Stability of M3S3 complexes on fcc M(111) surfaces: M = Au, Ag, Cu, and Ni
Abstract
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, M3S3. Scanning Tunneling Microscopy studies have identified structures proposed to be Ni3S3 on Ni(111), and Au3S3 on Au(111). In addition, Cu3S3 on Cu(111) has been suggested to facilitate enhanced Cu surface mass transport. Our analysis considers M3S3 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:
-
[1];
- Ames Lab. and Iowa State Univ., Ames, IA (United States)
- Ames Lab. and Iowa State Univ., Ames, IA (United States) and Dept. of Chemistry
- Ames Lab. and Iowa State Univ., Ames, IA (United States) and Dept. of Chemistry and Dept. of Materials Science and Engineering
- Ames Lab. and Iowa State Univ., Ames, IA (United States) and Dept. of Physics and Astronomy
- Publication Date:
- Research Org.:
- Ames Lab., Ames, IA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1422760
- Alternate Identifier(s):
- OSTI ID: 1562768
- Report Number(s):
- IS-J-9569
Journal ID: ISSN 0039-6028; PII: S0039602817309044
- Grant/Contract Number:
- AC02-05CH11231; CHE-1507223; AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Surface Science
- Additional Journal Information:
- Journal Volume: 276; Journal ID: ISSN 0039-6028
- Publisher:
- Elsevier
- 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
Citation Formats
Liu, Da-Jiang, Lee, Jiyoung, Windus, Theresa L., Thiel, Patricia A., and Evans, James W. Stability of M3S3 complexes on fcc M(111) surfaces: M = Au, Ag, Cu, and Ni. United States: N. p., 2018.
Web. doi:10.1016/j.susc.2018.02.004.
Liu, Da-Jiang, Lee, Jiyoung, Windus, Theresa L., Thiel, Patricia A., & Evans, James W. Stability of M3S3 complexes on fcc M(111) surfaces: M = Au, Ag, Cu, and Ni. United States. https://doi.org/10.1016/j.susc.2018.02.004
Liu, Da-Jiang, Lee, Jiyoung, Windus, Theresa L., Thiel, Patricia A., and Evans, James W. Thu .
"Stability of M3S3 complexes on fcc M(111) surfaces: M = Au, Ag, Cu, and Ni". United States. https://doi.org/10.1016/j.susc.2018.02.004. https://www.osti.gov/servlets/purl/1422760.
@article{osti_1422760,
title = {Stability of M3S3 complexes on fcc M(111) surfaces: M = Au, Ag, Cu, and Ni},
author = {Liu, Da-Jiang and Lee, Jiyoung and Windus, Theresa L. and Thiel, Patricia A. and Evans, James W.},
abstractNote = {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, M3S3. Scanning Tunneling Microscopy studies have identified structures proposed to be Ni3S3 on Ni(111), and Au3S3 on Au(111). In addition, Cu3S3 on Cu(111) has been suggested to facilitate enhanced Cu surface mass transport. Our analysis considers M3S3 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.},
doi = {10.1016/j.susc.2018.02.004},
journal = {Surface Science},
number = ,
volume = 276,
place = {United States},
year = {Thu Feb 08 00:00:00 EST 2018},
month = {Thu Feb 08 00:00:00 EST 2018}
}
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