Ultrafast X-Ray Scattering Measurements of Coherent Structural Dynamics on the Ground-State Potential Energy Surface of a Diplatinum Molecule.

We report x-ray free electron laser experiments addressing ground-state structural dynamics of the diplatinum anion Pt_{2}POP_{4} following photoexcitation. The structural dynamics are tracked with <100 fs time resolution by x-ray scattering, utilizing the anisotropic component to suppress contributions from the bulk solvent. The x-ray data exhibit a strong oscillatory component with period 0.28 ps and decay time 2.2 ps, and structural analysis of the difference signal directly shows this as arising from ground-state dynamics along the PtPt coordinate. These results are compared with multiscale Born-Oppenheimer molecular dynamics simulations and demonstrate how off-resonance excitation can be used to prepare a vibrationally cold excited-state population complemented by a structure-dependent depletion of the ground-state population which subsequently evolves in time, allowing direct tracking of ground-state structural dynamics.

Molecular scale structure and dynamics at an ionic liquid/electrode interface.

After a century of research, the potential-dependent ion distribution at electrode/electrolyte interfaces is still under debate. In particular for solvent-free electrolytes such as room-temperature ionic liquids, classical theories for the electrical double layer are not applicable. Using a combination of in situ high-energy X-ray reflectivity and impedance spectroscopy measurements, we determined this distribution with sub-molecular resolution. We find oscillatory charge density profiles consisting of alternating anion- and cation-enriched layers at both cathodic and anodic potentials. This structure is shown to arise from the same ion-ion correlations dominating the liquid bulk structure. The relaxation dynamics of the interfacial structure upon charging/discharging were studied by impedance spectroscopy and time resolved X-ray reflectivity experiments with sub-millisecond resolution. The analysis revealed three relaxation processes of vastly different characteristic time scales: a 2 ms scale interface-normal ion transport, a 100 ms scale molecular reorientation, and a minute scale lateral ordering within the first layer.

Disentangling detector data in XFEL studies of temporally resolved solution state chemistry.

With the arrival of X-ray Free Electron Lasers (XFELs), 2D area detectors with a large dynamic range for detection of hard X-rays with fast readout rates are required for many types of experiments. Extracting the desired information from these detectors has been challenging due to unpredicted fluctuations in the measured images. For techniques such as time-resolved X-ray Diffuse Scattering (XDS), small differences in signal intensity are the starting point for analysis. Fluctuations in the total detected signal remain in the differences under investigation, obfuscating the signal. To correct such artefacts, Singular Value Decomposition (SVD) can be used to identify and characterize the observed detector fluctuations and assist in assigning some of them to variations in physical parameters such as X-ray energy and X-ray intensity. This paper presents a methodology for robustly identifying, separating and correcting fluctuations on area detectors based on XFEL beam characteristics, to enable the study of temporally resolved solution state chemistry on the femtosecond timescale.