1999 Fiscal Year Annual Research Report

集積型金属錯体の電子構造理論

Research Project

Project/Area Number	10149105
Research Institution	Osaka University
Principal Investigator	山口兆大阪大学, 大学院・理学研究科, 教授 (80029537)
Co-Investigator(Kenkyū-buntansha)	米満賢治岡崎国立共同研究機構, 分子科学研究所, 助教授 (60270823) 古賀信明名古屋大学, 人間情報学部, 助教授 (80186650) 川村尚岐阜大学, 工学部, 教授 (40026125)
Keywords	有効交換積分 / ab initio計算 / 分子磁性の理論 / 量子トンネル効果 / 光誘起強磁性 / 量子位相ダイナミックス
Research Abstract	1.M(II)(hfac)_2(4-pyridylcarbene)_2の磁気的相互作用本研究では分子磁性の分野において理論的にも実験的にも注目されているd-p共役系としてM(II)(hfac)_2(4pyridylcarbene)_2(M=Mn、Cu)に着目し、UHF法、密度汎関数法(UB2LYP法、UB3LYP法、UBLYP法)による量子化学計算を行った。そしてその磁気的相互作用の機構を有効交換積分値(J_<ah>値)、電荷密度分布、スピン密度分布、自然軌道の観点から調べた。M=Mn(II)の場合ではすべての手法でJ_<ah>値が負になり、反強磁性的相互作用を示した。また、M=Cu(II)の場合はすべての手法でJ_<ah>値が正で、強磁性的相互作用を示した。これらの結果は実験の結果を定性的に再現した。特にUB3LYP法は定量的にも再現できた。また、自然軌道の解析から、M=Mnの場合はピリジン環のπ軌道を介したMnのdπ軌道とカルベンのπ軌道間の反強磁性的超交換相互作用によるものであった。一方、M=Cuの場合はスピン非局在化効果と軌道の直交性による強磁性的相互作用のためであった。なお、HOMOとLUMOの占有数が1.993と0.007となり、MnとCuの両方ともスピン分極の効果は小さいことが判明した。 2.気体吸蔵錯体の有機ラジカルスピンの整列制御への適用本研究では、これら集積型金属錯体中にラジカル分子を吸蔵するシュミレーションを行い、磁気的相互作用のデザインを行うための、有機ラジカルスピンの整列制御を試みた。森らが最初に発見した錯体(Cu-trans-1,4-cyclohexanedicarboxylic acid)(1)や、Yaghiらが報告したジカルボン酸のZn錯体(Zn(BDC)(BDC=1,4-benzenedicar-boxylate))(2)の様に、結晶内に一次元的空洞をもつ錯体に関してS=1のラジカルスピンを有する酸素分子をその空洞内に吸蔵させ一次元的配列の実現を試みた。まず量子化学計算を用いて各原子上の電荷密度を計算し、その結果を用いて、モンテカルロ法に基づく吸蔵シュミレーションを行い外部圧力依存性・温度依存性を調べた。その結果は、実験値と傾向が一致していたものの、その吸蔵量に関しては計算値の方が2倍程度多くなっている。次に、得られた結果に関して、量子化学計算手法を実行して、分子間の有効交換積分値(J)を求めた。得られたJ値は、J(UHF)=-0.030cm^<-1>,J(UB3LYP)=-1.158cm^<-1>となった。つまり、いずれの酸素分子間にも反強磁性的相互作用が働いていることが判明した。このことは、ハルダン系を構築するための整列制御が可能であることを示している。

Research Products

(27 results)

All Other

All Publications (27 results)

[Publications] M. Nishino: "Local magnetic Structure due to Inhomogeneity of Interaction in S=1/2 Antiferromagnetic Chains"Phys.. Rev.. B61. 4033-4040 (2000)
[Publications] M. Nakano: "Quantum-phase and Information-entropy Dynamics of a Two-state Molecular System Interacting with Strongly Amplitude- and Phase-squeezed Fields"J. Chem. Phys.. 112. 2769-2780 (2000)
[Publications] M. Nakano: "Electron-correlation Dynamics of a One-dimensional H2 Model in a Quantized Photon Field"Chem. Phys. Lett.. 317. 103-108 (2000)
[Publications] Y. Shigeta: "A Theoretical Study of Spin Level Crossing Induced by an External Magnetic Field of Ring Molecule Magnetic Models"Chem. Phys. Lett.. 315. 441-445 (1999)
[Publications] K. Yamaguchi: "Symmetry and Broken Symmetries in MO Descriptions of Unstable Molecules II. Alignment, Flustration and Tunnelling of Spins in Molecular magnets"Theoret. Chem. Acc.. 102. 328-325 (1999)
[Publications] M. Mitani: "Density Functional Study of Intermolecular Ferromagnetic Interaction Through m-Phenylene Coupling Unit. III. Possibility of High Spin Polymer"J. Chem. Phys.. 111. 1309-1324 (1999)
[Publications] M. Mitani: "Density Functional Investigation on the Ferromagnetic Coupling of Spins in Phenylenevinylene-bridged Nitroxide Radicals : Monomer and Polymer Cases"J. Chem. Phys.. 111. 2283-2294 (1999)
[Publications] Y. Shigeta: "Formulation and numerical approach to molecular system by the Green function method without the Born-Oppenheimer Approximation"J. Chem. Phys.. 111. 6171-6179 (1999)
[Publications] Y. Takano: "Theoretical Studies of the Effective Exchange Interactions and Photoinduced Magnetism in Manganese and Copper Di(4-pyridyl) Carbene Complexes"Chem. Phys. Lett.. 301. 309-316 (1999)
[Publications] G. Maruta: "Solid-State High-Resolution H and D-NMR Study of the Electron Spin Density Distribution of the Hydrogen-bonded Organic Ferromagnetic Compound 4-Hydroxyimino-Tempo"J. Am. Chem. Soc.. 121. 424-431 (1999)
[Publications] S. Yamada: "Structure-Property Correlation on Second Hyperpolarizabilities of Symmetric One-Center and Three-Center Radicals"J. Phys. Chem.. A103. 7105-7115 (1999)
[Publications] M. Nakano: "Dynamics of photon phase and information entropy for a two-state molecular system interacting with amplitude- and phase-squeezed fields"J. Phys. Chem.. A103. 6036-6048 (1999)
[Publications] M. Nakano: "Quantum Phase Dynamics of an Initially One-Mode Amplitude-Squeezed Field Interactiong with a Two-state Molecular System"Chem. Phys. Lett.. 304. 241-252 (1999)
[Publications] H. Nagao: "Theoretical Studies on the Magnetic Quantum Tunneling Rates in Mn Clusters by the Path Integral Method"Chem. Phys. Lett.. 302. 418-424 (1999)
[Publications] M. Nakano: "Theoretical Studies on Second Hyperpolarizabilities for Cation Radical States of Tetrathiafulvalene and Tetrathiapentalene"Chem. Phys. Lett.. 311. 221-230 (1999)
[Publications] T. Kobayashi: "Calculation of Frequency-Dependent First Hyperpolarizabilities Using the Second-Order Moller-Plesset Perturbation Theory"J. Chem. Phys.. 110. 11720-11733 (1999)
[Publications] T. Kobayashi: "Calculation of Frequency-Dependent Second Hyperpolarizabilities for Electronic Field Induced Second Harmonic Generation in the Second-Order Moller-Plesset Perturbation Theory"J. Chem. Phys.. 111. 842-848 (1999)
[Publications] M. Nakano: "Second Hyperpolarizability Density Analyses for Trithiapentalene and Dioxathiapentalene : Visualization of Unique p-Electron Contributions"Chem. Phys. Lett.. 306. 187-196 (1999)
[Publications] H. Nagao: "Theoretical Studies on Anomalous Phases in Molecular Systems with external Field : Possibility of Photo-Induced Superconductivity"Int. J. Quant. Chem.. 75. 549-561 (1999)
[Publications] Y. Shigeta: "Density Functional Theory without the Born-Oppenheimer Approximation. II. Green Function Techniques"Int. J. Quant. Chem.. 75. 875-883 (1999)
[Publications] D. Yamaki: "Visualization of Two-Body Electron Densities and Wave Functions of Magnetic Molecules"Int. J. Quant. Chem.. 75. 645-654 (1999)
[Publications] S. Kiribayashi: "Self-Confistent-Field Calculations of Molecular Magnetic Properties Using Gauge-invariant Atomic Orbitals"Int. Quant. Chem.. 75. 637-643 (1999)
[Publications] S. Yamada: "Electron correlation and structure dependences of second hyperpolarizability of ethylene"Int. J. Quant. Chem.. 71. 177-183 (1999)
[Publications] S. Yamada: "CAS-SCF and density functional calculations of second hyperpolariizabilities for a nitronyl nitroxide radical"Int. J. Quant. Chem.. 71. 329-336 (1999)
[Publications] M. Nakano: "Numericasl coupled Liouville approah : application to second hyperpolarizability of molecular aggregate"Int. J. Quant. Chem.. 71. 295-306 (1999)
[Publications] M. Nakano: "Analysis of Spatial Contribution to the Second Hyperpolarizabilities of π-Conjugated Systems Involving Sulfur Atoms"J. Phys. Chem.. A103. 3103-3109 (1999)
[Publications] M. Nakano: "Quantum Phase Dynamics of an Initially One-Mode Amplitude-Squeezed Field Interacting with a Two-State Molecular System"Chem. Phys. Lett.. 304. 241-252 (1999)

1999 Fiscal Year Annual Research Report

集積型金属錯体の電子構造理論

Principal Investigator

山口 兆 大阪大学, 大学院・理学研究科, 教授 (80029537)

Research Products

[Publications] M. Nishino: "Local magnetic Structure due to Inhomogeneity of Interaction in S=1/2 Antiferromagnetic Chains"Phys.. Rev.. B61. 4033-4040 (2000)

[Publications] M. Nakano: "Quantum-phase and Information-entropy Dynamics of a Two-state Molecular System Interacting with Strongly Amplitude- and Phase-squeezed Fields"J. Chem. Phys.. 112. 2769-2780 (2000)

[Publications] M. Nakano: "Electron-correlation Dynamics of a One-dimensional H2 Model in a Quantized Photon Field"Chem. Phys. Lett.. 317. 103-108 (2000)

[Publications] Y. Shigeta: "A Theoretical Study of Spin Level Crossing Induced by an External Magnetic Field of Ring Molecule Magnetic Models"Chem. Phys. Lett.. 315. 441-445 (1999)

[Publications] K. Yamaguchi: "Symmetry and Broken Symmetries in MO Descriptions of Unstable Molecules II. Alignment, Flustration and Tunnelling of Spins in Molecular magnets"Theoret. Chem. Acc.. 102. 328-325 (1999)

[Publications] M. Mitani: "Density Functional Study of Intermolecular Ferromagnetic Interaction Through m-Phenylene Coupling Unit. III. Possibility of High Spin Polymer"J. Chem. Phys.. 111. 1309-1324 (1999)

[Publications] M. Mitani: "Density Functional Investigation on the Ferromagnetic Coupling of Spins in Phenylenevinylene-bridged Nitroxide Radicals : Monomer and Polymer Cases"J. Chem. Phys.. 111. 2283-2294 (1999)

[Publications] Y. Shigeta: "Formulation and numerical approach to molecular system by the Green function method without the Born-Oppenheimer Approximation"J. Chem. Phys.. 111. 6171-6179 (1999)

[Publications] Y. Takano: "Theoretical Studies of the Effective Exchange Interactions and Photoinduced Magnetism in Manganese and Copper Di(4-pyridyl) Carbene Complexes"Chem. Phys. Lett.. 301. 309-316 (1999)

[Publications] G. Maruta: "Solid-State High-Resolution H and D-NMR Study of the Electron Spin Density Distribution of the Hydrogen-bonded Organic Ferromagnetic Compound 4-Hydroxyimino-Tempo"J. Am. Chem. Soc.. 121. 424-431 (1999)

[Publications] S. Yamada: "Structure-Property Correlation on Second Hyperpolarizabilities of Symmetric One-Center and Three-Center Radicals"J. Phys. Chem.. A103. 7105-7115 (1999)

[Publications] M. Nakano: "Dynamics of photon phase and information entropy for a two-state molecular system interacting with amplitude- and phase-squeezed fields"J. Phys. Chem.. A103. 6036-6048 (1999)

[Publications] M. Nakano: "Quantum Phase Dynamics of an Initially One-Mode Amplitude-Squeezed Field Interactiong with a Two-state Molecular System"Chem. Phys. Lett.. 304. 241-252 (1999)

[Publications] H. Nagao: "Theoretical Studies on the Magnetic Quantum Tunneling Rates in Mn Clusters by the Path Integral Method"Chem. Phys. Lett.. 302. 418-424 (1999)

[Publications] M. Nakano: "Theoretical Studies on Second Hyperpolarizabilities for Cation Radical States of Tetrathiafulvalene and Tetrathiapentalene"Chem. Phys. Lett.. 311. 221-230 (1999)

[Publications] T. Kobayashi: "Calculation of Frequency-Dependent First Hyperpolarizabilities Using the Second-Order Moller-Plesset Perturbation Theory"J. Chem. Phys.. 110. 11720-11733 (1999)

[Publications] T. Kobayashi: "Calculation of Frequency-Dependent Second Hyperpolarizabilities for Electronic Field Induced Second Harmonic Generation in the Second-Order Moller-Plesset Perturbation Theory"J. Chem. Phys.. 111. 842-848 (1999)

[Publications] M. Nakano: "Second Hyperpolarizability Density Analyses for Trithiapentalene and Dioxathiapentalene : Visualization of Unique p-Electron Contributions"Chem. Phys. Lett.. 306. 187-196 (1999)

[Publications] H. Nagao: "Theoretical Studies on Anomalous Phases in Molecular Systems with external Field : Possibility of Photo-Induced Superconductivity"Int. J. Quant. Chem.. 75. 549-561 (1999)

[Publications] Y. Shigeta: "Density Functional Theory without the Born-Oppenheimer Approximation. II. Green Function Techniques"Int. J. Quant. Chem.. 75. 875-883 (1999)

[Publications] D. Yamaki: "Visualization of Two-Body Electron Densities and Wave Functions of Magnetic Molecules"Int. J. Quant. Chem.. 75. 645-654 (1999)

[Publications] S. Kiribayashi: "Self-Confistent-Field Calculations of Molecular Magnetic Properties Using Gauge-invariant Atomic Orbitals"Int. Quant. Chem.. 75. 637-643 (1999)

[Publications] S. Yamada: "Electron correlation and structure dependences of second hyperpolarizability of ethylene"Int. J. Quant. Chem.. 71. 177-183 (1999)

[Publications] S. Yamada: "CAS-SCF and density functional calculations of second hyperpolariizabilities for a nitronyl nitroxide radical"Int. J. Quant. Chem.. 71. 329-336 (1999)

[Publications] M. Nakano: "Numericasl coupled Liouville approah : application to second hyperpolarizability of molecular aggregate"Int. J. Quant. Chem.. 71. 295-306 (1999)

[Publications] M. Nakano: "Analysis of Spatial Contribution to the Second Hyperpolarizabilities of π-Conjugated Systems Involving Sulfur Atoms"J. Phys. Chem.. A103. 3103-3109 (1999)

[Publications] M. Nakano: "Quantum Phase Dynamics of an Initially One-Mode Amplitude-Squeezed Field Interacting with a Two-State Molecular System"Chem. Phys. Lett.. 304. 241-252 (1999)

山口兆大阪大学, 大学院・理学研究科, 教授 (80029537)