Kinetics and Dynamics of Adsorption and Desorption on Chiral Surfaces

在过去的几十年里，人们对在表现出微观手性的表面进行不对称化学的前景产生了相当大的兴趣，无论是由于其固有的晶体结构还是通过涉及手性分子的修饰而赋予的。在大多数情况下，调查集中在阐明的平衡结构和能量的系统，只是推断可能的后果，而不是直接解决他们的动力学和动力学。然而，最近，实验设计，以揭示不对称的动力学效应（例如，在爆炸解吸）已被报道，似乎也有一些相当大的承诺，利用超声分子束来研究不对称吸附的动力学。第一性原理分子动力学的应用将使我们能够确认一系列候选系统的吸附和解吸过程中手性效应的存在（并评估其大小）。最初，我们将专注于固有手性Cu{531}表面，它结合了高密度的手性扭结网站与一个相对较低的反应性，适合结合比较微妙的手性分子，而不解离成非手性产物。探针分子可能包括手性和非手性物质，如有机酸和相关化合物。希望这项工作将促进这一令人兴奋的领域的实验工作。

There has been considerable interest, over the past couple of decades, in the prospects for asymmetric chemistry conducted at surfaces that exhibit microscopic chirality, either due to their inherent crystalline structure or conferred by modification involving chiral molecules. For the most part, investigations have focussed upon elucidation of the equilibrium structure and energetics of such systems, merely inferring likely consequences for dynamics and kinetics rather than addressing them directly. Recently, however, experiments designed to reveal asymmetric kinetic effects (for example, in explosive desorption) have been reported, and there would seem also to be some considerable promise in making use of supersonic molecular beams to study the dynamics of asymmetric adsorption.The present project aims to explore this same territory from a computational perspective. Application of first-principles molecular dynamics will allow usto confirm the existence of (and assess the magnitude of) chiral effects in both adsorption and desorption processes for a range of candidate systems. Initially, we will focus upon the intrinsically chiral Cu{531} surface, which combines a high density of chiral kink sites with a relatively low reactivity suitable for binding comparatively delicate chiral molecules without dissociation into achiral products. Probe molecules will likely include both chiral and achiral species, such as organic acids and related compounds. It is hoped that the work will stimulate experimental work in this exciting area.