Neutron diffraction study of the crystal and magnetic structures of antiferromagnetic manganese deuteride at high temperatures and high pressures

Machida, Akihiko*; Saito, Hiroyuki*; Aoki, Katsutoshi*; Komatsu, Kazuki*; Hattori, Takanori; Sano, Asami; Funakoshi, Kenichi*; Machida, Shinichi*; Sato, Toyoto*; Orimo, Shinichi*

Physical Review B, 111(22), p.224413_1 - 224413_6, 2025/06

https://doi.org/10.1103/yf8k-cy61

The crystal and magnetic structures of antiferromagnetic Mn deuterides formed by hydrogenating Mn metal at high temperature and high pressure, fcc -MnDx and hcp -MnDx, were investigated by in-situ neutron powder diffraction. Deuterium atoms partially occupied the octahedral interstitial positions of the fcc and hcp metal lattices. The site occupancies increased rapidly with decreasing temperature from 700 to 450 K and remained down to 300 K. Nel temperature of 543(10) K was determined for -MnD. For -MnD, saturation magnetic moment and Nel temperature were determined to be 0.82(1) and 347(3) K, respectively. The Nel temperatures determined for -MnD and -MnD are consistent with those predicted by the respective Slater-Pauling curves proposed in previous studies. The updated Nel temperatures provide insights into the development of more accurate Slater-Pauling curves based on electronic band structure calculations.

Hydroxyl group/fluorine disorder in deuterated magnesium hydroxyfluoride and behaviors of hydrogen bonds under high pressure

He, X.*; Kagi, Hiroyuki*; Komatsu, Kazuki*; Iizuka, Riko*; Okajima, Hajime*; Hattori, Takanori; Sano, Asami; Machida, Shinichi*; Abe, Jun*; Goto, Hirotada*; et al.

Journal of Molecular Structure, 1310, p.138271_1 - 138271_8, 2024/08

https://doi.org/10.1016/j.molstruc.2024.138271

High-pressure responses of the O-DF hydrogen bonds in deuterated magnesium hydroxyfluoride were investigated using neutron powder diffraction and Raman spectroscopy. The Rietveld analysis at ambient conditions revealed a chemical formula of Mg(OD)F and hydroxyl group/fluorine disorder (OD/F disorder) in the crystal structure, which gave rise to two hydrogen-bonding configurations. The Rietveld analysis showed the hydrogen-bonding geometries remains up to 9.8 GPa, indicating no pressure-induced strengthening of hydrogen bonds. The Raman spectra at ambient conditions showed three hydroxyl stretching bands at 2613, 2694, and 2718 cm. The high frequencies of the O-D stretching modes indicated that the hydroxyls should be involved in weak or none hydrogen-bonding interactions. Up to 20.2 GPa, the mode initially centered at 2694 cm displayed a pressure-induced blue shift, revealing no strengthening of hydrogen bonds under compression. We discuss the existence of hydrogen bonds and the causes of the blue-shifting hydroxyls at ambient and at high pressures.

Securing reversibility of UO/UOredox equilibrium in [emim]TfN-based liquid electrolytes towards uranium redox-flow battery

Takao, Koichiro*; Ouchi, Kazuki; Komatsu, Atsushi; Kitatsuji, Yoshihiro; Watanabe, Masayuki

European Journal of Inorganic Chemistry, 27(14), p.e202300787_1 - e202300787_7, 2024/05

https://doi.org/10.1002/ejic.202300787

Electrochemical behavior of UO/UO in 1-ethyl-3-methylimidazolium bis(trifluoromethyl)sulfonylamide ([emim]TfN) ionic liquid was studied to clarify what are required to attain its redox reversibility for utilizing depleted U as an electrode active material in a redox flow battery. As a result, reversibility of the UO/UO redox reaction was successfully achieved in use of a glassy carbon working electrode under presence of Cl in [emim]TfN. To improve diffusivity of solutes, [emim]TfN diluted with an auxiliary molecular solvent, N,N-dimethylformamide (DMF). We have succeeded in demonstrating a reversible redox reaction of [UOCl] + e = [UOCl] in the 50:50 v/v [emim]TfN-DMF liquid electrolyte containing Cl.

The Hydrogen-bond network in sodium chloride tridecahydrate; Analogy with ice VI

Yamashita, Keishiro*; Nakayama, Kazuya*; Komatsu, Kazuki*; Ohara, Takashi; Munakata, Koji*; Hattori, Takanori; Sano, Asami; Kagi, Hiroyuki*

Acta Crystallographica Section B; Structural Science, Crystal Engineering and Materials (Internet), 79(5), p.414 - 426, 2023/10

https://doi.org/10.1107/S2052520623007199

The structure of a recently-found hyperhydrated form of sodium chloride, NaCl 13H(D)O, has been determined by single-crystal neutron diffraction at 1.7 GPa and 298 K. It has large hydrogen-bond networks and some water molecules have distorted bonding features such as bifurcated hydrogen bonds and five-coordinated water molecules. The hydrogen-bond network has similarities to ice VI in terms of network topology and disordered hydrogen bonds. Assuming the equivalence of network components connected by pseudo symmetries, the overall network structure of this hydrate can be expressed by breaking it down into smaller structural units which correspond to the ice VI network structure. This hydrogen-bond network contains orientational disorder of water molecules in contrast to the known salt hydrates. Here, we present an example for further insights into a hydrogen-bond network containing ionic species.

Annual report on the effluent control of low level liquid waste in Nuclear Fuel Cycle Engineering Laboratories FY2021

Nakada, Akira; Kanai, Katsuta; Kokubun, Yuji; Nagaoka, Mika; Koike, Yuko; Yamada, Ryohei*; Kubota, Tomohiro; Hirao, Moe; Yoshii, Hideki*; Otani, Kazunori*; et al.

JAEA-Review 2022-079, 116 Pages, 2023/03

JAEA-Review-2022-079.pdf:2.77MB

Based on the regulations (the safety regulation of Tokai Reprocessing Plant, the safety regulation of nuclear fuel material usage facilities, the radiation safety rule, the regulation about prevention from radiation hazards due to radioisotopes, which are related with the nuclear regulatory acts, the local agreement concerning with safety and environment conservation around nuclear facilities, the water pollution control law, and by law of Ibaraki Prefecture), the effluent control of liquid waste discharged from the Nuclear Fuel Cycle Engineering Laboratories of Japan Atomic Energy Agency has been performed. This report describes the effluent control results of the liquid waste in the fiscal year 2021. In this period, the concentrations and the quantities of the radioactivity in liquid waste discharged from the reprocessing plant, the plutonium fuel fabrication facilities, and the other nuclear fuel material usage facilities were much lower than the limits authorized by the above regulations.

Atomic distribution and local structure in ice VII from in situ neutron diffraction

Yamashita, Keishiro*; Komatsu, Kazuki*; Klotz, S.*; Fabelo, O.*; Fernndez-Daz, M. T.*; Abe, Jun*; Machida, Shinichi*; Hattori, Takanori; Irifune, Tetsuo*; Shimmei, Toru*; et al.

Proceedings of the National Academy of Sciences of the United States of America, 119(40), p.e2208717119_1 - e2208717119_6, 2022/10

https://doi.org/10.1073/pnas.2208717119

Here we present the first elucidation of the disordered structure of ice VII, the dominant high-pressure form of water, at 2.2 GPa and 298 K from both single-crystal and powder neutron diffraction techniques. We reveal the three-dimensional atomic distributions from the maximum entropy method and unexpectedly find a ring-like distribution of hydrogen in contrast to the commonly-accepted discrete sites. In addition, total scattering analysis at 274 K clarified the difference in the intermolecular structure from ice VIII, the ordered counterpart of ice VII, despite an identical molecular geometry. Our complementary structure analyses robustly demonstrate the unique disordered structure of ice VII. Furthermore, these noble findings are related to the proton dynamics which drastically vary with pressure, and will contribute to an understanding of the structural origin of anomalous physical properties of ice VII under pressures.

Improvement of nano-polycrystalline diamond anvil cells with Zr-based bulk metallic glass cylinder for higher pressures; Application to Laue-TOF diffractometer

Yamashita, Keishiro*; Komatsu, Kazuki*; Ohara, Takashi; Munakata, Koji*; Irifune, Tetsuo*; Shimmei, Toru*; Sugiyama, Kazumasa*; Kawamata, Toru*; Kagi, Hiroyuki*

High Pressure Research, 42(1), p.121 - 135, 2022/03

https://doi.org/10.1080/08957959.2022.2045982

Bayesian sparse modeling of extended X-ray absorption fine structure to determine interstitial oxygen positions in yttrium oxyhydride epitaxial thin film

Kumazoe, Hiroyuki*; Igarashi, Yasuhiko*; Iesari, F.*; Shimizu, Ryota*; Komatsu, Yuya*; Hitosugi, Taro*; Matsumura, Daiju; Saito, Hiroyuki*; Iwamitsu, Kazunori*; Okajima, Toshihiko*; et al.

AIP Advances (Internet), 11(12), p.125013_1 - 125013_5, 2021/12

https://doi.org/10.1063/5.0071166

Thermally altered subsurface material of asteroid (162173) Ryugu

Kitazato, Kohei*; Milliken, R. E.*; Iwata, Takahiro*; Abe, Masanao*; Otake, Makiko*; Matsuura, Shuji*; Takagi, Yasuhiko*; Nakamura, Tomoki*; Hiroi, Takahiro*; Matsuoka, Moe*; et al.

Nature Astronomy (Internet), 5(3), p.246 - 250, 2021/03

https://doi.org/10.1038/s41550-020-01271-2

Here we report observations of Ryugu's subsurface material by the Near-Infrared Spectrometer (NIRS3) on the Hayabusa2 spacecraft. Reflectance spectra of excavated material exhibit a hydroxyl (OH) absorption feature that is slightly stronger and peak-shifted compared with that observed for the surface, indicating that space weathering and/or radiative heating have caused subtle spectral changes in the uppermost surface. However, the strength and shape of the OH feature still suggests that the subsurface material experienced heating above 300 C, similar to the surface. In contrast, thermophysical modeling indicates that radiative heating does not increase the temperature above 200 C at the estimated excavation depth of 1 m, even if the semimajor axis is reduced to 0.344 au. This supports the hypothesis that primary thermal alteration occurred due to radiogenic and/or impact heating on Ryugu's parent body.

Experimental evidence for the existence of a second partially-ordered phase of ice VI

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

https://doi.org/10.1038/s41467-021-21351-9

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.