Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Sulfur Atoms Adsorbed on Cu(100) at Low Coverage: Characterization and Stability against Complexation

Journal Article · · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
 [1];  [2];  [3];  [3];  [4];  [3];  [5]
  1. Iowa State Univ., Ames, IA (United States). Dept. of Chemistry; RIKEN Surface and Interface Science Lab., Saitama (Japan)
  2. Ames Lab., Ames, IA (United States)
  3. RIKEN Surface and Interface Science Lab., Saitama (Japan)
  4. Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
  5. Iowa State Univ., Ames, IA (United States). Dept. of Chemistry, Dept. of Materials Science and Engineering; Ames Lab., Ames, IA (United States)
+ Show Author Affiliations
By using scanning tunneling microscopy, we characterize the size and bias-dependent shape of sulfur atoms on Cu(100) at low coverage (below 0.1 monolayers) and low temperature (quenched from 300 to 5 K). Sulfur atoms populate the Cu(100) terraces more heavily than steps at low coverage, but as coverage approaches 0.1 monolayers, close-packed step edges become fully populated, with sulfur atoms occupying sites on top of the step. Density functional theory (DFT) corroborates the preferential population of terraces at low coverage as well as the step adsorption site. In experiment, small regions with p(2 × 2)-like atomic arrangements emerge on the terraces as sulfur coverage approaches 0.1 monolayer. Using DFT, a lattice gas model has been developed, and Monte Carlo simulations based on this model have been compared with the observed terrace configurations. A model containing eight pairwise interaction energies, all repulsive, gives qualitative agreement. Experiment shows that atomic adsorbed sulfur is the only species on Cu(100) up to a coverage of 0.09 monolayers. There are no Cu–S complexes. Conversely, prior work has shown that a Cu2S3 complex forms on Cu(111) under comparable conditions. On the basis of DFT, this difference can be attributed mainly to stronger adsorption of sulfur on Cu(100) as compared with Cu(111).
Research Organization:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231; AC02-07CH11358
OSTI ID:
1394812
Report Number(s):
IS-J--9377
Journal Information:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry Journal Issue: 2 Vol. 122; ISSN 1520-6106
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (66)

Dipole active displacements of ordered adsorbate layers on metal surfaces journal October 1984
Structure et conditions de formation de la couche d'adsorption du soufre sur le cuivre journal July 1968
The interaction of hydrogen sulphide with Cu(001) journal September 1971
The adsorption of sulfur on the (100) and (111) faces of platinum; A LEED and AES study journal April 1975
Partial disorder and LEED diagrams journal July 1983
A leed crystallographic analysis for the Cu(100)-(2 × 2)-S surface structure journal December 1986
Structural study of segregated sulphur on the stepped faces associated with Cu(100) journal January 1988
Imaging a p(2 × 2) layer of sulfur on Re(0001) with the scanning tunneling microscope: an experimental and theoretical study of the effect of adsorption site and tip structure journal August 1994
The origin of STM contrast differences for inequivalent S atoms on a Mo(100) surface journal September 1996
Sulfur induced Cu4 tetramers on Cu(111) journal October 1997
An LEED and STM study of the structures formed by sulfur on the Rh(111) surface journal January 1998
The role of surface relaxations in determining the STM images of sulfur adatoms and clusters on Re(0001): theory versus experiment journal July 1998
Identification of adatoms on metal surfaces by STM: experiment and theory journal December 1998
Gold adatom as a key structural component in self-assembled monolayers of organosulfur molecules on Au(111) journal May 2010
Realistic multisite lattice-gas modeling and KMC simulation of catalytic surface reactions: Kinetics and multiscale spatial behavior for CO-oxidation on metal (100) surfaces journal December 2013
Lattice-gas modeling of the formation and ordering of oxygen adlayers on Pd(100) journal August 2004
Adsorption of sulfur on Ag(100) journal March 2011
Adsorbate-induced surface stress, surface strain and surface reconstruction: S on Cu(100) and Ni(100) journal July 2013
One-dimensional nanoclustering of the Cu(100) surface under CO gas in the mbar pressure range journal September 2016
Long-Range Displacive Reconstruction of Au(110) Triggered by Low Coverage of Sulfur journal August 2015
Size Dependence of S-bonding on (111) Facets of Cu Nanoclusters journal May 2016
Structural Changes of Cu(110) and Cu(110)-(2 × 1)-O Surfaces under Carbon Monoxide in the Torr Pressure Range Studied with Scanning Tunneling Microscopy and Infrared Reflection Absorption Spectroscopy journal April 2016
Stabilization of X–Au–X Complexes on the Au(111) Surface: A Theoretical Investigation and Comparison of X = S, Cl, CH 3 S, and SiH 3 S journal February 2017
Adsorption and surface reactions of hydrogen sulfide and sulfur dioxide on copper(100) studied by electron energy loss spectroscopy journal August 1989
Long-Range Periodicity of S/Au(111) Structures at Low and Intermediate Coverages journal December 2013
Sulfur Interaction with Cu(100) and Cu(111) Surfaces: A Photoemission Study journal October 2014
X-ray Absorption Spectra of Dissolved Polysulfides in Lithium–Sulfur Batteries from First-Principles journal April 2014
Coadsorption of Sulfur and Carbon Monoxide on Platinum Single-Crystal Surfaces Studied by Scanning Tunneling Microscopy † journal March 1998
Visualizing nanoscale excitonic relaxation properties of disordered edges and grain boundaries in monolayer molybdenum disulfide journal August 2015
Identification of Au–S complexes on Au(100) journal January 2016
Far-ranged transient motion of “hot” oxygen atoms upon dissociation journal March 2001
Investigations on Silver Sulfide journal October 1953
Destabilization of Ag nanoislands on Ag(100) by adsorbed sulfur journal October 2011
Communication: Structure, formation, and equilibration of ensembles of Ag-S complexes on an Ag surface journal February 2013
Reconstruction of steps on the Cu(111) surface induced by sulfur journal May 2015
Self-organization of S adatoms on Au(111): √3R30° rows at low coverage journal July 2015
Comparison of S-adsorption on (111) and (100) facets of Cu nanoclusters journal October 2016
Geometry of (22)S/Cu(001) determined with use of angle-resolved-photoemission extended fine structure journal March 1987
Investigation with low-energy electron diffraction of the adsorbate-induced metal relaxations in the Cu(100)-( 2×2 )-S surface structure journal April 1989
Reply to ‘‘Investigation with low-energy electron diffraction of the adsorbate-induced metal relaxations in the Cu(100)-( 2×2 )-S surface structure’’ journal April 1989
Substrate surface relaxation for Cl and S on Cu(001) journal July 1989
Multiple sulfur sites in the Cu(100) p (2×2)-S surface structure journal March 1990
Structure determination of Cu(100)- p (2×2)-S using x-ray diffraction journal April 1990
Measurement of the binding energy of kink-site atoms of metals and alloys journal May 1991
Reevaluation of the p (2×2)S/Cu(001) structure using angle-resolved photoemission extended fine-structure spectroscopy journal June 1992
Projector augmented-wave method journal December 1994
Scanning-tunneling-microscopy studies of the S-induced reconstruction of Cu(100) journal September 1994
Sulfur chemisorption on Ni(111): The clock structure of the (5√3×2)S phase journal September 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Efficient method for the simulation of STM images. II. Application to clean Rh(111) and Rh ( 111 ) + c ( 4 × 2 ) − 2 S journal December 1997
Accuracy of first-principles lateral interactions: Oxygen at Pd(100) journal June 2007
Density functional analysis of key energetics in metal homoepitaxy: Quantum size effects in periodic slab calculations journal January 2010
Cu 2 S 3 complex on Cu(111) as a candidate for mass transport enhancement journal January 2015
Direct Surface Structure Determination with Photoelectron Diffraction journal July 1983
Apparent Size of an Atom in the Scanning Tunneling Microscope as a Function of Bias journal January 1987
Coverage and Chemical Dependence of Adsorbate-Induced Bond Weakening in Metal Substrate Surfaces journal September 1988
Structure of a Precursor State in Dissociative Chemisorption journal January 1990
Generalized Gradient Approximation Made Simple journal October 1996
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] journal February 1997
Formation and Diffusion of S-Decorated Cu Clusters on Cu(111) journal July 2000
Gold-Adatom-Mediated Bonding in Self-Assembled Short-Chain Alkanethiolate Species on the Au(111) Surface journal October 2006
Lattice parameters, densities, expansion coefficients and perfection of structure of Cu and of Cu–In α phase journal November 1969
Atomic and Molecular Manipulation with the Scanning Tunneling Microscope journal November 1991
Further observations with low-energy electron diffraction for the Cu(100)-(2 × 2)-S surface structure: spot-profile and multiple-scattering analyses journal May 1987
Fingerprinting Lithium-Sulfur Battery Reaction Products by X-ray Absorption Spectroscopy journal January 2014
Zur Thermodynamik von Schwefeldampf journal August 1967

Cited By (5)

Identification of an AgS2 Complex on Ag(110) journal December 2019
Sulfide Surface Dynamics on Cu(100) and Ag(100) Electrodes in the Presence of c(2×2) Halide Adlayers journal July 2018
Characteristics of sulfur atoms adsorbed on Ag(100), Ag(110), and Ag(111) as probed with scanning tunneling microscopy: experiment and theory journal January 2019
Sulfur adsorption on coinage metal(100) surfaces: propensity for metal–sulfur complex formation relative to (111) surfaces journal January 2019
Oxygen and sulfur adsorption on vicinal surfaces of copper and silver: Preferred adsorption sites journal March 2018

Similar Records

Destabilization of Ag nanoislands on Ag(100) by adsorbed sulfur
Journal Article · Mon Oct 17 00:00:00 EDT 2011 · Journal of Chemical Physics · OSTI ID:1037985
Oxygen and sulfur adsorption on vicinal surfaces of copper and silver: Preferred adsorption sites
Journal Article · Tue Mar 27 20:00:00 EDT 2018 · Journal of Chemical Physics · OSTI ID:1433658
Enhanced Nanostructure Dynamics on Au(111) with Adsorbed Sulfur due to Au–S Complex Formation
Journal Article · Sun Dec 27 19:00:00 EST 2020 · ChemPhysChem · OSTI ID:1764843

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS