The structure and crystallization of thin water films on Pt(111)

When water is adsorbed on Pt(111) above 135 K several different ice structures crystallize, depending on the thickness of the ice layer. At low coverage water forms extended islands of ice with a (square root(37) x square root(37))R25(o) unit cell, which compresses as the monolayer saturates to form a (square root(39) x square root(39))R16(o) structure. The square root(39) low-energy electron diffraction (LEED) pattern becomes more intense as the second layer grows, remaining bright for films up of 10-15 layers and then fading and disappearing for films more than ca. 40 layers thick. The ice multilayer consists of an ordered square root(39) wetting layer, on which ice grows as a crystalline film which progressively loses its registry to the wetting layer. Ice films more than ca. 50 layers thick develop a hexagonal LEED pattern, the entire film and wetting layer reorienting to form an incommensurate bulk ice. These changes are reflected in the vibrational spectra which show changes in line shape and intensity associated with the different ice structures. Thin amorphous solid water films crystallize to form the same phases observed during growth, implying that these structures are thermodynamically stable and not kinetic phases formed during growth. The change from a square root(39) registry to incommensurate bulk ice at ca. 50 layers is associated with a change in crystallization kinetics from nucleation at the Pt(111) interface in thin films to nucleation of incommensurate bulk ice in amorphous solid water films more than 50 layers thick.     

Crystalline ice growth on Pt(111) and Pd(111): nonwetting growth on a hydrophobic water monolayer

The growth of crystalline ice films on Pt(111) and Pd(111) is investigated using temperature programed desorption of the water films and of rare gases adsorbed on the water films. The water monolayer wets both Pt(111) and Pd(111) at all temperatures investigated [e.g., 20-155 K for Pt(111)]. However, crystalline ice films grown at higher temperatures (e.g., T>135 K) do not wet the monolayer. Similar results are obtained for crystalline ice films of D2O and H2O. Amorphous water films, which initially wet the surface, crystallize and dewet, exposing the water monolayer when they are annealed at higher temperatures. Thinner films crystallize and dewet at lower temperatures than thicker films. For samples sputtered with energetic Xe atoms to prepare ice crystallites surrounded by bare Pt(111), subsequent annealing of the films causes water molecules to diffuse off the ice crystallites to reform the water monolayer. A simple model suggests that, for crystalline films grown at high temperatures, the ice crystallites are initially widely separated with typical distances between crystallites of approximately 14 nm or more. The experimental results are consistent with recent theory and experiments suggesting that the molecules in the water monolayer form a surface with no dangling OH bonds or lone pair electrons, giving rise to a hydrophobic water monolayer on both Pt(111) and Pd(111).     

Vertical and lateral order in adsorbed water layers on anatase TiO2(101)

The structure and energetics of thin water overlayers on the (101) surface of TiO(2)-anatase have been studied through first-principles molecular dynamics simulations at T = 160 K. At one monolayer coverage, H(2)O molecules are adsorbed at the 5-fold Ti sites (Ti(5c)), forming an ordered crystal-like 2D layer with no significant water-water interactions. For an adsorbed bilayer, H(2)O molecules at both Ti(5c) and bridging oxygen (O(2c)) sites form a partially ordered structure, where the water oxygens occupy regular sites but the orientation of the molecules is disordered; in addition, stress-relieving defects are usually present. When a third layer is adsorbed, very limited parallel and perpendicular order is observed above the first bilayer. The calculated energetics of multilayer adsorption is in good agreement with recent temperature-programmed desorption data.     

Spectroscopic Monitoring of the Acidity of Water Films on Ru(0001): Orientation‐Specific Acidity of Adsorbed Water

We examined the acid–base properties of water films adsorbed onto a Ru(0001) substrate by using surface spectroscopic methods in vacuum environments. Ammonia adsorption experiments combined with low‐energy sputtering (LES), reactive ion scattering (RIS), reflection–absorption infrared spectroscopy (RAIRS) and temperature‐programmed desorption (TPD) measurements showed that the adsorbed water is acidic enough to transfer protons to ammonia. Only the water molecules in an intact water monolayer and water clusters larger than the hexamer exhibit such acidity, whereas small clusters, a thick ice film or a partially dissociated water monolayer that contains OH, H₂O and H species are not acidic. The observations indicate the orientation‐specific acidity of adsorbed water. The acidity stems from water molecules with H‐down adsorption geometry present in the monolayer. However, the dissociation of water into H and OH on the surface does not promote but rather suppresses the proton transfer to ammonia.     

Phase diagram of pentacene growth on Au(110)

We studied the growth of pentacene (C22H14) on the Au(110) surface by means of He atom scattering and Synchrotron X-ray photoemission. We found that two-dimensional commensurate growth only occurs in the monolayer range for a substrate temperature, T(s), higher than approximately 370 K. Larger amounts of deposited molecules forms three-dimensional uncorrelated clusters on the wetting layer. The desorption of second layer molecules occurs at T(s) > or = 420 K. The highest coverage ordered phase displays a (6 x 8) symmetry and corresponds to the saturation coverage at T(s) = 420 K. The (3 x 6) symmetry phase, recently reported for a multilayer planar film [Ph. Guaino, et al. Appl. Phys. Lett. 2004, 85, 2777], is only found at a coverage slightly lower than the (6 x 8) one. The (3 x 6) phase corresponds to the saturation coverage of the first layer at T(s) = 470 K.     

Hydrogen reactivity on highly-hydroxylated TiO2(110) surfaces prepared via carboxylic acid adsorption and photolysis

Combined scanning tunneling microscopy, temperature programmed desorption, photo stimulated desorption, and density functional theory studies have probed the formation and reactivity of highly-hydroxylated rutile TiO(2)(110) surfaces, which were prepared via a novel, photochemical route using trimethyl acetic acid (TMAA) dissociative adsorption and subsequent photolysis at 300 K. Deprotonation of TMAA molecules upon adsorption produces both surface bridging hydroxyls (OH(b)) and bidentate trimethyl acetate (TMA) species with a saturation coverage of nearly 0.5 monolayers (ML). Ultra-violet light irradiation selectively removes TMA species, producing a highly-hydroxylated surface with up to ~0.5 ML OH(b) coverage. At high coverages, the OH(b) species typically occupy second-nearest neighbor sites along the bridging oxygen row locally forming linear (2 × 1) structures of different lengths, although the surface is less ordered on a long scale. The annealing of the highly-hydroxylated surface leads to hydroxyl recombination and H(2)O desorption with ~100% yield, thus ruling out the diffusion of H into the bulk that has been suggested in the literature. In agreement with experimental data, theoretical results show that the recombinative H(2)O desorption is preferred over both H bulk diffusion and H(2) desorption processes.     

Electron attachment in ice-HCl clusters: an ab initio study

Experimental work has shown that small amounts of HCl strongly enhance electron capture in ice films. The purpose of the present study was to investigate the effect of adsorbed HCl on the interaction of electrons with small clusters of water. Studies were made with clusters of 6 and 12 water molecules with various geometries both with and without one HCl attached. A number of distinct HCl coordination motifs were examined. All of the neutral structures with HCl exhibited zero thresholds for electron attachment and formed dipole bound anionic states (DBS). The relaxation processes for these "initial DBS" depended on the number of H(2)O (n) and on the number and type of H-bonds to the HCl (x). The initial DBS of systems with only O-H...Cl H-binding underwent dissociative electron attachment (DEA), forming H atoms. Relaxation for systems with ClH...OH(2) bonds was more complex. For the two layer n = 12 systems with x = 2 or 3 the HCl proton moved to the nearest oxygen to form H(3)O(+). Then rearrangement of the proton network occurred, and the Cl(-) became solvated by three HO-H...Cl(-) bonds. The presence of Cl(-) and H(3)O(+) increases the dipole moment and the electron binding energy (EBE) of the network. Further stabilization is achieved by decay into deeper DBS electron traps and/or by reaction of the excess electron with H(3)O(+) to form H(*) atoms. The HCl(H(2)O)(6) clusters with a single Cl-H...OH(2) bond behaved differently. They increased their stability by becoming more linear. This raised the dipole moment and the EBE therefore increased, reducing the total energy. None of these species showed any signs of increasing the number of H-bonds to Cl. The implication of these observations for the interpretation of the results of the experiments with 0.2 monolayer of HCl on 5 monolayer of H(2)O at 20 K, and on the possible role of cosmic ray-induced ionization in polar stratospheric clouds in ozone depletion is discussed.     

Layer-by-layer growth of thin amorphous solid water films on Pt(111) and Pd(111)

The growth of amorphous solid water (ASW) films on Pt(111) is investigated using rare gas (e.g., Kr) physisorption. Temperature programmed desorption of Kr is sensitive to the structure of thin water films and can be used to assess the growth modes of these films. At all temperatures that are experimentally accessible (20-155 K), the first layer of water wets Pt(111). Over a wide temperature range (20-120 K), ASW films wet the substrate and grow approximately layer by layer for at least the first three layers. In contrast to the ASW films, crystalline ice films do not wet the water monolayer on Pt(111). Virtually identical results were obtained for ASW films on epitaxial Pd(111) films grown on Pt(111). The desorption rates of thin ASW and crystalline ice films suggest that the relative free energies of the films are responsible for the different growth modes. However, at low temperatures, surface relaxation or "transient mobility" is primarily responsible for the relative smoothness of the films. A simple model of the surface relaxation semiquantitatively accounts for the observations.     

Agostic interactions and dissociation in the first layer of water on Pt(111)

Recent quantum mechanical (QM) calculations for a monolayer of H(2)O on Ru(0001) suggested a novel stable structure with half the waters dissociated. However, different studies on Pt(111) suggested an undissociated bilayer structure in which the outer half of the water has the OH bonds toward the surface rather than the O lone pair. Since water layers on Pt are important in many catalytic processes (e.g., the fuel cell cathode), we calculated the energetics and structure of the first monolayer of water on the Pt(111) surface using QM [periodic slab using density functional calculations (DFT) with the PBE-flavor of exchange-correlation functional]. We find that the fully saturated surface ((2)/(3) ML) has half the water almost parallel to the surface (forming a Pt-O Lewis acid-base bond), whereas the other half are perpendicular to the surface, but with the H down toward the surface (forming a Pt-HO agostic bond). This leads to a net bond energy of 0.60 eV/water = 13.8 kcal/mol (the standard ice model with the H up configuration of the water molecules perpendicular to the surface is less stable by 0.092 eV/water = 2.1 kcal/mol). We examined whether the partial dissociation of water proposed for Ru(0001) could occur on Pt(111). For the saturated water layer ((2)/(3) ML) we find a stable structure with half the H(2)O dissociated (forming Pt-OH and Pt-H covalent bonds), which is less favorable by only 0.066 eV/water = 1.51 kcal/mol. These results confirm the interpretation of combined experimental (XAS, XES, XPS) and theoretical (DFT cluster and periodic including spectrum calculations) studies, which find only the H down undissociated case. We find that the undissociated structure leads to a vertical displacement between the two layers of oxygens of approximately 0.42 A (for both H down and H up). In contrast, the partially dissociated system leads to a flat structure with a separation of the oxygen layers of 0.08 A. Among the partially dissociated systems, we find that all subsurface positions for the dissociated hydrogen are less favorable than adsorbing on top of the free Pt surface atom. Our results suggest that for less than (1)/(3) ML, clustering would be observed rather than ordered monolayer structures.     

Clusters of hydrated methane sulfonic acid CH3SO3H.(H2O)n (n = 1-5): a theoretical study

Ab initio and density functional methods have been used to examine the structures and energetics of the hydrated clusters of methane sulfonic acid (MSA), CH3SO3H.(H2O)n (n = 1-5). For small clusters with one or two water molecules, the most stable clusters have strong cyclic hydrogen bonds between the proton of OH group in MSA and the water molecules. With three or more water molecules, the proton transfer from MSA to water becomes possible, forming ion-pair structures between CH3SO3- and H3O+ moieties. For MSA.(H2O)3, the energy difference between the most stable ion pair and neutral structures are less than 1 kJ/mol, thus coexistence of neutral and ion-pair isomers are expected. For larger clusters with four and five water molecules, the ion-pair isomers are more stable (>10 kJ/mol) than the neutral ones; thus, proton transfer takes place. The ion-pair clusters can have direct hydrogen bond between CH3SO3- and H3O+ or indirect one through water molecule. For MSA.(H2O)5, the energy difference between ion pairs with direct and indirect hydrogen bonds are less than 1 kJ/mol; namely, the charge separation and acid ionization is energetically possible. The calculated IR spectra of stable isomers of MSA.(H2O)n clusters clearly demonstrate the significant red shift of OH stretching of MSA and hydrogen-bonded OH stretching of water molecules as the size of cluster increases.     

Interaction of water with ordered theta-Al(2)O(3) ultrathin films grown on NiAl(100)

The structure of an ordered, ultrathin theta-Al(2)O(3) film grown on a NiAl(100) single-crystal surface was studied by Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and low-energy electron diffraction (LEED), and its interaction with water was investigated with temperature programmed desorption (TPD) and XPS. Our results indicate that H(2)O adsorption on the theta-Al(2)O(3)/NiAl(100) surface is predominantly molecular rather than dissociative. For theta(H)()2(O) < 1 ML (ML = monolayer), H(2)O molecules were found to populate Al(3+) cation sites to form isolated H(2)O species aligned in a row along the cation sites on the oxide surface with a repulsive interaction between them. For theta(H)()2(O) > 1 ML, three-dimensional ice multilayers were observed to form, which then desorb during TPD with approximate zero-order kinetics as expected. A small extent of H(2)O dissociation was observed to occur on the theta-Al(2)O(3)/NiAl(100) surface, which was attributed to the presence of a low concentration of oxygen atom vacancies. Titration of these defect sites with adsorbed H(2)O molecules revealed an estimated defect density of 0.05 ML for the theta-Al(2)O(3)/NiAl(100) system consistent with the ordered nature of the synthesized oxide film.     

Interstellar ice surface site modification induced by dicyanoacetylene adsorption

Dicyanoacetylene adsorbed on amorphous ice water at 10 K presents an interaction with the dangling H site and induces a s(4) adsorption site formation due to the restructuring of the ice bulk. Warming up the sample provokes the dicyanoacetylene desorption from the H(2)O ice film, which could be due to the beginning of the ice crystallization process. The desorption activation energy measured by temperature-programmed desorption (E(d) = 42 +/- 5 kJ x mol(-1)) is in good agreement with that calculated (E(d) = 46 kJ x mol(-1)) and gives evidence of a hydrogen-bonded adsorbed state on amorphous ice films.     

Site-dependent electron-stimulated reactions in water films on TiO2(110)

Electron-stimulated reactions in thin [<3 ML (monolayer)] water films adsorbed on TiO(2)(110) are investigated. Irradiation with 100 eV electrons results in electron-stimulated dissociation and electron-stimulated desorption (ESD) of adsorbed water molecules. The molecular water ESD yield increases linearly with water coverage theta for 0< or =theta< or =1 ML and 11 ML, the water ESD yield per additional water molecule adsorbed (i.e., the slope of the ESD yield versus coverage) is 3.5 times larger than for theta<1 ML. In contrast, the number of water molecules dissociated per incident electron increases linearly for theta< or =2 ML without changing slope at theta=1 ML. The total electron-stimulated sputtering rate, as measured by postirradiation temperature programmed desorption of the remaining water, is larger for theta>1 ML due to the increased water ESD for those coverages. The water ESD yields versus electron energy (for 5-50 eV) are qualitatively similar for 1, 2, and 40 ML water films. In each case, the observed ESD threshold is at approximately 10 eV and the yield increases monotonically with increasing electron energy. The results indicate that excitations in the adsorbed water layer are primarily responsible for the ESD in thin water films on TiO(2)(110). Experiments on "isotopically layered" films with D(2)O adsorbed on the Ti(4+) sites (D(2)O(Ti)) and H(2)O adsorbed on the bridging oxygen atoms (H(2)O(BBO)) demonstrate that increasing the water coverage above 1 ML rapidly suppresses the electron-stimulated desorption of D(2)O(Ti) and D atoms, despite the fact that the total water ESD and atomic hydrogen ESD yields increase with increasing coverage. The coverage dependence of the electron-stimulated reactions is probably related to the different bonding geometries for H(2)O(Ti) and H(2)O(BBO) and its influence on the desorption probability of the reaction products.     

Mechanistic study of proton transfer and HD exchange in ice films at low temperatures (100-140 K)

We have examined the elementary molecular processes responsible for proton transfer and HD exchange in thin ice films for the temperature range of 100-140 K. The ice films are made to have a structure of a bottom D(2)O layer and an upper H(2)O layer, with excess protons generated from HCl ionization trapped at the D(2)OH(2)O interface. The transport behavior of excess protons from the interfacial layer to the ice film surface and the progress of the HD exchange reaction in water molecules are examined with the techniques of low energy sputtering and Cs(+) reactive ion scattering. Three major processes are identified: the proton hopping relay, the hop-and-turn process, and molecular diffusion. The proton hopping relay can occur even at low temperatures (<120 K), and it transports a specific portion of embedded protons to the surface. The hop-and-turn mechanism, which involves the coupling of proton hopping and molecule reorientation, increases the proton transfer rate and causes the HD exchange of water molecules. The hop-and-turn mechanism is activated at temperatures above 125 K in the surface region. Diffusional mixing of H(2)O and D(2)O molecules additionally contributes to the HD exchange reaction at temperatures above 130 K. The hop-and-turn and molecular diffusion processes are activated at higher temperatures in the deeper region of ice films. The relative speeds of these processes are in the following order: hopping relay>hop and turn>molecule diffusion.     

Water adsorption, desorption, and clustering on FeO(111)

The adsorption of water on FeO(111) is investigated using temperature programmed desorption (TPD) and infrared reflection absorption spectroscopy (IRAS). Well-ordered 2 ML thick FeO(111) films are grown epitaxially on a Pt(111) substrate. Water adsorbs molecularly on FeO(111) and desorbs with a well resolved monolayer peak. IRAS measurements as a function of coverage are performed for water deposited at 30 and 135 K. For all coverages (0.2 ML and greater), the adsorbed water exhibits significant hydrogen bonding. Differences in IRAS spectra for water adsorbed at 30 and 135 K are subtle but suggest that water adsorbed at 135 K is well ordered. Monolayer nitrogen TPD spectra from water covered FeO(111) surfaces are used to investigate the clustering of the water as a function of deposition or annealing temperature. Temperature dependent water overlayer structures result from differences in water diffusion rates on bare FeO(111) and on water adsorbed on FeO(111). Features in the nitrogen TPD spectra allow the monolayer wetting and 2-dimensional (2D) ordering of water on FeO(111) to be followed. Voids in a partially disordered first water layer exist for water deposited below 120 K and ordered 2D islands are found when depositing water above 120 K.     

Thermally induced mixing of water dominated interstellar ices

Despite considerable attention in the literature being given to the desorption behaviour of smaller volatiles, the thermal properties of complex organics, such as ethanol (C(2)H(5)OH), which are predicted to be formed within interstellar ices, have yet to be characterized. With this in mind, reflection absorption infrared spectroscopy (RAIRS) and temperature programmed desorption (TPD) have been used to probe the adsorption and desorption of C(2)H(5)OH deposited on top of water (H(2)O) films of various thicknesses grown on highly oriented pyrolytic graphite (HOPG) at 98 K. Unlike many other molecules detected within interstellar ices, C(2)H(5)OH has a comparable sublimation temperature to H(2)O and therefore gives rise to a complicated desorption profile. RAIRS and TPD show that C(2)H(5)OH is incorporated into the underlying ASW film during heating, due to a morphology change in both the C(2)H(5)OH and H(2)O ices. Desorption peaks assigned to C(2)H(5)OH co-desorption with amorphous, crystalline (CI) and hexagonal H(2)O-ice phases, in addition to C(2)H(5)OH multilayer desorption are observed in the TPD. When C(2)H(5)OH is deposited beneath ASW films, or is co-deposited as a mixture with H(2)O, complete co-desorption is observed, providing further evidence of thermally induced mixing between the ices. C(2)H(5)OH is also shown to modify the desorption of H(2)O at the ASW-CI phase transition. This behaviour has not been previously reported for more commonly studied volatiles found within astrophysical ices. These results are consistent with astronomical observations, which suggest that gas-phase C(2)H(5)OH is localized in hotter regions of the ISM, such as hot cores.     

Glycine-ice nanolayers: morphology and surface energetics

Ultrathin glycine-ice films (nanolayers) have been prepared in ultrahigh vacuum by condensation of H(2)O and glycine at 110 K and 150 K on single crystalline Al(2)O(3) surfaces and have been investigated by temperature programed thermal desorption, x-ray photoelectron spectroscopy, and work function measurements. Various layer architectures have been considered, including glycine-on-ice, ice-on-glycine, and mixed glycine-ice nanolayers. Low coverages of adsorbed glycine molecules on amorphous ice surfaces suppress the amorphous-to-crystalline phase transition in the temperature range 140-160 K in near-surface regions and consequently lead to a lower desorption temperature of H(2)O molecules than from pure ice layers. Thicker glycine overlayers on ice provide a kinetic restriction to H(2)O desorption from the underlying ice layers until the glycine molecules become mobile and develop pathways for water desorption at higher temperature (>170 K). Ice overlayers do not wet glycine film surfaces, but the glycine molecules on ice are sufficiently immobile at 110 K, so that continuous glycine overlayers form. In mixed glycine-ice nanolayers the glycine phase displays hydrophobic behavior and a phase separation takes place, with the accumulation of glycine near the surfaces of the films.     

Structural evolution of perfluoro-pentacene films on Ag(111): transition from 2D to 3D growth

The structural evolution and thermal stability of perfluoro-pentacene (PF-PEN) thin films on Ag(111) have been studied by means of low-temperature scanning tunnelling microscopy (STM), low-energy electron diffraction (LEED), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and thermal desorption spectroscopy (TDS). Well-defined monolayer films can be prepared by utilizing the different adsorption energy of mono- and multilayer films and selectively desorbing multilayers upon careful heating at 380 K, whereas at temperatures above 400 K, a dissociation occurs. In the first monolayer, the molecules adopt a planar adsorption geometry and form a well-ordered commensurate (6 × 3) superstructure where molecules are uniformly oriented with their long axis along the <110> azimuth. This molecular orientation is also maintained in the second layer, where molecules exhibit a staggered packing motif, whereas further deposition leads to the formation of isolated, tall islands. Moreover, on smooth silver surfaces with extended terraces, growth of PF-PEN onto beforehand prepared long-range ordered monolayer films at elevated temperature leads to needle-like islands that are uniformly aligned at substrate steps along <110> azimuth directions.     

Molecular dynamics simulations of D2O ice photodesorption

Molecular dynamics (MD) calculations have been performed to study the ultraviolet (UV) photodissociation of D(2)O in an amorphous D(2)O ice surface at 10, 20, 60, and 90 K, in order to investigate the influence of isotope effects on the photodesorption processes. As for H(2)O, the main processes after UV photodissociation are trapping and desorption of either fragments or D(2)O molecules. Trapping mainly takes place in the deeper monolayers of the ice, whereas desorption occurs in the uppermost layers. There are three desorption processes: D atom, OD radical, and D(2)O molecule photodesorption. D(2)O desorption takes places either by direct desorption of a recombined D(2)O molecule, or when an energetic D atom produced by photodissociation kicks a surrounding D(2)O molecule out of the surface by transferring part of its momentum. Desorption probabilities are calculated for photoexcitation of D(2)O in the top four monolayers and are compared quantitatively with those for H(2)O obtained from previous MD simulations of UV photodissociation of amorphous water ice at different ice temperatures [Arasa et al., J. Chem. Phys. 132, 184510 (2010)]. The main conclusions are the same, but the average D atom photodesorption probability is smaller than that of the H atom (by about a factor of 0.9) because D has lower kinetic energy than H, whereas the average OD radical photodesorption probability is larger than that of OH (by about a factor of 2.5-2.9 depending on ice temperature) because OD has higher translational energy than OH for every ice temperature studied. The average D(2)O photodesorption probability is larger than that of H(2)O (by about a factor of 1.4-2.3 depending on ice temperature), and this is entirely due to a larger contribution of the D(2)O kick-out mechanism. This is an isotope effect: the kick-out mechanism is more efficient for D(2)O ice, because the D atom formed after D(2)O photodissociation has a larger momentum than photogenerated H atoms from H(2)O, and D transfers momentum more easily to D(2)O than H to H(2)O. The total (OD + D(2)O) yield has been compared with experiments and the total (OH + H(2)O) yield from previous simulations. We find better agreement when we compare experimental yields with calculated yields for D(2)O ice than when we compare with calculated yields for H(2)O ice.     

A detailed TPD study of H2O and pre-adsorbed O on the stepped Pt(553) surface

Water molecules desorbing from the bare Pt(553) surface desorb in a three peak structure, associated with, respectively, desorption from step and terrace sites and the water multilayer. Upon pre-covering the step sites with O(ad) we mainly observe OH formation on step sites. When terrace sites are also pre-covered with O(ad), OH(terrace) formation is favored over OH(step) formation, presumably because OH formed at terrace sites is more easily incorporated in a hydrogen bonded network of OH/H(2)O. This is a gradual process: with increasing θ(O) less OH(step) is formed. Thus, in spite of the fact that OH at step sites has a higher binding energy than OH at terrace sites, the possibility of the formation of OH at terrace sites actually inhibits the formation of OH at step sites, leaving O(step) as the most stable water dissociation product on the step.