skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Rethinking CO adsorption on transition-metal surfaces: Effect of density-driven self-interaction errors

Journal Article · · Physical Review B
 [1];  [2];  [3];  [2]
  1. Temple Univ., Philadelphia, PA (United States); Georgia Inst. of Technology, Atlanta, GA (United States)
  2. Temple Univ., Philadelphia, PA (United States)
  3. Tulane Univ., New Orleans, LA (United States)
+ Show Author Affiliations

Adsorption of the molecule CO on metallic surfaces is an important unsolved problem in Kohn-Sham density functional theory (KS-DFT). We present a detailed study of carbon monoxide adsorption on fcc (111) surfaces of 3d, 4d, and 5d metals using nonempirical semilocal density functionals for the exchange-correlation energy: the local-density approximation (LDA), two generalized gradient approximations or GGAs [Perdew-Burke-Ernzerhof (PBE) and PBE for solids (PBEsol)], and a meta-GGA [strongly constrained and appropriately normed (SCAN) functional]. The typical error pattern (as found earlier for free molecules and for free transition-metal surfaces), in which results improve from LDA to PBE or PBEsol to SCAN, due to the satisfaction of more exact constraints, is not found here. Instead, for CO adsorption on transition-metal surfaces, we find that, while SCAN overbinds much less than LDA, it overbinds slightly more than PBE. Moreover, the tested functionals often predict the wrong adsorption site, as first pointed out for LDA and GGA in the CO/Pt (111) puzzle. This abnormal pattern leads us to suspect that the errors of PBE and SCAN for this problem are density-driven self-interaction errors associated with incorrect charge transfer between molecule and metal surface. We point out that, by the variational principle, overbinding by an approximate functional would be reduced if that functional were applied not to its self-consistent density for the adsorbed system but to an exact or more correct density for that system. Finally, we show for CO on Pt(111) that the site preference is corrected and the adsorption energy is improved for the PBE functional by using not the self-consistent PBE density but a PBE+U density. The resulting correction to the PBE total energy is much larger for the adsorbed system than for its desorbed components, showing that the error is in the density of the adsorbed system. Furthermore, this seems to solve the Feibelman 2001 CO/Pt(111) puzzle, in principle if not fully in practice.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Complex Materials from First Principles (CCM); Temple Univ., Philadelphia, PA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012575
OSTI ID:
1611875
Alternate ID(s):
OSTI ID: 1545464
Journal Information:
Physical Review B, Vol. 100, Issue 3; ISSN 2469-9950
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 35 works
Citation information provided by
Web of Science

References (81)

Generalized Gradient Approximation Made Simple journal October 1996
Workhorse Semilocal Density Functional for Condensed Matter Physics and Quantum Chemistry journal July 2009
Projector augmented-wave method journal December 1994
Hybrid functionals based on a screened Coulomb potential journal May 2003
Accurate surface and adsorption energies from many-body perturbation theory journal July 2010
Molecular Orbital View of Chemisorbed Carbon Monoxide journal October 1964
Screened hybrid density functionals applied to solids journal April 2006
Theoretical Heterogeneous Catalysis: Scaling Relationships and Computational Catalyst Design journal June 2016
Ab-initio simulations of materials using VASP: Density-functional theory and beyond journal October 2008
Communication: xDH double hybrid functionals can be qualitatively incorrect for non-equilibrium geometries: Dipole moment inversion and barriers to radical-radical association using XYG3 and XYGJ-OS journal May 2018
mBEEF: An accurate semi-local Bayesian error estimation density functional journal April 2014
Successful a Priori Modeling of CO Adsorption on Pt(111) Using Periodic Hybrid Density Functional Theory journal August 2007
Beyond the random phase approximation: Improved description of short-range correlation by a renormalized adiabatic local density approximation journal September 2013
Mix of Molecular Adsorption Sites Detected for Disordered CO on Pt(111) by Diffuse Low-Energy Electron Diffraction journal November 1988
Density-Functional Theory for Fractional Particle Number: Derivative Discontinuities of the Energy journal December 1982
Understanding and Reducing Errors in Density Functional Calculations journal August 2013
Improved lattice constants, surface energies, and CO desorption energies from a semilocal density functional journal March 2011
CO adsorption on Cu(111) and Cu(001) surfaces: Improving site preference in DFT calculations journal October 2005
Density functional theory is straying from the path toward the exact functional journal January 2017
On the adsorption of CO on Pt(111) journal December 1982
CO Chemisorption at Metal Surfaces and Overlayers journal March 1996
An accurate first-principles treatment of doping-dependent electronic structure of high-temperature cuprate superconductors journal March 2018
The shortcomings of semi-local and hybrid functionals: what we can learn from surface science studies journal June 2008
Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation journal June 2012
Density functional theory in surface chemistry and catalysis journal January 2011
Accurate first-principles structures and energies of diversely bonded systems from an efficient density functional journal June 2016
Spatial structure determination of (√3×√3) R 30° and (1.5×1.5) R 18° CO or Cu(111) using angle-resolved photoemission extended fine structure journal October 1996
The adsorption of Xe and CO on Ag(111) journal March 1976
Theory of carbon monoxide chemisorption on transition metals journal May 1974
Adding Pieces to the CO/Pt(111) Puzzle: The Role of Dispersion journal February 2017
Strongly Constrained and Appropriately Normed Semilocal Density Functional journal July 2015
Self-Consistent Equations Including Exchange and Correlation Effects journal November 1965
Linear response approach to the calculation of the effective interaction parameters in the LDA + U method journal January 2005
Ab initio theory and modeling of water journal September 2017
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Efficient first-principles prediction of solid stability: Towards chemical accuracy journal March 2018
Density functional theory with nonlocal correlation: A key to the solution of the CO adsorption puzzle journal January 2010
LEED intensity analysis of the structures of clean Pt(111) and of CO adsorbed on Pt(111) in the c(4 × 2) arrangement journal August 1986
Spurious fractional charge on dissociated atoms: Pervasive and resilient self-interaction error of common density functionals journal November 2006
Exploring the random phase approximation: Application to CO adsorbed on Cu(111) journal July 2009
Properties of real metallic surfaces: Effects of density functional semilocality and van der Waals nonlocality journal October 2017
CO adsorption on Pd(111) and Pd(100): Low and high pressure correlations
  • Szanyi, János; Kuhn, W. Kevin; Goodman, D. Wayne
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 11, Issue 4 https://doi.org/10.1116/1.578532
journal July 1993
Desorption and molecular interactions on surfaces: , and journal June 1997
Assessment of the Perdew–Burke–Ernzerhof exchange-correlation functional journal March 1999
Toward reliable density functional methods without adjustable parameters: The PBE0 model journal April 1999
A photoelectron diffraction study of ordered structures in the chemisorption system Pd{111}-CO journal May 1998
CO on Pt(111) puzzle: A possible solution journal August 2002
Inhomogeneous Electron Gas journal November 1964
A look at the density functional theory zoo with the advanced GMTKN55 database for general main group thermochemistry, kinetics and noncovalent interactions journal January 2017
Climbing the Density Functional Ladder: Nonempirical Meta–Generalized Gradient Approximation Designed for Molecules and Solids journal September 2003
CO adsorption on metal surfaces: A hybrid functional study with plane-wave basis set journal November 2007
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces journal April 2008
Site preference of CO chemisorbed on Pt(111) from density functional calculations journal April 2003
Benchmarks and Reliable DFT Results for Spin Gaps of Small Ligand Fe(II) Complexes journal March 2018
CO on Pt(111): A puzzle revisited journal August 2003
Self-interaction correction to density-functional approximations for many-electron systems journal May 1981
Chemisorption of CO on differently prepared Cu(111) surfaces journal October 1977
Towards the computational design of solid catalysts journal April 2009
Versatile van der Waals Density Functional Based on a Meta-Generalized Gradient Approximation journal October 2016
Localized orbital scaling correction for systematic elimination of delocalization error in density functional approximations journal September 2017
Rationale for mixing exact exchange with density functional approximations journal December 1996
Climbing the ladder of density functional approximations journal September 2013
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields journal November 1994
Structural reanalysis of the Rh(111) + (√3 × √3)R30°-CO and Rh(111) + (2 × 2)-3CO phases using automated tensor LEED journal November 1997
The CO/Pt(111) Puzzle † journal May 2001
Ions in solution: Density corrected density functional theory (DC-DFT) journal May 2014
Influence of Dipole–Dipole Interactions on Coverage-Dependent Adsorption: CO and NO on Pt(111) journal May 2012
Communication: Self-interaction correction with unitary invariance in density functional theory journal March 2014
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect journal February 2020
Leed intensity analysis of the structures of clean Pt(111) and of CO adsorbed on Pt(111) in the c(4×2) arrangement journal August 1986
Workhorse Semilocal Density Functional for Condensed Matter Physics and Quantum Chemistry preprint January 2009
Understanding and reducing errors in density functional calculations text January 2012
Beyond the random phase approximation: Improved description of short range correlation by a renormalized adiabatic local density approximation text January 2013
Ions in solution: Density Corrected Density Functional Theory (DC-DFT) text January 2014
Strongly Constrained and Appropriately Normed Semilocal Density Functional preprint January 2015
Comparative first-principles studies of prototypical ferroelectric materials by LDA, GGA, and SCAN meta-GGA text January 2017
Ab initio theory and modeling of water text January 2017
CO on Pt(111) puzzle; A possible solution text January 2001
Climbing the Density Functional Ladder: Non-Empirical Meta-Generalized Gradient Approximation Designed for Molecules and Solids text January 2003
First-principles extrapolation method for accurate CO adsorption energies on metal surfaces text January 2003
CO adsorption on Cu(111) and Cu(001) surfaces: improving site preference in DFT calculations text January 2004

Similar Records

Nonempirical Meta-Generalized Gradient Approximations for Modeling Chemisorption at Metal Surfaces
Journal Article · Thu May 10 00:00:00 EDT 2018 · Journal of Chemical Theory and Computation · OSTI ID:1611875
Assessing electronic structure approaches for gas-ligand interactions in metal-organic frameworks: The CO{sub 2}-benzene complex
Journal Article · Fri Mar 14 00:00:00 EDT 2014 · Journal of Chemical Physics · OSTI ID:1611875
Applicability of Density Functional Theory in Reproducing Accurate Vibrational Spectra of Surface Bound Species
Journal Article · Sun Oct 05 00:00:00 EDT 2014 · Journal of Computational Chemistry, 35(26):1921–1929 · OSTI ID:1611875
+2 more

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
Materials Science
Physics
Adsorption
Chemisorption
Physisorption
Surface & interfacial phenomena
Surfaces
Density functional theory
First-principles calculations