固液界面电子结构和激发态动力学的第一性原理研究

在利用太阳光催化分解水的光电化学电池（PEC）中，光吸收/催化材料与溶液界面处的电荷输运性质决定了器件的综合性能和效率。界面的结构和电子特性之间存在复杂的相互耦合作用，这导致光吸收/催化材料的能带位置依赖于界面处的结构和化学细节。建立精确细致的固液界面模型，发展先进的描述界面复杂效应的电子结构的计算方法，对准确预测PEC材料的光电性能至关重要。此外，PEC界面处光催化分解水的反应是电子激发与原子振动耦合的非绝热过程。含时密度泛函理论可以精确描述激发电子的运动过程和电声耦合的相互作用，获得丰富的界面激发态动力学信息，进而深入理解材料界面处光催化反应的微观机制。发展建立的系统研究固液界面结构-电子性质-激发态动力学的完备理论模拟方案，将成为PEC新材料筛选、设计和性能调控研究中的强有力工具。

For solar water splitting, charge transport properties at photoelectrode/catalyst/solution interfaces determine the overall efficiency and performance of photoelectrochemical cell (PEC). Stemming from a complex interplay between structural and electronic properties of the interfaces, band edges of photoelectrode and catalyst are dependent on the detailed microscopic structure of solid/liquid interfaces. Establishing sophisticated interface model, explicitly including water layer, and developing advanced computational methods, accounting for the complex effects of solid/liquid interface, are essential for predicting the correct properties of PEC materials. In addition, solar water splitting reaction at the PEC interfaces is a non-adiabatic process, a coupled motion of electronic excitation and atomic vibration. A full description of excited states and electron-phonon coupling within time-dependent density functional theory is crucial for the fundamental understanding of photocatalytic reaction mechanism. The development of a complete computational scheme for the systematic study of solid/liquid interface structure - electronic properties - excited state dynamics will provide a powerful tool in material screening and design of the PEC devices.