Nature and Estimation of Functional Groups on Solid Surfaces

Boehm, H. P.; Knözinger, Helmut

doi:10.1007/978-3-642-93229-8_2

Cited by 95 publications

(48 citation statements)

References 673 publications

(881 reference statements)

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“…The curves in Figure 1b were obtained by subtracting the clean MgO spectrum, multiplied by a factor which takes the attenuated substrate intensity into account, from the data obtained after water dosage. Since the only features emerging from the difference spectra are the three water-induced bands 1b 1 , 3a 1 , and 1b 2 , the MIES data in Figure 1b support the model of nondissociative water adsorption on MgO(100) in a submonolayer coverage regime. It is important to point out that the difference spectra presented in Figure 1b do not provide the accuracy in terms of peak positions and intensities that are present in the original measurements of Figure 1a.…”

Section: Resultssupporting

confidence: 59%

“…29 On the other hand, since the emitted electron originates from the helium atom, the density of empty states in the conduction band need not be taken into consideration for the interpretation of the MIES data. 21 Starting from the bottom spectrum of the clean MgO surface in Figure 1a, there is a continuous build up of the water-induced features 1b 1 , 3a 1 , and 1b 2 and an attenuation of the substrate intensity visible. Binding energies and molecular orbital assignments for the water-induced structures based on gas-phase photoelectron spectra 37,38 and penning ionization electron spectra (PIES) 39 are also given.…”

Section: Resultsmentioning

confidence: 99%

“…It is also well-established that these hydroxyl groups play a decisive role in many chemical properties of oxide surfaces, including ion sorption, dissolution, and catalytic activity. 1 MgO surfaces and their interactions with water have been extensively studied both theoretically and experimentally; however, the primary reason for our interest in the MgO-water system is the unsettled problem regarding chemical reactivity of the most stable MgO(100) surface toward water molecules. Many experimental [2][3][4][5] and theoretical [6][7][8][9] studies have found that water molecules do not dissociate upon adsorption on the MgO-(100) crystal surface from vacuum.…”

Section: Introductionmentioning

confidence: 99%

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Dissociation of Water at the MgO(100)−Water Interface: Comparison of Theory with Experiment

Johnson¹,

Stefanovich²,

Truong³

et al. 1999

J. Phys. Chem. B

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Dissociative chemisorption of H 2 O at the MgO(100)-water interface has been investigated both experimentally and theoretically. In particular, metastable impact electron spectroscopy (MIES) was used to image the density of occupied states on the MgO(100)/Mo(100) surface for various degrees of water exposure. After multilayer water desorption, spectral features typical of surface hydroxyls are present. To further study the possibility of dissociative chemisorption of water, a theoretical and computational method called CECILIA (combined embedded cluster at the interface with liquid approach) was used to calculate the geometry, energetics, and electronic density of states (DOS) for interfacial species. Consistent with experiment, our theoretical results predict that dissociative adsorption of H 2 O at the MgO(100)-water interface is energetically more favorable than molecular adsorption. The stabilization of charged OH -and H + interface adsorbates is due to polarization of the surrounding solvent.

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Section: Resultssupporting

confidence: 59%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Dissociation of Water at the MgO(100)−Water Interface: Comparison of Theory with Experiment

Johnson¹,

Stefanovich²,

Truong³

et al. 1999

J. Phys. Chem. B

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show abstract

“…It is also well-established that these hydroxyl groups play a decisive role in all chemical properties of oxide surfaces, including ion sorption, dissolution, and catalytic activity. 1 Initially, model approaches based on bond valence analysis have been used to estimate stabilities of interfacial hydroxyl groups. [2][3][4][5][6] Recently, classical molecular mechanical models appeared which can address the structural properties of interfaces at an atomistic level.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Studies of Solid−Liquid Interfaces: Molecular Interactions at the MgO(001)−Water Interface

1998

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We have applied a novel theoretical and computational method called CECILIA (combined embedded cluster at the interface with liquid approach) to study adsorption of molecular water on the MgO(001) surface and its interface with water. The MgO(001) surface is modeled by a quantum cluster embedded in a field of pseudopotentials and point charges. The effects of an aqueous environment are included by placing a dielectric continuum in the region above the embedded cluster. Calculated geometry, energetics, and electronic spectra for adsorbed water are in good agreement with available experimental and theoretical data. In particular, many features of the interfacial structure and dynamics (McCarthy, M. I.; Schenter, G. K.; Scamehorn, C. A.; Nicholas, J. B. J. Phys. Chem. 1996, 100, 16989) are well-reproduced in our calculations. These results demonstrate the suitability of the CECILIA model for studying chemical processes at solid-liquid interfaces.

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“…Regardless of their form, the active catalytic component is located at the interface between the solid and the fluid and may consist of a wide diversity of species. Examples are: one or two atoms of the total surface (17), a larger ensemble of such surface atoms (18,19,20,21,22), an organometallic compound attached to the surface by covalent bonds (23), or a molecular cluster lying on the surface (24,25).…”

Section: •'mentioning

confidence: 99%