Ultrafast Soft X-ray Probing of Gas Phase Molecular Dynamics

The molecular ability to selectively and efficiently convert sunlight into other forms of energy like heat, bond change, or charge separation is truly remarkable. The decisive steps in these transformations often happen on a femtosecond timescale and require transitions among different electronic states that violate the Born-Oppenheimer approximation (BOA) [1 W. Domcke, D. Yarkony, and H. Köppel, Conical Intersections Electronic Structure, Dynamics &; Spectroscopy, World Scientific, Singapore (2004).[Crossref] , [Google Scholar]]. Non-BOA transitions pose challenges to both theory and experiment. From a theoretical point of view, excited state dynamics and nonadiabatic transitions both are difficult problems [2 F. Plasser, Theor. Chem. Acc. 131, 233902 (2012).[Crossref], [Web of Science ®] , [Google Scholar], 3 J. C. Tully, J. Chem. Phys. 137, 22A301 (2012).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]] (see Figure 1(a)). However, the theory on non-BOA dynamics has advanced significantly over the last two decades. Full dynamical simulations for molecules of the size of nucleobases have been possible for a couple of years [4 H. R. Hudock, J. Phys. Chem. A 111, 8500–8508 (2007).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar], 5 J. J. Szymczak, J. Phys. Chem. A 113, 12686–12693 (2009).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]] and allow predictions of experimental observables like photoelectron energy [6 S. Ullrich, Phys. Chem. Chem. Phys. 6, 2796 (2004).[Crossref], [Web of Science ®] , [Google Scholar]] or ion yield [7 H. Tao, J. Chem. Phys. 134, 244306 (2011).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]–9 M. Assmann, T. Weinacht, and S. Matsika, J. Chem. Phys. 144, 34301 (2016).[Crossref], [Web of Science ®] , [Google Scholar]]. The availability of these calculations for isolated molecules has spurred new experimental efforts to develop methods that are sufficiently different from all optical techniques. For determination of transient molecular structure, femtosecond X-ray diffraction [10 M. P. Minitti, Phys. Rev. Lett. 114, 255501 (2015).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar], 11 J. Küpper, Phys. Rev. Lett. 112, 083002 (2014). [Google Scholar]] and electron diffraction [12 J. Yang, Nat. Commun. 7, 11232 (2016).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]] have been implemented on optically excited molecules.     

Looking Deeper: Angle-Resolved Photoemission with Soft and Hard X-rays

Traditional angle-resolved photoemission (ARPES) with excitation in the ca. 20 to 150 eV range has clearly evolved to be the technique of choice for studying the electronic structure of surfaces and complex new strongly correlated and magnetic materials. However, it is clear that ARPES with excitation only up to 150 eV or so remains a very surface-sensitive probe, thus necessitating careful in-situ sample treatment, cleaving, or even synthesis to avoid the measurement of surface-associated artifacts. A key measure of this surface sensitivity is the electron inelastic mean free path (IMFP orΛ_e), which measures the mean depth of electron emission without inelastic scattering, and both experimental [1 Offi, F., Iacobucci, S., Vilmercati, P., Rizzo, A., Goldoni, A., Sacchi, M. and Panaccione, G. 2008. Physical Review B, 77: 201101R[Crossref] , [Google Scholar], 2 Offi, F., Iacobucci, S., Petaccia, L., Gorovikov, S., Vilmercati, P., Rizzo, A., Ruocco, A., Goldoni, A., Stefani, G. and Panaccione, G. 2010. Journal of Physics: Condensed Matter, 22: 305002[Crossref] , [Google Scholar]] and theoretical [3 Tanuma, S., Powell, C. J. and Penn, D. R. 2011. Surface and Interface Analysis, 43: 689[Crossref], [Web of Science ®] , [Google Scholar]] IMFP studies showing that the only reliable way to increase bulk or buried layer/interface sensitivity for all material types is to go to higher photon energies in the soft X-ray (ca. 0.5–2 keV) or hard X-ray (ca. 2–10 keV) regime.     

Thermodynamics of two-dimensional single-component elastic crystalline solids: single-wall carbon nanotubes

The thermodynamic behaviour of two-dimensional single-component elastic crystalline solids is developed: the surface Euler's equation, the surface Gibbs equation, the surface Gibbs–Duhem equation, and the conditions to be expected at equilibrium, including the stress-deformation behaviour of the crystal. The analysis recognizes that the surface Helmholtz free energy is an explicit function of the lattice vectors defining the crystalline structure. As an application, we obtain the stress-deformation behaviour of single-wall carbon nanotubes which are composed of a regular two-dimensional array of hexagonal lattices of carbon atoms. Using two potentials, Tersoff [1] Tersoff J Phys. Rev. B 37 6991 1988 [Crossref], [Web of Science ®] , [Google Scholar]–Brenner [2] Brenner DW Phys. Rev. B 42 9458 1990 [Crossref], [Web of Science ®] , [Google Scholar] and Brenner et al. [3] Brenner, DW, Shenderova, OA, Harrison, JA, Stuart, SJ, Ni, B and Sinnott, SB. 2002. J. Phys. Condens. Matter, 14: 783[Crossref], [Web of Science ®] , [Google Scholar] to describe interatomic potentials and hence the specific surface Helmholtz free energy, we compute the surface elastic properties for the single-wall carbon nanotubes. These are compared with the available experimental values.     

Femtosecond Structural Dynamics of Proteins

Proteins are the workhorses of living cells, providing essential functions such as structural support, signal transduction, enzymatic catalysis, transport and storage of small ligands. Atomic-resolution structures obtained with conventional X-ray crystallography show proteins essentially as static. In reality, however, proteins move and their motion is crucial for functioning. Although the structure and dynamics of proteins are intimately related, they are not equally well understood. A very large number of protein structures have been determined, but only a few studies have been able to monitor experimentally the dynamics of proteins in real time. In the last two decades, the availability of short (~100 ps) and intense (~10⁹–10¹⁰ photons) X-ray pulses produced by third-generation synchrotrons have allowed the implementation of structural methods like time-resolved X-ray crystallography and time-resolved X-ray solution scattering that have allowed us to monitor protein motion in the nanosecond-to-millisecond timescale [1 K. Moffat, Chem. Rev. 101, 1569–1582 (2001).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]–4 J. G. Kim, Acc. Chem. Res. 48, 2200–2208 (2015).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]]. Time-resolved X-ray crystallography has been used to monitor processes such as the migration of a ligand from the protein active site to the surrounding solvent [5 V. Srajer, Science 274, 1726–1729 (1996).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]–7 D. Bourgeois, Proc. Natl. Acad. Sci. U. S. A. 100, 8704–8709 (2003).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]] or tertiary structural changes associated with allosteric transitions [8 J. E. Knapp, Proc. Natl. Acad. Sci. 103, 7649–7654 (2006).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar], 9 J. G. Kim, Struct. Dyn. 3, 023610 (2016). [Google Scholar]]. On the other hand, time-resolved X-ray scattering in the so-called wide-angle X-ray scattering (WAXS) region [10 M. Cammarata, Nat. Methods 5, 881–886 (2008).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]] has been used to track conformational changes corresponding to large-amplitude protein motions such as the quaternary R-T transition of human hemoglobin [11 M. Cammarata, J. Mol. Biol. 400, 951–962 (2010).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]–13 A. Spilotros, Soft Matter 8, 6434–6437 (2012).[Crossref], [Web of Science ®] , [Google Scholar]], the relative motion of bacteriorhodopsin α-helices following retinal isomerization [14 M. Andersson, Structure 17, 1265–1275 (2009).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]], or the open-to-close transition in bacterial phytochromes [15 H. Takala, Nature 509, 245–8 (2014).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]].     

The pseudogap: friend or foe of high T c ?

Although nineteen years have passed since the discovery of high temperature cuprate superconductivity 1 Bednorz, JG and Müller, KA. 1986. Z. Phys. B, 64: 189[Crossref] , [Google Scholar], there is still no consensus on its physical origin. This is in large part because of a lack of understanding of the state of matter out of which the superconductivity arises. In optimally and underdoped materials, this state exhibits a pseudogap at temperatures large compared to the superconducting transition temperature 2 Warren, WW Jr., Walstedt, RE, Brennert, GF, Cava, RJ, Tycko, R, Bell, R and Dabbagh, G. 1989. Phys. Rev. Lett., 62: 1193[Crossref], [PubMed], [Web of Science ®] , [Google Scholar], 3 Alloul, H, Ohno, T and Mendels, P. 1989. Phys. Rev. Lett., 63: 1700[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]. Although discovered only three years after the pioneering work of Bednorz and Müller, the physical origin of this pseudogap behavior and whether it constitutes a distinct phase of matter is still shrouded in mystery. In the summer of 2004, a band of physicists gathered for five weeks at the Aspen Center for Physics to discuss the pseudogap. In this perspective, we would like to summarize some of the results presented there and discuss the importance of the pseudogap phase in the context of strongly correlated electron systems.

The pseudogap: friend or foe of high T _c ?

All authors

M. R. Norman, D. Pines &; C. Kallin

https://doi.org/10.1080/00018730500459906

Published online:

19 February 2007

Table     

Quantitative measurements of undiilator spatial coherence at the ALS

Modern synchrotron-based X-ray fluorescence microscopy (XFM) has become a critical tool for many a research program, addressing extremely broad and highly relevant scientific questions. Their ability to map trace elemental content and probe local chemical state has been applied to numerous scientific areas in the life sciences [1 Paunesku, T. 2006. J Cell Biochem, 99(6): 1489–502. [Crossref], [PubMed] , [Google Scholar]–3 Bohic, S. 2012. J Struct Biol, 177(2): 248–58. [Crossref], [PubMed] , [Google Scholar]], the environmental and earth sciences [4 Fittschen, U. E. A. and Falkenberg, G. 2011. Spectrochimica Acta Part B-Atomic Spectroscopy, 66(8): 567–580. [Crossref] , [Google Scholar], 5 Lombi, E. 2011. Analytical and Bioanalytical Chemistry, 400(6): 1637–1644. [Crossref], [PubMed] , [Google Scholar]], the materials sciences, as well as in cultural heritage studies. The newest generation of instruments utilizes high-brightness X-ray sources and incorporate state-of-the-art focusing optics and detector systems. Advances in X-ray sources and nanofocusing optics, for example, have allowed these instruments to achieve spatial resolutions of 20–30 nm using diffractive optics such as Fresnel zone plates and 200 nm using reflective optics such as Kirkpatrick-Baez mirrors. New beamlines, now in the design stage, aim to achieve similar (and better) resolutions within the next five years.     

Serial Femtosecond Crystallography

X-ray free-electron lasers produce brief flashes of X-rays that are of about a billion times higher peak brightness than achievable from storage ring sources. Such a tremendous jump in X-ray source capabilities, which came in 2009 when the Linac Coherent Light Source began operations, was unprecedented in the history of X-ray science. Protein structure determination through the method of macromolecular crystallography has consistently benefited from the many increases in source performance from rotating anodes to all generations of synchrotron facilities. But when confronted with the prospects of such bright beams for structural biology, enthusiastic proposals were tempered by trepidation of the effects of such beams on samples and challenges to record data [1 M. Wilmanns, J. Synchr. Rad. 7, 41 (2000).[Crossref], [PubMed] , [Google Scholar]]. A decade after these discussions (and others in the USA) on the applications of X-ray FELs for biology, the first experiments took place at LCLS, giving results that fulfilled many of the dreams of the early visionaries. In particular, the concept that diffraction representing the pristine object could be recorded before the X-ray pulse completely vaporizes the object was validated [2 H.N. Chapman, Nature 470, 73 (2011).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]], confirming predictions [3 R. Neutze, Nature 406, 753 (2000).[Crossref], [Web of Science ®] , [Google Scholar]] that established dose limits could be vastly exceeded using femtosecond-duration pulses. The first experiments illuminated a path to achieve room-temperature structures free of radiation damage, from samples too small to provide useful data at synchrotron facilities, as well as providing the means to carry out time-resolved crystallography at femtoseconds to milliseconds. In the five years since, progress has been substantial and rapid, invigorating the field of macromolecular crystallography [4 J.C.H. Spence and H.N. Chapman, Phi. Trans. Roy. Soc. B 369, 20130309 (2014).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar], 5 I. Schlichting, IUCrJ 2, 246 (2015).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]]. This phase of development is far from over, but with both the LCLS and the SPring-8 Ångström Compact Free-electron Laser (SACLA) providing facilities for measurements, the benefits of X-ray FELs are already being translated into new biological insights.     

Boundary conditions for phase transitions and interfacial reactions

Abstract

Si et al. [1 Si, X., Oh, E.S. and Slattery, J.C. 2010. Phil. Mag., 90: 655[Taylor & Francis Online] , [Google Scholar]] pointed out that it was inappropriate to use continuity of displacement at interfaces during phase transitions or in the case of reactions at interfaces as in the case of oxidation, since appropriate reference configurations cannot be identified. They instead derived a new compatibility constraint, when atleast one of the adjoining phases is crystalline. The test of these ideas offered by Slattery et al. [2 Slattery, J.C., Si, X., Fu, K.B. and Oh, E.S. 2010. Phil. Mag., 90: 665[Taylor & Francis Online] , [Google Scholar]] was successful, but it likely was too simple, since the deformations were so small. A more stringent and successful test has recently been offered by [3 Slattery, J.C., Fu, K-B and Philos, E-SOh. 2012. Mag., 92: 1788 [Google Scholar]]. Here, we analyze oxidation on the surface of a cylinder both using an extension of the compatibility constraint and using continuity of displacement, comparing the results with the experimental observations of Imbrie and Lagoudas [4 Imbrie, P.K. and Lagoudas, D.C. 2001. Oxid. Met., 55: 359[Crossref], [Web of Science ®] , [Google Scholar]].     

Seeded Multicolor FEL Pulses: Status and Future Plans

The advent of FEL sources delivering two synchronized pulses of different wavelengths has made available a whole range of novel pump-probe experiments [1 E. Ferrari, Nat. Commun. 7, 10343 (2016).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]], allowing the exploration of the dynamics of matter driven to extreme non-equilibrium states by an intense ultrashort X-ray pulse and then probing the sample response at variable time delay with a second pulse [2 E. Allaria, Nat. Commun. 4, 2476 (2013).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]].     

MXCuBE3: A New Era of MX-Beamline Control Begins

The outstanding success of structural biology within the last two decades is closely related to the development and evolution of macromolecular crystallography (MX) beamlines. Indeed, many of today's synchrotron-based MX experimental sessions aim for fast but rigorous evaluations and data collections from very large numbers of samples [1 A. Joachimiak, Current Opinion in Structural Biology 19, 573–584 (2009).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]–7 R. L. Owen, Archives of Biochemistry and Biophysics 602, 21–31 (2016).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]]. To facilitate this, sample changing on most MX beamlines is now carried out by robots and the centering of a crystal in the X-ray beam to micrometer precision is now automatically performed using either optical or diffraction-based techniques [8 D. Nurizzo, Acta Cryst. D 72, 966–975 (2016).[Crossref] , [Google Scholar]]. Once a crystal is centered, users have a wide array of options at their disposal to prepare any given experiment. This includes: X-ray fluorescence (XRF) [9 G. A. Leonard, Journal of Applied Crystallography 42, 333–335 (2009).[Crossref], [Web of Science ®] , [Google Scholar]] analysis to confirm the presence of anomalous scatterers in crystals; X-ray absorption near-edge scans (XANES) to determine the best X-ray wavelengths for MAD/SAD data collection [10 W. A. Hendrickson, Methods Enzymol. 276, 494–523 (1997).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]]; and the probing of the diffraction properties of crystals to determine the best crystal, or area of a crystal [11 M. W. Bowler, Acta Cryst. D 66, 855–864 (2010).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]], for data collection. All of these operations are now also automated, as is the collection of the final diffraction data set either from single or multiple crystals and the subsequent data analysis and reduction.     

Diverse Application Platform for Hard X-ray Diffraction in SACLA (DAPHNIS)

X-ray free electron lasers (XFELs) produce femtosecond X-ray pulses with nearly full spatial coherence and a peak power in the order of tens of GW [1 P. Emma et al., Nat. Photon. 4, 641–647 (2010).[Crossref], [Web of Science ®] , [Google Scholar], 2 T. Ishikawa et al., Nat. Photon. 6, 540–544 (2012).[Crossref], [Web of Science ®] , [Google Scholar]]. At present, two XFEL facilities, the Linac Coherent Light Source (LCLS) and SPring-8 Angstrom Compact free electron LAser (SACLA), offer research opportunities to scientists from various fields. The novel characteristics of XFELs necessitate new experimental styles, which are very different from those for conventional X-ray sources. Since many users were not familiar with these new styles in the early stage of scientific applications, user-friendly experimental systems were necessary to boost the XFEL applications into a state of practical use. XFELs are now producing unique results in, for example, structural biology [3 H. N. Chapman et al., Nature 470, 73–77 (2011).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]–6 M. Suga et al., Nature 517, 99–103 (2015).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]], nonlinear X-ray optics [7 K. Tamasaku et al., Nat. Photon. 8, 313–316 (2014).[Crossref], [Web of Science ®] , [Google Scholar], 8 H. Yoneda et al., Nature 524, 446–449 (2015).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]], ultrafast physics and chemistry [9 W. Zhang et al., Nature 509, 345–348 (2014).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]–11 K. H. Kim et al., Nature 518, 385–389 (2015).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]], and high-energy-density science [12 S. M. Vinko et al., Nature 482, 59–62 (2012).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]].     

Ambient-Pressure X-ray Photoelectron Spectroscopy to Characterize the Solid/Liquid Interface: Probing the Electrochemical Double Layer

Ambient-pressure X-ray photoelectron spectroscopy (APXPS) has contributed greatly to a wide range of research fields, including environmental science [1 H. Bluhm, Journal of Electron Spectroscopy and Related Phenomena 177, 71–84 (2010).[Crossref], [Web of Science ®] , [Google Scholar]], catalysis [2 D.E. Starr et al., Chemical Society Reviews 42, 5833–5857 (2013).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]], and electrochemistry [3 E.J. Crumlin, H. Bluhm, and Z. Liu, Journal of Electron Spectroscopy and Related Phenomena 190, 84–92 (2013).[Crossref], [Web of Science ®] , [Google Scholar]], to name a few. The use of this technique at synchrotron facilities primarily focused on probing the solid/gas interface; however, it quickly advanced to the probing of liquid/vapor interfaces [4 D.E. Starr et al., Physical Chemistry Chemical Physics 10, 3093–3098 (2008).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar], 5 M.A. Brown et al., Physical Chemistry Chemical Physics 10, 4778–4784 (2008).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]] and solid/liquid interfaces through an X-ray-transparent window [6 J. Kraus et al., Nanoscale 6, 14394–14403 (2014).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]–8 T. Masuda et al., Appl Phys Lett 103 (2013).[Crossref], [Web of Science ®] , [Google Scholar]]. Most recently, combining APXPS with “Tender” X-rays (~2.5 keV to 8 keV) on beamline 9.3.1 at the Advanced Light Source in Lawrence Berkeley National Laboratory (which can generate photoelectrons with much longer inelastic mean free paths) has enabled us to probe the solid/liquid interface without needing a window [9 S. Axnanda et al., Scientific Reports 5 (2015).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]]. This innovation allows us to probe interfacial chemistries of electrochemically controlled solid/liquid interfaces undergoing charge transfer reactions [9 S. Axnanda et al., Scientific Reports 5 (2015).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]]. These advancements have transitioned APXPS from a traditional surface science tool to an essential interface science technique.     

Lagrangian conditional moment closure model with flame group interaction for lifted turbulent spray jet flames

A new Lagrangian conditional moment closure (CMC) model is developed for multiple Lagrangian groups of sequentially evaporating fuel in turbulent spray combustion. Flame group interaction is taken into account as premixed combustion by the eddy breakup (EBU) model in terms of the probability of finding flame groups in the burned and the unburned state. Evaporation source terms are included in the two phase conditional transport equations, although they turn out to have negligible influence on the mean temperature field during combustion. The Lagrangian CMC model is implemented in OpenFOAM [1 H.G. Weller, G. Tabor, H. Jasak, and C. Fureby, A tensorial approach to computational continuum mechanics using object-oriented techniques, Comput. Phys. 12 (1998), pp. 620–631.[Crossref] [Google Scholar]] and validated for test cases in the Engine Combustion Network (ECN) [2 Engine Combustion Network. (2011). Available at http://www.sandia.gov/ecn. [Google Scholar],3 L.M. Pickett, C.L. Genzale, G. Bruneaux, L. Malbec, L. Hermant, C. Christian, and J. Schramm, Comparison of diesel spray combustion in different high-temperature, high-pressure facilities, SAE technical paper 2010-01-2106 (2010). [Google Scholar]]. Similar ignition delays and lift-off lengths are predicted by the incompletely stirred reactor (ISR) and the Eulerian CMC models due to relatively uniform conditional flame structure in the domain. The improved Lagrangian CMC model shows no abrupt reaction or oscillatory behaviour with an appropriate model constant K and gives results in better agreement with measurements lying between the predictions by ISR and Lagrangian CMC without flame group interaction.     

Data Analysis Environment for X-ray Free-Electron Laser Experiments at SACLA

X-ray free-electron lasers (XFELs) with full spatial coherence, extreme brilliance, and ultra-fast pulse duration [1 P. Emma et al., Nat. Photon. 4, 641–647 (2010).[Crossref], [Web of Science ®] , [Google Scholar], 2 T. Ishikawa et al., Nat. Photon. 6, 540–544 (2012).[Crossref], [Web of Science ®] , [Google Scholar]] allow the investigation of complex phenomena in physics, chemistry, and biology with angstrom and femtosecond resolutions. In particular, a concept of “diffraction before destruction” [3 R. Neutze et al., Nature 406, 752–757 (2000).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]] has been demonstrated for serial femtosecond crystallography (SFX) [4 H. N. Chapman et al., Nature 470, 73–77 (2011).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar], 5 S. Boutet et al., Science 337, 362–364 (2012).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]] and coherent diffractive imaging (CDI) [6 M. M. Seibert et al., Nature 470, 78–81 (2011).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]]. Using femto-second XFEL pulses, diffraction data are collected before radiation damage to samples has time to occur. Since samples are exchanged for each XFEL pulse, shot-to-shot data acquisition (DAQ) is mandatory to correlate the recorded data with the sample characteristics. The shot-to-shot DAQ must be synchronized with the repetition rate of the XFEL source, typically several tens to one hundred Hz for the machine based on normal-conducting accelerators. Shot-to-shot recording of XFEL pulse characteristics is also essential because they fluctuate due to the stochastic nature of a self-amplified spontaneous emission (SASE). We must carefully analyze a huge data set taking the fluctuation into account.     

Simulations of normal and inverse laminar diffusion flames under oxygen enhancement and gravity variation

Steady-state global chemistry calculations for 20 different flames were carried out using an axisymmetric Computational Fluid Dynamics (CFD) code. Computational results for 16 flames were compared with flame images obtained at the NASA Glenn Research Center. The experimental flame data for these 16 flames were taken from Sunderland et al. [4 Sunderland, P. B., Krishnan, S. S and Gore, J. P. 2004. Effects of oxygen enhancement and gravity on normal and inverse laminar jet diffusion flames. Combust. Flame, 136: 254–256. [Crossref], [Web of Science ®] , [Google Scholar]] which included normal and inverse diffusion flames of ethane with varying oxidiser compositions (21, 30, 50, 100% O₂ mole fraction in N₂) stabilised on a 5.5 mm diameter burner. The test conditions of this reference resulted in highly convective inverse diffusion flames (Froude numbers of the order of 10) and buoyant normal diffusion flames (Froude numbers ～0.1). Additionally, six flames were simulated to study the effect of oxygen enhancement on normal diffusion flames. The enhancement in oxygen resulted in increased flame temperatures and the presence of gravity led to increased gas velocities. The effect of gravity-variation and oxygen enhancement on flame shape and size of normal diffusion flames was far more pronounced than for inverse diffusion flames. For normal-diffusion flames, their flame-lengths decreased (1 to 2 times) and flames-widths increased (2 to 3 times) when going from earth-gravity to microgravity, and flame height decreased by five times when going from air to a pure oxygen environment.     

Ultrafast Electronic and Molecular Dynamics Induced by Ultrashort FEL Pulses

In recent years, short wavelength free electron lasers (FELs) have opened up access to ultrafast electronic and structural dynamics in matter. Currently, four FEL facilities are in operation in the world. FLASH [1 W. Ackermann, Nat. Photonics 1, 336 (2007).[Crossref], [Web of Science ®] , [Google Scholar]] in Germany and FERMI [2 P. Emma, Nat. Photonics 4, 641 (2010).[Crossref], [Web of Science ®] , [Google Scholar]] in Italy cover the range from extreme ultraviolet (EUV) to soft X-rays, while LCLS [3 T. Ishikawa, Nat. Photonics 6, 540 (2012).[Crossref], [Web of Science ®] , [Google Scholar]] in the U.S. and SACLA [4 E. Allaria, Nat. Photonics 6, 699 (2012).[Crossref], [Web of Science ®] , [Google Scholar]] in Japan provide pulses in the hard X-ray regime. In addition, an upgrade version of SCSS [5 T. Shintake, Nat. Photonics 2, 555 (2008).[Crossref], [Web of Science ®] , [Google Scholar]], nicknamed SCSS+, has also just started user operation as a beamline of SACLA [6 See http://xfel.riken.jp/eng/users/index.html [Google Scholar]]. These FELs deliver coherent pulses combining unprecedented power densities up to ~10²⁰ W/cm² and extremely short pulse durations down to a few femtoseconds. The intense coherent FEL pulse focused down to ~1 μm² makes single-shot diffractive imaging of nano-crystals or even non-crystallized bio-samples as well as other small objects a reality. Time-resolved spectroscopic and structural studies on the timescale of femtoseconds, having FEL pulses as a probe, allow us to probe electrons and atoms in action. Additionally, since FEL pulses are in a new regime of intensity, they are opening up new research fields that exploit the interaction between intense short wavelength pulses and matter, leading to matter at extremely high energy. Relevant theories dealing with such extreme conditions are also rapidly growing.     

Multilayer Laue Lens: A Brief History and Current Status

X-rays are intrinsically capable of being used for the study of non-periodic objects with atomic resolution, with high penetration, in applied electromagnetic fields, and in fluids and gases. For direct imaging via nanofocused X-ray beams, reflective [1 K. Yamauchi, Journal of Physics: Condensed Matter 23(39), 394206 (2011).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]], refractive [2 C.G. Schroer, Applied Physics Letters 87(12), 124103–3 (2005).[Crossref], [Web of Science ®] , [Google Scholar]], and diffractive [3 K. Burkhard, Journal of Physics: Condensed Matter 23(8), 083002 (2011).[Crossref], [Web of Science ®] , [Google Scholar], 4 J. Kirz, C. Jacobsen, and M. Howells, Quarterly Reviews of Biophysics 28(01), 33–130 (1995).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]] optics are used in various approaches for high-resolution imaging. Diffractive X-ray optics are endowed with the highest numerical aperture, in principle allowing focusing of X-rays to sub-nanometer dimensions. Lithographically produced Fresnel zone plates (FZP) find broad deployment around the globe, in both nanofocusing and full-field imaging approaches, and have, for many years, been workhorse optics in both synchrotron-based and laboratory-based X-ray imaging systems [4 J. Kirz, C. Jacobsen, and M. Howells, Quarterly Reviews of Biophysics 28(01), 33–130 (1995).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]]. A FZP consists of a series of radially symmetric rings, which are known as Fresnel zones, which alternate between transparent and opaque. Radiation traversing into the FZP diffracts around the opaque zones, which are placed in an arrangement where light constructively interferes at the focal plane.     

Advancement of Hard X-ray Nano-focusing Ellipsoidal Mirror at SPring-8

Ellipsoidal mirror optics can produce a smaller, two-dimensional focus with diffraction-limited properties than is possible when using mirror optics in Kirkpatrick–Baez (K–B) geometry [1 P. Kirkpatrick and A.V. Baez, Journal of the Optical Society of America 38, 766–773 (1948).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]]. This is because ellipsoidal focusing mirrors can be designed such that they have a larger numerical aperture in the sagittal focusing direction as compared to that in the meridional focusing direction. Although ellipsoidal focusing mirrors have this crucial advantage over K–B optics, K–B optics are widely utilized as micro-/nano-focusing devices [2 H. Mimura, Nature Physics 6, 122–125 (2010).[Crossref], [Web of Science ®] , [Google Scholar]–8 H. Mimura, Nature Communications 5, 3539 (2014).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]] in synchrotron radiation facilities and X-ray free electron laser facilities [9 P. Emma, Nature Photonics 4, 641–647 (2010).[Crossref], [Web of Science ®] , [Google Scholar], 10 T. Ishikawa, Nature Photonics 6, 540–544 (2012).[Crossref], [Web of Science ®] , [Google Scholar]]. Figure 1 shows a schematic of focusing mirror optics; Figure 1(a) shows the ellipsoidal mirror and Figure 1(b) the K–B mirror arrangement. In K–B geometry, two mirrors with a one-dimensionally curved surface, such as an elliptical cylinder, are orthogonally arranged in tandem to reflect and focus light independently in a direction perpendicular to each other under grazing-incidence conditions. Ellipsoidal focusing mirrors, which can generate a two-dimensional focusing beam by a single reflection, have a highly sloped surface with a two-dimensional aspherical shape, when compared to elliptical-cylinder mirrors that are used for line-focusing in K–B geometry. In addition, surface shapes of nano-focusing mirrors must be fabricated with nanometer-level accuracy. Therefore, fabrication of ellipsoidal nano-focusing mirrors is extremely difficult. There are no reports on ellipsoidal nano-focusing mirrors in the hard X-ray region with superior performances to provide diffraction-limited beams.