Surface Reactivity: beyond Born-Oppenheimer

多年来，理论表面科学的巨大努力一直指向理解表面形成和断裂键的过程。其目的不仅是能够预测反应机理和途径，而且还了解如何操纵这些途径，为控制表面化学反应开辟新的途径。目前关于表面反应的理论工作大多采用基于密度泛函理论(DFT)的从头算电子结构计算方法。这些计算的基础是Born-Oppenheimer近似，在该近似中，电子始终保持其基态构型。然而，最近的实验结果清楚地证明了电子激发在各种表面反应中的重要作用。标准的DFT方法在这里显然是不够的，但到目前为止，在开发超出Born-Oppenheimer近似的方法方面进展非常小。我们在这个提议中的目的是建立一个理论框架，它将提供对电子激发在表面反应中的影响的定量理解。

For many years, a huge effort in theoretical surface science has been directed towards understanding the processes of making and breaking bonds at surfaces. The aim is not only to be able to predict reaction mechanisms and pathways, but also to understand how to manipulate these pathways to open up new avenues for the control of surface chemical reactions. Most of the current theoretical work in surface reactivity uses ab initio electronic structure calculations based on density functional theory (DFT). Underlying these calculations is the Born-Oppenheimer approximation, in which the electrons always remain in their ground state configuration. However, recent experimental results have clearly demonstrated the significant role of electronic excitations in a wide variety of surface reactions. Standard DFT approaches are clearly inadequate here, but there has, to date, been remarkably little progress in developing methods that go beyond the Born-Oppenheimer approximation. It is our aim in this proposal to establish a theoretical framework that will provide a quantitative understanding of the effects of electronic excitations in surface reactions.