Fast ortho-to-para conversion of molecular hydrogen in chemisorption and matrix-isolation systems.

Molecular hydrogen has two nuclear-spin modifications called ortho and para. Because of the symmetry restriction with respect to permutation of the two protons, the ortho and para isomers take only odd and even values of the rotational quantum number, respectively. The ortho-to-para conversion is promoted in condensed systems, to which the excess rotational energy and spin angular momentum are transferred. We review recent studies on fast ortho-to-para conversion of hydrogen in molecular chemisorption and matrix isolation systems, discussing the conversion mechanism as well as rotational-relaxation pathways.

Rotational-Energy Transfer in H2 Ortho-Para Conversion on a Metal Surface: Interplay between Electron and Phonon Systems.

Clarifying energy transfer processes in molecular adsorption on solid surfaces is essential to understand the gas-surface interaction. Unlike the vibrational-energy transfer processes, which are thought to be well understood in detail, the rotational-energy transfer process still remains unclear. Considering the interconversion between ortho and para states of H2 is accompanied by the nuclear spin flip and the rotational-energy transfer, the surface-temperature dependence of the ortho-to-para conversion of molecularly chemisorbed H2 on Pd(210) is studied. The conversion rate is accelerated with an increase in surface temperature. Based on the conversion model proposed for metal surfaces, we analyze the temperature dependence of the conversion rate, taking into account both electron and phonon systems of the substrate. The rotational-energy transfer is most likely mediated by surface electrons with the assistance of the substrate phonons.

Probing Copper and Copper-Gold Alloy Surfaces with Space-Quantized Oxygen Molecular Beam.

The orientation and motion of reactants play important roles in reactions. The small rotational excitations involved render the reactants susceptible to dynamical steering, making direct comparison between experiments and theory rather challenging. Using space-quantized molecular beams, we directly probed the (polar and azimuthal) orientation dependence of O2 chemisorption on Cu(110) and Cu3Au(110). We observed polar and azimuthal anisotropies on both surfaces. Chemisorption proceeded rather favorably with the O-O bond axis oriented parallel (vs perpendicular) to the surface and rather favorably with the O-O bond axis oriented along [001] (vs along [1̅10]). The presence of Au hindered the surface from further oxidation, introducing a higher activation barrier to chemisorption and rendering an almost negligible azimuthal anisotropy. The presence of Au also prevented the cartwheel-like rotations of O2.

Steric effect in CO oxidation on Pt(111).

We present experimental evidence showing that the rate of CO oxidation on Pt(111) depends strongly on the geometry of an incident O2 molecule. The O2 sticking probability and the CO2 production rate on CO-covered Pt(111) surfaces during the alignment-controlled O2 beam irradiation were simultaneously monitored at a surface temperature of 330 K. The results indicate that, at the translational energy of 0.1-0.2 eV and at the CO coverage of <0.4 monolayers, both O2 adsorption and CO oxidation proceed exclusively when the O2 molecular axis is nearly parallel to the surface.

Dynamics of O2 Chemisorption on a Flat Platinum Surface Probed by an Alignment-Controlled O2 Beam.

O2 adsorption on Pt surfaces is of great technological importance owing to its relevance to reactions for the purification of car exhaust gas and the oxygen reduction on fuel-cell electrodes. Although the O2 /Pt(111) system has been investigated intensively, questions still remain concerning the origin of the low O2 sticking probability and its unusual energy dependence. We herein clarify the alignment dependence of the initial sticking probability (S0 ) using the single spin-rotational state-selected [(J,M)=(2,2)] O2 beam. The results indicate that, at low translational energy (E0 ) conditions, direct activated chemisorption occurs only when the O2 axis is nearly parallel to the surface. At high energy conditions (E0 >0.5 eV), however, S0 for the parallel O2 decreases with increasing E0 while that of the perpendicular O2 increases, accounting for the nearly energy-independent O2 sticking probability determined previously by a non-state-resolved experiment.

Surface Temperature Dependence of Hydrogen Ortho-Para Conversion on Amorphous Solid Water.

The surface temperature dependence of the ortho-to-para conversion of H_{2} on amorphous solid water is first reported. A combination of photostimulated desorption and resonance-enhanced multiphoton ionization techniques allowed us to sensitively probe the conversion on the surface of amorphous solid water at temperatures of 9.2-16 K. Within a narrow temperature window of 8 K, the conversion time steeply varied from ∼4.1×10^{3} to ∼6.4×10^{2} s. The observed temperature dependence is discussed in the context of previously suggested models and the energy dissipation process. The two-phonon process most likely dominates the conversion rate at low temperatures.

Bond-Selective and Mode-Specific Dissociation of CH3D and CH2D2 on Pt(111).

Infrared laser excitation of partially deuterated methanes (CH3D and CH2D2) 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.

Quantum tunneling observed without its characteristic large kinetic isotope effects.

Classical transition-state theory is fundamental to describing chemical kinetics; however, quantum tunneling is also important in explaining the unexpectedly large reaction efficiencies observed in many chemical systems. Tunneling is often indicated by anomalously large kinetic isotope effects (KIEs), because a particle's ability to tunnel decreases significantly with its increasing mass. Here we experimentally demonstrate that cold hydrogen (H) and deuterium (D) atoms can add to solid benzene by tunneling; however, the observed H/D KIE was very small (1-1.5) despite the large intrinsic H/D KIE of tunneling (≳ 100). This strong reduction is due to the chemical kinetics being controlled not by tunneling but by the surface diffusion of the H/D atoms, a process not greatly affected by the isotope type. Because tunneling need not be accompanied by a large KIE in surface and interfacial chemical systems, it might be overlooked in other systems such as aerosols or enzymes. Our results suggest that surface tunneling reactions on interstellar dust may contribute to the deuteration of interstellar aromatic and aliphatic hydrocarbons, which could represent a major source of the deuterium enrichment observed in carbonaceous meteorites and interplanetary dust particles. These findings could improve our understanding of interstellar physicochemical processes, including those during the formation of the solar system.

Ab Initio Molecular Dynamics Calculations versus Quantum-State-Resolved Experiments on CHD3 + Pt(111): New Insights into a Prototypical Gas-Surface Reaction.

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 CHD3 + Pt(111). The comparison suggests the use of the sudden approximation for treating the rotations even though CHD3 has large rotational constants and yields an estimated reaction barrier of 0.9 eV for CH4 + Pt(111).

Vibrational Activation of Methane Chemisorption: The Role of Symmetry.

Quantum state-resolved reactivity measurements probe the role of vibrational symmetry on the vibrational activation of the dissociative chemisorption of CH4 on Pt(111). IR-IR double resonance excitation in a molecular beam is used to prepare CH4 in all three different vibrational symmetry components A1, E, and F2 of the 2ν3 antisymmetric stretch overtone vibration. Methyl dissociation products chemisorbed on the cold Pt(111) surface are detected via reflection absorption infrared spectroscopy (RAIRS). We observe similar reactivity for CH4 prepared in the A1 and F2 sublevels but up to a factor of 2 lower reactivity for excitation of the E sublevel. It is suggested that differences in the localization of the C-H stretch amplitudes for the three states at the transition state leads to the observed difference in reactivity rather than state-specific vibrational energy transfer to electronic excitation of the metal.

Quantum Tunneling Hydrogenation of Solid Benzene and Its Control via Surface Structure.

Despite the rapid accumulation of structural information about organic materials, the correlation between the surface structure of these materials and their chemical properties, a potentially important aspect of their chemistry, is not fully understood. Here, we show that the amorphous or crystalline structure of a solid benzene surface controls its chemical reactivity toward hydrogen. In situ infrared spectroscopy revealed that cold hydrogen atoms can add to an amorphous benzene surface at 20 K to form cyclohexane by tunneling. However, hydrogenation is greatly reduced on crystalline benzene. We suggest that the origin of the high selectivity of this reaction is the large difference in geometric constraints between the amorphous and the crystalline surfaces. The present findings can lead us to a more complete understanding of heterogeneous reaction systems, especially those involving tunneling, as well as to the possibility of nonenergetic surface chemical modification without undesired side reactions or physical processes.

Quantum state-resolved CH4 dissociation on Pt(111): coverage dependent barrier heights from experiment and density functional theory.

The dissociative chemisorption of CH4 on Pt(111) was studied using quantum state-resolved methods at a surface temperature (T(s)) of 150 K where the nascent reaction products CH3(ads) and H(ads) are stable and accumulate on the surface. Most previous experimental studies of methane chemisorption on transition metal surfaces report only the initial sticking coefficients S0 on a clean surface. Reflection absorption infrared spectroscopy (RAIRS), used here for state resolved reactivity measurements, enables us to monitor the CH3(ads) uptake during molecular beam deposition as a function of incident translational energy (E(t)) and vibrational state (ν3 anti-symmetric C-H stretch of CH4) to obtain the initial sticking probability S0, the coverage dependence of the sticking probability S(θ) and the CH3(ads) saturation coverage θ(sat). We observe that both S0 and θ(sat) increase with increasing E(t) as well as upon ν3 excitation of the incident CH4 which indicates a coverage dependent dissociation barrier height for the dissociation of CH4 on Pt(111) at low surface temperature. This interpretation is supported by density functional calculations of barrier heights for dissociation, using large supercells containing one or more H and/or methyl adsorbates. We find a significant increase in the activation energies with coverage. These energies are used to construct simple models that reasonably reproduce the uptake data and the observed saturation coverages.

Quantum state-resolved gas/surface reaction dynamics probed by reflection absorption infrared spectroscopy.

We report the design and characterization of a new molecular-beam/surface-science apparatus for quantum state-resolved studies of gas/surface reaction dynamics combining optical state-specific reactant preparation in a molecular beam by rapid adiabatic passage with detection of surface-bound reaction products by reflection absorption infrared spectroscopy (RAIRS). RAIRS is a non-invasive infrared spectroscopic detection technique that enables online monitoring of the buildup of reaction products on the target surface during reactant deposition by a molecular beam. The product uptake rate obtained by calibrated RAIRS detection yields the coverage dependent state-resolved reaction probability S(θ). Furthermore, the infrared absorption spectra of the adsorbed products obtained by the RAIRS technique provide structural information, which help to identify nascent reaction products, investigate reaction pathways, and determine branching ratios for different pathways of a chemisorption reaction. Measurements of the dissociative chemisorption of methane on Pt(111) with this new apparatus are presented to illustrate the utility of RAIRS detection for highly detailed studies of chemical reactions at the gas/surface interface.

Vibrationally bond-selected chemisorption of methane isotopologues on Pt(111) studied by reflection absorption infrared spectroscopy.

Reflection absorption infrared spectroscopy (RAIRS) was used to probe for vibrational bond-selectivity in the dissociative chemisorption of three partially deuterated methane isotopologues on a Pt(111) surface. While a combination of incident translational energy and thermal vibrational excitation produces a nearly statistical distribution of C-H and C-D bond cleavage products, we observe that laser excitation of an infrared active C-H stretch normal mode leads to highly selective dissociation of a C-H bond for CHD3, CH2D2, and CH3D. Our results show that vibrational energy redistribution between C-H and C-D stretch modes due to methane/surface interactions is negligible during the sub-picosecond collision time which indicates that vibrational bond-selectivity may be the rule rather than the exception in heterogeneous reactions of small polyatomic molecules.

Evidence of stable high-temperature D(x)-CO intermediates on the Ru(0001) surface.

We demonstrate the formation of complexes involving attractive interactions between D and CO on Ru(0001) that are stable at significantly higher temperatures than have previously been reported for such intermediate species on this surface. These complexes are evident by the appearance of new desorption features upon heating of the sample. They decompose in stages as the sample temperature is increased, with the most stable component desorbing at >500 K. The D:CO ratio remaining on the surface during the final stages of desorption tends towards 1:1. The new features are populated during normally incident molecular beam dosing of D(2) on to CO pre-covered Ru(0001) surfaces (180 K) when the CO coverage exceeds 50% of the saturation value. The amount of complex formed decreases somewhat with increasing CO pre-coverage. It is almost absent in the case of dosing on to the fully saturated surface. The results are interpreted in terms of both local and long-range rearrangements of the overlayer that give rise to the observed CO coverage dependence and limit the amount of complex that can be formed.

The interaction of hyperthermal nitrogen with N-covered Ag(111).

A mixed beam of hyperthermal N atoms and N(2) molecules was scattered from the N-covered Ag(111) surface held at 300 K. The angular distribution of scattered N atoms is very broad. In contrast, N(2) molecules exhibit a sharp angular distribution. Taking into account the relative mass ratio, N loses more energy at the surface than N(2). In terms of energy loss, the atoms approximately follow the binary collision model while the molecules do not. Instead, the energy curves of scattered N(2) are more comparable to the parallel momentum conservation model for near specular outgoing angles (40°-65°). For both atoms and molecules the angle-resolved intensity and final energy curves are very similar to those from the bare surface. However, the N-covered surface yields non-negligible N(2) intensity for a broad range of outgoing angles, including along the surface normal. This was not the case from the clean surface, where the measured intensity distribution was confined to the narrower angular range indicated above. Backscattering and direct abstraction reactions are evaluated as possible origins of this additional N(2) signal. Of these, an abstraction mechanism appears to be the most consistent with the measured data.

The interaction of hyperthermal argon atoms with CO-covered Ru(0001): scattering and collision-induced desorption.

Hyperthermal Ar atoms were scattered under grazing incidence (θ(i) = 60°) from a CO-saturated Ru(0001) surface held at 180 K. Collision-induced desorption involving the ejection of fast CO (∼1 eV) occurs. The angularly resolved in-plane CO desorption distribution has a peak along the surface normal. However, the angular distribution varies with the fractional coverage of the surface. As the total CO coverage decreases, the instantaneous desorption maximum shifts to larger outgoing angles. The results are consistent with a CO desorption process that involves lateral interaction with neighboring molecules. Furthermore, the data indicate that the incident Ar cannot readily penetrate the saturated CO overlayer. Time-of-flight measurements of scattered Ar exhibit two components-fast and slow. The slow component is most evident when scattering from the fully covered surface. The ratio and origin of these components vary with the CO coverage.

Scattering of hyperthermal argon atoms from clean and D-covered Ru(0001) surfaces.

Hyperthermal Ar atoms were scattered from a Ru(0001) surface held at temperatures of 180, 400 and 600 K, and from a Ru(0001)-(1×1)D surface held at 114 and 180 K. The resultant angular intensity and energy distributions are complex. The in-plane angular distributions have narrow (FWHM ≤ 10°) near-specular peaks and additional off-specular features. The energy distributions show an oscillatory behavior as a function of outgoing angle. In comparison, scattered Ar atoms from a Ag(111) surface exhibit a broad angular intensity distribution and an energy distribution that qualitatively tracks the binary collision model. The features observed for Ru, which are most evident when scattering from the clean surface at 180 K and from the Ru(0001)-(1×1)D surface, are consistent with rainbow scattering. The measured TOF profiles cannot be adequately described with a single shifted Maxwell-Boltzmann distribution. They can be fitted by two components that exhibit complex variations as a function of outgoing angle. This suggests at least two significantly different site and∕or trajectory dependent energy loss processes at the surface. The results are interpreted in terms of the stiffness of the surface and highlight the anomalous nature of the apparently simple hcp(0001) ruthenium surface.

Scattering of hyperthermal nitrogen atoms from the Ag(111) surface.

Measurements on scattering of hyperthermal N atoms from the Ag(111) surface at temperatures of 500, 600, and 730 K are presented. The scattered atoms have a two-component angular distribution. One of the N components is very broad. In contrast, scattered Ar atoms exhibit only a sharp, single-component angular distribution. There are noteworthy features in the angle-resolved energy of the scattered N when compared with Ar. Taking into account the relative masses involved, N atoms lose significantly more energy at the surface than Ar. However, there is a preferential loss mechanism that predominantly affects low-energy N atoms with small total scattering angle trajectories. The results are interpreted in terms of probing of different interaction potentials: strongly attractive and almost purely repulsive, and spin-state changes during the interaction of N with the surface appear probable.

CO blocking of D2 dissociative adsorption on Ru(0001).

The influence of pre-adsorbed CO on the dissociative adsorption of D(2) on Ru(0001) is studied by molecular-beam techniques. We determine the initial dissociation probability of D(2) 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 D(2) 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 theta(CO) approximately 0.33 ML. In addition, at high D(2) 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 D(2) dissociation in the vicinity of CO molecules.