Reply to Comment on “First principles determination of the bonding mechanism and adsorption energy for CO/MgO(001)”1Re. to PII nr.: S0009-2614(99)00410-8.1

Wu, Ruqian; Zhang, Qiming

doi:10.1016/s0009-2614(99)00411-x

Cited by 14 publications

(5 citation statements)

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“…47,54 The values obtained with M06-2X and M06-HF are larger than the, in principle, best computational results reported in the past 20,26,29 but in nice agreement with the very recent CI value calculated by Qin. The values are even more redshifted than those calculated with the B3LYP computational approach.…”

Section: Resultssupporting

confidence: 83%

“…The most popular hybrid functional is B3LYP, 40,50,51 which has 20% HF exchange and therefore removes 20% of the self-interaction error. 53͒ density functional ͑a GGA͒ and a full potential linearized augmented plane-wave ͑FLAPW͒ method were performed by Wu and Zhang 26 and corrected previous exceedingly large binding energy values obtained with the LDA approximation 24 by the same group; the new calculations yielded 2.8 kcal/mol and 6 cm −1 for the interaction energy and vibrational shift, respectively, 26 whereas the LDA functional results were 6.5 kcal/mol and 33 cm −1 , respectively. 52 Importantly, the same hybrid functional and Mg 9 O 9 cluster model was used by Xu et al, 33 and their calculated interaction energy and frequency shift were 5.5 kcal/mol and +41 cm −1 , respectively.…”

Section: Introductionmentioning

confidence: 99%

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Good performance of the M06 family of hybrid meta generalized gradient approximation density functionals on a difficult case: CO adsorption on MgO(001)

Valero

Gomes

Truhlar

et al. 2008

The Journal of Chemical Physics

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The adsorption of CO on Mg(001) constitutes a challenge for current density functional approximations because of its weak interaction character. In the present work we show that the M06-2X and M06-HF exchange-correlation functionals are the first ones to provide a simultaneously satisfactory description of adsorbate geometry, vibrational frequency shift, and adsorption energy of CO on MgO(001). For a sufficiently large embedded cluster model, the three functionals of the M06 family-which contain a nonzero percentage of Hartree-Fock exchange (M06, M06-2X, and M06-HF)-all predict positive C-O vibrational shifts, in agreement with the experimental findings, while the local M06-L functional gives large negative shifts. Moreover, the shifts computed with the M06-2X and M06-HF potentials are in good agreement with the experimental shift of +14 cm(-1). The interaction energy (D(e)) calculated with M06-2X and M06-HF is approximately 6.0 kcal/mol, which agrees well with the D(e) value ( approximately 4 kcal/mol) deduced from the D(0) obtained in thermal desorption measurements on single-crystal surfaces.

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Section: Resultssupporting

confidence: 83%

Section: Introductionmentioning

confidence: 99%

Good performance of the M06 family of hybrid meta generalized gradient approximation density functionals on a difficult case: CO adsorption on MgO(001)

Valero

Gomes

Truhlar

et al. 2008

The Journal of Chemical Physics

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“…Therefore, our results support earlier suggestions 21,22 that the CO adsorption discussed by He et al does not take place on the perfect (001) surface of MgO, but rather at some sort of defect site. After our project had been completed, another DFT study with gradient-corrected functionals and periodic boundary conditions has been reported for CO adsorption on the MgO(001) regular site . Wu and Zhang found the binding energy of 2.8 kcal/mol in their full potential linearized augmented plane wave approach with the PBE96 functional, in qualitative agreement with our findings.…”

Section: Discussionsupporting

confidence: 84%

Periodic Density Functional LDA and GGA Study of CO Adsorption at the (001) Surface of MgO

et al. 2000

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The deficiencies of the local density approximation (LDA) to describe weakly adsorbed species on ionic surfaces are exposed in the current study of CO on the (001) surface of MgO. We applied a periodic formulation of density functional theory with crystal orbitals and charge density expanded as linear combinations of atomic orbitals of Gaussian form. The binding was investigated for four orientations of the CO molecule: either the carbon or oxygen atom of CO down over either the surface magnesium cation or oxygen anion. We find that the carbon down over the magnesium cation is the only noticeably attractive configuration, when basis set superposition error is corrected for, and we estimate the binding energy of CO to be 1.9 kcal/mol for the Perdew, Burke, and Enzerhof (PBE96) functional. The binding energy obtained in the LDA approximation is as large as 7.4 kcal/mol. For the C-down-over-Mg configuration, the CO stretching frequency shift is only 4 cm-1 for the PBE96 functional. This binding energy, vibrational shift, and our analysis of density of states indicate that little chemical bonding accompanies the adsorption. The values of our binding energy and vibrational shift support a suggestion by Nygren and Pettersson [J. Chem. Phys. 1996, 105, 9339] that the CO adsorption discussed by He et al. [Surf. Sci. 1992, 261, 164] actually takes place at defect sites on the (001) surface of MgO.

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“…The case of CO is particularly well-documented for adsorption of the molecule on MgO(100) 18,65,66 and TiO 2 (110). ,, CO interacts much stronger with metal centers of TiO 2 (110), band gap ∼2 eV 16 and not highly ionic, than with metal centers of MgO(100). In the CO/MgO(100) system the contributions to the chemisorption bond from band−orbital mixing are very weak, ,65a but become substantial in the CO/TiO 2 (110) system. , For the interaction of NO 2 with the cations of ZnO(0001), CASTEP predicts bonding energies that are larger than those found on the cations of MgO(100), a trend that reflects variations in the strength of band−orbital mixing, as was seen for the adsorption of the sulfur-containing molecules on the oxides . In the case of alkali metal adsorption, one finds very strong bonding interactions on oxides that have a narrow band gap (<4 eV) .…”

Section: Discussionmentioning

confidence: 99%

Adsorption and Decomposition of H₂S on MgO(100), NiMgO(100), and ZnO(0001) Surfaces: A First-Principles Density Functional Study

2000

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The adsorption and dissociation of H2S on MgO(100), Ni-doped MgO(100), and ZnO(0001) was studied using first-principles density-functional calculations (DFT-GGA) and periodic supercells. The bonding of H2S and its S-containing dissociated species (HS and S) is substantially stronger on ZnO(0001) than on MgO(100), making dissociation easier on zinc oxide. This behavior can be explained by the smaller ionicity in ZnO, which leads to a larger electron density around the Zn atoms and a larger reactivity toward S-containing molecules. Replacing some of the metal centers of MgO(100) with Ni atoms enhances the binding of S-containing species through new electronic states associated with the Ni 3d levels and located above the occupied {O 2p + Mg 3s} bands. In addition, structural defects, like steps, expose metal centers with lower coordination and larger reactivity than pentacoordinated Mg atoms in MgO(100). A simple model based on perturbation theory and band−orbital mixing is able to explain the differences in the reactivity of MgO(100) and ZnO(0001) and the behavior of other oxides (Al2O3, Cr2O3, Cr3O4, Cu2O) in the presence of sulfur-containing molecules. The model predicts a negative correlation between the reactivity of the oxides and the size of the electronic band gap, with the chemical activity of an oxide depending mainly on how well its bands mix with the orbitals of H2S. The electrostatic interactions between the Madelung field of the oxide and the dipole moment of the molecule play only a secondary role in bonding.

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Reply to Comment on “First principles determination of the bonding mechanism and adsorption energy for CO/MgO(001)”1Re. to PII nr.: S0009-2614(99)00410-8.1

Cited by 14 publications

References 14 publications

Good performance of the M06 family of hybrid meta generalized gradient approximation density functionals on a difficult case: CO adsorption on MgO(001)

Good performance of the M06 family of hybrid meta generalized gradient approximation density functionals on a difficult case: CO adsorption on MgO(001)

Periodic Density Functional LDA and GGA Study of CO Adsorption at the (001) Surface of MgO

Adsorption and Decomposition of H₂S on MgO(100), NiMgO(100), and ZnO(0001) Surfaces: A First-Principles Density Functional Study

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Reply to Comment on “First principles determination of the bonding mechanism and adsorption energy for CO/MgO(001)”1Re. to PII nr.: S0009-2614(99)00410-8.1

Cited by 14 publications

References 14 publications

Good performance of the M06 family of hybrid meta generalized gradient approximation density functionals on a difficult case: CO adsorption on MgO(001)

Good performance of the M06 family of hybrid meta generalized gradient approximation density functionals on a difficult case: CO adsorption on MgO(001)

Periodic Density Functional LDA and GGA Study of CO Adsorption at the (001) Surface of MgO

Adsorption and Decomposition of H2S on MgO(100), NiMgO(100), and ZnO(0001) Surfaces: A First-Principles Density Functional Study

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Adsorption and Decomposition of H₂S on MgO(100), NiMgO(100), and ZnO(0001) Surfaces: A First-Principles Density Functional Study