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Local field effects at the electrical double layer change the energies of reaction intermediates in heterogeneous electrocatalysis. The resulting dependence on (absolute) electrode potential can be pivotal to a catalyst's performance in acid or alkaline media. And yet, such local field effects are very difficult to describe theoretically and are often ignored. In this work, we focus on O2 adsorption as the first step of the oxygen reduction reaction (ORR) on Au(111). Different physical effects of the local field are elucidated and compared by systematically improving the model of the double layer: from an applied saw-tooth potential in vacuum, to an implicit solvent model, and explicitly modeled water via ab initio molecular dynamics (AIMD). We find all models predict a dominant dipole-field type interaction that significantly strengthens O2 binding at increasingly reducing conditions. However, only an atomically-resolved solvent model such as provided by AIMD can properly capture the additional stabilization due to explicit H-bonding from the water network. This contribution comes with the formation of a peroxo-like surface species and a more dramatic field response around the ORR onset. Our results overall demonstrate the importance of including local electric field effects in models of the electrochemical interface, while assessing the level of detail that is required to be accounted for.

The electronic excitation occurring on adsorbates at ultrafast time scales from optical lasers that initiate surface chemical reactions is still an open question. Here, we report the ultrafast temporal evolution of X-ray absorption spectroscopy (XAS) and X-ray emission spectroscopy (XES) of a simple well known adsorbate prototype system, namely carbon (C) atoms adsorbed on a nickel (Ni(100)) surface, following intense laser optical pumping at 400 nm. We observe ultrafast (~100 fs) changes in both XAS and XES showing clear signatures of the formation of a hot electron-hole pair distribution on the adsorbate. This is followed by slower changes on a few ps time scale, shown to be consistent with thermalization of the complete C/Ni system. Density functional theory spectrum simulations support this interpretation., 33 pages, 12 figures. Submitted to Physical Review Letters

We report optical pumping and X-ray absorption spectroscopy experiments at the PAL free electron laser that directly probe the electron dynamics of a graphene monolayer adsorbed on copper in the femtosecond regime. By analyzing the results with ab-initio theory we infer that the excitation of graphene is dominated by indirect excitation from hot electron-hole pairs created in the copper by the optical laser pulse. However, once the excitation is created in graphene, its decay follows a similar path as in many previous studies of graphene adsorbed on semiconductors, i e. rapid excitation of SCOPS (Strongly Coupled Optical Phonons) and eventual thermalization. It is likely that the lifetime of the hot electron-hole pairs in copper governs the lifetime of the electronic excitation of the graphene., Comment: 22 pages, 8 Figures including Supplementary Material

The journal of chemical physics 157(16), 164705 (2022). doi:10.1063/5.0114399, We report on carbon monoxide desorption and oxidation induced by 400 nm femtosecond laser excitation on the O/Ru(0001) surface probed by time-resolved x-ray absorption spectroscopy (TR-XAS) at the carbon K-edge. The experiments were performed under constant background pressures of CO (6 × 10$^{−8}$ Torr) and O$_2$ (3 × 10$^{−8}$ Torr). Under these conditions, we detect two transient CO species with narrow 2$π^*$ peaks, suggesting little 2π* interaction with the surface. Based on polarization measurements, we find that these two species have opposing orientations: (1) CO favoring a more perpendicular orientation and (2) CO favoring a more parallel orientation with respect to the surface. We also directly detect gas-phase CO2 using a mass spectrometer and observe weak signatures of bent adsorbed CO2 at slightly higher x-ray energies than the 2$π^*$ region. These results are compared to previously reported TR-XAS results at the O K-edge, where the CO background pressure was three times lower (2 × 10$^{−8}$ Torr) while maintaining the same O$_2$ pressure. At the lower CO pressure, in the CO 2$π^*$ region, we observed adsorbed CO and a distribution of OC–O bond lengths close to the CO oxidation transition state, with little indication of gas-like CO. The shift toward “gas-like” CO species may be explained by the higher CO exposure, which blocks O adsorption, decreasing O coverage and increasing CO coverage. These effects decrease the CO desorption barrier through dipole–dipole interaction while simultaneously increasing the CO oxidation barrier., Published by American Institute of Physics, Melville, NY

Physical review letters 127(1), 016802 (2021). doi:10.1103/PhysRevLett.127.016802, We use a pump-probe scheme to measure the time evolution of the C K-edge x-ray absorption spectrum from CO/Ru(0001) after excitation by an ultrashort high-intensity optical laser pulse. Because of the short duration of the x-ray probe pulse and precise control of the pulse delay, the excitation-induced dynamics during the first picosecond after the pump can be resolved with unprecedented time resolution. By comparing with density functional theory spectrum calculations, we find high excitation of the internal stretch and frustrated rotation modes occurring within 200 fs of laser excitation, as well as thermalization of the system in the picosecond regime. The ���100 fs initial excitation of these CO vibrational modes is not readily rationalized by traditional theories of nonadiabatic coupling of adsorbates to metal surfaces, e.g., electronic frictions based on first order electron-phonon coupling or transient population of adsorbate resonances. We suggest that coupling of the adsorbate to nonthermalized electron-hole pairs is responsible for the ultrafast initial excitation of the modes., Published by APS, College Park, Md.

The journal of chemical physics 149(23), 234707 (2018). doi:10.1063/1.5044579, We report on atom-specific activation of CO oxidation on Ru(0001) via resonant X-ray excitation. We show that resonant 1s core-level excitation of atomically adsorbed oxygen in the co-adsorbed phase of CO and oxygen directly drives CO oxidation. We separate this direct resonant channel from indirectly driven oxidation via X-ray induced substrate heating. Based on density functional theory calculations, we identify the valence-excited state created by the Auger decay as the driving electronic state for direct CO oxidation. We utilized the fresh-slice multi-pulse mode at the Linac Coherent Light Source that provided time-overlapped and 30 fs delayed pairs of soft X-ray pulses and discuss the prospects of femtosecond X-ray pump X-ray spectroscopy probe, as well as X-ray two-pulse correlation measurements for fundamental investigations of chemical reactions via selective X-ray excitation., Published by American Institute of Physics, Melville, NY

The dynamics of ultra-slow electrons in the combined potential of an ionic core and a static electric field is discussed. With state-of-the-art detection it is possible to create such electrons through strong intense-field photo-absorption and to detect them via high-resolution time-of-flight spectroscopy despite their very low kinetic energy. The characteristic feature of their momentum spectrum, which emerges at the same position for different laser orientations, is derived and could be revealed experimentally with an energy resolution of the order of 1meV., Comment: 5 pages, 5 figures

We determine quantitatively the laser pulse duration dependence of the low-energy structure (LES) in strong-field atomic ionization and establish its universal character. The electron energy measurement is performed on krypton and argon by varying the duration of a 1.8 $\ensuremath{\mu}\mathrm{m}$ midinfrared pulse from two to ten cycles. Comparing the experiment with analytical and numerical results, the soft-recollision mechanism leading to electron momentum bunching is confirmed as the origin of the LES. The universal behavior of the LES peak energy on pulse duration emerges from an analytical description as a product of two factors: one contains the influence of the laser parameters and the target, while the other one describes the pulse duration dependence in terms of optical cycles.

Atoms or molecules exposed to intense near-infrared laser pulses produces a considerable amount of slow electrons forming peaks in measured photo-electron spectra. We show that these peaks, namely the so called low-energy structure (les), higher-order variants and the very-low-energy structure (vles), can be understood as different solutions of the same soft- recollision mechanism. Additionally we explain the formation of a "zero-energy structure" ("zes") as a consequence of the release of Rydberg electrons by a static electric field.