Reduced Electron Density Research Articles

Redox-Induced Interconversion of Two Au8 Nanoclusters: the Mechanism and the Structure-Bond Dissociation Activity Correlations.

The interconversion of atomically precise nanoclusters represents an excellent platform to understand the structural correlations of nanomaterials at the atomic level. Herein, density functional theory calculations were performed to elucidate the mechanism of the redox-induced interconversion of [Au8(dppp)4]2+ and [Au8(dppp)4Cl2]2+ (dppp is short for 1,3-bis(diphenylphosphino)propane) nanoclusters. Reduction is the driving force for the conversion of [Au8(dppp)4Cl2]2+ to [Au8(dppp)4]2+, while the Au-Au and first Au-Cl bond dissociations occur asynchronously on the two different corner Au atoms to avoid the formation of an electron-deficient Au atom. By contrast, the reduced electron density of [Au8(dppp)4]2+ by oxidation with O2 weakens the outmost Au-Au bond therein and facilitates the coordination of the electron-rich chloride(s). The reduction- and oxidation-induced activations, respectively, of Au-Cl and Au-Au bonds and the elucidated principles on the structure-activity correlations might also be generalized to other size conversions upon redox treatment.

Electron acceleration at oblique angles via stimulated Raman scattering at laser irradiance >10^{16}Wcm^{-2}μm^{2}.

The generation of hot, directional electrons via laser-driven stimulated Raman scattering (SRS) is a topic of great importance in inertial confinement fusion (ICF) schemes. Little recent research has been dedicated to this process at high laser intensity, in which back, side, and forward scatter simultaneously occur in high energy density plasmas, of relevance to, for example, shock ignition ICF. We present an experimental and particle-in-cell (PIC) investigation of hot electron production from SRS in the forward and near-forward directions from a single speckle laser of wavelength λ_{0}=1.053μm, peak laser intensities in the range I_{0}=0.2-1.0×10^{17}Wcm^{-2} and target electron densities between n_{e}=0.3-1.6%n_{c}, where n_{c} is the plasma critical density. As the intensity and density are increased, the hot electron spectrum changes from a sharp cutoff to an extended spectrum with a slope temperature T=34±1keV and maximum measured energy of 350 keV experimentally. Multidimensional PIC simulations indicate that the high energy electrons are primarily generated from SRS-driven electron plasma wave phase fronts with k vectors angled ∼50^{∘} with respect to the laser axis. These results are consistent with analytical arguments that the spatial gain is maximized at an angle which balances the tendency for the growth rate to be larger for larger scattered light wave angles until the kinetic damping of the plasma wave becomes important. The efficiency of generated high energy electrons drops significantly with a reduction in either laser intensity or target electron density, which is a result of the rapid drop in growth rate of Raman scattering at angles in the forward direction.

Performance improvement with plasma edge biasing on SPECTOR

A description of an edge-biasing experiment conducted on the spherical compact toroid plasma injector is presented with results. The insertion of a disk-shaped molybdenum electrode (probe), biased at up to +100 V, into the edge of the Compact Torus (CT), resulted in up to 1.2 kA radial current being drawn from the probe to the wall. Core electron temperature, as measured with a Thomson-scattering diagnostic, and CT lifetime, more than doubled in the optimal configuration tested. Temperature and density profiles become more centrally peaked with biasing. In contrast to previous biasing experiments, a significant reduction in electron density was observed; this may be due to the effect of a transport barrier impeding CT fueling and associated cooling, where, as verified by MHD simulation, a principal fueling source is neutral gas that remains concentrated around the gas valves after CT formation.

Substituent-Mediated Transformation of Polynuclear Gold(I)-Sulfido Complexes—From Pentanuclear to Octadecanuclear Cluster-to-Cluster Transformation

Substituent-Mediated Transformation of Polynuclear Gold(I)-Sulfido Complexes—From Pentanuclear to Octadecanuclear Cluster-to-Cluster Transformation

Occurrence characteristics of equatorial plasma bubbles over Kisumu, Kenya during Solar maximum of Solar Cycle 24

Equatorial Plasma Bubbles (EPBs) are irregular plasma density depletions in the ambient electron density in the equatorial F-region ionosphere generated after sunset. EPBs are known to bring disruptions to telecommunication and navigation systems. This paper investigates the occurrence of EPBs over Kisumu, Kenya (Geomagnetic coordinates: 9.64o S, 108.59o E; Geographic coordinates: 0.02o S, 34.6o E) for a few selected quiet and storm days between 1st January 2013 and 31st December 2014 which was a high Solar activity period for Solar Cycle 24. The study brings out EPB occurrence pattern over Kisumu, Kenya for the selected quiet and storm days of 2013 and 2014. The Receiver Independent Exchange (RINEX) data was retrieved from the Kisumu high data-rate NovAtel GSV4004B SCINDA-GPS receiver. The data was unzipped and processed to obtain Vertical Total Electron Content (VTEC), amplitude scintillation (S4) and Universal Time (UT) which were then fed into MATLAB to generate VTEC and S4 plots against UT for each selected quiet and storm day within the years 2013 and 2014. The Total Electron Content (TEC) depletion depths and S4 index values between 16:00 and 20:00 UT for each selected quiet and storm day were extracted from the VTEC and S4 plots and used to plot TEC depletion depths and S4 plots. The Rate of Change of TEC (ROT) and Rate of Change of TEC Index (ROTI) between 16:00 and 20:00 UT were generated from VTEC and used to plot ROT and the corresponding ROTI plots against UT. TEC depletion depths and ROTI values for each selected quiet and storm day between 16:00 and 20:00 UT were extracted and used to plot TEC depletion depths and ROTI plots and S4 index and ROTI plots. In this study, the enhancement of S4 index corresponded well with TEC depletions, increased fluctuation of ROT and higher ROTI values between 16:00UT and 20:00UT for most days. This correspondence was used in inferring the occurrence of EPBs during the selected quiet and storm days of the years 2013 and 2014. The obtained results showed that the highest EPB occurrence was during March equinox with 33.33% occurrence in the year 2013 and 30.76% occurrence in the year 2014, followed by the September equinox which had 20.38% occurrence in 2013 and 17.26% occurrence in 2014. The seasonal variation of EPB occurrence was attributed to the variation in the daytime E x B drift velocities. Larger E x B drift velocities resulted in increased EPB occurrence in the equinoctial period (March, April, August and September) and November solstice period (November and December) while lower E x B drift velocities resulted in reduced EPB occurrence in the June solstice period (June and July). The percentage EPB occurrence in the year 2013 was 6.49% while in the year 2014 was 4.32%. The storm period had percentage EPB occurrence of 21.42% in the year 2013 and 21.88% in the year 2014 while the quiet period had percentage EPB occurrence of 18.75% in the year 2013 and 7.89% in the year 2014. These results clearly showed that the percentage EPB occurrence was higher during the storm period than in the quiet period. Hence the development of EPBs was enhanced by geomagnetic activity through several competing dynamics such as Prompt Penetration Electric Field (PPEF), Disturbance Dynamo Electric Field (DDEF) and reduction in electron density due to increased recombination rates. Â

Effect of ions on conductivity and permittivity in the Polar Mesosphere Summer Echoes region

For the first time, the effect of ions on complex conductivity and permittivity of dusty plasma at Polar Mesosphere Summer Echoes (PMSE) altitude is analyzed. Because of ions higher mass and smaller thermal velocity, generally, their effects are not considered in the study of electromagnetic properties of dusty plasmas. In this study, we modified the equations of conductivity and permittivity by adding the effect of ions. In the PMSE altitude region between 80 and 90 km, a local reduction in electron density (i.e., an electron bite-out), is produced by electron absorption onto dust particles. The bite-out condition contains high dust density and smaller electron density. From simulation results in comparatively strong bite-out conditions, we found that the ion effects on conductivity become significant with smaller dust size, lower electron temperature, and lower neutral density. For comparatively weak bite-out conditions, the ion effects on conductivity become significant with larger dust size, higher electron temperature, and higher neutral density. On the other hand, for different dust sizes, electron temperatures and neutral density, the ion effects on complex permittivity become significant only in very strong bite-out conditions. Based on these simulation results, we conclude that, in the absence of electron bite-out conditions, the effect of ions on complex conductivity and permittivity is not significant and can be ignored. However, during bite-out conditions, the effect of ions becomes significant and cannot be ignored because it significantly changes the conductivity and permittivity of dusty plasmas.

Tellurium-Polysulfide Chemistry Enables Stable Operation of Lithium-Sulfur Batteries with Limited Lithium Inventory and Electrolyte Supply

The practical realization of lithium-sulfur (Li-S) batteries with high energy density is currently limited by the poor cyclability of the lithium-metal anode. Lithium plating and stripping in the liquid ether-based electrolyte is irreversible over long-term cycling and this leads to rapid capacity fade. Due to the reducing nature of lithium, parasitic side reactions with the electrolyte also occur with considerable severity during cell operation. This eliminates a significant portion of the available lithium inventory and electrolyte supply, and the cell fails prematurely. These problems can be sidestepped by employing surplus lithium and electrolyte in the cell, but this compromises the stack-level energy density. Stabilizing lithium deposition and reducing electrolyte decomposition is of critical importance to enabling commercially viable Li-S batteries with high energy density and long cycle life.The chemistry of Li-S batteries is unique due to the generation of polysulfide intermediates at the cathode that are soluble in the electrolyte. The polysulfides migrate to the anode side, which fundamentally alters its interfacial chemistry by forming reduced sulfide species (Li2S/Li2S2) on the lithium surface. These species are known to have an intrinsically stabilizing effect on lithium deposition, although it is not sufficient to enable stable operation of Li-S batteries at reasonable current densities. Nevertheless, the modification of electrolyte-soluble polysulfide species offers a unique opportunity for tuning the interfacial chemistry of the lithium-metal anode towards stabilizing lithium deposition and reducing electrolyte decomposition.Tellurium, which sits two position below sulfur in Group 16 of the periodic table, is an excellent candidate element for modifying the composition of polysulfide intermediates in Li-S batteries and forming potentially favorable components in the lithium SEI layer. It was found that elemental tellurium (Te0) could be facilely assimilated into polysulfide species to form soluble mixed polytellurosulfide species when left in an ethereal solution of Li2S6. This was confirmed by the characteristic isotopic signature of tellurium using mass spectrometry. The polytellurosulfide species were found to reduce on the surface of lithium metal to form red-colored lithium thiotellurate (Li2TeS3), which was confirmed by X-ray techniques. In contrast to Li2S, Li2TeS3 is expected to be a significantly better ionic conductor due to the reduced electron density around the sulfur atoms. This would help engender a uniform lithium-ion flux on the lithium surface, enabling homogenous lithium deposition.Based on the results above, elemental tellurium was simply added in a 1 : 10 molar ratio to the sulfur/Li2S cathode to modify the chemistry of Li-S batteries. During cell operation, the generated polysulfides (Li2Sn) reacted with the Te0 additive in the cathode to form polytellurosulfide (Li2TexSy) species in-situ. The crossover of these tellurium-containing species to the anode side was confirmed by the detection of a significant amount of Li2TeS3 on the lithium surface. The favorable properties of Li2TeS3 as a lithium SEI component enabled the formation of dense and uniform lithium deposits and significantly improved lithium cycling efficiency. In the anode-free full cell configuration, which pairs a Li2S cathode with a bare anode current collector and contains zero excess lithium (N/P ratio = 1), the addition of tellurium improved cycle life by a factor of 7. The loss of the limited lithium inventory in the anode-free cell was reduced from 2% per cycle to 0.25% per cycle.Time-of-flight secondary ion mass spectrometry (ToF-SIMS) revealed the drastically reduced electrolyte decomposition on lithium surface due to tellurium-stabilized lithium deposition. The reduced electrolyte decomposition could allow a limited electrolyte supply to be retained for a longer number of cycles, thus enabling extended cyclability under lean-electrolyte conditions. This was confirmed using large-area pouch cells employing a high-loading sulfur cathode (5.2 mg cm-2), a lithium-foil anode, and a low electrolyte/sulfur (E/S) ratio of 4.5 µl mg-1. Under such stringent cell design conditions, the pouch cells could be cycled stably for nearly 100 cycles with the addition of tellurium. In contrast, the control cell failed within 25 cycles.This work demonstrates a novel, effective, and robust strategy of adding tellurium to the sulfur/Li2S cathode for stabilizing lithium deposition and reducing electrolyte decomposition in Li-S batteries. This improves cycle life in energy-dense cell configurations operating with a limited lithium inventory or electrolyte supply. Importantly, this approach is scalable as no expensive or complicated pre-treatments or coatings of the lithium-metal anode are necessary. The unique chemistry of tellurium in the polysulfide-rich environment of Li-S batteries opens a new frontier in research in Li-S batteries, bringing them one step closer to reality. Figure 1

Electron trapping and reinjection in prepulse-shaped gas targets for laser-plasma accelerators

A novel mechanism for injection, emittance selection, and postacceleration for laser wakefield electron acceleration is identified and described. It is shown that a laser prepulse can create an ionized plasma filament through multiphoton ionization and this heats the electrons and ions, driving an ellipsoidal blast-wave aligned with the laser-axis. The subsequent high-intensity laser-pulse generates a plasma wakefield which, on entering the leading edge of the blast-wave structure, encounters a sharp reduction in electron density, causing density down-ramp electron injection. The injected electrons are accelerated to $\ensuremath{\sim}2\text{ }\text{ }\mathrm{MeV}$ within the blast-wave. After the main laser-pulse has propagated past the blast-wave, it drives a secondary wakefield within the homogenous background plasma. On exiting the blast-wave structure, the preaccelerated electrons encounter these secondary wakefields, are retrapped, and accelerated to higher energies. Due to the longitudinal extent of the blast-wave, only those electrons with small transverse velocity are retrapped, leading to the potential for the generation of electron bunches with reduced transverse size and emittance.

The opposite pressure dependence of electron temperature with respect to O2/Ar mixing ratio in an inductively coupled plasma

To observe the evolution of electron temperature and electron density when varying gas mixing ratio and pressure, the measurement of electron energy probability functions (EEPFs) and a kinetic simulation are performed in an O2/Ar inductively coupled plasma. When O2 gas is diluted to pure Ar plasma, the electron density significantly drops regardless of gas pressures and the reduction of electron density increases with gas pressure. This sudden drop of plasma density is due to various inelastic collisions between electrons and O2 molecules. However, the trend of electron temperature variation with respect to the ratio of O2 and Ar is opposite at low and high pressures. At low pressure (5 mTorr), the electron temperature decreases with the addition of O2 up to a 10% O2 ratio. With further addition of O2, the electron temperature increases gradually. On the other hand, at high pressures (25 and 80 mTorr), the electron temperature rises with addition of O2 up to a 10%–20% O2 ratio and then falls gradually with further addition of O2. Simulations show a similar variation of EEPFs to the EEPFs from experiments. In addition, we measured the EEPFs along axial positions and the variation of electron temperature with respect to the ratio of O2 and Ar is opposite at low and high pressures, regardless of spatial positions. This result indicates that the opposite trend of electron temperature variation is mainly affected by the gas mixing ratio and gas pressure.

Impact of the temperature ratio on turbulent impurity transport in Wendelstein 7-X

First experimental observations in the Wendelstein 7-X stellarator indicate that the impurity confinement can be explained by turbulent processes. In particular, plasma discharges with increased ion to electron temperature ratio are accompanied by reduced electron density fluctuation amplitudes and anomalous impurity diffusion, suggesting a lower turbulent transport. Employing gyro-kinetic numerical simulations, we argue that the temperature ratio plays a key role for reducing the ion temperature gradient instability in Wendelstein 7-X, leading to an enhanced impurity confinement.

Mitigation of blackout problem for reentry vehicle in traveling magnetic field with induced current

In this paper, a novel solution mitigating the radio blackout problem is proposed, which improves existing traveling magnetic field (TMF)-based methods. The most significant advance lies in replacing the external injection with self-induced current, which does not require electrodes. The improved analytical model is derived to evaluate the electron density reduction taking into consideration the self-induced current for various TMF velocities. The plasma reduction performance is analyzed for several conditions including the total absence of injected current. The results show that the velocity may be used to trade off the injected current and, when sufficiently large, eliminates the need for an injected current while mitigating radio blackout. The effectiveness of this solution to the blackout problem is demonstrated in commonly used aerospace communication bands. With a field strength of less than 0.15 T, increasing the velocity from 40 m s−1 to 3100 m s−1 is all that is required to obviate the need for an injected current. Moreover, typical reduction ratios for electronic density tolerance (2, 1.9, 1.75 and 3 times for the L-, S-, C- and X-bands, respectively, at an altitude of 40 km) remain unchanged. Increasing the velocity of the TMF is much easier than injecting current via a metal electrode into a high-temperature flow field. The TMF method appears practical in regard to possible future applications.

A Double Hemispherical Probe for Characterizing and Minimizing the Self‐Wake Effects on Probe Measurements

AbstractSpace‐borne Langmuir probes generally have a self‐wake behind themselves due to supersonic relative velocities (Mach number M > 1) between the spacecraft and ambient plasma ions. Such a wake may create difficulties for correctly measuring plasma characteristics. Here we present a new technique—the Double Hemispherical Probe (DHP) to characterize and minimize the self‐wake effects on probe measurements. The DHP consists of two hemispheres that are simultaneously swept with a bias voltage to obtain two independent current‐voltage (I‐V) curves, which are used to identify the wake effects of the probe. A laboratory DHP model is inserted in plasma flows (M > 10) created in the Colorado Solar Wind Experiment (CSWE) chamber. In this case, the ion current is the ram current collected by the upstream hemisphere of the DHP, leaving an ion wake behind the downstream hemisphere. A wide range of the Debye ratio RD (ratio of the probe radius to electron Debye length) is tested, and it is found that (1) when RD < 1, the electron currents collected by the two hemispheres are similar, indicating a uniform electron density around the probe, and (2) when RD > 1, the electron current collected by the downstream hemisphere becomes lower than the upstream, indicating a reduced electron density in the probe's wake due to the ambipolar electric field effect. In this case, the electron density measured by traditional single Langmuir probes will be underestimated. With the DHP, we can use the upstream hemisphere measurements to minimize the self‐wake effects.

The effect of H2O on the vibrational populations of CO2 in a CO2/H2O microwave plasma: a kinetic modelling investigation

Plasma has been studied for several years to convert CO2 into value-added products. If CO2 could be converted in the presence of H2O as a cheap H-source for making syngas and oxygenates, it would mimic natural photosynthesis. However, CO2/H2O plasmas have not yet been extensively studied, not by experiments, and certainly not computationally. Therefore, we present here a kinetic modelling study to obtain a greater understanding of the vibrational kinetics of a CO2/H2O microwave plasma. For this purpose, we first created an electron impact cross section set for H2O, using a swarm-derived method. We added the new cross section set and CO2/H2O-related chemistry to a pure CO2 model. While it was expected that H2O addition mainly causes quenching of the CO2 asymmetric mode vibrational levels due to the additional CO2/H2O vibrational-translational relaxation, our model shows that the modifications in the vibrational kinetics are mainly induced by the strong electron dissociative attachment to H2O molecules, causing a reduction in electron density, and the corresponding changes in the input of energy into the CO2 vibrational levels by electron impact processes.

Borospherene molecular junction-based sensor for detecting radium and radon in water

Abstract

Complex of 4-(2-aminophenyl) −1,2,3- thiadiazole with 2,3-dichloro- 5,6-dicyano-1,4-benzoquinone: Experimental study and investigation at different exchange-correlation functionals. DOS, NBO, QTAIM and RDG analyses

The complex formation between 4-(2-aminophenyl) −1,2,3- thiadiazole (ATDZ) and 2,3-dichloro- 5,6-dicyano-1,4-benzoquinone (DDQ) was studied experimentally and with molecular modeling. The highlighting of the interaction, the stability constant and the thermodynamic parameters determinations in chloroform were performed with UV spectrophometry. The solid state complex was synthesized and characterized with FTIR and NMR.In the DFT/6–311++g(d,p) study, fifteen exchange-correlation functionals were used: B3LYP, B3LYP-GD3BJ, B2PLYP, B2PLYP-D3, CAM-B3LYP, M06, M06-HF, M06–2X, M08-HX, M11, M06-L,M11-L, N12, MN12-L and N12-SX, in order to determine their accuracy in the prediction of structural parameters and vibration frequencies.To gain further insights into the NCI in this system, MEP, natural bond orbital (NBO) and the density of states (DOS) analysis were carried out. In addition, the global and local reactivity descriptors of ATDZ and the complex were determined.The π-π stacking interactions in this system were explored and visualized in the three-dimensional space with the help of QTAIM and the reduced electron density gradient RDG approaches.

Dynamic Changes of the Ionospheric Artificial Airglow Region Caused by High-Power Radio Waves Based on a Joint Analysis of Night-Sky Snapshots in the 630 nm Line and Total Electron Content Variation Maps

We describe a method for joint analysis of the night-sky snapshots and total electron content (TEC) variation maps and present a dynamic spatiotemporal configuration of the TEC variation intensity in the ionospheric airglow region in the red line of atomic oxygen (λ = 630 nm) stimulated by high-power radio waves from the Sura facility. The measurements were performed on the 29th of August, 2016. Two-dimensional TEC variation maps were plotted according to a network of 30 GNSS stations located within a radius of 700 km from the Sura heater. It is shown that the region of the maximum brightness of the artificial ionospheric airglow spot is spatially localized in the region of the minimum intensity of TEC variations, while the region of the maximum intensity of TEC variations corresponds to the region of the minimum brightness of the artificial airglow spot. Quantitative estimates for a cavity with reduced electron density in the artificial airglow region, which forms after the Sura pump wave is switched on, vary in the range ΔNe/Ne ≈ 4–9%, where Ne is the electron density and ΔNe is its variation in the cavity. The proposed experimental technique eliminates the limitations associated with the need for a navigation satellite to flyby directly over the main lobe of the Sura antenna pattern, which significantly increases the chances of successful simultaneous measurements of TEC variations and artificial ionospheric airglow in the 630 nm line.

Electronic modulation of iron-bearing heterogeneous catalysts to accelerate Fe(III)/Fe(II) redox cycle for highly efficient Fenton-like catalysis

Heterogeneous Fenton-like reaction was a promising approach for generating •OH. However, the heterogeneous catalysts generally exhibited low activity because of slow reduction of Fe(III) in Fe(III)/Fe(II) redox cycle. Here, decreasing electron density was expected to quicken Fe(III) reduction and consequently enhance the catalytic activity of heterogeneous catalysts. This hypothesis was validated by the enhanced hydroxyl radicals generation and accelerated Fe(III) reduction on MIL-88B(Fe)-X (2-X-terephthalic acid, X = NH2, CH3, H, Br and NO2) by reducing electron density of Fe(III) with substituent of higher electrophilicity. MIL-88B(Fe)-NO2, with the substituent of highest electrophilicity among these catalysts, has the lowest electron density of Fe(III) and highest redox potential (EFe(III)/Fe(II) = 0.35 V). As a result, it exhibited the best catalytic performance, which was 1.7–20 times higher than that for other MIL-88B(Fe)-X and was comparable to that of homogeneous Fe2+. This study provides scientific basis for rational construction of highly effective heterogeneous Fenton-like catalyst.

Structural, Compositional, and Plasmonic Characteristics of Ti-Zr Ternary Nitride Thin Films Tuned by the Nitrogen Flow Ratio in Magnetron Sputtering.

Ternary nitride gives high diversity and tunability of the plasmonic materials. In this work, highly crystallized ternary (Ti, Zr)N films were prepared by magnetron co-sputtering with different nitrogen gas flow ratio . The structural and plasmonic properties of the films tuned by were investigated. All the films are solid solutions of TiN and ZrN with a rocksalt structure and (111) preferred orientation. The films are nitrogen-overstoichiometric and the main defects are cation vacancies. Increased reduces the zirconium content, and therefore leads to the reduction of lattice constant and enhancement of the crystallinity. As increases, the screened plasma frequency decreases for the reduction of free electron density. The maximum of the energy loss spectra of (Ti, Zr)N films shifts to long-wavelength with increasing. The calculated electronic structure shows that increased nitrogen content enhances the electronic density of states of nitrogen and reduces that of metal, and therefore elevates the energy level at which interband transition is exited. The results show that (Ti, Zr)N films give a relatively high plasmonic quality in the visible and near-infrared region, and the film properties can be significantly tuned by the nitrogen content.

Interface resolved magnetism at metal–organic (Fe/Alq3) interfaces under x-ray standing wave condition

The isotope selective grazing-incidence nuclear resonance scattering (GI-NRS) technique, which is a time analog to Mössbauer spectroscopy, is made depth resolved to probe the magnetism of the diffused Fe (Fediffused) and bulk Fe (Febulk) parts of the layer in an Fe/Alq3 [ferromagnetic (FM)/organic semiconductor (OSC)] bilayer structure. On the basis of theoretical simulations, it is demonstrated that the antinode regions of x-ray standing waves (XSWs) generated through wave guide structures allow one to measure the Fediffused and Febulk parts independently, providing evidence for a diffused layer with reduced electron density and hyperfine fields. Due to possible small isolated clusters of Fe in the diffused layer, Fe moments are found with random orientations, while in Febulk moments, they are aligned in the film plane due to shape anisotropy. GI-NRS under XSW is suitable for FM/OSC structures to obtain interface resolved magnetic information, which is otherwise difficult with any other available lab based conventional methods.

Remote Perfluoroalkyl Substituents are Key to Living Aqueous Ethylene Polymerization

AbstractIn various nickel(II) salicylaldiminato ethylene polymerization catalysts, which are a versatile mechanistic probe for substituent effects, longer perfluoroalkyl groups exert a strong effect on catalytic activities and polymer microstructures compared to the trifluoromethyl group. This effect is accounted for by a reduced electron density on the active sites, and is also supported by electrochemical studies. Thus, β‐hydride elimination, the key step of chain transfer and branching pathways, is disfavored while chain‐growth rates are enhanced. This enhancement occurs to an extent that enables living polymerizations in aqueous systems to afford ultra‐high‐molecular‐weight polyethylene for various chelating salicylaldimine motifs. These findings are mechanistically instructive as well as practically useful for illustrating the potential of perfluoroalkyl groups in catalyst design.