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

四分量狄拉克型电子相关理论：激发态化学和磁化学

基本信息

批准号：
14340179
负责人：
HADA Masahiko
金额：
$ 8万
依托单位：
Tokyo Metropolitan University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2005
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14340179/
关键词：
Dirac Method Nuclear Magnetic Shielding Tensor Molecular Magnetizability Relativistic Effect Magnetic Circular Dichroism Infinite-Order FW Method GUHF Method Heme 電子相関励起状態 NMR 磁気化学無限次FW 相対論的効果 CDスペクトル旋光強度 NMR化学シフトジカルコ

项目摘要

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.

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来重建。关于相对论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，特别是分子磁性质的计算来仔细检验。本项目就是基于上述观点进行规划的。在本项目的最后阶段，我们将结果简要总结如下。首先，我们开发了 4 分量狄拉克波函数的基函数。使用四分量电子相关（CCSD）方法计算核磁屏蔽张量。作为具体且经济的方法之一，我们开发了一种精确的二分量相对论方法，其中使用了有限阶 FW 变换。对需要相对论修正的分子及其性质进行了一系列的应用。我们展示如下清单：1。四分量 Dirac-Hartree-Fock-Roothaan 方法的基组2。无限阶FW变换方法3．应用(1) 圆二色性和磁圆二色性(2) 核磁屏蔽 Tensdrs(i) HX (X = F, Cl, Br, I)，采用 4 分量 CCSD 方法(ii) X(-) 和 XO4(-) (X = F, Cl, Br, I)：电子相关和相对论校正的协同效应。(iii) 顺磁性13-C NMR化学 Fe(III)-卟啉的铁结合CN的位移：(3)分子磁化率时变广义UHF(TD-GUHF)方法是与二阶自旋相关Douglas-Kroll方法结合开发的。我们展示了 TeH2 中分子磁化能力的相对论效应。