Document Type

Article

Original Publication Date

2013

Journal/Book/Conference Title

The Journal of Chemical Physics

Volume

139

Issue

16

DOI of Original Publication

10.1063/1.4827091

Comments

Originally published at http://dx.doi.org/10.1063/1.4827091

Date of Submission

October 2015

Abstract

The nature of the bonding in Ag n S m 0/− clusters, n = 1–7; m = 1–4, has been analyzed to understand its effect on the electronic shell structure of silver clusters. First-principle investigations reveal that the sulfur atoms prefer 2 or 3-coordinate sites around a silver core, and that the addition of sulfur makes the planar structures compact. Molecular orbital analysisfinds that the 3p orbitals of sulfur form a bonding orbital and two weakly bonding lone pairs withsilver. We examine the electronic shell structures of Ag 6Sm, which are two electrons deficient of a spherical closed electronic shell prior to the addition of sulfur, and Ag 7Sm clusters that contain closed electronic shells prior to the addition of sulfur. The Ag 6S4 cluster has a distorted octahedral silver core and an open shell with a multiplicity of 3, while the Ag 7Sn clusters have compact geometries with enhanced stability, confirming that the clusters maintain their electronic shell structure after bonding with sulfur.

Rights

Pedicini, A. F., Reber, A. C., & Khanna, S. N. The effect of sulfur covalent bonding on the electronic shells of silver clusters. The Journal of Chemical Physics, 139, 164317 (2013). Copyright © 2013 AIP Publishing LLC.

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