Identification of Hydroxyl on Ni(111)

Hydroxyl (OH) is identified and characterized on the Ni(111) surface by high‐resolution electron energy loss spectroscopy. We find clear evidence of stretching, bending, and translational modes that differ significantly from modes observed for H₂O and O on Ni(111). Hydroxyl may be produced from water by two different methods. Annealing of water co‐adsorbed with atomic oxygen at 85 K to above 170 K leads to the formation of OH with simultaneous desorption of excess water. Pure water layers treated in the same fashion show no dissociation. However, the exposure of pure water to 20 eV electrons at temperatures below 120 K produces OH in the presence of adsorbed H₂O. In combination with temperature‐programmed desorption studies, we show that the OH groups recombine between 180 and 240 K to form O and immediately desorbing H₂O. The lack of influence of co‐adsorbed H₂O at 85 K on the O? H stretching mode indicates that OH does not participate in a hydrogen‐bonding network.     

Tuning hydrophobicity of platinum by small changes in surface morphology

Stepped platinum surfaces can become hydrophobic when they are hydrogenated. Even though the Pt(533) and Pt(553) surfaces have similar geometries, the hydrophobicity on the deuterated surface is surprisingly different: on Pt(533) the surface is hydrophobic with water clustering at steps, whereas the entire surface is wet on Pt(553).     

Optimal broadcast on parallel locality models

In this paper matching upper and lower bounds for broadcast on general purpose parallel computation models that exploit network locality are proven. These models try to capture both the general purpose properties of models like the PRAM or BSP on the one hand, and to exploit network locality of special purpose models like meshes, hypercubes, etc., on the other hand. They do so by charging a cost l(|i−j|) for a communication between processors i and j, where l is a suitably chosen latency function.An upper bound T(p)=∑_i=0^loglogp2ⁱ·l(p^1/2i) on the runtime of a broadcast on a p processor H-PRAM is given, for an arbitrary latency function l(k).The main contribution of the paper is a matching lower bound, holding for all latency functions in the range from l(k)=Ω(logk/loglogk) to l(k)=O(log²k). This is not a severe restriction since for latency functions l(k)=O(logk/log¹⁺log(k)) with arbitrary >0, the runtime of the algorithm matches the trivial lower bound Ω(logp) and for l(k)=Θ(log¹⁺k) or l(k)=Θ(k), the runtime matches the other trivial lower bound Ω(l(p)). Both upper and lower bounds apply for other parallel locality models like Y-PRAM, D-BSP and E-BSP, too.     

State-resolved probes of methane dissociation dynamics

A new generation of experimental techniques quantifies the gas–surface reactivity of polyatomic reactants prepared in a single quantum state. These experiments eliminate internal state averaging and permit reactivity measurements on molecules with well-defined internal and translational energy. Varying the identity of the selected vibrational and rotational state and the molecule’s translational energy reveals how energy in specific energetic coordinates promotes reaction. When applied to methane’s dissociative chemisorption, which is rate-limiting in the industrial steam reforming reaction, these experiments reveal the molecular basis for activation, and they provide detailed insight into energy flow dynamics prior to reaction. This review will focus on experiments that quantify the reactivity of methane prepared in select rovibrational quantum states via optical excitation in a supersonic molecular beam. An overview will provide context, and a survey of experimental methods will emphasize features unique to these experiments. A presentation and discussion of state-resolved beam-surface scattering studies of methane activation on Ni(1 1 1), Ni(1 0 0), and Pt(1 1 1) will highlight the mechanistic and dynamical insights that such studies can provide. For example, while C–H stretching excitation best promotes transition state access on Ni(1 1 1) and Ni(1 0 0), bending excitation also activates dissociation, suggesting that many different energetic coordinates contribute to reactivity. Among those states studied, non-statistical behavior, including vibrational mode-specific and even bond-selective chemistry, is widespread, which indicates that the assumptions underlying statistical rate theories do not apply to this reaction. We examine the relevant timescales for energy exchange and reaction to provide a plausible explanation for the observation of non-statistical behavior. Finally, we suggest how these methods, and the results they have produced, might guide future work in the field.     

Comparative study of C-H stretch and bend vibrations in methane activation on Ni(100) and Ni(111)

State-resolved measurements on clean Ni(100) and Ni(111) surfaces quantify the reactivity of CH4 excited to v = 3 of the nu4 bend vibration. A comparison with prior data reveals that 3nu4 is significantly less effective than the nu3 C-H stretch at promoting dissociative chemisorption, even though 3nu4 contains 30% more energy. These results contradict statistical theories of gas-surface reactivity, provide clear evidence for vibrational mode specificity in a gas-surface reaction, and point to a central role for C-H stretching motion along the reaction path to dissociative chemisorption.     

Recent advances in the use of curved single crystal surfaces

In surface science, research traditionally employs macroscopically flat surfaces of single crystals. Curved surfaces have been applied more sporadically, but their history stretches back for many decades. Realization of the potential benefits and practical applications in surface physics and surface chemistry research progressed slowly in the 20th century. In more recent decades, research employing partial cylinders and dome-shaped crystals have found renewed interest. Modern surface sensitive techniques are being employed allowing the inherent large range of surface structures to reveal new insights. We briefly review the history, describe several types of surfaces and the range of structures they contain, suggest a notation for common types of curved surfaces, and discuss recent studies in more detail. We mainly focus on metal samples. We close with a short outlook.     

CO Blocking of D2 Dissociative Adsorption on Ru(0001)

The influence of pre‐adsorbed CO on the dissociative adsorption of D₂ on Ru(0001) is studied by molecular‐beam techniques. We determine the initial dissociation probability of D₂ as a function of its kinetic energy for various CO pre‐coverages between 0.00 and 0.67 monolayers (ML) at a surface temperature of 180 K. The results indicate that CO blocks D₂ dissociation and perturbs the local surface reactivity up to the nearest‐neighbour Ru atoms. Non‐activated sticking and dissociation become less important with increasing CO coverage, and vanish at θ_CO≈0.33 ML. In addition, at high D₂ kinetic energy (>35 kJ mol^?1) the site‐blocking capability of CO decreases rapidly. These observations are attributed to a CO‐induced activation barrier for D₂ dissociation in the vicinity of CO molecules.