First-principles molecular dynamics simulation of water dissociation on TiO2 (110)

Lindan, Philip J. D.; Harrison, N. M.; Holender, J. M.; Gillan, M. J.

doi:10.1016/0009-2614(96)00934-7

Cited by 169 publications

(142 citation statements)

References 27 publications

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“…Conclusively, it has been made clear that the symmetry-breaking induced by the interactions between adsorbates benefits the system energetically. Although the symmetry effects discussed above are quite crucial, they have not been described in detail in previous studies 34,[42][43][44][45][46][47][48]66,100 . 78 are shown for relaxed geometries in two-molecule adsorption.…”

Section: Appendix B: Effect Of Symmetry Constraintsmentioning

confidence: 97%

“…Semiempirical tight-binding studies based on cluster models by Goniakowski et al and Bredow et al show favorable dissociative adsorption at all coverages, [36][37][38] as do some early first-principles Hartree-Fock (HF) and density functional theory (DFT) studies. 39,40 A first-principles molecular dynamics (MD) study by Lindan et al, 47 using the generalized gradient approximation (GGA), employed a periodic slab approach to show that dissociation of water leads to stabilization at low coverages. In these calculations, all adsorbates are subject to symmetry constraints, so neighboring molecules are restricted to be at fixed orientation and separation.…”

Section: Introductionmentioning

confidence: 99%

“…This terminology has been used in the present study in order to highlight the importance of breaking translational symmetry in intermolecular interactions as well as to be consistent with the language adopted in previous theoretical water adsorption studies. 34,43,[46][47][48]50,66 Molecular, dissociative and mixed adsorption modes are considered at each coverage and/or arrangement of adsorbates on the surface. This paper is organised as follows.…”

Section: Introductionmentioning

confidence: 99%

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Water adsorption on rutile TiO2(110) for applications in solar hydrogen production: A systematic hybrid-exchange density functional study

et al. 2012

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Periodic hybrid-exchange density functional theory calculations are used to predict the structure of water on the rutile TiO 2 (110) surface ( 1 ML), which is an important first step towards understanding the photocatalytic processes that occur in solar water splitting. A detailed model describing the water-water and water-surface interactions is developed by exploring thoroughly the adsorption energetics. The possible adsorption mode-molecular, dissociative, or mixed-and the binding energy are studied as a function of coverage and arrangement, thus separation, of adsorbed species. These dependencies (coverage and arrangement) have a significant influence on the nature of the interactions involved in the H 2 O-TiO 2 system. The importance of both direct intermolecular and surface-mediated interactions between surface species is emphasized. Finally, to gain insight into the photooxidation of adsorbed species at the surface, the electronic structure of the predicted adsorbate-substrate geometries is analyzed in terms of total and projected density of states.

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Section: Appendix B: Effect Of Symmetry Constraintsmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Water adsorption on rutile TiO2(110) for applications in solar hydrogen production: A systematic hybrid-exchange density functional study

et al. 2012

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“…Similarly, Dyer et al (1993) used infrared and Raman spectroscopy and XRD to show that the hydrated surface of ~/-A1203 attains a bayerite-like configuration whereas bulk ~/-A1203 remains unreacted. Lindan et al (1996) showed that H20 molecules dissociate on the surface of TiO2 and SnO2. However, dissociation of H20 on MgO surfaces requires the presence of defects on the surface (Langel and Parrinello, 1995).…”

Section: Surface Enthalpies Of Other Ai-o-h Phasesmentioning

confidence: 99%

Surface Enthalpy of Boehmite

Majzlan

2000

Clays and clay miner.

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Abstract--The persistence of many seemingly metastable mineral assemblages in sediments and soils is commonly attributed to their sluggish transformation to the stable-phase assemblage. Although undoubtedly kinetics plays a major role, this study shows that thermodynamic factors, particularly surface energy, significantly influence the free energy. Enthalpies of formation of boehmite samples with variable surface area were derived using high-temperature oxide-melt calorimetry. The average surface enthalpy for all faces terminating boehmite particles was calculated at +0.52 -0.12 J/m z. This value represents the surface enthalpy for surfaces exposed to vacuum assuming that HzO adsorbed on the surface of boehmite is loosely bound. These results show that the enthalpy of formation of boehmite may vary by --<8 kJ/mol as a function of particle size. An overview of published values of surface energies of gibbsite, ~/-A1203, corundum, and the results here indicates that the hydrated phases (boehmite, gibbsite) have lower surface energies than the anhydrous phases (corundum, ~/-A1203). Lower surface energies allow the hydrated phases to maintain high surface area, i.e., small particle size. Similar surface energies of boehmite and gibbsite suggest kinetic control favoring the crystallization of boehmite or gibbsite from aqueous solution. The enthalpy of formation of bulk boehmite from the elements was calculated at -994.0 _+ 1.1 kJ/mol. Combining this result with the data in existing thermodynamic databases, we confirm that bulk boehmite is metastable with respect to bulk diaspore at ambient conditions.

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“…However, first-principles simulations, in which the electrons are treated quantum mechanically, are now being used to make very significant contributions to the understanding of oxide surfaces, for example, in MgO, 2 Al 2 O 3 , 3 SnO 2 , 4 and TiO 2 . [5][6][7][8][9][10][11] Our aim in the present paper is to use first-principles simulations to investigate the stoichiometric and reduced ͑110͒ surface of TiO 2 .…”

Section: Introductionmentioning

confidence: 99%

First-principles spin-polarized calculations on the reduced and reconstructedTiO2(110) surface

et al. 1997

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We have performed plane-wave pseudopotential density-functional theory calculations on the stoichiometric and reduced TiO 2 ͑110͒ surface, the 2ϫ1 and 1ϫ2 reconstructions of the surface formed by the removal of bridging-oxygen atoms, and on the oxygen vacancy in the bulk. The effect of including spin polarization is investigated, and it is found to give a qualitatively different electronic structure compared with a spin-paired description. In the spin-polarized solutions, the excess electrons generated by oxygen reduction occupy localized band-gap states formed from Ti (3d) orbitals, in agreement with experimental findings. In addition, the inclusion of spin polarization substantially lowers the energy of all the systems studied, when compared with spin-paired solutions. However, spin-polarization does not change the relative stability of the two reconstructions, which remain energetically equivalent. ͓S0163-1829͑97͒02724-0͔

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First-principles molecular dynamics simulation of water dissociation on TiO2 (110)

Cited by 169 publications

References 27 publications

Water adsorption on rutile TiO2(110) for applications in solar hydrogen production: A systematic hybrid-exchange density functional study

Water adsorption on rutile TiO2(110) for applications in solar hydrogen production: A systematic hybrid-exchange density functional study

Surface Enthalpy of Boehmite

First-principles spin-polarized calculations on the reduced and reconstructedTiO2(110) surface

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