Ab initio study of the optical transitions on low-coordinated sites of an intermediate F center: The Fs+(OH)− center on MgO(100) surface

Markovits, Alexis; Minot, Christian; Ménétrey, M.; Sousa, Carmen; Illas, Francesc

doi:10.1016/j.ssi.2006.12.005

Cited by 7 publications

(7 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…56 However, it has been theoretically shown that vacancies, such as those involved in F centers, easily react with water molecules, 57 with an important energy of -3.18 eV (-307 kJ.mol -1 ), suggesting that such a reaction will occur at very low water pressures. If present at any stage of the sample synthesis, F centers, for which a detailed assignment of luminescent properties has been theoretically proposed, 58 must thus have reacted before photoluminescence analysis in our experimental setup. Moreover, the quenching of species C and D by oxygen (section 4.1) demonstrates that they are located on the MgO surface.…”

Section: Discussionmentioning

confidence: 99%

Assignment of Photoluminescence Spectra of MgO Powders: TD-DFT Cluster Calculations Combined to Experiments. Part I: Structure Effects on Dehydroxylated Surfaces

et al. 2008

View full text Add to dashboard Cite

Photoluminescence excitation spectra of dehydroxylated MgO powders are assigned from a combined theoretical and experimental approach. Experimentally, a set of five species is identified, among which are two new species, by recording the spectra with enhanced resolution and at 77 K so as to minimize energy transfer along the surface. Performed on various clusters modeling terraces, edges, monatomic steps, corners, kinks, and divacancies, TD-DFT calculations show that the excitation energy depends not only on the coordination of surface ions, but also on the local topology (kinks versus corners for example). This, together with the fact that a single defect can be excited at several wavelengths, explains the complexity of the experimental spectra and the difficulty encountered so far for their assignment. Several groups of calculated excitation energies can be identified which enable to rationalize the assignment of the experimental spectra.

show abstract

Section: Discussionmentioning

confidence: 99%

Assignment of Photoluminescence Spectra of MgO Powders: TD-DFT Cluster Calculations Combined to Experiments. Part I: Structure Effects on Dehydroxylated Surfaces

et al. 2008

View full text Add to dashboard Cite

show abstract

“…Such a comparison is used in studies dealing with spectroscopy of the F°s center. 77 Adsorption Energies and Geometrical Parameters of Metal Atoms from K to Zn on top of the F°s Center. The adsorption energies and geometrical parameters of the adsorbed metal atom are reported in Table 1.…”

Section: Resultsmentioning

confidence: 99%

“…These levels have been shown to play a role in electronic transitions. 77 The vacancy orbital is quite high in energy while the energy levels of the metal orbitals vary. Compared with a 2p (O) orbital, the vacancy orbital is more diffuse and does not point in the z direction.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

First Row Transition Metal Atom Adsorption On-Top of F°_s Defects of a MgO(100) Surface

2008

Self Cite

View full text Add to dashboard Cite

We performed periodic density functional calculations to study the reactivity of F°s defects on MgO(100) toward the first row of transition metal atoms at low coverage. The F°s center interaction strength with the first row of transition metal atoms is explained by the filling of bonding and antibonding orbitals and by the respective positions of the metal and vacancy levels. The vacancy levels are those of a dummy atom with a diffuse s-type orbital and empty p-type orbitals. Under adsorption, most of the metal atoms maintain their atomic configuration. Exceptions concern Ti, Co, and Ni that have different spin states. Across the period, the adsorption energy exhibits two maxima. The largest metal adsorption energies are found for Ti and V on one hand and Co, Ni, and Cu on the other hand. For these atoms, the highest antibonding σ-orbital is empty and the occupancy of π-orbitals provides additional stability. Interactions of metal orbitals of appropriate symmetry with empty p-type vacancy orbitals and surface Mg 2+ orbitals yield stabilization.

show abstract

“…Both isolated defect species [6][7][8][9][10][11][12][13][14][15][16][17][18][19] and defect aggregates [20][21][22] have been studied in simple oxide materials (e.g. CaO, MgO and TiO 2 ) with density functional theory (DFT) calculations.…”

Section: Introductionmentioning

confidence: 99%

Electronic structure of defects in Sr2MgSi2O7:Eu2+,La3+ persistent luminescence material

Hassinen

Hölsä

Laamanen

et al. 2010

Journal of Non-Crystalline Solids

View full text Add to dashboard Cite

Ab initio study of the optical transitions on low-coordinated sites of an intermediate F center: The Fs+(OH)− center on MgO(100) surface

Cited by 7 publications

References 45 publications

Assignment of Photoluminescence Spectra of MgO Powders: TD-DFT Cluster Calculations Combined to Experiments. Part I: Structure Effects on Dehydroxylated Surfaces

Assignment of Photoluminescence Spectra of MgO Powders: TD-DFT Cluster Calculations Combined to Experiments. Part I: Structure Effects on Dehydroxylated Surfaces

First Row Transition Metal Atom Adsorption On-Top of F°_s Defects of a MgO(100) Surface

Electronic structure of defects in Sr2MgSi2O7:Eu2+,La3+ persistent luminescence material

Contact Info

Product

Resources

About

Ab initio study of the optical transitions on low-coordinated sites of an intermediate F center: The Fs+(OH)− center on MgO(100) surface

Cited by 7 publications

References 45 publications

Assignment of Photoluminescence Spectra of MgO Powders: TD-DFT Cluster Calculations Combined to Experiments. Part I: Structure Effects on Dehydroxylated Surfaces

Assignment of Photoluminescence Spectra of MgO Powders: TD-DFT Cluster Calculations Combined to Experiments. Part I: Structure Effects on Dehydroxylated Surfaces

First Row Transition Metal Atom Adsorption On-Top of F°s Defects of a MgO(100) Surface

Electronic structure of defects in Sr2MgSi2O7:Eu2+,La3+ persistent luminescence material

Contact Info

Product

Resources

About

First Row Transition Metal Atom Adsorption On-Top of F°_s Defects of a MgO(100) Surface