X-ray reflectivity of chemically vapor-deposited diamond single crystals in the Laue geometry.

The absolute X-ray reflectivity of chemically vapor-deposited (CVD) single-crystal diamond plates was measured in the Laue geometry in the double-crystal non-dispersive setting with an asymmetric Si beam-conditioner crystal. The measurements were supplemented by rocking-curve topography. The measured reflectivity curves are examined in the framework of the Darwin-Hamilton approach using a set of two independent parameters: the characteristic thickness of mosaic blocks and their average angular misorientation. Owing to strong extinction effects, the width of the reflectivity curves does not directly represent the average misorientation of the blocks. Two different sets of parameters were found for the 111 asymmetric reflection in the two different scattering configurations (beam compression and beam expansion). Analysis of the rocking-curve topographs shows that this discrepancy can be attributed to inhomogeneity of the diamond crystal microstructure.

Spatial displacement of forward-diffracted X-ray beams by perfect crystals.

Time-delayed, narrow-band echoes generated by forward Bragg diffraction of an X-ray pulse by a perfect thin crystal are exploited for self-seeding at hard X-ray free-electron lasers. Theoretical predictions indicate that the retardation is strictly correlated to a transverse displacement of the echo pulses. This article reports the first experimental observation of the displaced echoes. The displacements are in good agreement with simulations relying on the dynamical diffraction theory. The echo signals are characteristic for a given Bragg reflection, the structure factor and the probed interplane distance. The reported results pave the way to exploiting the signals as an online diagnostic tool for hard X-ray free-electron laser seeding and for dynamical diffraction investigations of strain at the femtosecond timescale.

Observation of a Charge Density Wave Incommensuration Near the Superconducting Dome in Cu_{x}TiSe_{2}.

X-ray diffraction was employed to study the evolution of the charge density wave (CDW) in Cu_{x}TiSe_{2} as a function of copper intercalation in order to clarify the relationship between the CDW and superconductivity. The results show a CDW incommensuration arising at an intercalation value coincident with the onset of superconductivity at around x=0.055(5). Additionally, it was found that the charge density wave persists to higher intercalant concentrations than previously assumed, demonstrating that the CDW does not terminate inside the superconducting dome. A charge density wave peak was observed in samples up to x=0.091(6), the highest copper concentration examined in this study. The phase diagram established in this work suggests that charge density wave incommensuration may play a role in the formation of the superconducting state.

Structural origin of the anomalous temperature dependence of the local magnetic moments in the CaFe2As2 family of materials.

We report a combination of Fe Kß x-ray emission spectroscopy and density functional reduced Stoner theory calculations to investigate the correlation between structural and magnetic degrees of freedom in CaFe2(As1-xPx)2. The puzzling temperature behavior of the local moment found in rare earth-doped CaFe2As2 [H. Gretarsson et al., Phys. Rev. Lett. 110, 047003 (2013)] is also observed in CaFe2(As1-xPx)2. We explain this phenomenon based on first-principles calculations with scaled magnetic interaction. One scaling parameter is sufficient to describe quantitatively the magnetic moments in both CaFe2(As1-xPx)2 (x=0.055) and Ca0.78La0.22Fe2As2 at all temperatures. The anomalous growth of the local moments with increasing temperature can be understood from the observed large thermal expansion of the c-axis lattice parameter combined with strong magnetoelastic coupling. These effects originate from the strong tendency to form As-As dimers across the Ca layer in the CaFe2As2 family of materials. Our results emphasize the dual local-itinerant character of magnetism in Fe pnictides.

A galaxy rapidly forming stars 700 million years after the Big Bang at redshift 7.51.

Of several dozen galaxies observed spectroscopically that are candidates for having a redshift (z) in excess of seven, only five have had their redshifts confirmed via Lyman α emission, at z = 7.008, 7.045, 7.109, 7.213 and 7.215 (refs 1-4). The small fraction of confirmed galaxies may indicate that the neutral fraction in the intergalactic medium rises quickly at z > 6.5, given that Lyman α is resonantly scattered by neutral gas. The small samples and limited depth of previous observations, however, makes these conclusions tentative. Here we report a deep near-infrared spectroscopic survey of 43 photometrically-selected galaxies with z > 6.5. We detect a near-infrared emission line from only a single galaxy, confirming that some process is making Lyman α difficult to detect. The detected emission line at a wavelength of 1.0343 micrometres is likely to be Lyman α emission, placing this galaxy at a redshift z = 7.51, an epoch 700 million years after the Big Bang. This galaxy's colours are consistent with significant metal content, implying that galaxies become enriched rapidly. We calculate a surprisingly high star-formation rate of about 330 solar masses per year, which is more than a factor of 100 greater than that seen in the Milky Way. Such a galaxy is unexpected in a survey of our size, suggesting that the early Universe may harbour a larger number of intense sites of star formation than expected.

Nonresonant inelastic x-ray scattering and energy-resolved Wannier function investigation of d-d excitations in NiO and CoO.

Nonresonant inelastic x-ray scattering measurements on NiO and CoO show that strong dipole-forbidden d-d excitations appear within the Mott gap at large wave vectors. These dominant excitations are highly anisotropic, and have [001] nodal directions for NiO. Theoretical analyses based on a novel, energy-resolved Wannier function (within the local density approximation+Hubbard U) show that the anisotropy reflects the local exciton wave functions and local point-group symmetry. The sensitivity to weak symmetry breaking in particle-hole wave functions suggests a wide application to strongly correlated systems.

Imaging density disturbances in water with a 41.3-attosecond time resolution.

We show that the momentum flexibility of inelastic x-ray scattering may be exploited to invert its loss function, allowing real time imaging of density disturbances in a medium. We show the disturbance arising from a point source in liquid water, with a resolution of 41.3 attoseconds (4.13 x 10(-17) s) and 1.27 A (1.27 x 10(-8) cm). This result is used to determine the structure of the electron cloud around a photoexcited chromophore in solution, as well as the wake generated in water by a 9 MeV gold ion. We draw an analogy with pump-probe techniques and suggest that energy-loss scattering may be applied more generally to the study of attosecond phenomena.

Spatial distribution of competing ions around DNA in solution.

The competition of monovalent and divalent cations for proximity to negatively charged DNA is of biological importance and can provide strong constraints for theoretical treatments of polyelectrolytes. Resonant x-ray scattering experiments have allowed us to monitor the number and distribution of each cation in a mixed ion cloud around DNA. These measurements provide experimental evidence to support a general theoretical prediction: the normalized distribution of each ion around polyelectrolytes remains constant when ions are mixed at different ratios. In addition, the amplitudes of the scattering signals throughout the competition provide a measurement of the surface concentration parameter that predicts the competition behavior of these cations. The data suggest that ion size needs to be taken into account in applying Poisson-Boltzmann treatments to polyelectrolytes such as DNA.

Counterion distribution around DNA probed by solution X-ray scattering.

Counterion atmospheres condensed onto charged biopolymers strongly affect their physical properties and biological functions, but have been difficult to quantify experimentally. Here, monovalent and divalent counterion atmospheres around DNA double helices in solution are probed using small-angle x-ray scattering techniques. Modulation of the ion scattering factors by anomalous (resonant) x-ray scattering and by interchanging ion identities yields direct measurements of the scattering signal due to the spatial correlation of surrounding ions to the DNA. The quality of the data permit, for the first time, quantitative tests of extended counterion distributions calculated from atomic-scale models of biologically relevant molecules.

Flash-cooling and annealing of protein crystals.

Flash-cooling and annealing of macromolecular crystals have been investigated using in situ X-ray imaging, diffraction-peak lineshape measurements and conventional crystallographic diffraction. The dominant mechanisms by which flash-cooling creates disorder are suggested and a fixed-temperature annealing protocol for reducing this disorder is demonstrated that should be more reliable and flexible than existing protocols. Flash-cooling tetragonal lysozyme crystals degrades diffraction resolution and broadens the distributions of lattice orientations (mosaicity) and lattice spacings. The diffraction resolution strongly correlates with the width of the lattice-spacing distribution. Annealing at fixed temperatures of 253 and 233 K consistently reduces the lattice-spacing spread and improves the resolution for annealing times up to approximately 30s. X-ray images show that this improvement arises from the formation of well ordered domains with characteristic sizes >10 microm and narrower mosaicities than the crystal as a whole. Flash-cooled triclinic crystals of lysozyme, which have a smaller water content than the tetragonal form, diffract to higher resolution with smaller mosaicities and exhibit pronounced ordered domain structure even before annealing. It is suggested that differential thermal expansion of the protein lattice and solvent may be the primary cause of flash-cooling-induced disorder. Mechanisms by which annealing at T << 273 K reduce this disorder are discussed.

Dynamic response of tetragonal lysozyme crystals to changes in relative humidity: implications for post-growth crystal treatments.

The dynamic response of tetragonal lysozyme crystals to dehydration has been characterized in situ using a combination of X-ray topography, high-resolution diffraction line-shape measurements and conventional crystallographic diffraction. For dehydration from 98% relative humidity (r.h.) to above 89%, mosaicity and diffraction resolution show little change and X-ray topographs remain featureless. Lattice constants decrease rapidly but the lattice-constant distribution within the crystal remains very narrow, indicating that water concentration gradients remain very small. Near 88% r.h., the c-axis lattice parameter decreases abruptly, the steady-state mosaicity and diffraction resolution degrade sharply and topographs develop extensive contrast. This transformation exhibits metastability and hysteresis. At fixed r.h. < 88% it is irreversible, but the original order can be almost completely restored by rehydration. These results suggest that this transformation is a first-order structural transition involving an abrupt loss of crystal water. The front between transformed and untransformed regions may propagate inward from the crystal surface and the resulting stresses along the front may degrade mosaicity. Differences in crystal size, shape and initial perfection may produce the observed variations in degradation timescale. Consequently, the success of more general post-growth treatments may often involve identifying procedures that either avoid lattice transitions, minimize disorder created during such transitions or maintain the lattice in an ordered metastable state.

Macromolecular impurities and disorder in protein crystals.

The mechanisms by which macromolecular impurities degrade the diffraction properties of protein crystals have been investigated using X-ray topography, high-resolution diffraction line shape measurements, crystallographic data collection, chemical analysis, and two-photon excitation fluorescence microscopy. Hen egg-white lysozyme crystals grown from solutions containing a structurally unrelated protein (ovotransferrin) and a related protein (turkey egg-white lysozyme) can exhibit significantly broadened mosaicity due to formation of cracks and dislocations but have overall B factors and diffraction resolutions comparable to those of crystals grown from uncontaminated lysozyme. Direct fluorescence imaging of the three-dimensional impurity distribution shows that impurities incorporate with different densities in sectors formed by growth on different crystal faces, and that impurity densities in the crystal core and along boundaries between growth sectors can be much larger than in other parts of the crystal. These nonuniformities create stresses that drive formation of the defects responsible for the mosaic broadening. Our results provide a rationale for the use of seeding to obtain high-quality crystals from heavily contaminated solutions and have implications for the use of crystallization for protein purification. Proteins 1999;36:270-281.

X-ray topographic studies of protein crystal perfection and growth.

The effects of solution variations during growth on the perfection of tetragonal lysozyme crystals have been characterized using X-ray topography and high angular and wavevector resolution reciprocal-space scans. X-ray images of crystals grown under nearly uniform conditions show little contrast or evidence of defects, and mosaic widths of these crystals are comparable with those reported for microgravity-grown crystals. Images of crystals for which solution conditions (temperature, pH or salt concentration) are changed after an initial period of uniform growth can show extensive contrast, indicating the presence of disorder. The X-ray mosaic widths of these crystals can be significantly broadened, but their radial widths are at most very slightly broadened, indicating that image contrast is primarily due to mosaicity. Comparison of X-ray images with mosaic scans indicates that regions grown after the change in solution conditions have broader mosaicities and are more disordered; that regions grown immediately after the change tend to have broader mosaicities than subsequent growth regions; and that the pre-change growth region is largely unaffected by solution changes. The observed disorder may arise from solution change-related transient growth instabilities, from transient liquid-liquid phase separation that can occur during the change, and from post-change relaxation of the lattice constant of the pre-change growth regions. These results suggest that solution variations during growth, including those typical of macroseeding, vapor-diffusion growth and other widely used techniques, may be an important source of disorder in some protein crystals.