Fractal morphology, imaging and mass spectrometry of single aerosol particles in flight.

The morphology of micrometre-size particulate matter is of critical importance in fields ranging from toxicology to climate science, yet these properties are surprisingly difficult to measure in the particles' native environment. Electron microscopy requires collection of particles on a substrate; visible light scattering provides insufficient resolution; and X-ray synchrotron studies have been limited to ensembles of particles. Here we demonstrate an in situ method for imaging individual sub-micrometre particles to nanometre resolution in their native environment, using intense, coherent X-ray pulses from the Linac Coherent Light Source free-electron laser. We introduced individual aerosol particles into the pulsed X-ray beam, which is sufficiently intense that diffraction from individual particles can be measured for morphological analysis. At the same time, ion fragments ejected from the beam were analysed using mass spectrometry, to determine the composition of single aerosol particles. Our results show the extent of internal dilation symmetry of individual soot particles subject to non-equilibrium aggregation, and the surprisingly large variability in their fractal dimensions. More broadly, our methods can be extended to resolve both static and dynamic morphology of general ensembles of disordered particles. Such general morphology has implications in topics such as solvent accessibilities in proteins, vibrational energy transfer by the hydrodynamic interaction of amino acids, and large-scale production of nanoscale structures by flame synthesis.

Femtosecond dark-field imaging with an X-ray free electron laser.

The emergence of femtosecond diffractive imaging with X-ray lasers has enabled pioneering structural studies of isolated particles, such as viruses, at nanometer length scales. However, the issue of missing low frequency data significantly limits the potential of X-ray lasers to reveal sub-nanometer details of micrometer-sized samples. We have developed a new technique of dark-field coherent diffractive imaging to simultaneously overcome the missing data issue and enable us to harness the unique contrast mechanisms available in dark-field microscopy. Images of airborne particulate matter (soot) up to two microns in length were obtained using single-shot diffraction patterns obtained at the Linac Coherent Light Source, four times the size of objects previously imaged in similar experiments. This technique opens the door to femtosecond diffractive imaging of a wide range of micrometer-sized materials that exhibit irreproducible complexity down to the nanoscale, including airborne particulate matter, small cells, bacteria and gold-labeled biological samples.

Nanoplasma dynamics of single large xenon clusters irradiated with superintense x-ray pulses from the linac coherent light source free-electron laser.

The plasma dynamics of single mesoscopic Xe particles irradiated with intense femtosecond x-ray pulses exceeding 10(16) W/cm2 from the Linac Coherent Light Source free-electron laser are investigated. Simultaneous recording of diffraction patterns and ion spectra allows eliminating the influence of the laser focal volume intensity and particle size distribution. The data show that for clusters illuminated with intense x-ray pulses, highly charged ionization fragments in a narrow distribution are created and that the nanoplasma recombination is efficiently suppressed.

The local neutron flux at low Earth-orbiting altitudes.

The COMPTEL instrument onboard the Compton Gamma Ray Observatory (CGRO) has been used to measure the variation of the atmospheric neutron flux below 5 MeV as a function of vertical cutoff rigidity and spacecraft orientation at an altitude of 450 km. The instrumental 2.2 MeV background line, resulting from thermal neutron capture on hydrogen, was used for the measurement. The dependence of the 2.2 MeV rate on rigidity and geocentre zenith can be described by an analytic function: the line rate decreases linearly with geocentre zenith, and decreases exponentially with the vertical cutoff rigidity. The flux varies on average by about a factor of 3.7 between the extremes in rigidity, and by a factor of 1.7 between the extremes of spacecraft orientation with respect to the Earth. We believe that mass shielding is more important in attenuating the atmospheric albedo than as a source of secondary neutrons. The COMPTEL instrument is well suited for a long-duration study of the dependence of the neutron flux on the vertical cutoff rigidity and the solar cycle.

COMPTEL measurements of the omnidirectional high-energy neutron flux in near-earth orbit.

On four occasions, twice in 1991 (near solar maximum) and twice in 1994 (near solar minimum), one COMPTEL D1 detector module was used as an omnidirectional detector to measure the high-energy (> 12.8 MeV) neutron flux near an altitude of 450 km. The D1 modules are cylindrical, with radius 13.8 cm and depth 8 cm, and are filled with liquid scintillator (NE213A). The combined flux measurements can be fit reasonably well by a product of the Mt. Washington neutron monitor rate, a linear function in the spacecraft geocenter zenith angle, and an exponential function of the vertical geomagnetic cutoff rigidity in which the coefficient of the rigidity is a linear function of the neutron monitor rate. When pointed at the nadir, the flux is consistent with that expected from the atmospheric neutron albedo alone. When pointed at the zenith the flux is reduced by a factor of about 0.54. Thus the production of secondary neutrons in the massive (16000 kg) Compton Gamma-Ray Observatory spacecraft is negligible. Rather, the mass of the spacecraft provides shielding from the earth albedo.

Toward atomic resolution diffractive imaging of isolated molecules with X-ray free-electron lasers.

We give a detailed account of the theoretical analysis and the experimental results of an X-ray-diffraction experiment on quantum-state selected and strongly laser-aligned gas-phase ensembles of the prototypical large asymmetric rotor molecule 2,5-diiodobenzonitrile, performed at the Linac Coherent Light Source [Phys. Rev. Lett.112, 083002 (2014)]. This experiment is the first step toward coherent diffractive imaging of structures and structural dynamics of isolated molecules at atomic resolution, i.e., picometers and femtoseconds, using X-ray free-electron lasers.

Single-particle structure determination by correlations of snapshot X-ray diffraction patterns.

Diffractive imaging with free-electron lasers allows structure determination from ensembles of weakly scattering identical nanoparticles. The ultra-short, ultra-bright X-ray pulses provide snapshots of the randomly oriented particles frozen in time, and terminate before the onset of structural damage. As signal strength diminishes for small particles, the synthesis of a three-dimensional diffraction volume requires simultaneous involvement of all data. Here we report the first application of a three-dimensional spatial frequency correlation analysis to carry out this synthesis from noisy single-particle femtosecond X-ray diffraction patterns of nearly identical samples in random and unknown orientations, collected at the Linac Coherent Light Source. Our demonstration uses unsupported test particles created via aerosol self-assembly, and composed of two polystyrene spheres of equal diameter. The correlation analysis avoids the need for orientation determination entirely. This method may be applied to the structural determination of biological macromolecules in solution.