Interfacial structure of water on Ru(001) investigated by vibrational spectroscopy

Denzler, Daniel N.; Heß, Christian; Dudek, Raymond C.; Wagner, Steffen; Frischkorn, Christian; Wolf, Martin; Ertl, G.

doi:10.1016/s0009-2614(03)01016-9

Cited by 84 publications

(78 citation statements)

References 28 publications

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“…In a water monolayer on metal surfaces, for example, water molecules are connected by H-bonds to form a hexagonal honeycomb structure where half of the water molecules are adsorbed in an oxygen-down configuration and the other half take a configuration of pointing a free (i.e., non H-bonded) OH either to a vacuum ("H-up") or to a metal surface ("H-down"). The recent UHV studies at low temperatures (<140 K) have provided the detailed insights into the branching of water between "H-up" and "H-down" configurations on several metal surfaces; water is adsorbed predominantly in the "H-down" configuration on Pt(111) [117,119] and on Ru(0001) [100,[120][121][122], while the mixed "H-up" and "H-down" configurations are found for water monolayer on Cu(110) (H-down: H-up = ~2:1)…”

Section: Discussionmentioning

confidence: 99%

In situx-ray photoelectron spectroscopy studies of water on metals and oxides at ambient conditions

Yamamoto

Bluhm

Andersson

et al. 2008

J. Phys.: Condens. Matter

256

241

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E d i t i o n o f a c t i v e P D F S o f t w a r e . V i s i t w w w . a c t i v e P D F . c o m f o r m o r e d e t a i l s .1In-situ X-ray photoelectron spectroscopy studies of water on metals and oxides at ambient conditions Abstract. X-ray photoelectron spectroscopy (XPS) is a powerful tool for surface and interface analysis, providing the elemental composition of surfaces and the local chemical environment of adsorbed species. Conventional XPS experiments have been limited to ultrahigh vacuum (UHV) conditions due to a short mean free path of electrons in a gas phase. The recent advances in instrumentation coupled with third-generation synchrotron radiation sources enables in-situ XPS measurements at pressures above 5 Torr. In this review, we describe the basic design of the ambient pressure XPS setup that combines differential pumping with an electrostatic focusing. We present examples of the application of in-situ XPS to studies of water adsorption on the surface of metals and oxides including Cu(110), Cu(111), TiO 2 (110) under environmental conditions of water vapor pressure. On all these surfaces we observe a general trend where hydroxyl groups form first, followed by molecular water adsorption. The importance of surface OH groups and their hydrogen bonding to water molecules in water adsorption on surfaces is discussed in detail. E v a l u a t i o n E d i t i o n o f a c t i v e P D FS o f t w a r e . V i s i t w w w . a c t i v e P D F . c o m f o r m o r e d e t a i l s .2

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Section: Discussionmentioning

confidence: 99%

In situx-ray photoelectron spectroscopy studies of water on metals and oxides at ambient conditions

Yamamoto

Bluhm

Andersson

et al. 2008

J. Phys.: Condens. Matter

256

241

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“…[1][2][3][4][5][6][7][8][9][10][11][12] At large water coverage, the determination of the most stable structures of the water adlayer becomes a quite challenging task. This is mainly due to the interplay between two interactions of similar strengths: the intermolecular hydrogen-bond ͑H bond͒ and the water-metal interaction.…”

Section: Introductionmentioning

confidence: 99%

“…This is mainly due to the interplay between two interactions of similar strengths: the intermolecular hydrogen-bond ͑H bond͒ and the water-metal interaction. 3,10 In the case of Ru, an additional complication comes from the competing stability of the partially dissociated and the intact-molecule adsorption configurations of water. 5,10,12 Using scanning tunnelling microscopy ͑STM͒ supplemented by density functional theory ͑DFT͒ calculations, Michaelides and Morgenstern 13 were recently able to resolve the structures of small water clusters adsorbed on Cu͑111͒ and Ag͑111͒.…”

Section: Introductionmentioning

confidence: 99%

Substrate-induced cooperative effects in water adsorption from density functional calculations

et al. 2010

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Density functional theory calculations are used to investigate the role of substrate-induced cooperative effects on the adsorption of water on a partially oxidized transition-metal surface, O͑2 ϫ 2͒ / Ru͑0001͒. Focusing particularly on the dimer configuration, we analyze the different contributions to its binding energy. A significant reinforcement of the intermolecular hydrogen bond ͑H bond͒, also supported by the observed frequency shifts of the vibration modes, is attributed to the polarization of the donor molecule when bonded to the Ru atoms in the substrate. This result is further confirmed by our calculations for a water dimer interacting with a small Ru cluster, which clearly show that the observed effect does not depend critically on fine structural details and/or the presence of coadsorbates. Interestingly, the cooperative reinforcement of the H bond is suppressed when the acceptor molecule, instead of the donor, is bonded to the surface. This simple observation can be used to rationalize the relative stability of different condensed structures of water on metallic substrates.

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“…While intrinsic discrepancies between this theoretical model and previous experimental evidences had been pointed out [44], a second theoretical work supported the half-dissociated bilayer picture [45], and vibrational features for this model were calculated [46]. The latter were subsequently investigated with sum frequency generation (SFG) vibrational spectroscopy [47], and a comparison with previous SFG studies of intact D 2 O interfaces [48,49], strongly suggested that the water bilayer at Ru(0001) is not dissociated.…”

Section: Water Adsorption On Ru(0001)mentioning

confidence: 68%

“…Extensive test calculations on Ru bulk, O/Ru system, various water structures and hexagonal ice were used to examine convergence with respect to system and integration parameters [56]. We performed electronic structure calculations and geometry optimizations for three alternative structures for the water bilayer on Ru(0001) [18,19,45,47], namely, the "H-up", "H-down", and half-dissociated bilayers, using a symmetric nine-layer slab. For the half-dissociated bilayer we also examined the structure with no hydrogens adsorbed on Ru at the center of the O hexagons [18,45].…”

Section: Water Adsorption On Ru(0001)mentioning

confidence: 99%

Chemistry at surfaces: from ab initio structures to quantum dynamics

et al. 2007

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Recent years have witnessed an ever growing interest in theoretically studying chemical processes at surfaces. Apart from the interest in catalysis, electrochemistry, hydrogen economy, green chemistry, atmospheric and interstellar chemistry, theoretical understanding of the molecule-surface chemical bonding and of the microscopic dynamics of adsorption and reaction of adsorbates are of fundamental importance for modeling known processes, understanding new experimental data, predicting new phenomena, controlling reaction pathways. In this work, we review the efforts we have made in the last few years in this exciting field. We first consider the energetics and the structural properties of some adsorbates on metal surfaces, as deduced by converged, first-principles, plane-wave calculations within the slab-supercell approach. These studies comprise water adsorption on Ru(0001), a subject of very intense debate in the past few years, and oxygen adsorption on aluminum, the prototypical example of metal passivation. Next, we address dynamical processes at surfaces with classical and quantum methods. Here the main interest is in hydrogen dynamics on metallic and semi-metallic surfaces, because of its importance for hydrogen storage and interstellar chem- istry. Hydrogen sticking is studied with classical and quasi-classical means, with particular emphasis on the relaxation of hot-atoms following dissociative chemisorption. Hot atoms dynamics on metal surfaces is investigated in the reverse, hydrogen recombination process and compared to Eley-Rideal dynamics. Finally, Eley-Rideal, collision-induced desorption, and adsorbate-induced trapping are studied quantum mechanically on a graphite surface, and unexpected quantum effects are observed.

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Interfacial structure of water on Ru(001) investigated by vibrational spectroscopy

Cited by 84 publications

References 28 publications

In situx-ray photoelectron spectroscopy studies of water on metals and oxides at ambient conditions

In situx-ray photoelectron spectroscopy studies of water on metals and oxides at ambient conditions

Substrate-induced cooperative effects in water adsorption from density functional calculations

Chemistry at surfaces: from ab initio structures to quantum dynamics

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