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

保证包含所有原子的所有类型分子的量子化学计算的准确性是量子化学的重要课题之一。电子相关方法必须用相对论性哈密顿量重新构造。关于相对论性电子相关的新理论和新方法需要通过应用于能量和分子性质，特别是分子磁性的计算来仔细检验。这个项目是根据上述观点来规划的。在项目的最后阶段，我们将结果简单总结如下。首先，我们建立了四分量狄拉克波函数的基函数。采用四分量电子相关（CCSD）方法计算了核磁屏蔽张量。作为一种具体而经济的方法，我们开发了一种精确的二分量相对论方法，其中使用有限阶FW变换。对需要相对论性修正的分子和分子性质进行了一系列的应用。我们显示了下面的清单1。四分量dirac - hartree - fock - roothan方法的基集无穷阶FW变换方法应用(1)圆二色性和磁性圆二色性(2)核磁屏蔽张量(i)用四分量CCSD方法得到的HX (X = F, Cl, Br, i) (ii) X（-）和XO4(-) (X = F, Cl, Br, i)：电子相关和相对论修正的协同效应。Fe(iii) -卟啉的铁结合CN的顺磁13-C核磁共振化学位移：(3)分子磁化率结合二阶自旋相关的Douglas-Kroll方法，建立了时间相关的广义UHF （TD-GUHF）方法。我们展示了在te2中分子磁化率的相对论效应。

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.