The adsorption of water on clean and oxygen predosed Rh(111): Surface templating via (1×1)-O/Rh(111) induces formation of a novel high-density interfacial ice structure

Gibson, K. D.; Viste, M.; Sibener, S. J.

doi:10.1063/1.481603

Cited by 60 publications

(42 citation statements)

References 32 publications

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“…We calculated proton-ordered H-up and H-down H 2 O bilayers on the Rh͑111͒ surface in a ͑ ͱ 3 ϫ ͱ 3͒ periodicity, 24 which was modeled by a five-layer slab separated by a vacuum equivalent to an eight-layer spacing, using 6 ϫ 6 k points and the first-order Hermite-Gaussian smearing 25 with the width of 0.05 eV. The lattice constant of 0.383 ͑0.386͒ nm for fcc Rh optimized by using the PBE ͑RPBE͒ functional was used to construct the slab.…”

Section: B Water Bilayer On Rh(111)mentioning

confidence: 99%

Interaction of water with a metal surface: Importance of van der Waals forces

2010

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Choosing the water bilayer/Rh͑111͒ interface as an example, we study the interaction of water with a metal surface, by taking into account the van der Waals ͑vdW͒ interactions using the vdW density functional ͑vdW-DF͒. There are two types of water in a water bilayer on the substrate, namely, chemisorbed and physisorbed ones. We show that for a chemisorbed water molecule, vdW-DF results agree well with those obtained using the Perdew-Burke-Ernzerhof ͑PBE͒ generalized gradient approximation. However, for a physisorbed water molecule, PBE severely underestimates the interaction energy. When we correctly include the vdW interaction, the relative strengths of the water-substrate and water-water interactions among different bilayer structures become comparable, and the water bilayer structures considered ͑H-up, buckled H-down, and H-flat water bilayers͒ become quasidegenerated, while PBE predicts one configuration more stable than the others. The structure of the water bilayer is determined by a delicate balance of Pauli repulsion and long-range vdW attractions in water-substrate and water-water interactions. Therefore, for the prediction of the water bilayer structure on the Rh͑111͒ surface, it is important to describe Pauli repulsion and vdW interactions correctly.

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Section: B Water Bilayer On Rh(111)mentioning

confidence: 99%

Interaction of water with a metal surface: Importance of van der Waals forces

2010

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“…The coverage was determined from the integrated TPD spectra, and was calibrated by comparing with the TPD signal from a monolayer (ML) grown on clean Rh(111) (1 ML = 1.07 × 10 15 molecules cm −2 ). 29 Dosing rates were estimated to be ∼0.5 ML s −1 at normal incidence. All of the dosing was done at an incident angle of θ = 45 • , and the total coverage was ∼750 ML.…”

Section: A Thermal Desorptionmentioning

confidence: 99%

Molecular interactions with ice: Molecular embedding, adsorption, detection, and release

Gibson

Langlois

et al. 2014

The Journal of Chemical Physics

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The interaction of atomic and molecular species with water and ice is of fundamental importance for chemistry. In a previous series of publications, we demonstrated that translational energy activates the embedding of Xe and Kr atoms in the near surface region of ice surfaces. In this paper, we show that inert molecular species may be absorbed in a similar fashion. We also revisit Xe embedding, and further probe the nature of the absorption into the selvedge. CF4 molecules with high translational energies (≥3 eV) were observed to embed in amorphous solid water. Just as with Xe, the initial adsorption rate is strongly activated by translational energy, but the CF4 embedding probability is much less than for Xe. In addition, a larger molecule, SF6, did not embed at the same translational energies that both CF4 and Xe embedded. The embedding rate for a given energy thus goes in the order Xe > CF4 > SF6. We do not have as much data for Kr, but it appears to have a rate that is between that of Xe and CF4. Tentatively, this order suggests that for Xe and CF4, which have similar van der Waals radii, the momentum is the key factor in determining whether the incident atom or molecule can penetrate deeply enough below the surface to embed. The more massive SF6 molecule also has a larger van der Waals radius, which appears to prevent it from stably embedding in the selvedge. We also determined that the maximum depth of embedding is less than the equivalent of four layers of hexagonal ice, while some of the atoms just below the ice surface can escape before ice desorption begins. These results show that energetic ballistic embedding in ice is a general phenomenon, and represents a significant new channel by which incident species can be trapped under conditions where they would otherwise not be bound stably as surface adsorbates. These findings have implications for many fields including environmental science, trace gas collection and release, and the chemical composition of astrophysical icy bodies in space.

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“…Indeed, on a Rh(111) surface with a dense oxygen overlayer forming a (1x1) structure, 5 it has been proposed that the first layer of water binds via formation of Hbonds with the surface O atoms. In a recent X-ray study 6 of water adsorption on O(2x2)/Ni(111) two different water structures have been identified.…”

Section: Introductionmentioning

confidence: 99%

Water adsorption onO(2×2)∕Ru(0001): STM experiments and first-principles calculations

et al. 2007

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We present a combined theoretical and experimental study of water adsorption on Ru(0001) pre-covered with 0.25 monolayers (ML) of oxygen forming a (2x2) structure.Several structures were analyzed by means of Density Functional Theory calculations for which STM simulations were performed and compared with experimental data. Up to 0.25 monolayers the molecules bind to the exposed Ru atoms of the 2x2 unit cell via the lone pair orbitals. The molecular plane is almost parallel to the surface with its H atoms pointing towards the chemisorbed O atoms of the 2x2 unit cell forming hydrogen bonds. The existence of these additional hydrogen bonds increases the adsorption energy of the water molecule to approximately 616 meV, which is ~220 meV more stable than on the clean Ru(0001) surface with a similar configuration. The binding energy shows only a weak dependence on water coverage, with a shallow minimum for a row structure at 0.125 ML. This is consistent with the STM experiments that show a tendency of the molecules to form linear rows at intermediate coverage. Our calculations also suggest the possible formation of water dimers near 0.25 ML.

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The adsorption of water on clean and oxygen predosed Rh(111): Surface templating via (1×1)-O/Rh(111) induces formation of a novel high-density interfacial ice structure

Cited by 60 publications

References 32 publications

Interaction of water with a metal surface: Importance of van der Waals forces

Interaction of water with a metal surface: Importance of van der Waals forces

Molecular interactions with ice: Molecular embedding, adsorption, detection, and release

Water adsorption onO(2×2)∕Ru(0001): STM experiments and first-principles calculations

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