Comparison of S-adsorption on (111) and (100) facets of Cu nanoclusters

Boschen, Jeffery S.; Lee, Jiyoung; Windus, Theresa L.; Evans, James W.; Thiel, Patricia A.; Liu, Da-Jiang

doi:10.1063/1.4966193

Title: Comparison of S-adsorption on (111) and (100) facets of Cu nanoclusters

Journal Article · Mon Oct 31 00:00:00 EDT 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4966193· OSTI ID:1342945

Boschen, Jeffery S. ^[1];

^[1]; Windus, Theresa L. ^[1];

^[1]; Thiel, Patricia A. ^[1];

^[2]

Ames Lab. and Iowa State Univ., Ames, IA (United States)
Ames Lab., Ames, IA (United States)

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. In addition, 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.

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Research Organization:: Ames Lab., Ames, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-07CH11358; CHE-1507223

OSTI ID:: 1342945

Alternate ID(s):: OSTI ID: 1330479

Report Number(s):: IS-J-9125; TRN: US1701302

Journal Information:: Journal of Chemical Physics, Vol. 145, Issue 16; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 6 works

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