特異な非線形光学特性を有する分子および分子集合体の理論設計

1999 Fiscal Year Annual Research Report

• Project/Area Number: 11166239
• Research Institution: Osaka University
• Principal Investigator: 中野 雅由 大阪大学, 大学院・理学研究科, 助手 (80252568)
• Keywords: 非線形光学 / 超分極率 / ラジカル / 電子相関 / 導電性 / 交差共役系 / 縮環共役系 / テトラチアフルバレン

Research Abstract

第二超分極率γの理論的解析は、非線形光学効果の解明や新規光機能性物質の設計に重要であるが,我々は、摂動論に基づく設計指針を新たに構築し、これまでに検討されたことがない、非共鳴領域で負のγを与える系、およびγの電子相関依存性が顕著で制御可能性がある新規系を提案した。一つは、強磁性物質のスピン源としても興味深いニトロニルニトロキシドラジカル系であり、もう一つは、交差/縮環共役系である。これらの系は共に開殻系を含んでいるが、そのような系のγに関しての構造-特性相関はいまだよく検討されていない。そこでまず第一に、n中心ラジカル系(n:整数)をモデル系として取り上げ、等電子構造の対称な1中心ラジカル(BH_3^-,CH_3,NH_3^+)および3中心ラジカル(BH(CH_2)_2^-,CH(CH_2)_2,NH(CH_2)_2^+)のγについて様々な電子相関手法および密度汎関数法を用いた計算を行い、そのγの特性を検討した。次に、我々の設計指針に基づく導電性-非線形光学特性の複合機能性物質系の提案を行い、その基本物質モデルとしてテトラチアフルバレン(TTF)およびテトラチアペンタレン(TTP)のγについて検討した。Ab initio計算の結果、我々の予想通り、共にラジカルカチオン状態が負のγを与え、電子相関依存性が顕著なことが判明した。これらの解析には、我々が開発した超分極率密度図を使用し、電子のγに対する空間的寄与を明らかにした。

Research Products

• [Publications] M. Nakano: "Analysis of spatial contribution to the second hyperpolarizabilities of π-conjugated systems involving sulfur atoms"J. Phys. Chem. 103. 3103-3109 (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. 103. 6036-6048 (1999)
• [Publications] S. Yamada: "Structure-Property Correlation on Second Hyperpolarizabilities of Symmetric One-Center and Three-Center Radicals"J. Phys. Chem. 103. 7105-7115 (1999)
• [Publications] M. Nakano: "Numerical coupled Liouville approah : application to second hyperpolarizability of molecular aggregate"Int. J. Quant. Chem.. 71. 295-306 (1999)
• [Publications] S. Yamada: "CAS-SCF and density functional calculaions of second hyperpolarizabilities for a nitronyl nitroxide radical"Int. J. Quant. Chem. 71. 329-336 (1999)
• [Publications] S. Yamada: "Electron correlation and structure dependences of second hyperpolarizability of ethylene"Int. J. Quant. Chem.. 71. 177-183 (1999)
• [Publications] S. Kiribayashi: "Self-consistent-field calculations of molecular magnetic properties using gauge-invariant atomic orbitals"Int. J. Quant. Chem.. 75. 637-643 (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] M. Nakano: "Quantum phase dynamics of an initially one-mode amplitude squeezed field interacting with a two-state molecular system"Chem. Phys. Lett.. 304. 241-253 (1999)
• [Publications] M. Nakano: "Second hyperpolarizability density analyses for trithiapentalene and dioxathiapentalene : visualization of unique π-electron contributions"Chem. Phys. Lett.. 306. 187-196 (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] S. Yamada: "Theoretical studies on the second hyperpolarizabilities of trithiapentalene and its donor and acceptor disubstituted species"Optical Review. 6. 232-236 (1999)
• [Publications] S. Yamada: "Theoretical study on the second hyperpolarizabilities for small radical systems"Optical Review. 6. 237-241 (1999)
• [Publications] H. Nagao: "Quantum phase dynamis of interaction between photon field and magnetic system : effects of magnetic qunatum tunneling"Optical Review. 6. 227-231 (1999)
• [Publications] D. Yamaki: "Visualization of two-body electron-densities and wavefunctions for several molecules"Synthetic Metals. 103. 2002-2003 (1999)
• [Publications] M. Nakano: "Polarizabilities of molecular clusters : linear dimer models composed of H2NO"Synthetic Metals. 102. 1542-1542 (1999)
• [Publications] M. Nakano: "Second hyperpolarizability of trithiapentalene"Synthetic Metals. 102. 1543-1543 (1999)
• [Publications] S. Yamada: "Second hyperpolarizabilities of 1-center radicals"Synthetic Metals. 102. 1554-1555 (1999)
• [Publications] I. Shigemoto: "Theoretical study on second hyperpolarizability of copper dimer"Synthetic Metals. 102. 1562-1562 (1999)
• [Publications] M. Nakano: "Quantum phase dynamics: collapse and revival behavior in atwo-and a three-state molecule systems interacting with an initially oone-mode coherent field"Synthetic Metals. 102. 1540-1541 (1999)
• [Publications] Y. Shigeta: "Theoretical study on polarizability of ethylene by path integral method"Synthetic Metals. 101. 513-513 (1999)
• [Publications] M. Nakano: "Third-order Nonlinear Optical Properties of π-Conjugated Systems Involving Sulfur Atoms : A Proposal of Multi-property Materials Combining Conductivity and Unique Third-order Nonlinearity"Mol. Cryst. Lig. Cryst.. 337. 369-372 (1999)
• [Publications] S. Yamada: "Theoretical Study on the Second Hyperpolarizabilities for Small Radical Systems"Mol. Cryst. Lig. Cryst.. 337. 393-396 (1999)
• [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-photon field dynamics: numerically exact calculation of multi-state molecule systems interacting with a single-mode coherent photon field"Chem. Phys. 252. 115-150 (2000)
• [Publications] M. Nakano: "Electron-correlation dynamics of one-dimensional H2 model in a photon field"Chem. Phys. Lett.. 317. 103-108 (2000)