Eliminating Delocalization Error to Improve Heterogeneous Catalysis Predictions with Molecular DFT + U.

  title={Eliminating Delocalization Error to Improve Heterogeneous Catalysis Predictions with Molecular DFT + U.},
  author={Akash Bajaj and Heather J. Kulik},
  journal={Journal of chemical theory and computation},
  • Akash BajajH. Kulik
  • Published 23 November 2021
  • Chemistry
  • Journal of chemical theory and computation
Approximate semilocal density functional theory (DFT) is known to underestimate surface formation energies yet paradoxically overbind adsorbates on catalytic transition-metal oxide surfaces due to delocalization error. The low-cost DFT + U approach only improves surface formation energies for early transition-metal oxides or adsorption energies for late transition-metal oxides. In this work, we demonstrate that this inefficacy arises due to the conventional usage of metal-centered atomic… 
5 Citations

Molecular orbital projectors in non-empirical jmDFT recover exact conditions in transition-metal chemistry.

Low-cost, non-empirical corrections to semi-local density functional theory are essential for accurately modeling transition-metal chemistry. Here, we demonstrate the judiciously modified density

Ligand Additivity and Divergent Trends in Two Types of Delocalization Errors from Approximate Density Functional Theory.

The predictive accuracy of density functional theory (DFT) is hampered by delocalization errors, especially for correlated systems such as transition-metal complexes. Two complementary strategies

Delocalization error: The greatest outstanding challenge in density‐functional theory

Every day, density‐functional theory (DFT) is routinely applied to computational modeling of molecules and materials with the expectation of high accuracy. However, in certain situations, popular

Resonantly Enhanced Electromigration Forces for Adsorbates on Graphene

We investigate the electromigration forces for weakly bonded adsorbates on graphene by using density-functional based calculations. We find that the nature of electromigration forces on an adsorbate

Machine-learning atomic simulation for heterogeneous catalysis

Heterogeneous catalysis is at the heart of chemistry. New theoretical methods based on machine learning (ML) techniques that emerged in recent years provide a new avenue to disclose the structures



Surface-Specific DFT + U Approach Applied to α-Fe2O3(0001)

We report the bulk properties and ab initio thermodynamics surface free energies for α-Fe2O3(0001) using density functional theory (DFT) with calculated Hubbard U values for chemically distinct

Where Does the Density Localize in the Solid State? Divergent Behavior for Hybrids and DFT+U.

Comparing density localization trends with DFT+U and global hybrids on a diverse set of 34 transition-metal-containing solids with varying magnetic state, electron configuration and valence shell, and coordinating-atom orbital diffuseness highlights the limited applicability of trends established for functional tuning on transition- metal complexes even to equivalent coordination environments in the solid state.

Stable Surfaces That Bind Too Tightly: Can Range-Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry?

Density analysis reveals why hybrid functionals correct both quantities, whereas DFT+U does not, and recommends local, range-separated hybrids for the accurate modeling of catalysis in transition metal oxides at only a modest increase in computational cost over semilocal DFT.

Challenges for density functional theory: calculation of CO adsorption on electrocatalytically relevant metals.

Overall, it is found that the surface modified RPBE functional performs reliably for many of the benchmarks examined here, and the meta-GGA functionals also show promising results.

Does DFT+U mimic hybrid density functionals?

This work examines the question of how a Hubbard U correction to a local exchange–correlation functional compares with adding Hartree–Fock exchange to a local functional for both solid-state and

Reaction pathways in the solid state and the Hubbard U correction.

It is shown that, depending on the occupation of the transition metal d orbitals, the Hubbard U correction can cause severe instabilities in the migration barrier energies predicted using generalized gradient approximation density functional theory (GGA DFT).

Quantifying the effects of the self-interaction error in DFT: when do the delocalized states appear?

Energy differences between delocalized and localized states are calculated with B3LYP and some charge-transfer complexes cannot be properly calculated and delocalization states may become a problem in large models of enzyme systems with multiple transition-metal complexes.

Optimal methodology for explicit solvation prediction of band edges of transition metal oxide photocatalysts

The conduction and valence band edges (EC and EV) of a material relative to the water redox potential levels are critical factors governing photocatalytic water splitting activity. Here we discuss

Ligand Effects on the Linear Response Hubbard U: The Case of Transition Metal Phthalocyanines.

The calculated multiple- site U is larger than the single-site U by as much as 1 eV and the ligand atoms that are mainly responsible for this difference are the isoindole nitrogen atoms directly bonded to the central metal atom.

Molecular adsorption on the surface of strongly correlated transition-metal oxides: A case study for CO/NiO(100)

It is well known that the physical properties of some transition-metal compounds (mostly oxides) are strongly affected by intra-atomic correlations. Very recently, investigations of the adsorption of