Haruhiko Yashiro

Multi-frequency and high-field EPR study of manganese(III) protoporphyrin IX reconstituted myoglobin with an S = 2 integer electron spin

We investigate the electronic state of Mn(III) center with an integer electron spin S=2 in the manganese(III) protoporphyrin IX reconstituted myoglobin, Mn(III)Mb, by means of multi-frequency electron paramagnetic resonance (MFEPR) spectroscopy. Using a bimodal cavity resonator, X-band EPR signal from Mn(III) center in the Mn(III)Mb was observed near zero-field region. The temperature dependence of this signal indicates a negative axial zero-field splitting value, D<0. The EPR analysis shows that this signal is attributed to the transition between the closely spaced M(s)=+/-2 energy levels for the z-axis, corresponding to the heme normal. To determine the zero-field splitting (ZFS) parameters, EPR experiments on the Mn(III)Mb were performed at various temperatures for some frequencies between 30GHz and 130GHz and magnetic fields up to 14T. We observed several EPR spectra which are analyzed with a spin Hamiltonian for S=2, yielding highly accurate ZFS parameters; D=-3.79cm(-1) and |E|=0.08cm(-1) for an isotropic g=2.0. These ZFS parameters are compared with those in some Mn(III) complexes and Mn(III) superoxide dismutase (SOD), and effects on these parameters by the coordination and the symmetry of the ligands are discussed. To the best of our knowledge, these EPR spectra in the Mn(III)Mb are the very first MFEPR spectra at frequencies higher than Q-band in a metalloprotein with an integer spin.

High Field and Multi-Frequency EPR in Single Crystals of Sperm Whale Met-Myoglobin: Determination of the Axial Zero-Field Splitting Constant and Frequency Dependence of the Linewidth

Electron paramagnetic resonance (EPR) measurements for frequencies from 28.5 GHz to 608.1 GHz and magnetic field up to 14 T have been performed on single crystals of sperm whale high-spin ( S =5/2) met-myoglobin. The EPR resonance field along the c * -axis deviates from the g =5.71 straight line at high frequencies. The axial zero-field splitting constant ( D ) of the met-myoglobin sample is evaluated to be 9.47±0.05 cm -1 by analyzing the resonance fields with the S =5/2 spin Hamiltonian including the D term. The angular dependence of EPR spectra in the a b plane has been also investigated at high frequencies. Two kinds of EPR spectra are observed corresponding to two kinds of different heme sites in the unit cell. A notable change in the linewidth of the spectrum along the c *-axis occurs above 350 GHz, suggesting that the dominant relaxation process changes around 350 GHz. The origins of the linewidth are discussed.

Theoretical and experimental studies of chemically induced electron-nuclear polarization in low magnetic fields

Chemically induced electron-nuclear polarization at low magnetic fields is considered theoretically for a radical with one magnetic nucleus. It is shown that large non-equilibrium populations of the radical spin levels are expected to exist under low magnetic fields. This large electron-nuclear polarization has been observed experimentally during the photolysis of two phosphine oxides using a modified L-band TREPR setup. The TREPR spectra and kinetics of dimethoxyphosphonyl and diphenylphosphonyl radicals have been measured and analysed in low magnetic fields, and excellent agreement between experiment and theory has been achieved.

Properties of trapped electromagnetic modes in coupled waveguides

The existence of trapped modes in coupled electromagnetic waveguides is experimentally investigated for configurations with different degrees of symmetry supporting hybrid modes. The occurrence of confined solutions in such open geometries is proven to be much more general than demonstrated so far, as predicted by Goldstone and Jaffe [J. Goldstone and R. L. Jaffe, Phys. Rev. B 45, 14100 (1992)]. The identification of the observed modes is based on the numerical modeling of the relative vector fields. The experimental results make evident that an increasing aperture of the configuration can improve the confinement of the mode instead of generating additional leakage channels. In particular, long-lived trapped modes can be easily obtained in geometries with a large aperture. Their resonance parameters can compete with those of standard close cavities working at millimeter wavelengths. The role of the symmetry on the properties of these trapped modes is discussed in detail.

Electron Spin Resonance in GaN Thin Film Doped with Fe

High-quality and high-resistivity semiconducting substrates are needed to fabricate high-frequency devices such as high-mobility transistors based on gallium nitride (GaN). A GaN thin film doped with Fe ions becomes one of such high-resistivity substrates. To obtain microscopic information on the Fe ions in the GaN:Fe film, we have performed electron spin resonance (ESR) measurements using a conventional X-band apparatus and home made Q-band equipment. The observed ESR signals were analyzed with a spin Hamiltonian given by considering the local symmetry of the Ga site (C3v) and assuming that the Fe3+ ions (S=5/2) are substituted for Ga3+ ions. As a result, the angular dependence of the resonance fields and the temperature dependence of the signal intensities are reproduced very well by the calculations. Consequently, we confirmed that the Fe3+ ions occupy some of the Ga sites in the GaN thin film.

Present status and future plan of research in high magnetic fields at KYOKUGEN in Osaka University

After brief introduction of history and facility of the High Magnetic Field Laboratory at KYOKUGEN in Osaka University, we describe our high field and multi-frequency electron spin resonance (ESR) apparatus by utilizing pulsed and superconducting magnets for the fields up to about 60 T. For the ESR measurements in pulsed magnetic fields, several Gunn and backward oscillators, and a far infrared laser are used as millimeter and submillimeter wave sources. In steady magnetic fields up to 16 T, we have utilized a vector network analyzer with extensions which covers the frequencies between 8 and 700 GHz almost continuously. The latter ESR apparatus is used not only dense magnetic materials but also weak ones, such as metalloproteins. Therefore, we have developed high sensitive multi-frequency ESR apparatus. To extend ESR studies further, we are now constructing ESR apparatus for much higher fields up to 70 T and the wide frequency range up to 7 THz. Magnetization and transport measurements are also performed in high magnetic fields up to 70 T and 60 T, respectively and magnetization measurements under high pressure up to 1 GPa. We plan to develop a 50 T wide bore pulsed magnet with the diameter of about 50 mm for the use of high sensitive ESR and high pressure measurements above 1 GPa.

Development of a multi-frequency ESR system with high sensitivity

We have developed a new Multi-Frequency (MF) ESR system for the frequencies between 35 to 130 GHz utilizing TE011 single mode resonators. Their sensitivities (1010spins/G at 1.5 K) are comparable to that of a conventional low frequency ESR resonator and an order of magnitude higher than that of a Fabry Perot resonator which was previously developed by us. Thanks to a newly developed precise and stable matching system, we observed for the first time MFESR spectra of a metalloprotein with an integer spin.

Magnetic properties of a Ni tetramer with a butterfly structure in high magnetic fields

We have performed magnetic susceptibility and low and high field magnetization measurements on single crystals of the Ni tetramer compound [Ni4(μ-CO3)2(aetpy)8] (ClO4)4 (aetpy = 2-aminoethyl-pyridine) with a butterfly (diamond) structure. We observed a two-step-like magnetization curve and a further increase of magnetization around 63 T in magnetic fields up to 68 T perpendicular to the Ni tetramer plane (c-axis). From the magnetic fields at steep jumps of the magnetization, we determine broadly the short diagonal (J1) and the side (J2) antiferromagnetic exchange constants between the Ni ions (J1/kB = 41.9 K and J2/kB = 9.2 K) in this compound. The long diagonal exchange interaction (J3) is ferromagnetic and the exchange constant is evaluated as J3/kB = −0.66± 0.04 K from the comparison between the magnetization measured in steady fields at 2 K and the calculated one. The origin of hysteresis of the magnetization in pulsed magnetic fields is discussed based on the calculated energy diagram.

A Possible Route for Left-Handed Meta-Materials Using Ferromagnetic-Metal Nanocomposite Films

Ferromagnetic-metal nanocomposite films as a candidate for left-handed meta-materials in microwave regions were experimentally studied. Electron magnetic resonance study suggests that the film microstructure influences resonance frequency around which the negative permeability may be obtained.