2000 年度実績報告書

金属フタロシアニン導体を主とするπ-d電子系の研究

研究課題

研究課題/領域番号	09440244
研究機関	岡崎国立共同研究機構
研究代表者	薬師久弥岡崎国立共同研究機構, 分子科学研究所, 教授 (20011695)
研究分担者	山本薫岡崎国立共同研究機構, 分子科学研究所, 助手 (90321603)
キーワード	フタロシアニン / 一次元導体 / π-d電子系 / 交換相互作用 / 希薄合金 / 電荷整列 / 反射率スペクトル / 偏光ラマン散乱
研究概要	1.有機希薄合金Co_<0.01>Ni_<0.99>Pc(AsF_6)_<0.5>は局在スピンと遍歴電子の共存する擬一次元電子系である。この希薄合金Co_<0.01>Ni_<0.99>Pc(AsF_6)_<0.5>のESRに現れる超微細構造を解析する事により、Coに局在するスピンは3d_z^2軌道を占めている事を明らかにした。また、この局在スピンと遍歴性π電子との交換相互作用を\|J_<πd>\|=0.013eV、フェルミ順位の1スピンあたりの状態密度をD_F=3.5eV^<-1>と実験的に見積もる事に成功した。またバンド幅と組み合わせて、この物質の近藤温度を見積もるとT_K=2×10^<-5>Kと非常に低い温度である事を明らかにした。そして、この弱い交換相互作用の原因がMPcに特徴的な電子構造と独特の積層構造にあることを明らかにした。またCoPc(AsF_6)_<0.5>とNiPc(AsF_6)_<0.5>の反射率の比較から、CoPc(AsF_6)_<0.5>のフェルミ準位付近には、かなり広いバンド幅のCo3d_z^2バンドが存在する事を明らかにした。ラマン散乱に合金に特有な共鳴効果を発見した。これをCo-Ni間の電荷移動遷移と帰属し、3d_x^2_<-y>^2バンドの位置を推定した。以上を総合して3dバンドを含む一次元バンド構造の模型を提唱した。 2.θ-(BDT-TTP)_2Cu(NCS)_2の電気抵抗に低温で電荷ギャップの大きくなる2次の相転移を見出した。反射率から求めた光学伝導度は相転移点温度以下で大きく変化した。低波数のスペクトル重みが高波数側ヘシフトし、明瞭なギャップが観測された。偏光ラマンスペクトルの因子群解析と励起光依存性の実験より、この物質で電荷の不均化が起こっている事を実験的に証明した。磁化率はこの不均化した電荷が分子の積層方向に平行な縦方向に整列している事を示唆している。

研究成果
(26件)

すべてその他

すべて文献書誌 (26件)

[文献書誌] Kyuya Yakushi,Mikio,Uruichi,and Yoshiro Yamashita: "Phase Transition in Narrow-band Organic Metals (BEDT-ATD)_2X (solvent)(X=PF_6, AsF_6, BF_4 ; solvent=THF, DHF, DO)"Synthetic Metals. 109. 33-37 (2000)
[文献書誌] C.Nakano,K.Yakushi,M.Kohama,K.Ueda and T.Sugimoto: "Estimation of the Site-Energy difference In the crystal of Et_4N (DMTCNQ)_2"Solid State Commun. 113. 677-682 (2000)
[文献書誌] K.Yakushi,J.Ulanski,H.Yamochi,and G.Saito: "Observation of Plasmons by Normal-incidence Reflectivity in Two-dimensional Organic Metals"Phys.Rev.B. 61. 9891-9894 (2000)
[文献書誌] X.Chen,C.Yang,J.Qin,K.Yakushi,Y.Nakazawa,K.Ichimira: "The intercalation reaction of 1,10-phenanthroline with layered compound FePS_3"J.Solid State Chem.. 150. 258-265 (2000)
[文献書誌] Olga Drozdova,Hideki,Yamochi,Kyuya Yakushi,Mikio Uruichi,Sachio Horiuchi,and Gunzi,Saito: "Determination of the Charge on BEDO-TTF in its Complexes by Raman Spectroscopy"J.Am.Chem.Soc.. 112. 4436-4442 (2000)
[文献書誌] K.Takeda,I.Shirotani,and K.Yakushi: "Pressure-induced insulator-to-metal-to-insulator transitions in one-dimensional bis (dimethylglyoximato) platinum (II), Pt (dmg)_2"Chemstry of Materials. 12. 912-916 (2000)
[文献書誌] C.Yang,X.Chen,J.Qin,K.Yakushi,Y.Nakazawa,and K.Ichimura: "Synthesis, Characterization, and Magnetic Properties of Intercalation Compound of 1,10-Phenanthroline with Layered MnPS_3"Materials Science and Engineering. A286. 183-187 (2000)
[文献書誌] D.Zhang,J.Qin,K.Yakushi,Y.Nakazawa,and K.Ichimura: "Preparation of a new nanocomposite of conducting polyaniline into layered MnP_3"Materials Science and Engineering. A286. 183-187 (2000)
[文献書誌] M.K.Bhide,M.D.Sastry,J.Qin,C.Yang,K.Yakushi,Y.Nakazawa,K.Ichimura.A.K.Sra.J.V.Yakhmi: "Electron magnetic resonance studies of the intercalation ferromagnet 2,2'-bipyridine-MnPS_3 above and below Curie temperature"Mol.Cryst.Liq.Cryst.. 348. 295-300 (2000)
[文献書誌] M.K.Bhide,R.M.Kadam,M.D.Sastry,J.Qin,C.Yang,K.Yakushi,Y.Nakazawa,K.Ichimura.A.K.Sra AK,J.V.Yakhmi: "Electron paramagnetic resonance study of magnetic ordering in MnPS_3, Mn_<0.79>PS_3(4,4'-bipy)_<(0.42)> and Mn_<0.84>PS_3(1,10-Phen)_<(0.64)> compounds"Mol.Cryst.Liq.Cryst.. 341. 923-928 (2000)
[文献書誌] Leokadiya V. Zorina, Salavat S. Khasanov, Rimma P. Shibaeva, Marc Gener, Roger Rousseau, Enric Canadell, Lyudmila A. Kushch, Eduard B. Yagubskii, Olga O. Drozdova, Kyuya Yakushi : "A new stable organic metal based on the BEDO-TTF donor and the doubly charged nitroprusside anion, (BEDO-TTF)_4[Fe(CN)_5NO]"J.Mater.Chem.. 10(9). 2017-2023 (2000)
[文献書誌] K.Takeda,I.Shirotani,C.Sekine,and K.Yakushi: "Metal to insulator transition of one-dimensional bis (1,2-benzoquinonedioximato) Platinum (II), Pt (bqd)_2, at low temperatures and high pressures"J.Phys.: Condens.Matter. 12. L483-L488 (2000)
[文献書誌] M.Uruichi,Y.Yamashita,and K.Yakushi: "Optical Properties and Metal-Insulator Transitions in (BEDT-ATD)_2X(solvent)(X=PF_6,AsF_6,BF_4,solvent=THF,DHF,DO)[BEDT-ATD=4,11-bis(4',5'-ethylenedithio-1',3'-dithiole-2'-ylidene)-4,11-dihydroanthra [2,3-c][1,2,5]thiadiazole]"J.Mater.Chem.. 10. 2716-2722 (2000)
[文献書誌] K.Yakushi: "Reflection spectroscopic study of organic conductors"Bull.Chem.Soc.Jpn.. 73. 2643-2662 (2000)
[文献書誌] J.Ouyang,K.Yakushi,Y.Misaki,and K.Tanaka: "Raman spectroscopic evidence for the charge disproportionation in a quasi-two-dimensional organic conductor θ-(BDT-TTP)_2Cu(NCS)_2"Phys.Rev.B. 63. 54301-54306 (2001)
[文献書誌] K.Yakushi,M.Simonyan,and Y.Ding: "Spectroscopic Studies of Solid Phthalocyanines and their Charge-transfer Salts"J.Porphyrins Phthalocyanines. 5. 13-24 (2001)
[文献書誌] M.Simonyan,Y.Yonehara,Y.Ding,and K.Yakushi: "Hyperfine structure and exchange coupling between local and itinerant magnetic moments in quasi-one-dimensional organic metal Co_<0.01>Ni_<0.99>Pc(AsF_6)_<0.5>"Phys.Rev.B.
[文献書誌] I.Shirotani,J.Hayashi,K.Yakushi,K.Takoda,T.Yokota,K.Shimizu,K.Amaya,A.Nakayama.and K.Aoki: "Pressure-induced insulator-to-metal transition and superconductivity in iodanil,C_6I_4O_2"Physica B.
[文献書誌] M.J.Konstantinovic,J.Dong,M.E.Ziaci,B.P.Clayman,J.C.Irwin.K.Yakushi,M.Isobc,and Y.Ueda: "Charge ordering and optical transitions of Li_2VO_5 and NaV_2O_5"Phys.Rev B.
[文献書誌] K.Yakushi,J.Ouyang,M.Simonyan,Y.Misaki,K.Tanaka: "Charge order in θ-(BDT-TTP)_2Cu(NCS)_2"Mol.Cryst.Liq.Cryst..
[文献書誌] Y.Ding,M.Simonyan,Y.Yonehara,M.Uruichi,K.Yakushi: "Formation of mixed crystal system Co_xNi_<1-x>Pc(AsF_6)_<0.5>"Mol.Cryst.Liq.Cryst..
[文献書誌] K.Yamamoto,K.Yakushi,M.Inokchi,M.Kinoshita,G.Saito: "Charge disproportionation and its ordering pattern in θ and α types of BEDT-TTF salts studied by Raman and infrared spectroscopy"Mol.Cryst.Liq.Cryst..
[文献書誌] T.Nakamura,K.Takahashi,T.Ise,T.Shirahata,M.Uruichi,K.Yakushi,T.Mori: "Magnetic properties of organic spin-ladder systems,(BDTFP)_2X (PhCl)_<0.5>"Mol.Cryst.Liq.Cryst..
[文献書誌] O.Drozdova,H.Yamochi,K.Yakushi,M.Uruichi,G.Saito: "Charge transfer degree of BO complexes"Mol.Cryst.Liq.Cryst..
[文献書誌] M.Tokumoto,T.Mizutani,T.Kinoshita,J.S.Brooks,Y.Uwatoko,O.Drozdova,K.Yakushi,I.Tumuru,H.Kobayashi,T.Manpetsu,J.Yamada,K.Ishida: "Effect of uniaxial pressure in organic superconductor κ-(BEDT-TTF)_2Cu (NCS)_2"Mol.Cryst.Liq.Cryst..
[文献書誌] Y.Ding,M.Simonyan,Y.Yonehara,M.Uruichi,and K.Yakushi: "Preparation and characterization of organic alloy Co_xNi_<1-x>Pc (AsF_6)_<0.5>(0【less than or equal】x【less than or equal】1)"J.Mater.Chem..

2000 年度 実績報告書

金属フタロシアニン導体を主とするπ-d電子系の研究

研究代表者

薬師 久弥 岡崎国立共同研究機構, 分子科学研究所, 教授 (20011695)

研究成果

[文献書誌] Kyuya Yakushi,Mikio,Uruichi,and Yoshiro Yamashita: "Phase Transition in Narrow-band Organic Metals (BEDT-ATD)_2X (solvent)(X=PF_6, AsF_6, BF_4 ; solvent=THF, DHF, DO)"Synthetic Metals. 109. 33-37 (2000)

[文献書誌] C.Nakano,K.Yakushi,M.Kohama,K.Ueda and T.Sugimoto: "Estimation of the Site-Energy difference In the crystal of Et_4N (DMTCNQ)_2"Solid State Commun. 113. 677-682 (2000)

[文献書誌] K.Yakushi,J.Ulanski,H.Yamochi,and G.Saito: "Observation of Plasmons by Normal-incidence Reflectivity in Two-dimensional Organic Metals"Phys.Rev.B. 61. 9891-9894 (2000)

[文献書誌] X.Chen,C.Yang,J.Qin,K.Yakushi,Y.Nakazawa,K.Ichimira: "The intercalation reaction of 1,10-phenanthroline with layered compound FePS_3"J.Solid State Chem.. 150. 258-265 (2000)

[文献書誌] Olga Drozdova,Hideki,Yamochi,Kyuya Yakushi,Mikio Uruichi,Sachio Horiuchi,and Gunzi,Saito: "Determination of the Charge on BEDO-TTF in its Complexes by Raman Spectroscopy"J.Am.Chem.Soc.. 112. 4436-4442 (2000)

[文献書誌] K.Takeda,I.Shirotani,and K.Yakushi: "Pressure-induced insulator-to-metal-to-insulator transitions in one-dimensional bis (dimethylglyoximato) platinum (II), Pt (dmg)_2"Chemstry of Materials. 12. 912-916 (2000)

[文献書誌] C.Yang,X.Chen,J.Qin,K.Yakushi,Y.Nakazawa,and K.Ichimura: "Synthesis, Characterization, and Magnetic Properties of Intercalation Compound of 1,10-Phenanthroline with Layered MnPS_3"Materials Science and Engineering. A286. 183-187 (2000)

[文献書誌] D.Zhang,J.Qin,K.Yakushi,Y.Nakazawa,and K.Ichimura: "Preparation of a new nanocomposite of conducting polyaniline into layered MnP_3"Materials Science and Engineering. A286. 183-187 (2000)

[文献書誌] M.K.Bhide,M.D.Sastry,J.Qin,C.Yang,K.Yakushi,Y.Nakazawa,K.Ichimura.A.K.Sra.J.V.Yakhmi: "Electron magnetic resonance studies of the intercalation ferromagnet 2,2'-bipyridine-MnPS_3 above and below Curie temperature"Mol.Cryst.Liq.Cryst.. 348. 295-300 (2000)

[文献書誌] K.Takeda,I.Shirotani,C.Sekine,and K.Yakushi: "Metal to insulator transition of one-dimensional bis (1,2-benzoquinonedioximato) Platinum (II), Pt (bqd)_2, at low temperatures and high pressures"J.Phys.: Condens.Matter. 12. L483-L488 (2000)

[文献書誌] K.Yakushi: "Reflection spectroscopic study of organic conductors"Bull.Chem.Soc.Jpn.. 73. 2643-2662 (2000)

[文献書誌] J.Ouyang,K.Yakushi,Y.Misaki,and K.Tanaka: "Raman spectroscopic evidence for the charge disproportionation in a quasi-two-dimensional organic conductor θ-(BDT-TTP)_2Cu(NCS)_2"Phys.Rev.B. 63. 54301-54306 (2001)

[文献書誌] K.Yakushi,M.Simonyan,and Y.Ding: "Spectroscopic Studies of Solid Phthalocyanines and their Charge-transfer Salts"J.Porphyrins Phthalocyanines. 5. 13-24 (2001)

[文献書誌] M.Simonyan,Y.Yonehara,Y.Ding,and K.Yakushi: "Hyperfine structure and exchange coupling between local and itinerant magnetic moments in quasi-one-dimensional organic metal Co_<0.01>Ni_<0.99>Pc(AsF_6)_<0.5>"Phys.Rev.B.

[文献書誌] I.Shirotani,J.Hayashi,K.Yakushi,K.Takoda,T.Yokota,K.Shimizu,K.Amaya,A.Nakayama.and K.Aoki: "Pressure-induced insulator-to-metal transition and superconductivity in iodanil,C_6I_4O_2"Physica B.

[文献書誌] M.J.Konstantinovic,J.Dong,M.E.Ziaci,B.P.Clayman,J.C.Irwin.K.Yakushi,M.Isobc,and Y.Ueda: "Charge ordering and optical transitions of Li_2VO_5 and NaV_2O_5"Phys.Rev B.

[文献書誌] K.Yakushi,J.Ouyang,M.Simonyan,Y.Misaki,K.Tanaka: "Charge order in θ-(BDT-TTP)_2Cu(NCS)_2"Mol.Cryst.Liq.Cryst..

[文献書誌] Y.Ding,M.Simonyan,Y.Yonehara,M.Uruichi,K.Yakushi: "Formation of mixed crystal system Co_xNi_<1-x>Pc(AsF_6)_<0.5>"Mol.Cryst.Liq.Cryst..

[文献書誌] K.Yamamoto,K.Yakushi,M.Inokchi,M.Kinoshita,G.Saito: "Charge disproportionation and its ordering pattern in θ and α types of BEDT-TTF salts studied by Raman and infrared spectroscopy"Mol.Cryst.Liq.Cryst..

[文献書誌] T.Nakamura,K.Takahashi,T.Ise,T.Shirahata,M.Uruichi,K.Yakushi,T.Mori: "Magnetic properties of organic spin-ladder systems,(BDTFP)_2X (PhCl)_<0.5>"Mol.Cryst.Liq.Cryst..

[文献書誌] O.Drozdova,H.Yamochi,K.Yakushi,M.Uruichi,G.Saito: "Charge transfer degree of BO complexes"Mol.Cryst.Liq.Cryst..

[文献書誌] M.Tokumoto,T.Mizutani,T.Kinoshita,J.S.Brooks,Y.Uwatoko,O.Drozdova,K.Yakushi,I.Tumuru,H.Kobayashi,T.Manpetsu,J.Yamada,K.Ishida: "Effect of uniaxial pressure in organic superconductor κ-(BEDT-TTF)_2Cu (NCS)_2"Mol.Cryst.Liq.Cryst..

[文献書誌] Y.Ding,M.Simonyan,Y.Yonehara,M.Uruichi,and K.Yakushi: "Preparation and characterization of organic alloy Co_xNi_<1-x>Pc (AsF_6)_<0.5>(0【less than or equal】x【less than or equal】1)"J.Mater.Chem..

2000 年度実績報告書

薬師久弥岡崎国立共同研究機構, 分子科学研究所, 教授 (20011695)