Construction and development of the future field of theoretical chemistry

未来理论化学领域的建设与发展

• 批准号: 10102005
• 负责人: NAKATSUJI Hiroshi
• 金额: $ 105.86万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Specially Promoted Research
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10102005/
• 关键词: exact wave function; molecular excited states; photosynthetic reaction; biological quantum chemistry; relativistic quantum chemistry; magnetic quantum chemistry; reactions on surface; direct determination of density matrix; シュレディンガー方程式の厳密解; 励起分子

(1) Exact wave function : Structure of the exact wave function of the Schrodinger equation has been studied. We proposed ICI (Iterative CI) and ECC (Extended Coupled Cluster) methods, in which numbers of variables are from one to singles and doubles. These theories were formulated for both the ground and excited states. They were applied to the simple system and were shown to be useful.(2) Theory for molecular excited states : Analytical energy gradients of the SAC/SAC-CI method were developed and implemented. The method was extended to the SAC-CI general-R method that is useful for the multi-electron process. Accurate theoretical spectroscopy has been achieved for the satellite peaks appearing in the ionization spectra and the excitation spectra of various aromatic compounds.(3) Photosynthetic reaction center and biological quantum chemistry : Excitation spectrum of whole photosynthetic reaction center was theoretically assigned by the SAC-CI calculations. The origin of the unidirecti … More onality of the electron transfer was elucidated to be the electronic factor in the rate constant. Perturbation theoretical method was developed for evaluating the electronic factor of the electron transfer in the protein, by which theoretical mutation is feasible.(4) Relativistic quantum chemistry : Two-component quasi-relativistic theory of the NMR has been established. GIAO method was introduced for eliminating the dependence of guage-origin dependence. Finite nucleus model was also included. Full-relativistic four-component Dirac-Fock theory of the NMR was developed and the results were compared with the two-component theory.(5) Reactions on surface : Oxidation mechanism of the propylene and acetylene on Ag surface was studied by the Dipped Adcluster Model (DAM). Mechanism of the methanol synthesis by the hydrogenation of the CO_2 on Cu (100) and Zn/Cu (100) was studied.(6) Direct determination of the density matrix : Time-dependent density equation and the perturbation theory for the density equation were formulated. Density equation method was extended to the open-shell system and the excited states. Density matrix variational method was developed. Less

(1)精确波函数：研究了薛定谔方程精确波函数的结构。我们提出了ICI（迭代CI）和ECC（扩展耦合簇）方法，其中变量的数目从一个到单变量和双变量。这些理论是为基态和激发态制定的。它们被应用到简单的系统，并被证明是有用的。(2)分子激发态理论：SAC/SAC-CI方法的分析能量梯度被开发和实施。将该方法推广到适用于多电子过程的SAC-CI广义R方法。对各种芳香族化合物的电离光谱和激发光谱中出现的卫星峰进行了精确的理论谱学计算。(3)光合反应中心与生物量子化学：通过SAC-CI计算，对整个光合反应中心的激发光谱进行了理论归属。单向阀的起源 ...更多信息 电子转移的速率常数是电子因素。提出了微扰理论方法来计算蛋白质中电子转移的电子因子，使理论突变成为可能。(4)相对论量子化学：建立了核磁共振的双组分准相对论理论。引入GIAO方法消除语言依赖。还包括有限核模型。发展了核磁共振的全相对论四分量Dirac-Fock理论，并与二分量理论的结果进行了比较。(5)表面反应：用浸渍吸附团簇模型（DAM）研究了丙烯和乙炔在银表面的氧化机理。研究了Cu（100）和Zn/Cu（100）催化剂上CO_2加氢合成甲醇的反应机理。(6)密度矩阵的直接确定：建立了含时密度方程和密度方程的微扰理论。将密度方程方法推广到开壳层体系和激发态。发展了密度矩阵变分法。少