Reaction dynamics studied via femtosecond X-ray liquidography at X-ray free-electron lasers

X-ray free-electron lasers (XFELs) provide femtosecond X-ray pulses suitable for pump–probe time-resolved studies with a femtosecond time resolution. Since the advent of the first XFEL in 2009, recent years have witnessed a great number of applications with various pump–probe techniques at XFELs. Among these, time-resolved X-ray liquidography (TRXL) is a powerful method for visualizing structural dynamics in the liquid solution phase. Here, we classify various chemical and biological molecular systems studied via femtosecond TRXL (fs-TRXL) at XFELs, depending on the focus of the studied process, into (i) bond cleavage and formation, (ii) charge distribution and electron transfer, (iii) orientational dynamics, (iv) solvation dynamics, (v) coherent nuclear wavepacket dynamics, and (vi) protein structural dynamics, and provide a brief review on each category. We also lay out a plausible roadmap for future fs-TRXL studies for areas that have not been explored yet.

Femtosecond X-ray liquidography using X-ray free-electron lasers (XFELs) visualizes various aspects of reaction dynamics.     

Epitaxial growth of MgO films on Si(1 1 1) by metal organic chemical vapor deposition

Epitaxial MgO films were grown on Si(1 1 1) substrates at 800°C using methylmagnesium tert-butoxide (MeMgO^tBu) as a single precursor under high-vacuum conditions (5×10⁻⁶ Torr). The crystalline structure, morphology, and chemical composition of the deposited films were investigated by X-ray diffraction, X-ray pole figure analysis, scanning electron microscopy, and X-ray photoelectron spectroscopy. The results show that epitaxial MgO films with correct stoichiometry can be deposited on Si(1 1 1) at 800°C. The single precursor methylmagnesium tert-butoxide has been found suitable for the epitaxial growth of MgO on Si(1 1 1) substrates.     

Global estimates of fundamental solutions for higher-order Schr?dinger equations

In this paper we first establish global pointwise time-space estimates of the fundamental solution for Schr?dinger equations, where the symbol of the spatial operator is a real non-degenerate elliptic polynomial. Then we use such estimates to establish related L ^p ?CL ^q estimates on the Schr?dinger solution. These estimates extend known results from the literature and are sharp. This result was lately already generalized to a degenerate case (cf. [4]).     

Progressive formation of fine and coarse ripples on SiC surface by repeated irradiation of femtosecond laser pulses

In this work, we report the progressive formation of first nanoparticles, next fine ripples, and eventually coarse ripples during the irradiation of single-crystal 6H-SiC surfaces with increasing number of femtosecond laser pulses (λ = 515 nm, τ = 250 fs, repetition rate = 100 kHz). At laser fluences greater than the single-pulse ablation threshold, nanoparticles were produced on the surface by the first few pulses over which fine ripple patterns overlapped at increased pulse numbers. As the pulse number was further increased over ten, the surface was gradually transformed into a coarse ripple–covered one. At laser fluence below the threshold, however, only fine ripples were formed nonuniformly.     

Analysis of creep due to grain-boundary diffusion in hexagonal microstructures

For steady-state deformation caused by grain-boundary diffusion in hexagonal microstructures, the stress distribution on grain boundaries and the macroscopic strain rates are analysed by taking the effects of viscous grain-boundary sliding into account. The maximum normal stress and the extent of stress concentration are shown to decrease as the grain-boundary viscosity increases. For infinite viscosity and/or extremely small grain sizes, the distribution of the normal stress becomes uniform on grain boundaries. The strain rates are predicted by both the stress analysis and the energy balance method, and the two strain rates are consistent with each other. The predicted strain rates also decrease as the grain-boundary viscosity increases. The present analysis reveals that the grain-size exponent is dependent on the grain size and the grain-boundary viscosity: the exponent becomes unity for small grain sizes and/or high viscosity, while it is three for large grain sizes and/or low viscosity. Recent experimental observations that the strain rates of nano-sized grain are much lower than those predicted by grain-boundary diffusion are explained by the increasing contribution of viscous grain-boundary sliding with decreasing grain size.     

Sputter-deposited ZnO thin films consisting of nano-networks for binder-free dye-sensitized solar cells

ZnO nano-network structures with high porosity were prepared for use in the photoelectrodes of binder-free dye-sensitized solar cells (DSSCs) by DC sputtering and subsequent thermal oxidation. Zn thin films prepared at 100 °C showed nano-network structures with high porosity, while those prepared at 25 °C did not. This was partially attributed to the high mobility of sputter-deposited particles that arrived at the surface of the substrate and partially to a supersaturation mechanism. The prepared nano-network Zn was successfully transformed to ZnO without a morphological change via subsequent annealing in air. The power conversion efficiency of DSSCs based on the ZnO nano-network structures exhibited 10 times higher efficiency than those based on ZnO film prepared at 25 °C because of its large surface area for adsorption of dye molecules. The thickness of the ZnO nano-network structures increased linearly at 10 μm h^?1 as a function of sputter time. As the film thickness increased, the power conversion efficiency of DSSCs increased from 1.09% to 1.82%.     

Novel fabrication route for carbon-free and dense CuInSe2 (CIS) thin films via a non-vacuum process for solar cell application

Carbon-free CuInSe₂ (CIS) thin film with a dense microstructure has been prepared using a novel non-vacuum based fabrication route. Cu_xS_y and In₂Se₃ binary nanoparticles, approximately 10 nm in size, were synthesized by a low temperature colloidal process. The precursor film was deposited using the coating ink formulated with the binary nanoparticles and pyridine, and then annealed in the rapid thermal annealing (RTA) chamber at 540 °C for 15 min under selenium (Se) atmosphere. Scanning electron micrographs, X-ray diffraction patterns and Raman spectra showed a phase pure carbon-free and dense CIS thin film was prepared in this method. A solar cell device fabricated using this CIS thin film showed the following photovoltaic characteristics: V_OC = 350 mV, J_SC = 24.72 mA cm⁻², FF = 38.73% and η = 3.36% under standard AM 1.5 condition.     

Graphene Modified Lipophilically by Stearic Acid and its Composite With Low Density Polyethylene

Graphene, prepared by the thermal reduction of graphite oxide (GO), was modified with stearic acid to enhance its lipophilicity. A novel method, using the intrinsic epoxy groups on the graphene, was utilized for reaction with stearic acid to minimize the negative impact of the normal functionalization method on the π-electronic system of graphene. Gravimetric analysis, thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS) showed that the stearic acid was effectively attached to the graphene. In addition, Raman spectroscopy and electric conductivity of the graphene showed that this novel modification method, utilizing intrinsic defects, did not damage the π-electronic system of the sp² bonded carbons. The dispersion of graphene in a low density polyethylene (LDPE) matrix was enhanced; consequently, the reinforcing effect in tensile testing was improved by the lipophilic modification. The crystallization behavior observed by differential scanning calorimetry (DSC) showed that the crystallization of LDPE was hindered by dispersed graphene, more evidently when dispersed uniformly.     

Pionic K X-rays in liquid He

Energies and lorentzian widths of pionic K X-ray transitions have been measured in liquid ³He with improved accuracy. The strong interaction on the π³He 1s level is found to be attractive and to produce an increase in the K transition energies of 34 ± 4 eV; the measured lorentzian width is 36 ±7 eV. Measured values are also presented for K X-ray energies in liquid π⁴He and μ⁴He, the lorentzian width of the 1s level in π⁴He, and relative intensities of K X-ray transitions in π³He, π⁴He and μ⁴He. The measurements are compared with those of others and with recent theoretical calculations.     

The Peierls instability in one-dimensional conductors with arbitrary bandfilling

Mean field calculations of the Peierls instability have been carried out for arbitrary bandfilling both in the case of free electrons as well as for the tightbinding approximation. New expressions for Δ(0) and T_p are derived which change the experimentally derived λ to a more reasonable value. Δ(0)/k_BT_p may differ significantly from the BCS value 1.76 in the tightbinding approximation.