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

• 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

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.

保证量子化学计算的准确性在所有类型的分子中，包含所有原子是量子化学中最重要的主题之一。电子相关方法必须与相对论的哈密顿人重建。需要在特殊的分子磁性特性中应用计算能量和分子特性来仔细检查有关相对论电子相关的新理论和方法。该项目是根据上述观点计划的。在该项目的最后阶段，我们简要总结了结果。首先，我们为4组分DIRAC波函数开发了基础函数。使用4-分量电子相关（CCSD）方法计算核磁屏蔽量张量。作为具体和经济方法之一，我们开发了一种准确的2组分相对论方法，其中使用有限的FW转换。对分子和分子特性进行了一系列应用，这些应用需要相对论校正。我们在下面显示清单1。四组分迪拉克 - 哈特里 - 佛教 - 根源方法的基集2。无限阶FW转换方法3。应用（1）循环二分法和磁性圆形二分法（2）核磁屏蔽tensdrs（i）HX（x = f，cl，br，i）通过4-成分的CCSD方法（ii）x（ii）x（ii）x（ - ）和xo4（ - ）和xo4（ - ）（x = f，cl，br，i）：Electron-corthistion and reserron-cormentiment（II II II）（II II）（II II）。 Fe（iii）-Porphyrins的铁结合的CN的转移：（3）分子磁化性时间依赖性的广义UHF（TD-GUHF）方法是与二阶自旋依赖性的Douglas-Kroll方法合并的。我们展示了对TEH2中分子磁化的相对论影响。

项目成果

Orientational Effect of Aryl Group on ^<77>Se NMR Chemical Shifts : Experimental and Theoretical Investigations

芳基对^ 77 Se NMR化学位移的取向影响：实验和理论研究

• 发表时间: 2006
• 期刊: Chemistry - A European Journal 12・14
• 作者: W.Nakanishi;S.Hayashi;D.Shimizu;M.Hada
• 通讯作者: M.Hada

Theoretical studies on magnetic circular dichroism by the finite perturbation method with relativistic corrections

相对论修正有限摄动法对磁圆二色性的理论研究

• 发表时间: 2005
• 期刊: J.Chem.Phys. 123
• 作者: Y.Honda;M.Hada;M.Ehara;H.Nakatsuji;J.Michl
• 通讯作者: J.Michl