一些重要有机功能分子间弱相互作用的密度泛函研究

项目名称： 一些重要有机功能分子间弱相互作用的密度泛函研究

项目编号： No.20803083

项目类型： 青年科学基金项目

立项/批准年度： 2009

项目学科： 轻工业、手工业

项目作者： 丁迅雷

作者单位： 中国科学院化学研究所

项目金额： 18万元

中文摘要： 三年来，我们根据研究计划，选择了一些典型的有机分子体系进行研究。考虑了不同的量子化学计算水平如密度泛函的不同泛函以及从头算的MP2和CCSD(T)等对计算结果的影响以及基组重叠误差的重要性，使用了多种理论分析方法如Mulliken布局分析、自然键轨道（NBO）分析、分子中的原子（AIM）分析、能量分解等，从而给出弱相互作用的多种微观信息。研究取得了以下重要成果：（1）研究得到了卟啉二酸聚集体的稳定构型，并讨论了水分子对聚集体结构的影响，研究结果与晶体数据一致，表明对两个或几个气态分子间相互作用的研究可以用来理解凝聚相聚集体系的一些性质；（2）研究得到了杂环化合物（呋喃、噻吩、吡啶）与 Lewis 酸HCl和ClF间相互作用的情况，发现其中一些体系违反了Legon-Millen规则；（3）我们还研究了有机分子与团簇之间的相互作用情况，指出氧化物团簇中的氧自由基是与有机分子反应的活性中心。本项目的研究结果给出了有机分子之间以及有机分子与团簇之间相互作用的一些重要规律，有益于推测有机物聚集/反应的微观机理，在能源、化工等领域具有一定的指导作用。

中文关键词： 密度泛函; 弱相互作用; 有机分子; 团簇

英文摘要： We have studied several typical organic molecular systems according to the proposal of the project in the past three years. We have considered the influences of theoretical levels of quantum chemistry to the calculation results, such as different functionals of density functional theory, MP2 and CCSD(T) of ab initio methods, as well as the basis set superposition error (BSSE). Various theoretical analysis methods were used such as Mulliken population analysis, Natural Bond Orbital (NBO) analysis, Atoms in Molecules (AIM) analysis, and energy decomposition analysis, so that micro-information of weak interactions can be revealed. Several achievements have been obtained: (1) Stable structures of meso-tetraphenylporphyrin diacid dimer (H4TPPCl2)2 are determined, and the influence of water molecules is also considered. Our results are supported by the crystal structure data, which indicates that study of the interactions between two or a small number of gas molecules can provide important information for understanding the main interactions and stable structures in related condensed-phase systems; (2) The weak interactions between heteroaromatic rings (C4H4O, C4H4S and C5H5N) and Lewis acids (ClF, HCl) have been studied, and some of these weak interaction systems are found to violate the Legon-Millen rule. （3）The interactions of organic molecules with clusters have also been studied, and oxygen-centered radicals in oxide clusters are found to be the active sites in the reactions with organic molecules. In summary, results in this project provide some general rules of the weak interactions among organic molecules or interactions between organic molecules with clusters. These finding are useful to predict the mechanisms of aggregation or reaction of organic molecules, and may provide some theoretical guidances in energy and chemical industries.

英文关键词： Density functional theory; weak interaction; organic molecule; cluster