The time-resolved atomic, molecular and optical science instrument at the Linac Coherent Light Source.

The newly constructed time-resolved atomic, molecular and optical science instrument (TMO) is configured to take full advantage of both linear accelerators at SLAC National Accelerator Laboratory, the copper accelerator operating at a repetition rate of 120 Hz providing high per-pulse energy as well as the superconducting accelerator operating at a repetition rate of about 1 MHz providing high average intensity. Both accelerators power a soft X-ray free-electron laser with the new variable-gap undulator section. With this flexible light source, TMO supports many experimental techniques not previously available at LCLS and will have two X-ray beam focus spots in line. Thereby, TMO supports atomic, molecular and optical, strong-field and nonlinear science and will also host a designated new dynamic reaction microscope with a sub-micrometer X-ray focus spot. The flexible instrument design is optimized for studying ultrafast electronic and molecular phenomena and can take full advantage of the sub-femtosecond soft X-ray pulse generation program.

Adaptive shape control of wavefront-preserving X-ray mirrors with active cooling and heating.

This article describes the development and testing of a novel, water-cooled, active optic mirror system (called "REAL: Resistive Element Adjustable Length") that combines cooling with applied auxiliary heating, tailored to the spatial distribution of the thermal load generated by the incident beam. This technique is theoretically capable of sub-nanometer surface figure error control even at high power density. Tests conducted in an optical metrology laboratory and at synchrotron X-ray beamlines showed the ability to maintain the mirror profile to the level needed for the next generation storage rings and FEL mirrors.

Completeness condition for unambiguous profile reconstruction by sub-aperture stitching.

We describe the conditions required for a set of displaced sub-aperture measurements to contain sufficient information to reconstruct the stitched mirror profile removing all additive systematic errors of the measuring instrument, independent of the reference surface and of the guidance error of the linear stage used for the translation. We show that even-spaced stitching must be avoided and that the pitch error of the linear stage or the curvature of the reference must be measured, to avoid periodic errors and curvature errors in the reconstructed profile. We show that once these uncertainties are solved, the 1D profile can be reconstructed free of any additive systematic error. The theory is supported by computer simulations and by experimental results using two different instruments.

Reversible modification of the structural and electronic properties of a boron nitride monolayer by CO intercalation.

We demonstrate the reversible intercalation of CO between a hexagonal boron nitride (h-BN) monolayer and a Rh(111) substrate above a threshold CO pressure of 0.01 mbar at room temperature. The intercalation of CO results in the flattening of the originally corrugated h-BN nanomesh and an electronic decoupling of the BN layer from the Rh substrate. The intercalated CO molecules assume a coverage and adsorption site distribution comparable to that on the free Rh(111) surface at similar conditions. The pristine h-BN nanomesh is reinstated upon heating to above 625 K. These observations may open up opportunities for a reversible tuning of the electronic and structural properties of monolayer BN films.

In†situ observation of surface species on iridium oxide nanoparticles during the oxygen evolution reaction.

An iridium oxide nanoparticle electrocatalyst under oxygen evolution reaction conditions was probed in situ by ambient-pressure X-ray photoelectron spectroscopy. Under OER conditions, iridium undergoes a change in oxidation state from Ir(IV) to Ir(V) that takes place predominantly at the surface of the catalyst. The chemical change in iridium is coupled to a decrease in surface hydroxide, providing experimental evidence which strongly suggests that the oxygen evolution reaction on iridium oxide occurs through an OOH-mediated deprotonation mechanism.

Sub-micron thick liquid sheets produced by isotropically etched glass nozzles.

We report on the design and testing of glass nozzles used to produce liquid sheets. The sheet nozzles use a single converging channel chemically etched into glass wafers by standard lithographic methods. Operation in ambient air and vacuum was demonstrated. The measured sheet thickness ranges over one order of magnitude with the smallest thickness of 250 nm and the largest of 2.5 µm. Sheet thickness was shown to be independent of liquid flow rate, and dependent on the nozzle outlet area. Sheet surface roughness was dependent on nozzle surface finish and was on the order of 10 nm for polished nozzles. Electron transmission data is presented for various sheet thicknesses near the MeV mean free path and the charge pair distribution function for D2O is determined from electron scattering data.

Role of Undercoordinated Sites for the Catalysis in Confined Spaces Formed by Two-Dimensional Material Overlayers.

Adding a two-dimensional (2D) overlayer on a metal surface is a promising route for activating reactants confined in the interfacial space. However, an atomistic understanding of the role played by undercoordinated sites of the 2D overlayer in the activation of molecules in this nanoscaled confined space is yet to be developed. In this paper, we study CO dissociation as a prototypical reaction to investigate CO activation in the confined space enclosed by Rh(111) and a monolayer of hexagonal boron nitride (h-BN). The effect of the space size (i.e., the distance between h-BN and the metal surface), the type of undercoordinated sites, and the size of the defect are explicitly studied by density functional theory with dispersion correction. The following temperature-programmed X-ray photoelectron spectroscopy measurement suggests that a small portion of the CO dissociated during the desorption, leaving the residual atomic oxygen incorporated into the h-BN lattice, which validates the theoretical prediction. The combination of theory and experiment calls for further attention to be paid to the role of undercoordinated sites in the 2D overlayers in confined systems forming potential new catalytic environments.

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.