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

近年来，界面光分子科学从光致发光和光能转换的角度得到了很大的发展。为了在合理的计算成本中适当地模拟复杂的界面系统，我们开发了新的代码，在开边界簇模型的基础上计算物理正确的一般界面系统的电子结构。在该模型中，模型团簇被视为开放体系，用所开发的程序计算了Cs/Cu（111）的激发态能量和电子寿命，与实验值比较，结果合理。此外，计算结果的基础上，揭示了新的激发机制的光诱导相干动力学的吸附在金属表面。 此外，它表明，电极的化学现象也适当地模拟与我们的方法相结合的巨正则概括和介电建模的液体。

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.