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.     

Fourth User Workshop on High-Power Lasers at the Linac Coherent Light Source

The fourth international user workshop focusing on high-power lasers at the Linac Coherent Light Source (LCLS) was held in Menlo Park, CA, USA, on October 3–4, 2016 [1 R. Falcone, S. Glenzer, and S. Hau-Riege, Synchrotron Radiation News 27(2), 56–58 (2014).[Taylor &; Francis Online] , [Google Scholar]–3 C. Bolme, S. Glenzer, and A. Fry, Synchrotron Radiation News 29(2), 14–17 (2016).[Taylor &; Francis Online] , [Google Scholar]]. The workshop was co-organized by Los Alamos National Laboratory and SLAC National Accelerator Laboratory (SLAC), and garnered the attendance of more than 110 scientists. Participants discussed the warm dense matter and high-pressure science that is being conducted using high-power lasers at the LCLS Matter in Extreme Conditions (MEC) endstation. During the past year, there have been seven journal articles published from research at the MEC instrument [4 L. B. Fletcher et al., Review of Scientific Instruments 87(11), 11E524 (2016).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]–10 P. Sperling et al., Physical Review Letters 115(11), 115001 (2015).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]]. The specific topics discussed at this workshop were experimental highlights from the past year, current status and future commissioning of MEC capabilities, and future facility upgrades that will enable the expanded science reach of the facility.     

Studies on the σ–hole bonds (halogen,chalcogen, pnicogen and carbon bonds) based on the orientation of crystal structure

ABSTRACT

The 4,7-dibromo-5,6-dinitro-2,1,3-benzothiadiazole (DDBT) crystal has two polymorphic forms [1 M.S. Pavan, A.K. Jana, S. Natarajan, and T.N. Guru Row, J. Phys. Chem. B 119, 11382 (2015).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]], where the close contacts between two electronegative atoms are identified and studied through Hirshfeld surface analysis. Br---Br and O---O cut-off distances are addressed and analysed. The σ–hole of bromine, sulphur, oxygen atoms and π-hole of carbon and nitrogen atoms were subjected to study using molecular electrostatic potential map and 3D-deformation density map. Sixteen types of dimers from the two forms of crystal structure (6 for form I and 10 for form II) were studied using the charge transfer properties and interaction energies and made detailed analysis of halogen bond (Br---N), dihalogen bond (Br---Br), chalcogen bond (O---Br and S---Br), dichalcogen bond (S---O, O---S and O---O), pnicogen bond (N---O) and carbon bond (C---O and C---Br) interactions. The impact of orientations is discussed to define the type of interaction and its strength through charge transfer mechanism. The contribution of bond angle values for the σ-hole and π–hole bonds are discussed. Utilisation of σ–hole in smaller bond angle values (above 30°) of |θ₁ ? θ₂| existing in type II halogen–halogen bond have been examined in the two forms.     

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     

LURE in the 1970s

In France, Yvette Cauchois, Director of the Laboratoire de Chimie Physique in Paris, was the first person who came up with the idea of using synchrotron radiation. The experiment was done in collaboration with Italian scientists at the Frascati synchrotron in 1963 [1 Y. Cauchois, C. Bonnelle and G. Missoni, C. R. Acad. Sci. Paris, 257, 409 (1963a) and 1242 (1963b). [Google Scholar]]. For a few years, interesting results were obtained by her group and that of Pierre Jaéglé (Orsay) [2 P. Jaeglé, P. Missoni and P. Dhez, Phys. Rev. Lett., 18, 887 (1967).[Crossref], [Web of Science ®] , [Google Scholar]]. After that, they contacted the laboratory for high-energy physics at Orsay (LAL), hoping to install a beamline on the ACO (electron-positron collider), but their request was turned down.     

Low-temperature high-resolution absorption spectrum of 14NH3 in the ν1+ν3 band region (1.51 μm)

Jet-cooled spectra of ¹⁴NH₃ and ¹⁵NH₃ in natural abundance were recorded using cavity ring-down (CRDS, 6584–6670 cm^?1) and cavity enhanced absorption (CEAS, 6530–6700 cm^?1) spectroscopy. Line broadening effects in the CRDS spectrum allowed lines with J ^″-values between 0 and 3 to be identified. Intensity ratios in ¹⁴NH₃ between the jet-cooled CRDS and literature room-temperature data from Sung et al. (J. Quant. Spectrosc. Radiat. Transfer, 113 (2012 K. Sung , L.R. Brown , X. Huang , D.W. Schwenke , T.J. Lee , S.L. Coy , and K.K. Lehmann , J. Quant. Spectrosc. Radiat. Transfer 113 , 1066 (2012).[Crossref], [Web of Science ®] , [Google Scholar]), 1066) further assisted the line assignments. Ground state combination differences were extensively used to support the assignments, providing reliable values for J, K and inversion symmetry of the ground state vibrational levels. CEAS data helped in this respect for the lowest J lines, some of which are saturated in the CRDS spectrum. Further information on a/s doublets arose from the observed spectral structures. Thirty-two transitions of ¹⁴NH₃ were assigned in this way and a limited but significant number (19) of changes in the assignments results, compared to Sung et al. or to Cacciani et al. (J. Quant. Spectrosc. Radiat. Transfer, 113 (2012 P. Cacciani , P. Cermak , J. Cosleou , M. Khelkhal , P. Jeseck , and X. Michaut , J. Quant. Spectrosc. Radiat. Transfer 113 , 1084 (2012).[Crossref], [Web of Science ®] , [Google Scholar]), 1084). Sixteen known and 25 new low-J transitions were identified for ¹⁵NH₃ in the CRDS spectrum but the much scarcer literature information did not allow for any more refined assignment. The present line position measurements improve on literature values published for ¹⁵NH₃ and on some line positions for ¹⁴NH₃.     

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.     

Future light sources based upon photo-injected energy recovery linacs

X-ray scattering techniques have long ranked among the most important methods for studying amorphous materials and other highly disordered targets. Well-established X-ray scattering methods often consist of recording time-averaged scattered intensity maps which, under the Born approximation, straightforwardly reveal information about ensemble-averaged, two-point, electron density correlations within the target. In the case of isotropic targets that consist of disordered ensembles of randomly oriented particles, scattering data are typically reduced to a histogram of electron pair distances (the “pair distribution function,” or PDF). While the information contained in the one-dimensional PDF is limited, a rich set of structural properties can often be determined straightforwardly (e.g., radius of gyration, surface area, short-range correlation length scales, fractal dimension). One of the well-known pinnacles of the methodology is the application of small-angle X-ray scattering (SAXS) to solutions of identical biological macromolecules [1 Elser, V. 2011. New J. Phys., 13: 123014[Crossref] , [Google Scholar]–3 Putnam, C. D., Hammel, M., Hura, G. L. and Tainer, J. A. 2007. Quarterly Reviews of Biophysics, 40: 191–285. [Crossref], [PubMed], [Web of Science ®] , [Google Scholar]], which is now routinely used to rapidly determine ab initio low-resolution (>1 nm) protein structures [4 Hura, G. L. 2009. Nature Methods, 6: 606–614. [Crossref], [PubMed] , [Google Scholar]].     

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]].     

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.     

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.     

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.     

Third User Workshop on High-Power Lasers at the Linac Coherent Light Source

On October 5–6, 2015, the third international user workshop focusing on high-power lasers at the Linac Coherent Light Source (LCLS) was held in Menlo Park, CA, USA [1 R. Falcone, S. Glenzer, and S. Hau-Riege, Synchrotron Radiation News 27(2), 56–58 (2014).[Taylor &; Francis Online] , [Google Scholar], 2 P. Heimann and S. Glenzer, Synchrotron Radiation News 28(3), 54–56 (2015).[Taylor &; Francis Online] , [Google Scholar]]. The workshop was co-organized by Los Alamos National Laboratory and SLAC National Accelerator Laboratory. More than 110 scientists attended from North America, Europe, and Asia to discuss high-energy-density (HED) science that is enabled by the unique combination of high-power lasers with the LCLS X-rays at the LCLS-Matter in Extreme Conditions (MEC) endstation.     

Optical,Dielectric, and Conduction Properties of New Phosphorus-Modified Polysulfones

New phosphorus-modified polysulfones with different substitution degrees, obtained from chloromethylated polysulfones, were analyzed in terms of their optical, dielectric, and conduction properties. In order to obtain the optical parameters, the approach proposed by Tauc for amorphous semiconductors was used.^{[ 23} Tauc, J., Menth, A. and Wood, D. L. 1970. Optical and magnetic investigations of the localized states in semiconducting glasses. Phys. Rev. Lett., 25: 749–752. [Crossref] , [Google Scholar] ^{, 24} Tauc, J. and Menth, A. 1972. States in the gap. J. Non-Cryst. Solids, 8–10: 569–585. [Crossref] , [Google Scholar] ^] The determined parameters were found to be related to the influence of the polymer chain structure and the history of films’ preparations. The temperature and frequency dependence of dielectric constant and dielectric relaxation were investigated by AC-dielectric measurements. The nature of the relaxation mechanisms was established on the basis of the dielectric measurement results. The samples displayed two sub-glass relaxations, i.e. γ relaxation – where the activation energy changes insignificantly with the substitution degree, and β relaxation – with higher apparent activation energy for lower substitution degrees. The results obtained from Tauc's law and AC-conduction studies indicated that the conduction mechanism in the phosphorus-modified polysulfone was due to electronic hopping, and that a model based on the energy bandgap representation could be suitable for explaining the temperature dependence of electrical conductivity.     

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.     

Photon-In/Photon-Out Soft X-ray Spectroscopy at the TPS 45A Beamline

Owing to the current energy crisis and extreme changes in the global climate, there is great interest in finding renewable energy resources. Vast progress has been made in the development of new materials related to renewable energy, and their physical/chemical properties can be tailored by nanostructuring and other advanced synthetic approaches. In many important energy systems, such as solar hydrogen systems, the atomic/electronic structures of materials and fundamental interfacial phenomena of systems critically determine the energy conversion efficiency of materials [1 S. Shen et al., Energy Environ. Sci. 9, 2744 (2016).[Crossref], [Web of Science ®] , [Google Scholar], 2 J. Chen et al., J. Mater. Chem. A 2, 4605 (2014).[Crossref], [Web of Science ®] , [Google Scholar]]. Without knowledge of the fundamental electronic structures of the materials during conversion reactions, better engineering of the material for practical use is difficult. Understanding and controlling the interfaces in energy generation/conversion/storage materials requires in-situ/operando approaches [3 V. Iablokov et al., Nano Lett. 12, 2091 (2012).[Crossref], [Web of Science ®] , [Google Scholar], 4 F. Zheng et al., Nano Lett. 11, 847 (2011).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]]. The Taiwan Photon Source (TPS) Soft X-ray Spectroscopic beamline provides the capabilities for X-ray absorption (XAS) and X-ray emission (XES) spectroscopies, which can be utilized to investigate unoccupied (conduction-band) and occupied (valence-band) electronic states, respectively. Moreover, resonant inelastic X-ray scattering (RIXS) can be used to study intra-band (including d-d or f-f excitations) and inter-band (charge transfer) transitions [5 S. M. Butorin et al., Phys. Rev. Lett. 77, 574 (1996).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar], 6 P. Kuiper et al., Phys. Rev. Lett. 80, 5204 (1988).[Crossref], [Web of Science ®] , [Google Scholar]]. The former provides details about electronic energy splitting in various crystal fields and the latter involves electron transfer between a metal and a ligand, which determines chemical activity [7 H. Liu, Nano Lett. 7, 1919 (2007).[Crossref], [Web of Science ®] , [Google Scholar], 8 V. Bisogni et al., Phys. Rev. Lett. 114, 096402 (2015).[Crossref], [Web of Science ®] , [Google Scholar]].     

An efficient basis set representation for calculating electrons in molecules

ABSTRACT

The method of McCurdy, Baertschy, and Rescigno, J. Phys. B, 37, R137 (2004) [1 C.W. McCurdy, M. Baertschy, and T.N. Rescigno, J. Phys. B 37, R137 (2004).[Crossref], [Web of Science ®] , [Google Scholar]] is generalised to obtain a straightforward, surprisingly accurate, and scalable numerical representation for calculating the electronic wave functions of molecules. It uses a basis set of product sinc functions arrayed on a Cartesian grid, and yields 1 kcal/mol precision for valence transition energies with a grid resolution of approximately 0.1 bohr. The Coulomb matrix elements are replaced with matrix elements obtained from the kinetic energy operator. A resolution-of-the-identity approximation renders the primitive one- and two-electron matrix elements diagonal; in other words, the Coulomb operator is local with respect to the grid indices. The calculation of contracted two-electron matrix elements among orbitals requires only O(Nlog?(N)) multiplication operations, not O(N⁴), where N is the number of basis functions; N = n³ on cubic grids. The representation not only is numerically expedient, but also produces energies and properties superior to those calculated variationally. Absolute energies, absorption cross sections, transition energies, and ionisation potentials are reported for 1- (He⁺, H⁺₂), 2- (H₂, He), 10- (CH₄), and 56-electron (C₈H₈) systems.     

Magnetic Measurement Techniques for the Large-Scale Production of Undulator Segments for the European XFEL

The European X-ray free electron laser (EXFEL) facility is currently under construction [1 M. Altarelli, The European X-ray Free-electron Laser, Technical Design Report (2006). [Google Scholar]]. Using the principle of self-amplified spontaneous emission (SASE) [2 A.M. Kondratenko and E.L. Saldin, Part. Accel., 10, 207 (1980). [Google Scholar], 3 R. Bonifacio, C. Pellegrini, and L.M. Narducci, Opt. Commum. 50, 373 (1984).[Crossref], [Web of Science ®] , [Google Scholar]], intense FEL radiation is generated in three gap-tuneable undulator systems called SASE1, SASE2, and SASE3. The electron beam energy of the EXFEL is variable between 8.5 and 17.5 GeV. SASE1 and SASE2 are hard X-ray FELs using planar undulators with a period length of 40 mm, called U40s. By a suitable choice of the beam energy and undulator gap, the wavelength can be tuned from 0.05 to 0.4 nm. SASE3 is a soft X-ray FEL using planar undulators with a period length of 68 mm, called U68s. Under the same conditions, the wavelength can be tuned from 0.4 to 5.2 nm.     

Results and Perspectives for Short-Wavelength,Four-Wave-Mixing Experiments with Fully Coherent Free Electron Lasers

The discovery of the nonlinear optical response [1 P.A. Franken, A.E. Hill, and C.W. Peters, Physical Review Letters 7(4), 118–119 (1961).[Crossref], [Web of Science ®] , [Google Scholar]] has triggered the development of new theoretical and experimental approaches. These are based on the perspective that light-matter interactions are not necessarily cast in the picture of “one photon at a time,” typical of linear processes, but more photons can “work together” in order to coherently stimulate and probe (via nonlinear interactions) different kinds of dynamics in a sample. Nowadays, such a “multi-wave” concept is extensively used in a large array of methods, also termed wave-mixing, that have found numerous applications in almost all fields of physics, chemistry, and biology [2 N. Bloembergen, Review of Modern Physics 54(3), 685–695 (1982).[Crossref], [Web of Science ®] , [Google Scholar], 3 R.W. Boyd, Nonlinear Optics, 3^rd ed., Academic Press, New York (2008). [Google Scholar]]. Such methods are often based on third-order processes, referred to as four-wave-mixing (FWM), in which a threefold light-matter interaction results in the generation of a (fourth) signal photon, whose photon parameters (frequency, wave vector, polarization, etc.) may differ from those of the input fields. The possibility to control the latter parameters turns into the capability to selectively probe different FWM processes, which can contain distinct and complementary information. In addition to this high degree of selectivity, FWM is often featured in ultrafast time resolution and can be used to study dynamics hardly accessible by linear methods [3 R.W. Boyd, Nonlinear Optics, 3^rd ed., Academic Press, New York (2008). [Google Scholar]], such as spin waves and relaxations [4 A.R. Cameron, P. Riblet, and A. Miller, Physical Review Letters 76(25), 7493–7496 (1996).[Crossref], [Web of Science ®] , [Google Scholar], 5 C.P. Weber, Nature 437(7063), 1330–1333 (2005).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]] or Raman transitions between unoccupied electronic states [6 Y. Prior, Phys. Rev. Lett. 46(2), 111–114 (1981).[Crossref], [Web of Science ®] , [Google Scholar], 7 J.R. Andrews and R.M. Hochstrasser, Chemical Physics Letters 82(3), 381–385 (1981).[Crossref], [Web of Science ®] , [Google Scholar]].     

Cryogenic Permanent Magnet Undulator Development at HZB/BESSY II

The costs of a synchrotron radiation facility scales approximately linearly with the length (FEL) or the circumference (storage ring) of the machine. It is always beneficial for the reduction in overall expenses to utilize short period in-vacuum undulators (IVUs) for X-ray production. This is the reason for the success of the IVU development which was started almost 20 years ago in Japan [1 T. Hara, J. Synch. Rad., 5, 403–405 (1998).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]–3 T. Tanaka, Proc. FEL Conf., Stanford, CA, 370–377 (2005). [Google Scholar]]. Today, IVUs are implemented into nearly all third-generation storage rings. Ten years ago, the concept of cryogenically cooled permanent magnet undulators (CPMUs) was proposed [4 T. Hara, Phys. Rev. ST Accel. Beams, 7, 050702-1-6 (2004).[Crossref] , [Google Scholar]]. The magnetic properties of rare earth magnets (i.e., the remanence and the coercivity) improve substantially at low temperatures. The remanence increases by about 15%, whereas the coercivity grows by a factor of three to four. Due to the performance gain and the low technical risk of CPMUs, such devices are under development all over the world. The first generation of CPMUs, with period lengths well below 20 mm, is successfully operated at ESRF [5 J. Chavanne, AIP Conf. Proc., SRI 2009, Melbourne, Australia 1234, 25–28 (2010). [Google Scholar], 6 J. Chavanne, Proc. PAC, Vancouver, BC, Canada, 2414–2416 (2009). [Google Scholar]], PSI [7 T. Tanaka et al, Phys. Rev. ST Accel. Beams, 12, 120702-1-5 (2009).[Crossref] , [Google Scholar]], DIAMOND [8 C. Ostenfeld and M. Pedersen, Proc. IPAC, Kyoto, Japan, 3093–3095 (2010). [Google Scholar]], SOLEIL [9 C. Benabderrahmane, J. Phys., Conf. Ser., SRI 2012, Lyon, France 425, 032019-1-4 (2013). [Google Scholar]], and SPring-8 [10 T. Tanaka, Private communication (2015). [Google Scholar]].