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Journal Articles

Complexation and bonding studies on [Ru(NO)(H$$_{2}$$O)$$_{5}$$]$$^{3+}$$ with nitrate ions by using density functional theory calculation

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

RSC Advances (Internet), 10(41), p.24434 - 24443, 2020/06

 Times Cited Count:1 Percentile:34.67(Chemistry, Multidisciplinary)

Complexation reactions of ruthenium-nitrosyl complexes in HNO$$_{3}$$ solution were investigated by density functional theory (DFT) calculations in order to predict the stability of Ru species in high-level radioactive liquid waste (HLLW) solution. Equilibrium structure of [Ru(NO)(NO$$_{3}$$)$$_{3}$$(H$$_{2}$$O)$$_{2}$$] obtained by DFT calculations reproduced the experimental Ru-ligands bond lengths and IR frequencies reported previously. Comparison of the Gibbs energies among the geometrical isomers revealed that the complexation reactions of the ruthenium-nitrosyl complexes with NO$$_{3}$$$$^{-}$$ proceed via the NO$$_{3}$$$$^{-}$$ coordination to the equatorial plane toward the Ru-NO axis. We also estimated Gibbs energy differences on the stepwise complexation reactions to succeed in reproducing the fraction of Ru-NO species in 6 M HNO$$_{3}$$ solution, such as in HLLW, by considering the association energy between the Ru-NO species and the substituting ligands. Electron density analyses of the complexes indicated that the strength of the Ru-ligands coordination bonds depends on the stability of the Ru species and the Ru complex without NO$$_{3}$$$$^{-}$$ at the axial position is more stable than that wit NO$$_{3}$$$$^{-}$$, which might attribute to the difference in the trans influence between H$$_{2}$$O and NO$$_{3}$$$$^{-}$$. Finally, we demonstrated the complexation kinetics in the reactions $$x = 1 rightarrow x = 2$$. The present study is expected to enable us to model the precise complexation reactions of platinum-group metals in HNO$$_{3}$$ solution.

Journal Articles

Density Functional Theory (DFT)-based bonding analysis correlates ligand field strength with $$^{99}$$Ru M$"o$ssbauer parameters of ruthenium-nitrosyl complexes

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

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

 Times Cited Count:1 Percentile:74.85(Chemistry, Inorganic & Nuclear)

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 $$^{99}$$Ru M$"o$ssbauer spectroscopic parameters ($$delta$$ and $$Delta$$$$E_{rm Q}$$) and ligand field strength ($$Delta$$$$_{rm o}$$) for the first time. The structures of the series of complexes, [Ru(NO)L$$_{5}$$] (L = Br$$^{-}$$, Cl$$^{-}$$, NH$$_{3}$$, 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$$_{5}$$] complexes were the most stable. The calculated results of both the $$delta$$ and $$Delta$$$$E_{rm Q}$$ values reproduced the experimental results by reported previously and increased in the order of L = Br$$^{-}$$, Cl$$^{-}$$, NH$$_{3}$$, CN$$^{-}$$. Finally, we estimated the ligand field strength ($$Delta$$$$_{rm o}$$) based on molecular orbitals, assuming C$$_{rm 4v}$$ symmetry and showed the increase of $$Delta$$$$_{rm o}$$ values in that order, being consistent with well-known spectrochemical series of ligands. The increase attributes to the strengthening of the abilities of $$sigma$$-donor and $$pi$$-acceptor of the L-ligands to the Ru atom, resulting in the increase of the $$delta$$ values.

Journal Articles

Extraction method of swimming trajectory for behavior analysis of medaka (${it Oryzias Latipes}$)

Matsuda, Asahi*; Takahashi, Satoru*; Kawabata, Kuniaki; Oda, Shoji*; Kaneko, Shunichi*

Denki Gakkai Rombunshi, D, 139(4), p.424 - 432, 2019/04

Journal Articles

Benchmark study of DFT with Eu and Np M$"o$ssbauer isomer shifts using second-order Douglas-Kroll-Hess Hamiltonian

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

Hyperfine Interactions, 239(1), p.20_1 - 20_10, 2018/12

 Times Cited Count:0 Percentile:100

We optimized a mixing ratio of exchange energy between pure DFT and exact Hartree-Fock using TPSS exchange-correlation functional to estimate the accurate coordination bonds in f-block complexes by numerically benchmarking with the experimental data of M$"o$ssbauer isomer shifts for $$^{151}$$Eu and $$^{237}$$Np nuclides. Second-order Douglas-Kroll-Hess Hamiltonian with segmented all-electron relativistically contracted basis set was employed to calculate the electron densities at Eu and Np nuclei, i.e. contact densities, for each five complexes for Eu(III) and Np(IV) systems. We compared the root mean square deviation values of their isomer shifts between experiment and calculation by changing the mixing ratio of Hartree-Fock exchange parameter from 0 to 100 % at intervals of 10 %. As the result, it was indicated that the mixing ratio of 30 and 60 % for Eu and Np benchmark systems, respectively, gives the smallest deviation values. Mulliken's spin population analysis indicated that the covalency in the metal-ligand bonds for both Eu and Np complexes decreases with increasing the Hartree-Fock exchange admixture.

Journal Articles

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

 Times Cited Count:1 Percentile:33.33

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 $$pi$$-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.

Journal Articles

Computational chemical analysis of Eu(III) and Am(III) complexes with pnictogen-donor ligands using DFT calculations

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

Dalton Transactions (Internet), 47(42), p.14924 - 14931, 2018/11

 Times Cited Count:2 Percentile:73.48(Chemistry, Inorganic & Nuclear)

We demonstrated density functional calculations of Eu(III) and Am(III) complexes with pnictogen-donor (X) ligands, CH$$_{3}$$)$$_{2}$$X-CH$$_{2}$$-CH$$_{2}$$-X(CH$$_{3}$$)$$_{2}$$ (X = N, P, As and Sb). We investigated the optimized structures of the cmoplexes and the Gibbs energy differences in the complex formation reactions. Those results indicated that the N- and P-donor ligands have Am(III) ion selectivity over Eu(III) ion, especially, the P-donor ligand showed the highest selectivity. The tendency of the Am(III)/Eu(III) selectivity by the pnictogen-dono ligands was found to be comparable to that of soft acid classification in hard and soft acids and bases rule. Mulliken's spin population analysis indicated that the bonding property between the metal ion and the pnictogen atoms correlated with the Am(III)/Eu(III) selectivity. In particular, the participation of f-orbital electrons of the metal ion in the covalency was indicated to have an important role for the selectivity.

Journal Articles

Application of JSME Seismic Code Case by elastic-plastic response analysis to practical piping system

Otani, Akihito*; Kai, Satoru*; Kaneko, Naoaki*; Watakabe, Tomoyoshi; Ando, Masanori; Tsukimori, Kazuyuki*

Proceedings of 2018 ASME Pressure Vessels and Piping Conference (PVP 2018), 10 Pages, 2018/07

This paper demonstrates an application result of the JSME Seismic Code Case to an actual complex piping system. The secondary coolant piping system of Japanese Fast Breeder Reactor, Monju, was selected as a representative of the complex piping systems. The elastic-plastic time history analysis for the piping system was performed and the piping system has been evaluated according to the JSME Seismic Code Case. The evaluation by the Code Case provides a reasonable result in terms of the piping fatigue evaluation that governs seismic integrity of piping systems.

Journal Articles

Estimation of $$Delta$$${it R}$/${it R}$ values by benchmark study of the M$"o$ssbauer Isomer shifts for Ru, Os complexes using relativistic DFT calculations

Kaneko, Masashi; Yasuhara, Hiroki*; Miyashita, Sunao*; Nakashima, Satoru*

Hyperfine Interactions, 238(1), p.36_1 - 36_9, 2017/11

AA2016-0447.pdf:0.46MB

 Times Cited Count:1 Percentile:29.73

We aim to evaluate the validity of density functional calculations to the bonding property for Ru and Os complexes. We performed the benchmarking of theoretical computational method with $$^{99}$$Ru, $$^{189}$$Os M$"o$ssbauer isomer shifts. As the result, the computational values of the electron densities at nucleus position correlated with the experimental M$"o$ssbauer isomer shifts.

Journal Articles

Bonding study on trivalent europium complexes by combining M$"o$ssbauer isomer shifts with density functional calculations

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

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

Scalar-relativistic density functional calculations applied to some trivalent europium complexes. Five Eu(III) complexes whose $$^{151}$$Eu M$"o$ssbauer 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 $$^{151}$$Eu M$"o$ssbauer 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 $$^{151}$$Eu M$"o$ssbauer 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.

Journal Articles

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

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(H$$_{2}$$O)$$_{9}$$]$$^{3+}$$ 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.

Journal Articles

A Spin-crossover phenomenon depending on the environment around an iron atom for the assembled coordination polymers

Nakashima, Satoru*; Kaneko, Masashi

Advances in Chemistry Research, Vol.36, p.171 - 195, 2017/01

Spin-crossover (SCO) phenomena of the assembled coordination polymers are introduced. When the bridging ligand is flexible like 1,2-bis(4-pyridyl)ethane, 1,3-bis(4-pyridyl)propane, a variety of assembled structure can be obtained, depending on the conformer of the ligand and the guest molecules. Guest-dependent SCO phenomena of the assembled iron complexes are shown. Density functional theory is applied to know the cause of guest-dependent SCO phenomena. The validity of an iron mono-nucleus model is evaluated for the coordination polymers. It is shown that SCO occurs or not depends on the local structure around iron ion.

Journal Articles

Generation method of underwater landmarks for ocean observation

Takahashi, Satoru*; Nota, Yoshiki*; Matsuda, Asahi*; Kawabata, Kuniaki; Suzuki, Tsuyoshi*; Takemura, Fumiaki*; Ogasawara, Kei*; Kaneko, Shunichi*

Journal of Signal Processing, 21(1), p.15 - 24, 2017/01

In recent years, many researchers try to observe the state of the global environment from marine information for the understanding of the global environment change. First, we introduce the recording system of underwater environment which is made by the authors. By using this system, we want to observe the change of global environment from the coral bleaching. In this paper, especially, we propose the generation method of underwater landmark which is used to measure the position of robot of oceanographic observation based on the dynamic image processing. In here, underwater landmark means the feature point in underwater image.

Journal Articles

Study on piping response under multiple excitation (validation for elastic-plastic analysis of piping)

Kai, Satoru*; Watakabe, Tomoyoshi; Kaneko, Naoaki*; Tochiki, Kunihiro*; Moriizumi, Makoto; Tsukimori, Kazuyuki

Proceedings of 2014 ASME Pressure Vessels and Piping Conference (PVP 2014) (DVD-ROM), 10 Pages, 2014/07

Piping in a nuclear power plant is usually laid across several floors of a single building or adjacent buildings, and is supported at many points. As the piping is excited by a large earthquake through multiple supporting points, seismic response analysis by multiple excitations within the range of plastic deformation of piping material is necessary to obtain the precise seismic response of the piping. This paper reports the validation results of the seismic elastic-plastic time history analysis of piping compared with the results of the shaking test of a 3-dimensional piping model under a plastic deformation range using triple uni-axial shake table.

Journal Articles

Study on piping response under multiple excitation; Validation for multiple excitation analysis of piping

Kai, Satoru*; Watakabe, Tomoyoshi; Kaneko, Naoaki*; Tochiki, Kunihiro*; Moriizumi, Makoto; Tsukimori, Kazuyuki

Dynamics and Design Conference 2013 (D&D 2013) Koen Rombunshu (USB Flash Drive), 10 Pages, 2013/08

The piping in a nuclear power plant is laid across multiple floors of a single building or multiple buildings which support the piping at many points. As the piping is excited by multiple-inputs from the supporting points during an earthquake, seismic response analysis by multiple excitations is needed to obtain the exact seismic response of the piping. However, only a few experiments involving such multiple excitations have been performed to verify the validity of multiple excitation analysis. To perform rational seismic design and evaluation, it is important to investigate the seismic response by multiple excitations and to verify the validity of the analytical method by multiple excitation tests. This paper reports the validation results of the multiple excitation analysis of piping compared with the results of the multiple excitations shaking test using triple uni-axial shaking table and a 3-dimensional piping model.

Journal Articles

Study on piping response under multiple excitation, 2; Validation for multiple analysis of piping

Kai, Satoru*; Watakabe, Tomoyoshi; Kaneko, Naoaki*; Tochiki, Kunihiro*; Moriizumi, Makoto; Tsukimori, Kazuyuki

Proceedings of 2013 ASME Pressure Vessels and Piping Conference (PVP 2013) (DVD-ROM), 9 Pages, 2013/07

The piping in a nuclear power plant is laid across multiple floors of a single building or two buildings, which are supported at many points. As the piping is excited by multiple inputs from the supporting points during an earthquake, seismic response analysis by multiple excitations is needed to obtain the exact seismic response of the piping. However, few experiments involving such multiple excitations have been performed to verify the validity of multiple excitation analysis. To perform rational seismic design and evaluation, it is important to investigate the seismic response by multiple excitations and verify the validity of the analysis method by multiple excitation test. This paper reports the validation result of the multiple excitation analysis of piping compared with the results of the multiple excitations shaking test by using triple uni-axial shaking table and a 3-dimensional piping model (89.1 mm diameter and 5.5 mm thickness).

Journal Articles

Isotope dilution inductively coupled plasma mass spectrometry for determination of $$^{126}$$Sn content in spent nuclear fuel sample

Asai, Shiho; Toshimitsu, Masaaki; Hanzawa, Yukiko; Suzuki, Hideya; Shinohara, Nobuo; Inagawa, Jun; Okumura, Keisuke; Hotoku, Shinobu; Kimura, Takaumi; Suzuki, Kensuke*; et al.

Journal of Nuclear Science and Technology, 50(6), p.556 - 562, 2013/06

 Times Cited Count:7 Percentile:41.73(Nuclear Science & Technology)

The $$^{126}$$Sn content in a spent nuclear fuel solution was determined by ICP-MS for its inventory estimation in high-level radioactive waste. An irradiated UO$$_{2}$$ fuel was used as a sample to evaluate the reliability of the methodology. Prior to the measurement, Sn was separated from $$^{126}$$Te, which causes major isobaric interference in the determination of $$^{126}$$Sn content, along with highly radioactive coexisting elements using an anion-exchange column. The absence of counts attributed to Te in the Sn-containing effluent indicates that Te was completely removed. After washing, Sn retained on the column was readily eluted with 1 M HNO$$_{3}$$. The isotope ratios of Sn were successfully determined and showed good agreement with those obtained through ORIGEN2 calculations. The results reported in this paper are the first experimental values of $$^{126}$$Sn content in the spent nuclear fuel solution originating in spent nuclear fuel irradiated at a nuclear power plant in Japan.

Journal Articles

Uniaxial-pressure control of magnetic phase transitions in a frustrated magnet CuFe$$_{1-x}$$Ga$$_{x}$$O$$_{2}$$ (x =0, 0.018)

Nakajima, Taro*; Mitsuda, Setsuo*; Takahashi, Keiichiro*; Yoshitomi, Keisuke*; Masuda, Kazuya*; Kaneko, Chikafumi*; Homma, Yuki*; Kobayashi, Satoru*; Kitazawa, Hideaki*; Kosaka, Masashi*; et al.

Journal of the Physical Society of Japan, 81(9), p.094710_1 - 094710_8, 2012/09

Journal Articles

Uniaxial-pressure control of magnetic phase transitions in a frustrated magnet CuFe$$_{1-x}$$Ga$$_{x}$$O$$_{2}$$ ($$x$$ = 0, 0.018)

Nakajima, Taro*; Mitsuda, Setsuo*; Takahashi, Keiichiro*; Yoshitomi, Keisuke*; Masuda, Kazuya*; Kaneko, Chikafumi*; Homma, Yuki*; Kobayashi, Satoru*; Kitazawa, Hideaki*; Kosaka, Masashi*; et al.

Journal of the Physical Society of Japan, 81(9), p.094710_1 - 094710_8, 2012/09

 Times Cited Count:10 Percentile:39.9(Physics, Multidisciplinary)

Journal Articles

Simple cation-exchange separation for ICP-MS measurement of $$^{79}$$Se in spent nuclear fuel sample

Asai, Shiho; Hanzawa, Yukiko; Suzuki, Hideya; Toshimitsu, Masaaki; Okumura, Keisuke; Shinohara, Nobuo; Kimura, Takaumi; Inagawa, Jun; Suzuki, Kensuke*; Kaneko, Satoru*

Proceedings of International Conference on Toward and Over the Fukushima Daiichi Accident (GLOBAL 2011) (CD-ROM), 5 Pages, 2011/12

Journal Articles

New ORIGEN2 libraries based on JENDL-4.0 and their validation for long-lived fission products by post irradiation examination analyses of LWR spent fuels

Kojima, Kensuke; Okumura, Keisuke; Asai, Shiho; Hanzawa, Yukiko; Okamoto, Tsutomu; Toshimitsu, Masaaki; Inagawa, Jun; Kimura, Takaumi; Kaneko, Satoru*; Suzuki, Kensuke*

Proceedings of International Conference on Toward and Over the Fukushima Daiichi Accident (GLOBAL 2011) (CD-ROM), 5 Pages, 2011/12

Accurate inventory estimation of long-lived fission products (LLFPs) in LWR spent fuels is important for the quality management and for long-term safety assessment of high-level radioactive vitrified wastes. In Japan, ORIGEN2 has been widely used to estimate the fuel compositions. However, equipped library data in the original ORIGEN2 are old and are not validated enough for LLFPs, such as $$^{79}$$Se, $$^{99}$$Tc, $$^{126}$$Sn and $$^{135}$$Cs, because available post irradiation examination (PIE) data are limited for these nuclides, which have difficulties in radiochemical analyses. For more accurate the estimation, new ORIGEN2 libraries are developed from the latest nuclear data library JENDL-4.0 for cross sections and fission yields, and from other libraries for half-lives, and so on. The new libraries are validated by PIE analyses of the sample fuels irradiated in Cooper, Calvert-Cliffs-1, H. B. Robinson-2, and Ohi-1. As a result, it was found that the new library gives good results for the estimation.

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