Jan M. Feldkamp

Ultrafast X-ray probing of water structure below the homogeneous ice nucleation temperature

Water has a number of anomalous physical properties, and some of these become drastically enhanced on supercooling below the freezing point. Particular interest has focused on thermodynamic response functions that can be described using a normal component and an anomalous component that seems to diverge at about 228 kelvin (refs 1,2,3 ). This has prompted debate about conflicting theories that aim to explain many of the anomalous thermodynamic properties of water. One popular theory attributes the divergence to a phase transition between two forms of liquid water occurring in the ‘no man’s land’ that lies below the homogeneous ice nucleation temperature (TH) at approximately 232 kelvin and above about 160 kelvin, and where rapid ice crystallization has prevented any measurements of the bulk liquid phase. In fact, the reliable determination of the structure of liquid water typically requires temperatures above about 250 kelvin. Water crystallization has been inhibited by using nanoconfinement, nanodroplets and association with biomolecules to give liquid samples at temperatures below TH, but such measurements rely on nanoscopic volumes of water where the interaction with the confining surfaces makes the relevance to bulk water unclear. Here we demonstrate that femtosecond X-ray laser pulses can be used to probe the structure of liquid water in micrometre-sized droplets that have been evaporatively cooled below TH. We find experimental evidence for the existence of metastable bulk liquid water down to temperatures of  kelvin in the previously largely unexplored no man’s land. We observe a continuous and accelerating increase in structural ordering on supercooling to approximately 229 kelvin, where the number of droplets containing ice crystals increases rapidly. But a few droplets remain liquid for about a millisecond even at this temperature. The hope now is that these observations and our detailed structural data will help identify those theories that best describe and explain the behaviour of water.

X-ray and optical wave mixing

Light–matter interactions are ubiquitous, and underpin a wide range of basic research fields and applied technologies. Although optical interactions have been intensively studied, their microscopic details are often poorly understood and have so far not been directly measurable. X-ray and optical wave mixing was proposed nearly half a century ago as an atomic-scale probe of optical interactions but has not yet been observed owing to a lack of sufficiently intense X-ray sources. Here we use an X-ray laser to demonstrate X-ray and optical sum-frequency generation. The underlying nonlinearity is a reciprocal-space probe of the optically induced charges and associated microscopic fields that arise in an illuminated material. To within the experimental errors, the measured efficiency is consistent with first-principles calculations of microscopic optical polarization in diamond. The ability to probe optical interactions on the atomic scale offers new opportunities in both basic and applied areas of science.

A single-shot transmissive spectrometer for hard x-ray free electron lasers

We report hard x-ray single-shot spectral measurements of the Linac Coherent Light Source. The spectrometer is based on a 10 μm thick cylindrically bent Si single crystal operating in the symmetric Bragg geometry to provide dispersion and high transmission simultaneously. It covers a spectral range >1% using the Si(111) reflection. Using the Si(333) reflection, it reaches a resolving power of better than 42 000 and transmits >83% of the incident flux at 8.3 keV. The high resolution enabled the observation of individual spectral spikes characteristic of a self-amplified spontaneous emission x-ray free electron laser source. Potential applications of the device are discussed.

A single-shot intensity-position monitor for hard x-ray FEL sources

An inline diagnostics device was developed to measure the intrinsic shot-to-shot intensity and position fluctuations of the SASE-based LCLS hard X-ray FEL source. The device is based on the detection of back-scattered X-rays from a partially-transmissive thin target using a quadrant X-ray diode array. This intensity and position monitor was tested for the first time with FEL X-rays on the XPP instrument of the LCLS. Performance analyses showed that the relative precision for intensity measurements approached 0.1% and the position sensitivity was better than 5 μm, limited only by the Poisson statistics of the X-rays collected in a single shot.

Design and operation of a hard x-ray transmissive single-shot spectrometer at LCLS

We describe the design and operation of a transmissive single-shot spectrometer for the measurement of hard x-ray free electron laser (FEL) source spectrum at the Linac Coherent Light Source (LCLS). The spectrometer was built around a 10 μm thick near-perfect silicon single crystal that was cylindrically bent. Its energy range covered the full FEL bandwidth while its resolution was sufficient for resolving single spectral spikes characteristics of the FELs. Its application will not only greatly facilitate the understanding and optimization of the x-ray FEL sources, but can also serve as an invaluable inline diagnostic tool for experiments where the spectral content of the source plays an important role in data interpretation.

Ultra-thin Bragg crystals for LCLS beam-sharing operation

The advent of X-ray Free-electron Laser (FEL) such as the Linac Coherent Light Source (LCLS) has and will continue to enable breakthroughs and discoveries in a wide range of scientific disciplines including physics, chemistry, structural biology, and material science. It has created high demand on user beamtime that is often left unfulfilled. We report here the fabrication, characterization and X-ray measurements of ultra-thin silicon single-crystal membranes for potentially beam-sharing the LCLS beam. Using a special fabrication process, samples of (111), (110), and (100) orientations were made with thicknesses ranging from 5 to 20 μm. Both high-resolution rocking curves and white-beam topographic data were first obtained using synchrotron X-rays, demonstrating near ideal diffraction qualities. Subsequent tests using the full LCLS FEL beam revealed lattice distortions from beam-induced membrane vibrations, which were then shown to be effectively reduced by ambient air or with smaller membrane dimensions. These findings are paving a way for a practical beam-sharing implementation at LCLS in the near future.

Experimental Measurements of Ultra-Thin Bragg Crystals for LCLS Beam-Sharing Operation

The successful lasing and operation of the LCLS hard X-ray FEL has brought tremendous interest to the user community spanning a wide range of scientific disciplines including physics, chemistry, structural biology, and material science. It created demand on beam time that is often left unfulfilled. Here we report experimental measurements of ultra-thin silicon single-crystal membranes for potentially beam-sharing the LCLS beam. The samples included the (111), (220), and (400) orientations with thicknesses ranging from 5 to 20 μm. Both high-resolution rocking curves and topographic data were first obtained using synchrotron X-rays, demonstrating near ideal diffraction qualities. Subsequent tests using the full LCLS beam revealed lattice distortions from beam-induced membrane vibrations, which were shown to be effectively reduced by ambient air and smaller membrane dimensions. High diffraction quality thin-diamonds in the (111) orientation are also being pursued as a parallel effort. Both approaches are paving a way for a practical beam-sharing implementation at LCLS in the near future.

X-ray / optical sum frequency generation

We report observation of x-ray and optical sum frequency generation. An ultrafast optical pulse drives charge oscillations to the chemical bonds in diamond. A co-propagating x-ray pulse probes the accompanying atomic-scale chemical bond distortion.