The development of accurate electronic structure theory for large systems and its application to interface systems

本研究的目的是为大规模系统，特别是由活性分子部分和为活性分子提供环境的背景组成的界面系统，开发精确的电子结构理论和程序包。重点关注以下主题：1.大型系统电子相关方法的开发，特别是基于多参考（MR）的微扰理论（PT），2.大型系统相对论方法的开发，3.包括电子相关和相对论方法在内的高效程序包的开发，以及4.大型系统的电子结构和化学反应的研究。1.在电子相关方法中，准确高效的方案至关重要。利用多参考扰动方案，我们开发了具有优化哈密顿划分的多配置扰动理论和具有最大收敛半径的扰动理论。我们还提出了非正交局域轨道的Kohn-Sham DFT方法。2.除了电子相关效应之外，相对论效应对于包括重原子的大尺度系统也很重要。我们开发了四分量多参考扰动（相对论 GMC-QDPT）和配置交互（CI）方法。还提出了使用这些 MRPT 和 MRCI 方法的相对论高斯基组。3.这些方法已在从头计算程序包 UTChem 中实现。4.通过这些电子关联和相对论方法，我们在包括大型系统在内的分子中进行了以下应用：硅碳簇的最稳定结构、层状无机化合物矿化的模板效应、长多烯的电子结构、NO 的选择性催化还原氨、部花青染料的结构和电子激发态、OH自由基对甲基乙烯基醚的链式氧化反应、二酮的光解反应、过渡金属水配合物的激发光谱以及N-混乱的卟啉的激发态性质。较少的

The aim of the present research was to develop an accurate electronic structure theory and a program package for large-scale systems, especially for the interface systems which consist of an active molecular part and the background giving environment to the active molecule. The focus was especially on the following topics : 1.Development of electron correlation methods for large-scale systems, in particular a multireference (MR) based perturbation theory (PT), 2.Development of relativistic methods for large-scale systems, 3.Development of an efficient program package including the electron correlation and relativistic methods, and 4.Studies on the electronic structure and chemical reaction of large-scale systems.1.In the electron correlation method, an accurate and efficient scheme is essential. Utilizing the multireference perturbation scheme, we have developed a multiconfigurational perturbation theory with optimized Hamiltonian partitioning and a perturbation theory with the maximum … More radium of convergence. We have also presented Kohn-Sham DFT method with non-orthogonal localized orbitals.2.In addition to the electron correlation effect, the relativistic effect is also important for the large-scale system including heavy atoms. We have developed four-component multireference perturbation (relativistic GMC-QDPT) and configuration interaction (CI) methods. Relativistic Gaussian basis sets for the use of these MRPT and MRCI methods were also proposed.3.The methods have been implemented into an ab initio program package, UTChem.4.With these electron correlation and relativistic methods, we have made the following applications to molecules including large-scale systems : the most stable structure of silicon-carbon clusters, templating effects on the mineralization of layered inorganic compounds, the electronic structure of long polyenes, the selective catalytic reduction of NO by ammonia, the structure and electronic excited states of merocyanine dyes, the chain oxydation reactions of methyl vinyl ether by OH radical, the photodissociation reaction of diketones, the excitation spectra of transition metal aqua complexes, and the excited state properties of N-confused porphyrin. Less