Vibrational Energy Redistribution in a Gas-Surface Encounter: State-to-State Scattering of CH_{4} from Ni(111).

The fate of vibrational energy in the collision of methane (CH_{4}) in its antisymmetric C-H stretch vibration (ν_{3}) with a Ni(111) surface has been studied in a state-to-state scattering experiment. Laser excitation in the incident molecular beam prepared the J=1 rotational state of ν_{3}, and a bolometer in combination with selective laser excitation detected the scattered methane. The rovibrationally resolved scattering distributions reveal very efficient vibrational energy redistribution from ν_{3} to the symmetric C-H stretch vibration (ν_{1}). The branching ratio ν_{1}/ν_{3} is near 0.4 and insensitive to changes in incident kinetic energy in the range from 100 to 370 meV. State-resolved angular distributions and measurements of the residual Doppler linewidths prove that the scattering is direct. The observed vibrationally inelastic scattering provides direct experimental evidence for surface-induced vibrational energy redistribution.

CO desorption from a catalytic surface: elucidation of the role of steps by velocity-selected residence time measurements.

Directly measuring the rate of a surface chemical reaction remains a challenging problem. For example, even after more than 30 years of study, there is still no agreement on the kinetic parameters for one of the simplest surface reactions: desorption of CO from Pt(111). We present a new experimental technique for determining rates of surface reactions, the velocity-selected residence time method, and demonstrate it for thermal desorption of CO from Pt(111). We use UV−UV double resonance spectroscopy to record surface residence times at selected final velocities of the desorbing CO subsequent to dosing with a pulsed molecular beam. Velocity selection differentiates trapping-desorption from direct scattering and removes influences on the temporal profile arising from the velocity distribution of the desorbing CO. The kinetic data thus obtained are of such high quality that bi-exponential desorption kinetics of CO from Pt(111) can be clearly seen. We assign the faster of the two rate processes to desorption from (111) terraces, and the slower rate process to sequential diffusion from steps to terraces followed by desorption. The influence of steps, whose density may vary from crystal to crystal, accounts for the diversity of previously reported (single exponential) kinetics results. Using transition-state theory, we derive the binding energy of CO to Pt(111) terraces, D(0)(terr) (Pt−CO) = 34 ± 1 kcal/mol (1.47 ± 0.04 eV) for the low coverage limit (≤0.03 ML) where adsorbate−adsorbate interactions are negligible. This provides a useful benchmark for electronic structure theory of adsorbates on metal surfaces.

Electron hole pair mediated vibrational excitation in CO scattering from Au(111): incidence energy and surface temperature dependence.

We investigated the translational incidence energy (Ei) and surface temperature (Ts) dependence of CO vibrational excitation upon scattering from a clean Au(111) surface. We report absolute v = 0 → 1 excitation probabilities for Ei between 0.16 and 0.84 eV and Ts between 473 and 973 K. This is now only the second collision system where such comprehensive measurements are available - the first is NO on Au(111). For CO on Au(111), vibrational excitation occurs via direct inelastic scattering through electron hole pair mediated energy transfer - it is enhanced by incidence translation and the electronically non-adiabatic coupling is about 5 times weaker than in NO scattering from Au(111). Vibrational excitation via the trapping desorption channel dominates at Ei = 0.16 eV and quickly disappears at higher Ei.

Observation of the adsorption and desorption of vibrationally excited molecules on a metal surface.

The most common mechanism of catalytic surface chemistry is that of Langmuir and Hinshelwood (LH). In the LH mechanism, reactants adsorb, become thermalized with the surface, and subsequently react. The measured vibrational (relaxation) lifetimes of molecules adsorbed at metal surfaces are in the range of a few picoseconds. As a consequence, vibrational promotion of LH chemistry is rarely observed, with the exception of LH reactions occurring via a molecular physisorbed intermediate. Here, we directly detect adsorption and subsequent desorption of vibrationally excited CO molecules from a Au(111) surface. Our results show that CO (v = 1) survives on a Au(111) surface for ~1 × 10-10 s. Such long vibrational lifetimes for adsorbates on metal surfaces are unexpected and pose an interesting challenge to the current understanding of vibrational energy dissipation on metal surfaces. They also suggest that vibrational promotion of surface chemistry might be more common than is generally believed.