Abstract
Understanding the molecular interaction behavior of transition metal nanoclusters lies at the heart of their efficient use in, e.g., heterogeneous catalysis, medical therapy and solar energy harvesting. For this purpose, we have evaluated the applicability of the surface electrostatic potential [VS(r)] and the local surface electron attachment energy [ES(r)] properties for characterizing the local Lewis acidity of a series of low-energy TM13 transition metal nanoclusters (TM = Au, Cu, Ru, Rh, Pd, Ir, Pt, Co), including also Pt7Cu6. The clusters have been studied using hybrid Kohn–Sham density functional theory (DFT) calculations. The VS(r) and ES(r), evaluated at 0.001 a.u. isodensity contours, are used to analyze the interactions with H2O. We find that the maxima of VS(r), σ-holes, are either localized or diffuse. This is rationalized in terms of the nanocluster geometry and occupation of the clusters’s, p and d valence orbitals. Our findings motivate a new scheme for characterizing σ-holes as σs (diffuse), σp (localized) or σd (localized) depending on their electronic origin. The positions of the maxima in VS(r) (and minima in ES(r)) are found to coincide with O-down adsorption sites of H2O, whereas minima in VS(r) leads to H-down adsorption. Linear relationships between VS,max (and ES,min) and H2O interaction energies are further discussed.
Highlights
Surface maxima in the molecular electrostatic potential (V S,max ) along the lateral extensions of intramolecular bonds are known as σ-holes [1]
In the present contribution we introduce new categories of σ-holes based on the electronic origin of the V S,max ; if the V S,max arises primarily as a consequence of electron deficiencies in the valence s-orbitals of the compound, we shall denote it an σs -hole
In thisand part,Discussion we will examine the different kinds of σ-holes that emerge on transition metal (TM) nanoclusters, when to expect them andwe how influence the local Lewis of on the TM
Summary
Surface maxima in the molecular electrostatic potential (V S,max ) along the lateral extensions of intramolecular bonds are known as σ-holes [1]. These have been widely used to rationalize molecular interaction behavior and reactivity [2]. V S,max originating from deficiencies in the p- or d-orbitals will be referred to as σp - or σd -holes. We will here show that σ-holes are useful guides for TM interactions with clear similarities to halogen or hydrogen bonding
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