Four-Component Dirac-type Electron-Correlation Theory : Excited State Chemistry and Magnetic Chemistry

保证所有类型的全原子分子的量子化学计算的准确性是量子化学中最重要的课题之一。电子相关方法必须用相对论哈密顿量重建。相对论电子关联的新理论和新方法需要在能量和分子性质，特别是分子磁性的计算中得到仔细的检验。本项目就是按照上述观点进行规划的。在本项目的最后阶段，我们简要地总结了以下成果。首先，我们发展了四分量狄拉克波函数的基函数。用四分量电子相关(CCSD)方法计算了核磁屏蔽张量。作为一种具体而经济的方法，我们发展了一种使用有限阶FW变换的精确二分量相对论方法。对需要相对论修正的分子和分子性质进行了一系列的应用。我们列出了下面的清单。四组分Dirac-Hartree-Fock-Roothaan方法的基组2。无限阶FW变换方法3.应用(1)圆二色和磁性圆二色谱(2)用四分量CCSD方法计算的核磁屏蔽张量(I)HX(X=F，Cl，Br，I)(II)X(-)和XO4(-)(X=F，Cl，Br，I)：电子关联和相对论修正的协同效应。(Iii)Fe(III)-卟啉的铁键CN的顺磁13-C核磁共振化学位移：(3)分子磁化率。含时广义超高频(TD-GUHF)方法与二阶自旋相关的Douglas-Kroll方法相结合。我们研究了相对论效应对TeH2分子磁化率的影响。

Guarantee on the accuracy of quantum-chemical calculations over all types of molecules containing all atoms is one of the most important subjects in the quantum chemistry. Electron-correlation methods must be re-constructed with relativistic hamiltonians. The new theories and methods concerning relativistic electronic-correlation are required to be checked carefully by applying to calculations of energies and molecular properties, in special, molecular magnetic properties. This project was planed on the viewpoint described above.At the Final stage of this project, we summarize the results briefly as follows. First, we developed the basis functions for 4-component Dirac wave-functions. The nuclear magnetic shielding tensor was calculated using the 4-component electron-correlation (CCSD) method. As one of the concrete and economic methods, we developed an accurate 2-component relativistic method in which the finite-order FW transformation is used. A series of applications were carried out for molecules and molecular properties which are required the relativistic corrections. We show the listing below.1. Basis Sets for the Four-Component Dirac-Hartree-Fock-Roothaan Method2. Infinite-Order FW transformation Method3. Applications(1) Circular Dichroism and Magnetic Circular Dichroims(2) Nuclear Magnetic Shielding Tensdrs(i) HX (X = F, Cl, Br, I) by the 4-component CCSD method(ii) X(-) and XO4(-) (X = F, Cl, Br, I) : Synergistic effects of electron-correlations and relativistic corrections.(iii) Paramagnetic 13-C NMR chemical shifts of iron-bounded CN of Fe(III)-porphyrins :(3) Molecular MagnetizabilityThe Time-Dependent Generalized UHF (TD-GUHF) method was developed incorporating with the second-order spin-dependent Douglas-Kroll method. We showed the relativistic effects on the molecular magnetizabilities in TeH2.