Exothermic water dissociation on the rutile<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:mi mathvariant="normal">Ti</mml:mi><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn>2</mml:mn></mml:msub><mml:mrow><mml:mo>(</mml:mo><mml:mn>110</mml:mn><mml:mo>)</mml:mo></mml:mrow></mml:mrow></mml:math>surface

Lindan, Philip J. D.; Zhang, Changjun

doi:10.1103/physrevb.72.075439

Cited by 130 publications

(125 citation statements)

References 45 publications

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“…In previous studies, 34,46,74 single-molecule adsorption calculations using this slab size were performed; our results are in agreement with the reported relative stabilities of the adsorption modes (molecular versus dissociative) for 9, 15, and 21-atomic-layer slabs. The convergence with respect to slab thickness can be analyzed by considering the percentage difference between 9AL and 15AL systems.…”

Section: Computational Detailssupporting

confidence: 76%

“…They suggested that a barrier to dissociation explains why molecular adsorption is observed experimentally below 160 K, and that neighboring molecules lower this dissociation barrier through hydrogen bonding. The important role of intermolecular interactions has been stressed, 34,46,48,49 suggesting a more complex picture at monolayer coverage, in which both molecular and dissociated water coexist on the surface, stabilized by a hydrogen bond. From the extensive literature on theoretical studies, it is clear that the adsorption energetics are very sensitive to intermolecular interactions, electronic structure methods, e.g., DFT functional adopted, and differences in computational models (see detailed review in Ref.…”

Section: Introductionmentioning

confidence: 99%

“…[36][37][38][39][40][41][42][43][44][45][46] It should be noted, however, that many of these simulations are based on structural models characterized by either point group or translational symmetry constraints. 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.…”

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: Computational Detailssupporting

confidence: 76%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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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“…Thus, ab-initio molecular dynamics investigations considering the water liquid phase in contact with titania have been carried out only in a limited number of occasions, to address the rutile (110) [58][59][60][61] and the anatase (101) and (001) surfaces [62]. Instead, there is a large number of DFT studies which have examined stoichiometric and defective titania interfaces in the presence of just a few water monolayers, typically ranging from one to three [63][64][65][66][67][68][69][70][71]. In this section we illustrate the applicability of our hybrid quantum- The DFT parameters concerning planewave basis, pseudopotentials, and exchange correlation functional, were the same as employed to describe the water bulk phase in the previous section.…”

Section: Anatasementioning

confidence: 99%

A quantum-mechanics molecular-mechanics scheme for extended systems

Hunt¹,

Sánchez²,

Scherlis³

2016

J. Phys.: Condens. Matter

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We introduce and discuss a hybrid quantum-mechanics molecular-mechanics (QM-MM) approach for Car-Parrinello DFT simulations with pseudopotentials and planewaves basis, designed for the treatment of periodic systems. In this implementation the MM atoms are considered as additional QM ions having fractional charges of either sign, which provides conceptual and computational simplicity by exploiting the machinery already existing in planewave codes to deal with electrostatics in periodic boundary conditions.With this strategy, both the QM and MM regions are contained in the same supercell, which determines the periodicity for the whole system. Thus, while this method is not meant to compete with non-periodic QM-MM schemes able to handle extremely large but finite MM regions, it is shown that for periodic systems of a few hundred atoms, our approach provides substantial savings in computational times by treating classically a fraction of the particles. The performance and accuracy of the method is assessed through the study of energetic, structural, and dynamical aspects of the water dimer and of the aqueous bulk phase. Finally, the QM-MM scheme is applied to the computation of the vibrational spectra of water layers adsorbed at the TiO 2 anatase (101) solid-liquid interface. This investigation suggests that the inclusion of a second monolayer of H 2 O molecules is sufficient to induce on the first adsorbed layer, a vibrational dynamics similar to that taking place in the presence of an aqueous environment. The present QM-MM scheme appears as a very interesting tool to efficiently perform molecular dynamics simulations of complex condensed matter systems, from solutions to nanoconfined fluids to different kind of interfaces.

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Modeling and Simulation of Photocatalytic Reactions at TiO2 Surfaces

Kamisaka

Yamashita

On Solar Hydrogen &Amp; Nanotechnology

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Since the discovery of the Fujishima-Honda effect [1], the surface chemistry of TiO 2 has been expected to play a central role in solar hydrogen generation processes. In addition, strong photocatalytic activity [2] and photoinduced hydrophilic conversion phenomena [3] have been observed on TiO 2 surfaces. A dye-sensitized TiO 2 surface can be used as a building block for solar-cell devices [4]. Introduction of some impurities in TiO 2 thin films induces significant changes in their magnetic [5] and conducting properties [6]. All these characteristic features show the large number of possible industrial applications that are yet to materialize; for example, the fabrication of new catalysis and optoelectronic devices and solar cells. Some of these features have already been utilized in industrial applications [7]. Because TiO 2 is nontoxic and has a low cost, it will improve such processes. Most of the applications of TiO 2 are related to clean chemical processes and reusable-energy resources. From these favorable features, the importance of TiO 2 in the next-generation chemical industry cannot be overemphasized.However, despite intensive research into TiO 2 , from both experimental and theoretical aspects, the understanding of the fundamentals of TiO 2 chemistry is still limited. Most of the microscopic mechanisms of the properties mentioned above have not been clarified. Even some basic quantities, such as the effective mass of the electrons and the stoichiometry of bulk TiO 2 ,

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Exothermic water dissociation on the rutileTiO2(110)surface

Cited by 130 publications

References 45 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

A quantum-mechanics molecular-mechanics scheme for extended systems

Modeling and Simulation of Photocatalytic Reactions at TiO2 Surfaces

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