The local adsorption geometry of CO and NH3 on NiO(100) determined by scanned-energy mode photoelectron diffraction

Kittel, Martin; Hoeft, J.; Bao, Sheng; Polčík, Martin; Toomes, Rachel L.; Kang, Jingoo; Woodruff, D.P.; Pascal, Mathieu; Lamont, Christine L. A.

doi:10.1016/s0039-6028(01)01957-4

Cited by 30 publications

(20 citation statements)

References 50 publications

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“…We see that the computational approaches considered in the present work predict negative vibrational frequency shifts ͑ranging between Ϫ5 and −123 cm −1 ͒ while the experimental frequency shift is positive ͑+9 cm −1 ͒. The M06-L functional still predicts a 0.1 Å too short Ni-C distance, but, as for NO interacting with the Nidoped MgO͑100͒ surface, it agrees better with experiment than all of the local GGA functionals and the TPSS, meta-GGA, which give significantly too short distances, whereas at one time 27,28 DFT was thought to overestimate this distance. 27,28,31 The calculated B3LYP vibrational frequency shift is −45 cm −1 .…”

Section: B Co Adsorptionmentioning

confidence: 70%

“…For the interaction of adsorbates with metal surfaces, a reasonable description has been achieved with density functional theory ͑DFT͒ applied to periodic slab models. Nevertheless, the combination of several experimental techniques ͓infrared ͑IR͒ spectroscopy, 11,23-26 thermal desorption spectroscopy, 14,20,21 ultraviolet photoelectron spectroscopy, 21 photoelectron diffraction͔ 22,27,28 and several surface science spectroscopic techniques 29 ͓such as x-ray photoelectron spectroscopy, 29 or high-resolution electronenergy-loss spectroscopy͔ 29 yielded a clear picture of the geometries and strengths of the interactions of CO, NO, and NH 3 with either the Ni-doped MgO͑100͒ surface or the NiO͑100͒ surface, on which, due in part to a close lattice match of the isostructural MgO and NiO, 20 Ni sites have similar characteristics to Ni sites on Ni-doped MgO. [7][8][9][10][11][12][13][14][15][16][17][18][19] Many transition metals form solid solutions with MgO, and such metal-doped MgO materials have varying catalytic capabilities.…”

Section: Introductionmentioning

confidence: 99%

“…Experimentally, the use of a variety of methods for the preparation and cleaning of metal oxide surfaces ͑epitaxial metal oxide film grown on a metal surface, [20][21][22] surfaces obtained by cleaving single crystals under ultra high vacuum conditions, 14 metal oxide powder, 7 or sintered polycrystalline metal oxide solid solutions͒ 11 yields substrates with diverse compositions and different numbers and types of defects; and the adsorbate-substrate bonding energy, especially when weak, is very sensitive to these variables. The C-Ni and C-O bond lengths are 2.07Ϯ 0.02 and 1.15Ϯ 0.09 Å, respectively; 27,28 the Ni-C and C-O bonds are aligned with respect to the surface normal with angles of ϳ7͑+5 / −3͒°and ϳ12Ϯ 12°, respectively. 18,21,25 The number of techniques employed to understand these systems is comparable to previous work aimed to accurately describe adsorption of CO and NO on MgO͑001͒.…”

Section: Introductionmentioning

confidence: 99%

“…Nevertheless, the combination of several experimental techniques ͓infrared ͑IR͒ spectroscopy, 11,23-26 thermal desorption spectroscopy, 14,20,21 ultraviolet photoelectron spectroscopy, 21 photoelectron diffraction͔ 22,27,28 and several surface science spectroscopic techniques 29 ͓such as x-ray photoelectron spectroscopy, 29 or high-resolution electronenergy-loss spectroscopy͔ 29 yielded a clear picture of the geometries and strengths of the interactions of CO, NO, and NH 3 with either the Ni-doped MgO͑100͒ surface or the NiO͑100͒ surface, on which, due in part to a close lattice match of the isostructural MgO and NiO, 20 Ni sites have similar characteristics to Ni sites on Ni-doped MgO. 27,28 The shift in the C-O stretching frequency upon adsorption is +9 cm −1 . 2,19,21 The same investigations traced the influence of surface defects on the adsorbate-surface bonding properties.…”

Section: Introductionmentioning

confidence: 99%

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Density functional study of CO and NO adsorption on Ni-doped MgO(100)

Valero

Gomes

Truhlar

et al. 2010

The Journal of Chemical Physics

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The adsorption of small molecules such as NO or CO on surfaces of magnetic oxides containing transition metals is difficult to model by current density functional approximations. Two such oxides are NiO(100) and Ni-doped MgO(100). Here we compare the results of a theoretical model of the Ni-doped MgO(100) surface with experimental results on NiO(100), which introduces some uncertainty into a quantitative theory-experiment comparison. In the present work, we tested seven meta-GGA and hybrid metafunctionals, in particular, three developed by the Minnesota group (M05, M06-L, and M06), and TPSS, TPSSh, TPSSKCIS, and B1B95; six GGA functionals, including BP86, PBE, and four other functionals that are modifications of PBE (PBEsol, SOGGA, revPBE, and RPBE); five hybrid GGA functionals (B3LYP, PBE0, B97-2, B97-3, and MPWLYP1M); and one unconventional functional of the generalized gradient type with scaled correlation called MOHLYP. The Minnesota meta-GGA functionals were found in the past to be very good choices when transition metal atoms were present; the other functionals chosen are a selection from the most currently used and most promising sets of functionals for bulk solids and surfaces and for transition metals. The difficulty is due to the charge transfer between open shells in the case of NO and to the weak character of the interaction in the case of CO. It is shown that the M06 hybrid meta functional applied to NO or CO on a model of the Ni-doped MgO(100) surface is able to provide a good description of both adsorbate geometries and binding energies. The M06 vibrational frequency shifts are more accurate than for other functionals, but there is still room for improvement.

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Section: B Co Adsorptionmentioning

confidence: 70%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Density functional study of CO and NO adsorption on Ni-doped MgO(100)

Valero

Gomes

Truhlar

et al. 2010

The Journal of Chemical Physics

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“…In particular, this is true for cases where the interaction is dominated by van der Waals forces, which are more difficult to treat theoretically than genuine chemical bonds. Quite recently, Hoeft and et al 1,2 stated, when presenting their PhD (photoelectron diffraction) results for the geometrical structure of CO, NO, and NH 3 adsorbed on the NiO(100) surface, that ''the current theoretically derived adsorbate-substrate bond lengths on this surface are very seriously in error'' and gave their paper the provocative title: ''Molecular Adsorption Bond Lengths at Metal Oxide Surfaces: Failure of Current Theoretical Methods''. 1 Pacchioni et al 3 arrived at similar conclusions for the adsorption of small molecules on NiO.…”

Section: Introductionmentioning

confidence: 99%

The method of local increments for the calculation of adsorption energies of atoms and small molecules on solid surfaces : Part I. A single Cu atom on the polar surfaces of ZnO

Schmitt

Fink

Staemmler

2009

Phys. Chem. Chem. Phys.

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The method of local increments is used in connection with the supermolecule approach and an embedded cluster model to calculate the adsorption energy of single Cu atoms at different adsorption sites at the polar surfaces of ZnO. Hartree-Fock calculations for the full system, adsorbed atom and solid surface, and for the fragments are the first step in this approach. In the present study, restricted open-shell Hartree-Fock (ROHF) calculations are performed since the Cu atom possesses a singly-occupied 4s orbital. The occupied Hartree-Fock orbitals are then localized by means of the Foster-Boys localization procedure. The correlation energies are expanded into a series of many-body increments which are evaluated separately and independently. In this way, the very time-consuming treatment of large systems is replaced with a series of much faster calculations for small subunits. In the present application, these subunits consist of the orbitals localized at the different atoms. Three adsorption situations with rather different bonding characteristics have been studied: a Cu atom atop a threefold-coordinated O atom of an embedded Zn(4)O(4) cluster, a Cu atom in an O vacancy site at the O-terminated ZnO(000-1) surface, and a Cu atom in a Zn vacancy site at the Zn-terminated ZnO(0001) surface. The following properties are analyzed in detail: convergence of the many-body expansion, contributions of the different n-body increments to the adsorption energy, treatment of the singly-occupied orbital as "localized" or "delocalized". Big savings in computer time can be achieved by this approach, particularly if only the localized orbitals in the individual increment under consideration are described by a large correlation adapted basis set, while all other orbitals are treated by a medium-size Hartree-Fock-type basis set. In this way, the method of local increments is a powerful alternative to the widely used methods like DFT or RI-MP2.

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Ultrathin Oxide Films

Freund

Goodman

2008

Handbook of Heterogeneous Catalysis

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The sections in this article are Introduction Magnesium Oxide Mg O (100)/ Mo (100) Mg O (100)/ Ag (100) Mg O (111)/ Mo (110) Nickel Oxide Ni O (100)/ Ni (100), Mo (100) Ni O (111)/ Ni (111) Alumina Alumina/ Ni Al (110) Alumina/ Ni 3 Al (111) Al 2 O 3 (111)/ Ta (110) Al 2 O 3 (111)/ Mo (110) and Cu / Al 2 O 3 (111)/ Mo (110) Silica Si O 2 / Mo (110) Si O 2 / Mo (211) Cu / Si O 2 / Mo (110) Pd / Si O 2 / Mo (110) Au / Si O 2 / Mo (211) and Au / Ti O 2 / Si O 2 / Mo (211) Titania Ti x O y / Mo (100), Mo (110), Pt (111), Ni (110), W (100) Au / Ti O x / Mo (211) Chromia Cr 2 O 3 (111)/ Cr (11O) Vanadia Vanadium Sesquioxide Iron oxides Fe O / Pt (111), Fe 2 O 3 (0001)/ Pt (111), Fe 3 O 4 (001)/ Pt (111) Pd , Au on Iron Oxides Niobia Molybdenum Oxide Ceria Binary Oxides Ni O / Mg O , Ni O / Ca O , Mg O / Ni O , Ca O / Ni O / Mo (100) Conclusions Acknowledgments

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The local adsorption geometry of CO and NH3 on NiO(100) determined by scanned-energy mode photoelectron diffraction

Cited by 30 publications

References 50 publications

Density functional study of CO and NO adsorption on Ni-doped MgO(100)

Density functional study of CO and NO adsorption on Ni-doped MgO(100)

The method of local increments for the calculation of adsorption energies of atoms and small molecules on solid surfaces : Part I. A single Cu atom on the polar surfaces of ZnO

Ultrathin Oxide Films

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