Stabilization of X–Au–X complexes on the Au(111) surface: A theoretical investigation and comparison of X = S, Cl, CH3S, and SiH3S
Abstract
Alnico alloys have long been used as strong permanent magnets because of their ferromagnetism and high coercivity. Understanding their structural details allows for better prediction of the resulting magnetic properties. However, quantitative three-dimensional characterization of the phase separation in these alloys is still challenged by the spatial quantification of nanoscale phases. Herein, we apply a dual tomography approach, where correlative scanning transmission electron microscopy (STEM) energy-dispersive X-ray spectroscopic (EDS) tomography and atom probe tomography (APT) are used to investigate the initial phase separation process of an alnico 8 alloy upon non-magnetic annealing. STEM-EDS tomography provides information on the morphology and volume fractions of Fe–Co-rich and Νi–Al-rich phases after spinodal decomposition in addition to quantitative information of the composition of a nanoscale volume. Subsequent analysis of a portion of the same specimen by APT offers quantitative chemical information of each phase at the sub-nanometer scale. Furthermore, APT reveals small, 2–4 nm Fe-richα1 phases that are nucleated in the Ni-richα2 matrix. From this information, we show that phase separation of the alnico 8 alloy consists of both spinodal decomposition and nucleation and growth processes. The complementary benefits and challenges associated with correlative STEM-EDS and APT are discussed.
- Publication Date:
- Research Org.:
- Ames Laboratory (AMES), Ames, IA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1349895
- Report Number(s):
- IS-J-9124
Journal ID: ISSN 1932-7447; PII: S1431927616012496
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 121; Journal Issue: 7; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Lee, Jiyoung, Boschen, Jeffery S., Windus, Theresa L., Thiel, Patricia A., and Liu, Da -Jiang. Stabilization of X–Au–X complexes on the Au(111) surface: A theoretical investigation and comparison of X = S, Cl, CH3S, and SiH3S. United States: N. p., 2017.
Web. doi:10.1021/acs.jpcc.6b11120.
Lee, Jiyoung, Boschen, Jeffery S., Windus, Theresa L., Thiel, Patricia A., & Liu, Da -Jiang. Stabilization of X–Au–X complexes on the Au(111) surface: A theoretical investigation and comparison of X = S, Cl, CH3S, and SiH3S. United States. https://doi.org/10.1021/acs.jpcc.6b11120
Lee, Jiyoung, Boschen, Jeffery S., Windus, Theresa L., Thiel, Patricia A., and Liu, Da -Jiang. Fri .
"Stabilization of X–Au–X complexes on the Au(111) surface: A theoretical investigation and comparison of X = S, Cl, CH3S, and SiH3S". United States. https://doi.org/10.1021/acs.jpcc.6b11120. https://www.osti.gov/servlets/purl/1349895.
@article{osti_1349895,
title = {Stabilization of X–Au–X complexes on the Au(111) surface: A theoretical investigation and comparison of X = S, Cl, CH3S, and SiH3S},
author = {Lee, Jiyoung and Boschen, Jeffery S. and Windus, Theresa L. and Thiel, Patricia A. and Liu, Da -Jiang},
abstractNote = {Alnico alloys have long been used as strong permanent magnets because of their ferromagnetism and high coercivity. Understanding their structural details allows for better prediction of the resulting magnetic properties. However, quantitative three-dimensional characterization of the phase separation in these alloys is still challenged by the spatial quantification of nanoscale phases. Herein, we apply a dual tomography approach, where correlative scanning transmission electron microscopy (STEM) energy-dispersive X-ray spectroscopic (EDS) tomography and atom probe tomography (APT) are used to investigate the initial phase separation process of an alnico 8 alloy upon non-magnetic annealing. STEM-EDS tomography provides information on the morphology and volume fractions of Fe–Co-rich and Νi–Al-rich phases after spinodal decomposition in addition to quantitative information of the composition of a nanoscale volume. Subsequent analysis of a portion of the same specimen by APT offers quantitative chemical information of each phase at the sub-nanometer scale. Furthermore, APT reveals small, 2–4 nm Fe-richα1 phases that are nucleated in the Ni-richα2 matrix. From this information, we show that phase separation of the alnico 8 alloy consists of both spinodal decomposition and nucleation and growth processes. The complementary benefits and challenges associated with correlative STEM-EDS and APT are discussed.},
doi = {10.1021/acs.jpcc.6b11120},
journal = {Journal of Physical Chemistry. C},
number = 7,
volume = 121,
place = {United States},
year = {Fri Jan 27 00:00:00 EST 2017},
month = {Fri Jan 27 00:00:00 EST 2017}
}
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Works referenced in this record:
Formation and Structure of Self-Assembled Monolayers
journal, January 1996
- Ulman, Abraham
- Chemical Reviews, Vol. 96, Issue 4, p. 1533-1554
Self-Assembled Monolayers of Thiolates on Metals as a Form of Nanotechnology
journal, April 2005
- Love, J. Christopher; Estroff, Lara A.; Kriebel, Jennah K.
- Chemical Reviews, Vol. 105, Issue 4
The Chemistry of the Sulfur–Gold Interface: In Search of a Unified Model
journal, March 2012
- Pensa, Evangelina; Cortés, Emiliano; Corthey, Gastón
- Accounts of Chemical Research, Vol. 45, Issue 8
Functional Gold Nanoparticles as Potent Antimicrobial Agents against Multi-Drug-Resistant Bacteria
journal, September 2014
- Li, Xiaoning; Robinson, Sandra M.; Gupta, Akash
- ACS Nano, Vol. 8, Issue 10
Alkanethiol-based single-molecule transistors
journal, December 2008
- Ma, Chun-Lan; Nghiem, Diu; Chen, Yu-Chang
- Applied Physics Letters, Vol. 93, Issue 22
Single-Molecule Circuits with Well-Defined Molecular Conductance
journal, February 2006
- Venkataraman, Latha; Klare, Jennifer E.; Tam, Iris W.
- Nano Letters, Vol. 6, Issue 3
Synthesis of a gold nanoparticle dimer plasmonic resonator through two-phase-mediated functionalization
journal, September 2008
- Yim, Tae-Jin; Wang, Yuan; Zhang, Xiang
- Nanotechnology, Vol. 19, Issue 43
Novel Self-Organized Structure of a Ag−S Complex on the Ag(111) Surface below Room Temperature
journal, February 2008
- Shen, Mingmin; Liu, Da-Jiang; Jenks, Cynthia J.
- The Journal of Physical Chemistry C, Vol. 112, Issue 11
Communication: Structure, formation, and equilibration of ensembles of Ag-S complexes on an Ag surface
journal, February 2013
- Russell, Selena M.; Kim, Yousoo; Liu, Da-Jiang
- The Journal of Chemical Physics, Vol. 138, Issue 7
complex on Cu(111) as a candidate for mass transport enhancement
journal, January 2015
- Walen, Holly; Liu, Da-Jiang; Oh, Junepyo
- Physical Review B, Vol. 91, Issue 4
Identification of Au–S complexes on Au(100)
journal, January 2016
- Walen, Holly; Liu, Da-Jiang; Oh, Junepyo
- Physical Chemistry Chemical Physics, Vol. 18, Issue 6
Long-Range Displacive Reconstruction of Au(110) Triggered by Low Coverage of Sulfur
journal, August 2015
- Walen, Holly; Liu, Da-Jiang; Oh, Junepyo
- The Journal of Physical Chemistry C, Vol. 119, Issue 36
The interface structure of n-alkylthiolate self-assembled monolayers on coinage metal surfaces
journal, January 2008
- Woodruff, D. P.
- Physical Chemistry Chemical Physics, Vol. 10, Issue 48
Quantum sized, thiolate-protected gold nanoclusters
journal, January 2010
- Jin, Rongchao
- Nanoscale, Vol. 2, Issue 3
Self-organization of S adatoms on Au(111): √3R30° rows at low coverage
journal, July 2015
- Walen, Holly; Liu, Da-Jiang; Oh, Junepyo
- The Journal of Chemical Physics, Vol. 143, Issue 1
Structural paradox in submonolayer chlorine coverage on Au(111)
journal, May 2014
- Zheltov, V. V.; Cherkez, V. V.; Andryushechkin, B. V.
- Physical Review B, Vol. 89, Issue 19
The Role of Gold Adatoms and Stereochemistry in Self-Assembly of Methylthiolate on Au(111)
journal, September 2009
- Voznyy, Oleksandr; Dubowski, Jan J.; Yates, J. T.
- Journal of the American Chemical Society, Vol. 131, Issue 36
The Structure of Atomic Sulfur Phases on Au(111)
journal, June 2007
- Yu, Miao; Ascolani, H.; Zampieri, G.
- The Journal of Physical Chemistry C, Vol. 111, Issue 29
Self-Organization of Gold Chloride Molecules on Au(111) Surface
journal, November 2013
- Andryushechkin, Boris V.; Cherkez, Vladimir V.; Gladchenko, Eugeny V.
- The Journal of Physical Chemistry C, Vol. 117, Issue 47
Complete Structural Phases for Self-Assembled Methylthiolate Monolayers on Au(111)
journal, October 2013
- Tang, L.; Li, F. S.; Guo, Q.
- The Journal of Physical Chemistry C, Vol. 117, Issue 41
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Long-Range Periodicity of S/Au(111) Structures at Low and Intermediate Coverages
journal, December 2013
- Abufager, P. N.; Zampieri, G.; Reuter, K.
- The Journal of Physical Chemistry C, Vol. 118, Issue 1
Phase diagram of oxygen adsorbed on platinum (111) by first-principles investigation
journal, July 2004
- Tang, Hairong; Van der Ven, Anton; Trout, Bernhardt L.
- Physical Review B, Vol. 70, Issue 4
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010
- Valiev, M.; Bylaska, E. J.; Govind, N.
- Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999
- Adamo, Carlo; Barone, Vincenzo
- The Journal of Chemical Physics, Vol. 110, Issue 13
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
journal, July 2007
- Zhao, Yan; Truhlar, Donald G.
- Theoretical Chemistry Accounts, Vol. 120, Issue 1-3
Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg
journal, January 1985
- Hay, P. Jeffrey; Wadt, Willard R.
- The Journal of Chemical Physics, Vol. 82, Issue 1
Ab initio effective core potentials for molecular calculations. Potentials for main group elements Na to Bi
journal, January 1985
- Wadt, Willard R.; Hay, P. Jeffrey
- The Journal of Chemical Physics, Vol. 82, Issue 1
Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals
journal, January 1985
- Hay, P. Jeffrey; Wadt, Willard R.
- The Journal of Chemical Physics, Vol. 82, Issue 1, p. 299-310
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005
- Weigend, Florian; Ahlrichs, Reinhart
- Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18
journal, May 1980
- McLean, A. D.; Chandler, G. S.
- The Journal of Chemical Physics, Vol. 72, Issue 10, p. 5639-5648
Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions
journal, January 1980
- Krishnan, R.; Binkley, J. S.; Seeger, R.
- The Journal of Chemical Physics, Vol. 72, Issue 1
Efficient diffuse function-augmented basis sets for anion calculations. III. The 3-21+G basis set for first-row elements, Li-F
journal, October 1983
- Clark, Timothy; Chandrasekhar, Jayaraman; Spitznagel, G�nther W.
- Journal of Computational Chemistry, Vol. 4, Issue 3
Property-optimized Gaussian basis sets for molecular response calculations
journal, October 2010
- Rappoport, Dmitrij; Furche, Filipp
- The Journal of Chemical Physics, Vol. 133, Issue 13
A fifth-order perturbation comparison of electron correlation theories
journal, May 1989
- Raghavachari, Krishnan; Trucks, Gary W.; Pople, John A.
- Chemical Physics Letters, Vol. 157, Issue 6
Evaluation of the contribution from triply excited intermediates to the fourth-order perturbation theory energy on Intel distributed memory supercomputers
journal, January 1993
- Rendell, Alistair P.; Lee, Timothy J.; Komornicki, Andrew
- Theoretica Chimica Acta, Vol. 84, Issue 4-5
A direct coupled cluster algorithm for massively parallel computers
journal, January 1997
- Kobayashi, Rika; Rendell, Alistair P.
- Chemical Physics Letters, Vol. 265, Issue 1-2
Systematically convergent basis sets for transition metals. II. Pseudopotential-based correlation consistent basis sets for the group 11 (Cu, Ag, Au) and 12 (Zn, Cd, Hg) elements
journal, August 2005
- Peterson, Kirk A.; Puzzarini, Cristina
- Theoretical Chemistry Accounts, Vol. 114, Issue 4-5
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989
- Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 90, Issue 2
Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon
journal, January 1993
- Woon, David E.; Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 98, Issue 2
Basis-set convergence in correlated calculations on Ne, N2, and H2O
journal, April 1998
- Halkier, Asger; Helgaker, Trygve; Jørgensen, Poul
- Chemical Physics Letters, Vol. 286, Issue 3-4
Self-ordered nanoporous lattice formed by chlorine atoms on Au(111)
journal, January 2016
- Cherkez, V. V.; Zheltov, V. V.; Didiot, C.
- Physical Review B, Vol. 93, Issue 4
Cis–trans conversion of the CH3S–Au–SCH3 complex on Au(111)
journal, January 2009
- Jiang, De-en; Dai, Sheng
- Physical Chemistry Chemical Physics, Vol. 11, Issue 38
Study of Alkylthiolate Self-assembled Monolayers on Au(111) Using a Semilocal meta-GGA Density Functional
journal, March 2012
- Ferrighi, Lara; Pan, Yun-xiang; Grönbeck, Henrik
- The Journal of Physical Chemistry C, Vol. 116, Issue 13
Gold adatom as a key structural component in self-assembled monolayers of organosulfur molecules on Au(111)
journal, May 2010
- Maksymovych, Peter; Voznyy, Oleksandr; Dougherty, Daniel B.
- Progress in Surface Science, Vol. 85, Issue 5-8
Chemical accuracy for the van der Waals density functional
journal, December 2009
- Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos
- Journal of Physics: Condensed Matter, Vol. 22, Issue 2
Van der Waals density functionals applied to solids
journal, May 2011
- Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos
- Physical Review B, Vol. 83, Issue 19
Van der Waals Density Functional for General Geometries
journal, June 2004
- Dion, M.; Rydberg, H.; Schröder, E.
- Physical Review Letters, Vol. 92, Issue 24
A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006
- Zhao, Yan; Truhlar, Donald G.
- The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101
The structure of methylthiolate and ethylthiolate monolayers on Au(111): Absence of the (√3 × √3)R30° phase
journal, March 2012
- Tang, Lin; Li, Fangsen; Zhou, Wancheng
- Surface Science, Vol. 606, Issue 5-6
Structural defects in self‐assembled organic monolayers via combined atomic beam and x‐ray diffraction
journal, July 1993
- Camillone, N.; Chidsey, C. E. D.; Eisenberger, P.
- The Journal of Chemical Physics, Vol. 99, Issue 1
Self-assembled monolayers of thiols and dithiols on gold: new challenges for a well-known system
journal, January 2010
- Vericat, C.; Vela, M. E.; Benitez, G.
- Chemical Society Reviews, Vol. 39, Issue 5
Gold−Thiolate Complexes Form a Unique c (4 × 2) Structure on Au(111)
journal, September 2008
- Grönbeck, Henrik; Häkkinen, Hannu; Whetten, Robert L.
- The Journal of Physical Chemistry C, Vol. 112, Issue 41
Coverage Effects and the Nature of the Metal−Sulfur Bond in S/Au(111): High-Resolution Photoemission and Density-Functional Studies
journal, January 2003
- Rodriguez, José A.; Dvorak, Joseph; Jirsak, Tomas
- Journal of the American Chemical Society, Vol. 125, Issue 1
Destabilization of Ag nanoislands on Ag(100) by adsorbed sulfur
journal, October 2011
- Shen, Mingmin; Russell, Selena M.; Liu, Da-Jiang
- The Journal of Chemical Physics, Vol. 135, Issue 15
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008
- Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I.
- Physical Review Letters, Vol. 100, Issue 13
Rungs 1 to 4 of DFT Jacob’s ladder: Extensive test on the lattice constant, bulk modulus, and cohesive energy of solids
journal, May 2016
- Tran, Fabien; Stelzl, Julia; Blaha, Peter
- The Journal of Chemical Physics, Vol. 144, Issue 20
The shortcomings of semi-local and hybrid functionals: what we can learn from surface science studies
journal, June 2008
- Stroppa, A.; Kresse, G.
- New Journal of Physics, Vol. 10, Issue 6
Self-consistent meta-generalized gradient approximation within the projector-augmented-wave method
journal, July 2011
- Sun, Jianwei; Marsman, Martijn; Csonka, Gábor I.
- Physical Review B, Vol. 84, Issue 3
Workhorse Semilocal Density Functional for Condensed Matter Physics and Quantum Chemistry
journal, July 2009
- Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I.
- Physical Review Letters, Vol. 103, Issue 2
Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006
- Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.
- The Journal of Chemical Physics, Vol. 125, Issue 22
Atomic reference energies for density functional calculations
journal, February 1997
- Baerends, E. J.; Branchadell, V.; Sodupe, M.
- Chemical Physics Letters, Vol. 265, Issue 3-5
Revisiting the Structure of the Surface Oxide on Ag(111)
journal, April 2006
- Schnadt, J.; Michaelides, A.; Knudsen, J.
- Physical Review Letters, Vol. 96, Issue 14
Structure of : No Silver Oxide
journal, April 2006
- Schmid, M.; Reicho, A.; Stierle, A.
- Physical Review Letters, Vol. 96, Issue 14
Adsorption of sulfur on Ag(100)
journal, March 2011
- Russell, Selena M.; Shen, Mingmin; Liu, Da-Jiang
- Surface Science, Vol. 605, Issue 5-6
Works referencing / citing this record:
Oxygen and sulfur adsorption on vicinal surfaces of copper and silver: Preferred adsorption sites
journal, March 2018
- Liu, Da-Jiang; Thiel, Patricia A.
- The Journal of Chemical Physics, Vol. 148, Issue 12
Gold adatoms modulate sulfur adsorption on gold
journal, January 2019
- Carro, Pilar; Salvarezza, Roberto C.
- Nanoscale, Vol. 11, Issue 41