Electronic Function Simulation of Surface Coordination Space

应用电子结构方法对表面配位空间的电子函数进行了理论研究。在本项目中，我们研究了金属电极间配位化合物的电流-电压（I-V）特性、分子表面的拓扑分析、CdS纳米团簇的光学性质、Au表面吡啶硫醇的电化学还原消除。我们将非平衡格林函数理论应用于两个金属电极之间的铂乙基化合物的I-V特性。研究了Au和Li的一维链电极。对于金链电极，我们预测电流明显增强。这是由于电极的费米能级非常接近铂化合物的HOMO能级。在分子表面分析方面，我们开发了一种表征分子表面拓扑特征的新方法。在我们的方法中，我们引入离子作为探针。分子表面是根据探针离子与靶分子之间的相互作用能来定义的。利用该计算方法对环冠醚的内表面形状进行了研究。在CdS纳米团簇上，我们进行了电子激发态计算，以研究有机分子表面配位对电子光谱的影响。在电化学还原消除上，我们发现消除电压与表面的Au-S结合能有很好的相关性。除此之外，还开展了一些合作研究：(1)金属团簇化合物的电子结构和光学性质，对Fe-salen配合物的结构进行了计算研究。研究了氮化还原酶的Cu模型化合物，以了解Cu与NO2之间的配位几何形状和结合能。

Electronic structure methods were applied to theoretically investigate electronic functions of surface-coordination space. In this project, we studied current-voltage (I-V) characteristics of coordination compounds between metal electrodes, topological analysis of molecular surfaces, optical properties of CdS nanoclusters, electrochemical reductive elimination of pyridine thiol on the Au Surface. We applied the nonequilibrium Green's function theory to the I-V characteristics of Pt acetylide compounds between two metal electrodes. The one-dimensional chain electrodes of Au and Li were investigated. For the Au chain electrode, we predicted that the electric current is appreciably enhanced. This is due to the fact that the Fermi level of the electrode is very close to the HOMO level of the Pt compound. On the molecular surface analysis, we developed a new method to characterize topological features of molecular surfaces. In our approach, we introduce an ion as a probe. The molecular surface is defined on the basis of the interaction energy between the probe ion and the target molecule. By using this computational method, the shape of the inner surface of a cyclic crown ether was investigated. On the CdS nanoclusters, we carried out electronically excited state calculations to investigate how the electronic spectra were influenced by the surface coordination by organic molecules.On the electrochemical reductive elimination, we showed that the elimination voltage is well correlated to the Au-S binding energy of a surface. In addition to these works, some collaborative studies were carried out: (i) electronic structure and optical properties of metal cluster compounds, Structures of Fe-salen complexes were computationally investigated. The Cu model compounds for the nitride reductase were investigated to understand the coordination geometries and binding energy between Cu and NO2.