Re-thinking CO adsorption on transition-metal surfaces: Density-driven error?

Abstract

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 (PBE and PBEsol), and a meta-GGA (SCAN). 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 selfconsistent 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 selfconsistent 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. This seems to solve the ``CO/Pt (111) puzzle", in principle if not fully in practice.

References in corpus (8)

• Restoring the density-gradient expansion for exchange in solids and surfaces
• Generalized gradient approximation for solids and their surfaces
• Ab initio theory and modeling of water
• Comparative first-principles studies of prototypical ferroelectric materials by LDA, GGA, and SCAN meta-GGA
• Properties of real metallic surfaces: Effects of density functional semilocality and van der Waals nonlocality
• Localized Orbital Scaling Correction for Systematic Elimination of Delocalization Error in Density Functional Approximations
• Ions in solution: Density Corrected Density Functional Theory (DC-DFT)
• 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

Cited by in corpus (16)

• Even-handed subsystem selection in projection-based embedding
• Combining Machine Learning and Many-Body Calculations: Coverage-Dependent Adsorption of CO on Rh(111)
• Periodic Trends in Adsorption Energies Around Single-Atom Alloy Active Sites
• Selectivity Trends and Role of Adsorbate-Adsorbate Interactions in CO Hydrogenation on Rhodium Catalysts
• Accurate non-empirical range-separated hybrid van der Waals density functional for complex molecular problems, solids, and surfaces
• Improving the applicability of the Pauli kinetic energy density based semilocal functional for solids
• vdW-DF-ahcx: a range-separated van der Waals density functional hybrid
• Quantum Simulation of Realistic Materials in First Quantization Using Non-local Pseudopotentials
• Spin-state Gaps and Self-Interaction-Corrected Density Functional Approximations: Octahedral Fe(II) Complexes as Case Study
• Comparative density functional theory study for predicting oxygen reduction activity of single-atom catalyst
• Charge-Order on the Triangular Lattice: A Mean-Field Study for the Lattice $S=1/2$ Fermionic Gas
• Density-corrected DFT explained: Questions and answers
• General linear correction method for DFT+X energy: application to U-M (M=Al, Ga, In) alloys under high pressure
• Understanding the roles of electronic effect in CO on Pt-Sn alloy surface via band structure measurements
• Revealing the role of van der Waals interactions in thiophene adsorption on copper surfaces
• Correlating surface energy with adsorption energy by means of intrinsic characteristics of substrates