Quantum chemical and quantum dynamical studies of the photocatalytic water splitting on titanium dioxide surfaces

一个精心设计的战略，为发展新的概念和技术的主题光催化分解水的无机材料（人工光合作用）是基于一个详细的，即原子理解的基本过程。当前研究提案的具体目标包括尽可能准确地模拟（金红石和金红石）二氧化钛-TiO 2的理想、含缺陷和氮掺杂表面上的光催化水裂解。这些表面代表了足够简单的模型系统，允许通过现代量子化学和量子动力学方法研究相关的光催化过程，而不依赖于实验数据。这种从头算方法是基于嵌入式簇模型的电子基态和电子激发态参与光催化水分解的H2O/TiO 2（110）-系统，并追求精确的量子化学方法超越电流密度泛函理论（DFT），即CASSCF和CASPT-2。这些方法允许精确的，五维的电子基态和电子激发态的势能面的计算，形成了在随机波包计算的框架内的精确量子动力学模拟的基础铺平了道路的基本洞察机制的人工晶体直接与实验结果比较。

A well-designed strategy for the development of new concepts and technologies on the subject of photocatalytic water splitting by inorganic materials (artificial photosynthesis) is based on a detailed, i.e. atomistic understanding of the underlying elementary processes. The specific goal of the current research proposal consists of the effort to simulate the photocatalytic water splitting on ideal, defect containing, and nitrogen-doped surfaces of (rutile and anatase) titania-TiO2 as accurately as possible. These surfaces represent sufficiently simple model systems which allow for the study of the relevant photocatalytic processes by modern quantum chemical and quantum dynamical approaches without relying on experimental data. This ab initio approach is based on embedded cluster models of the electronic ground state and electronically excited states involved in photocatalytic water splitting of the H2O/TiO2(110)-system and pursues accurate quantum chemical methodology beyond current density functional theory (DFT), i.e. CASSCF and CASPT-2. These methods allow for the calculation of accurate, five-dimensional potential energy surfaces of the electronic ground state and electronically excited states which form the basis for exact quantum dynamical simulations within the framework of stochastic wave packet calculations paving the way for fundamental insight into the mechanism of artificial photocatalysis in direct comparison with experimental results.