Coverage effects in the adsorption of H2 on Pd(100) studied by ab initio molecular dynamics simulations

The interaction of hydrogen with palladium surfaces represents one of the model systems for the study of the adsorption and absorption at metal surfaces. Theoretical gas-surface dynamics studies have usually concentrated on the adsorption dynamics on clean surfaces. Only recently it has become possible, based on advances in the electronic structure codes and improvements in the computer power, to address the much more complex problem of the adsorption dynamics on precovered surfaces. Here, I present ab initio molecular dynamics (AIMD) simulations based on periodic density functional theory (DFT) calculations of the adsorption of H(2) on hydrogen-precovered Pd(100) for a broad variety of different hydrogen coverage structures. The stability of the adsorbate structures and the adsorption dynamics are analyzed in detail. Calculated sticking probabilities are larger than expected for pure site-blocking consistent with experimental results. It turns out that the adsorption dynamics on the strongly corrugated surfaces depends sensitively on the dynamic response of the substrate atoms upon the impact of the impinging H(2) molecules. In addition, for some structures the adsorption probability was evaluated as a function of the kinetic energy. Adsorbate structures corresponding to the same coverage but with different arrangements of the adsorbed atoms can lead to a qualitatively different dependence of the adsorption probability on the kinetic energy changing also the order of the preferred structures, as far as the adsorption is concerned, as a function of the kinetic energy. This indicates that dynamical effects such as steering and dynamical trapping play an important role in the adsorption on these precovered substrates.     

Theoretical study of NO adsorption/dissociation on Pd (100) and (111) surfaces

Both adsorption and dissociation of the diatomic molecular NO on Pd (100) and (111) surfaces are studied using the extended London‐Eyring‐Polyani‐Sato (LEPS) method constructed by means of 5‐MP (the 5‐parameter Morse potential). All critical characteristics of the system that we obtain, such as adsorption geometry, binding energy, eigenvalues for vibration, are in good agreement with the experimental results. On Pd (100) surface, NO prefers to adsorb in fourfold hollow site (H) uprightly at low coverage. With increase in the coverage NO gradually tilts in fourfold hollow and bridge sites. For NO? Pd (111) system, two adsorption states are found at low coverage, of which one adsorption state is the B(tilt) state that the centroid of NO projects at bridge site, another (H? B? H state) that NO almost parallels to the (111) surface with the vibration frequency of 610 cm^?1, but the frequency is near to that of the atoms, which is easy to be ignored in experiments. At high coverage, two transitional states (BH and HT) are found. NO is difficult to dissociate on Pd (100) and (111) surfaces. Especially for NO? Pd (111) system, the three‐well‐potential dissociation mode is initially put forward to show the remarkable dissociation process with two dissociation transitional states of NO on Pd (111). Copyright © 2008 John Wiley & Sons, Ltd.     

Theoretical analysis of dissociative adsorption of H2O on Ni(100)

In conclusion, let us note the principal results of the calculation.

Vibrational spectroscopy study of H2O on Pd/MgO(100) films

A study of water on Pd/MgO(100) films prepared in situ upon Mo(100) single crystals has been performed by using low-energy electron diffraction, high-resolution electron energy-loss spectroscopy, and ultraviolet photoelectron spectroscopy in an ultrahigh vacuum system. The results show that the adsorption of water on MgO(100) film surfaces is enhanced significantly owing to the presence of Pd particles. The formation of a hydroxyl group suggests a dissociation of the water. The size and density of Pd particles on the substrate of MgO(100) films play an important part in the adsorption of water.     

Study of adsorption and decomposition of H2O on Ge(100)

The adsorption and decomposition of water on Ge(100) have been investigated using real-time scanning tunneling microscopy (STM) and density-functional theory (DFT) calculations. The STM results revealed two distinct adsorption features of H2O on Ge(100) corresponding to molecular adsorption and H-OH dissociative adsorption. In the molecular adsorption geometry, H2O molecules are bound to the surface via Ge-O dative bonds between the O atom of H2O and the electrophilic down atom of the Ge dimer. In the dissociative adsorption geometry, the H2O molecule dissociates into H and OH, which bind covalently to a Ge-Ge dimer on Ge(100) in an H-Ge-Ge-OH configuration. The DFT calculations showed that the dissociative adsorption geometry is more stable than the molecular adsorption geometry. This finding is consistent with the STM results, which showed that the dissociative product becomes dominant as the H2O coverage is increased. The simulated STM images agreed very well with the experimental images. In the real-time STM experiments, we also observed a structural transformation of the H2O molecule from the molecular adsorption to the dissociative adsorption geometry.     

The adsorption and decomposition of ethylene on Ni(100)

The adsorption behavior of ethylene on Ni(100) at a variety of temperatures has been studied using temperature programmed desorption, and X-ray and UV photoemission. The adsorption of ethylene at 98 K results in molecular adsorption with a saturation C/Ni ratio of 0.76. Heating this surface to any temperature between 213 and 683 K reduces the C/Ni ratio to 0.5. Exposure to ethylene at 300 K leads to decomposition producing surface carbide, adsorbed hydrogen atoms and an adsorbed C_xH_2x species. A comparison with other work on Ni(111) indicates that ethylene adsorption processes are structure sensitive.     

CO adsorption on Ag(100) and Ag/MgO(100)

Theoretical studies of CO adsorption on a two-layer Ag(100) film and on a two-layer Ag film on a MgO(100) support are reported. Ab initio calculations are carried at the configuration interaction level of theory using embedding methods to treat the metal-adsorbate region and the extended ionic solid. The metal overlayer is considered in two different structures: where Ag-Ag distances are equal to the value in the bulk solid, and for a slightly expanded lattice in which the Ag-Ag distances are equal to the O-O distance on the MgO(100) surface. The calculated adsorption energy of Ag(100) on MgO(100) is 0.58 eV per Ag interfacial atom; the Ag-O distance is 2.28 A. A small transfer of electrons from MgO to Ag occurs on deposition of the silver overlayer. CO adsorption at an atop Ag site is found to be the most stable for adsorption on the two-layer Ag film and also for adsorption on Ag deposited on the oxide; CO adsorption energies range from 0.12 to 0.19 eV. The CO adsorption energy is reduced for the Ag/MgO system compared to adsorption on the unsupported metal film thereby providing evidence for a direct electronic effect of the oxide support at the metal overlayer surface. Expansion of the Ag-Ag distance in the two-layer system also reduces the adsorption energy.     

Multiconfigurational time-dependent Hartree calculations for dissociative adsorption of H2 on Cu(100)

The efficiency of the multiconfigurational time-dependent Hartree (MCTDH) method for calculating the initial-state selected dissociation probability of H(2)(v=0,j=0) on Cu(100) is investigated. The MCTDH method is shown to be significantly more efficient than standard wave packet methods. A large number of single-particle functions is required to converge the initial-state selected reaction probability for dissociative adsorption. Employing multidimensional coordinates in the MCTDH ansatz (mode combination) is found to be crucial for the efficiency of these MCTDH calculations. Perspectives towards the application of the MCTDH approach to study dissociative adsorption of polyatomic molecules on surfaces are discussed.     

Lattice-gas modeling of CO adlayers on Pd(100)

Using a lattice-gas model with pairwise interactions, we study the ordered structures, coverage dependence of the heat of adsorption, and other experimentally observable behavior of adsorbed CO overlayers on Pd(100) single crystal surfaces. Transfer matrix and Monte Carlo methods give accurate information regarding the lattice-gas model that often contradicts simple mean-field-like analysis. We demonstrate the usefulness of the model by reproducing experimental results over a large range of pressures and temperatures.     

Effect of Zn on the adsorption of CO on Pd(111)

Introduction of a second metal can greatly modify the surface reactivity of a host metal. Recently Jeroro and Vohs found that Pd(111) deposited with 0.03-0.06 monolayer of Zn might possess unique activity to methanol steam reforming reaction. To investigate the distribution of the deposited Zn, we examined the adsorption of CO on two types of model systems. In the first model, Zn is in the top-layer of Pd(111) only, while in the second model Zn is placed in the subsurface exclusively. It is found that Zn atoms in the topmost layer show negligible effect on CO adsorption especially at hollow sites, whereas the second layer Zn atoms affect significantly the interaction of CO with the substrate. It is revealed that the negligible influence of the first layer Zn on CO adsorption is due to the offsetting of the ligand effect by the strain effect. On the other hand, the ligand effect dominates the CO adsorption in the second model where the strain effect is insignificant. It is demonstrated that the d-band centers correlate well with the binding energies of the second model, whereas no such good correlation exists for the first model. Our results show that the subsurface plays a more important role and the observed dramatic modification of surface reactivity of Pd(111) deposited with 0.03-0.06 ML Zn is most likely originated from the subsurface Zn atoms, if the coverage is not underestimated and the deposited Zn atoms are distributed uniformly within a layer.     

Structure and reactivity of intermediates. N-overlayer on Pd(100), Rh(100) and Pt-Rh(110) and its reaction with H2

Rh(100), Pt(100), and Pt-Rh(100) surfaces are inert for the dissociative adsorption of N₂, but they are active for the catalytic reaction of NO with H₂ During the reaction on Rh(100) and Pt-Rh(100) surfaces, N atoms are accumulated by making a c(2x2)-N overlayer, but no accumulation of N atoms occurs on Pt(100) surface. The fact that N atoms on the Pt-Rh(100) surface gives the c(2x2) structure indicates that the N atoms have equal affinity to Pt and Rh on the alloy surface. When the c(2x2)-N surface was exposed to H₂ of 10^-7 to 10^-8 Torr, a prominent loss peak being assignable to NH_x appeared at 3200 – 3240 cm^-1 at around 400 K. The in-situ HREELS study proved that NH are prominent species which are formed during the hydrogenation of the c(2x2)-N, that is, a quasi-equilibrium of N + 1/2 H₂ - NH is established. When a clean Pt-Rh(100) (Pt/Rh = 1/3) alloy surface is exposed to NO at about 440 K, the LEED pattern changes sequentially as (1x1) → c(2x2) → c(2x2) + p(3x1) → p(3x1), where the c(2x2) pattern appears instantaneously on the alloy surface of any Pt/Rh ratio but the p(3x1) pattern accompanies a certain characteristic interval times being responsible to the segregation of Rh. The p(3x1) surface reflects the formation of an intermediate of Rh-O complex overlayer and it reacts rapidly with H₂.     

Low temperature adsorption of oxygen on Ni(100)

LEED, AES and data indicate the nonreconstructive character of oxygen adsorption on Ni(100) at 170 K and reconstructive chemisorption at T>270 K with the formation of a c(2×2)0 structure.

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, , Ni (100) 170 >270 (2×2)0.

     

Quantum dynamics of dissociative adsorption of H2 on Ni(100) using the dynamical Lie algebraic method

A dynamical Lie algebraic method has been applied to treating the quantum dynamics of dissociative adsorption of H₂ on a static flat metal surface. An LEPS potential energy surface has been used to describe the interaction of H₂ with Ni(100) surface. The dependence of the initial state-selected dissociation probability was obtained analytically on the initial kinetic energy and time. A comparison with other theoretical calculations and experiments is made. The results show that the method can be effectively used to describe the dynamics of reactive gas-sdace scattering. Project supported by the National Natural Science Foundation of China (Grant No. 19694033) and partially by the State Key Laboratory of Theoretical and Computational Chemistry of Jilin University (Grant No. 9801).     

The influence of preadsorbed hydrogen and CO on adsorption of ethylene on the Pd(111) surface

The coadsorption of C₂H₄ with H₂ and CO on Pd(111) has been investigated at 300 and 330 K At 300 K two forms of adsorbed ethylene coexist on the surface in the presence of ethylene gas: a molecular form desorbing as C₂H₄ at 330 K and a dissociatively adsorbed form (giving only hydrogen in desorption spectra) which is stable both in vacuum and in hydrogen at 10^?8 Torr. The molecular form seems to be a precursor state for hydrogenation and for dissociative adsorption. Both processes are controlled by the amount of coadsorbed hydrogen which in turn is controlled by CO coverage.     

Steering and ro-vibrational effects on dissociative adsorption and associative desorption of H2/Pd(100)

The interaction of hydrogen with many transition metal surfaces is characterized by a coexistence of activated with non-activated paths to adsorption with a broad distribution of barrier heights. By performing six-dimensional quantum dynamical calculations using a potential energy surface derived from ab initio calculations for the system H₂/Pd(100) we show that these features of the potential energy surface lead to strong steering effects in the dissociative adsorption and associative desorption dynamics.

In particular, we focus on the coupling of the translational, rotational and vibrational degrees of freedom of the hydrogen molecule in the reaction dynamics.     

Metal adsorption and adhesion energies on MgO(100)

The calormetically measured heats of adsorption of Cu, Ag, and Pb on MgO(100), previously measured in our group, are correlated with bulk properties of the metals and their sticking probabilities and film morphologies. The low-coverage heats of adsorption (when the metals are mainly in two-dimensional (2D) islands) are used to estimate metal-MgO(100) bond energies within a pairwise bond additivity model. These values correlate well with the observed initial sticking probabilities and saturation island densities of the metals. This supports a transient mobile precursor model for adsorption. The values also correlate with their bulk sublimation energies, which suggests that covalent metal-Mg bonding dominates the interaction at low coverage, probably due to very strong bonding at defects. The heats of adsorption integrated up to multilayer coverages provide the metal-MgO(100) adhesion energies and metal-MgO(100) bond energies for metals in 3D films. These values correlate with the sum of magnitudes of the metal's bulk sublimation energy plus the heat of formation of the bulk oxide of the metal per mole of metal atoms. This suggests that local chemical bonds, both metal-oxygen and covalent metal-Mg, dominate the interfacial bonding for 3D films.     

In situ radiotracer study of thiourea adsorption on n-Si (100) and p-Si (100) electrodes

The application of a radiotracer method to in situ studies of the adsorption of thiourea labelled with either C-14 or S-35 nuclides on smooth n-type and p-type Si (100) electrodes and on rough p-Si electrodes is described. The adsorption takes place over the whole potential range studied, i.e. −0.5 to 1.2 V. It was found that during the interaction of thiourea with the silicon surface, two different products are formed. The dependence of the surface concentration of the adsorbates on the electrode potential and on the bulk concentration of thiourea was determined. Two different species are proposed to be present on the electrode surface as a result of surface processes: physically adsorbed thiourea molecules and sulphur atoms which are chemically bonded to the surface. Different activities of smooth and rough silicon electrodes towards the adsorption of thiourea were demonstrated.     

Water molecule adsorption properties on the BiVO4 (100) surface

The water absorption properties at the surface of BiVO4 are attracting a great deal of attention because the system is a promising candidate as a photocatalyst operating in the visible light range. This has motivated the present investigation via first principles molecular dynamics, which has revealed that a H2O molecule is adsorbed molecularly, instead of dissociatively, at the fivefold Bi site with an adsorption energy of approximately 0.58 eV/molecule. The band gap of the system shrinks slightly (by approximately 0.2 eV) upon water adsorption and it is likely that oxygen atoms belonging to the adsorbed water molecules to the Bi sites are oxidized, as inferred by the small Bi-Owater equilibrium distance (approximately 2.6-2.8 A) very close to the Bi-O bond in the bulk crystal. In the case of water adsorption at a Bi site, the distance between Hwater and V, which is a reduction site, is larger than in the case of adsorption at a V site, indicating that the proton reduction processes may be suppressed.