Vibrating Water Apart The main route for producing hydrogen for industrial chemical synthesis is steam reforming, in which water and methane react at high temperatures on nickel catalysts to produce hydrogen and carbon dioxide. For both water and methane, the initial dissociation step can be promoted by the translational energy of a molecule as well as its internal vibrational energy, and fundamental studies of these reactions try to determine the relative contributions of these pathways. Although the methane reaction has been well studied, only recently have lasers been available to excite the higher stretching vibrations of water. Hundt et al. (p. 504 ) now report a joint experimental and theoretical study of D 2 O dissociation on the Ni(111) surface. For a given input of energy, vibrational energy was more effective for surmounting the reaction barrier than translational energy.

ABSTRACT:The dissociative chemisorption of methane on metal surfaces is of fundamental and practical interest, being a rate-limiting step in the steam reforming process. The reaction is best modeled with quantum dynamics calculations, but these are currently not guaranteed to produce accurate results because they rely on potential energy surfaces based on untested density functionals and on untested dynamical approximations. To help overcome these limitations, here we present for the first time statistically accurate reaction probabilities obtained with ab initio molecular dynamics (AIMD) for a polyatomic gas-phase molecule reacting with a metal surface. Using a general purpose density functional, the AIMD reaction probabilities are in semiquantitative agreement with new quantum-state-resolved experiments on CHD 3 + Pt(111). The comparison suggests the use of the sudden approximation for treating the rotations even though CHD 3 has large rotational constants and yields an estimated reaction barrier of 0.9 eV for CH 4 + Pt(111). SECTION: Surfaces, Interfaces, Porous Materials, and Catalysis T he steam reforming process, in which methane and water react over a Ni catalyst, is the main commercial source of molecular hydrogen. The dissociation (or dissociative chemisorption) of CH 4 on the catalyst into CH 3 (ad) + H(ad) is a rate-determining step of the full process. 1 Moreover, dissociation of methane on metal surfaces is of fundamental interest. 2−13 Already from early molecular beam experiments, it is known that vibration is very effective in promoting reactivity. 3,4,14 More recently, it has been shown that the reaction is mode-specific, that is, the degree to which energizing the molecule promotes reaction depends on whether the energy is put in translation or vibration and even on which vibration it is put in (vibrational mode specificity). 5−8 These observations, which have been explained qualitatively on the basis of different models, 9,15 rule out the application of fully statistical models. For some vibrational modes, the vibrational efficacy, which measures how effective putting energy into vibration is at promoting reaction relative to increasing the incidence energy (E i ), is even larger than one. 7,10 In addition, the dissociation of partially deuterated molecules shows bond selectivity; for instance, in CHD 3 , the CH bond can be selectively broken upon excitation to an appropriate initial vibrational state. 11,12 Finally, dissociative chemisorption of methane on metal surfaces represents a current frontier in the theoretical description of the dynamics of reactions of gas-phase molecules on metal surfaces, 15−24 with much current efforts now being aimed at achieving an accurate description of this reaction through high-dimensional quantum dynamics calculations. 16,23,24 A wealth of experiments exist for the methane + Pt(111) system. 3,8,12,17,25−29 There has been considerable debate 2,25 concerning the importance of tunneling in this and similar systems. Recent calculations 17,23,30 suggest only a...

In this work, we study the relatively weak H 2 O− Au interaction on the highly stepped and anisotropic (310) surface with temperature-programmed desorption and X-ray photoelectron spectroscopy. Compared to Au(111), we report an enhanced adsorption energy of H 2 O−Au(310) as observed from the (sub)monolayer desorption peak. This peak shows zero-order desorption kinetics, which we do not explain with a typical two-phase coexistence model but rather by desorption from the ends of one-dimensional structures. These could cover both the steps and (part of) the terraces. We do not observe crystallization of ice clusters as observed on Au(111). This leads to the conclusion that this stepped surface forms a hydrophilic template for H 2 O adsorption. We also notice that the precise orientation of the steps determines the H 2 O binding strength. Despite the surface's enhanced H 2 O interaction, we do not observe any significant H 2 O dissociation. This indicates that the presence of low-coordinated Au atoms is not enough to explain the role of H 2 O in Au catalysis.

Infrared laser excitation of partially deuterated methanes (CH 3 D and CH 2 D 2 ) in a molecular beam is used to control their dissociative chemisorption on a Pt(111) single crystal and to determine the quantum state-resolved dissociation probabilities. The exclusive detection of C−H cleavage products adsorbed on the Pt(111) surface by infrared absorption reflection spectroscopy indicates strong bond selectivity for both methane isotopologues upon C−H stretch excitation. Furthermore, the dissociative chemisorption of both methane isotopologues is observed to be mode-specific. Excitation of symmetric C−H stretch modes produces a stronger reactivity increase than excitation of the antisymmetric C−H stretch modes, whereas bend overtone excitation has a weaker effect on reactivity. The observed mode specificity and bond selectivity are rationalized by the sudden vector projection model in terms of the overlap of the reactant's normal mode vectors with the reaction coordinate at the transition state.

Highly efficient preparation of molecules in a specific rovibrationally excited state for gas/surface reactivity measurements is achieved in a molecular beam using tunable infrared (IR) radiation from a single mode continuous wave optical parametric oscillator (cw-OPO). We demonstrate that with appropriate focusing of the IR radiation, molecules in the molecular beam crossing the fixed frequency IR field experience a Doppler tuning that can be adjusted to achieve complete population inversion of a two-level system by rapid adiabatic passage (RAP). A room temperature pyroelectric detector is used to monitor the excited fraction in the molecular beam and the population inversion is detected and quantified using IR bleaching by a second IR-OPO. The second OPO is also used for complete population transfer to an overtone or combination vibration via double resonance excitation using two spatially separated RAP processes. © 2014 AIP Publishing LLC.