Campus Units

Physics and Astronomy, Mathematics, Materials Science and Engineering, Chemistry, Ames Laboratory

Document Type

Article

Publication Version

Published Version

Publication Date

10-28-2016

Journal or Book Title

The Journal of Chemical Physics

Volume

145

Issue

16

First Page

164312

DOI

10.1063/1.4966193

Abstract

In order to gain insight into the nature of chemical bonding of sulfur atoms on coinage metal surfaces, we compare the adsorption energy and structural parameters for sulfur at four-fold hollow (4fh) sites on (100) facets and at three-fold hollow (3fh) sites on (111) facets of Cu nanoclusters. Consistent results are obtained from localized atomic orbital and plane-wave based density functional theory using the same functionals. PBE and its hybrid counterpart (PBE0 or HSE06) also give similar results. 4fh sites are preferred over 3fh sites with stronger bonding by ∼0.6 eV for nanocluster sizes above ∼280 atoms. However, for smaller sizes there are strong variations in the binding strength and the extent of the binding site preference. We show that suitable averaging over clusters of different sizes, or smearing the occupancy of orbitals, provide useful strategies to aid assessment of the behavior in extended surface systems. From site-projected density of states analysis using the smearing technique, we show that S adsorbed on a 4fh site has similar bonding interactions with the substrate as that on a 3fh site, but with much weaker antibonding interactions.

Comments

Boschen, Jeffery S., Jiyoung Lee, Theresa L. Windus, James W. Evans, Patricia A. Thiel, and Da-Jiang Liu. "Comparison of S-adsorption on (111) and (100) facets of Cu nanoclusters." The Journal of chemical physics 145, no. 16 (2016): 164312, doi:10.1063/1.4966193. Posted with permission.

Copyright Owner

American Institute of Physics

Language

en

File Format

application/pdf

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