Oxygen and sulfur adsorption on vicinal surfaces of copper and silver: Preferred adsorption sites

Liu, Da-Jiang; Thiel, Patricia A.

doi:10.1063/1.5021091

Title: Oxygen and sulfur adsorption on vicinal surfaces of copper and silver: Preferred adsorption sites

Journal Article · 28 March 2018 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.5021091 · OSTI ID:1433658

^[1];

^[2]

Ames Lab., Ames, IA (United States)
Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States). Dept. of Chemistry, and Dept. of Materials Science and Engineering

We present an extensive density functional theory (DFT) study of adsorption site energetics for oxygen and sulfur adsorbed on two vicinal surfaces of Cu and Ag, with the goal of identifying the most stable adsorption site(s), identifying trends and common themes, and comparing with experimental work in the literature where possible. We also present benchmark calculations for adsorption on the flat (111) and (100) surfaces. The first vicinal surface is the (211), and results are similar for both metals. Here, we find that the step-doubling reconstruction is favored with both adsorbates and is driven by the creation of a special stable fourfold hollow (4fh) site at the reconstructed step. Zig-zag chain structures consisting of X–M–X units (X = chalcogen, M = metal) at the step edge are considered, in which the special 4fh site is partially occupied. The zig-zag configuration is energetically competitive for oxygen but not sulfur. DFT results for oxygen agree with experiment in terms of the stability of the reconstruction, but contradict the original site assignment. The second vicinal surface is the (410), where again results are similar for both metals. For oxygen, DFT predicts that step sites are filled preferentially even at lowest coverage, followed by terrace sites, consistent with the experiment. For sulfur, in contrast, DFT predicts that terrace sites fill first. Oxygen forms O–M–O rows on the top edge of the step, where it occupies incomplete 4fh sites. This resolves an experimental ambiguity in the site assignment. Finally, for both the (211) and (410) surfaces, the interaction energy that stabilizes the X–M–X chain or row correlates with the linearity of the X–M–X unit, which may explain key differences between oxygen and sulfur.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231; AC02-07CH11358

OSTI ID:: 1433658

Report Number(s):: IS-J--9605

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 12 Vol. 148; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

References (66)

Formation of Two-Dimensional Copper Selenide on Cu(111) at Very Low Selenium Coverage Walen, Holly; Liu, Da-Jiang; Oh, Junepyo ChemPhysChem, Vol. 17, Issue 14 https://doi.org/10.1002/cphc.201600207	journal	May 2016
Islands, Mounds and Atoms Michely, Thomas; Krug, Joachim Springer Series in Surface Sciences https://doi.org/10.1007/978-3-642-18672-1	book	January 2004
Finite-Size Effects in O and CO Adsorption for the Late Transition Metals Peterson, Andrew A.; Grabow, Lars C.; Brennan, Thomas P. Topics in Catalysis, Vol. 55, Issue 19-20 https://doi.org/10.1007/s11244-012-9908-x	journal	November 2012
Parallel Nanoimprint Forming of One-Dimensional Chiral Semiconductor for Strain-Engineered Optical Properties Wang, Yixiu; Jin, Shengyu; Wang, Qingxiao Nano-Micro Letters, Vol. 12, Issue 1 https://doi.org/10.1007/s40820-020-00493-3	journal	August 2020
LEED studies of adsorption on vicinal copper surfaces Perdereau, J.; Rhead, G. E. Surface Science, Vol. 24, Issue 2 https://doi.org/10.1016/0039-6028(71)90281-0	journal	February 1971
The adsorption and incorporation of oxygen on Cu(100) at T ⩾ 300 K Hofmann, P.; Unwin, R.; Wyrobisch, W. Surface Science, Vol. 72, Issue 4 https://doi.org/10.1016/0039-6028(78)90351-5	journal	April 1978
X-ray photoelectron diffraction study of oxygen adsorption on the stepped copper surfaces (410) and (211) Thompson, K. A.; Fadley, C. S. Surface Science, Vol. 146, Issue 1 https://doi.org/10.1016/0039-6028(84)90243-7	journal	October 1984
Further LEED investigations of missing row models for the surface structure Zeng, H. C.; Mitchell, K. A. R. Surface Science, Vol. 239, Issue 3 https://doi.org/10.1016/0039-6028(90)90220-3	journal	December 1990
The structure of oxygen adsorption phases on Cu(100) Asensio, M. C.; Ashwin, M. J.; Kilcoyne, A. L. D. Surface Science, Vol. 236, Issue 1-2 https://doi.org/10.1016/0039-6028(90)90755-w	journal	October 1990
Do oxygen-induced Cu(410) facets reconstruct? Lloyd, G. W.; Woodruff, D. P. Surface Science, Vol. 285, Issue 3 https://doi.org/10.1016/0039-6028(93)90421-f	journal	April 1993
Oxygen chemisorption on metal surfaces: General trends for Cu, Ni and Ag Besenbacher, Flemming; Nørskov, Jens K. Progress in Surface Science, Vol. 44, Issue 1 https://doi.org/10.1016/0079-6816(93)90006-h	journal	September 1993
X-ray photoelectron diffraction study of oxygen adsorption on the stepped copper surfaces (410) and (211) Thompson, K. A.; Fadley, C. S. Surface Science Letters, Vol. 146, Issue 1 https://doi.org/10.1016/0167-2584(84)90810-7	journal	October 1984
Do oxygen-induced Cu(410) facets reconstruct? Lloyd, G. W.; Woodruff, D. P. Surface Science Letters, Vol. 285, Issue 3 https://doi.org/10.1016/0167-2584(93)90356-n	journal	April 1993
Bridging the structure gap: Chemistry of nanostructured surfaces at well-defined defects Vattuone, L.; Savio, L.; Rocca, M. Surface Science Reports, Vol. 63, Issue 3 https://doi.org/10.1016/j.surfrep.2007.11.001	journal	March 2008
Initial sticking probability of O2 on Cu(410) Vattuone, Luca; Savio, Letizia; Okada, Michio Surface Science, Vol. 602, Issue 15 https://doi.org/10.1016/j.susc.2008.06.031	journal	August 2008
Surface relaxation in Cu(410)–O: A medium energy ion scattering study Sheppard, D. C.; Parkinson, G. S.; Hentz, A. Surface Science, Vol. 604, Issue 9-10 https://doi.org/10.1016/j.susc.2010.02.001	journal	May 2010
Adsorption of sulfur on Ag(100) Russell, Selena M.; Shen, Mingmin; Liu, Da-Jiang Surface Science, Vol. 605, Issue 5-6 https://doi.org/10.1016/j.susc.2010.12.010	journal	March 2011
Structure determination of Cu()–O using X-ray diffraction and DFT calculations Vlieg, E.; Driver, S. M.; Goedtkindt, P. Surface Science, Vol. 516, Issue 1-2 https://doi.org/10.1016/s0039-6028(02)02066-6	journal	September 2002
The adsorption and dissociation of O 2 molecular precursors on Cu: the effect of steps Xu, Ye; Mavrikakis, Manos Surface Science, Vol. 538, Issue 3 https://doi.org/10.1016/s0039-6028(03)00787-8	journal	July 2003
Oxygen-induced faceting on Cu(115) Reiter, S.; Taglauer, E. Surface Science, Vol. 367, Issue 1 https://doi.org/10.1016/s0039-6028(96)00846-1	journal	November 1996
Scanning tunnelling microscopy investigation of the oxygen-induced faceting and “nano-faceting” of a vicinal copper surface Knight, P. J.; Driver, S. M.; Woodruff, D. P. Surface Science, Vol. 376, Issue 1-3 https://doi.org/10.1016/s0039-6028(96)01328-3	journal	April 1997
Sulfur induced Cu4 tetramers on Cu(111) Foss, M.; Feidenhans'l, R.; Nielsen, M. Surface Science, Vol. 388, Issue 1-3 https://doi.org/10.1016/s0039-6028(97)00071-x	journal	October 1997
Catalytic activity of Au nanoparticles Hvolbæk, Britt; Janssens, Ton V. W.; Clausen, Bjerne S. Nano Today, Vol. 2, Issue 4 https://doi.org/10.1016/s1748-0132(07)70113-5	journal	August 2007
Sulfur Atoms Adsorbed on Cu(100) at Low Coverage: Characterization and Stability against Complexation Walen, Holly; Liu, Da-Jiang; Oh, Junepyo The Journal of Physical Chemistry B, Vol. 122, Issue 2 https://doi.org/10.1021/ACS.JPCB.7b07046	journal	September 2017
Finding Needles in Haystacks: Scanning Tunneling Microscopy Reveals the Complex Reactivity of Si(100) Surfaces Skibinski, Erik S.; Hines, Melissa A. Accounts of Chemical Research, Vol. 48, Issue 7 https://doi.org/10.1021/acs.accounts.5b00136	journal	June 2015
Long-Range Displacive Reconstruction of Au(110) Triggered by Low Coverage of Sulfur Walen, Holly; Liu, Da-Jiang; Oh, Junepyo The Journal of Physical Chemistry C, Vol. 119, Issue 36 https://doi.org/10.1021/acs.jpcc.5b06559	journal	August 2015
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 Lee, Jiyoung; Boschen, Jeffery S.; Windus, Theresa L. The Journal of Physical Chemistry C, Vol. 121, Issue 7 https://doi.org/10.1021/acs.jpcc.6b11120	journal	February 2017
Enantioselective Separation on a Naturally Chiral Surface Horvath, Joshua D.; Koritnik, Anjanette; Kamakoti, Preeti Journal of the American Chemical Society, Vol. 126, Issue 45 https://doi.org/10.1021/ja045537h	journal	November 2004
High-resolution Electron Energy Loss Spectroscopy Study of O-Cu(410) Vattuone, Luca; Savio, Letizia; Gerbi, Andrea The Journal of Physical Chemistry B, Vol. 111, Issue 7 https://doi.org/10.1021/jp0667083	journal	February 2007
Unravelling the Role of Steps in Cu ₂ O Formation via Hyperthermal O ₂ Adsorption at Cu(410) Okada, Michio; Vattuone, Luca; Gerbi, Andrea The Journal of Physical Chemistry C, Vol. 111, Issue 46 https://doi.org/10.1021/jp074520t	journal	October 2007
Long-Range Periodicity of S/Au(111) Structures at Low and Intermediate Coverages Abufager, P. N.; Zampieri, G.; Reuter, K. The Journal of Physical Chemistry C, Vol. 118, Issue 1 https://doi.org/10.1021/jp408340d	journal	December 2013
Search for the Structure of a Sulfur-Induced Reconstruction on Cu(111) Liu, Da-Jiang; Walen, Holly; Oh, Junepyo The Journal of Physical Chemistry C, Vol. 118, Issue 50 https://doi.org/10.1021/jp505351g	journal	August 2014
Novel Self-Organized Structure of a Ag−S Complex on the Ag(111) Surface below Room Temperature Shen, Mingmin; Liu, Da-Jiang; Jenks, Cynthia J. The Journal of Physical Chemistry C, Vol. 112, Issue 11 https://doi.org/10.1021/jp710751b	journal	February 2008
Accurate first-principles structures and energies of diversely bonded systems from an efficient density functional Sun, Jianwei; Remsing, Richard C.; Zhang, Yubo Nature Chemistry, Vol. 8, Issue 9 https://doi.org/10.1038/nchem.2535	journal	June 2016
The role of steps in surface catalysis and reaction oscillations Hendriksen, Bas L. M.; Ackermann, Marcelo D.; van Rijn, Richard Nature Chemistry, Vol. 2, Issue 9 https://doi.org/10.1038/nchem.728	journal	July 2010
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect Tatemizo, Nobuyuki; Imada, Saki; Okahara, Kizuna Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-58835-5	journal	February 2020
Identification of Au–S complexes on Au(100) Walen, Holly; Liu, Da-Jiang; Oh, Junepyo Physical Chemistry Chemical Physics, Vol. 18, Issue 6 https://doi.org/10.1039/c5cp07817b	journal	January 2016
The effect of step geometry in copper oxidation by hyperthermal O ₂ molecular beam: Cu(511) vs Cu(410) Okada, Michio; Vattuone, Luca; Rocca, Mario The Journal of Chemical Physics, Vol. 136, Issue 9 https://doi.org/10.1063/1.3690019	journal	March 2012
Communication: Structure, formation, and equilibration of ensembles of Ag-S complexes on an Ag surface Russell, Selena M.; Kim, Yousoo; Liu, Da-Jiang The Journal of Chemical Physics, Vol. 138, Issue 7 https://doi.org/10.1063/1.4790571	journal	February 2013
Reconstruction of steps on the Cu(111) surface induced by sulfur Walen, Holly; Liu, Da-Jiang; Oh, Junepyo The Journal of Chemical Physics, Vol. 142, Issue 19 https://doi.org/10.1063/1.4921258	journal	May 2015
Self-organization of S adatoms on Au(111): √3R30° rows at low coverage Walen, Holly; Liu, Da-Jiang; Oh, Junepyo The Journal of Chemical Physics, Vol. 143, Issue 1 https://doi.org/10.1063/1.4922929	journal	July 2015
Erratum: The NBS tables of chemical thermodynamic properties. Selected values for inorganic and C1 and C2 organic substances in SI units [J. Phys. Chem. Ref. Data 11, Suppl. 2 (1982)] Wagman, Donald D.; Evans, William H.; Parker, Vivian B. Journal of Physical and Chemical Reference Data, Vol. 18, Issue 4 https://doi.org/10.1063/1.555845	journal	October 1989
Dynamics of the interaction of O2 with stepped and damaged Ag surfaces Savio, L.; Vattuone, L.; Rocca, M. Journal of Physics: Condensed Matter, Vol. 14, Issue 24 https://doi.org/10.1088/0953-8984/14/24/310	journal	June 2002
Dynamics of the interaction of O ₂ with stepped and damaged Ag surfaces Savio, L.; Vattuone, L.; Rocca, M. Journal of Physics: Condensed Matter, Vol. 15, Issue 13 https://doi.org/10.1088/0953-8984/15/13/501	journal	March 2003
Chemical accuracy for the van der Waals density functional Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos Journal of Physics: Condensed Matter, Vol. 22, Issue 2 https://doi.org/10.1088/0953-8984/22/2/022201	journal	December 2009
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Density functional analysis of key energetics in metal homoepitaxy: Quantum size effects in periodic slab calculations Liu, Da-Jiang Physical Review B, Vol. 81, Issue 3 https://doi.org/10.1103/PhysRevB.81.035415	journal	January 2010
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 78, Issue 7 https://doi.org/10.1103/PhysRevLett.78.1396	journal	February 1997
Oxygen-induced missing-row reconstruction of Cu(001) and Cu(001)-vicinal surfaces Robinson, I. K.; Vlieg, E.; Ferrer, S. Physical Review B, Vol. 42, Issue 11 https://doi.org/10.1103/physrevb.42.6954	journal	October 1990
Dynamics of oxygen-induced reconstruction of Cu(100) studied by scanning tunneling microscopy Jensen, F.; Besenbacher, F.; Laegsgaard, E. Physical Review B, Vol. 42, Issue 14 https://doi.org/10.1103/physrevb.42.9206	journal	November 1990
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/physrevb.47.558	journal	January 1993
Sulfur chemisorption on Ni(111): The clock structure of the (5√3×2)S phase Foss, M.; Feidenhans’l, R.; Nielsen, M. Physical Review B, Vol. 50, Issue 12 https://doi.org/10.1103/physrevb.50.8950	journal	September 1994
Oxygen-induced reconstructions on Cu(211) Witte, G.; Braun, J.; Nowack, D. Physical Review B, Vol. 58, Issue 19 https://doi.org/10.1103/physrevb.58.13224	journal	November 1998
Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals Hammer, B.; Hansen, L. B.; Nørskov, J. K. Physical Review B, Vol. 59, Issue 11 https://doi.org/10.1103/physrevb.59.7413	journal	March 1999
Electronic structure of atomic chains on vicinal Si(111)-Au Altmann, K. N.; Crain, J. N.; Kirakosian, A. Physical Review B, Vol. 64, Issue 3 https://doi.org/10.1103/physrevb.64.035406	journal	June 2001
Structure and dynamics of oxygen adsorbed on Ag(100) vicinal surfaces Bonini, N.; Kokalj, A.; Dal Corso, A. Physical Review B, Vol. 69, Issue 19 https://doi.org/10.1103/physrevb.69.195401	journal	May 2004
Density-functional theory investigation of oxygen adsorption at Pd ( 11 N ) vicinal surfaces ( N = 3 , 5 , 7 ) : Influence of neighboring steps Zhang, Yongsheng; Rogal, Jutta; Reuter, Karsten Physical Review B, Vol. 74, Issue 12 https://doi.org/10.1103/physrevb.74.125414	journal	September 2006
Quantum size effects in metal nanofilms: Comparison of an electron-gas model and density functional theory calculations Han, Yong; Liu, Da-Jiang Physical Review B, Vol. 80, Issue 15 https://doi.org/10.1103/physrevb.80.155404	journal	October 2009
Cu 2 S 3 complex on Cu(111) as a candidate for mass transport enhancement Walen, Holly; Liu, Da-Jiang; Oh, Junepyo Physical Review B, Vol. 91, Issue 4 https://doi.org/10.1103/physrevb.91.045426	journal	January 2015
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/physrevlett.77.3865	journal	October 1996
Role of Steps and of Terrace Width in Gas-Surface Interaction: O 2 / Ag ( 410 ) Savio, L.; Vattuone, L.; Rocca, M. Physical Review Letters, Vol. 87, Issue 27 https://doi.org/10.1103/physrevlett.87.276101	journal	December 2001
Identification of the "Active Sites" of a Surface-Catalyzed Reaction Zambelli, T.; Wintterlin, J.; Trost, J. Science, Vol. 273, Issue 5282 https://doi.org/10.1126/science.273.5282.1688	journal	September 1996
Atomic structure of the Cu(410)-O surface: STM visualization of oxygen and copper atoms Chaika, A. N.; Bozhko, S. I. Journal of Experimental and Theoretical Physics Letters, Vol. 82, Issue 7 https://doi.org/10.1134/1.2142868	journal	October 2005
Role of Steps and of Terrace Width in Gas-Surface Interaction: O2/Ag(410) Rocca, M.; Savio, L.; Vattuone, L. The American Physical Society https://doi.org/10.17877/de290r-11723	text	January 2001
Sulfur chemisorption on Ni(111): The clock structure of the (5$\sqrt 3$×2)S phase Foss, M.; Feidenhans’l, R.; Nielsen, M. Deutsches Elektronen-Synchrotron, DESY, Hamburg https://doi.org/10.3204/pubdb-2017-04510	text	January 1994
Chemical accuracy for the van der Waals density functional Klimes, J.; Bowler, D. R.; Michaelides, A. arXiv https://doi.org/10.48550/arxiv.0910.0438	preprint	January 2009

Similar Records

Oxygen adsorption on spontaneously reconstructed Au(511)

Journal Article · 2019 · Surface Science · OSTI ID:1566480

Xu, Fang; Montemore, Matthew M.; O'Connor, Christopher R.; +4 more

Oxygen adsorption on spontaneously reconstructed Au(511)

Journal Article · 2018 · Surface Science · OSTI ID:1597444

Xu, Fang; Montemore, Matthew M.; O'Connor, Christopher R.; +4 more

Reaction properties of NO and CO over an Ir(211) surface

Journal Article · 2007 · Journal of Vacuum Science and Technology. A, International Journal Devoted to Vacuum, Surfaces, and Films · OSTI ID:20979469

Nakamura, I; Suzuki, K; Takahashi, A; +3 more

Related Subjects

36 MATERIALS SCIENCE

Title: Oxygen and sulfur adsorption on vicinal surfaces of copper and silver: Preferred adsorption sites

Citation Formats

References (66)

Similar Records

Related Subjects