Hidden Beneath the Surface: Origin of the Observed Enantioselective Adsorption on PdGa(111),Journal of the American Chemical Society

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Hidden Beneath the Surface: Origin of the Observed Enantioselective Adsorption on PdGa(111)
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-01-19 , DOI: 10.1021/jacs.7b10980
Aliaksandr V. Yakutovich ₁ , Johannes Hoja ₂ , Daniele Passerone ₁ , Alexandre Tkatchenko ₂ , Carlo A. Pignedoli ₁

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We unravel the origin of the recently observed striking enantioselectivity of the PdGa(111) surface with respect to the adsorption of a small organic molecule, 9-ethynylphenanthrene, using first-principles calculations. It turns out that the key ingredient to understand the experimental evidence is the appropriate description of van der Waals interactions beyond the widely employed atomic pairwise approximation. A recently developed van der Waals-inclusive density functional method, which encompasses dielectric screening effects, reveals the origin of the experimentally observed enantioselectivity and provides conclusive evidence of chiral recognition on a bimetallic surface driven by dispersion interactions. The incorporation of dielectric screening leads to a renormalization of the dispersion interaction range, allowing for the appropriate weighting of the molecule-substrate interactions at intermediate distances between 2.5 and 5 Å. Our findings have implications for the structure and stability of complex organic/inorganic systems where dielectric screening effects are expected to be of general importance.

中文翻译：

隐藏在表面之下：在 PdGa(111) 上观察到的对映选择性吸附的起源

我们使用第一性原理计算揭示了最近观察到的 PdGa(111) 表面对有机小分子 9-乙炔基菲的吸附具有惊人的对映选择性的起源。事实证明，理解实验证据的关键因素是对范德瓦尔斯相互作用的适当描述，超出了广泛采用的原子成对近似。最近开发的包含介电屏蔽效应的范德华密度泛函方法揭示了实验观察到的对映选择性的起源，并提供了由分散相互作用驱动的双金属表面手性识别的确凿证据。介电屏蔽的加入导致色散相互作用范围的重整化，允许在 2.5 和 5 Å 之间的中间距离处适当加权分子-底物相互作用。我们的发现对复杂的有机/无机系统的结构和稳定性有影响，其中介电屏蔽效应预计具有普遍重要性。

更新日期：2018-01-19

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