1995 Fiscal Year Annual Research Report

パルスESR法を用いた過渡的電子スピン章動分光法による多重項スピン状態の研究

Research Project

Project/Area Number	07740468
Research Institution	Osaka City University
Principal Investigator	佐藤和信大阪市立大学, 理学部, 助手 (90264796)
Keywords	パルスESR / フーリエ変換ESR / 過渡的章動 / 高スピン有機分子 / スピンニューテーション / 微細構造
Research Abstract	分子磁性体の研究分野において困難になりつつある物性評価を正確に行うため、新しい方法としてパルスESRを用いた過渡的電子スピン章動分光法を開発し、その有用性を検証する目的でMgO粉末中のCr(III)イオンや安定なπアリール型高スピン有機分子に適用した。その結果、以下に示すように従来のcw-ESR法では得ることができなかった新しい電子状態に関する知見を得た。過渡的電子スピン章動の測定には、Bruker社製ESP380E分光器を使用し、温度制御のためにターボ分子ポンプ(購入備品)を組み込んだクライオスタット断熱部を構成することにより液体ヘリウムの温度領域(〜4K)で測定を行った。 1.MgO粉末中に希釈されたCr(III)イオンに過渡的電子スピン章動分光法を適用し、従来のcw-ESR法では線幅内に隠れているためにMgOの高い対称性から零であると長年思われてきたCr(III)イオンの微細構造定数が実際は有限の値をもち、MgOの格子が歪んでいることを明らかにした。さらに、密度行列法を用いて時間に依存する運動方程式を厳密に取り扱うことにより、観測されたMgO中Cr(III)のフーリエ変換章動スペクトルからMgO中Cr(III)の微細構造定数の大きさを見積もった。 2.室温で安定なπアリール型高スピン有機分子に過渡的スピン章動分光法を適用し、章動周波数が多重項分子の有効電子スピン量子数S、Msに依存することを利用して有効スピン量子数を直接的に決定した。πアリール型の分子は立体障害によりその分子構造がかなり歪んでいることが予測されるが、分子の多重項状態の形成が証明されたことによりπ共役系におけるトポロジー的スピン整列機構が非常に強固なものであることを立証した。

Research Products

(18 results)

All Other

All Publications (18 results)

[Publications] 工位武治: "FT pulsed ESR/electron spin transient nutation spectroscopy in the study of molecular based magnetism:Applications to high-spin polymers and ferromagnetic materials" Molecular Crystals and Liquid Crystals. 271. 191-212 (1995)
[Publications] 工位武治: "Topological spin polarization and a VB picture of infinite model systems for organic polymer magnets in terms of electronic band calculations" Molecular Crystals and Liquid Crystals. 272. 1-22 (1995)
[Publications] 中澤重顕: "Electronic and molecular structures of a 2D septet-tris(p-methoxyphenyl-methylene)benzene as studied by ESR:A model for discotic high-spin assemblages" Molecular Crystals and Liquid Crystals. 271. 163-171 (1995)
[Publications] 山口陽司: "Electronic and molecular structures of p-phenylenebis(phenylmethylene)in its thermally excited triplet state as studied by single-crystal ^1H-ENDOR" Molecular Crystals and Liquid Crystals. 271. 67-78 (1995)
[Publications] Andrew S.Ichimura: "An electron spin resonance study of persistent dinitrenes" Molecular Crystals and Liquid Crystals. 272. 57-66 (1995)
[Publications] 伊藤公一: "New Aspects of High-Spin Chemistry" Molecular Crystals and Liquid Crystals. 271. 129-146 (1995)
[Publications] 塩見大輔: "FT pulsed and cw EPR studies of stable molecular spin crystals" Molecular Crystals and Liquid Crystals. 271. 173-182 (1995)
[Publications] 佐藤和信: "An FT-pulsed ESR/electron spin transient nutation study of hyperbranched π-aryl stable triplet and quartet molecules" Molecular Crystals and Liquid Crystals. (印刷中).
[Publications] 中澤重顕: "Electronic and molecular structures of 1,3,5-tris-(phenylmethylene)-benzene(S=3)as models for discotic high-spin liquid crystals:Single crystal ESR and X-ray diffraction studies" Molecular Crystals and Liquid Crystals. (印刷中).
[Publications] 福澤明: "Electronic and molecular structures of quintet bisnitrenes as studied by fine-structure ESR spectra from random orientation:Are the documented ZFS constants correct?" Molecular Crystals and Liquid Crystals. (印刷中).
[Publications] 塩見大輔: "One-dimensional ferrimagnetic behavior of a hetero-spin chain in an organic radical crystal as probed by susceptibility and relaxation time measurements" Molecular Crystals and Liquid Crystals. (印刷中).
[Publications] 工位武治: "FT pulsed ESR/ESTN(electron spin transient nutation)spectroscopy applied to high-spin systems:" Molecular Crystals and Liquid Crystals. (印刷中).
[Publications] 佐藤和信: "An FT pulsed ESR/electron spin transient nutation study of the quartet state of Cr(III)in MgO powder:Detection of its apparently vanishing ZFS" Bulletin of Magnetic Resonance. (印刷中).
[Publications] 佐藤和信: "Exact analytical solutions of eigenfields and eigenenergies for high spins(S【less than or eq " Bulletin of Magnetic Resonance. (印刷中).
[Publications] 佐藤和信: "A powder pattern ESR study of the quartet states of the precursors of a square-pyramidal nitridochromium(V)complex,Cr(III)(bpb)Cl(H_2O)and Cr(III)(bpb)(N_3)_2:" Bulletin of Magnetic Resonance. (印刷中).
[Publications] 塩見大輔: "FT pulsed ESR of exchange-coupled spin systems in transition metal clusters and low-dimensional molecular magnets" Bulletin of Magnetic Resonance. (印刷中).
[Publications] 工位武治: "An FT pulsed ESR/ESTN(Electron Spin Transient Nutation)study of hyperbranched π-aryl-based stable high-spins as models for organic superpara-and ferro-magnets" Bulletin of Magnetic Resonance. (印刷中).
[Publications] Andrew.S.Ichimura: "Ferric iron porphyrin as studied by single-crystal cw and pulsed ESR/ESTN(Electron Spin Transient Nutation)spectroscopy" Bulletin of Magnetic Resonance. (印刷中).

1995 Fiscal Year Annual Research Report

パルスESR法を用いた過渡的電子スピン章動分光法による多重項スピン状態の研究

Principal Investigator

佐藤 和信 大阪市立大学, 理学部, 助手 (90264796)

Research Products

[Publications] 工位 武治: "FT pulsed ESR/electron spin transient nutation spectroscopy in the study of molecular based magnetism:Applications to high-spin polymers and ferromagnetic materials" Molecular Crystals and Liquid Crystals. 271. 191-212 (1995)

[Publications] 工位 武治: "Topological spin polarization and a VB picture of infinite model systems for organic polymer magnets in terms of electronic band calculations" Molecular Crystals and Liquid Crystals. 272. 1-22 (1995)

[Publications] 中澤 重顕: "Electronic and molecular structures of a 2D septet-tris(p-methoxyphenyl-methylene)benzene as studied by ESR:A model for discotic high-spin assemblages" Molecular Crystals and Liquid Crystals. 271. 163-171 (1995)

[Publications] 山口 陽司: "Electronic and molecular structures of p-phenylenebis(phenylmethylene)in its thermally excited triplet state as studied by single-crystal ^1H-ENDOR" Molecular Crystals and Liquid Crystals. 271. 67-78 (1995)

[Publications] Andrew S.Ichimura: "An electron spin resonance study of persistent dinitrenes" Molecular Crystals and Liquid Crystals. 272. 57-66 (1995)

[Publications] 伊藤 公一: "New Aspects of High-Spin Chemistry" Molecular Crystals and Liquid Crystals. 271. 129-146 (1995)

[Publications] 塩見 大輔: "FT pulsed and cw EPR studies of stable molecular spin crystals" Molecular Crystals and Liquid Crystals. 271. 173-182 (1995)

[Publications] 佐藤 和信: "An FT-pulsed ESR/electron spin transient nutation study of hyperbranched π-aryl stable triplet and quartet molecules" Molecular Crystals and Liquid Crystals. (印刷中).

[Publications] 中澤 重顕: "Electronic and molecular structures of 1,3,5-tris-(phenylmethylene)-benzene(S=3)as models for discotic high-spin liquid crystals:Single crystal ESR and X-ray diffraction studies" Molecular Crystals and Liquid Crystals. (印刷中).

[Publications] 福澤 明: "Electronic and molecular structures of quintet bisnitrenes as studied by fine-structure ESR spectra from random orientation:Are the documented ZFS constants correct?" Molecular Crystals and Liquid Crystals. (印刷中).

[Publications] 塩見 大輔: "One-dimensional ferrimagnetic behavior of a hetero-spin chain in an organic radical crystal as probed by susceptibility and relaxation time measurements" Molecular Crystals and Liquid Crystals. (印刷中).

[Publications] 工位 武治: "FT pulsed ESR/ESTN(electron spin transient nutation)spectroscopy applied to high-spin systems:" Molecular Crystals and Liquid Crystals. (印刷中).

[Publications] 佐藤 和信: "An FT pulsed ESR/electron spin transient nutation study of the quartet state of Cr(III)in MgO powder:Detection of its apparently vanishing ZFS" Bulletin of Magnetic Resonance. (印刷中).

[Publications] 佐藤 和信: "Exact analytical solutions of eigenfields and eigenenergies for high spins(S【less than or eq " Bulletin of Magnetic Resonance. (印刷中).

[Publications] 佐藤 和信: "A powder pattern ESR study of the quartet states of the precursors of a square-pyramidal nitridochromium(V)complex,Cr(III)(bpb)Cl(H_2O)and Cr(III)(bpb)(N_3)_2:" Bulletin of Magnetic Resonance. (印刷中).

[Publications] 塩見 大輔: "FT pulsed ESR of exchange-coupled spin systems in transition metal clusters and low-dimensional molecular magnets" Bulletin of Magnetic Resonance. (印刷中).

[Publications] 工位 武治: "An FT pulsed ESR/ESTN(Electron Spin Transient Nutation)study of hyperbranched π-aryl-based stable high-spins as models for organic superpara-and ferro-magnets" Bulletin of Magnetic Resonance. (印刷中).

[Publications] Andrew.S.Ichimura: "Ferric iron porphyrin as studied by single-crystal cw and pulsed ESR/ESTN(Electron Spin Transient Nutation)spectroscopy" Bulletin of Magnetic Resonance. (印刷中).

佐藤和信大阪市立大学, 理学部, 助手 (90264796)

[Publications] 工位武治: "FT pulsed ESR/electron spin transient nutation spectroscopy in the study of molecular based magnetism:Applications to high-spin polymers and ferromagnetic materials" Molecular Crystals and Liquid Crystals. 271. 191-212 (1995)

[Publications] 工位武治: "Topological spin polarization and a VB picture of infinite model systems for organic polymer magnets in terms of electronic band calculations" Molecular Crystals and Liquid Crystals. 272. 1-22 (1995)

[Publications] 中澤重顕: "Electronic and molecular structures of a 2D septet-tris(p-methoxyphenyl-methylene)benzene as studied by ESR:A model for discotic high-spin assemblages" Molecular Crystals and Liquid Crystals. 271. 163-171 (1995)

[Publications] 山口陽司: "Electronic and molecular structures of p-phenylenebis(phenylmethylene)in its thermally excited triplet state as studied by single-crystal ^1H-ENDOR" Molecular Crystals and Liquid Crystals. 271. 67-78 (1995)

[Publications] 伊藤公一: "New Aspects of High-Spin Chemistry" Molecular Crystals and Liquid Crystals. 271. 129-146 (1995)

[Publications] 塩見大輔: "FT pulsed and cw EPR studies of stable molecular spin crystals" Molecular Crystals and Liquid Crystals. 271. 173-182 (1995)

[Publications] 佐藤和信: "An FT-pulsed ESR/electron spin transient nutation study of hyperbranched π-aryl stable triplet and quartet molecules" Molecular Crystals and Liquid Crystals. (印刷中).

[Publications] 中澤重顕: "Electronic and molecular structures of 1,3,5-tris-(phenylmethylene)-benzene(S=3)as models for discotic high-spin liquid crystals:Single crystal ESR and X-ray diffraction studies" Molecular Crystals and Liquid Crystals. (印刷中).

[Publications] 福澤明: "Electronic and molecular structures of quintet bisnitrenes as studied by fine-structure ESR spectra from random orientation:Are the documented ZFS constants correct?" Molecular Crystals and Liquid Crystals. (印刷中).

[Publications] 塩見大輔: "One-dimensional ferrimagnetic behavior of a hetero-spin chain in an organic radical crystal as probed by susceptibility and relaxation time measurements" Molecular Crystals and Liquid Crystals. (印刷中).

[Publications] 工位武治: "FT pulsed ESR/ESTN(electron spin transient nutation)spectroscopy applied to high-spin systems:" Molecular Crystals and Liquid Crystals. (印刷中).

[Publications] 佐藤和信: "An FT pulsed ESR/electron spin transient nutation study of the quartet state of Cr(III)in MgO powder:Detection of its apparently vanishing ZFS" Bulletin of Magnetic Resonance. (印刷中).

[Publications] 佐藤和信: "Exact analytical solutions of eigenfields and eigenenergies for high spins(S【less than or eq " Bulletin of Magnetic Resonance. (印刷中).

[Publications] 佐藤和信: "A powder pattern ESR study of the quartet states of the precursors of a square-pyramidal nitridochromium(V)complex,Cr(III)(bpb)Cl(H_2O)and Cr(III)(bpb)(N_3)_2:" Bulletin of Magnetic Resonance. (印刷中).

[Publications] 塩見大輔: "FT pulsed ESR of exchange-coupled spin systems in transition metal clusters and low-dimensional molecular magnets" Bulletin of Magnetic Resonance. (印刷中).

[Publications] 工位武治: "An FT pulsed ESR/ESTN(Electron Spin Transient Nutation)study of hyperbranched π-aryl-based stable high-spins as models for organic superpara-and ferro-magnets" Bulletin of Magnetic Resonance. (印刷中).