An ab initio path integral treatment of hydrogenation reactions at metal surfaces

金属表面氢原子键的形成和断裂是多相催化的基础。例如，从其元素形成水是通过H2分子中的H-H键的断裂，随后原子氧和羟基的氢化反应产生水来进行的。量子核效应（如隧道效应和量子离域效应）在决定这些过程的机制和速率方面所起的作用在很大程度上尚未探索。这是真的，尽管知道氢的量子核效应在室温和更低的温度下可能是显着的，尽管经济和环境需要在越来越低的温度下更好地理解和利用催化。在这里，我们计划开始在解决这种情况下与国家的最先进的第一原则电子结构的方法。具体从头算路径积分技术将被开发和应用，严格探索量子核效应在基本扩散过程中发挥的作用，并涉及氢在金属表面的反应事件，最终在完全量子从头算处理的水形成反应的Pt。这是一个非常冒险但可行的项目。这里提出的方法学发展需要一名博士后的参与，这是在项目的三年生命周期内要求的。同样，该项目将在很大程度上依赖于英国的下一代万亿级高性能计算设施（HECToR），事实上，只有现在HECToR即将安装，这个高度计算要求的项目才能在英国实现。

The making and breaking of bonds involving hydrogen atoms at metal surfaces is the bread and butter of heterogeneous catalysis. Water formation from its elements, for example, proceeds through the cleavage of the H-H bond in the H2 molecule followed by subsequent hydrogenation reactions of atomic oxygen and hydroxyl to yield water. The role quantum nuclear effects - such as tunnelling and quantum delocalization - play in determining the mechanisms and rates of these processes remains largely unexplored. This is true despite knowledge that the quantum nuclear effects of hydrogen can be significant at room temperature and below and despite the growing economic and environmental needs to better understand and exploit catalysis at increasingly low temperatures. Here we plan to make a start at addressing this situation with state-of-the-art first principles electronic structure approaches. Specifically ab initio path integral techniques will be developed and applied to rigorously explore the role quantum nuclear effects play in elementary diffusion processes and reaction events involving hydrogen at metal surfaces, culminating in the fully quantum ab initio treatment of the water formation reaction on Pt. This is a highly adventurous yet feasible project. The methodological developments proposed here require the involvement of a post-doc, which is requested for the three year lifetime of the project. Likewise this project will rely heavily on the UK's next generation terascale high performance computing facility (HECToR), and, indeed, only now with the imminent installation of HECToR does this highly computationally demanding project become feasible in the UK.