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Crystals 2017, 7(7), 222; doi:10.3390/cryst7070222

σ-Holes on Transition Metal Nanoclusters and Their Influence on the Local Lewis Acidity

1
Applied Physical Chemistry, School of Chemical Science and Engineering, KTH Royal Institute of Technology, Teknikringen 36, SE-100 44 Stockholm, Sweden
2
Swedish Nuclear Fuel and Waste Management Company (SKB), Evenemangsgatan 13, Box 3091, SE-169 03 Solna, Sweden
*
Author to whom correspondence should be addressed.
Academic Editors: Peter Politzer and Jane S. Murray
Received: 10 June 2017 / Revised: 10 July 2017 / Accepted: 11 July 2017 / Published: 14 July 2017
(This article belongs to the Special Issue Analysis of Halogen and Other σ-Hole Bonds in Crystals)
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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. View Full-Text
Keywords: σ-holes; surface electrostatic potential; local electron attachment energy; H2O interactions; transition metal nanoparticles; Lewis acidity σ-holes; surface electrostatic potential; local electron attachment energy; H2O interactions; transition metal nanoparticles; Lewis acidity
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Stenlid, J.H.; Johansson, A.J.; Brinck, T. σ-Holes on Transition Metal Nanoclusters and Their Influence on the Local Lewis Acidity. Crystals 2017, 7, 222.

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