Theory

与其他funCOS项目密切合作，funCOS 6专注于对结构化金属氧化物表面上功能化有机分子的吸附物-基底和吸附物-吸附物相互作用的全面理论原子级理解，旨在最终实现具有特定结构，电子和光学特性的有机薄膜的可控形成。改变吸附物-基质相互作用的方法是用特定的连接基团取代有机分子或修饰基质，例如通过表面羟基化。以这种方式，可以影响在原始表面上或在纳米结构的金属氧化物衬底处的低配位位点处的吸附位点和几何形状。吸附物与基质的相互作用包括诸如卟啉自金属化等化学反应。吸附物-吸附物相互作用通过相邻吸附位点之间的距离取决于吸附物-基质相互作用，可以通过官能团进行调节。funCOS理论领域追求基于密度泛函理论的这些主题的理论建模，并辅以范德华修正和Hubbard-U方法，从头算分子动力学模拟以及其他高级电子结构方法，即含时密度泛函理论，多体微扰理论（GW/BSE）和基于波函数的方法。调查将采用funCOS在第一个资助期内获得的关于连接分子、较小有机分子网络和功能化卟啉的金属化反应的知识。金属吸附原子与功能化有机分子的结合可能为创建2D金属有机网络提供新的机会。建模将预测吸附原子和连接基团的组合是有希望的自组装这种网络。金属氧化物衬底是结构形成的关键元素，因此是关于其电子性质和低配位位点（例如表面缺陷、金属吸附原子或羟基）的研究主题。将研究MgO、TiO 2和不同的钴氧化物的表面以及金属上的相应的薄氧化物膜，特别是MgO/Ag（100）、CoO（100）/Ir（100）和Co 3 O 4（111）/Ir（100）。在这方面，新型纳米颗粒系统，如Mg（1-x）Co（x）O纳米晶体和MgO纳米立方体堆叠，是特别感兴趣的，因为它们的特征在于Co原子在表面，不同取向的表面和连接元素作为功能分子的吸附位点。从溶液中沉积大的有机分子是一种非常有吸引力的，实验上容易处理的气相制备的替代方法。将从头算模型超越表面科学方法应用于金属氧化物/液体界面是一个巨大的进步。funCOS理论领域将研究液体与金属氧化物的相互作用以及液体/氧化物界面处的化学反应。

In close collaboration with the other funCOS projects, funCOS 6 focuses on a comprehensive theoretical atomic-scale understanding of the adsorbate-substrate and adsorbate-adsorbate interactions of functionalized organic molecules on structured metal-oxide surfaces, with the aim to eventually enable a controlled formation of organic films with specific structural, electronic and optical properties. Means to alter the adsorbate-substrate interaction are the substitution of organic molecules with specific linker groups or the modification of the substrate, for instance via a surface hydroxylation. In this way, adsorption sites and geometries on pristine surfaces or at low-coordinated sites at nano-structured metal-oxide substrates may be influenced. The adsorbate-substrate interaction includes chemical reactions like the self-metallization of porphyrins. The adsorbate-adsorbate interaction, which hinges on the adsorbate-substrate interaction via the distance between adjacent adsorption sites, can be tuned via functional groups. The funCOS theory area pursues theoretical modeling of these topics based on density- functional theory supplemented by Van-der-Waals corrections and Hubbard-U approaches, ab initio molecular dynamic simulations, and additional high-level electronic structure methods, i.e. time-dependent density functional theory, many-body perturbation theory (GW/BSE), and wave- function-based methods. Investigations will take up the knowledge gained in the first funding period of funCOS on linker molecules, networks of smaller organic molecules, and metalation reactions of functionalized porphyrins. Metal adatoms in combination with functionalized organic molecules may open new opportunities to create 2D metal-organic networks. Modeling will predict which combinations of adatoms and linker groups are promising for the self-assembly of such networks. The metal-oxide substrate is a key element of structure formation and thus a topic of investigations regarding its electronic properties and low-coordinated sites such as surface defects, metal adatoms or hydroxyl groups. The surfaces of MgO, TiO2, and different cobalt oxides and corresponding thin oxide films on metals, specifically MgO/Ag(100), CoO(100)/Ir(100), and Co3O4(111)/Ir(100) will be investigated. In this respect, novel nanoparticle systems, like Mg(1-x)Co(x)O nanocrystals and MgO nanocube stacks, are of particular interest as they feature Co atoms at the surface, surfaces of different orientation and connecting elements as adsorption sites for functional molecules. Deposition of large organic molecules from solution is a very appealing, experimentally easy to handle alternative to the gas phase preparation. To take ab initio modeling beyond the surface science approach to the metal oxide/liquid interface is a huge step. The funCOS theory area will investigate interactions of liquids with metal oxides and chemical reactions at the liquid/oxide interface.