Study of terahertz pulses at an edge

The propagation behaviour of terahertz(THz)pulses at an edge is characterized.The phenomenon that the amplitude oscillates periodically in the frequency spectrum is similar to Young's interference,if the absorption effect is neglected.The oscillation cycle is shorter for a thicker sample.THz pulses at an edge are analyzed by the broadband Huygens-Fresnel diffraction integral.The experimental results are in agreement with the simulation results approximately.The simulation errors are also analyzed.     

Can tetra‐tert‐butylethylene be formed by ion–ion recombination or ion–molecule reaction of two di‐tert‐butylcarbene units?—a DFT study

The reaction channels of di‐tert‐butylcarbene ( 2 ), its radical anion, ( 3 ) and its radical cation ( 4 ) were investigated theoretically by using DFT/B3LYP with 6‐31+G(d) basis set and 6‐311+G(2d,p) for single point energy calculations. Conversion of the neutral carbene 2 to the charged species 3 and 4 results in significant geometric changes. In cation 4 two different types of C? (CH₃)₃ bonds are observed: one elongated sigma bond called “axial” with 1.61 Å and two normal sigma bonds with a bond length of 1.55 Å. Species 2 and 4 have an electron deficient carbon center; therefore, migration of CH₃ and H is observed from adjacent tert‐butyl groups with low activation energies in the range of 6–9 kcal/mol like similar Wagner–Meerwein rearrangements in the neopentyl‐cation system. Neutral carbene 2 shows C? H insertion to give a cyclopropane derivative with an activation energy of 6.1 kcal/mol in agreement with former calculations. Contrary to species 2 and 4 , the radical anion 3 has an electron rich carbon center which results in much higher calculated activation energies of 26.3 and 42.1 kcal/mol for H and CH₃ migrations, respectively. NBO charge distribution indicates that the hydrogen migrates as a proton. The central issue of this work is the question: how can tetra‐tert‐butylethylene ( 1 ) be prepared from reaction of either species 2 , 3 , or 4 as precursors? The ion–ion reaction between 3 and 4 to give alkene 1 with a calculated reaction enthalpy of 203.5 kcal/mol is extremely exothermic. This high energy decomposes alkene 1 after its formation into two molecules of carbene 2 spontaneously. Ion–molecule reaction of radical anion 3 with the neutral carbene 2 is a much better choice: via a proper oriented charge–transfer complex the radical anion of tetra‐tert‐butylethylene (11) is formed. The electron affinity of 1 was calculated to be negligible. Copyright © 2010 John Wiley & Sons, Ltd.     

Self‐trapped N?H vibrational states in the polymorphs of glycine,L‐ and DL‐alanine

The polarized Raman spectra of the oriented single crystals of L ‐ and DL ‐alanine, α‐, β‐ and γ‐polymorphs of glycine have been studied at 3–300 K. Regularly spaced band packets have been observed in the spectral range of 2500–3000 cm⁻¹, with intensity decreasing noticeably on heating. These band packets were interpreted as the manifestations of the existence of N H self‐trapped states in these systems at low temperatures. The analysis of the polarized spectra has shown that the self‐trapping is observed exclusively for the NH stretching vibration of the amino groups, which is related to the NH···O hydrogen bonds along the head‐to‐tail chains of zwitterions in the crystal structures. The wavenumber of this NH stretching vibration, however, was proposed to depend not solely on the length of this NH···O hydrogen bond, but also on the lengths of all the other NH···O hydrogen bonds formed by the NH₃⁺ and the COO⁻ groups in the structure linking the head‐to‐tail chains with each other. The arguments in favor of the hypothesis that the self‐trapping in these systems can be mediated by zero‐point quantum motions, and not by lattice phonons, are considered. The unusually low wavenumber (2500 cm⁻¹) observed for the NH stretching vibration and indicating at the formation of a very strong NH···O bond is interpreted based on considering the effect of the crystalline environment on the formation and properties of the NH···O bonds in the head‐to‐tail chains of amino acid zwitterions. The results are interesting for understanding the factors determining the dynamics and structural instability of crystalline amino acids and also for biophysical chemistry, as the hydrogen bonded chains formed by amino acid zwitterions in the crystals can mimic the peptide chains. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of temperature on refractive index match of laser glass edge cladding

An Nd：glass disc requires an edge cladding to absorb the amplified spontaneous emission. The absorption is determined by reflections （R） from disc edges. R is primarily induced by the refractive index （n） mismatch. Thus, the temperature at the cladding interface increases due to absorption, and leads to the variation of n. In order to investigate the effect of temperature on the refractive index match, temperature coefficients （dn/dT） of the laser glass, adhesive polymer, and cladding glass are measured. The effect of temperature on the refractive index match is discussed. Results show that the indices match below 40 ℃.     

Computational study of singlet and triplet sulfonylnitrenes insertion into 1,3‐butadienes: 1,2‐ or 1,4‐cycloaddition?

The formation of N‐trifluoromethylsulfonyl‐2‐vinylaziridine and N‐trifluoromethylsulfonyl‐3‐pyrroline by the reaction of the singlet and triplet trifluoromethanesulfonylnitrenes with s‐cis‐ and s‐trans‐1,3‐butadienes was studied theoretically at the B3LYP/6‐311++G(d,p) and M06‐2X/6‐311++G(d,p) levels of theory. The singlet trifluoromethanesulfonylnitrene adds to s‐cis‐ and s‐trans‐1,3‐butadiene exothermally in one step to give the product of 1,2‐cycloaddition, N‐trifluoromethylsulfonyl‐2‐vinylaziridine, the energy decreasing by 88.5 and 86.2 kcal/mol at the B3LYP level and by 105.2 and 103.0 kcal/mol at the M06‐2X level, respectively. The formed 2‐vinylaziridine can undergo rotation about the C(2)–C_sp2 bond with the barrier not exceeding 3.5 kcal/mol and to rearrange into N‐trifluoromethylsulfonyl‐3‐pyrroline. The triplet trifluoromethanesulfonylnitrene reacts with s‐cis‐ and s‐trans‐1,3‐butadiene in two steps. The first exothermic step is the formation of the triplet diradical adducts. The second step is the spin inversion with the energy raising by 5.8 and 17.8 kcal/mol at the B3LYP level and by 11.0 and 20.8 kcal/mol at the M06‐2X level for the adducts to s‐cis‐ and s‐trans‐1,3‐butadiene, respectively. Recombination of the radical centers occurs selectively to give N‐trifluoromethylsulfonyl‐2‐vinylaziridine that is exothermally rearranged into N‐trifluoromethylsulfonyl‐3‐pyrroline with the energy barrier of 40 kcal/mol at the B3LYP level and of 50 kcal/mol at the M06‐2X level. Copyright © 2014 John Wiley & Sons, Ltd.     

Symmetry dependence of x—ray absorption near—edge structure at rhe metal K edge of 3d transition metal compounds

The pre-edge features in system with “even” symmetry,apart from quadrupolar tranition contribution,are mainly dipolar in character,associated with the existence of unoccupied states made up of mixed cation np with higher-neighboring cation-(n-l)d orbitals,and reflect the density of states due to the medium-range order of the system,while in “ood” symmetry materials these pre-edge features are the result of a transition from the 1s to final denisty of states of p symmetry due to an unsymmetrical mixing of the ligand wave functions with the central cation d orbitals.In the latter case,they contain not only the p but also the d base of orbitals,similar to a tetrahedral configuration.These results are validated for Fe as a photoabsorber by comparing x-ray absorption near-edge spectra of Fe2SiO4(fayalite) and Fe2O3(hematite) to ab initio full multiple scattering calculations at the Fe K edge,but pertain to all systems containing sixfold-coordinated cations.     

X‐ray absorption spectroscopy at the Ni?K edge in Stackhousia tryonii Bailey hyperaccumulator

Young plants of Stackhousia tryonii Bailey were exposed to 34 mM Ni kg^?1 in the form of NiSO₄· 6H₂O solution and grown under controlled glasshouse conditions for a period of 20 days. Fresh leaf, stem and root samples were analysed in vivo by micro x‐ray absorption spectroscopy (XAS) at the Ni? K edge. Both x‐ray absorption near edge structure and extended x‐ray absorption fine structure spectra were analysed, and the resulting spectra were compared with spectra obtained from nine biologically important Ni‐containing model compounds. The results revealed that the majority of leaf, stem and root Ni in the hyperaccumulator was chelated by citrate. Our results also suggest that in leaves Ni is complexed by phosphate and histidine, and in stems and roots, phytate and histidine. The XAS results provide an important physiological insight into transport, detoxification and storage of Ni in S. tryonii plants. Copyright © 2008 John Wiley & Sons, Ltd.     

A new discovery of edge localized modes suppression using ICRH

The high-confinement mode(H-mode) is very important for the fusion performance of ITER and future fusion reactors[1]. The H-mode pedestal is a region featuring strongly reduced turbulence and transport just inside the limiting flux surface with strong plasma gradients, which drive edge localized modes(ELMs) in tokamaks [2].     

Intra‐ and intermolecular N?H···O hydrogen bonds in pyrrolyl derivatives of indane‐1,3‐dione – experimental and theoretical study

2‐(Pyrrol‐2‐ylmethylene)‐1,3‐indandione ( 4 ) and 2‐(pyrrol‐2‐ylmethylene)‐3‐dicyanomethylidene‐1‐indanone ( 5 ) were synthesized. Multinuclear and 2D‐NMR, IR, UV spectroscopic investigations as well as quantum chemical calculations showed the presence of strong hydrogen bonding in these molecules. For both molecules, the presence of two conformers, with and without H‐bond, was experimentally detected in the basic solvents (DMSO, acetone, pyridine) and the solvate complexes were theoretically calculated. Specific behavior of the intramolecular H‐bonded complexes different from that of the intermolecular H‐complexes is discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Determination of conduction band edge characteristics of strained Si/Si1-xGex

The feature of conduction band （CB） of Tensile-Strained Si（TS-Si） on a relaxed Si1-xGex substrate is systematically investigated, including the number of equivalent CB edge energy extrema, CB energy minima, the position of the extremal point, and effective mass. Based on an analysis of symmetry under strain, the number of equivalent CB edge energy extrema is presented; Using the K.P method with the help of perturbation theory, dispersion relation near minima of CB bottom energy, derived from the linear deformation potential theory, is determined, from which the parameters, namely, the position of the extremal point, and the longitudinal and transverse masses （m1^＊ and mt^＊）are obtained.     

Atomistic simulation of kink structure on edge dislocation in bcc iron

Based on the general theory of dislocation and kink, we have constructed the three kink models corresponding to the 1/2 （111）{011} and 1/2 （111）{112} edge dislocations （EDs） in bcc Fe using the molecular dynamics method. We found that the geometric structure of a kink depends on the type of ED and the structural energies of the atom sites in the dislocation core region, as well as the geometric symmetry of the dislocation core and the characteristic of the stacking sequence of atomic plane along the dislocation line. The formation energies and widths of the kinks on the 1/2 （111）{011} and 1/2 （111）{112} EDs are calculated, the formation energies are 0.05eV and 0.04eV, and widths are 6.02b and 6.51b, respectively （b is the magnitude of the Burgers vector）. The small formation energies indicate that the formation of kink in the edge dislocation is very easy in bcc Fe.     

Optical absorption edge of As<Subscript>40–<Emphasis Type="Italic">x</Emphasis></Subscript>Sb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>60</Subscript> glassy alloys

The fundamental absorption edge of glassy alloys of an As–Sb–S system was studied in the temperature range 77–300 K. The spectral and thermal behavior of the fundamental absorption edge of As_40–x Sb_xS₆₀ glasses was shown to be described by an exponential function of phonon energy. The temperature and concentration behavior of the optical band gap in the studied glasses was established. The well-known Varshni relationship was used to describe the temperature dependence of the optical band gap.     

A new prediction method at the edge of optical burst switching network

To achieve lower assembly delay at optical burst switching edge node, this paper proposes an approach called current weight length prediction (CWLP) to improve existing estimate mechanism in burst assembly. CWLP method takes into account the arrived traffic in prediction time adequately. A parameter 'weight' is introduced to make a dynamic tradeoff between the current and past traffic under different offset time. Simulation results show that CWLP can achieve a significant improvement in terms of traffic estimation in various offset time and offered load.     

Fundamental absorption edge and normal dispersion of β-LiNaSO4 single crystal

Lithium sodium sulfate (LiNaSO₄)single crystal is synthesized and grown by the slow evaporation of supersaturated aqueous solution at constant temperature (303 K). Powder X-ray diffraction is measured at room temperature in order to identify the grown crystal. Transmittance and reflectance measurements are used to study the optical properties of this crystal at room temperature phase (β-LiNaSO₄). The type of transition is determined. The values of optical energy gap, phonon energy and phonon equivalent temperature are calculated. Refractive index and extinction coefficient are calculated as functions of photon energy. The obtained optical data of β-LiNaSO₄ crystal are used to check the validity of both Wemple-DiDomenico and Cauchy-Sellimaier dispersion relations. Normal dispersion parameters of this crystal are calculated for the first time.     

Observation of acoustic edge magnetoplasmons near the filling factor ν = 1

Investigation of acoustic edge magnetoplasma excitations in micrometer two-dimensional electron disks has been carried out. It has been shown that additional acoustic edge magnetoplasma modes associated with the existence of incompressible strips in the two-dimensional electron system caused by Zeeman spin splitting can appear in the system at temperatures below the Zeeman energy. The magnetic dispersion of the first “spin” branch of acoustic edge magnetoplasmons has been studied. It has been shown that this mode vanishes as the filling factor ν = 1 is approached. The dependence of the relative amplitude of acoustic edge magnetoplasmons on the filling factor has also been investigated.     

Do formalin fixation and freeze‐thaw affect near‐infrared Raman spectroscopy of cartilaginous tissue? A preliminary ex vivo analysis of native human articular cartilage

Near‐infrared (NIR) Raman microprobe spectroscopy has been applied to the non‐invasive characterization of the biochemical structure of extracellular matrix in articular cartilage, a step forward along the path of in vivo diagnostic application of chondropathy. In most studies handling ex vivo cartilage specimens, formalin fixation or freeze‐thaw treatments have been applied in order to stabilize tissue and cell constituents prior to spectroscopic measurements. However, these pre‐processing manipulations might significantly affect certain target bands of the cartilage spectra, thus introducing biases in the characterizations, and potentially leading to data misinterpretation. In this study, we evaluated how formalin fixing and freeze‐thaw processes affect Raman spectra from human femur cartilage. Healthy cartilage specimens were fixed/stored either in a 10% neutral buffered formalin solution or in a deep freezer set at −80 °C. The results of this study show that formalin fixation significantly affects the NIR Raman spectra of cartilage specimens due to concurrent formalin absorption and water dehydration within both collagen and glycosaminoglycan macromolecules. Water dehydration was also confirmed in the amide I structure in the frozen‐thawed specimen, but to a much lesser extent. Furthermore, soaking the tissues in phosphate‐buffered saline solution minimized the storage‐induced Raman artifacts, but its immersion had limited effectiveness in formalin‐fixed specimens, predominantly due to an overlap of signals from the formalin liquid (i.e. emitting at 1046 and 1492 cm⁻¹). Therefore, to provide a highly accurate biochemical evaluation of extracellular matrix using NIR Raman spectroscopy, freeze‐thaw processes are more suitable for ex vivo samples of human cartilage than formalin fixation. Copyright © 2015 John Wiley & Sons, Ltd.     

Laser detection of elastic waves diffraction by the crack’s edge

Diffraction effects and features of acoustic wave propagation in elastic media with the surface-breaking microcrack were investigated in detail for the pulse probing signals. The crack’s plane was oriented along the direction of longitudinal ultrasonic wave incidence in such a way that the detection of the crack with such an unfavorable spatial location was difficult by means of traditional acoustic techniques. Using laser Doppler interferometer a set of instantaneous pictures of acoustic field on the specimen’s surface, corresponding to the different moments of time was obtained. This allowed us to investigate and visualize the diffraction effects of acoustic field in dynamics. Using numerical modeling of diffraction processes of acoustic waves on the crack’s edge and top for pulse signals the origin of V-like structures on the snapshots of acoustic fields was explained and analyzed.     

Effects of oxygen partial pressure on optical absorption edge and UV emission energy of ZnO films

ZnO, with a band-gap of 3.37 eV and a large exciton binding energy (about 60 meV) at room temperature, is a promising material for optoelectronic devices, field- emission displays, and gas sensors. Recently, the interest in short wavelength display device is on the increase. In this regard, ZnO is a promising material[1-6]. High quality ZnO films have been prepared by many methods such as sputtering[7], reactive thermal and electron-beam evaporation[8], pulse laser deposition[9], chemical v…