2001 Fiscal Year Annual Research Report

π-dおよびπ電子系分子導体の磁性電気伝導性の研究

Research Project

Project/Area Number	11224212
Research Institution	Okazaki National Research Institutes
Principal Investigator	薬師久弥岡崎国立共同研究機構, 分子科学研究所, 教授 (20011695)
Co-Investigator(Kenkyū-buntansha)	山本薫岡崎国立共同研究機構, 分子科学研究所, 助手 (90321603) 山下敬郎東京工業大学, 総合理工学研究科, 教授 (90116872)
Keywords	フタロシアニン導体 / π-d相互作用 / 混晶・合金 / 磁性 / 反射率 / 分子導体 / 電荷整列 / ラマン分光
Research Abstract	π-d電子系物質についてはCoPc(AsF_6)_<0.5>の3dバンドとπバンドの混成状況を調べるためにCoPc,CoPc^+,NiPc,NiPc^+について非経験的な方法で分子軌道計算を行った。計算結果を中性分子および陽イオンラジカル塩の振動スペクトルと比較した。ラジカル塩に特有な振動のマーカーバンドの強度を良く再現する事ができた。この方法により計算したa_<lu>HOMOと隣接するCoPcの3d_<z2>軌道との重なり積分を計算したところ10^<-5>程度であり、非常に小さい事が分かった。このことから一次元性のa_<lu>HOMOと3d_<z2>バンドの混成は無視できる事がわかった。このことからCoPc(AsF_6)_<0.5>を加圧するとリトルの励起子超伝導模型に合致する電子構造をもつ事が結論される。現在ダイヤモンドアンビルを用いた電気抵抗測定の予備実験の結果、4GPaまで加圧できる状態になっている。 π電子系物質については電荷整列を伴う相転移を起こす分子導体を赤外・ラマン分光法で研究した。まず、θ-(BDT-TTP)2Cu(NCS)2における相転移がラマンスペクトルの励起光依存性から電荷の不均化を伴うものである事を証明し、磁化率、光学スペクトルから電荷配列の方向を推定した。この実験から1300-1600cm^<-1>領域のラマンスペクトルが不均化に敏感に反応して変化する事を見出した。系統的な研究を進めるために、θ-(BEDT-TTF)_2RbZn(SCN)_4の相転移点以下の複雑なラマンスペクトルの帰属を行った。^<13>Cを同位体置換した分子を用い、偏光ラマン・偏光赤外スペクトルを比較することによって帰属を確立した。この帰属の方法は全てのBEDT-TTF電荷移動塩のラマンスペクトルを解釈する際に適用できる。

Research Products
(33 results)

All Other

All Publications (33 results)

[Publications] J. Ouyang, K. Yakushi, Y. Misaki, 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)
[Publications] K. Yakushi, M. Simonyan, Y. Ding: "Spectroscopic Studies of Solid Phthalocyanines and their Charge-transfer Salts"J. Porphyrins Phthalocyanines. 5. 13-24 (2001)
[Publications] M. Simonyan, Y. Yonehara, Y. Ding, 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. 63. 113103-113106 (2001)
[Publications] Y. Haruyama, T. Kinoshita, K. Takimiya, T. Otsubo, C. Nakano, K. Yakushi: "Electronic structures of organic salt DMTSA-BF_4 using photoelectron spectromicroscopy"J. Electron Spectrosc.. 114-116. 1013-1018 (2001)
[Publications] M. J. Konstantinovic, J. Dong, M. E. Ziaei, B. P. Clayman, J. C. Irwin, K. Yakushi, M. Isobe, Y. Ueda: "Charge ordering and optical transitions of Li_2VO_5 and NaV_2O_5"Phys. Rev B. 63. 121102-121105 (2001)
[Publications] Lee Martin, Scott S, Turner, Peter Day, Philippe Guionneau, Judith A. K. Howard, Dai E. Hibbs, Mark E. Light, Michael B. Hursthouse, Mikio Uruichi, Kyuya Yakushi: "Crystal Chemistry and Physical Properties of Superconducting and Semiconducting Charge Transfer Salts of the Type (BEDT-TTF)_4[A^IM^<III>(C_2O_4)_3]・PhCN (A^I = H_3O, NH_4, K ; M^<III> = Cr, Fe, Co, Al; BEDT-TTF=Bis(ethylenedithio)tetrathiafulvalene)"Inorg. Chem.. 40. 1363-1371 (2001)
[Publications] Y. Ding, M. Simonyan, Y. Yonehara, M. Uruichi, 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.. 11. 1469-1475 (2001)
[Publications] J. Ulanski, K. Yakushi, H. Yamochi, G. Saito: "Observation of plasmons in 2-D organic metal BO_<2.4>I_3 by reflection spectroscopy"Synthetic Metals. 120. 721-722 (2001)
[Publications] K. Yamamoto, K. Yakushi: "Electronic ground state of θ-(BEDT-TTF)_2RbZn(SCN)_4 studied by Raman spectroscopy"Synthetic Metals. 120. 791-792 (2001)
[Publications] J. Ouyang, K. Yakushi, Y. Misaki, K. Tanaka: "Phase transition of θ-(BDT-TTP)_2Cu(NCS)_2"Synthetic Metals. 120. 843-844 (2001)
[Publications] O. Drozdova, H. Yamochi, K. Yakushi, M. Uruichi, S. Horiuchi, G. Saito: "Raman spectroscopy as a method of determination of the charge on BO in its complexes"Synthetic Metals. 120. 739-740 (2001)
[Publications] T. Yamamoto, H. Hanasaki, J. Yamaura, S. Aonuma, H. Tajima, K. Yakushi, M. Uruichi, R. Kato: "Phase diagrams of (DMe-DCNQI)_2Li_<1-x>Cu_x system"Synthetic Metals. 120. 873-874 (2001)
[Publications] T. Kambe, N. Fujimura, Y. Nogami, K. Oshima, K. Yakushi, J. Dong, K. Takimiya, T. Otsubo: "Low temperature X-ray and ESR study of Quasi-1D DMTCA-BF_4 (C=S,Se) with half-filled band"Synthetic Metals. 120. 931-932 (2001)
[Publications] M. Meneghetti, C. Pecile, K. Kanoda, K. Hiraki, K. Yakushi: "Study of the phase transitions of (DI-DCNQI)_2X using vibronic and vibrational spectra"Synthetic Metals. 120. 1091-1092 (2001)
[Publications] O. Drozdova, G. Saito, H. Yamochi, K. Ookubo, K. Yakushi, M. Uruichi, L. Ouahab: "Composition and structure of the anion layer in the organic superconductor κ'-(ET)_2Cu_2(CN)_3 : optical study"Inorg. Chem.. 40. 3265-3266 (2001)
[Publications] I. Shirotani, J. Hayashi, K. Yakushi, K. Takeda, T. Yokota, K. Shimizu, K. Amaya, A. Nakayama, K. Aoki: "Pressure-induced insulator-to-metal transition and superconductivity in iodanil, C_6I_4O_2"Physica B. 304. 6-11 (2001)
[Publications] M. Maksimuk, K. Yakushi, H. Taniguchi, K. Kanoda, A. Kawamoto: "The C=C stretching vibrations of κ-(BEDT-TTF)_2Cu[N(CN)_2]Br and its deuterated analogues"J. Phys. Soc. Jpn.. 70. 3728-3738 (2001)
[Publications] K. Yamamoto, K. Yakushi, K. Miyagawa, K. Kanoda, A. Kawamoto: "Charge ordering in θ-(BEDT-TTF)_2RbZn(SCN)_4 studied by vibration spectroscopy"Phys. Rev. B. 65. 85110-85117 (2001)
[Publications] K. Yakushi, J. Ouyang, M. Simonyan, Y. Misaki, K. Tanaka: "Charge order in θ-(BDT-TTP)_2Cu(NCS)_2"Mol. Cryst. Liq. Cryst.. (印刷中).
[Publications] 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.. (印刷中).
[Publications] 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.. (印刷中).
[Publications] 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.. (印刷中).
[Publications] O. Drozdova, H. Yamochi, K. Yakushi, M. Uruichi, G. Saito: "Charge transfer degree of BO complexes"Mol. Cryst. Liq. Cryst.. (印刷中).
[Publications] M. Tokumoto, T. Mizutani, T. Kinoshita, J. S. Brooks, Y. Uwatoko, O. Drozdova, K. Yakushi, I. Tamura, H. Kobayashi, T. Mangetsu, J. Yamada, K. Ishida: "Effect of uniaxial pressure in organic superconductor κ-(BEDT-TTF)_2Cu(NCS)_2"Mol. Cryst. Liq. Cryst.. (印刷中).
[Publications] J. Ouyang, K. Yakushi, T. Kinoshita, N. Nanbu, M. Aoyagi, Y. Misaki, K. Tanaka: "The assignment of the in-plane molecular vibrations of the BDT-TTP electron-donor molecule based on the polarized Raman and infrared spectra, where BDT-TTP is 2,5-bis(1,3-dithol-2-ylidene)-1,3,4,6-tetrathiapentalene"Spectrochim. Acta A. (印刷中).
[Publications] P. Toman, S. Nespurek, K. Yakushi: "Electronic states and infrared spectroscopy of nickel and cobalt phthalocyanines : Ab initio calculations for the neutral and cation state"Synthetic Metals. (印刷中).
[Publications] J. Ulanski, K. Yakushi, M. Uruichi, O. Drozdova, H. Yamochi, G. Saito: "Re-examination of Bromide, Chloride, and Iodide Salts of Bis(ethylenedioxy)tetrathia-fulvalene by Spectroscopic Methods"Mol. Cryst. Liq. Cryst.. (印刷中).
[Publications] K. Yakushi, K. Yamamoto, J. Ouyang, M. Simonyan, C. Nakano, Y. Misaki, K. Tanaka: "Charge ordering and phase transition in θ-(BDT-TTP)_2Cu(NCS)_2"Synthetic Metals. (印刷中).
[Publications] K. Yamamoto, K. Yakushi, K. Miyagawa, K. Kanoda, A. Kawamoto, J. Yamaura, T. Enoki: "Vibrational spectra of BEDT-TTF based 2D charge ordering systems"Synthetic Metals. (印刷中).
[Publications] M. Uruichi, K. Yakushi, T. Shirahata, K. Takahashi, T. Mori, T. Nakamura: "Characterization of quasi-1D conductors, (BDTFP)_2X(PhCl)_<0.5>(X=PF_6,AsF_6)"Synthetic Metals. (印刷中).
[Publications] O. Drozdova, K. Yakushi, A. Ota, H. Yamochi, G. Saito: "Spectroscopic study of the [0110] charge ordering in (EDO-TTF)_2PF_6"Synthetic Metals. (印刷中).
[Publications] O. Drozdova, K. Yakushi, H. Yamochi, G. Saito, D. B. Tanner: "Infrared study of the properties of the normal (metallic) phase of κ-(ET-^<13>C_4)_2Cu(CN)[N(CN)_2]"Synthetic Metals. (印刷中).
[Publications] K. Takeda, I. Shirotani, K. Yakushi: "Insulator to metal transition and electronic spectra of bis(1,2-benzoquinonedioximato)-platinum(II), Pt(bqd)_2 at high pressure"Synthetic Metals. (印刷中).

2001 Fiscal Year Annual Research Report

π-dおよびπ電子系分子導体の磁性電気伝導性の研究

Principal Investigator

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

Research Products

[Publications] J. Ouyang, K. Yakushi, Y. Misaki, 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)

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

[Publications] M. Simonyan, Y. Yonehara, Y. Ding, 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. 63. 113103-113106 (2001)

[Publications] Y. Haruyama, T. Kinoshita, K. Takimiya, T. Otsubo, C. Nakano, K. Yakushi: "Electronic structures of organic salt DMTSA-BF_4 using photoelectron spectromicroscopy"J. Electron Spectrosc.. 114-116. 1013-1018 (2001)

[Publications] M. J. Konstantinovic, J. Dong, M. E. Ziaei, B. P. Clayman, J. C. Irwin, K. Yakushi, M. Isobe, Y. Ueda: "Charge ordering and optical transitions of Li_2VO_5 and NaV_2O_5"Phys. Rev B. 63. 121102-121105 (2001)

[Publications] Y. Ding, M. Simonyan, Y. Yonehara, M. Uruichi, 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.. 11. 1469-1475 (2001)

[Publications] J. Ulanski, K. Yakushi, H. Yamochi, G. Saito: "Observation of plasmons in 2-D organic metal BO_<2.4>I_3 by reflection spectroscopy"Synthetic Metals. 120. 721-722 (2001)

[Publications] K. Yamamoto, K. Yakushi: "Electronic ground state of θ-(BEDT-TTF)_2RbZn(SCN)_4 studied by Raman spectroscopy"Synthetic Metals. 120. 791-792 (2001)

[Publications] J. Ouyang, K. Yakushi, Y. Misaki, K. Tanaka: "Phase transition of θ-(BDT-TTP)_2Cu(NCS)_2"Synthetic Metals. 120. 843-844 (2001)

[Publications] O. Drozdova, H. Yamochi, K. Yakushi, M. Uruichi, S. Horiuchi, G. Saito: "Raman spectroscopy as a method of determination of the charge on BO in its complexes"Synthetic Metals. 120. 739-740 (2001)

[Publications] T. Yamamoto, H. Hanasaki, J. Yamaura, S. Aonuma, H. Tajima, K. Yakushi, M. Uruichi, R. Kato: "Phase diagrams of (DMe-DCNQI)_2Li_<1-x>Cu_x system"Synthetic Metals. 120. 873-874 (2001)

[Publications] T. Kambe, N. Fujimura, Y. Nogami, K. Oshima, K. Yakushi, J. Dong, K. Takimiya, T. Otsubo: "Low temperature X-ray and ESR study of Quasi-1D DMTCA-BF_4 (C=S,Se) with half-filled band"Synthetic Metals. 120. 931-932 (2001)

[Publications] M. Meneghetti, C. Pecile, K. Kanoda, K. Hiraki, K. Yakushi: "Study of the phase transitions of (DI-DCNQI)_2X using vibronic and vibrational spectra"Synthetic Metals. 120. 1091-1092 (2001)

[Publications] O. Drozdova, G. Saito, H. Yamochi, K. Ookubo, K. Yakushi, M. Uruichi, L. Ouahab: "Composition and structure of the anion layer in the organic superconductor κ'-(ET)_2Cu_2(CN)_3 : optical study"Inorg. Chem.. 40. 3265-3266 (2001)

[Publications] I. Shirotani, J. Hayashi, K. Yakushi, K. Takeda, T. Yokota, K. Shimizu, K. Amaya, A. Nakayama, K. Aoki: "Pressure-induced insulator-to-metal transition and superconductivity in iodanil, C_6I_4O_2"Physica B. 304. 6-11 (2001)

[Publications] M. Maksimuk, K. Yakushi, H. Taniguchi, K. Kanoda, A. Kawamoto: "The C=C stretching vibrations of κ-(BEDT-TTF)_2Cu[N(CN)_2]Br and its deuterated analogues"J. Phys. Soc. Jpn.. 70. 3728-3738 (2001)

[Publications] K. Yamamoto, K. Yakushi, K. Miyagawa, K. Kanoda, A. Kawamoto: "Charge ordering in θ-(BEDT-TTF)_2RbZn(SCN)_4 studied by vibration spectroscopy"Phys. Rev. B. 65. 85110-85117 (2001)

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

[Publications] 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.. (印刷中).

[Publications] 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.. (印刷中).

[Publications] 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.. (印刷中).

[Publications] O. Drozdova, H. Yamochi, K. Yakushi, M. Uruichi, G. Saito: "Charge transfer degree of BO complexes"Mol. Cryst. Liq. Cryst.. (印刷中).

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

[Publications] P. Toman, S. Nespurek, K. Yakushi: "Electronic states and infrared spectroscopy of nickel and cobalt phthalocyanines : Ab initio calculations for the neutral and cation state"Synthetic Metals. (印刷中).

[Publications] J. Ulanski, K. Yakushi, M. Uruichi, O. Drozdova, H. Yamochi, G. Saito: "Re-examination of Bromide, Chloride, and Iodide Salts of Bis(ethylenedioxy)tetrathia-fulvalene by Spectroscopic Methods"Mol. Cryst. Liq. Cryst.. (印刷中).

[Publications] K. Yakushi, K. Yamamoto, J. Ouyang, M. Simonyan, C. Nakano, Y. Misaki, K. Tanaka: "Charge ordering and phase transition in θ-(BDT-TTP)_2Cu(NCS)_2"Synthetic Metals. (印刷中).

[Publications] K. Yamamoto, K. Yakushi, K. Miyagawa, K. Kanoda, A. Kawamoto, J. Yamaura, T. Enoki: "Vibrational spectra of BEDT-TTF based 2D charge ordering systems"Synthetic Metals. (印刷中).

[Publications] M. Uruichi, K. Yakushi, T. Shirahata, K. Takahashi, T. Mori, T. Nakamura: "Characterization of quasi-1D conductors, (BDTFP)_2X(PhCl)_<0.5>(X=PF_6,AsF_6)"Synthetic Metals. (印刷中).

[Publications] O. Drozdova, K. Yakushi, A. Ota, H. Yamochi, G. Saito: "Spectroscopic study of the [0110] charge ordering in (EDO-TTF)_2PF_6"Synthetic Metals. (印刷中).

[Publications] O. Drozdova, K. Yakushi, H. Yamochi, G. Saito, D. B. Tanner: "Infrared study of the properties of the normal (metallic) phase of κ-(ET-^<13>C_4)_2Cu(CN)[N(CN)_2]"Synthetic Metals. (印刷中).

[Publications] K. Takeda, I. Shirotani, K. Yakushi: "Insulator to metal transition and electronic spectra of bis(1,2-benzoquinonedioximato)-platinum(II), Pt(bqd)_2 at high pressure"Synthetic Metals. (印刷中).

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