Construction and development of the future field of theoretical chemistry

(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(扩展耦合聚类)方法，其中变量的个数从1到单变量和双变量。这些理论既适用于基态，也适用于激发态。分子激发态理论：发展并实现了SAC/SAC-CI方法的能量梯度分析。将该方法推广到适用于多电子过程的SAC-CI General-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光谱分析。(3)光合作用反应中心与生物量子化学：通过SAC-CI计算对整个光合作用反应中心的激发光谱进行了理论归属。单向…的起源电子转移的更多共性被阐明为速率常数中的电子因素。建立了微扰理论方法来计算蛋白质中电子转移的电子因子，理论突变是可行的。(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。为了消除量具来源依赖关系，引入了Giao方法。有限核模型也包括在内。建立了核磁共振全相对论四组分Dirac-Fock理论，并与二组分理论的计算结果进行了比较。(5)表面反应：采用浸渍Adcluster模型(DAM)研究了丙烯和乙炔在银表面的氧化反应机理。研究了CO_2在铜(100)和锌/铜(100)上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摄动理论。将密度方程方法推广到开壳体系和激发态。发展了密度矩阵变分方法。较少

(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