Quantum critical behavior of the hyperkagome magnet MnCoSi

山内 宏樹; Sari, D. P.*; 安井 幸夫*; 坂倉 輝俊*; 木村 宏之*; 中尾 朗子*; 大原 高志; 本田 孝志*; 樹神 克明; 井川 直樹; et al.

Physical Review Research (Internet), 6(1), p.013144_1 - 013144_9, 2024/02

https://doi.org/10.1103/PhysRevResearch.6.013144

-Mn-type family alloys Mn have three-dimensional antiferromagnetic (AFM) corner-shared triangular network. The antiferromagnet MnRhSi shows magnetic short-range order (SRO) over a wide temperature range of approximately 500 K above the Nel temperature = 190 K. MnCoSi has the smallest lattice parameter and the lowest in the family compounds. The quantum critical point (QCP) from AFM to the quantum paramagnetic state is expected near a cubic lattice parameter of 6.15 of MnCoSi is only 140 K, quantum critical behavior is observed in MnCoSi as the enhancement of the electronic specific heat coefficient . We study how the magnetic SRO appears in MnCoSi by using neutron scattering, SR, and physical property measurements. The experimental results show that the neutron scattering intensity of the magnetic SRO does not change much regardless of the suppressed magnetic moment in the long-range magnetic ordered state compared to those of MnRhSi. The initial asymmetry drop ratio of SR above becomes small, and the magnetic SRO temperature is suppressed to 240 K. The results suggest that the MnCoSi is close to the QCP in the Mn system.

Development of an iron(II) complex exhibiting thermal- and photoinduced double proton-transfer-coupled spin transition in a short hydrogen bond

中西 匠*; 堀 優太*; 重田 育照*; 佐藤 寛泰*; 鬼柳 亮嗣; 宗像 孝司*; 大原 高志; 岡澤 厚*; 島田 林太郎*; 坂本 章*; et al.

Journal of the American Chemical Society, 145(35), p.19177 - 19181, 2023/08

https://doi.org/10.1021/jacs.3c06323

Multiple proton transfer (PT) controllable by external stimuli plays a crucial role in fundamental chemistry, biological activity, and material science. However, in crystalline systems, controlling multiple PT, which results in a distinct protonation state, remains challenging. In this study, we developed a novel tridentate ligand and iron(II) complex with a short hydrogen bond (HB) that exhibits a PT-coupled spin transition (PCST). Single-crystal X-ray and neutron diffraction measurements revealed that the positions of the two protons in the complex can be controlled by temperature and photoirradiation based on the thermal- and photoinduced PCST. The obtained results suggest that designing molecules that form short HBs is a promising approach for developing multiple PT systems in crystals.

Observation of proton-transfer-coupled spin transition by single-crystal neutron-diffraction measurement

中西 匠*; 堀 優太*; 重田 育照*; 佐藤 寛泰*; Wu, S.-Q.*; 鬼柳 亮嗣; 宗像 孝司*; 大原 高志; 佐藤 治*

Physical Chemistry Chemical Physics, 25(17), p.12394 - 12400, 2023/05

https://doi.org/10.1039/D3CP00527E

The application of single-crystal neutron diffraction (SCND) to observe proton-transfer phenomena in crystalline compounds exhibiting unusual protonation states or proton dynamics has garnered significant research interest in recent years. However, proton tautomerism, which results in different protonation states before and after proton transfer, has never been observed using the SCND technique. Thus, to observe the proton tautomerism phenomenon by SCND measurements, we developed an iron(II) complex that forms a large crystal and exhibits a proton-transfer-coupled spin transition (PCST). The presence of the two types of proton tautomers was determined by conventional analysis of the proton position by X-ray crystallography, infrared spectroscopy, and density functional theory calculations. Finally, our results confirmed that proton tautomerism was successfully observed for the first time using variable-temperature SCND measurements.

Partial breakdown of translation symmetry at a structural quantum critical point associated with a ferroelectric soft mode

石井 悠衣*; 山本 有梨沙*; 佐藤 直大*; 南部 雄亮*; 河村 聖子; 村井 直樹; 尾原 幸治*; 河口 彰吾*; 森 孝雄*; 森 茂生*

Physical Review B, 106(13), p.134111_1 - 134111_7, 2022/10

https://doi.org/10.1103/PhysRevB.106.134111

We report that complete suppression of a phonon-driven structural phase transition causes partial breakdown of a three-dimensional translation symmetry in a well-defined sublattice. This state is revealed for a dielectric compound, BaSrAlO, that comprises an AlO network incorporated into a hexagonal Ba(Sr) sublattice. Pair distribution function analyses and inelastic neutron scattering experiments provide clear-cut evidence of the AlO network forming a continuum of Al-O short-range correlations similar to glasses, whereas the Ba(Sr) sublattice preserves the original translational symmetry. This glassy network significantly dampens the phonon spectrum and transforms it into the broad one resembling those typically observed in glass materials.

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

山下 恵史朗*; 小松 一生*; 大原 高志; 宗像 孝司*; 入舩 徹男*; 新名 亨*; 杉山 和正*; 川又 透*; 鍵 裕之*

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

https://doi.org/10.1080/08957959.2022.2045982

We improved diamond anvil cells with a tubular frame made of Zr-based bulk metallic glass and nano-polycrystalline diamond anvils for single-crystal neutron diffraction. The thicker tubular frame was confirmed through experimentation as stably generating 4.5 GPa. Its feasibility for neutron diffraction was assessed at the Laue-TOF diffractometer at the BL18 (SENJU) beamline in the MLF J-PARC using time-resolved two-dimensional detectors covering wide solid angles. In addition to ambient-pressure measurements of NHCl, diffraction patterns of a high-pressure phase of ice were also collected in-situ. The obtained intensities are of refinable quality sufficient for structure analysis.

Microscopic dynamics of lithium diffusion in single crystal of the solid-state electrolyte LaLiTiO (x = 0.13) studied by quasielastic neutron scattering

松浦 直人*; 藤原 靖幸*; 森分 博紀*; 尾原 幸治*; 川北 至信

Physical Review B, 104(9), p.094305_1 - 094305_7, 2021/09

https://doi.org/10.1103/PhysRevB.104.094305

Quasielastic neutron scattering (QENS) measurements combined with first principles based molecular dynamics calculations were conducted to study the dynamics of Li ions in a solid-state electrolyte LaLiTiO (LLTO) with . By using a large Li-enriched single crystal sample, a QENS signal was clearly observed along the three principal axes [110], [111], and [001] at a temperature () of 600 K. Wave vector dependence of the linewidth of the QENS signal along each direction was explained well using the Chudley-Elliot model for jumps between the A sites of the perovskite lattice through the bottleneck square, which was also supported by molecular dynamics calculations. The estimated self-diffusion coefficient of Li () in the ab plane was slightly larger than that along the c axis, suggesting quasi-isotropic diffusion, that is, the three-dimensional diffusion of Li ions. The decrease in with decreasing was reasonably explained by a thermal activation process with the activation energy determined from ionic-conductivity measurements. Furthermore, the estimated values of the self-diffusion coefficient are comparable to those in the sulfide-based Li ion conductor, LiPS, with 10 times larger ionic conductivity, which clarifies how to understand the Li conduction mechanism in LLTO and LiPS in a unified manner.

Charge-density-wave order and multiple magnetic transitions in divalent europium compound EuAl

金子 耕士; 川崎 卓郎; 仲村 愛*; 宗像 孝司*; 中尾 朗子*; 花島 隆泰*; 鬼柳 亮嗣; 大原 高志; 辺土 正人*; 仲間 隆男*; et al.

Journal of the Physical Society of Japan, 90(6), p.064704_1 - 064704_6, 2021/06

https://doi.org/10.7566/JPSJ.90.064704

Multiple transition phenomena in divalent Eu compound EuAl with the tetragonal structure were investigated via single crystal time-of-flight neutron Laue technique. At 30 K below a charge-density-wave (CDW) transition, superlattice peaks emerge near nuclear Bragg peaks described by an ordering vector = (0 0 ). In contrast, magnetic peaks appear at with = 0.09 below = 15.4 K, and moves to with = 0.19 below =12.2 K, whereas no distinct change in the magnetic Bragg peak was detected at and . The structural modification with is characterized by an absence of the superlattice peak in (0 0 ). Considering an absence of splitting in magnetic peaks along , the structural transition is mainly ascribed to a displacement of Al ions within the tetragonal -plane. Complex incommensurate magnetic transitions are in stark contrast to a simple collinear commensurate structure in isovalent EuGa. This could stem from incompatible electronic structures with the CDW transition between two compounds.

Mechanistic study on the removal of Cs from contaminated soil by rapid ion exchange in subcritical water

福田 達弥*; 高橋 亮*; 原 卓飛*; 尾原 幸治*; 加藤 和男*; 松村 大樹; 稲葉 優介*; 中瀬 正彦*; 竹下 健二*

Journal of Nuclear Science and Technology, 58(4), p.399 - 404, 2021/04

https://doi.org/10.1080/00223131.2020.1830866

As a result of the Fukushima nuclear power plant accident in March 2011, massive amounts of soil were contaminated with radioactive Cs. To remediate the contaminated soil, we are developing a desorption technique for removing Cs from soil using subcritical water. We found that rapid ion exchange of Cs with multivalent cations in subcritical water is an effective desorption technique. To understand the mechanism and structural aspects of this process, in situ observations of the soil layer in subcritical water were carried out by high-energy X-ray diffraction together with pair distribution function analysis, and extended X-ray absorption fine structure analysis. Both the desorption experiments and structural studies indicated that conformational changes of the layer containing Cs under subcritical water conditions promoted intercalation of the hydrated Mg and trapped Cs, which facilitated a rapid ion-exchange reaction of Mg and Cs.

断層変位地形が不明瞭なひずみ集中帯におけるリニアメントカタログの作成; 南九州せん断帯における事例(受託研究)

後藤 翠; 佐々木 亮道*; 小松 哲也; 三輪 敦志*; 照沢 秀司*; 楮原 京子*; 島田 耕史

JAEA-Research 2020-013, 88 Pages, 2020/11

JAEA-Research-2020-013.pdf:22.86MB
JAEA-Research-2020-013-appendix(CD-ROM).zip:0.18MB

活断層を見出す調査技術の向上は、地層処分事業を進めるにあたって、断層のずれに伴う透水性の増加が生じる場所を避ける観点から重要である。通常、活断層の存在は、断層運動の地形学的痕跡である断層変位地形の空中写真判読と、現地の地質調査により確認する。しかし、地形学的な痕跡が不明瞭な場合の調査手法は十分整備されていない。そこで、本研究では、既往の地形学的手法を高度化する観点から、活断層を見出す指標となり得る地形学的特徴の直線状ないし弧状配列(リニアメント)を、通常の活断層研究ではほとんど無視されるような明瞭さが乏しいランクまで判読した。調査地域は、測地学的なひずみ集中帯であり、1997年鹿児島県北西部地震(Mj 6.6)の震源断層が伏在している南九州せん断帯である。本研究では、1/25,000地形図62枚の範囲の空中写真判読を実施し、得られた1,327条のリニアメントを地形図上に示し、リニアメントの分布密度,方向性,長さ,地形,地質などの項目について整理した。その結果、南九州せん断帯方向の東西系のリニアメントが西部で卓越し、鹿児島県北西部地震の余震分布域ではリニアメントが高密度で分布することが明らかとなった。これらの結果とともに、明瞭さ,方向,長さなどと地形的特徴の組み合わせによる類型化に基づく代表的な13条のリニアメントについてカタログをとりまとめた。

Successive phase transitions in IrSn (: La and Ce) investigated using neutron and X-ray diffraction

中里 晟也*; 岩佐 和晃*; 橋本 大輔*; 塩澤 真未*; 桑原 慶太郎*; 中尾 裕則*; 佐賀山 基*; 石角 元志*; 大原 高志; 中尾 朗子*; et al.

JPS Conference Proceedings (Internet), 30, p.011128_1 - 011128_6, 2020/03

https://doi.org/10.7566/JPSCP.30.011128

Successive phase transitions of IrSn (: La and Ce) were studied using neutron and X-ray diffraction techniques. A semimetal CeIrSn undergoes three phase transitions: an antiferromagnetic ordering characterized by a propagation vector = (1/2, 1/2, 2/5) below 0.6 K, a structural transformation with = (1/4, 1/4, 1/4) at 2.0 K, and another structural transformation with = (1/2, 1/2, 0) above room temperature. LaIrSn was confirmed to be a superconductor below 2.5 K under the = (1/2, 1/2, 0) structure that also appears above room temperature.