Angle and speed distributions of hydrogen desorbing thermally from metal surfaces

On the basis of the theory developed in a previous paper (Part I), the angle and speed distributions of D₂ molecules desorbing thermally from the Ni(111) surface are numerically calculated in the present paper (Part II). The dynamical motion of the activated complex of the recombinative desorption process is calculated by using a model potential surface, which involves a few parameters introduced to describe the necessary features of the potential surface at the transition state. Numerical calculations are carried out, and the results show that the present dynamical theory reproduces very well a variety of the characteristic features of the experimental results, e.g., sharply focused angular distribution, mean translational energy lower than 2k _B T at grazing angle, and the non-Maxwellian profile of the TOF distribution.     

Angle and speed distributions of hydrogen desorbing thermally from metal surfaces

A quantum theoretical treatment of the angle and speed distributions of recombinatively desorbing hydrogen from metal surfaces is proposed. The desorption rate is discussed in the framework of the transition state theory. The recombinative reaction process of hydrogen due to thermal activation leads to the formation of an activated complex in the transition state. In the vicinity of a saddle point on a three-dimensional potential energy surface, the translational motion of the activated complex in the direction perpendicular to the metal surface is accompanied by its center-of-mass vibrational motion parallel to the metal surface. In order to carry out the quantum mechanical calculation, the potential surface is replaced by a simplified model potential, which provides a square potential barrier along the surface normal. It is shown that, on leaving the potential barrier, the activated complex is reflected by the boundary of the potential barrier with a certain probability and, at the same time, the center-of-mass modes of vibration with frequencies v ₁ and v ₂ are coupled with the translational motion along the surface normal. Vibrational wave functions in the momentum representation are used to calculate the transmission coefficient, which is incorporated into the conventional rate formula. The angle-dependent speed distributions of desorbing molecules are derived from the rate formula.     

Laser-induced desorption of overlayer films off a heated metal substrate

The temperature-induced desorption of adsorbed overlayer films with thicknesses between 4 and 200 ML off a suddenly heated metal substrate is studied using molecular-dynamics simulation. We observe that the rapid heating vaporizes the surface-near part of the overlayer film. The initial heating-induced thermoelastic pressure and the vapor pressure in the vapor film drive the remaining film as a large relatively cold cluster away from the surface. In our simulations, the material present in the developing vapor film amounts to roughly 2 ML and is quite independent of the overlayer film thickness. For cluster thicknesses beyond 40 ML, the desorption time increases only little with film thickness, while the resulting cluster velocity decreases only slightly.     

Isotope effects in the kinetics of simultaneous H and D thermal desorption from Pd

The kinetics of simultaneous hydrogen and deuterium thermal desorption from PdH_xD_y has been investigated. A novel experimental approach for the study of the transition state (TS) characteristics of the surface recombination reaction is proposed based on the analysis of the H and D partitioning into H₂, HD and D₂ molecules. It has been found that the hydrogen molecular isotopes distribution is determined by the energy differences of the corresponding TS of the atom-atom recombination reactions. On the other hand, the mechanisms and activation energies of the desorption process have been obtained. At 420 K, the desorption reaction changes from a surface recombination limiting mechanism during desorption from β-PdH_xD_y to a reaction limited by the rate of β to α phase transformation during the two phase coexistence. Surface recombination reaction becomes again rate limiting above 480 K, due to a change in the catalytic properties of the Pd surface. TS energies obtained from the kinetic analysis of the thermal desorption spectra are in good accordance with those obtained from the analysis of the H₂, HD and D₂ distributions. Anomalous TS energies have been observed for the H-D recombination reaction, which may be related to the heteronuclear character of this molecule.     

Kinetic lattice gas model: Langmuir,Ising and interaction kinetics

The kinetic lattice gas model is formulated properly to account for adsorption, desorption, and diffusion at surfaces. We examine three choices for the transition probabilities in the master equation, which we term Langmuir, Ising and interaction kinetics, and show how they lead to different sticking coefficients and desorption rates.     

Visualisation of a supersonic free-jet expansion using laser-induced fluorescence spectroscopy: Application to the measurement of rate constants at ultralow temperatures

2 Σ⁺, v^′=0) by air at 26±4 K. A value of 2.56±0.40×10^-10 molecule^-1 cm³ s^-1 was obtained, a factor of more than four higher than at room temperature, and consistent with attractive forces dominating the quenching of OH(A²Σ⁺). A d etailed computational fluid dynamics (CFD) simulation of the supersonic free-jet expansion was performed, providing a two-dimensional visualisation of temperature and density variations throughout the expansion. The CFD calculations reproduced the salient features of the experimental temperature and density profiles along the centreline. Comparison between experiment and computation has allowed validation of CFD codes. Received: 31 January 1997/Revised version: 24 March 1997     

The influence of the “hot”-dimer adsorption mechanism on the kinetics of a monomer-dimer surface reaction

Hot dimers are molecules which after adsorption dissociate and each of the remaining hot monomers fly apart up to a maximum distance R from the original adsorption site. The influence of the hot-dimer adsorption mechanism on relevant aspects of the bimolecular catalyzed reaction of the type A – (1/2)B ₂(hot) AB is studied by means of the Monte-Carlo simulation technique. The temporal evolution of both the reactant's coverages as well as the rate of AB-production is evaluated and discussed. Due to the enhanced probability of hot species for encounters with other adsorbed particles, the rate of AB-production becomes faster when increasing R. This behavior may be relevant in the dynamic of some catalyzed reactions such as for example the oxidation of carbon monoxide on transition metal surfaces, i.e. ACO, B ₂O₂, and ABCO₂. Also the sticking coefficient of hot dimers and the average distance traveled by the hot monomers are evaluated and discussed.     

Kinetics of domain wall pinning in an incommensurate Pb overlayer on a Cu(110) surface

We have used grazing incidence X-ray scattering to study the kinetics of domain wall pinning during the transition between an incommensurate phase and a domain wall glass phase. The growth of both domain wall density and domain size are described by power-laws. The results are discussed in the context of recent theoretical models of growth.     

In situ investigation of the catalytic reaction H2+< ![IGNORE[O2→H2 O with second-harmonic generation

2 +O₂→H₂ O in the pressure range 0.2 Torr≤p_tot≤10 Torr on Pt(111) surface. At a catalyst temperature of T=700 K the equilibrium oxygen coverage θ_o is determined as a function of hydrogen partial pressure α. The experimentally obtained θ_o is modelled in a two step process considering the mass transport in the gas phase as well as the catalytic reaction on the surface. In this pressure range the mass transport in the gas phase changes from molecular flow conditions to laminar flow, inducing a strong modification of the gas phase present at the catalyst through different diffusivities of the reactants as well as through desorbing reaction products from the catalyst. It is shown that these gas phase alterations have to be taken into account for a proper modelling of the surface mechanism. Simulation calculations allow one to identify the sequential hydrogen addition reaction as the main reaction path for water production in this parameter range. Excellent agreement with previous investigations is obtained for the determined activation energies of the water-producing reaction steps equal to E^f _H2O≥0.7 eV. Received: 20 September 1998 / Revised version: 15 December 1998     

Small rafts of xenon physisorbed on Pt(111)

The behavior of small rafts of xenon (<50 particles) is illustrated. Events which involve collective motion of raft atoms are shown to occur. These events are persistent below a transition temperature and are not persistent above this temperature. A video of the events is available.     

Atomic dynamics of explosive boiling of liquid-argon films

Using molecular-dynamics simulation, we study the explosive boiling of thin liquid-argon films adsorbed on a metal surface. This process might be induced by heating the metal substrate by an ultra-fast laser. Upon sudden heating of the metal to temperatures well beyond the critical temperature of Ar, the film starts boiling. While thin films, with thickness below seven monolayers, fragment completely, in larger films only the near-surface Ar layers vaporize. The resulting vapor pressure drives the expansion of the remaining liquid overlayers. By monitoring the space and time dependence of the hydrodynamic variables density, pressure, and temperature, as well as the local thermodynamic state in the Ar sample, we obtain a detailed microscopic picture of the explosive boiling process. Finally, as a result of the fragmentation process, the abundance distribution of the clusters formed in the expansion follows a power-law distribution for cluster sizes m ≲ 10.     

Dynamical anomalies in physisorbed films of Sn(CH3) and Fe(CO)5 on graphite basal plane

Several dynamical properties of Sn(CH₃)₄ and Fe(CO)₅ molecules physisorbed on graphite, are influenced by the form of two-dimensional solid growth. As inferred from Mössbauer results, at temperatures where the molecules form solid superstructures and below monolayer coverages, abnormal changes are observed in the mean squared displacement of the molecules. It is suggested that these dynamical anomalies are associated with substrate-adsorbate registry.     

Interaction of atomic hydrogen with metal surfaces

Received: 23 March 1998/Accepted: 21 August 1998     

Chemical adsorption of C60 on diamond (100)(2×1) surfaces

Molecular-dynamics simulations (MDSs) and ab initiocalculations are used to investigate the adsorption behavior of C₆₀ molecules on a clean dimer-reconstructed (100)(2×1) diamond surface. C₆₀ molecules have some probability to be adsorbed on the diamond surface at low incident energy (6∼45 eV). Electron-density contours show strong chemical interaction between C₆₀ molecules and the substrate surface. The adsorption property depends strongly on the incident energy and the impacting point. An incident energy of 18 eV may be an appropriate energy to grow a sub-monolayer or monolayer C₆₀ film on a clean C(100)(2×1) surface at room temperature. Received: 5 July 2000 / Accepted: 17 October 2000 / Published online: 28 February 2001     

Kinetics of laser-induced Au pyrolytic deposition from the liquid phase

Kinetics of Au pyrolytic deposition from organic solutions of triphenyl phosphine complexes induced by a copper-vapor laser beam is studied experimentally. Activation energies T _a and pre-exponential factors are determined for 7 different Au complexes. Measured T _a values range from 1800 K to 9400 K. The average temperature of the GaAs wafer is found to be 70° C for a laser beam power of 10 mW.     

A polarized CARS investigation of the fine structure population inversion of Cl atoms from laser photolysis of ICl and the quenching of Cl(2 P 1/2) by O2

The time resolved polarized CARS technique has been used to detect Cl atoms produced by photolysis of ICl in the presence and absence of O₂. A population inversion was observed between the ground state electronic levels Cl(² P _1/2) and Cl(² P _3/2). The rate constant for Cl(² P _1/2) decay (quenching + reaction) in ICl was determined to be (3.2±0.2)×10^–13 cm³/molecule×s; the rate constant for Cl(² P _3/2) reaction with ICl was determined to be (7.8±0.5)×10^–12 cm³/molecule×s; and the rate constant for Cl(² P _1/2) quenching by O₂ was determined to be (1.9±0.2)×10^–13 cm³/molecule×s.     

On the adsorption and desorption of H2 at metal surfaces

Recent technological developments have made possible measurements of the distribution of internal levels of molecules desorbing from a hot surface. Such measurements provide new information concerning the desorption process and the potential energy surface (PES) that governs it. Associative, or re-combinative desorption is of particular interest because the distributions of internal levels reflect the manner in which the molecular bond is formed as the desorbing species leaves the surface. As the simplest associative desorption systems, H₂ and D₂ adsorbing on and desorbing from metal surfaces deserve special attention and serve as prototypes for systems with a more complex chemistry. In this note I review briefly from the theoretical point of view some features of the interaction of H₂ with metals and their relevance to associative adsorption and dissociative sticking.     

Valence and core excitations in rare gas mono- and multilayers: Production,decay, and desorption of neutrals and ions

The aim of this survey is the understanding of the dynamics of medium to high energy excitations in simple condensed systems on very short time scales. For this purpose we examine the modifications of the electronic excitations and their evolution in rare gases (mainly Ar and Kr) due to a nearby metal surface (monolayer case) or by embedding into a rare gas condensate (multilayers). Ionic excitations are shifted to lower energies compared to the gas phase by polarization of the surroundings, while neutral excitations stay constant or are shifted to somewhat higher energies. This decreases the spacing between excitonic and ionic states from both sides. Deexcitation events can be analysed by linewidths for valence excitations, and by comparison of autoionisation and Auger spectra for core excitations. For monolayers, we conclude that excitonic states are unstable relative to ionic states but nevertheless are quite long-lived. For multilayers, only minor modifications relative to the gas phase are usually found. All electronic excitations in Ar and Kr mono- or multilayers lead to desorption of neutrals; core excitations in multilayers also lead to ions and cluster ions. The probable mechanisms in all cases are discussed, and open questions are pointed out.