Marking actinides for separation; Resonance-enhanced multiphoton charge transfer in actinide complexes

Matsuda, Shohei; Yokoyama, Keiichi; Yaita, Tsuyoshi; Kobayashi, Toru; Kaneta, Yui; Simonnet, M.; Sekiguchi, Tetsuhiro; Honda, Mitsunori; Shimojo, Kojiro; Doi, Reisuke; et al.

Science Advances (Internet), 8(20), p.eabn1991_1 - eabn1991_11, 2022/05

https://doi.org/10.1126/sciadv.abn1991

no abstracts in English

PSTEP: Project for solar-terrestrial environment prediction

Kusano, Kanya*; Ichimoto, Kiyoshi*; Ishii, Mamoru*; Miyoshi, Yoshizumi*; Yoden, Shigeo*; Akiyoshi, Hideharu*; Asai, Ayumi*; Ebihara, Yusuke*; Fujiwara, Hitoshi*; Goto, Tadanori*; et al.

Earth, Planets and Space (Internet), 73(1), p.159_1 - 159_29, 2021/12

https://doi.org/10.1186/s40623-021-01486-1

The PSTEP is a nationwide research collaboration in Japan and was conducted from April 2015 to March 2020, supported by a Grant-in-Aid for Scientific Research on Innovative Areas from the Ministry of Education, Culture, Sports, Science and Technology of Japan. It has made a significant progress in space weather research and operational forecasts, publishing over 500 refereed journal papers and organizing four international symposiums, various workshops and seminars, and summer school for graduate students at Rikubetsu in 2017. This paper is a summary report of the PSTEP and describes the major research achievements it produced.

Density functional study on Am(III)/Eu(III) selectivity using crown ether type ligands

Fukasawa, Yuto*; Kaneko, Masashi; Nakashima, Satoru*

Journal of Radioanalytical and Nuclear Chemistry, 329(1), p.77 - 84, 2021/07

https://doi.org/10.1007/s10967-021-07685-0

Density functional theory calculations were applied to understand the selectivity between Am and Eu ions with the crown ethers type ligands. 18C6 is predicted to form the most stable complex with Eu and show the higher stability for Am over Eu, being consistent with previously reported Am/Eu selectivity. We modeled N- and S-donor complexes by using framework of 18C6 complex and analyzed the complexation Gibbs energies, indicating that 18C6 with N-donor atoms is suitable for both complexation and higher Am stability over Eu due to the stronger covalent interaction.

Interim activity status report of "the group for investigation of reasonable safety assurance based on graded approach" (from September, 2019 to September, 2020)

Yonomoto, Taisuke; Nakashima, Hiroshi*; Sono, Hiroki; Kishimoto, Katsumi; Izawa, Kazuhiko; Kinase, Masami; Osa, Akihiko; Ogawa, Kazuhiko; Horiguchi, Hironori; Inoi, Hiroyuki; et al.

JAEA-Review 2020-056, 51 Pages, 2021/03

JAEA-Review-2020-056.pdf:3.26MB

A group named as "The group for investigation of reasonable safety assurance based on graded approach", which consists of about 10 staffs from Sector of Nuclear Science Research, Safety and Nuclear Security Administration Department, departments for management of nuclear facility, Sector of Nuclear Safety Research and Emergency Preparedness, aims to realize effective graded approach (GA) about management of facilities and regulatory compliance of JAEA. The group started its activities in September, 2019 and has had discussions through 10 meetings and email communications. In the meetings, basic ideas of GA, status of compliance with new regulatory standards at each facility, new inspection system, etc were discussed, while individual investigation at each facility were shared among the members. This report is compiled with expectation that it will help promote rational and effective safety management based on GA by sharing contents of the activity widely inside and outside JAEA.

Density Functional Theory (DFT)-based bonding analysis correlates ligand field strength with Ru Mssbauer parameters of ruthenium-nitrosyl complexes

Kaneko, Masashi; Kato, Akane*; Nakashima, Satoru*; Kitatsuji, Yoshihiro

Inorganic Chemistry, 58(20), p.14024 - 14033, 2019/10

https://doi.org/10.1021/acs.inorgchem.9b02024

We applied density functional theory calculations to ruthenium-nitrosyl complexes, which are known to exist in high-level radioactive waste, to give a theoretical correlation between Ru Mssbauer spectroscopic parameters ( and ) and ligand field strength () for the first time. The structures of the series of complexes, [Ru(NO)L] (L = Br, Cl, NH, CN), were modeled based on the corresponding single-crystal X-ray coordinates. The comparisons of the geometries and total energies between the different spin states suggested that the singlet spin state of [Ru(II)(NO)L] complexes were the most stable. The calculated results of both the and values reproduced the experimental results by reported previously and increased in the order of L = Br, Cl, NH, CN. Finally, we estimated the ligand field strength () based on molecular orbitals, assuming C symmetry and showed the increase of values in that order, being consistent with well-known spectrochemical series of ligands. The increase attributes to the strengthening of the abilities of -donor and -acceptor of the L-ligands to the Ru atom, resulting in the increase of the values.

Study on loss-of-cooling and loss-of-coolant accidents in spent fuel pool, 4; Investigation of fuel loading effects in BWR spent fuel rack

Tojo, Masayuki*; Kanazawa, Toru*; Nakashima, Kazuo*; Iwamoto, Tatsuya*; Kobayashi, Kensuke*; Goto, Daisuke*; Nemoto, Yoshiyuki; Kaji, Yoshiyuki

Proceedings of 27th International Conference on Nuclear Engineering (ICONE-27) (Internet), 13 Pages, 2019/05

In this study, fuel loading effects in BWR spent fuel rack accidents are widely investigated using three-dimensional analysis methods from both nuclear and thermal hydraulics viewpoints, including: (a) Decay heat of spent fuel after discharge, (b) The maximum temperature of spent fuel cladding in the spent fuel rack depending on heat transfer phenomena, and (c) Criticality of the spent fuel rack after collapsing of the fuel due to a severe accidents in the BWR spent fuel pool (SFP).

On/off spin-crossover phenomenon and control of the transition temperature in assembled Iron(II) complexes

Nakashima, Satoru*; Kaneko, Masashi; Yoshinami, Keisuke*; Iwai, Saki*; Dote, Haruka*

Hyperfine Interactions, 239(1), p.39_1 - 39_15, 2018/12

https://doi.org/10.1007/s10751-018-1512-4

The present study reveals the on/off of spin-crossover (SCO) phenomenon in assembled Fe(II) complexes bridged by bis(pyridyl) type ligand. Whether SCO phenomenon occurs or not in assembled Fe(II) complexes bridged by bis(pyridyl) type ligand is determined by local structure around iron atom. SCO phenomenon occurs when the coordinating pyridines facing to each other across the iron atom are propeller type, while the phenomenon does not occur when they are parallel type or distorted propeller type. DFT calculation explained that, in the shortening of Fe-pyridine bonds when changing from high-spin state to low-spin state, the pyridines of propeller type can approach the iron atom with smaller steric hindrance than those of parallel and distorted propeller type complexes. The local structure is controlled by introducing methyl substituent and introducing -system, changing SCO phenomenon. And the transition temperature of SCO is also controlled in assembled complexes bridged by 1,2-bis(4-pyridyl)ethane by mixing anionic ligand.

Study on oxidation model for Zircalloy-2 cladding in SFP accident condition

Nemoto, Yoshiyuki; Kaji, Yoshiyuki; Onizawa, Takashi*; Kanazawa, Toru*; Nakashima, Kazuo*; Tojo, Masayuki*

Proceedings of Annual Congress of the European Federation of Corrosion (EUROCORR 2018) (USB Flash Drive), 8 Pages, 2018/09

The authors proposed oxidation models based on oxidation data which previously obtained in high temperature oxidation tests on small sample of Zircalloy-2 (Zry2) cladding in dry air and in air/steam mixture environment. The oxidation models were implemented in computational fluid dynamics (CFD) code to analyse oxidation behavior of long cladding sample in hypothetical spent fuel pool (SFP) accident conditions. The oxidation tests were conducted using Zry2 cladding sample 500 mm in length. The oxide layer growth in dry air was well reproduced in the calculation using the oxidation model, meanwhile which in air/steam mixture was overestimated atmosphere composition change anticipated in the spent fuel rack during the accident, and its influence on the oxidation behaviour of the cladding were discussed in consideration of the oxidation model improvement.

Bonding study on trivalent europium complexes by combining Mssbauer isomer shifts with density functional calculations

Kaneko, Masashi; Watanabe, Masayuki; Miyashita, Sunao*; Nakashima, Satoru*

Radioisotopes, 66(8), p.289 - 300, 2017/08

https://doi.org/10.3769/radioisotopes.66.289

Scalar-relativistic density functional calculations applied to some trivalent europium complexes. Five Eu(III) complexes whose Eu Mssbauer isomer shifts vary from -1.8 to 0.5 mm/s are referred by previously reported results. Geometrical optimizations of their complexes reproduces the experimental coordination structures. Single-point calculations are applied to their optimized geometries at three density functionals, namely, BP86, B3LYP, and B2PLYP, to obtain their electron densities at Eu nucleus. A comparison of the linearity between the electron densities and the corresponding Eu Mssbauer isomer shifts reveals that B2PLYP functional shows the best linearity. Electron population and bond analyses indicate that d- and f-orbital electrons of Eu ion in the complexes are found to be correlated to the experimental Eu Mssbauer isomer shifts. This indicates that the d- and f-orbital electrons are involved in the covalent interaction of the coordination bond between the Eu ion and the ligands.

Roles of d- and f-orbital electrons in the complexation of Eu(III) and Am(III) ions with alkyldithiophosphinic acid and alkylphosphinic acid using scalar-relativistic DFT calculations

Kaneko, Masashi; Watanabe, Masayuki; Miyashita, Sunao*; Nakashima, Satoru*

Journal of Nuclear and Radiochemical Sciences (Internet), 17, p.9 - 15, 2017/03

http://www.radiochem.org/en/paper/JN171/jn17102.pdf

Density functional calculations were applied to the complexation of Eu(III) and Am(III) ions with phosphinic acid (O-donor) and dihiophosphinic acid (S-donor) from the viewpoint of the bonding nature of valence orbitals in metal ion. Two and four conformers for S-donor and O-donor complexes, respectively were optimized. Their stabilization energies by complex formation toward [M(HO)] were estimated. As the result, the energies reproduced the experimental Am(III)/Eu(III) selectivity that O-donor ligand preferably coordinates to Eu(III) ion, whereas S-donor ligand selectively coordinates to Am(III) ion. Focused on the bonding natures of d and f-orbital electrons, it was indicated that the d-orbital electrons in both Eu and Am complexes participate in the covalency as bonding-type nature and have the almost same contribution. Meanwhile, the contribution of the f-orbital electrons was different between Eu and Am complexes and indicated that in the case of S-donor complex, non-bonding type and bonding type contributions were observed for Eu and Am complexes, respectively and in the case of O-donor complex, bonding type and anti-bonding type contributions were observed for Eu and Am complexes, respectively. This result suggested that the bonding natures of d-orbital electrons contribute to the geometrical similarity of molecular structures for Eu and Am complexes and the bonding natures of f-orbital electrons contribute to the difference in the selectivity of Eu and Am ions.