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In ultrawide bandgap (UWBG) nitride and oxide semiconductors, increased bandgap (Eg) correlates with greater ionicity and strong electron–phonon coupling. This limits mobility through phonon scattering, localizes carriers via polarons and self-trapping, broadens optical transitions via dynamic disorder, and modifies the breakdown field. Herein, we use polarized optical transmission spectroscopy from 77 to 633 K to investigate the Urbach energy (Eu) for many orientations of Fe- and Sn-doped β-Ga2O3 bulk crystals. We find Eu values ranging from 60 to 140 meV at 293 K and that static (structural defects plus zero-point phonons) disorder contributes more to Eu than dynamic (finite temperature phonon-induced) disorder. This is evidenced by lack of systematic Eu anisotropy, and Eu correlating more with x-ray diffraction rocking-curve broadening than with Sn-doping. The lowest measured Eu are ∼10× larger than for traditional semiconductors, pointing out that band tail effects need to be carefully considered in these materials for high field electronics. We demonstrate that, because optical transmission through thick samples is sensitive to sub-gap absorption, the commonly used Tauc extraction of a bandgap from transmission through Ga2O3 >1–3 μm thick is subject to errors. Combining our Eu(T) from Fe-doped samples with Eg(T) from ellipsometry, we extract a measure of an effective electron–phonon coupling that increases in weighted second order deformation potential with temperature and a larger value for E||b than E||c. The large electron–phonon coupling in β-Ga2O3 suggests that theories of electrical breakdown for traditional semiconductors need expansion to account not just for lower scattering time but also for impact ionization thresholds fluctuating in both time and space. [ABSTRACT FROM AUTHOR]

For microscale gaps, DC breakdown voltage is described theoretically and through simulation by accounting for field emission generated electrons and the subsequent ionization of neutral gas and ion-induced secondary electron emission. Here, we extend DC microscale breakdown theory to AC. Particle-in-cell (PIC) simulations show that breakdown voltage V varies linearly with gap distance d independent of frequency and the ion-induced secondary electron coefficient γ S E for d ≲ 4 μ m , where field emission dominates breakdown over ionization and avalanche. For d ≳ 4 μ m and γ S E = 0 , DC breakdown voltage increases linearly with d; for γ S E = 0.05 , DC breakdown voltage decreases to a minimum before beginning to increase at larger gap distances. For AC fields with γ S E = 0.05 , V behaves similarly to the DC case with the decrease corresponding to secondary emission occurring at higher voltages and larger gap distances with increasing frequency. At 10 GHz and γ S E = 0.05 , V resembles that of the DC case with γ S E = 0 up to ∼8 μm, suggesting that increasing the frequency effectively changes the number of ions striking the electrodes and the resulting electrons released. Phase space plots showing electron and ion velocities as a function of position across the gap show that electrons and ions are increasingly trapped within the gap with increasing frequency, reducing the number of ions that can strike the cathode and the subsequent secondary emission. Incorporating the resulting effective secondary emission coefficient for AC microscale gaps yields a simple phenomenologically based modification of the DC microscale gas breakdown equation. [ABSTRACT FROM AUTHOR]

We present an experimental study of multiple-electron capture-induced fragmentation dynamics of Ar 2 m + (4 ≤ m ≤ 7) dimer ions in 4 keV/u Ar8+–Ar2 collisions. The fragment recoil ion pairs and the charge-changing projectiles are coincidentally measured using a double coincidence technique. The branching ratios between the different charge-sharing fragmentation channels show an inherent enhancement of the asymmetric channels. The kinetic energy release (KER) distributions for the associated electron capture process show a shift in the mean KER values toward the higher side with increasing capture stabilization. The interplay between the different projectile autoionization processes sheds light on the energy depositions to the system during collisions. The Coulomb potential energy curves give a physical insight into the role of the projectile final states in the dimer fragmentation dynamics. The dimer-axis orientation-dependent cross sections for the asymmetric fragmentation channels reveal a forward–backward asymmetry that arises from the geometry of the collision system. Our findings thus give insight into the impact parameter-controlled fragmentation dynamics of multiply charged Ar 2 m + dimer ions in highly charged ion–dimer slow collisions. [ABSTRACT FROM AUTHOR]

Superfluid helium nanodroplets are unique nanomatrices for the isolation and study of transient molecular species, such as radicals, carbenes, and ions. In this work, isomers of C3H4+ were produced upon electron ionization of propyne and allene molecules and interrogated via infrared spectroscopy inside He nanodroplet matrices. It was found that the spectrum of C3H4+ has at least three distinct groups of bands. The relative intensities of the bands depend on the precursor employed and its pickup pressure, which indicates the presence of at least three different isomers. Two isomers were identified as allene and propyne radical cations. The third isomer, which has several new bands in the range of 3100–3200 cm−1, may be the elusive vinylmethylene H2C=CH–CH+ radical cation. The observed bands for the allene and propyne cations are in good agreement with the results of density functional theory calculations. However, there is only moderate agreement between the new bands and the theoretically calculated vinylmethylene spectrum, which indicates more work is necessary to unambiguously assign it. [ABSTRACT FROM AUTHOR]

The dissociative double ionization of CH3I and CH2I2 irradiated with extreme ultraviolet light at hv = 100 eV is investigated by multi-electron–ion coincidence spectroscopy using a magnetic bottle type electron spectrometer. The spin–orbit state-resolved Auger electron spectra for the I 4d core-hole states, (I 4d3/2)−1 and (I 4d5/2)−1, provide clear identifications of electronic states of CH3I2+ and CH2I22+. The dominant ion species produced after the double ionization correlate with the Auger electron energy, showing that different fragmentation pathways are open depending on the electronic states populated by the Auger decay. Theoretical calculations are performed to understand the fragmentation from the doubly charged states and the observed spin–orbit specificity in the Auger decay. [ABSTRACT FROM AUTHOR]

The interaction between electrons and methane is studied with a particular focus on describing the dynamics of elastic and electronic excitation processes under the influence of the multichannel coupling effects. Elastic and electronically inelastic integral and differential cross sections are reported. These cross sections were calculated with the Schwinger multichannel method implemented with norm-conserving pseudopotentials within the minimal orbital basis for single-configuration interaction approach with up to 181 open channels. While an excellent agreement with previously published data is found in the elastic channel, the comparisons involving electronic excitation cross sections reveal significant discrepancies. Furthermore, the lack of reliable experimental data regarding the electronically inelastic channels hampers a more detailed analysis of the theoretical results. Additionally, total ionization and total cross sections for electron collisions with methane are also presented. By highlighting the current theoretical challenges in dealing with electron-induced electronic excitation of molecules, we seek to contribute to a deeper understanding of this scattering process and, thus, pave the way for future research. [ABSTRACT FROM AUTHOR]

We calculate electron impact partial and total ionization cross sections of R-carvone (C10H14O), 2-butanol (C4H10O), imidazole (C3H4N2), and 2-nitroimidazole (C3H3N3O2). We have used the Binary Encounter Bethe (BEB) model to obtain total electron impact ionization cross sections (TICSs). The modified BEB method in combination with mass spectrum data of the molecules is used to calculate the partial ionization cross section (PICS) of the cationic fragments dissociating from the parent molecule. Our PICS data for R-carvone and 2-butanol are in good agreement with the experimental data for all the cation fragments along with the TICS data. For imidazole and 2-nitroimidazole, the estimates of the PICS are reported for the first time in the present study. We have found that both the modified BEB method and the mass spectrum dependence method work effectively to estimate PICS if we have information about the appearance energies and relative abundance data of the target under investigation. [ABSTRACT FROM AUTHOR]

Pathways of two-body fragmentation of BrCNq+ (q = 2, 3) have been explored by combined experimental and theoretical studies. In the experiment, the BrCN molecule is ionized by 1 keV electron impact and the created fragment ions are detected using an ion momentum imaging spectrometer. Six two-body fragmentation channels are identified. By measuring the momentum vectors of the fragment ions, the kinetic energy release (KER) distributions for these channels have been determined. Theoretically, the potential energy curves of BrCNq+ (q = 2, 3) as a function of Br–C and C–N internuclear distances are calculated by the complete active space self-consistent field method. By comparing the measured KER and theoretical predictions, pathways for the fragmentation channels are assigned. The relative branching ratios of the channels are also determined. [ABSTRACT FROM AUTHOR]

This work studied the rovibrational absorption spectral line-shape parameters of the P(1)–P(10) and R(0)–R(9) lines for Hydrogen fluoride perturbed by argon in the 0–0, 1–0, and 2–0 vibrational bands at 20–1000 K. A dataset of beyond-Voigt line-shape parameters (pressure broadening and shifting parameters, their speed dependencies, and the complex Dicke parameters) has been theoretically determined for the first time from generalized spectroscopic cross-section calculated by the full quantum scattering calculations. Then these parameters were employed to predict the line shape and asymmetry based on the partially-correlated speed-dependent hard-collision and the partially-correlated quadratic-speed-dependent hard-collision profiles. The effect of each parameter on the line shape and line asymmetry was further studied, which revealed that the beyond-Voigt effects were indispensable to accurately describe the line shape contour. Our results are in good agreement with the available experimental observations and provide a comprehensive set of theoretical references for further experimental measurements. [ABSTRACT FROM AUTHOR]

The fragmentation of fulminic acid, HCNO, after excitation and ionization of core electrons was investigated using Auger-electron–photoion coincidence spectroscopy. A considerable degree of site-selectivity is observed. Ionization of the carbon and oxygen 1s electron leads to around 70% CH+ + NO+, while ionization at the central N-atom produces only 37% CH+ + NO+, but preferentially forms O+ + HCN+ and O+ + CN+. The mass-selected Auger-electron spectra show that these fragments are associated with higher binding energy final states. Furthermore, ionization of the C 1s electron leads to a higher propensity for C–H bond fission compared to O 1s ionization. Following resonant Auger–Meitner decay after 1s → 3π excitation, 12 different ionic products are formed. At the C 1s edge, the parent ion HCNO+ is significantly more stable compared to the other two edges, which we also attribute to the higher contribution of final states with low binding energies in the C 1s resonant Auger electron spectra. [ABSTRACT FROM AUTHOR]

Rationale: Ceria‐based systems are of great interest because of their unique properties. Such systems may be used as anode materials for SOFCs or in oxygen sensors. The exploitation of these materials often requires high temperatures. In such conditions, the partial or complete evaporation of materials is possible. Therefore, knowledge of the values of partial pressures and thermodynamic properties is essential to predict and/or prevent possible consequences and accidents. Methods: Knudsen effusion mass spectrometry was used to determine partial pressures of vapor species over the SrO–CeO2 and CaO‐CeO2 systems. Measurements of partial pressures were performed with a MS‐1301 mass spectrometer. Vaporization was carried out using molybdenum or tungsten effusion cells. A theoretical study of gaseous strontium and calcium cerates was performed by several quantum chemical methods: density functional theory (DFT) M06, DFT PBE0, and MP2. Results: The minimum value of relative electron ionization cross‐section for CeO2 was estimated. In the temperature range of 2218–2249 K above the SrO‐CeO2 system and of 2128–2208 K above the CaO‐CeO2 system, gaseous M, MO, MO, CeO2, O, O2 and MCeO3 (M = Sr, Ca) were found. Energetically favorable structures of gaseous SrCeO3 and CaCeO3 were found, and vibrational frequencies were evaluated in the "rigid rotor‐harmonic oscillator" approximation. On the basis of the equilibrium constants of gaseous reaction MO + CeO2 = MCeO3, the standard formation enthalpy of gaseous SrCeO3 (−913 ± 26 kJ/mol) and of gaseous CaCeO3 (−917 ± 26 kJ/mol) at 298 K were determined. Conclusions: The estimated value of relative electron ionization cross‐section for CeO2 is in agreement with the general rule applicable for dioxides. The stability of SrCeO3 and CaCeO3 gaseous species was confirmed by KEMS. Gas‐phase reactions involving gaseous SrO (CaO) and CeO2 with gaseous SrCeO3(CaCeO3) were studied. Enthalpy of formation reaction of gaseous SrCeO3(CaCeO3) from gaseous SrO (CaO) were evaluated theoretically, and the obtained value is in agreement with the experimental one. [ABSTRACT FROM AUTHOR]

The reactions of a series of organic polynitriles with [Te4][AsF6]2 in liquid SO2 solution lead either to reduction of [Te4]2+ to elemental tellurium or to the formation of coordination polymers. With 1,3‐dicyanobenzene (1,3‐DCB), 1,4‐dicyanobenzene (1,4‐DCB), 1,2,4,5‐tetracyanobenzene (TCB), tetracyanoethylene (TCNE) and tetracyanochinodimethane (TCNQ) the coordination complexes [Te4][AsF6]2 ⋅ 2(1,3‐DCB), [Te4][AsF6]2 ⋅ 3(1,4‐DCB) ⋅ 2SO2, [Te4][AsF6]2 ⋅ TCB, [Te4][AsF6]2 ⋅ TCNE and [Te4][AsF6]2 ⋅ TCNQ ⋅ 8 SO2 were isolated and characterized by crystal structure analyses and vibrational Raman spectroscopy. The nitriles are coordinated to the square‐planar clusters forming 1D chains, 2D arrangements and 3D networks. Tetrakis(dicyanomethylene)cyclobutendiide [C4(C{CN}2)4]2− is oxidized by [Te4]2+ to the neutral cyanocarbon C4(C{CN}2)4, structurally representing a 4[radialene]. The ionization potentials and electron affinities of the cyanamide anion, cyanogen, 1,2‐DCB, 1,3‐DCB, 1,4‐DCB, TCB, C4(C{CN}2)4, TCNE and TCNQ and those polynitriles, which cause reduction of [Te4]2+, were calculated at coupled‐cluster level of theory in order to examine possible reasons for the stability of the coordination polymers based on electronic properties of the nitriles. [ABSTRACT FROM AUTHOR]

Sodium alkylbenzene sulfonates (ABS), or linear alkylbenzene sulfonates (LAS), are among the most common synthetic anionic surfactants and water pollutants, capable of causing both acute and chronic toxic effects on aquatic organisms. The selective determination of sodium alkylbenzene sulfonates as a distinct class of anionic surfactants in complex natural matrices is feasible by gas chromatography with mass spectrometric detection (GC–MS) in the form of linear alkylbenzenesulfonic acid methyl esters (LABSA ME). The behavior of LAS and LABSA ME was studied under ascending high-performance thin-layer chromatography (HPTLC) using Kieselgel 60 F254 and Sorbfil plates to purify extracts and preconcentrate analytes. A mixture of n-hexane with methanol (23 : 1, v/v) is proposed as a mobile phase. Under these conditions, sodium alkylbenzene sulfonates remain at the start line, while their derivatives (LABSA ME), obtained by methylation with trimethyl orthoformate in the presence of trifluoroacetic acid (yield η = 98%), form zones characterized by retention factors Rf of 0.62–0.71 on Kieselgel 60 F254 and Sorbfil plates, respectively. The repeatability of Rf values is characterized by a relative standard deviation of 6.1 and 5.9%, respectively (n = 16). The completeness of the extraction (95.0–100.0%) of analytes from the plates is noted using descending HPTLC with acetonitrile. The applicability of the HPTLC method for preconcentrating analytes and purifying extracts is demonstrated using real water samples. Using GC–MS with electron impact ionization, concentrations of sodium alkylbenzene sulfonates were found in water sampled from the southern basin of Lake Baikal at a depth of 400 m (0.24 ± 0.02 µg/L) and in water obtained from melting snow collected from the ice of the Krestovka River at its mouth near the settlement of Listvyanka (31.1 ± 1.0 µg/L). [ABSTRACT FROM AUTHOR]

We present the angular distribution of the ejected electron for single ionization of He by fast proton impact. A four-body formalism of the three-Coulomb wave is applied to calculate the triple differential cross sections at several impact energies in the scattering, perpendicular and azimuthal planes. Moreover, the three-body formalism of three-Coulomb, two-Coulomb and first Born approximation models has also been used to study the many-body effect on electron emission and the validity of the models. In the three-Coulomb wave model, the final state wave function incorporates distortion due to the three-body mutual Coulombic interaction. In this formalism, we use an uncorrelated and correlated Born initial state, which consists of a plane wave for the incoming projectile times a two-electron bound state wavefunction of the helium atom representing the 1s2(1S) state. But, in the case of the three-body formalism, the initial state wavefunction consists of a long-range Coulomb distortion for the incoming projectile and one active electron of the He atom described by the Roothaan–Hartree–Fock wavefunction. The structure with a single or two peaks with unequal intensity is observed in the angular distributions of the triple differential cross sections for the different kinematic conditions. In addition, the influence of static electron correlations is investigated using different bound state wavefunctions for the ground state of the He target. In the four-body formalism, the present computations are very fast by reducing a nine-dimensional integral to a two-dimensional real integral. Despite the simplicity and speed of the proposed quadrature, the comparison shows that the obtained results are in reasonable agreement with the experiment and are compatible with those of other theories. [ABSTRACT FROM AUTHOR]

This study investigates the structure and electronic properties of the A‐center in Si1−xGex alloys (x = 0, 0.25, 0.50, 0.75, and 1), using the Heyd–Scuseria–Ernzerhof hybrid functional. It is found that the most stable structures form SiOSi bonds, with the other two atoms surrounding the A‐center being Ge atoms, which form a long bond between them. The behavior of the O atoms is significantly influenced by the Ge content. As it increases, the position of the O atom shifts relative to the surrounding atoms, thereby affecting the bond lengths and angles. The formation energy of the A‐center first decreases with increasing Ge content up to 0.75, which enhances the defect production; however, then it decreases from 0.75 to 1, thus suppressing defect production. The calculations are consistent with the experimental data, showing that the distance of the defect level from the conduction band minimum increases with Ge content, supporting the observed enthalpy changes in electron ionization. [ABSTRACT FROM AUTHOR]

This study employs a high‐dimensional consensus mass spectral (HDCMS) similarity scoring technique to discriminate isomers collected using an electron ionization mass spectrometer. The HDCMS method was previously introduced and applied to the discrimination of mass spectra of constitutional isomers, methamphetamine and phentermine, collected with direct analysis real‐time mass spectrometry (DART‐MS). The method formulates the problem of discriminating mass spectra in a mathematical Hilbert space and is hence called "high dimensional." It requires replicate mass spectra to build a Gaussian model and evaluate the inner products between these functions. The resulting measurement variability is used as a signature by which to discriminate spectra. In this work, HDCMS is tested on electron impact ionization (EI) mass spectra of 7 terpene and terpene‐related (C10H16 and C10H14) isomers with experimental retention indices that differ by less than 30 and with traditional cosine similarity scores greater than 0.9, on a scale of 0 to 1, when compared with at least one other compound in the test set. Using identical instrument parameters, 15 replicate gas chromatography–electron ionization–mass spectrometry (GC‐EI‐MS) spectra of each isomer were collected and separated into distinct library and query sets. The HDCMS algorithm discriminated each isomer, indicating the method's potential. Because the method requires replicate measurements, observations from a simple heuristic study of the number of replicates required to discriminate these isomers is presented. The paper concludes with a discussion of compound discrimination using HDCMS and the benefits and drawbacks of applying the method to EI‐MS data. [ABSTRACT FROM AUTHOR]

Branched‐chain fatty acids (BCFAs) are mostly saturated fatty acids with a methyl branch at the penultimate or antepenultimate position to the CH3 end. Very‐long‐chain BCFAs (C ≥ 20) are uniquely found in surface lipids. Human and California sea lion (Zalophus californianus) are the only two species that possess vernix at birth, and vernix particles carry loads of BCFA to the gut, potentially influencing the establishment of the first microbiota. Horse (Equus caballus) contains high levels of BCFA in its surface lipids, and the current study aims to investigate if BCFA are components of a neonatal foal's gut. Electron ionization tandem mass spectrometry was used to distinguish iso‐ and anteiso‐form of BCFA from straight‐chain fatty acids. Abundant very‐long‐chain iso‐BCFA, mainly even‐numbered iso‐20:0, iso‐22:0, iso‐24:0, and iso‐26:0 were found in horse meconium but not in their manure collected a few months later. There are little differences in BCFA types and concentrations between foal manure and adult manure. Moderate to high levels of very‐long‐chain anteiso‐BCFA were also found. Comparisons of horse meconium BCFA to horse skin cholesterol ester BCFA content and to meconium from human and sea lion suggest its skin derived origin. The study expands our knowledge on the gut nutritional environment of a newborn horse, and further study is needed to establish the relationship between gut BCFA and microbiota composition in the first few hours of life. Practical Applications: Branched‐chain fatty acids (BCFA) are bioactive compounds found in vernix caseosa, the lipid‐laden material covering the surface of a newborn baby. BCFA also reaches high concentrations from the third trimester of gestation until birth. However, the exact functionality and mechanisms of BCFA in the surface and gut of a fetus remain unclear. The current study aims to clarify the lipid conditions in the gut of newborn foals and to identify the associations between BCFA in the gut and on the skin at a critical point when the horse's microbiota establishes itself. The findings of the current study lay a path for studying the physiological functions of BCFA in horse models, potentially accelerating research related to BCFA. [ABSTRACT FROM AUTHOR]

Modern gas chromatography-mass spectrometry (GC–MS) allows for the analysis of complex samples, such as fragrances. However, identifying all the constituents in natural fragrance mixtures, especially allergens that need to be listed on product labels, is a significant challenge. This is primarily due to the high complexity of the sample and the fact that electron ionization, the most commonly used ionization method in GC–MS, produces numerous nonspecific fragment ions, often resulting in the absence or very low abundance of the molecular ion. These factors affect confidence in assigning the analyte. In this study, we demonstrate that the combination of GC × GC separation, with high mass resolution and accurate mass measurements, as well as chemical ionization in addition to traditional electron ionization, becomes an efficient tool for reliable qualitative analysis of a mixture containing 100 fragrance allergens, even when many of them are closely related species or isomers. The proposed approach expands the applicability of the comprehensive GC × GC-HRMS method, which includes complementary ionization techniques, from studies on anthropogenic priority pollutants and emerging contaminants to the analysis of natural products. Although targeted qualitative and quantitative analysis of allergens in the modern laboratories is well organized, GC × GC-HRMS, being a useful complement to routine quality control of volatile allergens in fragrances, definitely gives an additional contribution to the analytical cases when conventional 1D-GC–MS faces some problems or uncertainties. [ABSTRACT FROM AUTHOR]

An Addendum to the AAPM's TG‐51 protocol for the determination of absorbed dose to water is presented for electron beams with energies between 4 MeV and 22 MeV (1.70cm≤R50≤8.70cm$1.70\nobreakspace {\rm cm} \le R_{\text{50}} \le 8.70\nobreakspace {\rm cm}$). This updated formalism allows simplified calibration procedures, including the use of calibrated cylindrical ionization chambers in all electron beams without the use of a gradient correction. New kQ$k_{Q}$ data are provided for electron beams based on Monte Carlo simulations. Implementation guidance is provided. Components of the uncertainty budget in determining absorbed dose to water at the reference depth are discussed. Specifications for a reference‐class chamber in electron beams include chamber stability, settling, ion recombination behavior, and polarity dependence. Progress in electron beam reference dosimetry is reviewed. Although this report introduces some major changes (e.g., gradient corrections are implicitly included in the electron beam quality conversion factors), they serve to simplify the calibration procedure. Results for absorbed dose per linac monitor unit are expected to be up to approximately 2 % higher using this Addendum compared to using the original TG‐51 protocol. [ABSTRACT FROM AUTHOR]

A simultaneous ultra-performance liquid chromatography photodiode array detection method was developed and validated for Elvitegravir, Tenofovir and Emtricitabine and Cobicistat drugs in tablet dosage forms. Effective liquid chromatographic quantification was achieved using a Luna C18 (100 × 2.6 mm, 1.6 μ) column with an acetonitrile: 0.1% v/v trifluoro acetic acid (80:20% v/v) mobile phase and a photo diode array detector at 260 nm for a shorter run time of 3 min. The respective retention times for Elvitegravir, Tenofovir, Emtricitabine and Cobicistat were 0.311, 0.792, 1.379 and 2.045 min. The range of linearity was 37.50–225.00, 2.50–15.00, 50.00–300.00 and 37.50–225.00 μg/mL for Elvitegravir, Tenofovir, Emtricitabine and Cobicistat, respectively. A mass spectrometer was employed for quantitative analysis using electron spray ionization multiple reaction monitoring in positive mode. The developed method was validated for different parameters to meet the acceptance criteria as per ICH Q2 (R1) guidelines. Using UPLC–ESI–MS, 12 degradants were identified and their mechanisms were studied. [ABSTRACT FROM AUTHOR]

Here we present measurements of dissociative and non-dissociative cross-sections for the electron impact of the CF4 molecule. The present experiments are based on a Recoil Ion Momentum Spectrometer (RIMS), a standard gas mixing setup for CF4, and a reference gas. The measurements were carried out at several electron energies up to 1 keV, covering the energy range of previous experiments. We apply the relative flow technique (RFT) to convert the relative cross-sections measured by the RIMS into absolute values. Using the combination of RIMS and RFT, ion collection and calibration errors were minimized. The results were compared with theoretical and experimental studies available in the literature. Previous electron impact experiments present relative cross-sections or use correction terms for the absolute cross-sections due to losses of energetic ions. We elucidate the differences between the new measurement method and the existing ones in the literature and explain why the present method can be considered reliable. Furthermore, we show how reducing correction terms affects the results. [ABSTRACT FROM AUTHOR]

The kinetics of electrons and negative ions was numerically studied under the conditions, which are typical for multi-pulsed guided ionization waves in He flows ejected into ambient air. It was shown that, in He with a small admixture of O2 or air, O2− ions formed due to three-body electron attachment in the discharge afterglow are rapidly converted to O4− cluster ions in pulse off time. We suggested that seed electrons are generated at the leading edge of a pulse in two steps, and these steps are dissociation of O4− ions to form O2− ions followed by electron detachment from the O2− ions. The rate of O4− dissociation was calculated in He–O2 mixtures for various reduced electric fields on the basis of a Monte Carlo simulation. This rate, as well as the rate of electron detachment from O2− ions calculated previously, was used to simulate seed electron generation in a high-voltage nanosecond pulse in He–O2 mixtures for different gas pressures. It was shown that the formation of O4− ions drastically hinders the generation of seed electrons in multi-pulsed guided ionization waves in He–O2 and He–air mixtures. [ABSTRACT FROM AUTHOR]

Different factors such as gas composition inside the low voltage circuit breaker (LVCB) chamber and the residual plasma in the post-arc stage affect the breakdown process, which in turn affects the breaking capacity of LVCBs. In this paper, the effects of non-parallel electrode structure, gas temperature and pressure, electrode temperature, and gap distance on gap breakdown of hot electrode under high temperature gas conditions were studied, for which a particle-in-cell/Monte-Carlo collision simulation model has been established, which takes into account the effects of high-temperature gas components, cathode electron thermal emission, electron collision ionization and other effects, and simulation studies have been conducted. The simulation results show that the increase in gap gas temperature, the decrease in air pressure, and the increase in electrode temperature will lead to the gap breakdown more easily. With the increase in the gap length, the breakdown voltage increases, but the average electric field intensity required for breakdown decreases. In the non-parallel electrode structure, the breakdown occurs first at the position with the shortest gap distance, then the cathode sheath forms and extends along the electrode surface to other areas, and finally, the entire gap breaks down. [ABSTRACT FROM AUTHOR]

The effect of a copper chromite (CC) catalyst on the decomposition of ammonium perchlorate (AP) was investigated using thermo gravimetric analysis (TGA) in conjunction with Fourier transform infrared (FTIR) spectroscopy and electron ionization (EI) mass spectrometry (MS) of the evolved gases. To determine the activation energy of AP samples, the Kissinger–Akahira–Sunose iso-conversional method was used, which shed more light on the effect of copper chromite on both the low-temperature decomposition (LTD) and high-temperature decomposition (HTD) stages. The FTIR and mass spectra revealed species O2, N2O, Cl2, NO2, HCl, HNO3, H2O, ClO, HOCl, and m/z equal to 30. Using a CC catalyst, an increment in the species mole fraction was detected in the HTD stage for all the AP samples. After the catalyst was brought closer, especially when it was embedded with AP, significant changes were observed in the LTD stage as well. MS revealed the formation of new species such as HClO4, ClO4, HClO3, and ClO3 when CC is embedded in AP. Additionally, increased ClO2 due to CC enhances the decomposition reactions near the subsurface. C-DTA proves that the effect in LTD is more due to exothermic decomposition reactions. Consequently, this overall increase in species generation leads to greater mass loss during the LTD stage decomposition. The accelerated path of NO2 production for the pellet of mixed ammonium perchlorate and copper chromite, as well as Copper chromite embedded AP in the LTD stage, is attributed to the presence of ClO2 and the oxidation of CC. These findings demonstrate that the presence of CC near AP causes aging, resulting in a decrease in burn rate over time. Understanding these results will aid in building a detailed chemical kinetic mechanism (DCKM) and open new avenues for researchers to use it wisely in the real world. [ABSTRACT FROM AUTHOR]

Per- and polyfluoroalkyl substances (PFAS) are used in food contact materials (FCMs), e.g. as production aids in the fabrication of PTFE based coatings for kitchenware or as additives in paper and board. Growing concerns about the environment and health related to PFAS have led to an increasing interest in monitoring PFAS levels in FCMs as well as their migration into food. In this study, method development for the analysis of PFAS by thermal desorption – gas chromatography – mass spectrometry (TD-GC-MS) was done. In addition to fluorotelomer alcohols (FTOHs), which are the only PFAS commonly analysed by GC-MS, it was proven that perfluorocarboxylic acids (PFCAs) and per- and polyfluoroether carboxylic acids (PFECAs) as well as their thermolysis products, perfluoroethers (PFEs) and perfluoroalkenes, can be analysed by GC-MS without prior derivatization. Screening for PFCAs and FTOHs was possible by electron impact ionization (EI) using group specific SIM fragments. Confirmation of identity has been done by EI scans as well as chemical ionization (CI) SIM measurements. LODs (limits of detection) of PFCAs, FTOHs and PFECAs in the TD-GC-MS instrument were in the low pg range. Thermal degradation of PFCAs and PFECAs during TD-GC-MS measurement was investigated. [ABSTRACT FROM AUTHOR]

Inside extreme-ultraviolet (EUV) lithography machines, a hydrogen plasma is generated by ionization of the background gas by EUV photons. This plasma is essential for preventing carbon build-up on the optics, but it might affect functional performance and the lifetime of other elements inside the machine. The interaction of scanner materials and components with hydrogen plasma is investigated in controlled experiments using laboratory (off-line) setups, where the properties of EUV-generated plasmas are mimicked. Here, we present a novel experimental setup at TNO, where a low-temperature hydrogen plasma is generated by means of electron-impact ionization using a high-current, high-pressure electron beam (e-beam) gun. We show that the produced ion flux, peak ion energies, and radical-to-ion ratio are similar to that of the EUV-generated plasma. Since the e-gun has the option of operating the e-gun in the pulsed mode, it is possible to reproduce the time-dependent behavior of the scanner plasma as well. Moreover, as shown by Luo et al. [RSC Adv. 10, 8385 (2020)], electrons that impinge on surfaces mimic EUV photons in the generation of secondary electrons, which often drive radiation-induced processes (e.g., surface oxidation, reduction, and growth of carbon). We conclude that e-beam generated hydrogen plasma is a very promising technology for cost-effective lifetime testing of materials and optics, as compared to setups with EUV sources. [ABSTRACT FROM AUTHOR]

We present the generation of attosecond gamma rays via inverse Compton scattering within the framework of laser wakefield acceleration through 2D Particle-In-Cell simulations. Utilizing the near-threshold ionization injection mechanism, an attosecond micro-bunched electron beam characterized by a comb-like current density profile can be achieved with a linearly polarized laser at an intensity of a0 = 1.5. The micro-bunched beam provides a beam energy of approximately 300 MeV and achieves a minimum relative energy spread of about 1.64% after undergoing 2 mm of acceleration. In the inverse Compton scattering scheme, these attosecond electron micro-bunches interact with the reflected driving laser pulse, resulting in the attosecond gamma-ray radiation exhibiting similar structures. Individual spatial-separated gamma-ray pulses exhibit a length of approximately 260–300 as, with a critical energy of 2.0 ± 0.2 MeV. The separated attosecond gamma-ray source owns a peak brilliance of ~1022 photons s−1 mm−2 mrad−2 0.1% BW. This brilliance is competitive in a laboratory for multi-MeV γ-ray sources with a laser intensity of I = 5 × 1018 W/cm2. Such attosecond gamma-ray radiation offers promising applications requiring ultrashort X-ray/gamma ray sources. [ABSTRACT FROM AUTHOR]

This study aimed to clarify the dosimetric impact of calibration beam quality for calibration coefficients of the absorbed dose to water for an ionization chamber in an on-site dosimetry audit. Institution-measured doses of 200 photon and 184 electron beams were compared with the measured dose using one year data before and after the calibration of the ionization chamber used. For photon and electron reference dosimetry, the agreements of the institution-measured dose against two measured doses in this audit were evaluated using the calibration coefficients determined using 60Co (⁠|${N}_{D,\mathrm{w},{}^{60}\mathrm{Co}}$|⁠) and linear accelerator (linac) (⁠|${N}_{D,\mathrm{w},Q}$|⁠) beams. For electron reference dosimetry, the agreement of two institution-measured doses against the measured dose was evaluated using |${N}_{D,\mathrm{w},Q}$|⁠. Institution-measured doses were evaluated using direct- and cross-calibration coefficients. For photon reference dosimetry, the mean differences and standard deviation (SD) of institution-measured dose against the measured dose using |${N}_{D,\mathrm{w},{}^{60}\mathrm{Co}}$| and |${N}_{D,\mathrm{w},Q}$| were −0.1% ± 0.4% and −0.3% ± 0.4%, respectively. For electron reference dosimetry, the mean differences and SD of institution-measured dose using the direct-calibration coefficient against the measured dose using |${N}_{D,\mathrm{w},{}^{60}\mathrm{Co}}$| and |${N}_{D,\mathrm{w},Q}$| were 1.3% ± 0.8% and 0.8% ± 0.8%, respectively. Further, the mean differences and SD of institution-measured dose using the cross-calibration coefficient against the measured dose using |${N}_{D,\mathrm{w},Q}$| were −0.1% ± 0.6%. For photon beams, the dosimetric impact of introducing calibration coefficients determined using linac beams was small. For electron beams, it was larger, and the measured dose using |${N}_{D,\mathrm{w},Q}$| was most consistent with the institution-measured dose, which was evaluated using a cross-calibration coefficient. [ABSTRACT FROM AUTHOR]

We here report theoretical triply differential cross sections (TDCS) for 250 eV electron and positron impact ionization of the methane molecule calculated within the second-order distorted-wave Born approximation (DWBA2) for various momentum transfer conditions. The experimental data taken from Işık et al. [J. Phys. B: At., Mol. Opt. Phys. 49, 065203 (2016)] will be compared with the current theoretical predictions as well as molecular three body distorted wave (M3DW) approximation and generalized Sturmian function (GSF) theoretical models in a non-coplanar geometry. In the low analyzer scattering plane, the results obtained within the DWBA2 theory show better agreement with the experimental results compared to the GSF results. The M3DW results also exhibit agreement with the experimental results, in particular in the perpendicular plane geometry. Furthermore, significant differences between electron and positron TDCS were observed. [ABSTRACT FROM AUTHOR]

Infrared (IR) spectroscopy using ultracold helium nanodroplet matrices has proven to be a powerful method to interrogate encapsulated ions, molecules, and clusters. Due to the helium droplets' high ionization potential, optical transparency, and ability to pick up dopant molecules, the droplets offer a unique modality to probe transient chemical species produced via photo- or electron impact ionization. In this work, helium droplets were doped with acetylene molecules and ionized via electron impact. Ion-molecule reactions within the droplet volume yield larger carbo-cations that were studied via IR laser spectroscopy. This work is focused on cations containing four carbon atoms. The spectra of C4H2+, C4H3+, and C4H5+ are dominated by diacetylene, vinylacetylene, and methylcyclopropene cations, respectively, which are the lowest energy isomers. On the other hand, the spectrum of C4H4+ ions hints at the presence of several co-existing isomers, the identity of which remains to be elucidated. [ABSTRACT FROM AUTHOR]

We investigate the optimization of flexible tailored real-space Jastrow factors for use in the transcorrelated (TC) method in combination with highly accurate quantum chemistry methods, such as initiator full configuration interaction quantum Monte Carlo (FCIQMC). Jastrow factors obtained by minimizing the variance of the TC reference energy are found to yield better, more consistent results than those obtained by minimizing the variational energy. We compute all-electron atomization energies for the challenging first-row molecules C2, CN, N2, and O2 and find that the TC method yields chemically accurate results using only the cc-pVTZ basis set, roughly matching the accuracy of non-TC calculations with the much larger cc-pV5Z basis set. We also investigate an approximation in which pure three-body excitations are neglected from the TC-FCIQMC dynamics, saving storage and computational costs, and show that it affects relative energies negligibly. Our results demonstrate that the combination of tailored real-space Jastrow factors with the multi-configurational TC-FCIQMC method provides a route to obtaining chemical accuracy using modest basis sets, obviating the need for basis-set extrapolation and composite techniques. [ABSTRACT FROM AUTHOR]

Rationale: 1,4‐Cyclohexanedicarboxylic acid and its esters are widely used as building blocks in the production of polymers and copolymers. The properties of such compounds directly depend on the ratio of cis‐ and trans‐isomers in the starting materials. The identification of such stereoisomers by mass spectrometry can be used for the analysis of complex reactions and pyrolysis mixtures. Methods: 1,4‐Cyclohexanedicarboxylic acid propyl, isopropyl, butyl, 2‐butyl, pentyl, 2‐pentyl, 4‐methylpentyl, heptyl, octyl, and nonyl esters were synthesized and analyzed by gas chromatography‐electron ionization mass spectrometry. The general fragmentation patterns of the synthesized compounds in electron ionization conditions were determined using high‐resolution mass spectrometry. The relative response factors for the isomers were established on the basis of NMR and GC–MS data. Results: Regardless of the structure of the alkyl groups, the EI mass spectra of cis‐ and trans‐dialkyl 1,4‐cyclohexanedicarboxylates differ very sharply. The stereoselectivity of fragmentation processes is due to the steric proximity of the substituents in the case of cis‐isomers. Elemental composition of all ions appearing in the mass spectra of the analytes under study was confirmed by high‐resolution mass spectrometry. Despite the perceptible differences in the EI mass spectra of the isomers their ionization efficiencies are close. Conclusions: The possibility of the unambiguous identification of stereoisomeric dialkyl cis and trans 1,4‐cyclohexanedicarboxylates on the basis of their EI mass spectra was shown. The differences in mass spectra of the isomers are due to the conformational rigidity of the considered monocyclic molecules, which ensures the unique stereoselectivity of the elimination of neutral molecules owing to the 1,3‐cis‐diaxial proximity effect. [ABSTRACT FROM AUTHOR]

We present an optimization strategy for atom‐specific spin‐polarization constants within the spin‐polarized GFN2‐xTB framework, aiming to enhance the accuracy of molecular simulations. We compare a sequential and global optimization of spin parameters for hydrogen, carbon, nitrogen, oxygen, and fluorine. Sensitivity analysis using Sobol indices guides the identification of the most influential parameters for a given reference dataset, allowing for a nuanced understanding of their impact on diverse molecular properties. In the case of the W4‐11 dataset, substantial error reduction was achieved, demonstrating the potential of the optimization. Transferability of the optimized spin‐polarization constants over different properties, however, is limited, as we demonstrate by applying the optimized parameters on a set of singlet‐triplet gaps in carbenes. Further studies on ionization potentials and electron affinities highlight some inherent limitations of current extended tight‐binding methods that can not be resolved by simple parameter optimization. We conclude that the significantly improved accuracy strongly encourages the present re‐optimization of the spin‐polarization constants, whereas the limited transferability motivates a property‐specific optimization strategy. [ABSTRACT FROM AUTHOR]

The sensitivity and accuracy of identifying volatile organic compounds using mass spectrometric gas analyzers operation in the electron ionization mode can be enhanced by increasing the number of ions formed in the ion source by varying the energy of ionizing electrons. The paper presents a comparison of data obtained by electron impact ionization at electron energy (EE) in the range of 25–105 eV for a number of organic substances belonging to different classes of organic compounds. an analysis using similarity matrices based on various similarity metrics was performed to interpret the dynamics of changes in the intensities of fragment ion peaks, and the influence of EE on the formation probability of the main fragment species of the substances under study and, accordingly, on the resemblance of a recorded mass spectrum to the reference mass spectrum from the database was shown. [ABSTRACT FROM AUTHOR]

Oxygen vacancy is the most common type of point defects in functional oxides, and it is known to have profound influence on their properties. This is particularly true for ferroelectric oxides since their interaction with ferroelectric polarization often dictates the ferroelectric responses. Here, we study the influence of the concentration of oxygen vacancies on the stability of ferroelectric domain walls (DWs) in BiFeO3, a material with a relatively narrow bandgap among all perovskite oxides, which enables strong interactions among electronic charge carriers, oxygen vacancies, and ferroelectric domains. It is found that the electronic charge carriers in the absence of oxygen vacancies have essentially no influence on the spatial polarization distribution of the DWs due to their low concentrations. Upon increasing the concentration of oxygen vacancies, charge‐neutral DWs with an originally symmetric polarization distribution symmetric around the center of the wall can develop a strong asymmetry of the polarization field, which is mediated by the electrostatic interaction between polarization and electrons from the ionization of oxygen vacancies. Strongly charged head‐to‐head DWs that are unstable without oxygen vacancies can be energetically stabilized in the off‐stoichiometric BiFeO3−δ with δ ∼ 0.02 where ionization of oxygen vacancies provides sufficient free electrons to compensate the bound charge at the wall. Our results delineate the electrostatic coupling of the ionic defects and the associated free electronic charge carriers with the bound charge in the vicinity of neutral and charged DWs in perovskite ferroelectrics. [ABSTRACT FROM AUTHOR]

In the field of chemical warfare agents (CWAs), ethanolamines are important building blocks for the preparation of nerve agents belonging to the V-series such as VX and VR as well as the nitrogen-based mustards. In this work, the determination of three members in this class of Schedule 2B reportable chemicals, namely N,N-dimethylethanolamine (DMEA), N,N-diethylethanolamine (DEEA), and N,N-diisopropylethanolamine (DIEA) by electron ionization gas chromatography-mass spectrometry (EI-GC-MS) is presented. The three dialkylethanolamines were spiked in a high organic content soil matrix featured during the 45th Organization for the Prohibition of Chemical Weapons (OPCW) proficiency test (PT) at two separate concentrations each (1 and 10 µg/g separately), simulating values often encountered during these tests. The N,N-dialkylethanolamines were O-alkylated using benzyl bromide and sodium carbonate at 55 °C and were detected as their benzylated versions by electron ionization GC-MS. The benzylation of each dialkylethanolamine yielded derivatives with higher molecular weight and therefore different GC-MS profiles such as longer retention times and sharper peak chromatography relative to their unmodified counterparts. These characteristics enable the analytical chemist to detect and confirm these important CWA-related chemicals specifically in instances where they are present in low concentrations (i.e. <10 µg/g) among more abundant interferences. [ABSTRACT FROM AUTHOR]

Oxygen vacancy is the most common type of point defects in functional oxides, and it is known to have profound influence on their properties. This is particularly true for ferroelectric oxides since their interaction with ferroelectric polarization often dictates the ferroelectric responses. Here, we study the influence of the concentration of oxygen vacancies on the stability of ferroelectric domain walls (DWs) in BiFeO3, a material with a relatively narrow bandgap among all perovskite oxides, which enables strong interactions among electronic charge carriers, oxygen vacancies, and ferroelectric domains. It is found that the electronic charge carriers in the absence of oxygen vacancies have essentially no influence on the spatial polarization distribution of the DWs due to their low concentrations. Upon increasing the concentration of oxygen vacancies, charge‐neutral DWs with an originally symmetric polarization distribution symmetric around the center of the wall can develop a strong asymmetry of the polarization field, which is mediated by the electrostatic interaction between polarization and electrons from the ionization of oxygen vacancies. Strongly charged head‐to‐head DWs that are unstable without oxygen vacancies can be energetically stabilized in the off‐stoichiometric BiFeO3−δ with δ ∼ 0.02 where ionization of oxygen vacancies provides sufficient free electrons to compensate the bound charge at the wall. Our results delineate the electrostatic coupling of the ionic defects and the associated free electronic charge carriers with the bound charge in the vicinity of neutral and charged DWs in perovskite ferroelectrics. [ABSTRACT FROM AUTHOR]

Atractylodis macrocephalae rhizome (AMR) belongs to medicine food homology. Its' clinical application of invigorating the spleen-stomach of AMR was applied to various diseases. In this research, a UPLC-QTOF-MS method was developed for qualitative and quantitative analysis of AMR, simultaneously. A Waters Acquity BEH C18 column (2.1 mm × 100 mm, 1.7 μm particle size) was used for separation of AMR multi-components. The column was eluted with a mobile phase of 0.1% formic acid-water and 0.1% formic acid-acetonitrile. Electron spray ionization with positive-ion mode and external standard method was utilized for quantifying the nine analytes in AMR. Constituents of AMR were scanned by UPLC-QTOF-MS and then identified by mass fragments and chromatographic information compared with the published literature and reference standards. Under positive mode, a total of 61 chemical compositions including 16 terpenoids, 8 polyacetylenes, 6 aromatics, 5 flavonoids, 5 coumarins, 5 organic acids, 4 amino acids, 3 fatty acids, 3 aliphatics, 2 steroids, and 2 alkenes, a nucleoside and an aldehyde were identified. Simultaneously, the contents of three amino acids (L-tyrosine, L-phenylalanine, and L-tryptophan), three sesquiterpenoids (atractylenolide Ⅲ, atractylenolide Ⅱ, and atractylenolide Ⅰ), a flavonoid (rutin), an organic acid (ferulic acid), and a pentacyclic triterpenoid (oleanolic acid) were determined in seventeen AMR batches. Amino acids and triterpenoid were quantified for the first time in AMR. The UPLC-QTOF-MS method developed in this article was reliable, practical, and useful for qualitative and quantitative evaluation of AMR multi-components. [ABSTRACT FROM AUTHOR]

Characterization of the inner-shell decay processes in molecules containing heavy elements is key to understanding x-ray damage of molecules and materials and for medical applications with Auger-electron-emitting radionuclides. The 1s hole states of heavy atoms can be produced by absorption of tunable x rays and the resulting vacancy decays characterized by recording emitted photons, electrons, and ions. The 1s hole states in heavy elements have large x-ray fluorescence yields that transfer the hole to intermediate electron shells that then decay by sequential Auger-electron transitions that increase the ion's charge state until the final state is reached. In molecules, the charge is spread across the atomic sites, resulting in dissociation to energetic atomic ions. We have used x-ray/ion coincidence spectroscopy to measure charge states and energies of Iq+ and Brq′+ atomic ions following 1s ionization at the I and Br K-edges of IBr. We present the charge states and kinetic energies of the two correlated fragment ions associated with core-excited states produced during the various steps of the cascades. To understand the dynamics leading to the ion data, we develop a computational model that combines Monte-Carlo/Molecular-Dynamics (MC/MD) simulations with a classical over-the-barrier model to track inner-shell cascades and redistribution of electrons in valence orbitals and nuclear motion of fragments. [ABSTRACT FROM AUTHOR]

Rationale: The Chemical Weapons Convention (CWC) mandates rigorous screening of chemical weapons and their potential degradation/reaction products, which is essential to identify such products in suspected samples. The reaction between 2‐(N,N‐dialkylamino)ethylchlorides and 2‐(N,N‐dialkylamino)ethanols (precursors/degradation products of VX agents) produces a new class of reaction products that are not explored. Methods: The reaction products, bis(2‐N,N‐dialkylaminoethyl)ethers (1–10), were synthesized using established synthetic procedures, and gas chromatography/mass spectrometry (GC/MS) (electron ionization [EI] and chemical ionization [CI]) methods were developed for their identification. The GC/MS experiments were performed on an Agilent GC/MSD system using an HP‐5MS capillary column. Methane gas was used as the CI reagent gas for GC/CIMS experiments. GC/retention index (RI) values of 1–10 were calculated using the retention times of the hydrocarbon mixture and the analytes. Results: The GC/EI spectra of 1–10 exhibited [M‐H]+ ions and distinctive fragments that provided valuable structural information. The selective fragmentation of the alkyl groups on nitrogen facilitated the discrimination of possible isomeric compounds. Interpretation of EI fragments in the high mass region is important for unambiguous identification of 1–10, because the major ions significantly match other CWC‐related compounds containing the 2‐(N,N‐dialkylaminoethyl) group. GC/CI (methane) spectra included M+., [M + H]+, [M‐H]+, reagent‐specific adduct ions, and a few structure‐indicative fragments. The spiking experiments in soil and water samples revealed that the target analytes were stable, easily extractable, and detectable using GC/MS. Conclusions: The reaction products, 1–10, could be successfully synthesized and characterized using GC/MS (EI and CI). The GC/MS and GC/RI data provide important insights into the unambiguous identification of the target molecules in challenging CWC verification and are helpful in participation in the Organization for the Prohibition of Chemical Weapons proficiency tests. [ABSTRACT FROM AUTHOR]

The synthetic 20‐keto‐steroid S42 (1) demonstrated selective androgen receptor modulator (SARM) properties in preclinical studies and, consequently, received growing attention also in the context of sports drug testing programs. Fundamental understanding of the behavior of S42 (1) and of relevant derivatives in gas chromatography‐electron ionization MS experiments at high resolution (GC‐EI‐HRMS) is indispensable to develop a reliable qualitative and quantitative doping control method for S42 (1) and its metabolites in body fluid matrices. We present important fundamental mechanistic data on the EI fragmentation behavior of S42 (1) and of silyl ether derivatives as well as of stable isotope‐labelled reference material. [ABSTRACT FROM AUTHOR]

Under atmospheric pressure, partial discharge initiated by free metallic particles has consistently been a significant factor leading to failures in high-voltage electrical equipment. Simulating the propagation of negative streamer discharge in N2/O2 mixtures contributes to a better understanding of the occurrence and evolution of partial discharge, optimizing the insulation performance of electrical equipment. In this study, a two-dimensional plasma fluid dynamics model coupled with the current module was employed to simulate the evolution process of negative streamer discharge caused by one free metallic particle under a suspended potential at 220 kV applied voltage conditions. Simulation results indicated that the discharge process could be divided into two distinct stages: In the first stage, the electron ionization region detached from the electrode surface and propagated independently. During this stage, the corona discharge on the negative electrode surface provided seed electrons crucial for the subsequent development of negative corona discharge. The applied electric field played a dominant role in the propagation of the electron region, especially in the electron avalanche region. In the second stage, space charge gradually took over, causing distortion in the spatial field, particularly generating a substantial electric field gradient near the negative electrode surface, forming an ionization pattern dominated by ionization near the negative electrode surface. These simulation results contribute to a comprehensive understanding of the complex dynamic process of negative streamer discharge initiated by free metallic particles, providing essential insights for optimizing the design of electrical equipment and insulation systems. [ABSTRACT FROM AUTHOR]

In the field of quality analysis of food and flavoring products, gas chromatography–quadrupole mass spectrometry–ion mobility spectrometry (GC-QMS-IMS) is a powerful technique for the simultaneous detection of volatile organic compounds (VOCs) by both QMS and IMS. GC is an established technique for the separation of complex VOC-rich food products. While subsequent detection by IMS features soft ionization of fragile compounds (e.g., terpenes) with characteristic drift times, MS provides analytes' m/z values for database substance identification. A limitation of the prominently used static-headspace-based GC-QMS-IMS systems is the substantially higher sensitivity of IMS in comparison to full-scan QMS. The present study describes a new prototypic trapped-headspace (THS)-GC-QMS-IMS setup using mango purees. This approach ultimately allows the combination of soft ionization with m/z values obtained from database-searchable electron ionization (EI) spectra. The new setup features aligned retention times for IMS and MS and sufficient signal intensities for QMS and IMS. The results demonstrate that THS-GC-QMS-IMS allows for the classification of mango purees from different cultivars and that it could be a promising alternative method for authenticity control of food, flavors, and beverages. [ABSTRACT FROM AUTHOR]

Rationale: Gas chromatography–mass spectrometry (GC–MS) combines chromatography and MS, providing full play to the advantages of high separation efficiency of GC, strong qualitative ability of MS, and high sensitivity of detector. In GC–MS data processing, determining the experimental compounds is one of the most important analytical steps, which is usually realized by one‐to‐one similarity calculations between the experimental mass spectrum and the standard mass spectrum library. Although the accuracy of the algorithm has been improved in recent years, it is still difficult to distinguish structurally similar mass spectra, especially isomers. At the same time, the library capacity is very large and increasing every year, and the algorithm needs to perform large numbers of calculations with irrelevant compounds in the library to recognize unknown compounds, which leads to a significant reduction in efficiency. Methods: This work proposed to exclude a large number of irrelevant mass spectra by presearching, perform preliminary similarity calculations using similarity algorithms, and finally improve the accuracy of similarity calculations using deep classification models. The replica library of NIST17 is used as the query data, and the master library is used as the reference database. Results: Compared with the traditional recognition algorithm, the preprocessing algorithm has reduced the time by 4.2 h, and by adding the deep learning models 1 and 2 as the final determination, the recognition accuracy has been improved by 1.9% and 6.5%, respectively, based on the original algorithm. Conclusions: This method improves the recognition efficiency compared to conventional algorithms and at the same time has better recognition accuracy for structurally similar mass spectra and isomers. [ABSTRACT FROM AUTHOR]

AbstractMass spectrometry (MS) enables precise identification and quantification of molecules, particularly when combined with chromatography. The advent of atmospheric pressure ionization (API) techniques allowed the efficient coupling of liquid chromatography with MS (LC-MS), extending analyses to nonvolatile and thermolabile compounds. API techniques present limitations such as low informative capacity and reproducibility of mass spectra, increasing instrument complexity and costs. Other challenges include analyzing poorly polar molecules and matrix effects (ME), which negatively impact quantitative analyses, necessitating extensive sample purification or using expensive labeled standards. These limitations prompted the exploration of alternative solutions, leading to the development of the Liquid Electron Ionization (LEI) interface. The system has demonstrated excellent robustness and reproducibility. LEI has been employed to analyze various compounds, including pesticides, drugs of abuse, phenols, polycyclic aromatic hydrocarbons (PAHs), phthalates, and many others. Its versatility has been validated with single quadrupole, triple quadrupole, and QToF detectors, operating in electron ionization (EI) or chemical ionization (CI) modes and with both reverse phase liquid chromatography (RPLC) and normal phase liquid chromatography (NPLC). LEI has also been successfully integrated with the Microfluidic Open Interface (MOI), Membrane Introduction Mass Spectrometry (MIMS), and Microfluidic Water-Assisted Trap Focusing (M-WATF), broadening its application scope and consistently demonstrating promising results in terms of sensitivity and identification power. The most recent advancement is the development of Extractive-Liquid Sampling Electron Ionization-Mass Spectrometry (E-LEI-MS), a surface sampling and real-time analysis technique based on the LEI concept. This review article offers a comprehensive and up-to-date picture of the potential of LEI. [ABSTRACT FROM AUTHOR]

The paper presents the results of a theoretical study of the electron- impact ionization of the 6p, 6s, and 5d shells of the Pb and Bi atoms. Calculations are performed using three relativistic approximations, namely distorted waves, Coulomb-Born, and binary-encounter-dipole, in a wide range of collision energies from thresholds to 700 eV. The ionization cross sections of the sub valent 5d shell of the Pb and Bi atoms are calculated for the first time. It is established that this shell contributes to the total direct ionization cross section twice as much as the 6s shell (up to 26% for Pb and up to 38% for Bi), which shows the importance of taking this process into account in modeling different types of plasma. We analyzed the behavior of the partial ionization cross sections of these atoms calculated using various approximations. Comparison of the resultant full direct ionization cross sections with the data of other authors shows that they satisfactorily describe the process of direct ionization. However, for a more detailed analysis and comparison with experimental data additional calculations of the main process of indirect ionization, namely excitation of autoionization, for the Pb and Bi atoms are required. Analysis of the influence of the third valence electron of the Bi atom compared to the Pb atom on the core-valence interaction shows that this influence is the most significant in the case of the distorted waves approximation. The difference in the behavior of the direct ionization cross sections is caused, in our opinion, by the interaction of valence electrons among themselves. [ABSTRACT FROM AUTHOR]

This article discusses the modular synthesis of conjugated aromatic boronate esters through radical xanthate addition. The researchers successfully synthesized xanthates with phenylboronate groups and demonstrated their potential for synthesizing boronate-containing conjugated aromatic compounds. The document provides detailed information about the synthesis and characterization of various compounds, including their chemical structures, spectroscopic data, and yields. It can be useful for researchers studying organic synthesis and compound characterization. [Extracted from the article]

The research includes Preparation of chalcones Preparation of chalcones in alkaline medium and reacting two types of ketones, Acetylnaphthalene-2 and 4-morpholino acetophenone, with four types of aldehydes, as eight types of new chalcones were prepared (H1, H4, H5, H6, H8) The compounds were identified by FT-IR, proton nuclear magnetic resonance spectra (1HNMR) and electron aerosol ionization mass spectrometry (ESI), where this was confirmed by the compositions of the new chalcones prepared. The biological activity of the prepared compounds was studied for two types of pathogenic bacteria for humans, which are bacteria Gram-negative Escherichia coli, and Gram-positive bacteria Staphylococcus aureus that cause skin infections. Where the compound gave the highest efficacy compound H8 against both types of pathological bacteria under test, followed by compound H4 and then compound H6. [ABSTRACT FROM AUTHOR]

High power impulse magnetron sputtering (HiPIMS) discharges with a zirconium target are studied experimentally and by applying the ionization region model (IRM). The measured ionized flux fraction lies in the range between 25% and 59% and increases with increased peak discharge current density ranging from 0.5 to 2 A/cm 2 at a working gas pressure of 1 Pa. At the same time, the sputter rate-normalized deposition rate determined by the IRM decreases in accordance with the HiPIMS compromise. For a given discharge current and voltage waveform, using the measured ionized flux fraction to lock the model, the IRM provides the temporal variation of the various species and the average electron energy within the ionization region, as well as internal discharge parameters such as the ionization probability and the back-attraction probability of the sputtered species. The ionization probability is found to be in the range 73%–91%, and the back-attraction probability is in the range 67%–77%. Significant working gas rarefaction is observed in these discharges. The degree of working gas rarefaction is in the range 45%–85%, higher for low pressure and higher peak discharge current density. We find electron impact ionization to be the main contributor to working gas rarefaction, with over 80% contribution, while kick-out by zirconium atoms and argon atoms from the target has a smaller contribution. The dominating contribution of electron impact ionization to working gas rarefaction is very similar to other low sputter yield materials. [ABSTRACT FROM AUTHOR]