Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations
Abstract
Large-scale first-principles density functional theory calculations are performed to investigate the adsorption and diffusion of Ru adatoms on monolayer graphene (G) supported on Ru(0001). The G sheet exhibits a periodic moiré-cell superstructure due to lattice mismatch. Within a moiré cell, there are three distinct regions: fcc, hcp, and mound, in which the C6-ring center is above a fcc site, a hcp site, and a surface Ru atom of Ru(0001), respectively. The adsorption energy of a Ru adatom is evaluated at specific sites in these distinct regions. We find the strongest binding at an adsorption site above a C atom in the fcc region, next strongest in the hcp region, then the fcc-hcp boundary (ridge) between these regions, and the weakest binding in the mound region. Behavior is similar to that observed from small-unit-cell calculations of Habenicht et al. [Top. Catal. 57, 69 (2014)], which differ from previous large-scale calculations. We determine the minimum-energy path for local diffusion near the center of the fcc region and obtain a local diffusion barrier of ~0.48 eV. We also estimate a significantly lower local diffusion barrier in the ridge region. These barriers and information on the adsorption energy variation facilitate development of a realisticmore »
- Authors:
-
- Iowa State Univ., Ames, IA (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Ames Lab., Ames, IA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1234535
- Report Number(s):
- IS-J-8857
Journal ID: ISSN 0021-9606; JCPSA6
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 143; Journal Issue: 16; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 97 MATHEMATICS AND COMPUTING; adsorption; diffusion barriers; Moire patterns; density functional theory; Monte Carlo methods
Citation Formats
Han, Yong, and Evans, James W. Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations. United States: N. p., 2015.
Web. doi:10.1063/1.4934349.
Han, Yong, & Evans, James W. Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations. United States. https://doi.org/10.1063/1.4934349
Han, Yong, and Evans, James W. Tue .
"Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations". United States. https://doi.org/10.1063/1.4934349. https://www.osti.gov/servlets/purl/1234535.
@article{osti_1234535,
title = {Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations},
author = {Han, Yong and Evans, James W.},
abstractNote = {Large-scale first-principles density functional theory calculations are performed to investigate the adsorption and diffusion of Ru adatoms on monolayer graphene (G) supported on Ru(0001). The G sheet exhibits a periodic moiré-cell superstructure due to lattice mismatch. Within a moiré cell, there are three distinct regions: fcc, hcp, and mound, in which the C6-ring center is above a fcc site, a hcp site, and a surface Ru atom of Ru(0001), respectively. The adsorption energy of a Ru adatom is evaluated at specific sites in these distinct regions. We find the strongest binding at an adsorption site above a C atom in the fcc region, next strongest in the hcp region, then the fcc-hcp boundary (ridge) between these regions, and the weakest binding in the mound region. Behavior is similar to that observed from small-unit-cell calculations of Habenicht et al. [Top. Catal. 57, 69 (2014)], which differ from previous large-scale calculations. We determine the minimum-energy path for local diffusion near the center of the fcc region and obtain a local diffusion barrier of ~0.48 eV. We also estimate a significantly lower local diffusion barrier in the ridge region. These barriers and information on the adsorption energy variation facilitate development of a realistic model for the global potential energy surface for Ru adatoms. Furthermore, this in turn enables simulation studies elucidating diffusion-mediated directed-assembly of Ru nanoclusters during deposition of Ru on G/Ru(0001).},
doi = {10.1063/1.4934349},
journal = {Journal of Chemical Physics},
number = 16,
volume = 143,
place = {United States},
year = {2015},
month = {10}
}
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Works referenced in this record:
The surface science of graphene: Metal interfaces, CVD synthesis, nanoribbons, chemical modifications, and defects
journal, March 2012
- Batzill, Matthias
- Surface Science Reports, Vol. 67, Issue 3-4
A versatile fabrication method for cluster superlattices
journal, October 2009
- N'Diaye, Alpha T.; Gerber, Timm; Busse, Carsten
- New Journal of Physics, Vol. 11, Issue 10
Deposition of metal clusters on single-layer graphene/Ru(0001): Factors that govern cluster growth
journal, July 2010
- Zhou, Zihao; Gao, Feng; Goodman, D. Wayne
- Surface Science, Vol. 604, Issue 13-14
Growth morphology and properties of metals on graphene
journal, December 2015
- Liu, Xiaojie; Han, Yong; Evans, James W.
- Progress in Surface Science, Vol. 90, Issue 4
Monolayer Graphene and h -BN on Metal Substrates as Versatile Templates for Metallic Nanoclusters
journal, August 2011
- Wang, Bin; Bocquet, Marie-Laure
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 18
Directed assembly of Ru nanoclusters on Ru(0001)-supported graphene: STM studies and atomistic modeling
journal, August 2012
- Engstfeld, Albert K.; Hoster, Harry E.; Behm, R. Juergen
- Physical Review B, Vol. 86, Issue 8
Adsorption and diffusion of the Rh and Au adatom on graphene moiré/Ru(0001)
journal, May 2013
- Semidey-Flecha, Lymarie; Teng, Dieh; Habenicht, Bradley F.
- The Journal of Chemical Physics, Vol. 138, Issue 18
Adsorption and Diffusion of 4d and 5d Transition Metal Adatoms on Graphene/Ru(0001) and the Implications for Cluster Nucleation
journal, October 2013
- Habenicht, Bradley F.; Teng, Dieh; Semidey-Flecha, Lymarie
- Topics in Catalysis, Vol. 57, Issue 1-4
On the Self‐Diffusion of Ions in a Polyelectrolyte Solution
journal, May 1962
- Lifson, Shneior; Jackson, Julius L.
- The Journal of Chemical Physics, Vol. 36, Issue 9
Note: Effective diffusion coefficient in heterogeneous media
journal, October 2012
- Kalnin, Juris R.; Kotomin, Eugene
- The Journal of Chemical Physics, Vol. 137, Issue 16
Level set simulation of directed self-assembly during epitaxial growth
journal, November 2006
- Niu, X.; Vardavas, R.; Caflisch, R. E.
- Physical Review B, Vol. 74, Issue 19
Atomistic modeling of Ru nanocluster formation on graphene/Ru(0001): Thermodynamically versus kinetically directed-assembly
journal, January 2013
- Han, Y.; Engstfeld, A. K.; Wang, C. -Z.
- MRS Proceedings, Vol. 1498
Atomistic modeling of the directed-assembly of bimetallic Pt-Ru nanoclusters on Ru(0001)-supported monolayer graphene
journal, April 2013
- Han, Yong; Engstfeld, Albert K.; Behm, R. Juergen
- The Journal of Chemical Physics, Vol. 138, Issue 13
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 49, Issue 20, p. 14251-14269
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
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
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
Chemical origin of a graphene moiré overlayer on Ru(0001)
journal, January 2008
- Wang, B.; Bocquet, M. -L.; Marchini, S.
- Physical Chemistry Chemical Physics, Vol. 10, Issue 24
First principles study of the graphene/Ru(0001) interface
journal, February 2009
- Jiang, De-en; Du, Mao-Hua; Dai, Sheng
- The Journal of Chemical Physics, Vol. 130, Issue 7
Size-Selected Monodisperse Nanoclusters on Supported Graphene: Bonding, Isomerism, and Mobility
journal, October 2012
- Wang, Bo; Yoon, Bokwon; König, Michael
- Nano Letters, Vol. 12, Issue 11
Exploring the structure and chemical activity of 2-D gold islands on graphene moiré/Ru(0001)
journal, January 2011
- Xu, Ye; Semidey-Flecha, Lymarie; Liu, Li
- Faraday Discussions, Vol. 152
Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006
- Grimme, Stefan
- Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
Scanning tunneling microscopy of graphene on Ru(0001)
journal, August 2007
- Marchini, S.; Günther, S.; Wintterlin, J.
- Physical Review B, Vol. 76, Issue 7
Formation of graphene on Ru(0001) surface
journal, November 2007
- Yi, Pan; Dong-Xia, Shi; Hong-Jun, Gao
- Chinese Physics, Vol. 16, Issue 11
Graphene on Ru(0001): A Supercell
journal, September 2008
- Martoccia, D.; Willmott, P. R.; Brugger, T.
- Physical Review Letters, Vol. 101, Issue 12
Comment on “Periodically Rippled Graphene: Growth and Spatially Resolved Electronic Structure”
journal, August 2008
- Wang, B.; Bocquet, M-L.; Günther, S.
- Physical Review Letters, Vol. 101, Issue 9
Structure Determination of the Coincidence Phase of Graphene on Ru(0001)
journal, April 2010
- Moritz, W.; Wang, B.; Bocquet, M. -L.
- Physical Review Letters, Vol. 104, Issue 13
Periodicity, work function and reactivity of graphene on Ru(0001) from first principles
journal, April 2010
- Wang, B.; Günther, S.; Wintterlin, J.
- New Journal of Physics, Vol. 12, Issue 4
A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000
- Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points
journal, December 2000
- Henkelman, Graeme; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 113, Issue 22
Growth Mechanism of Metal Clusters on a Graphene/Ru(0001) Template
journal, February 2014
- Zhang, L. Z.; Du, S. X.; Sun, J. T.
- Advanced Materials Interfaces, Vol. 1, Issue 3
Comparative study of the nature of chemical bonding of corrugated graphene on Ru(0001) and Rh(111) by electronic structure calculations
journal, August 2011
- Iannuzzi, Marcella; Hutter, Jürg
- Surface Science, Vol. 605, Issue 15-16
Vázquez de Parga et al. Reply:
journal, August 2008
- de Parga, A. L. Vázquez; Calleja, F.; Borca, B.
- Physical Review Letters, Vol. 101, Issue 9
Inhomogeneous electronic properties of monolayer graphene on Ru(0001)
journal, April 2011
- Gyamfi, M.; Eelbo, T.; Waśniowska, M.
- Physical Review B, Vol. 83, Issue 15
Arrays of Ru nanoclusters with narrow size distribution templated by monolayer graphene on Ru
journal, September 2011
- Sutter, Eli; Albrecht, Peter; Wang, Bin
- Surface Science, Vol. 605, Issue 17-18
Adsorption and diffusion of Rh and Au dimers and trimers on graphene/Ru(0001)
journal, August 2014
- Teng, Dieh; Sholl, David S.
- Surface Science, Vol. 626
Some aspects of cluster diffusion on surfaces
journal, July 1982
- Titulaer, U. M.; Deutch, J. M.
- The Journal of Chemical Physics, Vol. 77, Issue 1
Quantum size effects in metal nanofilms: Comparison of an electron-gas model and density functional theory calculations
journal, October 2009
- Han, Yong; Liu, Da-Jiang
- Physical Review B, Vol. 80, Issue 15
<I>Crystallographic Properties of Ruthenium</I>
journal, April 2013
- Arblaster, John W.
- Platinum Metals Review, Vol. 57, Issue 2
The surface energy of metals
journal, August 1998
- Vitos, L.; Ruban, A. V.; Skriver, H. L.
- Surface Science, Vol. 411, Issue 1-2
Band structure of Au layers on the Ru(0001) and graphene/Ru(0001) surfaces
journal, February 2012
- Yakovkin, I. N.
- The European Physical Journal B, Vol. 85, Issue 2
Nanoscale “Quantum” Islands on Metal Substrates: Microscopy Studies and Electronic Structure Analyses
journal, July 2010
- Han, Yong; Ünal, Bariş; Jing, Dapeng
- Materials, Vol. 3, Issue 7
A theory of thin metal films: electron density, potentials and work function
journal, May 1976
- Schulte, F. K.
- Surface Science, Vol. 55, Issue 2
Surface free energies of solid metals: Estimation from liquid surface tension measurements
journal, January 1977
- Tyson, W. R.; Miller, W. A.
- Surface Science, Vol. 62, Issue 1
Surface energy and work function of elemental metals
journal, September 1992
- Skriver, H. L.; Rosengaard, N. M.
- Physical Review B, Vol. 46, Issue 11
Works referencing / citing this record:
Electronic effects and fundamental physics studied in molecular interfaces
journal, January 2018
- Pope, Thomas; Du, Shixuan; Gao, Hong-Jun
- Chemical Communications, Vol. 54, Issue 44
Reverse-engineering of graphene on metal surfaces: a case study of embedded ruthenium
journal, October 2018
- Lii-Rosales, Ann; Han, Yong; Yu, Ka Man
- Nanotechnology, Vol. 29, Issue 50