Enantioselectivity on naturally chiral surfaces is a classical manifestation of structure sensitive surface chemistry; the branching between enantiospecific reaction pathways is dictated only by the relative handedness of chiral adsorbate and chiral substrate. The challenge to controlling enantioselectivity on chiral surfaces is that the enantiospecificity of reaction energetics is relatively small, e.g. a few kJ/mole. Equally challenging to the design of chiral surfaces optimized for enantiospecificity is the fact that chiral metal surface structures span a 2D continuum defined by the orientation vectors of surfaces cut from 3D crystal lattices. We have demonstrated that the non-linear kinetics of surface explosion reactions such as tartaric and aspartic acid decomposition on chiral Cu{hkl}R&S surfaces yield extremely highly enantiospecific reaction rates. We have mapped these decomposition rates across the surfaces of curved Cu single crystals that expose continuous regions of Cu surface structure space. By doing so, we can map reactivity and enantioselectivity as functions of surface orientation. Coupled with STM measurements of surface structure we are able to determine the structural origins of enantioselectivity.

Structure sensitive chiral surface chemistry: Enantioselectivity on chiral surfaces

255th National Meeting (2018)

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