Surface chemistry of oxygen on aluminum-Performance of the density functionals: PBE, PBE0, M06, and M06-L

Lousada, Cláudio M.; Korzhavyi, Pavel A.

doi:10.1002/jcc.24233

Cited by 7 publications

(7 citation statements)

References 83 publications

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“…In general, bonding accompanied by larger charge transfer implies less geometric degrees of freedom in the overlap between orbitals of the adsorbate with surface states when compared to smaller transfers of charge. [41,42] For larger transfers of charge, less surface sites obey the symmetry criteria that are required for a favorable overlap with the orbitals of the adsorbate. This makes the reaction become more surface site sensitive when compared with adsorption that is accompanied with smaller charge transfers.…”

Section: Single Adsorbatesmentioning

confidence: 99%

Adsorption of Hydrogen Sulfide, Hydrosulfide and Sulfide at Cu(110) ‐ Polarizability and Cooperativity Effects. First Stages of Formation of a Sulfide Layer.

2018

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Understanding the surface site preference for single adsorbates, the interactions between adsorbates, how these interactions affect surface site specificity in adsorption and perturb the electronic states of surfaces is important for rationalizing the structure of interfaces and the growth of surface products. Herein, using density functional theory (DFT) calculations, we investigated the adsorption of H S, HS and, S onto Cu(110). The surface site specificity observed for single adsorbates can be largely affected by the presence of other adsorbates, especially S that can affect the adsorption of other species even at distances of 13 Å. The large supercell employed with a surface periodicity of (6×6) allowed us to safely use the Helmholtz method for the determination of the dipole of the surface-adsorbate complex at low adsorbate coverages. We found that the surface perturbation induced by S can be explained by the charge transfer model, H S leads to a perturbation of the surface that arises mostly from Pauli exclusion effects, whereas HS shows a mix of charge transfer and Pauli exclusion effects. These effects have a large contribution to the long range adsorbate-adsorbate interactions observed. Further support for the long range adsorbate-adsorbate interactions are the values of the adsorption energies of adsorbate pairs that are larger than the sum of the adsorption energies of the single adsorbates that constitute the pair. This happens even for large distances and thus goes beyond the H-bond contribution for the H-bond capable adsorbate pairs. Exploiting this knowledge we investigated two models for describing the first stages of growth of a layer of S-atoms at the surface: the formation of islands versus the formation of more homogeneous surface distributions of S-atoms. We found that for coverages lower than 0.5 ML the S-atoms prefer to cluster as islands that evolve to stripes along the [1 1‾ 0] direction with increasing coverage. At 0.5 ML a homogeneous distribution of S-atoms becomes more stable than the formation of stripes. For the coverage equivalent to 1 ML, the formation of two half-monolayers of S-atoms that disrupt the Cu-Cu bonds between the first and second layer is more favorable than the formation of 1 ML homogeneous coverage of S-atoms. Here the S-Cu bond distances and geometries are reminiscent of pyrite, covellite, and to some extent chalcocite. The small energy difference of ≈0.1 eV that exists between this structure and the formation of 1 ML suggests that in a real system at finite temperature both structures may coexist leading to a structure with even lower symmetry.

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Section: Single Adsorbatesmentioning

confidence: 99%

Adsorption of Hydrogen Sulfide, Hydrosulfide and Sulfide at Cu(110) ‐ Polarizability and Cooperativity Effects. First Stages of Formation of a Sulfide Layer.

2018

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“…For the homogeneous model, the reactions with oxygen were investigated by placing the O-atoms at their preferred binding sites following the existing knowledge on the binding sites for single O-atoms at these surfaces, based on our and other groups' previous studies. 20,21,30 This approach is valid to a large extent because for non-neighboring sites, even though the adsorbate-adsorbate interactions can change the reaction energies considerably and be long ranged, reaching several Å distance, the long range adsorbate-adsorbate interactions seldom change the preferences for binding sites. 58,59 These effects have been studied in our previous works and will not be discussed here with further detail For the cluster models where the O-atoms are placed at neighboring sites, however, we observed that for many of the cases the initial guesses based on the preferred binding sites for single O-atoms led to other geometries after optimization.…”

Section: The Oxide Growth Modelsmentioning

confidence: 99%

“…Aluminum reacts readily with oxygen and there are plenty of experimental [6][7][8][9][10][11][12][13] and computational [14][15][16][17][18][19][20][21] data available on these reactions especially at low Miller index surfaces such as the (111) and (100). However, the mechanisms of the initial stages of oxide growth remain fairly obscure and mechanistic data is scarce.…”

Section: Introductionmentioning

confidence: 99%

The first stages of oxide growth at the low index Al surfaces (100), (110), (111): clusters and stripes vs. homogeneous growth

Lousada

Korzhavyi

2018

Phys. Chem. Chem. Phys.

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“…All functional are K-meta-GGA, with the exception of B98 and EDMGGACS which are LK-meta-GGA in both exchange and correlation (as they both depend on the q B ingredient) The most popular oneparameter global hybrid meta-GGA functionals are those belonging to the family of the Minnesota functionals (e.g., M05, [341] M06 [343] ), which have proved to be rather successful in different applications. [343,[361][362][363][364][365][366][367] In addition to one-parameter meta-GGA hybrids, also different hybridization schemes have been considered. Among others we mention, three-parameters hybrids (based on the B3-LYP construction [368] )…”

Section: Hybrid Meta-gga Functionalsmentioning

confidence: 99%

“…This group considers the atomization energies of small molecules (AE6, [374,375] G2, [194,376] and W4 [286,361,377] ) and of molecules with nonsingle-reference character (W4-MR [286,361,377] ), proton affinities (PA12 [91,92,286,[361][362][363][364][365][366][367][368][369][370][371][372][373][374][375][376][377][378][379][380] ) and ionization potentials (G21IP [286,361,381] ), different barrier heights (BH76 [286,353,355,361] ), reaction energies (BH76RC [286,353,354,361] and OMRE [382,383] ), and both barrier heights and reaction energies (K9 [374,…”

Section: Computational Detailsmentioning

confidence: 99%

Kinetic‐energy‐density dependent semilocal exchange‐correlation functionals

Sala

Fabiano

Constantin

2016

Int J of Quantum Chemistry

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We present the theory of semilocal exchange-correlation (XC) energy functionals which depend on the Kohn-Sham kinetic energy density (KED), including the relevant class of meta-generalized gradient approximation (meta-GGA) functionals. Thanks to the KED ingredient, meta-GGA functionals can satisfy different exact constraints for XC energy and can be made one-electron selfcorrelation free. This leads to a better accuracy over a wider range of properties with respect to GGAs, often reaching the accuracy of hybrid functionals, but at much reduced computational cost.An extensive survey of the relevant literature on existing KED dependent XC functionals is provided, considering nonempirical, semi-empirical, and fully empirical ones. A deeper analysis and a wide benchmark are presented for functionals derived considering only exact constraints and parameters obtained from model and/or atomic systems. K E Y W O R D Sdensity functional theory, kinetic energy, meta-GGA | I N T R O D U C T I O NKohn-Sham (KS)-density functional theory (DFT) [1][2][3][4][5] is nowadays one of the most popular computational approaches in quantum chemistry, solid-state physics, and materials science. [6][7][8][9][10][11] While the ground-state description of a real system of interacting electrons requires a complicate N-electron wavefunction, in KS-DFT this is mapped onto an auxiliary system of noninteracting electrons having the same ground-state density, which can be easily described using N single-particle KS orbitals. [1,2] The correspondence between the many-electron problem and the KS system is in principle exact [1,3] and it is based on the so called exchange-correlation (XC) energy functional, which collects all the quantum electron-electron interaction terms beyond the Hartree one. [12] Within the constrained-search formalism, [13] the XC energy functional is:E xc ½q 5 min W!q hWjT 1V ee jWi2T s ½q 2J½q 5E x ½q 1U c ½q 1T c ½q ;(1) where W is an N-electron ground-state wavefunction yielding the electron density q,T is the kinetic energy (KE) operator,V ee is the electron-electron interaction operator, T s is the KE of the noninteracting system, J is the Coulomb energy, E x is the exact exchange energy, and U c and T c represent, respectively, the potential and the kinetic contributions to the DFT correlation energy E c 5U c 1T c . The important point of Equation1 is that it is an universal functional of the electron density. However, its explicit functional form is not known, and any practical realization of KS-DFT is based on an approximated XC functional. The latter determines in practice the overall accuracy of the KS-DFT calculation.The study of the exact properties of the XC energy functional as well as the development of new and improved approximations have been hot research topics in DFT for more than three decades, and a large number of XC approximations has been proposed. [12,14,15] The different XC functionals are usually classified, according to their complexity, on the so called Jacob's ladder of DFT [14,16] whic...

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Surface chemistry of oxygen on aluminum-Performance of the density functionals: PBE, PBE0, M06, and M06-L

Cited by 7 publications

References 83 publications

Adsorption of Hydrogen Sulfide, Hydrosulfide and Sulfide at Cu(110) ‐ Polarizability and Cooperativity Effects. First Stages of Formation of a Sulfide Layer.

Adsorption of Hydrogen Sulfide, Hydrosulfide and Sulfide at Cu(110) ‐ Polarizability and Cooperativity Effects. First Stages of Formation of a Sulfide Layer.

The first stages of oxide growth at the low index Al surfaces (100), (110), (111): clusters and stripes vs. homogeneous growth

Kinetic‐energy‐density dependent semilocal exchange‐correlation functionals

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