Density functional theory study on the Ir Mssbauer spectroscopic parameters of Vaska's complexes and their oxidative adducts

Kaneko, Masashi; Nakashima, Satoru*

Inorganic Chemistry, 60(17), p.12740 - 12752, 2021/09

https://doi.org/10.1021/acs.inorgchem.1c00239

In the present study, density functional theory (DFT) calculation was applied to Vaska's complexes of formula -[IrCl(CO)(PPh)], and their oxidative adducts with small molecules (YZ) including H, i.e., -[IrCl(YZ)(CO))(PPh)], to successfully correlate the electronic states of the complexes with the corresponding Ir Mssbauer spectroscopic parameters. After confirming the reproducibility of the DFT methods for elucidating the equilibrium structures and Ir Mssbauer isomer shifts of the octahedral Ir complexes, the isomer shifts and quadrupole splitting values of Vaska's complexes and their oxidative adducts were calculated. A bond critical point analysis revealed that the tendency in the isomer shifts was correlated with the strength of the covalent interaction in the coordination bonds. In an electric field gradient (EFG) analysis of the oxidative adducts, the sign of the principal axis was found to be positive for the complex with YZ = Cl and negative for the complex with YZ = H. This reversal of the sign of the EFG principal axis was caused by the difference in the electron density distribution for the coordination bonds between Ir and YZ, according to a density of states analysis.

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.

Estimation of / values by benchmark study of the Mssbauer 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

https://doi.org/10.1007/s10751-017-1413-y

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 Ru, Os Mssbauer isomer shifts. As the result, the computational values of the electron densities at nucleus position correlated with the experimental Mssbauer isomer shifts.

Bonding study on d- and f-block coordination compounds by combining density functional calculations with Mssbauer spectroscopic parameters

Kaneko, Masashi

Hosha Kagaku, (35), p.36 - 39, 2017/03

http://www.radiochem.org/pdf/rad_nw35.pdf

This paper is an article for research introduction by winner of the Japan Society of Nuclear and Radiochemical Sciences Encouragement Price 2016. It was mentioned about the achievements which revealed the spin transition behavior of iron complex and the separation mechanism of actinides from lanthanides.

Ni synchrotron radiation-based Mssbauer spectroscopy of nickel-based nanoparticles with hexagonal structure

Masuda, Ryo*; Kobayashi, Yasuhiro*; Kitao, Shinji*; Kurokuzu, Masayuki*; Saito, Makina*; Yoda, Yoshitaka*; Mitsui, Takaya; Hosoi, Kohei*; Kobayashi, Hirokazu*; Kitagawa, Hiroshi*; et al.

Scientific Reports (Internet), 6, p.20861_1 - 20861_8, 2016/02

https://doi.org/10.1038/srep20861

Fe polarization dependent synchrotron Mssbauer spectroscopy using a diamond phase plate and an iron borate nuclear Bragg monochromator

Mitsui, Takaya; Imai, Yasuhiko*; Masuda, Ryo*; Seto, Makoto*; Mibu, Ko*

Journal of Synchrotron Radiation, 22(2), p.427 - 435, 2015/03

https://doi.org/10.1107/S1600577514028306

Development of Te synchrotron-radiation-based Mssbauer spectroscopy

Kurokuzu, Masayuki*; Kitao, Shinji*; Kobayashi, Yasuhiro*; Saito, Makina*; Masuda, Ryo*; Mitsui, Takaya; Yoda, Yoshitaka*; Seto, Makoto*

Hyperfine Interactions, 226(1), p.687 - 691, 2014/04

https://doi.org/10.1007/s10751-013-0995-2

Synchrotron radiation-based Mssbauer spectra of Yb measured with internal conversion electrons

Masuda, Ryo*; Kobayashi, Yasuhiro*; Kitao, Shinji*; Kurokuzu, Masayuki*; Saito, Makina*; Yoda, Yoshitaka*; Mitsui, Takaya; Iga, Fumitoshi*; Seto, Makoto

Applied Physics Letters, 104(8), p.082411_1 - 082411_5, 2014/02

https://doi.org/10.1063/1.4866280

A detection system for synchrotron-radiation (SR)-based Mssbauer spectroscopy was developed to enhance the nuclear resonant scattering counting rate and thus increase the available nuclides. In the system, a windowless avalanche photodiode (APD) detector was combined with a vacuum cryostat to detect the internal conversion (IC) electrons and fluorescent X-rays accompanied by nuclear de-excitation. As a feasibility study, the SR-based Mssbauer spectrum using the 76.5 keV level of Yb was observed without Yb enrichment of the samples. The counting rate was five times higher than that of our previous system, and the spectrum was obtained within 10 h. This result shows that nuclear resonance events can be more efficiently detected by counting IC electrons for nuclides with high IC coefficients. Furthermore, the windowless detection system enables us to place the sample closer to the APD elements and is advantageous for nuclear resonant inelastic scattering measurements. Therefore, this detection system can not only increase the number of nuclides accessible in SR-based Mssbauer spectroscopy but also allows the nuclear resonant inelastic scattering measurements of small single crystals or enzymes with dilute probe nuclides that are difficult to measure with the previous detection system.

Radiochemical studies of iodine, tritium and neptunium

Saeki, Masakatsu

JAERI-Review 2004-011, 54 Pages, 2004/03

JAERI-Review-2004-011.pdf:5.21MB

In this review, experimental results on studies of radioactive iodine, tritium and neptunium are summarized. On studies of radioactive iodine, from various experimental results, the process establishing the formation mechanism of organic iodides was fully described. On the basis of formation mechanism, possibilities for the formation of organic iodides under nuclear reactor accidents and so on were also discussed. On studies of tritium, three topics were concisely described on the isotopic composition of tritium gases, the chemical forms and the diffusivity of tritium in various materials, and the sorption and desorption behaviors of tritium on surfaces of various materials. On the neptunium chemistry, the relationship between the structure of neptunium compound and the Moessbauer isomer shift and experimental results on neptunyl(VI) hydroxides were discussed.

U Mssbauer study of UPt

Tsutsui, Satoshi; Nakada, Masami; Nasu, Saburo*; Haga, Yoshinori; Yamamoto, Etsuji; Kimura, Noriaki*; Onuki, Yoshichika

Journal of Magnetism and Magnetic Materials, 226-230(Part.1), p.87 - 88, 2001/05

no abstracts in English