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Zero-Field Splitting Parameters of Hemin Investigated by High-Frequency and High-Pressure Electron Paramagnetic Resonance Spectroscopy

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Abstract

We systematically studied the zero-field splitting (ZFS) parameters of Fe(III) protoporphyrin IX chloride, or hemin, using the terahertz electron paramagnetic resonance (EPR) spectroscopy technique at ambient and high pressures. Although hemin is known as a model substance of hemoproteins, the pressure effect on the electronic structure has not yet been explored owing to the large ZFS. In this study, high-field and high-frequency EPR measurements were carried out in the frequency range up to 700 GHz and at hydrostatic pressures up to 2 GPa. At ambient pressure, multiple EPR branches were clearly observed, and the axial and rhombic components of ZFS were determined as \(D = 6.90\pm 0.01\hbox { cm}^{-1}\) and \(E = 0.055 \pm 0.005\hbox { cm}^{-1}\), respectively. Upon pressure application, we observed a systematic shift of the resonance field, indicating a monotonous increase of the axial component from D = 6.9 to 7.9 \(\hbox {cm}^{-1}\) at 2 GPa. The origin of this unusually large shift was discussed from a microscopic viewpoint of the electronic structure of iron under pressure.

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Acknowledgements

The authors thank Y. Kobori (Molecular Photoscience Research Center, Kobe University) for fruitful discussions. This study was partly supported by a Grant-in-Aid for Scientific Research (B) (Grant No. 26287081), by a Grant-in-Aid for Scientific Research (C) (Grant No. 26400335), by a Grant-in-Aid for Challenging Exploratory Research (Grant No. 26610104) from JSPS, and by the Asahi Glass Foundation.

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Authors and Affiliations

  1. Graduate School of Science, Kobe University, 1-1 Rokkodai-cho, Nada, Kobe, 657-8501, Japan

    Eiji Ohmichi & Tsubasa Okamoto

  2. Research Facility Center for Science and Technology, Kobe University, 1-1 Rokkoadai-cho, Nada, Kobe, 657-8501, Japan

    Takahiro Sakurai

  3. Molecular Photoscience Research Center, Kobe University, 1-1 Rokkodai-cho, Nada, Kobe, 657-8501, Japan

    Hideyuki Takahashi, Susumu Okubo & Hitoshi Ohta

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  1. Eiji Ohmichi
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  2. Tsubasa Okamoto
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Correspondence to Hitoshi Ohta.

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Ohmichi, E., Okamoto, T., Sakurai, T. et al. Zero-Field Splitting Parameters of Hemin Investigated by High-Frequency and High-Pressure Electron Paramagnetic Resonance Spectroscopy . Appl Magn Reson 51, 1103–1115 (2020). https://doi.org/10.1007/s00723-020-01239-5

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  • DOI: https://doi.org/10.1007/s00723-020-01239-5

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