Project 7 Project Research on Advances in Isotope-Specific Studies Using Muti-Element Mössbauer Spectroscopy (R3P7)

概要

TITLE:

Project 7 Project Research on Advances in
Isotope-Specific Studies Using Muti-Element
Mössbauer Spectroscopy (R3P7)

AUTHOR(S):

Seto, M.

CITATION:

Seto, M.. Project 7 Project Research on Advances in Isotope-Specific Studies Using Muti-Element Mössbauer
Spectroscopy (R3P7). KURNS Progress Report 2022, 2021: 71-85

ISSUE DATE:
2022-07

URL:
http://hdl.handle.net/2433/275843
RIGHT:

I-1.

PROJECT RESEARCHES
Project 7

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PR7

Project Research on Advances in Isotope-Specific Studies Using Muti-Element
Mössbauer Spectroscopy

M. Seto
Institute for Integrated Radiation and Nuclear Science,
Kyoto University
OBJECTIVES OF RESEARCH PROJECT:
One of the most irreplaceable features of the Mössbauer
spectroscopy is to extract several information such as
electronic states for a specific isotope. The main objectives of this project research are the investigation in the
frontier of the materials science and the development of
advanced experimental methods by using multi-element
Mössbauer spectroscopy. Promotion of variety of Mössbauer isotope provides more useful and valuable methods
in modern materials science even for complicated systems.
In this project research, each group performed their research by specific isotopes:
57
Fe in P7-1, P7-2, P7-3, P7-4, P7-5, P7-9, and P7-13
61
Ni in P7-8
119
Sn in P2-5, P7-7 and P7-10
151
Eu in P2-5, P7-9, P7-10 and P7-11
197
Au in P7-6 and P7-7
Other isotopes in P7-11 and P7-12
MAIN SUBJECTS AND RESULTS OF THIS REPORT:
Main subjects and results from these researches are as
follows:
(P7-1, K. Shinoda) Intensity Tensor of Fe2+ in the M2
Site of Hypersthene by Single Crystal Mössbauer Microspectroscopy
K. Shinoda et al. characterized the electric field gradient tensor of single crystals of hypersthene as small
as 1mm3 by developed Mössbauer microspectrometer.
(P7-2, H. Fujii) Mössbauer Study of the Model Complexes of Heme Enzymes
H. Fujii et al. investigated model complexes of cytochrome P450 in different solvents of acetonitrile, tetrahydrofuran and methanol to obtain comparable results
from the EPR experiments.
(P7-3, Y. Akiyama) Analysis of Iron-based Products
Using Mössbauer Spectroscopy - Iron Oxide Scale
Generated in the Boiler Feed-water in Thermal Power
Plant Y. Akiyama et al. are investigating a design for the
magnetic separation system of the iron oxide scale from
power plant through evaluation of ferromagnetic and
paramagnetic components.
(P7-4, I. Mashino) Electrical Conductivity and the
Iron Valence State of Enstatite Glasses up to Mbar

R3P7
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Pressures
I. Mashino et al. investigated pressure dependence of
electrical conductivity of Fe-bearing enstatite glasses.
The Mössbauer spectroscopy is used to determine the
composition ratio of Fe2+ and Fe3+components.
(P7-5, Y. Matsushi) The Role of Iron in the Differential Weathering Processes of Volcanic Fall Deposit
H. Fukui et al. investigated several soil samples with
different weathering patten to reveal the crucial role of
iron in the weathering process.
(P7-6, H. Ohashi) Rough Estimation of Debye Temperature for Precursor of Supported Gold Cluster Catalysts Derived from Recoil-Free Fraction in 197Au
Mössbauer Spectroscopy
H. Ohashi et al. investigated Au2Sx, a precursor of
supported Au cluster and evaluated its Debye temperature, which was quite low but appropriate as Au catalysts.
(P7-7, Y. Kobayashi) Recoilless Fraction on 197Au
Mössbauer Spectroscopy
Y. Kobayashi has investigated the evaluation method
of the Debye temperature for Au compounds.
(P7-8, T. Kitazawa) 61Ni Mössbauer Spectroscopy for
Supramolecular Bridging Cyanide Complexes
T. Kitazawa et al. have investigated several Ni cyanides to evaluate slight difference of Ni environments.
(P7-9, H. Wadachi) Mössbauer Spectroscopy of a
Perovskite-Type Iron Oxide Ba2/3La1/3FeO3
M. Onose et al. have revealed the temperature dependence of Mössbauer spectra of Ba2/3La1/3FeO3 to
find the magnetic structure of spin charge ordering.
(P7-10, Y. Kamihara) Research on Magnetism in a
Novel Kondo Lattice III
Y. Kamihara et al. studied the temperature dependence of EuSn2P2 by using both 151Eu and 119Sn Mössbauer spectroscopy to elucidate its magnetic ordering.
(P7-11, R. Masuda) Optimization for the Energy
Standard Material for Mössbauer Spectroscopy
R. Masuda et al. evaluated the efficiency of a standard material for Mössbauer spectroscopy using EuF3.
(P7-12, S. Kitao) Development of 180Hf Mössbauer
Spectroscopy
S. Kitao et al. have attempted to observe 180Hf Mössbauer spectra using a HfC source material.
(P7-13, K. Yonezu) Experimental Preliminary Approach on the Precipitation Mechanism of Banded Iron
Formation (BIF)
K. Yonezu et al. are investigating sedimentary rock to
understand its formation mechanism.

PR7-1

Intensity tensor of Fe2+ in the M2 site of hypersthene by single crystal Mössbauer
microspec-troscopy

K. Shinoda1, K. Onoue1, Y. Kobayashi2
1

Department of Geosciences, Graduate School of Science, Osaka Metropolitan University
2
Institute for Integrated Radiation and Nuclear Science,
Kyoto University
INTRODUCTION: Pyroxene is a major rock-forming
mineral and a typical multi-site solid solution. Common
chemical formula of natural pyroxene is (Ca, Fe, Mg)2 Si2
O6. Occupying sites of divalent cations are the M1 and M2
sites. In pyroxene, Fe2+ in M1, Fe2+ in M2 and Fe3+ in M1
sites are possible. Fe2+ in the M1 site shows a little wider
quadrupole doublet than Fe2+ in the M2 site in Mössbauer
spectra. Fe3+ in the M1 site shows the narrower quadrupole
doublet than Fe2+. Intensities of component peaks in a
quadrupole doublet of a thin section as a single crystal are
asymmetric and vary depending on the angle between the
direction of incident g-rays and the crystallographic orientation of the thin section. Intensity of quadrupole doublet
(Ih / Itotal ) means a ratio between area of the peak of the
higher energy (Ih) and total area of the doublet (Itotal= Ih +
Il) (sum of Ih and area of the lower energy (Il)). In tensity
of quadrupole doublet can be calculated from the intensity
tensor. In Mössbauer spectrum of pyroxene in which three
doublets are overlapping, it is important to know intensity
tensors of the three doublets to separate overlapping doublets. Zimmermann (1975, 1983) showed relationships between the intensity tensor and electric field gradient (EFG)
tensor and introduced experimental determination of the
intensity tensor from the Mössbauer spectrum of a single
crystal. Shinoda and Kobayashi (2019) revealed EFG tensor due to Fe2+ in M2 site of ortho-enstatite, which is orthorhombic Fe-poor pyroxene of chemical formula (Mg2.03,
Fe0.16) (Si1.78, Al0.13) O6. However, the intensity tensor of
Fe-rich orthopyroxene has not been revealed. In this study,
the intensity tensor of Fe2+ at the M2 site of hypersthene
(Ca0.06, Mg1.26, Fe0.68) (Si1.95, Al0.05) O6 by EDS analyses
were determined by single crystal 57Fe Mössbauer spectra
using crystallographically oriented thin sections.
EXPERIMENTS and RESULTS: Single crystals of hypersthene as small as 1mm3 from Inawashiro-ko, Aizuwakamatsu, Fukushima, Japan were used for this study.
Three crystallographically oriented thin sections perpendicular to a*, b* and c* were prepared by measuring Xray diffraction using Laue and precession camera. Seven
Mössabuer spectra of oriented thin sections were measured.
In this study, Cartesian coordinate (X Y Z) is set as X//c*,
Y//a*, Z//b*, where a*, b*, c* are reciprocal lattice vectors

of hypersthene. Mössbauer measurements were carried out
in transmission mode on a constant acceleration spectrometer with an Si-PIN semiconductor detector (XR-100CR,
AMPTEK Inc.) and multi-channel analyzer of 1024 channels. A 3.7GBq 57Co/Rh of 4mmf in diameter was used as
g-ray source. An 57Fe-enriched iron foil was used as velocity calibrant. The two symmetric spectra were folded and
velocity range was ±4mm/s. Thickness corrections of raw
spectra were not done.

Fig.1 Mössbauer spectrum of hypersthene measured under
g-ray parallel to the a*-axis.
Fig.1 shows Mössbauer specrtum of hypersthene measured under incident g-ray parallel to a*-axis. A doublet due
to Fe2+ in M2 site of hypersthene was observed. Averages
of isomer shift, Q-splitting, and line width were 1.15 2.13
and 0.39 mm/s, respectively. From seven sets of intensity
of quadrupole doublet, three components (IXX, IYY, and IZZ)
of the intensity tensor of Fe2+ in the M2 site of hypersthene
are obtained as 0.577, 0.453 and 0.470. three components
of the intensity tensor of Fe2+ in the M2 site of ortho-enstatite were 0.615, 0.455 and 0.424 (Shinoda and Kobayashi,
2019). Three components of the intensity tensor of Fe-poor
and Fe-rich ortho-pyroxene suggest that IXX and IZZ show
weak chemical dependence of Fe2+ and IYY is independent
of Fe2+ components.
REFERENCES
[1] Zimmermann, R. (1983) Advances in Mössbauer spectroscopy (Thosar, B.V. Ed.). pp.273-315, Elsevier
Sci-entific Publishing Co. Amsterdam.
[2] Zimmermann, R. (1975) Nucl. Instr. and Meth. 128,
537-543.
[3] Shinoda and Kobayashi (2019) KURNS Progress Report 2019.

R3P7-1
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PR7-2

Mössbauer Study of the Model Complexes of Heme Enzymes

H. Fujii, Y. Kobayashi1, A. Takeda, S. Iwamoto
5.52

Graduate School of Science, Nara Women’s University
1
Graduate School of Science, Kyoto University

5.51
x10

6

INTRODUCTION: Iron porphyrin complexes are active sites of many heme proteins in nature. For example,
cytochrome P450 generates a high-valent oxoiron(IV) porphyrin π-cation radical species called compound I in the
catalytic cycle. The oxidation state and the spin state of the
compound I are key for controlling the function of tcytochrome P450.
In this project, we prepared a model
complex (FeS) of cytochrome P450 and studied the oxidation state and the spin state of FeS by using Mössbauer
spectroscopy.

x10

6

5.13

5.12

FeS_THF
6K

5.11
5.10

EXPERIMENTS: Mössbauer spectroscopy was conducted in conventional transmission geometry by using
57
Co-in-Rh(50 mCi) as γ-ray source. ...

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