Relativistic Electronic Structure Theory and Its Applications to Chemical Reactions

相对论电子结构理论及其在化学反应中的应用

• 批准号: 11166259
• 负责人: YABUSHITA Satoshi
• 金额: $ 7.36万
• 依托单位: Keio University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas (A)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11166259/
• 关键词: Relativistic theory; Relativistic effect; Spin-obit interaction; SOCI method; Non-adiabatic interaction; L-uncoupling interaction; Herzberg band; Rozen-Zener-Demkov type; ヘルツベルグ吸収帯; 非断熱過程; 微細構造準位; 相対論; ランタノイドイオン

1. For the electronic structure calculations for molecules containing heavy atoms, an efficient spin-orbit (SO) CI method was formulated and implemented in the Columbus program system. For the efficient calculations, various group theories, such as unitary group, time-reversal symmetry, and double point group have been employed. SO interactions have been included in the SCF and MCSCF methods and the programs have been used to analyze the LS and jj coupling schemes in various atoms and cations.2. Photodissociation of Cl_2 molecule has been studied with the SOCI method and a Rosen-Zener-Demkov type non-adiabatic interaction at about R=6 bohr was found to be responsible for the wavelength dependence of the product branching ratio, anisotropy parameter, and quantum mechanical interference of the orientation of angular momentum j=l/2 of the product Cl(^2P_<1/2>) atom.3. Vibrational and rotational absorption intensities of the O_2 Herzberg band have been studied by the SOCI method with the theoretically obtained electronic transition moments and L-uncoupling matrix elements. In spite of the very weak intensities, fairly good agreement with experimental data was obtained. As for the anisotropy parameter, our data support the experimental results of Parker et al. The branching ratios of the products were determined by the multi-level and multi-step non-adiabatic interactions at longer bond distances.4. We have also studied theoretically on Icl, I^-_3, Xe+I_2, HgCO, HgAr, lanthanide cations, and transition metal-benzene complexes and so on.

1. 对于含重原子分子的电子结构计算，提出了一种有效的自旋轨道CI方法，并在Columbus程序系统中实现。为了提高计算效率，使用了各种群论，如酉群、时间反转对称性和双点群。在SCF和MCSCF方法中包含了SO相互作用，并使用程序分析了各种原子和阳离子的LS和jj耦合方案。用SOCI方法研究了Cl_2分子的光解作用，发现在R=6玻尔时，产物分支比、各向异性参数的波长依赖性和产物Cl（^2P_<1/2>）原子角动量j=l/2取向的量子力学干涉是由Rosen-Zener-Demkov型非绝热相互作用引起的。利用理论得到的电子跃迁矩和l -解耦矩阵元素，用SOCI方法研究了O_2赫兹伯格带的振动和旋转吸收强度。尽管强度很弱，但与实验数据相当吻合。对于各向异性参数，我们的数据支持Parker等人的实验结果。在较长的键距下，多阶非绝热相互作用决定了产物的支化率。对Icl、I^-_3、Xe+I_2、HgCO、HgAr、镧系离子、过渡金属-苯配合物等进行了理论研究。

项目成果

O. Takahashi: "Simple SCF Method with Spin-orbit Interaction : SOSCF Method"International Journal of Quantum Chemistry. 74. 515-530 (1999)

O. Takahashi：“具有自旋轨道相互作用的简单 SCF 方法：SOSCF 方法”国际量子化学杂志。

Y. Asano: "Theoretical study on the nonadiabatic transitions in the photodissociation processes of Cl_2"Journal of Physical Chemistry, A. 105. 9873-9882 (2001)

Y. Asano：“Cl_2 光解离过程中非绝热转变的理论研究”物理化学杂志，A. 105. 9873-9882 (2001)

K. Takahashi: "Theoretical analysis of the CH stretching overtone vibration of 1,2-dichloroethylene"Journal of Physical Chemistiy, A. in press. (2002)

K. Takahashi：“1,2-二氯乙烯的CH伸缩泛音振动的理论分析”物理化学杂志，A.正在出版。

Y.Asano: "Theoretical study on the nonadiabatic transitions in the photodissociation processes of Cl_2"Journal of Physical Chemistry, A. 105・43. 9873-9882 (2001)

Y.浅野：“Cl_2光解离过程中非绝热转变的理论研究”物理化学杂志，A. 105・43（2001）。

S.Yabushita: "Spin-Orbit Configuration Interaction Using the Graphical Unitary Group Approach and Relativistic Core Potential and Spin-Orbit Opnerators"Journal of Physical Chemistry, A. 103. 5791-5800 (1999)

S.Yabushita：“使用图形酉群方法和相对论核心势和自旋轨道算子的自旋轨道构型相互作用”物理化学杂志，A. 103. 5791-5800 (1999)