Experimental observation of 5f valence fluctuations by high-resolution X-ray absorption spectroscopy in UPdCd

Hirose, Yusuke; Honda, Fuminori*; Doto, Hiroshi*; Kawamura, Naomi*; Kvashnina, K. O.*; Amidani, L.*; Uhlov, K.*; Koloren, J.*; Havela, L.*

Physical Review B, 113(24), p.L241103_1 - L241103_6, 2026/06

https://doi.org/10.1103/g9y8-7lq9

Adsorption structures and bonding states of cesium and barium adsorbed on various sites of vermiculite

Yamaguchi, Akiko; Okumura, Masahiko; Kawamura, Naomi*; Takahashi, Yoshio*

Science of the Total Environment, 964, p.178585_1 - 178585_13, 2025/02

https://doi.org/10.1016/j.scitotenv.2025.178585

There are many unresolved issues in the adsorption reactions of clay minerals. One of the reasons is the existence of multiple adsorption sites. It is known that the contribution of each adsorption site depends on the concentration of adsorbed ions, and there is a challenge in comprehensively correlate the results of atomic-level simulations that employ limited number of atoms and inevitably deal high-concentration samples with actual environmental samples where concentrations are orders of magnitude lower. In this study, we combined experiments using synchrotron radiation and first-principles calculations to comprehensively elucidate the systematic changes in the local structure of adsorption sites and adsorbed ions based on the adsorption concentration at the atomic level, and demonstrated that the interaction between adsorbed ions and clay minerals involves ionic bonding.

Application of high-energy-resolution X-ray absorption spectroscopy at the U L-edge to assess the U(V) electronic structure in FeUO

Yomogida, Takumi; Akiyama, Daisuke*; Ouchi, Kazuki; Kumagai, Yuta; Higashi, Kotaro*; Kitatsuji, Yoshihiro; Kirishima, Akira*; Kawamura, Naomi*; Takahashi, Yoshio*

Inorganic Chemistry, 61(50), p.20206 - 20210, 2022/12

https://doi.org/10.1021/acs.inorgchem.2c03208

FeUO was studied to clarify the electronic structure of U(V) in a metal monouranate compound. We obtained the peak splitting of HERFD-XANES spectra utilizing high-energy-resolution fluorescence detection-X-ray absorption near edge structure (HERFD-XANES) spectroscopy at the U L-edge, which is a novel technique in the U(V) compounds. Theoretical calculations revealed that the peak splitting was caused by splitting the 6d orbital of U(V). Such distinctive electronic states are of major interest to researchers and engineers working in various fields, from fundamental physics to the nuclear industry and environmental sciences for actinide elements.

Highly-sensitive analysis of fluorescence XANES at Europium (Eu) L-edge for the determination of oxidation state for trace amount of Eu in natural samples by bragg-type crystal analyzer system

Konagaya, Rimi*; Kawamura, Naomi*; Yamaguchi, Akiko; Takahashi, Yoshio*

Chemistry Letters, 50(8), p.1570 - 1572, 2021/08

https://doi.org/10.1246/cl.210249

no abstracts in English

Thermal expansion of a Au-Al-Yb intermediate valence quasicrystal

Watanuki, Tetsu; Kashimoto, Shiro*; Ishimasa, Tsutomu*; Machida, Akihiko; Yamamoto, Shin*; Tanaka, Yukinori*; Mizumaki, Masaichiro*; Kawamura, Naomi*; Watanabe, Shinji*

Solid State Communications, 211, p.19 - 22, 2015/06

https://doi.org/10.1016/j.ssc.2015.03.008

The thermal expansion of a Au-Al-Yb intermediate-valence quasicrystal has been studied by X-ray diffraction measurements. We have found anomalous thermal expansion behavior, namely zero thermal expansion below 50 K. By comparison with an isostructural Au-Al-Tm quasicrystal, the contribution of the Yb valence variation was extracted, and it was shown that its negative thermal expansion component due to the valence shift toward the divalent state by cooling compensated for the positive thermal expansion of the original lattice.

X-ray absorption spectroscopy and novel electronic properties in heavy fermion compounds YbTZn (T: Rh and Ir)

Honda, Fuminori*; Hirose, Yusuke*; Miyake, Atsushi*; Mizumaki, Masaichiro*; Kawamura, Naomi*; Tsutsui, Satoshi*; Watanuki, Tetsu; Watanabe, Shinji*; Takeuchi, Tetsuya*; Settai, Rikio*; et al.

Journal of Physics; Conference Series, 592(1), p.012021_1 - 012021_5, 2015/03

https://doi.org/10.1088/1742-6596/592/1/012021

no abstracts in English

Temperature and magnetic field dependent Yb valence in YbRhSi observed by X-ray absorption spectroscopy

Nakai, Hirohito*; Ebihara, Takao*; Tsutsui, Satoshi*; Mizumaki, Masaichiro*; Kawamura, Naomi*; Michimura, Shinji*; Inami, Toshiya; Nakamura, Toshiyuki*; Kondo, Akihiro*; Kindo, Koichi*; et al.

Journal of the Physical Society of Japan, 82(12), p.124712_1 - 124712_5, 2013/12

https://doi.org/10.7566/JPSJ.82.124712

The temperature and magnetic field dependences of Yb valence were observed in the heavy fermion compoundYbRhSi by X-ray absorption spectroscopy. The measurements revealed that the Yb valence decreases with decreasing temperature in the range from 200 to 2 K and increases with increasing magnetic field in the range from 0 to 33 T without showing an abrupt change in the Yb valence. The Yb valence is in the range from 2.92 to 2.96 depending on temperature and magnetic field. With respect to the valence being 2.92 at 0 T and 2.93 at 33 T in 2 K, YbRhSi is a valence fluctuation compound and does not reach the integer trivalent state at high magnetic field. These results endorse the conventional knowledge that the valence of Yb is very close to the integer value of 3+, decreases with decreasing temperature, and becomes closer to 3+ with increasing magnetic field.

High-magnetic-field X-ray absorption and magnetic circular dichroism spectroscopy in the mixed-valent compound YbAgCu

Nakamura, Toshiyuki*; Matsuda, Yasuhiro*; Her, J.-L.*; Kindo, Koichi*; Michimura, Shinji*; Inami, Toshiya; Mizumaki, Masaichiro*; Kawamura, Naomi*; Suzuki, Motohiro*; Chen, B.*; et al.

Journal of the Physical Society of Japan, 81(11), p.114702_1 - 114702_11, 2012/11

https://doi.org/10.1143/JPSJ.81.114702

The X-ray absorption and magnetic circular dichroism (MCD) spectra at the Yb L edge were measured in the mixed-valent heavy fermion compound YbAgCu at high magnetic fields and low temperatures. The magnetic-field-temperature (H-T) phase boundary determined by the valence state is in very good agreement with that determined by the magnetization. It is clearly found that the metamagnetism of this compound is due to the field induced valence transition. A distinctive positive peak of the XMCD spectra appears in the vicinity of the white line of the absorption due to Yb state, while no feature is observed in the XMCD spectra corresponding to the Yb state. A small negative XMCD peak was observed at a lower energy and was attributed to the quadrupole trasition from theoretical calcuration, which explains its peculicar magnetic field dependence.

Orbital magnetism in CdOsO studied by X-ray magnetic circular dichroism

Matsuda, Yasuhiro*; Her, J.-L.*; Michimura, Shinji*; Inami, Toshiya; Suzuki, Motohiro*; Kawamura, Naomi*; Mizumaki, Masaichiro*; Kindo, Koichi*; Yamaura, Junichi*; Hiroi, Zenji*

Physical Review B, 84(17), p.174431_1 - 174431_5, 2011/11

https://doi.org/10.1103/PhysRevB.84.174431

X-ray magnetic circular dichroism (XMCD) at the -edge of Os has been investigated in the antiferromagneticphase of CdOsO, which exhibits a metal-insulator transition around 227 K. According to the sum rule, the XMCD spectra at 10 and 37 T clearly show that the ratio between the orbital magnetic moment () and spinmagnetic moment () is , and that and are coupled in parallel (). These phenomena are unusual in that the expected ground state of Os (5) is an orbital singlet in a cubic crystal field, and and should be antiparallel for a less than half-filled system in accordance with Hund's third rule. It is likely that the spin-orbit coupling is important for explaining the observed orbital magnetism.

Effect of hydrogenation on the electronic state of metallic La hydrides probed by X-ray absorption sectroscopy at the La -edges

Ishimatsu, Naoki*; Sasada, Ryohei*; Maruyama, Hiroshi*; Ichikawa, Takayuki*; Miyaoka, Hiroki*; Kimura, Toru*; Tsubota, Masami*; Kojima, Yoshitsugu*; Tsumuraya, Takao*; Oguchi, Tamio*; et al.

Journal of Physics; Conference Series, 190, p.012070_1 - 012070_4, 2009/11

https://doi.org/10.1088/1742-6596/190/1/012070

We have investigated the effect of hydrogenation on La and electronic states in metallic LaH by X-ray absorption near edge structure at the La -edges. As the hydrogen content increases from 0 to 2.6, white-line intensity at the La -edges shows a remarkable increase in the range of 2.0. This is interpreted as the increase in La hole induced by interstitial H atoms on the octahedral sites. On the other hand, the shoulder structure at the La -edge disappears in the process of = 0.0 2.0, indicating that the - hybridization is weakened by H atoms on the tetrahedral sites. This study demonstrates that H atoms on the two interstitial H sites provide different contribution to the modification of the electronic states.