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This content will become publicly available on February 8, 2019

Title: Stability of M 3S 3 complexes on fcc M(111) surfaces: M = Au, Ag, Cu, and Ni

Density Functional Theory is utilized to assess the stability of metal (M)-sulfur (S) complexes adsorbed on fcc M(111) surfaces, specifically considering S-decorated planar M trimers, M 3S 3. Scanning Tunneling Microscopy studies have identified structures proposed to be Ni 3S 3 on Ni(111), and Au 3S 3 on Au(111). In addition, Cu 3S 3 on Cu(111) has been suggested to facilitate enhanced Cu surface mass transport. Our analysis considers M 3S 3 complexes for M = Au, Ag, Cu, and Ni, assessing key measures of stability on surfaces, and also comparing behavior with trends in gas-phase stability. These surface and gas-phase analyses are systematically related within the framework of Hess’s law, which allows elucidation of various contributions to the overall energetics. In all cases, the adsorbed complex is stable relative to its separated constituents adsorbed on the terrace. However, only for Ag does one find a negative energy of formation from excess S on terraces and M extracted from kink sites along step edges, implying spontaneous complex formation for this pathway. We interpret various experimental observations in the context of our results for energetics.
Authors:
ORCiD logo [1] ;  [2] ;  [2] ;  [3] ;  [4]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States)
  2. Ames Lab. and Iowa State Univ., Ames, IA (United States) and Dept. of Chemistry
  3. Ames Lab. and Iowa State Univ., Ames, IA (United States) and Dept. of Chemistry and Dept. of Materials Science and Engineering
  4. Ames Lab. and Iowa State Univ., Ames, IA (United States) and Dept. of Physics and Astronomy
Publication Date:
Report Number(s):
IS-J-9569
Journal ID: ISSN 0039-6028; PII: S0039602817309044
Grant/Contract Number:
AC02-05CH11231; CHE-1507223; AC02-07CH11358
Type:
Accepted Manuscript
Journal Name:
Surface Science
Additional Journal Information:
Journal Name: Surface Science; Journal ID: ISSN 0039-6028
Publisher:
Elsevier
Research Org:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; Complexation; Sulfur on metal(111) surfaces; Density functional theory
OSTI Identifier:
1422760