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，特别是由活性分子组成的界面系统和活性分子所处的背景环境，建立精确的电子结构理论和程序包。会议的重点特别放在下列主题上：2.大系统电子相关方法的发展，特别是基于多参考点（MR）的微扰理论（PT）。大尺度系统的相对论方法的发展，3。开发一个高效的程序包，包括电子相关和相对论方法；大尺度体系的电子结构与化学反应研究。在电子相关法中，精确、高效的方案是至关重要的。利用多参考摄动格式，我们建立了一个具有优化哈密顿分划的多构型摄动理论和一个具有最大收敛半径的摄动理论。我们还提出了非正交定域轨道的Kohn-Sham DFT方法。除了电子相关效应外，相对论效应对于包含重原子的大尺度系统也很重要。我们发展了四分量多参考微扰（相对论GMC-QDPT）和组态相互作用（CI）方法。本文还提出了用于MRPT和MRCI方法的相对论高斯基集。这些方法已在一个从头算程序包UTChem.4中实现。利用这些电子相关和相对论方法，我们在包括大尺度系统在内的分子中进行了以下应用：硅碳团簇最稳定的结构、层状无机化合物矿化的模板效应、长多烯的电子结构、氨对NO的选择性催化还原、merocyanine染料的结构和电子激发态、甲基乙烯醚OH自由基的链氧化反应、二酮的光解反应、过渡金属水络合物的激发光谱、以及n掺杂卟啉的激发态性质。少

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