Surface Reactivity: beyond Born-Oppenheimer

多年来，理论表面科学的巨大努力一直致力于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制和途径，而且还要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。目前大多数表面反应性的理论工作都是基于密度泛函理论（DFT）的从头计算电子结构。这些计算的基础是玻恩-奥本海默近似，其中电子总是保持在它们的基态构型。然而，最近的实验结果已经清楚地表明了电子激发在各种各样的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，但迄今为止，在发展超越玻恩-奥本海默近似的方法方面进展甚微。这是我们的目标，在这个建议中，建立一个理论框架，将提供一个定量的了解，在表面反应中的电子激发的影响。

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.