Nakano, Satoshi*; Sano, Asami; Hattori, Takanori; Machida, Shinichi*; Komatsu, Kazuki*; Fujihisa, Hiroshi*; Yamawaki, Hiroshi*; Goto, Yoshito*; Kikegawa, Takumi*
Inorganic Chemistry, 60(5), p.3065 - 3073, 2021/03
X-ray and neutron diffraction analyses of ammonia borane were conducted at ambient and high pressures. The H-H distance in dihydrogen bonds was shorter than twice the van der Waals radius (2.4 ). The half of the dihydrogen bonds were broken on phase transition from AP to the first high pressure phase (HP1) at approximately 1.2 GPa as revealed by an increase in the H-H distances. On further pressure increase, all of the H-H distances became shorter than 2.4 again, implying the pressure-induced reformation of the dihydrogen bonds. Furthermore, the HP1 transformed to the second one with the structure of (Z = 2) at about 11 GPa. In this phase transition, the inclination of the molecule axis became larger and the number of types of dihydrogen bonds increased from 6 to 11. Just before the third transition at 18.9 GPa, the shortest dihydrogen bond decreased to 1.65 . The present study experimentally first confirmed the breakage and reformation of the dihydrogen bonds by the structural change under pressure.
Miao, P.*; Tan, Z.*; Lee, S. H.*; Ishikawa, Yoshihisa*; Torii, Shuki*; Yonemura, Masao*; Koda, Akihiro*; Komatsu, Kazuki*; Machida, Shinichi*; Sano, Asami; et al.
Physical Review B, 103(9), p.094302_1 - 094302_18, 2021/03
The layered perovskite PrBaCoO demonstrates a strong negative thermal expansion (NTE) which holds potential for being fabricated into composites with zero thermal expansion. The NTE was found to be intimately associated with the spontaneous magnetic ordering, known as magneto-volume effect (MVE). Here we report with compelling evidences that the continuous-like MVE in PrBaCoO is intrinsically of discontinuous character, originating from an magnetoelectric transition from an antiferromagnetic insulating large-volume (AFILV) phase to a ferromagnetic less-insulating small-volume (FLISV) phase. Furthermore, the magnetoelectric effect (ME) shows high sensitivity to multiple external stimuli such as temperature, carrier doping, hydrostatic pressure, magnetic field etc. In contrast to the well-known ME such as colossal magnetoresistance and multi-ferroic effect which involve symmetry breaking of crystal structure, the ME in the cobaltite is purely isostructural. Our discovery provides a new path way to realizing the ME as well as the NTE, which may find applications in new techniques.
Yamane, Ryo*; Komatsu, Kazuki*; Gochi, Jun*; Uwatoko, Yoshiya*; Machida, Shinichi*; Hattori, Takanori; Ito, Hayate*; Kagi, Hiroyuki*
Nature Communications (Internet), 12, p.1129_1 - 1129_6, 2021/02
Ice exhibits extraordinary structural variety in its polymorphic structures. The existence of a new form of diversity in ice polymorphism has recently been debated in both experimental and theoretical studies, questioning whether hydrogen-disordered ice can transform into multiple hydrogen-ordered phases, contrary to the known one-to-one correspondence between disordered ice and its ordered phase. Here we report a new high-pressure phase, ice XIX, which is a second hydrogen-ordered phase of ice VI. This is the first discovery to demonstrate that disordered ice undergoes different manners of hydrogen ordering. Such multiplicity can appear in all disordered ice, and it widely provides a new research approach to deepen our knowledge, for example of the crucial issues of ice: the centrosymmetry of hydrogen-ordered configurations and potentially induced (anti-)ferroelectricity. Ultimately, this research opens up the possibility of completing the phase diagram of ice.
Bauer, R.*; Tse, J. S.*; Komatsu, Kazuki*; Machida, Shinichi*; Hattori, Takanori
Nature, 585(7825), p.E9 - E10, 2020/09
Pressure-induced structural transformations in deuterated crystalline ice-Ih were studied in-situ at 100 K using neutron diffraction. Very long relaxation time was allowed between small pressure increments to promote transformations to the thermodynamic stable high pressure crystalline phases. The results contradict a recent report in which measurements under similar temperature and pressure environment show successive crystal-to-crystal transformations (Tulk, et.al., Nature 2019). Instead, ice Ih was found to transform partially to an amorphous form (high density amorphous, HDA) at 1.0 GPa and then ice VII started to emerge at 1.5 GPa, a pressure substantially lower than all earlier studies. During this pressure interval, crystalline ice Ih or ice VII co-exist with HDA. The ice VII formed is stable upon pressure release down to 0.1 GPa. The very low compression rate has a profound effect on the crystallinity in the amorphous regime. Gathering all the existing experimental evidences allows an unambiguous description of the phenomenon of pressure induced amorphization. The onset of the phase transition is triggered by a shear instability of the ice lattice. The co-existence ice VII with HDA, instead of the equilibrium thermodynamic stable and proton-ordered ice-VIII under the same pressure-temperature condition reveals at low temperature there is insufficient thermal energy to overcome the substantial geometrical rearrangement from a single proton disordered H-bond network to an interpenetrating proton ordered H-bond crystalline network. Thus, leaving the proton disordered H-network intact. The analysis shows unequivocally that the structure obtained from the compression of ice is controlled by kinetics and dependent on the temperature.
Komatsu, Kazuki*; Klotz, S.*; Machida, Shinichi*; Sano, Asami; Hattori, Takanori; Kagi, Hiroyuki*
Proceedings of the National Academy of Sciences of the United States of America, 117(12), p.6356 - 6361, 2020/03
Above 2 GPa the phase diagram of water simplifies considerably and exhibits only two solid phases up to 60 GPa, ice VII and ice VIII. The two phases are related to each other by hydrogen ordering, with the oxygen sub-lattice being essentially the same. Here we present neutron diffraction data to 15 GPa which reveal that the rate of hydrogen-ordering at the ice VII-VIII transition decreases strongly with pressure to reach time scales of minutes at 10 GPa. Surprisingly, the ordering process becomes more rapid again upon further compression. We show that such an unusual change in transition rate can be explained by a slowing-down of the rotational dynamics of water molecules with a simultaneous increase of translational motion of hydrogen under pressure, as previously suspected. The observed crossover in the hydrogen dynamics in ice is likely the origin of various hitherto unexplained anomalies of ice VII in the 10-15 GPa range reported by Raman spectroscopy, X-ray diffraction, and proton conductivity.
Komatsu, Kazuki*; Klotz, S.*; Nakano, Satoshi*; Machida, Shinichi*; Hattori, Takanori; Sano, Asami; Yamashita, Keishiro*; Irifune, Tetsuo*
High Pressure Research, 40(1), p.184 - 193, 2020/02
A new high pressure cells for neutron diffraction experiments using nano-polycrystalline anvil is presented. The cell design, off-line pressure generation tests and a gas-loading procedure for this cell are described. The performance is illustrated by powder neutron diffraction patterns of ice VII to 82 GPa. We also demonstrate the feasibility of single crystal neutron diffraction experiments of FeO at ambient conditions using this cell and discuss the current limitation and future developments.
Komatsu, Kazuki*; Machida, Shinichi*; Noritake, Fumiya*; Hattori, Takanori; Sano, Asami; Yamane, Ryo*; Yamashita, Keishiro*; Kagi, Hiroyuki*
Nature Communications (Internet), 11(1), p.464_1 - 464_5, 2020/02
Water freezes below 0C at ambient pressure ordinarily to ice I, with hexagonal stacking sequence. Under certain conditions, ice with a cubic stacking sequence can also be formed, but ideal ice I without stacking-disorder has never been formed until recently. Here we demonstrate a route to obtain ice I without stacking-disorder by degassing hydrogen from the high-pressure form of hydrogen hydrate, C, which has a host framework isostructural with ice I. The stacking-disorder free ice I is formed from C via an intermediate amorphous or nano-crystalline form under decompression, unlike the direct transformations occurring in ice XVI from neon hydrate, or ice XVII from hydrogen hydrate. The obtained ice I shows remarkable thermal stability, until the phase transition to ice I at 250 K, originating from the lack of dislocations. This discovery of ideal ice I will promote understanding of the role of stacking-disorder on the physical properties of ice as a counter end-member of ice I.
Klotz, S.*; Komatsu, Kazuki*; Polian, A.*; Machida, Shinichi*; Sano, Asami; Iti, J.-P.*; Hattori, Takanori
Physical Review B, 101(6), p.064105_1 - 064105_6, 2020/02
Manganese oxide (MnO) is a prototype of an antiferromagnetic Mott-insulator. Here we investigate the interplay of magnetic ordering and lattice distortion across the Nel temperature under pressure using neutron and X-ray diffraction. We find an increase of with a rate of = +4.5(5) K/GPa, an increase of the rhombohedral distortion by = +0.018/GPa, as well as a volume striction which is insensitive to pressure. These results allow to retrieve the dependence of the coupling constants and on interatomic distances and compare it to first-principles predictions. Antiferromagnetic diffuse scattering was observed up to 1.2 , and long-range magnetic order appears at room temperature at 42 GPa.
Yamashita, Keishiro*; Komatsu, Kazuki*; Hattori, Takanori; Machida, Shinichi*; Kagi, Hiroyuki*
Acta Crystallographica Section C; Structural Chemistry (Internet), 75(12), p.1605 - 1612, 2019/12
A crystal structure of a high-pressure phase of magnesium chloride hexahydrate (MgCl 6HO-II) and its deuterated counterpart (MgCl 6DO-II) have been identified for the first time by in-situ single-crystal X-ray and powder neutron diffraction. The crystal structure was analyzed by the Rietveld method for the neutron diffraction pattern based on the initial structure determined by single-crystal X-ray diffraction. This high-pressure phase has a similar framework to that in the known ambient-pressure phase, but exhibits some structural changes with symmetry reduction caused by a subtle modification in the hydrogen-bond network around the Mg(HO) octahedra. These structural features reflect the strain in the high-pressure phases of MgCl hydrates.
Klotz, S.*; Casula, M.*; Komatsu, Kazuki*; Machida, Shinichi*; Hattori, Takanori
Physical Review B, 100(2), p.020101_1 - 020101_5, 2019/07
Ytterbium dihydride (YbH) shows a well-known transition at 16 GPa from a CaH-type structure to a high-pressure (high-) phase with Yb at hcp sites and unknown H-positions. Here, we report its complete structure determination by neutron diffraction at 34 GPa. Hydrogen(deuterium) is located at 2 and 2 positions of space group , thus forming a high-symmetry "collapsed" close-packed lattice. The transition is sluggish and can be seen as a transfer of 1/2 of the hydrogen atoms from strongly corrugated H-layers to interstitial sites of the Yb-lattice. We demonstrate by first-principles calculations that the transition is related to a change from a completely filled -electron configuration to a fractional -hole (0.25 h) occupation in the high- phase. The charge transfer closes the gap at the transition and leads to a metallic ground state with sizeable electron-phonon interaction involving out-of-plane vibrational modes of interstitial hydrogen.
Sano, Asami; Hattori, Takanori; Komatsu, Kazuki*; Kagi, Hiroyuki*; Nagai, Takaya*; Molaison, J. J.*; Dos Santos, A. M.*; Tulk, C. A.*
Scientific Reports (Internet), 8(1), p.15520_1 - 15520_9, 2018/10
The pressure response of hydrogen bond in aluminous hydroxide -AlOOH, which is an important candidate for water carrier to the deep Earth in a subducting slab, was investigated using neutron diffraction under high pressure. The symmetrization of hydrogen bond in which hydrogen locates at the center between two oxygen atoms was observed directly for the first time. The present result indicates that the changes of mineral properties such as increase in bulk modulus and sound velocities, which were previously found, were induced by the symmetrization and disorder state that was also found at just below the symmetrization pressure. Even the symmetrization is a small change in the hydrogen location but it is playing an important role in determining the physical properties of minerals.
Ishii, Yusuke*; Komatsu, Kazuki*; Nakano, Satoshi*; Machida, Shinichi*; Hattori, Takanori; Sano, Asami; Kagi, Hiroyuki*
Physical Chemistry Chemical Physics, 20(24), p.16650 - 16656, 2018/06
The structure of an aluminum layered hydroxide, boehmite (-AlOOH), as a function of pressure was studied by using synchrotron X-ray and neutron diffraction. Peak broadening and subsequent splitting, which are only found for hkl (h 0) peaks in the X-ray diffraction patterns above 25 GPa, are explained by stacking disorder accompanied with a continuously increasing displacement of the AlO octahedral layer along a-axis. This finding could be the first experimental result for the pressure-induced stacking disorder driven by the continuous layer displacement. The magnitude of the layer displacement was estimated from the X-ray scattering profile calculation based on the stacking disordered structure model. Hydrogen bond geometries of boehmite, obtained by structure refinements on the observed neutron diffraction patterns for deuterated sample up to 10 GPa, show linearly approaching O-D covalent and DO hydrogen bond distances and they could merge below 26 GPa. The pressure-induced stacking disorder would make the electrostatic potential of hydrogen bonds asymmetric, yielding less chance for the proton-tunnelling.
Klotz, S.*; Komatsu, Kazuki*; Kagi, Hiroyuki*; Kunc, K.*; Sano, Asami; Machida, Shinichi*; Hattori, Takanori
Physical Review B, 95(17), p.174111_1 - 174111_7, 2017/05
The compression behaviour of deuterated ice VII and VIII was investigated by high pressure neutron scattering in the pressure range 2-13.7 GPa between 93 K and 300 K. We establish equations-of-state which contain accurate values for the bulk moduli B, their pressure derivatives B', as well as the ambient pressure volumina V. These equations-of-state hold over a large part of the stability domain of ice VII, by comparison with available X-ray data, and to at least 13 GPa for ice VIII. They are indistinguishable at low pressures, but beyond 7 GPa and at low temperatures ice VIII appears to become stiffer than expected. This might be related to an anomalous phonon hardening observed previously in ice VIII in this range [D.D. Klug et al., Physical Review B, 70, 144113 (2004)].
Shinozaki, Ayako*; Komatsu, Kazuki*; Kagi, Hiroyuki*; Fujimoto, Chikako*; Machida, Shinichi*; Sano, Asami; Hattori, Takanori
Journal of Chemical Physics, 148(4), p.044507_1 - 044507_8, 2017/01
Pressure-response on the crystal structure of deuterated -glycine was investigated at room temperature, using powder and single-crystal X-ray diffraction, and powder neutron diffraction measurements under high pressure. No phase change was observed up to 8.7 GPa, although anisotropy of the lattice compressibility was found. Neutron diffraction measurements indicated the distance of the intermolecular DO bond along with the -axis increase with compression up to 6.4 GPa. The distance of another DO bond along with the -axis decreased with increasing pressure, and became the shortest intermolecular hydrogen bond above 3 GPa. In contrast, the lengths of the bifurcated N-DO and C-DO hydrogen bonds, which are formed between the layers of the -glycine molecules along the -axis, decreased significantly with increasing pressure. The decrease of the intermolecular distances resulted in the largest compressibility of the -axis, compared to the other two axes. Hirshfeld analysis suggested that the reduction of the void region size, rather than shrinkage of the strong N-DO hydrogen bonds, occurred with compression.
Klotz, S.*; Komatsu, Kazuki*; Pietrucci, F.*; Kagi, Hiroyuki*; Ludl, A.-A.*; Machida, Shinichi*; Hattori, Takanori; Sano, Asami; Bove, L. E.*
Scientific Reports (Internet), 6, p.32040_1 - 32040_8, 2016/08
It has been known since decades that certain aqueous salt solutions of LiCl and LiBr readily form glasses when cooled to below 160 K. This fact has recently been exploited to produce a salty high pressure ice form: When the glass is compressed at low temperatures to pressures higher than 4 GPa and subsequently warmed, it crystallizes into ice VII with the ionic species trapped inside the ice lattice. Here we report the extreme limit of salt incorporation into ice VII, using high pressure neutron diffraction and molecular dynamics simulations. We show that high-pressure crystallization of aqueous solutions of LiCl5.6HO and LiBr5.6HO leads to solids with strongly expanded volume, a destruction of the hydrogen-bond network with an isotropic distribution of water-dipole moments, as well as a crystal to-amorphous transition on decompression. This highly unusual behavior constitutes an interesting pathway from a glass to a crystal where translational periodicity is restored but the rotational degree of freedoms remaining completely random.
Komatsu, Kazuki*; Noritake, Fumiya*; Machida, Shinichi*; Sano, Asami; Hattori, Takanori; Yamane, Ryo*; Kagi, Hiroyuki*
Scientific Reports (Internet), 6, p.28920_1 - 28920_11, 2016/07
We investigate in-situ neutron diffraction measurements and density functional theory calculations to revisit the structure and stability of ice XV. We find that none of the completely ordered configurations are particular favored; instead, partially ordered states are established as a mixture of ordered domains in disordered ice VI. This scenario in which several kinds of ordered configuration coexist dispels the contradictions in previous studies. It means that the order disorder pairs in ice polymorphs are not one-to-one correspondent pairs but rather have one-to-n correspondence, where there are possible configurations at finite temperature.
Hattori, Takanori; Sano, Asami; Arima, Hiroshi*; Komatsu, Kazuki*; Yamada, Akihiro*; Inamura, Yasuhiro; Nakatani, Takeshi; Seto, Yusuke*; Nagai, Takaya*; Utsumi, Wataru; et al.
Nuclear Instruments and Methods in Physics Research A, 780, p.55 - 67, 2015/04
PLANET is a time-of-flight (ToF) neutron beamline dedicated to high-pressure and high-temperature experiments. The large six-axis multi-anvil high-pressure press designed for ToF neutron diffraction experiments enables routine data collection at high pressures and high temperatures up to 10 GPa and 2000 K, respectively. To obtain clean data, the beamline is equipped with the incident slits and receiving collimators to eliminate parasitic scattering from the high-pressure cell assembly. The high performance of the diffractometer for the resolution ( / 0.6%) and the accessible -spacing range (0.2-8.4 ) together with low-parasitic scattering characteristics enables precise structure determination of crystals and liquids under high pressure and temperature conditions.
Komatsu, Kazuki*; Shinozaki, Ayako*; Machida, Shinichi*; Matsubayashi, Takuto*; Watanabe, Mao*; Kagi, Hiroyuki*; Sano, Asami; Hattori, Takanori
Acta Crystallographica Section B; Structural Science, Crystal Engineering and Materials (Internet), 71(1), p.74 - 80, 2015/02
Magnesium dichloride decahydrate (MgCl10HO) and its deuterated counterpart (MgCl10DO) are identified for the first time by in-situ powder synchrotron X-ray and spallation neutron diffraction. These substances are crystallized from a previously unidentified nanocrystalline compound, which originates from an amorphous state at low temperature. A combination of a recently developed autoindexing procedure and the charge-flipping method reveals that the crystal structure of MgCl 10HO consists of an ABCABC... sequence of Mg(HO) octahedra. The Cl anions and remaining water molecules unconnected to the Mg cations bind the octahedra, similar to other water-rich magnesium dichloride hydrates. The D positions in MgCl10DO, determined by the difference Fourier methods using the neutron powder diffraction patterns at 2.5 GPa, show the features such as bifurcated hydrogen bonds and tetrahedrally coordinated O atoms.
Iizuka, Riko*; Komatsu, Kazuki*; Kagi, Hiroyuki*; Nagai, Takaya*; Sano, Asami; Hattori, Takanori; Goto, Hirotada*; Yagi, Takehiko*
Journal of Solid State Chemistry, 218, p.95 - 102, 2014/10
In situ neutron diffraction measurements combined with the pulsed neutron source at the Japan Proton Accelerator Research Complex (J-PARC) were conducted on high-pressure polymorphs of deuterated portlandite (Ca(OD)) using a Paris-Edinburgh cell and a multi-anvil press. The atomic positions including hydrogen for the unquenchable high-pressure phase at room temperature (phase II') were first clarified. The bent hydrogen bonds under high pressure were consistent with results from Raman spectroscopy. The structure of the high-pressure and high-temperature phase (Phase II) was concordant with that observed previously by another group for a recovered sample. The observations elucidate the phase transition mechanism among the polymorphs, which involves the sliding of CaO polyhedral layers, position modulations of Ca atoms, and recombination of Ca-O bonds accompanied by the reorientation of hydrogen to form more stable hydrogen bonds.
Katsuyama, Chie*; Nashimoto, Hiroaki*; Nagaosa, Kazuyo*; Ishibashi, Tomotaka*; Furuta, Kazuki*; Kinoshita, Takeshi*; Yoshikawa, Hideki; Aoki, Kazuhiro; Asano, Takahiro*; Sasaki, Yoshito; et al.
FEMS Microbiology Ecology, 86(3), p.532 - 543, 2013/12
Anaerobic microbial activity has a major influence on the subsurface environment, and should be considered in subsurface activities including the construction of radioactive waste repositories. We investigated denitrification and methanogenesis in anoxic groundwater from 140 m depth in two boreholes, where the redox potential fluctuated. The average maximum potential denitrification rates, measured under anaerobic conditions in the two boreholes using an N tracer. Methanogenesis candidates were detected by 16S rRNA gene analysis. Although the stable isotope signatures suggested that some of the dissolved methane was of biogenic origin, no potential for methane production was evident during the incubations. The groundwater at 140 m depth did not contain oxygen, had an Eh ranging from -144 to 6.8 mV, and was found to be a potential field for denitrification.