含氮杂环钆(III)配合物电子结构与化学成键的理论研究

项目名称： 含氮杂环钆(III)配合物电子结构与化学成键的理论研究

项目编号： No.21501189

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 数理科学和化学

项目作者： 熊孝根

作者单位： 中国科学院上海应用物理研究所

项目金额： 20万元

中文摘要： 镧系元素的含氮杂环配合物由于其在发光材料及镧锕分离中的应用而逐渐受到人们的重视。含氮杂环类配体作为最有希望的提取剂被广泛地用于镧锕分离研究；此外，镧系离子由于其复杂的4f电子态使得其配合物具有丰富的发光现象。本项目选取镧系元素钆的含氮杂环配合物作为研究对象，研究钆离子与含氮杂环配体间的相互作用及形成配合物的基态和激发态电子结构。尽管在实验研究中已有大量积累，但由于镧系特有的复杂电子相关及相对论效应，使得该类配合物的精确量子化学计算尚处于非常初步的阶段。本项目拟采用最新的量子化学计算方法并结合现代化学成键理论，从理论上研究该类配合物的电子结构及化学成键。通过化学成键分析阐述含氮杂环萃取剂在镧锕分离中的作用机理；通过基态及激发态电子结构计算，掌握含氮杂环钆配合物的发光现象的机理和规律。本研究项目从分子水平上研究含氮杂环钆配合物的功能机理及特征，为解释相关实验现象奠定理论基础。

中文关键词： 含氮杂环钆（III）配合物；计算镧系化学；化学成键；激发态；静态电子相关

英文摘要： Lanthanide complexes with N-containing heterocyclic ligands have attracted considerable attention due to their applications in luminescent materials and lanthanide/actinide (Ln/An) separation process. N-containing heterocyclic ligands are the most promising candidates among the selective extracting agents used in Ln/An separation. Lanthanide ions also possess fascinating optical properties ascribing to the complicated 4f electronic structures. This program will focus on the electronic structure of ground state and excited states and chemical interactions in Gd(III) complexes with N-containing heterocyclic ligands. Comparing with the extensive investigations in experimental studies, the accurate quantum chemical calculations of these complexes are very rudimentary due to the complicated electron correlation and relativistic effects of lanthanide ions. The state-of-art quantum chemical methods and modern chemical bonding analyses will be used to study the electronic structures and chemical interactions in Gd(III) complexes with N-containing heterocyclic ligands. The mechanism of the extract agents in Ln/An separation and functionality of Gd(III)-containing luminescent materials will be illustrated. This program will be tailored for understanding the character and functionality of Gd(III) complexes at the molecular level and building up the basis for the interpretation of the related experimental studies.

英文关键词： Gd(III) complexes with N-containing heterocyclic ligands;computational lanthanide chemistry;chemical bonding;excited state;static electron correlation