and K 0=296 (4) GPa and K′0=4 (fixed) for the post-corundum phase. The molar volume decreases by 12% across the phase transition at around 20 GPa. The structural identification was carried out on a recovered sample by the Rietveld method, and a new polymorph of Ti2O3 can be identified as Th2S3-type rather than U2S3-type structure. The transition from corundum-t...

Self-assembly of polythiophenes with –C≡CR (R = alkyl, phenyl, etc.) side chains has been investigated. Seven new polymers consisting of head-to-head and tail-to-tail 2,2′-bithiophenes with –C≡CR s...

The stability and equation of state for the cotunnite phase in TiO2 were investigated up to a pressure of about 70 GPa by high-pressure in situ X-ray diffraction measurements using a laser-heated diamond anvil cell. The transition sequence under high pressure was rutile → α-PbO2 phase → baddeleyite phase → OI phase → cotunnite phase with increasing pressure. The cotunnite phase was the most stable phase at pressures from 40 GPa to at least 70 GPa. The equation of state parameters for the cotunnite phase were established on the platinum scale using the volume data at pressures of 37–68 GPa after laser annealing, in which the St value, an indicator of the magnitude of the uniaxial stress component in the samples, indicates that these measurements were performed under quasi-hydrostatic conditions. The third-order Birch-Murnaghan equation of state at K 0′ = 4.25 yields V 0 = 15.14(5) cm3/mol and K 0 = 294(9), and the second-order Birch-Murnaghan equation of state yields V 0 = 15.11(5) cm3/mol and K 0 = 306(9). Therefore, we conclude that the bulk modulus for the cotunnite phase is not comparable to that of diamond.

We performed high-pressure and high-temperature X-ray diffraction experiments on InOOH using laser heated diamond anvil cells. After heating at 1300 K, pyrite-type InOOH was formed at 14 GPa and it was stable up to at least 30 GPa. Pyrite-type InOOH partially transformed back to distorted rutile-type InOOH after recovery. The lattice constant and unit-cell volume of pyrite-type InOOH were determined to be a0 = 5.3151(8) A and V0 = 150.15 (7) A3 at ambient conditions, respectively. The density difference between pyrite-type and distorted rutile-type InOOH was 5% at ambient condition.

The Raman spectra of MgXO 3 -ilmenites (X = Si, Ge, Ti) were recorded up to 773 K at ambient pressure and up to 20–30 GPa at room temperature. Temperature and pressure dependence of the force constant of X-O stretching bands revealed that the expansion and compression behavior of XO 6 octahedra differed in the three ilmenites. For SiO 6 and GeO 6 octahedra, the shorter Si-O or Ge-O bonds became more lengthened with temperature and more shortened with pressure than did the longer Si-O or Ge-O bonds. In contrast, for TiO 6 octahedra, the longer Ti-O bonds became more lengthened with temperature and more shortened with pressure than did the shorter Ti-O bonds. For SiO 6 and GeO 6 at high temperatures and TiO 6 at high pressures, the cation positions moved in the direction of the c axis and tended to approach the center of the octahedra, decreasing the distortion of XO 6 . For SiO 6 and GeO 6 at high pressures and TiO 6 at high temperatures, the cations moved away from the center, increasing the distortion of XO 6 . One of the anharmonic correction terms on isochoric specific heat was also elucidated. The anharmonic effects were related to the elastic Debye temperature of the three ilmenites.

A ferroelectric KNbO 3 has been investigated to 11.4 GPa at room temperature by angle-dispersive powder diffraction with diamond anvil cell using synchrotron radiation, which was performed by a high-resolution evaluation setting. KNbO 3 transforms from orthorhombic to tetragonal lattice at around 6 GPa, and further transforms to a cubic lattice at about 9.2 GPa. Single-crystal X-ray diffraction studies under pressures clarified the space groups of the three phases and their lattice constants. The extinction rule of the observed reflections and diffraction intensity distribution proved Cm2m, P4mm and Pm3m for orthorhombic, tetragonal and cubic polymorphs, respectively.

Bixbyite (Mn,Fe)2O3has a C-type rare-earth oxide structure with space group ofIa-3 and different from corundum structureR-3c. Single-crystal structure analyses and powder diffraction experiments were carried out using synchrotron radiation under high pressures up to 41.21 GPa. Lattice constants and bond distances were elucidated as a function of pressure. Single crystal structure analyses under high pressures up to 9.64 GPa have been executed using DAC. There are two octahedral Mn3+sites: M1 (-3) and M2 (-2.). M1O6and M2O6octahedral volumes and void space of vacant sites show different compression curves. M1O6octahedron is less compressive than M2O6octahedron. The former is a little deformed from an ideal octahedron withm-3mof MnO6but the latter is a largely distorted octahedron. The quadratic elongation is applied in order to comprehend the polyhedral distortion and finite homogeneous strain. Both octahedra do not show a noticeable Jahn-Teller distortion induced from Mn3+. Six bond lengths of M1O6are equivalent but the octahedron more elongates along the direction of -3 axis with increasing pressure and is more deformed from the regular octahedron. The M2O6octahedron has two long bond distances among six bonds, which are most compressive. The octahedral deformations seem to reduce the Jahn-Teller effect due to the compression. The bulk modulus:Ko= 169.1(4.9) GPa andKo′ = 7.35(0.99), was observed from the volume change with pressure.Pressure-induced phase transition was confirmed at about 21 GPa with a large hysteresis. The transition is reversible and non-quenchable. Powder indexing of the high-pressure phase was carried out using diffraction pattern taken at 35.06 GPa. It has a monoclinic symmetry and is not a corundum, Rh2O3(II) or perovskite structure.

Pressure responses of hydrogen bonding interactions were compared between potassium hydrogen carbonate (KHCO3) and sodium hydrogen carbonate (NaHCO3). KHCO3 undergoes a pressure-induced structural change at 2.8 GPa and room temperature whereas no phase transition has been found so far for NaHCO3 up to 11 GPa. KHCO3 exhibits a substantial decrease in the O-H O angle with increasing pressure. This change could be a trigger for the phase transition at 2.8 GPa. By contrast, no significant change in O-H O angle was observed for NaHCO3 up to 7 GPa. Based on the observations using neutron diffraction, X-ray diffraction and vibrational spectroscopy at high pressure, a possible mechanism for the phase transition of KHCO3 is suggested. In addition, the phase boundary of KHCO3 caused by the pressure-induced transition was determined using in situ Raman spectroscopy at high pressure.

OH stretching vibration modes for F-rich natural topaz (F-topaz) and for fully hydrated topaz (topaz-OH) synthesized at high pressure, were observed using IR and Raman spectroscopies at pressures up to 30.4 GPa and 17.3 GPa, respectively. In F-topaz, the pressure derivative of the frequency of the OH stretching band observed at 3650 cm ' at ambient pressure was 0.91(3) cm - 1 /GPa, which was consistent with the value recently reported by Bradbury and Williams (2003). On the other hand, in topaz-OH, the pressure derivatives of the bands initially at 3599 and 3522 cm - 1 were -5.2(2) and -2.56(6) cm - 1 /GPa, respectively. This contrasting behavior between the two forms of topaz at high pressures suggests that the OH substitution for F in topaz affects the hydrogen-bonding behavior under high pressure.

The location of the liquidus in the low-pressure crystalline phase of SnI(4) was determined utilizing in situ x-ray diffraction measurements under pressures up to approximately 3.5 GPa. The liquidus is not well fitted to a monotonically increasing curve such as Simon's equation, but breaks near 1.5 GPa and then becomes almost flat. The results are compared to those from molecular dynamics simulations. Ways to improve the model potential adopted in the simulations are discussed.

The graphite-diamond transformation was investigated by in situ time-resolved X-ray diffraction experiments using aqueous fluid containing dissolved MgO as the diamond-forming catalyst under conditions of 6.6–8.9 GPa and 1400–1835 °C. The transformed volume fractions of diamond as a function of time under various pressure-temperature conditions were obtained and analyzed using the JMAK rate equation. Variations in the nucleation and growth processes during diamond formation as a function of pressure and temperature were clarified.

In situ x-ray diffraction studies of graphite–diamond transitions with various solvent catalysts under high pressures and high temperatures at the Photon Factory and SPring-8 are reviewed. By combining synchrotron radiation and a large-volume multi-anvil high-pressure apparatus, real-time observations have been successful in the diamond formation process with the help of various catalysts, such as transition metals, carbonates and aqueous fluids. The experimental procedures and the technical details are described. The diffraction data with various catalysts are shown and the problems and limitations of this method are discussed.

Crystallization, melting and structural evolution upon crystallization in Nd60Al10Fe20Co10 bulk metallic glass (BMG) are in situ investigated by x-ray diffraction with synchrotron radiation under high pressure. It is found that the crystallization is pressure promoted, while the melting is inhibited. The crystallization and melting process are also changed under high pressure. The features of the crystallization and melting under high pressure are discussed.

The formation of CuZrHfTi bulk metallic glasses (BMGs) and the crystallization of the typical Cu60Zr20Hf10Ti10 BMG under ambient conditions and high pressure have been investigated by differential scanning calorimetry, x-ray diffraction (XRD) and in situ synchrotron radiation XRD. The effects of high pressure on crystallization and formation of the CuZrHfTi alloy are discussed. The Kauzmann temperature, TK, where the entropy of the undercooled liquid equals that of the crystal, is also determined to be 724 K. The TK is compared with the experimentally observed rate-dependent glass transition, Tg. The kinetic study of the crystallization shows that the Cu-based BMG has much larger activation energies obtained using Kissinger analysis and is markedly different in crystallization kinetic behaviour compared to that of other BMGs with better glass forming abilities. An apparent correlation between crystallization temperature and activation energy is found in various metallic glasses. The correlation is discussed and connected with the thermal stability of metallic glasses.

Since first opening its doors to public research in 1997, SPring-8 has seen the accomplishment of many important studies in a wide variety of fields through its stable operation and cutting edge technology. High-pressure experiments have been carried out on a number of beamlines using a diamond anvil cell or a multi-anvil press. Here, we review the multi-anvil presses installed on the SPring-8 beamlines and a few research projects currently utilizing this technology. The significant difference in post-spinel boundary between multi-anvil experiments and diamond anvil studies will also be discussed.

The diamond formation process in aqueous fluid catalyst under high-pressure and high-temperature conditions has been observed for the first time. Quench experiments and in situ x-ray diffraction experiments using synchrotron radiation have been performed upon a mixture of brucite (Mg(OH)2) and graphite as the starting material. It was confirmed that brucite decomposed into periclase and H2O at 3.6 GPa and 1050°C while its complete melting occurred at 6.2 GPa and 1150°C, indicating that the solubility of MgO in H2O greatly increases with increasing pressure. The conversion of carbon from its graphite to its diamond form in aqueous fluid was observed at 7.7 GPa and 1835°C.

Kinetics of diamond spontaneous crystallization from the Fe–Al–C system melt in equilibrium with graphite has been studied in situ at 6.5 GPa in the range 1720–1920 K using diffraction of synchrotron radiation. The process under consideration is controlled by carbon diffusion in the melt at 1720 and 1820 K. Kinetics data might be best fitted by a model that assumes instantaneous nucleation. At 1920 K the mechanism of diamond crystallization changes; during growth, continuous nucleation is observed and the kinetics of the processes on the surface of growing crystals becomes the stage that controls the crystallization. The rate of spontaneous crystallization in the Fe–Al–C system decreases with increasing temperature as the graphite–diamond equilibrium line is approached.

An experimental technique to make real-time observations at high pressure and temperature of the diamond-forming process in candidate material of mantle fluids as a catalyst has been established for the first time. In situ X-ray diffraction experiments using synchrotron radiation have been performed upon a mixture of brucite [Mg(OH)2] and graphite as starting material. Brucite decomposes into periclase (MgO) and H2O at 3.6 GPa and 1050 °C while no periclase is formed after the decomposition of brucite at 6.2 GPa and 1150 °C, indicating that the solubility of the MgO component in H2O greatly increases with increasing pressure. The conversion of graphite to diamond in aqueous fluid has been observed at 7.7 GPa and 1835 °C. Time-dependent X-ray diffraction profiles for this transformation have been successfully obtained.

The effect of Fe-site substitution on structural and physical properties of the infinite layer iron oxide SrFeO2 was investigated under high pressure by 57Fe Mossbauer spectroscopy, X-ray diffraction, X-ray absorption spectroscopy, X-ray magnetic circular dichroism, and electrical resistance measurements using a diamond-anvil cell. Both 20% Mn- and Co-substituted samples exhibit spin transitions from a high-spin (S = 2) to an intermediate-spin (S = 1) state at Pc ∼ 32 GPa, which is much the same pressure 33 GPa observed in SrFeO2. This result indicates that the spin transition pressure is insensitive to the d-orbital electron counts [Mn2+ (d5), Fe2+ (d6), Co2+ (d7)], but is governed by the local structure around the Fe site.

It was discovered that a peak appears near a pressure of Pc = 10 GPa in the electrical conductivity of ice VII as measured through impedance spectroscopy in a diamond anvil cell (DAC) during the process of compression from 2 GPa to 40 GPa at room temperature. The activation energy for the conductivity measured in the cooling/heating process between 278 K and 303 K reached a minimum near Pc. Theoretical modelling and molecular dynamics simulations suggest that the origin of this unique peak is the transition of the major charge carriers from the rotational defects to the ionic defects.

The Fe–FeS melt is thought to be the major candidate of the outer core material. Its viscosity is one of the most important physical properties to study the dynamics of the convection in the outer core. We performed the in situ viscosity measurement of the Fe–FeS melt under high pressure using X-ray radiography falling sphere method with a novel sample assembly. Viscosity was measured in the temperature, pressure, and compositional conditions of 1233–1923 K, 1.5–6.9 GPa, and Fe–Fe 72 S 28 (wt%), respectively. The viscosity coefficients obtained by 17 measurements change systematically in the range of 0.008–0.036 Pa s. An activation energy of the viscous flow, Q =30.0±8.6 kJ/mol, and the activation volume, Δ V =1.5±0.7×10 −6 m 3 /mol, are determined as the temperature and pressure dependence, and the viscosity of the Fe 72 S 28 melt is found to be smaller than that of the Fe melt by 15±10%. These tendencies can be well correlated with the structural variation of the Fe–FeS melt.

The phase boundary between wadsleyite and ringwoodite in Mg2SiO4 composition was determined by in situ observation using synchrotron X-ray and multi anvil apparatus in KEK, Tsukuba, Japan. An energy dispersive method was employed using the Ge solid state detector and the white X-ray beam from the synchrotron radiation source. The pressure was determined by the equation of state of NaCl. The stability field was identified by the change in intensities of diffraction lines of each phases. As a result, the phase boundary is expressed as a linear equation P=10.32(28)+0.00691(9)×T, where P is pressure in gigapascals and T is temperature in degrees Celsius.

Suppose that each arc in a digraph D = (V, A) has two costs of non-negative integers, called a spine cost and a leaf cost. A caterpillar is a directed tree consisting of a single directed path (of spine arcs) and leaf vertices each of which is incident to the directed path by exactly one incoming arc (leaf arc). For a given terminal set K ⊆ V, we study the problem of finding a caterpillar in D such that it contains all terminals in K and its total cost is minimized, where the cost of each arc in the caterpillar depends on whether it is used as a spine arc or a leaf arc. In this paper, we first study the complexity status of the problem with respect to the number of terminals: the problem is solvable in polynomial time for any digraph with two terminals, while it is NP-hard for three terminals. We then give a linear-time algorithm to solve the problem for digraphs with bounded treewidth, where the treewidth for a digraph D is defined as the one for the underlying graph of D. Our algorithm runs in linear time even if |K| = O(|V|).