Harris and Quong Reply:

Harris, Leonard A.; Quong, Andrew A.

doi:10.1103/physrevlett.95.029602

Cited by 72 publications

(149 citation statements)

References 4 publications

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“…41,68,69,100 The adsorption energy is calculated as (14) where E(hydrated slab) is the energy of the slab with one adsorbed water molecule, E(dry slab) is the energy of an isolated and relaxed slab, and E(H 2 O) is the energy of an isolated water molecule for the same system (all calculations are carried out with identical simulation parameters). The calculated adsorption energies (and net atomic charges, 23 reported in Table S1 of the supplementary material) were in good agreement with previously reported results 41,42,68,69,101,102 with the partial exception of anatase (100) and (001), where we found slightly larger ∆E ads compared to the work of Arrouvel et al 68 This difference can be attributed to the significantly lower energy cutoff used in that study compared to the present work. …”

Section: A Adsorption Of Single Water Molecules On Tiosupporting

confidence: 65%

“…47 With such a low free energy barrier, thermal fluctuations will lead to coexistence of molecular and dissociated waters at full hydration. 42,45,50,70,122 The subtle surface energetics renders theoretical calculations sensitive to modeling details such as TiO 2 slab thickness 43,46 and choice of the xc-functional. 46 A single water dissociation event on rutile (110) was detected during the 50 ps-simulation carried out in the present work.…”

Section: Diffusion In the Hydration Layersmentioning

confidence: 99%

“…Water dissociation on defect-free rutile (110) is a long-standing debate within the scientific community. 42,43,45,46,70,71 For each surface, we analyze the hydration layer structure with a threedomain model that differentiates water molecules based on lateral mobility and orientation freedom. Surface reactivity is analyzed at full hydration (and compared to neardry conditions), and graph theory is used to connect water reaction pathways to TiO 2 surface structures under ambient conditions.…”

Section: Introductionmentioning

confidence: 99%

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Diffusion and reaction pathways of water near fully hydrated TiO2 surfaces from ab initio molecular dynamics

Agosta

Brandt

Lyubartsev

2017

The Journal of Chemical Physics

104

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Ab initio molecular dynamics simulations are reported for water-embedded TiO2 surfaces to determine the diffusive and reactive behavior at full hydration. A three-domain model is developed for six surfaces [rutile (110), (100), and (001), and anatase (101), (100), and (001)] which describes waters as “hard” (irreversibly bound to the surface), “soft” (with reduced mobility but orientation freedom near the surface), or “bulk.” The model explains previous experimental data and provides a detailed picture of water diffusion near TiO2 surfaces. Water reactivity is analyzed with a graph-theoretic approach that reveals a number of reaction pathways on TiO2 which occur at full hydration, in addition to direct water splitting. Hydronium (H3O+) is identified to be a key intermediate state, which facilitates water dissociation by proton hopping between intact and dissociated waters near the surfaces. These discoveries significantly improve the understanding of nanoscale water dynamics and reactivity at TiO2 interfaces under ambient conditions.

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Section: A Adsorption Of Single Water Molecules On Tiosupporting

confidence: 65%

Section: Diffusion In the Hydration Layersmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Diffusion and reaction pathways of water near fully hydrated TiO2 surfaces from ab initio molecular dynamics

Agosta

Brandt

Lyubartsev

2017

The Journal of Chemical Physics

104

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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: 89%

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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“…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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Harris and Quong Reply:

Cited by 72 publications

References 4 publications

Diffusion and reaction pathways of water near fully hydrated TiO2 surfaces from ab initio molecular dynamics

Diffusion and reaction pathways of water near fully hydrated TiO2 surfaces from ab initio molecular dynamics

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

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