Interfacial photo-molecular processes by open-system electronic structure theory

近年来，界面光分子科学从光催化和光能转换的角度得到了很大的拓展。为了在合理的计算成本下对复杂界面系统进行适当的建模，我们在开边界簇模型的基础上开发了计算一般界面系统物理正确电子结构的新代码。在该模型中，模型集群被视为开放系统。用所编制的程序计算的Cs/Cu（111）的激发能和激发态电子寿命与实验值比较合理。此外，在计算结果的基础上，揭示了金属表面吸附物光致相干动力学的新激发机制。此外，我们的方法结合了大规范泛化和液体介电模型，也能很好地模拟电极化学现象。

Recently, the interfacial photo-molecular science have largely been expanded from the viewpoint of photocatalysis and photo-energy conversion. To appropriately model complicated interfacial systems in reasonable computational costs, we developed the novel code that calculate physically correct electronic structures of general interfacial systems on the basis of the open-boundary cluster model. In this model, a model cluster is treated as the open system.The excitation energy and electronic lifetime of excited states for Cs/Cu(111), calculated with the developed code, were reasonable as compared with the experimental values. Moreover, the novel excitation mechanisms for photo-induced coherent dynamics of adsorbates on metal surfaces were revealed on the basis of the computational results. Moreover, it was shown that the electrode chemical phenomena are also properly modelled with our methodology by the combination of grand-canonical generalisation and dielectric modelling of liquid.