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This content will become publicly available on October 31, 2017

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

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.
Authors:
 [1] ; ORCiD logo [1] ;  [1] ; ORCiD logo [1] ;  [1] ; ORCiD logo [2]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States)
  2. Ames Lab., Ames, IA (United States)
Publication Date:
Report Number(s):
IS-J-9125
Journal ID: ISSN 0021-9606; TRN: US1701302
Grant/Contract Number:
AC02-07CH11358; CHE-1507223
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 16; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS
OSTI Identifier:
1342945
Alternate Identifier(s):
OSTI ID: 1330479