σ-Holes and σ-lumps direct the Lewis basic and acidic interactions of noble metal nanoparticles: introducing regium bonds

作者：Joakim Halldin Stenlid, Adam Johannes Johansson, Tore Brinck · 发表于：Physical Chemistry Chemical Physics · 年份：2017 · DOI：10.1039/c7cp06259a · 被引用次数：162 · 研究领域：Advanced Chemical Physics Studies、Molecular Junctions and Nanostructures、Machine Learning in Materials Science

) compounds. The probes include the local electron attachment energy [E(r)], the average local ionization energy [Ī(r)], and the electrostatic potential [V(r)] and are evaluated on isodensity surfaces located at distances corresponding to typical interaction distances. These probes have previously been successful in characterizing molecular interactions. Good correlations are found between Lewis acidity and maxima in V(r), appearing as a consequence of σ-holes, as well as minima in E(r), of the noble metal nanoparticles. Similarly are Lewis basic sites successfully described by surface minima in V(r) and Ī(r); the former are indicative of σ-lumps, i.e. regions of enhanced σ-density. The investigated probes are anticipated to function as reliable tools in nanoparticle reactivity and interaction characterization, and may act as suitable descriptors in large-scale screenings for materials of specific properties, e.g. in heterogeneous catalysis. Because of the similarity between the noble metal nanoparticle's interactions with Lewis bases and the concepts of halogen and hydrogen bonding, a new class of bonds is introduced - regium bonds - taking place between a σ-hole of a Cu, Ag or Au compound and an electron donor.