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At least 1,081 records · Page 60

Femtosecond laser produced periodic plasma in a colloidal crystal probed by XFEL radiation

With the rapid development of short-pulse intense laser sources, studies of matter under extreme irradiation conditions enter further unexplored regimes. In addition, an application of X-ray Free-Electron Lasers (XFELs) delivering intense femtosecond X-ray pulses, allows to investigate sample evolution in IR pump - X-ray probe experiments with an unprecedented time resolution. Here we present a detailed study of the periodic plasma created from the colloidal crystal. Both experimental data and theory modeling show that the periodicity in the sample survives to a large extent the extreme excitation and shock wave propagation inside the colloidal crystal. This feature enables probing the excited crystal, using the powerful Bragg peak analysis, in contrast to the conventional studies of dense plasma created from bulk samples for which probing with Bragg diffraction technique is not possible. X-ray diffraction measurements of excited colloidal crystals may then lead towards a better understanding of matter phase transitions under extreme irradiation conditions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Soil gas probes for monitoring trace gas messengers of microbial activity

Abstract Soil microbes vigorously produce and consume gases that reflect active soil biogeochemical processes. Soil gas measurements are therefore a powerful tool to monitor microbial activity. Yet, the majority of soil gases lack non-disruptive subsurface measurement methods at spatiotemporal scales relevant to microbial processes and soil structure. To address this need, we developed a soil gas sampling system that uses novel diffusive soil probes and sample transfer approaches for high-resolution sampling from discrete subsurface regions. Probe sampling requires transferring soil gas samples to above-ground gas analyzers where concentrations and isotopologues are measured. Obtaining representative soil gas samples has historically required balancing disruption to soil gas composition with measurement frequency and analyzer volume demand. These considerations have limited attempts to quantify trace gas spatial concentration gradients and heterogeneity at scales relevant to the soil microbiome. Here, we describe our new flexible diffusive probe sampling system integrated with a modified, reduced volume trace gas analyzer and demonstrate its application for subsurface monitoring of biogeochemical cycling of nitrous oxide (N 2 O) and its site-specific isotopologues, methane, carbon dioxide, and nitric oxide in controlled soil columns. The sampling system observed reproducible responses of soil gas concentrations to manipulations of soil nutrients and redox state, providing a new window into the microbial response to these key environmental forcings. Using site-specific N 2 O isotopologues as indicators of microbial processes, we constrain the dynamics of in situ microbial activity. Unlocking trace gas messengers of microbial activity will complement -omics approaches, challenge subsurface models, and improve understanding of soil heterogeneity to disentangle interactive processes in the subsurface biome.

04 OIL SHALES AND TAR SANDS↗

Off-harmonic optical probing of high intensity laser plasma expansion dynamics in solid density hydrogen jets

Due to the non-linear nature of relativistic laser induced plasma processes, the development of laser-plasma accelerators requires precise numerical modeling. Especially high intensity laser-solid interactions are sensitive to the temporal laser rising edge and the predictive capability of simulations suffers from incomplete information on the plasma state at the onset of the relativistic interaction. Experimental diagnostics utilizing ultra-fast optical backlighters can help to ease this challenge by providing temporally resolved inside into the plasma density evolution. We present the successful implementation of an off-harmonic optical probe laser setup to investigate the interaction of a high-intensity laser at 5.4 x 10 21 W/cm 2 peak intensity with a solid-density cylindrical cryogenic hydrogen jet target of 5μm diameter as a target test bed. The temporal synchronization of pump and probe laser, spectral filtering and spectrally resolved data of the parasitic plasma self-emission are discussed. The probing technique mitigates detector saturation by self-emission and allowed to record a temporal scan of shadowgraphy data revealing details of the target ionization and expansion dynamics that were so far not accessible for the given laser intensity. Plasma expansion speeds of up to (2.3 ± 0.4)x 10 7 m/s followed by full target transparency at 1.4ps after the high intensity laser peak are observed. A three dimensional particle-in-cell simulation initiated with the diagnosed target pre-expansion at -0.2ps and post processed by ray tracing simulations supports the experimental observations and demonstrates the capability of time resolved optical diagnostics to provide quantitative input and feedback to the numerical treatment within the time frame of the relativistic laser-plasma interaction.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Using “Tender” x-ray ambient pressure x-Ray photoelectron spectroscopy as a direct probe of solid-liquid interface

We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquid and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt²⁺ and Pt⁴⁺ interfacial species on the Pt working electrode in situ . We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.

25 ENERGY STORAGE↗

Space and time-resolved probing of heterogeneous catalysis reactions using lab-on-a-chip

Probing catalytic reactions on a catalyst surface in real time is a major challenge. In this paper, we demonstrate the utility of a continuous flow millifluidic chip reactor coated with a nanostructured gold catalyst as an effective platform for in situ investigation of the kinetics of catalytic reactions by taking 5-(hydroxymethyl)furfural (HMF) to 2,5-furandicarboxylic acid (FDCA) conversion as a model reaction. The idea conceptualized in this paper can not only dramatically change the ability to probe the time-resolved kinetics of heterogeneous catalysis reactions but also used for investigating other chemical and biological catalytic processes, thereby making this a broad platform for probing reactions as they occur within continuous flow reactors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A simple vaporous probe with atomic-scale sensitivity to structural ordering and orientation of molecular assembly

Understanding the structural ordering and orientation of interfacial molecular assemblies requires an insight into the penetration depth of the probe molecules which determines the interfacial reactivity. In contrast to the conventional liquid probe-based contact angle measurement in which penetration depth is complicated by the liquid cohesive interaction, we report here a new approach that features a simple combination of vaporous hexane, which involves only van der Waals interaction, and quartz crystal microbalance operated at the third harmonic resonance, which is sensitive to sub-monolayer (0.2%) adsorption. Using this combination, we demonstrated the ability of probing the structural ordering and orientation of the self-assembled monolayers with a sensitivity from penetrating the top portion of the monolayers to interacting with the very top atomic structure at the interface. The determination of the dependence of the adsorption energy of vaporous hexane on the penetration depth in the molecular assembly allowed us to further reveal the atomic-scale origin of the odd–even oscillation, which is also substantiated by density functional theory calculations. The findings have broader implications for designing interfacial reactivities of molecular assemblies with atomic-scale depth precision.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Time-resolved luminescence detection of peroxynitrite using a reactivity-based lanthanide probe

Peroxynitrite (ONOO - ) is a powerful and short-lived oxidant formed in vivo, which can react with most biomolecules directly. To fully understand the roles of ONOO - in cell biology, improved methods for the selective detection and real-time analysis of ONOO - are needed. We present a water-soluble, luminescent europium(III) probe for the rapid and sensitive detection of peroxynitrite in human serum, living cells and biological matrices. We have utilised the long luminescence lifetime of the probe to measure ONOO - in a time-resolved manner, effectively avoiding the influence of autofluorescence in biological samples. To demonstrate the utility of the Eu(III) probe, we monitored the production of ONOO - in different cell lines, following treatment with a cold atmospheric plasma device commonly used in the clinic for skin wound treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Are you using the right probe molecules for assessing the textural properties of metal–organic frameworks?

Textural properties—such as the surface area, pore size distribution, and pore volume—are at the forefront of characterization for porous materials. Therefore, it is essential to accurately and reproducibly report a material's textural properties as they could ultimately dictate its applicability. This work aims to provide insightful and comprehensive studies of textural properties for a set of metal–organic frameworks (MOFs), a class of porous materials, using various gases to equip researchers in the field with a helpful guide and reference. Here, we selected a series of nine MOFs with different surface areas, pore sizes, shapes, and chemical environments to represent a wide range of materials. We probed the textural properties of these MOFs using traditional and distinctive gases: N 2 , Kr and O 2 at 77 K, Ar at 87 K, and CO 2 at 195 and 273 K. With regard to surface area, we discuss the validity and challenges associated with the current BET method, the importance of utilizing the Rouquerol et al. consistency criteria to ensure accuracy and reproducibility, and the recommended gas probes for certain materials. For pore size distribution, we discuss the efficacy of each probe for determining the pore sizes within a porous material relative to the calculated distribution from its crystal structure, the limitations of current computational kernels used to calculate pore size distributions, and the need for advanced kernels to envelope the diversity of porous materials. Finally, for pore volume, we discuss the use of the Gurvich rule to obtain the total pore volume in comparison with calculated values from crystal structures and its consistency as a metric for porous materials. Ultimately, we hope that this article will aid researchers in characterizing the textural properties of porous materials and encourage the development of new kernels capable of encompassing the complexity of MOFs and other porous materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Challenges and strategies for probing the composite interface of PEM electrolyzers and fuel cells using operando AP-XPS

Left: cross-section schematic of a membrane electrode assembly, the working electrode changing state with applied potential. Center: the operando cell design that enables snapshot data acquisition during trajectory movement. Right: resulting spectra. Understanding the surface chemistry of electrocatalyst systems under operando conditions is central to revealing the electrocatalytic cell's working mechanisms. Determination of these catalytic processes on a molecular scale and the involved components is fundamental to streamlining material design for energy conversion and storage applications. X-ray photoelectron spectroscopy (XPS) is an established technique used to study the chemical and electronic states of materials. While the surface sensitivity of XPS is typically high, use of tender X-ray energies and technical advancements have allowed for the direct probing of solid–vapor and solid–liquid interfaces. However, protocols and documentation of experimental considerations for operando XPS probing of working electrolyzers and fuel cells remain scarce. Herein, we report an approach for the study of working polymer electrolyte membrane (PEM) electrolysis cells using ambient pressure X-ray photoelectron spectroscopy (AP-XPS). This approach directly probes the composite electrode surface on the membrane electrode assembly (MEA) in 100% relative humidity to establish a meaningful liquid layer for electrocatalysis. We carry out a systematic investigation from the cell constituent components to a fully assembled working operando electrolytic system and establish a method for AP-XPS study of the complex composite MEA, providing recommendations for data acquisition and component analysis.

Hamlyn, Rebecca↗

Direct Measurement of ICRF-Enhanced Plasma Potentials on WEST Using Reciprocating Emissive Probes

An extensive documentation of ICRF-enhanced plasma potentials has been conducted over two experimental campaigns on the WEST tokamak using reciprocating emissive probes magnetically connected to two ICRF antennas. The collected data spans a wide range of antenna electrical settings (coupled power, toroidal phasing, left–right power balance) and plasma parameters (density at the antenna limiter above and below the lower hybrid resonance, plasma current, minority fraction). By scanning the edge safety factor across multiple probe plunges, the magnetic connection between the probe and the antenna varied, enabling the construction of a 2D map of the plasma and floating potentials around an active ICRF antenna. This dataset will be used to validate RF simulation tools equipped with the sheath boundary condition and used to predict RF rectified potentials and ICRF-induced impurity sputtering in future machines. This paper presents the diagnostic and some initial measurements, while the rest will be reported elsewhere.

Diab, Raymond [Massachusetts Inst. of Technology (↗

Real-time crystallization in fluorinated parylene probed by conductivity spectra

Dielectric relaxation spectroscopy experiments were performed at high temperature on fluorinated parylene films during the occurrence of the isothermal crystalline phase transition. For this polymer, since the difference between the glass transition temperature (T{sub g}) and the phase transition temperature (T{sub c}) is very strong (T{sub c} ≥ 4T{sub g}), segmental and dipolar relaxation usually used to probe the crystallization are not shown in the experiment frequency window (10{sup −1} to 10{sup 6} Hz) during the crystallization. The charge diffusion becomes the only electrical marker that allows probing the phase transition. During the transition phase, a continuous decrease of about two orders of magnitude is observed in the conductivity values below an offset frequency (f{sub c}) with a tendency to stabilization after 600 min. Below the offset frequency, the decrease of the normalized conductivity to the initial value as function of time is frequency independent. The same behavior is also observed for the f{sub c} values that decrease from 160 Hz to about 20 Hz. Above the offset frequency, the electronic hopping mechanism is also affected by the phase transition and the power law exponent (n) of the AC conductivity shows a variation from 0.7 to 0.95 during the first 600 min that tend to stabilize thereafter. Accordingly, three parameters (n, f{sub c}, and AC conductivity values for frequencies below f{sub c}) extracted from the AC conductivity spectra in different frequency windows seem suitable to probe the crystalline phase transition.

36 MATERIALS SCIENCE↗

Using neutral beams as a light ion beam probe (invited)

By arranging the particle first banana orbits to pass near a distant detector, the light ion beam probe (LIBP) utilizes orbital deflection to probe internal fields and field fluctuations. The LIBP technique takes advantage of (1) the in situ, known source of fast ions created by beam-injected neutral particles that naturally ionize near the plasma edge and (2) various commonly available diagnostics as its detector. These born trapped particles can traverse the plasma core on their inner banana leg before returning to the plasma edge. Orbital displacements (the forces on fast ions) caused by internal instabilities or edge perturbing fields appear as modulated signal at an edge detector. Adjustments in the q-profile and plasma shape that determine the first orbit, as well as the relative position of the source and detector, enable studies under a wide variety of plasma conditions. This diagnostic technique can be used to probe the impact on fast ions of various instabilities, e.g., Alfvén eigenmodes (AEs) and neoclassical tearing modes, and of externally imposed 3D fields, e.g., magnetic perturbations. To date, displacements by AEs and by externally applied resonant magnetic perturbation fields have been measured using a fast ion loss detector. Comparisons with simulations are shown. In addition, nonlinear interactions between fast ions and independent AE waves are revealed by this technique.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Customized atomic force microscopy probe by focused-ion-beam-assisted tip transfer

We present a technique for transferring separately fabricated tips onto tipless atomic force microscopy (AFM) cantilevers, performed using focused ion beam-assisted nanomanipulation. This method addresses the need in scanning probe microscopy for certain tip geometries that cannot be achieved by conventional lithography. For example, in probing complex layered materials or tall biological cells using AFM, a tall tip with a high-aspect-ratio is required to avoid artifacts caused by collisions of the tip's sides with the material being probed. We show experimentally that tall (18 μm) cantilever tips fabricated by this approach reduce squeeze-film damping, which fits predictions from hydrodynamic theory, and results in an increased quality factor (Q) of the fundamental flexural mode. We demonstrate that a customized tip's well-defined geometry, tall tip height, and aspect ratio enable improved measurement of elastic moduli by allowing access to low-laying portions of tall cells (T lymphocytes). This technique can be generally used to attach tips to any micromechanical device when conventional lithography of tips cannot be accomplished.

36 MATERIALS SCIENCE↗

Site-specific probing of charge transfer dynamics in organic photovoltaics

We report the site-specific probing of charge-transfer dynamics in a prototype system for organic photovoltaics (OPVs) by picosecond time-resolved X-ray photoelectron spectroscopy. A layered system consisting of approximately two monolayers of C{sub 60} deposited on top of a thin film of Copper-Phthalocyanine (CuPC) is excited by an optical pump pulse and the induced electronic dynamics are probed with 590 eV X-ray pulses. Charge transfer from the electron donor (CuPC) to the acceptor (C{sub 60}) and subsequent charge carrier dynamics are monitored by recording the time-dependent C 1s core level photoemission spectrum of the system. The arrival of electrons in the C{sub 60} layer is readily observed as a completely reversible, transient shift of the C{sub 60} associated C 1s core level, while the C 1s level of the CuPC remains unchanged. The capability to probe charge transfer and recombination dynamics in OPV assemblies directly in the time domain and from the perspective of well-defined domains is expected to open additional pathways to better understand and optimize the performance of this emerging technology.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Charge transport in molecular junctions: From tunneling to hopping with the probe technique

We demonstrate that a simple phenomenological approach can be used to simulate electronic conduction in molecular wires under thermal effects induced by the surrounding environment. This “Landauer-Büttiker’s probe technique” can properly replicate different transport mechanisms, phase coherent nonresonant tunneling, ballistic behavior, and hopping conduction. Specifically, our simulations with the probe method recover the following central characteristics of charge transfer in molecular wires: (i) the electrical conductance of short wires falls off exponentially with molecular length, a manifestation of the tunneling (superexchange) mechanism. Hopping dynamics overtakes superexchange in long wires demonstrating an ohmic-like behavior. (ii) In off-resonance situations, weak dephasing effects facilitate charge transfer, but under large dephasing, the electrical conductance is suppressed. (iii) At high enough temperatures, k{sub B}T/ϵ{sub B} > 1/25, with ϵ{sub B} as the molecular-barrier height, the current is enhanced by a thermal activation (Arrhenius) factor. However, this enhancement takes place for both coherent and incoherent electrons and it does not readily indicate on the underlying mechanism. (iv) At finite-bias, dephasing effects may impede conduction in resonant situations. We further show that memory (non-Markovian) effects can be implemented within the Landauer-Büttiker’s probe technique to model the interaction of electrons with a structured environment. Finally, we examine experimental results of electron transfer in conjugated molecular wires and show that our computational approach can reasonably reproduce reported values to provide mechanistic information.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A new B-dot probe-based diagnostic for amplitude, polarization, and wavenumber measurements of ion cyclotron range-of frequency fields on ASDEX Upgrade

A new B-dot probe-based diagnostic has been installed on an ASDEX Upgrade tokamak to characterize ion cyclotron range-of frequency (ICRF) wave generation and interaction with magnetized plasma. The diagnostic consists of a field-aligned array of B-dot probes, oriented to measure fast and slow ICRF wave fields and their field-aligned wavenumber (k{sub //}) spectrum on the low field side of ASDEX Upgrade. A thorough description of the diagnostic and the supporting electronics is provided. In order to compare the measured dominant wavenumber of the local ICRF fields with the expected spectrum of the launched ICRF waves, in-air near-field measurements were performed on the newly installed 3-strap ICRF antenna to reconstruct the dominant launched toroidal wavenumbers (k{sub tor}). Measurements during a strap current phasing scan in tokamak discharges reveal an upshift in k{sub //} as strap phasing is moved away from the dipole configuration. This result is the opposite of the k{sub tor} trend expected from in-air near-field measurements; however, the near-field based reconstruction routine does not account for the effect of induced radiofrequency (RF) currents in the passive antenna structures. The measured exponential increase in the local ICRF wave field amplitude is in agreement with the upshifted k{sub //}, as strap phasing moves away from the dipole configuration. An examination of discharges heated with two ICRF antennas simultaneously reveals the existence of beat waves at 1 kHz, as expected from the difference of the two antennas’ operating frequencies. Beats are observed on both the fast and the slow wave probes suggesting that the two waves are coupled outside the active antennas. Although the new diagnostic shows consistent trends between the amplitude and the phase measurements in response to changes applied by the ICRF antennas, the disagreement with the in-air near-field measurements remains. An electromagnetic model is currently under development to address this issue.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Focal overlap gating in velocity map imaging to achieve high signal-to-noise ratio in photo-ion pump-probe experiments

We demonstrate a technique in velocity map imaging (VMI) that allows spatial gating of the laser focal overlap region in time resolved pump-probe experiments. This significantly enhances signal-to-noise ratio by eliminating background signal arising outside the region of spatial overlap of pump and probe beams. This enhancement is achieved by tilting the laser beams with respect to the surface of the VMI electrodes which creates a gradient in flight time for particles born at different points along the beam. By suitably pulsing our microchannel plate detector, we can select particles born only where the laser beams overlap. Furthermore, this spatial gating in velocity map imaging can benefit nearly all photo-ion pump-probe VMI experiments especially when extreme-ultraviolet light or X-rays are involved which produce large background signals on their own.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Photoinduced molecular chirality probed by ultrafast resonant X-ray spectroscopy

Recently developed circularly polarized X-ray light sources can probe the ultrafast chiral electronic and nuclear dynamics through spatially localized resonant core transitions. Here, we present simulations of time-resolved circular dichroism signals given by the difference of left and right circularly polarized X-ray probe transmission following an excitation by a circularly polarized optical pump with the variable time delay. Application is made to formamide which is achiral in the ground state and assumes two chiral geometries upon optical excitation to the first valence excited state. Probes resonant with various K-edges (C, N, and O) provide different local windows onto the parity breaking geometry change thus revealing the enantiomer asymmetry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗