Mechanisms of H2 dissociative adsorption on the Pt(211) stepped surface

We utilize classical trajectory calculations to study the reaction dynamics of the dissociative adsorption of H2 on the stepped Pt(211) surface. The potential-energy surface has been obtained through an accurate interpolation of density-functional theory data at the generalized gradient approximation level, using the corrugation reduction procedure. New techniques for visualizing the collective dynamics of trajectories are introduced to elucidate the reaction mechanisms involved. Reaction exhibits a nonmonotonic dependence on collision energy, first decreasing with energy, and then increasing. A strong component of direct nonactivated reaction exists at the top edge of the step over the entire range of energies. The inverse relationship between reaction and collision energy at low energies is attributed to trapping in weak chemisorption wells. These wells also influence the direct reaction at the step, leading to a strong asymmetric dependence on incidence angle. Reaction on the terrace is activated, and only contributes significantly at high energies. Agreement with experiments on Pt(533) [A. T. Gee, B. E. Hayden, C. Mormiche, and T. S. Nunney, J. Chem. Phys. 112, 7660 (2000); Surf. Sci. 512, 165 (2002)] is good, and we are able to suggest new interpretations of the experimental data.     

Six-dimensional quantum dynamics of H2 dissociative adsorption on the Pt(211) stepped surface

Results of experimental studies, and theoretical calculations utilizing classical trajectories, have shown that dissociation of H2 on the Pt(211) stepped surface is enhanced at low energies by a molecular trapping mechanism. Because quantum effects can play a large role at the low energies and long lifetimes that characterize molecular trapping, we have undertaken quantum dynamics calculations for this system, the first to treat all molecular degrees of freedom of a gas molecule reacting on a stepped metallic surface. The calculations show that molecular trapping persists in the quantum system, but only at much lower energies than experimentally seen, pointing to possible deficiencies in the potential energy surface. Classical and quasiclassical trajectory calculations on the same potential provide a reasonable picture of reaction overall, but many of the finer details are inaccurate, and certain classical reaction mechanisms are entirely invalid. We conclude that some skepticism should be shown toward any classical study for which long-lived trapping states play a role.     

On the kinetics of oxygen adsorption over stepped Pt surface

A model of adsorption kinetics is considered in which adsorption proceeds at a high rate (s_o=1.0) on steps only, and then Oads can migrate to terraces and back. For E_dif from steps on terraces 75 kJ/mol, the lg s vs. () dependence at 300 K is close to linear.     

Kinetics of dissociative adsorption on stepped surfaces of platinum

The kinetics of dissociative adsorption of oxygen was studied by the Monte Carlo method for a model which supposed that absorption occurs with a high rate only on steps and that O_ads may migrate from steps onto terraces and backward. At the relatively low activation energy of diffusion from steps onto terraces E_dif∼ 75 kJ/mol (E_dif is lower by 4 kJ/mol in the back direction), the function log(s(θ)), wheres is the sticking coefficient and θ is the surface coverage by oxygen atoms, is almost linear at 300 K; that is, the Roginskii-Elovich adsorption equation is obeyed. If it is supposed that the bonding energy of adatoms on terraces is slightly higher than that on steps, and the sticking coefficient is constant and equal to s₀ up to high degrees of coverage as well as in the model of the kinetics of adsorption with a precursor state. Deceased.     

Adsorption and diffusion on a stepped surface: atomic hydrogen on Pt(211)

We present density functional theory calculations for atomic hydrogen interacting with a stepped surface, the Pt(211) surface. The calculations have been performed at the generalized gradient approximation level, using a slab representation of the surface. This is the state-of-the-art method for calculating the interaction of atoms or molecules with metal surfaces, nevertheless only few studies have used it to study atoms or molecules interacting with stepped surfaces, and none, to the best of our knowledge, have considered hydrogen interacting with stepped platinum surfaces. Our goal has been to initiate a systematic study of this topic. We have calculated the full three-dimensional potential energy surface (PES) for the H/Pt(211) system together with the vibrational band structure and vibrational eigenfunctions of H. A deep global minimum of the PES is found for bridge-bonded hydrogen on the step edge, in agreement with experimental results for the similar H/Pt(533) system. All the local vibrational excitations at the global minimum have been identified, and this will serve as a helpful guide to the interpretation of future experiments on this (or similar) system(s). Furthermore, from the calculated PES and vibrational band structure, we identify a number of consequences for the interpretation or modelling of diffusion experiments studying the coverage and directional dependence of atomic hydrogen diffusion on stepped platinum surfaces.     

On the dynamics of H2 adsorption on the Pt(111) surface

The dynamics and kinetics of the dissociation of hydrogen over the hexagonal close packed platinum (Pt(111)) surface are investigated using Car–Parrinello molecular dynamics and static density functional theory calculations of the potential energy surfaces. The calculations model the reference energy‐resolved molecular beam experiments, considering the degrees of freedom of the catalytic surface. Two‐dimensional potential energy surfaces above the main sites on Pt(111) are determined. Combined with Car–Parrinello trajectories, they confirm the dissociative adsorption of H₂ as the only adsorption pathway on this surface at H₂ incindence energies above 5 kJ/mol. A direct determination of energy‐resolved sticking coefficients from molecular dynamics is also performed, showing an excellent agreement with the experimental data at incidence energies in the 5–30 kJ/mol range. Application of dispersion corrections does not lead to an improvement in the prediction of the H₂ sticking coefficient. The adsorption reaction rate obtained from the calculated sticking coefficients is consistent with experimentally derived literature values.     

Direct sticking and differential adsorption heats as probes of structural transitions: O2 on the stepped Ni[211] surface

Coverage-dependent heats of adsorption and sticking probabilities for oxygen on Ni[211] have been measured at 300 K using single-crystal adsorption calorimetry. The data are consistent with a switch from dissociative chemisorption at low coverage to oxide formation above 2 ML adatom coverage. The initial heat of adsorption is 620 kJ mol(-)(1), considerably higher than for any low Miller index nickel surface; this is attributed to the presence of low coordination step atoms that are preferably occupied up to 1 ML. As the coverage increases, the heat is found to drop very rapidly, indicating the presence of strong lateral adatom repulsions, which ultimately drive a transition from the chemisorption regime to oxide film formation at higher coverage. The shape of the coverage-dependent sticking probability is consistent with a direct adsorption mechanism at low coverage. At higher coverage, the transition between the chemisorption and oxidation regimes is relatively complex compared with low Miller index nickel surfaces. This is discussed in terms of the influence of the step sites on the [211] surface.     

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.     

TPD and FT-IRAS investigation of ethylene oxide (EtO) adsorption on a Au(211) stepped surface

Adsorption of ethylene oxide, CH(2)CH(2)O (EtO), on a Au(211) stepped surface was studied by temperature programmed desorption (TPD) and Fourier transform infrared reflection-absorption spectroscopy (FT-IRAS). Ethylene oxide was completely reversibly adsorbed, and desorbed molecularly during TPD following adsorption on Au(211) at 85 K. EtO TPD peaks appeared at 115 K from the multilayer film and 140 and 170 K from the monolayer. Desorption at 140 K was attributed to EtO desorption from terrace sites, and that at 170 K to EtO desorption from step sites. Desorption activation energies and corresponding adsorption energies were estimated to be 8.4 and 10.3 kcal mol(-1), respectively. The EtO ring (C(2)O) deformation band appeared in IRAS at 865 cm(-1) for EtO in multilayer films and when adsorbed in the monolayer at terrace sites. The stronger chemisorption bonding of EtO at Au step sites slightly weakens the bonding within the molecule and causes a small red-shift of this band to 850 cm(-1) for adsorption at step sites. EtO presumably binds via the oxygen atom to the surface, and observation of the EtO-ring absorption band in IRAS establishes that the molecular ring plane of EtO adsorbed at step and terrace sites is nearly upright with respect to the crystal surface plane.     

Calculation of the adsorption of interacting molecules on a stepped surface

A theory of adsorption which allows simultaneously for the nonuniformity of a surface and for lateral interactions between the adsorbed species is able to account for the main features of a stepped surface. The effect of the above factors on the adsorption isotherm and the heat of adsorption is investigated. A sudden increase in the heat of adsorption is predicted when an ordered distribution of the adsorbed species has been realized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1943–1948, September, 1989.     

The reaction rate for dissociative adsorption of N2 on stepped Ru(0001): six-dimensional quantum calculations

Quantum-mechanical calculations of the reaction rate for dissociative adsorption of N2 on stepped Ru(0001) are presented. Converged six-dimensional quantum calculations for this heavy-atom reaction have been performed using the multiconfiguration time-dependent Hartree method. A potential-energy surface for the transition-state region is constructed from density-functional theory calculations using Shepard interpolation. The quantum results are in very good agreement with the results of the harmonic transition-state theory. In contrast to the findings of previous model calculations on similar systems, the tunneling effect is found to be small.     

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

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

Vibrational analysis of H2 and D2 adsorption on Pt/SiO2

Vibrational properties of surface species formed upon H2 and D2 exposure of silica supported platinum particles have been investigated with in situ diffuse reflection infrared Fourier transform spectroscopy. Experiments have been performed at 50-250 degrees C, using different platinum loading of the samples in the absence and presence of oxygen. In addition, electronic structure calculations and vibrational analysis have been performed within the density functional theory for H adsorption on a silica cluster, (HO)3SiOSi(OH)3. The spectroscopy experiments showed reversible formation of isolated OH and OD groups on the silica surface when the samples were exposed to H2 and D2, respectively. In addition to the absorption peak corresponding to isolated OH and OD groups, an intense broad band was observed around 3270 cm(-1) (2500 cm(-1)) during H2 (D2) exposure. Supported by the calculations, this band was assigned to perturbed OH groups on the silica surface. The surface coverage of new OH groups was found to correlate to the platinum loading in the samples, indicating that the new silanol groups were formed in the vicinity of the Pt particles. In the investigated temperature interval, the formation rate of OH groups was not found to be temperature dependent.     

On the different adsorption behavior of bismuth,sulfur, selenium and tellurium on a Pt(775) stepped surface

The deposition behavior of sulfur, selenium, tellurium and bismuth on the Pt(775) surface has been studied by cyclic voltammetry. It has been found that bismuth and tellurium deposit preferentially on the step sites. Once the step sites are fully covered by these adatoms, the deposition on the terrace starts. Conversely, step decoration cannot be achieved with sulfur and selenium. For these adatoms, the deposition takes place preferentially on the terrace. The different behavior of the adatoms is related to differences in their electronic properties.     

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.     

Theoretical study of hydrogen dissociative adsorption on the Cu(110) surface

We have calculated the six-dimensional (6D) potential energy surface for H2 in front of a frozen Cu(110) surface using density functional theory for 22 H2-surface configurations and the corrugation reducing procedure to interpolate between them. We carry out classical trajectory calculations on the dissociative adsorption process and find excellent agreement with measurements. We find that it is of prominent importance to account for the rovibrational state distribution in the incident H2 beam. A straightforward analysis leads to the conclusion that the motion along the surface does not play an appreciable role in the dynamics whereas the dynamical role of molecular rotation is crucial. The latter fact precludes any interpretation of dissociation in terms of a static concept such as "barrier distributions."     

Methane dissociative adsorption on the Pt(111) surface over the 300-500 K temperature and 1-10 Torr pressure ranges

The dissociative adsorption of methane on the Pt(111) surface has been investigated and characterized over the 1-10 Torr pressure and 300-500 K temperature ranges using sum frequency generation (SFG) vibrational spectroscopy and Auger electron spectroscopy (AES). At a reaction temperature of 300 K and a pressure of 1 Torr, C-H bond dissociation occurs in methane on the Pt(111) surface to produce adsorbed methyl (CH(3)) groups, carbon, and hydrogen. SFG results suggest that C-C coupling occurs at higher reaction temperatures and pressures. At 400 K, methyl groups react with adsorbed C to form ethylidyne (C(2)H(3)), which dehydrogenates at 500 K to form ethynyl (C(2)H) and methylidyne (CH) species, as shown by SFG. By 600 K, all of the ethylidyne has reacted to form the dissociation products ethynyl and methylidyne. Calculated C-H bond dissociation probabilities for methane, determined by carbon deposition measured by AES, are in the 10(-8) range and increase with increasing reaction temperature. A mechanism has been developed and is compared with conclusions from other experimental and theoretical studies using single crystals.     

A density functional theory study of molecular and dissociative adsorption of H2 on active sites in mordenite

Adsorption and chemisorption of H2 in mordenite is studied using ab initio density functional theory (DFT) calculations. The geometries of the adsorption complex, the adsorption energies, stretching frequencies, and the capacity to dissociate the adsorbed molecule are compared for different active sites. The active centers include a Br?nsted acid site, a three-coordinated surface Al site, and Lewis sites formed by extraframework cations: Na+, Cu+, Ag+, Zn2+, Cu2+, Ga3+, and Al3+. Adsorption properties of cations are compared for a location of the cation in the five-membered ring. This location differs from the location in the six-membered ring observed for hydrated cations. The five-membered ring, however, represents a stable location of the bare cation. In this position any cation exhibits higher reactivity compared with the location in the six-membered ring and is well accessible by molecules adsorbed in the main channel of the zeolite. Calculated adsorption energies range from 4 to 87 kJ/mol, depending on electronegativity and ionic radius of the cation and the stability of the cation-zeolite complex. The largest adsorption energy is observed for Cu+ and the lowest for Al3+ integrated into the interstitial site of the zeolite framework. A linear dependence is observed between the stretching frequency and the bond length of the adsorbed H2 molecule. The capacity of the metal-exchanged zeolite to dissociate the H2 molecule does not correlate with the adsorption energy. Dissociation is not possible on single Cu+ cation. The best performance is observed for the Ga3+, Zn2+, and Al3+ extraframework cations, in good agreement with experimental data.     

On the adsorption and formation of Pt dimers on the CeO2(111) surface

The direct adsorption of Pt(2) dimers on CeO(2)(111) and their formation from isolated adsorbed Pt atoms have been studied using periodic slab model calculations based on density functional theory and including the so-called on-site Hubbard parameter (GGA + U). In the most stable configuration Pt(2) is found to be almost parallel to the surface; the electronic ground state is closed shell and there is no evidence of charge transfer towards or from the surface. The formation of Pt(2) from two single adsorbed Pt atoms involves a rather small energy barrier of ~0.10 eV only. On the contrary, dissociation of adsorbed Pt(2) requires to overcome a considerable barrier of ~1.43 eV. This indicates that once Pt(2) is formed it will remain on the surface, thus likely triggering the growth of larger supported Pt particles.