Giuseppe Mercurio

Probing the transition state region in catalytic CO oxidation on Ru

Catching CO oxidation Details of the transition state that forms as carbon monoxide (CO) adsorbed on a ruthenium surface is oxidized to CO2 have been revealed by ultrafast excitation and probe methods. Öström et al. initiated the reaction between CO and adsorbed oxygen atoms with laser pulses that rapidly heated the surface and then probed the changes in electronic structure with oxygen x-ray absorption spectroscopy. They observed transition-state configurations that are consistent with density functional theory and a quantum oscillator model. Science, this issue p. 978 Ultrafast x-ray spectroscopy reveals electronic changes that occur during the oxidation of carbon monoxide on a ruthenium surface. Femtosecond x-ray laser pulses are used to probe the carbon monoxide (CO) oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and oxygen (O) on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the O K-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC–O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model.

Quantification of finite-temperature effects on adsorption geometries of π-conjugated molecules : Azobenzene/Ag(111)

The adsorption structure of the molecular switch azobenzene on Ag(111) is investigated by a combination of normal incidence x-ray standing waves and dispersion-corrected density functional theory. The inclusion of non-local collective substrate response (screening) in the dispersion correction improves the description of dense monolayers of azobenzene, which exhibit a substantial torsion of the molecule. Nevertheless, for a quantitative agreement with experiment explicit consideration of the effect of vibrational mode anharmonicity on the adsorption geometry is crucial.

Chemical Bond Activation Observed with an X-ray Laser

The concept of bonding and antibonding orbitals is fundamental in chemistry. The population of those orbitals and the energetic difference between the two reflect the strength of the bonding interaction. Weakening the bond is expected to reduce this energetic splitting, but the transient character of bond-activation has so far prohibited direct experimental access. Here we apply time-resolved soft X-ray spectroscopy at a free-electron laser to directly observe the decreased bonding-antibonding splitting following bond-activation using an ultrashort optical laser pulse.

Statistical properties of a free-electron laser revealed by Hanbury Brown–Twiss interferometry

We present a comprehensive experimental analysis of statistical properties of the self-amplified spontaneous emission (SASE) free-electron laser (FEL) FLASH at DESY in Hamburg by means of Hanbury Brown and Twiss (HBT) interferometry. The experiments were performed at the FEL wavelengths of 5.5 nm, 13.4 nm, and 20.8 nm. We determined the 2-nd order intensity correlation function for all wavelengths and different operation conditions of FLASH. In all experiments a high degree of spatial coherence (above 50%) was obtained. Our analysis performed in spatial and spectral domains provided us with the independent measurements of an average pulse duration of the FEL that were below 60 fs. To explain complicated behaviour of the 2-nd order intensity correlation function we developed advanced theoretical model that includes the presence of multiple beams and external positional jitter of the FEL pulses. By this analysis we determined that in most experiments several beams were present in radiating field and in one of the experiments external positional jitter was about 25% of the beam size. We envision that methods developed in our study will be used widely for analysis and diagnostics of the FEL radiation.

Quantum imaging with incoherently scattered light from a free-electron laser

The intensity correlations in incoherently scattered X-rays from a free-electron laser can be exploited to image 2D objects with a resolution close to or below the diffraction limit.

Real-Time Elucidation of Catalytic Pathways in CO Hydrogenation on Ru

The direct elucidation of the reaction pathways in heterogeneous catalysis has been challenging due to the short-lived nature of reaction intermediates. Here, we directly measured on ultrafast time scales the initial hydrogenation steps of adsorbed CO on a Ru catalyst surface, which is known as the bottleneck reaction in syngas and CO2 reforming processes. We initiated the hydrogenation of CO with an ultrafast laser temperature jump and probed transient changes in the electronic structure using real-time X-ray spectroscopy. In combination with theoretical simulations, we verified the formation of CHO during CO hydrogenation.

X-ray standing wave simulations based on Fourier vector analysis as a method to retrieve complex molecular adsorption geometries

We present an analysis method of normal incidence x-ray standing wave (NIXSW) data that allows detailed adsorption geometries of complex molecules to be retrieved. This method (Fourier vector analysis) is based on the comparison of both the coherence and phase of NIXSW data to NIXSW simulations of different molecular geometries as the relevant internal degrees of freedom are tuned. We introduce this analysis method using the prototypical molecular switch azobenzene (AB) adsorbed on the Ag(111) surface as a model system. The application of the Fourier vector analysis to AB/Ag(111) provides, on the one hand, detailed adsorption geometries including dihedral angles, and on the other hand, insights into the dynamics of molecules and their bonding to the metal substrate. This analysis scheme is generally applicable to any adsorbate, it is necessary for molecules with potentially large distortions, and will be particularly valuable for molecules whose distortion on adsorption can be mapped on a limited number of internal degrees of freedom.