Kinetics and Dynamics of Adsorption and Desorption on Chiral Surfaces

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 us
to 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.