Co adsoprtion on MgO crystals: Hartree-fock calculations for regular adlayers on a (001) lattice plane

Dovesi, Roberto; Orlando, Roberto; Ricca, F.; Roetti, C.

doi:10.1016/s0039-6028(87)80048-1

Cited by 94 publications

(16 citation statements)

References 11 publications

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“…In parallel to these experimental works, several theoretical studies appeared in literature, at first using Hartree-Fock ͑HF͒ theory [9][10][11][12][13][14][15][16] and the local density approximation ͑LDA͒ ͑Refs. 5 and 6͒ and making use of either periodic boundary conditions 12,13 or cluster models.…”

Section: Introductionmentioning

confidence: 99%

“…However, HF cluster model calculations corrected for BSSE yielded 7,8 a smaller value of ϳ4 kcal/ mol. Employing also a similar cluster model with the LDA exchange-correlation potential, Neyman and Rösch 5,6 obtained much larger binding energy estimates, [9][10][11][12][13] even after BSSE corrections. Furthermore, the LDA calculations by Neyman and Rösch 5,6 showed significant charge transfer from CO to the surface, whereas other works 15,35 indicated that the interaction is a purely electrostatic interaction of the ionic surface with the multipoles of the CO molecule.…”

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: Introductionmentioning

confidence: 99%

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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“…21 Theoretical studies of CO adsorbed on MgO(100) at lower coverages (Ѳ≤½ ML) have shown that the most energetically favored position for adsorption is above a Mg ++ site and that the CO bond axis is perpendicular to the surface at these sites. [35][36][37][38] Positions above the O -sites and the Mg::O bonds are energetically disallowed. [36][37][38] Theoretical studies have also determined binding energies which depend on vertical orientation.…”

Section: A Determination Of Substrate Field Strength Parametersmentioning

confidence: 99%

“…[36][37][38] Theoretical studies have also determined binding energies which depend on vertical orientation. 22,35,36,39,40 A wide range of binding energies for CO on MgO are reported in the literature. 38 We apply our model to a range of differences in binding energies for the two orientations (Table 3), based on extremes in the listed binding energies ( Table 2).…”

Section: A Determination Of Substrate Field Strength Parametersmentioning

confidence: 99%

Physisorbed CO on ionic crystals: an extended BEG spin-lattice model of adsorbed dipolar molecules

Burns

Dennison

1998

Surface Science

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The 2D dielectric phases and phase transitions of adsorbed dipolar molecules are studied using a dilute spin-one Ising model. The spin-one formulation assigns a spin S i = ±1 to a (up/down) dipole occupying a lattice site i adsorbed perpendicular to the substrate surface and S i = 0 to unoccupied sites. We relate the mean field expression for the spin-model interaction energy to a more detailed microscopic model involving dipolar, quadrupolar and dispersive interactions beyond nearest neighbor. Analytic solutions in the mean field approximation are discussed for dipole-orientation order-disorder transitions and ferroelectric-to-antiferroelectric transitions as a function of temperature and coverage. The model is applied to two prototypical dipolar physisorbed systems, CO on MgO(100) and CO on NaCl(100), using previous experimental and theoretical studies to determine the interaction energy parameters. We find, for most of these model parameters, that only temperature-dependent ferroelectric dipole order-disorder phase transitions can occur for these two systems. However, we find that phase transitions between the two ferroelectric states, driven by changes in coverage, should also be observed for some predicted values of the parameters. Phase diagrams are presented. Application of the model to other related adsorbed dipolar systems is also discussed.

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“…A wide range of techniques [6][7][8][9] are used to improve the knowledge of the adsorption process by giving information on the isosteric heat of adsorption and to assess phase diagrams. In parallel way, calculations based either on ab initio methods [10] or on semi-empirical interaction potentials [11] have been performed to interpret the experimental findings on the statics and dynamics of these molecular monolayers. The present work deals with both neutron diffraction experiments and theoretical interaction potential calculations of the neopentane monolayer adsorbed on the square symmetry surface MgO(0 0 1).…”

Section: Introductionmentioning

confidence: 99%

Structure of the neopentane monolayer adsorbed on MgO(001): experiments and calculations

et al. 2004

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Co adsoprtion on MgO crystals: Hartree-fock calculations for regular adlayers on a (001) lattice plane

Cited by 94 publications

References 11 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)

Physisorbed CO on ionic crystals: an extended BEG spin-lattice model of adsorbed dipolar molecules

Structure of the neopentane monolayer adsorbed on MgO(001): experiments and calculations

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