d9离子功能材料的电磁特性与微观结构调控研究

d9离子功能材料广泛应用于光催化、传感器、生物医学等领域，其电子结构和顺磁参量对理解此类材料的光电磁特性有重要的科学价值。目前，人们对单一样品材料(或最近邻配位为同一配体的材料体系)进行了广泛的研究，而涉及多类型样品材料(以及最近邻配位为多类型配体的功能材料)的系统性分析较少，因此该类功能材料的结构与性能之间的规律性关系尚不清晰。本项目将按照配体类型和配位构型对d9离子功能材料进行统计分类，并结合半经验参量法和第一性原理的电子结构计算，分析离子掺杂、电荷补偿、氢键作用等因素对各类材料微结构的影响；探讨多类型配体对体系顺磁参量的定量贡献，掌握配体种类/配位构型与晶体场参量/能级结构之间的依赖关系，建立此类材料的普适性理论模型；在合理解释实验现象的基础上设计出新型的d9离子功能材料，为进一步的实验合成与功能开发提供前期的理论指导。

The electronic structures and magnetic parameters of d9-ion functional materials have significant scientific value to understand the optical, electronic and magnetic properties of transition-metal functional materials which have been widely utilized in fields of photocatalysis, sensor, and biomedicine and so on. Although abundant studies on the single sample (or the system in which the d9 ions are nearest-neighborly coordinated with the same kind of ligand) have been carried out, the systematic analysis for the multi-types samples (or d9 ions are nearest-neighborly coordinated with different kinds of ligands) has been rarely reported. As a result, the regular relationship between the structure and property for the above functional materials is still unclear. In this program, firstly, the functional materials containing d9 ions will be sorted and counted according to the type of ligand and the coordination geometry. And then the role of doping, charge compensation and hydrogen bonding and other effects playing on the local structure are to be acquired with the aid of the combination of first principles calculation and semi-empirically parametric method. Furthermore, the quantitative contributions arising from different species to the paramagnetic parameters of hosts and the general dependency laws among the intermediate variable (such as the crystal field parameters and the energy levels and et al.) and the types of ligands (or the local symmetry) will be obtained. Finally, the experimental phenomena for these functional materials containing d9 ions will be reasonably explained by means of the valid model established in this work, new type of functional materials will be designed and preceding theoretical guidance will be achieved for the further synthesis of materials with presupposed function.