Electronic structure calculations of sub-nanometer oxide-supported transition metal particles

该项目旨在增加我们对支撑在具有重要技术意义的氧化物衬底表面上的小型亚纳米级过渡金属物种的结构、成键和电子性质的了解，这些氧化物衬底包括镁、铝、二氧化钛和二氧化硅。为此，将使用申请人小组中开发的并行计算机程序PARAGAUSS进行充分嵌入的表面团簇模型的高水平密度泛函计算。该程序提供了各种功能，对项目目标有利，例如，氧化物衬底团簇的一致嵌入，标量相对论和自旋轨道效应的自洽处理，计算激发能和电子g张量的选项。这一理论工作将补充优先项目中的实验项目，例如乌尔姆大学的U·海兹和汉堡大学的W·沃思。在第一个资助期内，工作重点将集中在两类具有明显量子尺寸效应的支撑金属系统的几何结构和电子结构以及各种光谱参数上：(1)铁、钴和镍亚组的高自旋原子的低核度团簇，强调表面不规则性的影响；(2)铸币金属在不同载体上的小颗粒，追踪氧化物支撑与沉积相互作用的特殊性。

The project aims at increasing our understanding of the structure, bonding and electronic properties of small sub-nanoscale transition metal species supported on surfaces of technologically important oxide substrates, like Mg0, Al203, TiO2 und SiO2. For this purpose, high-level density functional calculations of adequately embedded surface cluster models will be carried out, using the parallel computer code PARAGAUSS developed in the group of the applicant. This program provides various features, advantageous for the goals of the project, e.g. a consistent embedding for oxide substrate clusters, self-consistent treatment of scalar relativistic and spin-orbit effects, options for calculating excitation energies and electronic g tensors. This theoretical effort will supplement experimental projects within the priority program, e.g. by U. Heiz, University of Ulm, and W. Wurth, University of Hamburg. During the first funding period, work will focus on the geometric and electronic structure as well as various spectroscopic parameters of two types of supported metal systems that exhibit pronounced quantum size effects: (i) low nuclearity clusters of high-spin atoms of the Fe, Co and Ni subgroups on the well-characterized substrate MgO, emphasizing the influence of surface irregularities; (ii) small particles of the coinage metals on varying supports, tracing the specificity of the oxide support for interactions with the deposits.