CO adsorption on metal surfaces: A hybrid functional study with plane-wave basis set

Stroppa, Alessandro; Termentzidis, Konstantinos; Paier, Joachim; Kresse, Georg; Hafner, J.

doi:10.1103/physrevb.76.195440

Cited by 143 publications

(178 citation statements)

References 75 publications

Supporting

Mentioning

152

Contrasting

Order By: Relevance

“…35,36 For example, in HSE06, 33, 37 ω = 0.11a −1 0 (a 0 is the Bohr radius) and in Perdew-Burke-Ernzerhof (PBEh) global hybrid, 38 it is 25 % short-range exact exchange and 75 % short-range PBE exchange. Even though the HSE functional, in most cases, accurately reproduces the optical gap in semiconductors, it severely underestimates the gap in insulators 36,39 and its band width in metallic systems is generally too large. 36,[39][40][41] The Engel and Vosko 42 (EV) GGA and the Tran and Blaha 43 modified Becke-Johnson (TB-mBJ) have also provided some improvements to the band gap of materials.…”

Section: Introductionmentioning

confidence: 99%

First principle electronic, structural, elastic, and optical properties of strontium titanate

et al. 2012

View full text Add to dashboard Cite

We report self-consistent ab-initio electronic, structural, elastic, and optical properties of cubic SrTiO3 perovskite. Our non-relativistic calculations employed a generalized gradient approximation (GGA) potential and the linear combination of atomic orbitals (LCAO) formalism. The distinctive feature of our computations stem from solving self-consistently the system of equations describing the GGA, using the Bagayoko-Zhao-Williams (BZW) method. Our results are in agreement with experimental ones where the later are available. In particular, our theoretical, indirect band gap of 3.24 eV, at the experimental lattice constant of 3.91 Å, is in excellent agreement with experiment. Our predicted, equilibrium lattice constant is 3.92 Å, with a corresponding indirect band gap of 3.21 eV and bulk modulus of 183 GPa

show abstract

Section: Introductionmentioning

confidence: 99%

First principle electronic, structural, elastic, and optical properties of strontium titanate

et al. 2012

View full text Add to dashboard Cite

show abstract

“…The sX(1.44) gives the largest difference of adsorption energies between the atop and fcc adsorption, which is difficult to achieve by other functionals including some approaches by the HSE06. 35 This is closely related to the larger HOMO-LUMO gap of CO from the sX(1.44) that prevents the predominant contribution of back-donation in the bond formation, which is inherently strong for the fcc adsorption 46,52 and becomes more effectively if the CO HOMO-LUMO gap is small.…”

Section: Resultsmentioning

confidence: 99%

“…It was noted that increasing the energy difference between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) might cure this problem of DFT, [32][33][34] and that this could be achieved by using hybrid functionals. 33,[35][36][37][38] However, the B3LYP functional marginally failed to achieve this site preference, 33 as did a study using the HSE06 hybrid functional. 35 A recent work found that the PBEh hybrid functional can give the correct site preference by treating the 5s and 5p states as the core states.…”

Section: Introductionmentioning

confidence: 96%

“…33,[35][36][37][38] However, the B3LYP functional marginally failed to achieve this site preference, 33 as did a study using the HSE06 hybrid functional. 35 A recent work found that the PBEh hybrid functional can give the correct site preference by treating the 5s and 5p states as the core states. 36 Alternatively, inclusion of non-local correlation effects corresponding to dispersion-type van der Waals interactions in density functional 39 and embedded, correlated wavefunction-based method with a kinetic energy density functional approach 40 are reported to improve the prediction of the correct adsorption site.…”

Section: Introductionmentioning

confidence: 96%

See 1 more Smart Citation

The screening effects of the screened exchange hybrid functional in surface systems: A case study on the CO/Pt(111) problem

2016

View full text Add to dashboard Cite

The screened exchange (sX) hybrid functional has been widely used in computational material science. Although it has widely been studied in bulk systems, less is known about its functional behavior in surface systems which are crucial to many technologies such as materials synthesis and nano-electronic devices. Assessing the screening dependent functional behaviors in the surface systems is therefore important for its application in such systems. In this work, we investigate the screening effects of the sX in CO adsorption on Pt(111) surface. The differences between the sX and Heyd-Scuseria-Ernzerhof (HSE06) hybrid functionals, and the effects of screening parameters are studied. The screening has two effects: first, the HOMO-LUMO gap is screening dependent. This affects the site preference most significantly. In this work, atop adsorption of CO/Pt (111) is predicted by the hybrid functionals with screened exchange potential. The sX(1.44) gives the largest HOMO-LUMO gap for the isolated CO molecule. The adsorption energy difference between the atop and fcc site is also the largest by the sX(1.44) which is explained by the reduced metal d states to the CO 2π* state back-donation, with stronger effect for the fcc adsorption than for the atop adsorption; second, the adsorption energy is screening dependent. This can be seen by comparing the sX(2.38) and HSE06 which have different screening strengths. They show similar surface band structures for the CO adsorption but different adsorption energies, which is explained by the stronger CO 5σ state to the metal d states donation or the effectively screened Pauli repulsion. This work underlines the screening strength as a main difference between sX and HSE06, as well as an important hybrid functional parameter for surface calculation. C 2016 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license

show abstract

“…To this end, DFT can be utilized to explicitly describe electronic structures of the system particles in greater details, which can help in extending the conceptual model of CO chemisorption [90][91][92][93][94]. Unfortunately, due to the inherent wrong description of the electronic structure by DFT, wrong predictions of CO preferred adsorption sites are observed that contradict experimental results, especially for the (111) surface facets of transition metals, leading to the so-called "CO adsorption Puzzle" [95,96]. The root of this DFT problem resides on the fact that both local density and generalized gradient approximation functionals underestimate the CO bandgap, predicting wrong positions of the CO frontier orbitals, which results in an overestimated bond strength between the substrate and surface molecules [97].…”

Section: Solving the Co Adsorption Puzzle With The U Correctionmentioning

confidence: 99%

The DFT+U: Approaches, Accuracy, and Applications

Tolba¹,

Gameel²,

Ali³

et al. 2018

Density Functional Calculations - Recent Progresses of Theory and Application

View full text Add to dashboard Cite

This chapter introduces the Hubbard model and its applicability as a corrective tool for accurate modeling of the electronic properties of various classes of systems. The attainment of a correct description of electronic structure is critical for predicting further electronic-related properties, including intermolecular interactions and formation energies. The chapter begins with an introduction to the formulation of density functional theory (DFT) functionals, while addressing the origin of bandgap problem with correlated materials. Then, the corrective approaches proposed to solve the DFT bandgap problem are reviewed, while comparing them in terms of accuracy and computational cost. The Hubbard model will then offer a simple approach to correctly describe the behavior of highly correlated materials, known as the Mott insulators. Based on Hubbard model, DFT+U scheme is built, which is computationally convenient for accurate calculations of electronic structures. Later in this chapter, the computational and semiempirical methods of optimizing the value of the Coulomb interaction potential (U) are discussed, while evaluating the conditions under which it can be most predictive. The chapter focuses on highlighting the use of U to correct the description of the physical properties, by reviewing the results of case studies presented in literature for various classes of materials.

show abstract

CO adsorption on metal surfaces: A hybrid functional study with plane-wave basis set

Cited by 143 publications

References 75 publications

First principle electronic, structural, elastic, and optical properties of strontium titanate

First principle electronic, structural, elastic, and optical properties of strontium titanate

The screening effects of the screened exchange hybrid functional in surface systems: A case study on the CO/Pt(111) problem

The DFT+U: Approaches, Accuracy, and Applications

Contact Info

Product

Resources

About