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At least 181 records · Page 10

Trace Analysis and Reaction Monitoring by Nanophotonic Ionization Mass Spectrometry from Elevated Bowtie and Silicon Nanopost Arrays

We present that silicon nanopost arrays (NAPA) are used in trace analysis by mass spectrometry (MS) because they enable highly efficient ion production from small molecules and thin tissue sections by UV laser desorption ionization (LDI). Such nanophotonic ionization of adsorbates relies on localized interactions between a nanostructured substrate and laser radiation. In LDI from NAPA, only the component of the oscillating electric field vector that is parallel with the posts couples the laser energy into the nanostructure. Enhancements in control over adsorbate ionization and fragmentation are expected if the surface-parallel component can also interact with the nanostructure. Here, an alternative nanophotonic ionization platform is introduced for LDI-MS, the elevated bowtie (EBT) array by adding triangular chromium features on top of silicon post pairs to form bowties. Compared to NAPA, the threshold fluence for ionization from EBT is lower, and at low laser fluences the ionization efficiency is increased by a factor of ≈17. The EBT platform with optimized apex angle exhibits a higher survival yield for molecular ions produced from biomolecules and xenobiotics and allows more control over fragmentation by adjusting the fluence. Finally, these unique nanophotonic ionization attributes are utilized for trace analysis and reaction monitoring in complex biological samples.

36 MATERIALS SCIENCE↗

Bond Dissociation Energy, Ionization Energy, and Electronic Structure of Thorium Dimer

Diatomic thorium, Th 2 , has been investigated using a laser ablation, supersonic expansion source to produce the molecule and resonant two-photon ionization spectroscopy to measure its bond dissociation energy (BDE) and ionization energy (IE). The molecule has a high density of states in the vicinity of its bond dissociation energy, leading to rapid predissociation as soon as this energy is exceeded. The BDE is identified from this predissociation threshold as D 0 (Th 2 ) = 2.857(7) eV, where the assigned error limit is provided in parentheses in units of the last quoted digit. Similarly, the one-photon ionization threshold has been measured, providing the ionization energy IE(Th 2 ) = 5.042(4) eV. Together with a thermochemical cycle and the atomic ionization energy, these values provide the BDE of the cation, giving D 0 (Th 2 + ) = 4.122(8) eV. Computations show that Th 2 has three nearly degenerate low-lying electronic states (1 3 Σ u + , 1 1 Σ g + , and 1 3 Δ g ) with bonding dominated by 7s and 6d orbitals, indicating predominantly transition-metal-like behavior. The 1 3 Σ u + state exhibits a triple bond, whereas the 1 1 Σ g + and 1 3 Δ g states possess quadruple-bond character and correspondingly shorter bonds. Although 1 3 Σ u + is predicted to be the lowest state without spin–orbit coupling, the large spin–orbit stabilization of the 1 3 Δ g state makes its Ω = 1 g component the ground state. Furthermore, the calculated dissociation energy (2.840 eV) and ionization energy of Th 2 (5.098 eV) are both in excellent agreement with experiment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomistic characterization of hydration-dependent fuel cell ionomer nanostructure: validation by vibrational spectroscopy

The development of Nafion alternatives for fuel cells and electrolyzers requires a fundamental understanding of hydration-dependent ion-exchange site acid/base chemistry. We present here reactive force field (ReaxFF) molecular dynamics (MD) simulations of Nafion at varying molar water/ion-exchange-site ratios (λ), which we correlate to our experimental and density functional theory-based vibrational spectra. ReaxFF describes the formation and breaking of covalent bonds, enabling simulations of proton exchange between sulfonic acid/sulfonate groups and water/hydronium. Our MD simulations determine the λ-dependent equilibrium proportions of protonated and deprotonated sites. We find that protonated sites persist across all λ from 0 to 20, challenging the widely accepted notion that all sites are ionized above a threshold λ value (e.g., 3 or 4). Our simulations generate hundreds of realistic exchange site environments, the characterization of which are based on 6 Å radii sulfur-centered ‘inner-spheres’. These inner- and outer-sphere regions elucidate an interplay of stereoelectronic factors that influence protonation states, including the number of inner-sphere waters (Λ). Our simulations produce broad λ-dependent distributions of Λ values, representing non-uniform exchange site hydration. Moreover, we demonstrate that these distributions are specific to both protonated and deprotonated sites, with significant overlap between the two distributions for all non-zero λ. These distributions underpin the IR spectra of hydrated membranes, with each exchange site contributing an IR spectrum characteristic of its protonation state and Λ. We expect that these nanostructural characterizations of Nafion exchange sites will contribute to the development of new ionomers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Near edge X-ray absorption mass spectrometry on coronene

We have investigated the photoionization and photodissociation of free coronene cations C{sub 24}H{sub 12}{sup +} upon soft X-ray photoabsorption in the carbon K-edge region by means of a time-of-flight mass spectrometry approach. Core excitation into an unoccupied molecular orbital (below threshold) and core ionization into the continuum both leave a C 1s vacancy, that is subsequently filled in an Auger-type process. The resulting coronene dications and trications are internally excited and cool down predominantly by means of hydrogen emission. Density functional theory was employed to determine the dissociation energies for subsequent neutral hydrogen loss. A statistical cascade model incorporating these dissociation energies agrees well with the experimentally observed dehydrogenation. For double ionization, i.e., formation of intermediate C{sub 24}H{sub 12}{sup 3+⋆}trications, the experimental data hint at loss of H{sup +} ions. This asymmetric fission channel is associated with hot intermediates, whereas colder intermediates predominantly decay via neutral H loss.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The NEWS-G detector at SNOLAB

The New Experiments With Spheres-Gas (NEWS-G) collaboration intends to achieve sub-GeV/c 2 Weakly Interacting Massive Particles (WIMPs) detection using Spherical Proportional Counters (SPCs). SPCs are gaseous detectors relying on ionisation with a single ionization electron energy threshold. The latest generation of SPC for direct dark matter searches has been installed at SNOLAB in Canada in 2021. This article details the different processes involved in the fabrication of the NEWS-G experiment. Also outlined in this paper are the mitigation strategies, measurements of radioactivity of the different components, and estimations of induced background event rates that were used to quantify and address detector backgrounds.

47 OTHER INSTRUMENTATION↗

Effects of screening and pressure ionization on the electron broadening of spectral lines in dense plasmas

Collisions between electrons and radiating atoms broaden spectral absorption and emission lines in dense plasmas. High densities also introduce screening and pressure ionization effects that distort the wave functions of both bound and free electrons. In order to study how dense plasma effects influence the electron broadening of spectral lines, this paper incorporates electron wave functions from an average-atom (AA) model to calculate the linewidth of the B III 2⁢𝑝−2⁢𝑠 transition at 𝑇 = 10 eV for mass densities ranging from 𝜌 = 10 −4 to 0.4⁢ g⁡/cc. The calculation method uses the impact approximation, allowing the linewidth to be written in terms of electron-collision cross sections and an interference term. Compared to an otherwise identical calculation that uses Coulomb free wave functions, the AA method is found to modify both the cross sections and the resulting linewidth at sufficiently high density by introducing screening and pressure-ionized bound states. Screening lowers the cross sections at low energies and near electron excitation thresholds, while pressure-ionized bound states introduce resonances into the continuum. Thus, as the density increases, the relative linewidth between the AA and Coulomb calculations follows a general decrease because of screening, with sharp increases at various intervals due to pressure ionization. Finally, the AA results are also compared with a common approach to introduce screening through the interaction potential and reduced models that use the Bethe formula for the inelastic electron-collision cross sections.

electronic excitation & ionization↗

Laser-induced breakdown and damage generation by nonlinear frequency conversion in ferroelectric crystals: Experiment and theory

Using our experimental data for ns pulsed second harmonic generation (SHG) by periodically poled stoichiometric LiTaO{sub 3} (PPSLT) crystals, we consider in detail the mechanism underlying laser-induced damage in ferroelectric crystals. This mechanism involves generation and heating of free electrons, providing an effective kinetic pathway for electric breakdown and crystal damage in ns pulsed operation via combined two-photon absorption (TPA) and induced pyroelectric field. In particular, a temperature increase in the lattice of ≈1 K induced initially by ns SHG and TPA at the rear of operating PPSLT crystal is found to induce a gradient of spontaneous polarization generating a pyroelectric field of ≈10 kV/cm, accelerating free electrons generated by TPA to an energy of ≈10 eV, followed by impact ionization and crystal damage. Under the damage threshold for ns operation, the impact ionization does not lead to the avalanche-like increase of free electron density, in contrast to the case of shorter ps and fs pulses. However, the total number of collisions by free electrons, ≈10{sup 18} cm{sup −3} (generated during the pulse and accelerated to the energy of ≈10 eV), can produce widespread structural defects, which by entrapping electrons dramatically increase linear absorption for both harmonics in subsequent pulses, creating a positive feedback for crystal lattice heating, pyroelectric field and crystal damage. Under pulse repetition, defect generation starting from the rear of the crystal can propagate towards its center and front side producing damage tracks along the laser beam and stopping SHG. Theoretical analysis leads to numerical estimates and analytical approximation for the threshold laser fluence for onset of this damage mechanism, which agree well with our (i) experiments for the input 1064 nm radiation in 6.8 kHz pulsed SHG by PPSLT crystal, (ii) pulsed low frequency 532 nm radiation transmission experiments, and also (iii) with the data published for other nonlinear crystals and operated wavelengths.

36 MATERIALS SCIENCE↗

Dynamics of ionization-induced electron injection in the high density regime of laser wakefield acceleration

The dynamics of ionization-induced electron injection in high density (∼1.2 × 10{sup 19} cm{sup −3}) regime of laser wakefield acceleration is investigated by analyzing the betatron X-ray emission. In such high density operation, the laser normalized vector potential exceeds the injection-thresholds of both ionization-injection and self-injection due to self-focusing. In this regime, direct experimental evidence of early on-set of ionization-induced injection into the plasma wave is given by mapping the X-ray emission zone inside the plasma. Particle-In-Cell simulations show that this early on-set of ionization-induced injection, due to its lower trapping threshold, suppresses the trapping of self-injected electrons. A comparative study of the electron and X-ray properties is performed for both self-injection and ionization-induced injection. An increase of X-ray fluence by at least a factor of two is observed in the case of ionization-induced injection due to increased trapped charge compared to self-injection mechanism.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Indirect dark matter signatures in the cosmic dark ages. II. Ionization, heating, and photon production from arbitrary energy injections

Any injection of electromagnetically interacting particles during the cosmic dark ages will lead to increased ionization, heating, production of Lyman-a photons and distortions to the energy spectrum of the cosmic microwave background, with potentially observable consequences. Here, we describe numerical results for the low-energy electrons and photons produced by the cooling of particles injected at energies from keV to multi-TeV scales, at arbitrary injection redshifts (but focusing on the post-recombination epoch). We use these data, combined with existing calculations modeling the cooling of these low-energy particles, to estimate the resulting contributions to ionization, excitation and heating of the gas, and production of low-energy photons below the threshold for excitation and ionization. We compute corrected deposition-efficiency curves for annihilating dark matter, and demonstrate how to compute equivalent curves for arbitrary energy-injection histories. These calculations provide the necessary inputs for the limits on dark matter annihilation presented in the accompanying paper I, but also have potential applications in the context of dark matter decay or deexcitation, decay of other metastable species, or similar energy injections from new physics. Lastly, we make our full results publicly available at http://nebel.rc.fas.harvard.edu/epsilon, to facilitate further independent studies. In particular, we provide the full low-energy electron and photon spectra, to allow matching onto more detailed codes that describe the cooling of such particles at low energies.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

A vacuum ultraviolet laser pulsed field ionization-photoion study of methane (CH 4 ): Determination of the appearance energy of methylium from methane with unprecedented precision and the resulting impact on the bond dissociation energies of CH 4 and CH 4 +

Here, we report on the successful implementation of a high-resolution vacuum ultraviolet (VUV) laser pulsed field ionization-photoion (PFI-PI) detection method for the study of unimolecular dissociation of quantum-state- or energy-selected molecular ions. As a test case, we have determined the 0 K appearance energy (AE 0 ) for the formation of methylium, CH 3 + , from methane, CH 4 , as AE 0 (CH 3 + /CH 4 ) = 14.32271 ± 0.00013 eV. This value has a significantly smaller error limit, but is otherwise consistent with previous laboratory and/or synchrotron-based studies of this dissociative photoionization onset. Furthermore, the sum of the VUV laser PFI-PI spectra obtained for the parent CH 4 + ion and the fragment CH 3 + ions of methane is found to agree with the earlier VUV pulsed field ionization-photoelectron (VUV-PFI-PE) spectrum of methane, providing unambiguous validation of the previous interpretation that the sharp VUV-PFI-PE step observed at the AE 0 (CH 3 + /CH 4 ) threshold ensues because of higher PFI detection efficiency for fragment CH 3 + than for parent CH 4 + . This, in turn, is a consequence of the underlying high- n Rydberg dissociation mechanism for the dissociative photoionization of CH 4 , which was proposed in previous synchrotron-based VUV-PFI-PE and VUV-PFI-PEPICO studies of CH 4 . The present highly accurate 0 K dissociative ionization threshold for CH 4 can be utilized to derive accurate values for the bond dissociation energies of methane and methane cation. For methane, the straightforward application of sequential thermochemistry via the positive ion cycle leads to some ambiguity because of two competing VUV-PFI-PE literature values for the ionization energy of methyl radical. The ambiguity is successfully resolved by applying the Active Thermochemical Tables (ATcT) approach, resulting in D 0 (H-CH 3 ) = 432.463 ± 0.027 kJ/mol and D 0 (H-CH 3 + ) = 164.701 ± 0.038 kJ/mol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microwave breakdown of sub-atmospheric argon gas in the vicinity of a microgap

The microwave electric field at breakdown for argon gas in a microgap (generally, gap size <1 mm) over a wide range of pressures and gap sizes was found to exhibit two behavioral pressure regimes. A high microwave electric field was established in the gap of a re-entrant mode resonator. By slowly raising the microwave electric field level, a breakdown level is reached where impact ionization induces low pressure argon gas to breakdown preferentially outside of the gap. At high pressure, breakdown is found to occur preferentially inside the gap, but only after the pressure is high enough for impact ionization to produce breakdown there. Impact ionization has a lower threshold electric field than the boundary-controlled processes, such as secondary electron emission, that would eventually produce breakdown inside the microgap if impact ionization did not occur first. Thus, the lower pressure regime is characterized by breakdown outside of the gap, while in the high-pressure regime, breakdown occurs inside the gap, in both cases by impact ionization. The transition pressure P T between these two pressure regimes depends on the gap size d gap , roughly as P T ∝ d gap –2 . Consistent with the model developed here, this corresponds to the full-amplitude of electron oscillation in the gap field being commensurate with the gap size.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

The effect of autoionization on the HBr + X 2 Π 3/2,1/2 state photoelectron angular distributions

A double-imaging photoelectron-photoion spectrometer and synchrotron radiation have been used to measure the HBr + X 2 Π 3/2 v + = 0, 1, 2 and the 2 Π 1/2 v + = 0 state photoelectron angular distributions, as characterized by the anisotropy parameter β , the total ion yield, and the threshold photoelectron spectrum. Particular attention has been focussed on the photon energy range between the 2 Π 3/2 and the 2 Π 1/2 spin–orbit components of the ground ionic state. This region encompasses Rydberg states, belonging to series converging onto the upper 2 Π 1/2 ionization limit, which may decay by autoionization into the 2 Π 3/2 ionization continuum. A detailed study has been performed on the effects of autoionization on the 2 Π 3/2 v + = 0 state photoelectron angular distributions. Furthermore, the observed energy dependent variations in the β -values exhibit a regular pattern that correlates with excitation into members of a very broad d-type Rydberg series. Additional rapid variations in the β -parameters, which occur over a narrow energy range, appear to coincide with sharp autoionizing Rydberg states belonging to s, p and d series. The present experimental results for the HBr + X 2 Π 3/2 v + = 0 state photoelectron anisotropy parameter are compared to previously reported theoretical predictions and to earlier studies of the Kr + 4p 5 2 P 3/2 state β -parameter. The threshold photoelectron spectrum of the X 2 Π 3/2 v + = 0 band exhibits partially resolved rotational structure. A simulation of this structure yields an ionization threshold of 11.6673 ± 0.0010 eV, which is consistent with previous measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic and Molecular Physics in Strong Fields

In this project, we have investigated a broad range of atomic, molecular, and optical (AMO) processes of current significance in strong-field and ultrafast science and technology. The main goals are to develop new theoretical formalisms and accurate computational methods for ab initio and in-depth non-perturbative study of time-resolved multiphoton quantum dynamics and spectroscopy, very-high-order harmonic generation, optimal control of ultrafast attosecond pulse generation, and resonance-enhanced below threshold harmonics in intense ultrashort laser fields. We have worked on the following projects and we have published 20 top 15 % SCI journal articles during the last 3.5 years (Jan. 1, 2016 to June 30, 2019), including one article in top raking Physical Review Letters, and 3 articles in top ranking (Nature) Scientific Reports, and one Physical Review A article was chosen as Editors’ suggestion paper, etc. (a) Development of new time-dependent methods for accurate and efficient solution of multi-dimensional time-dependent Schrödinger equation and time-dependent density functional theory. (b) Non-perturbative treatment of very-high order (1000th – 5000th order) harmonic generation and broadband supercontinuum spectra from XUV to soft x-ray regime. (c) Development of synchrosqueezing transform (SST) for precision time-frequency analysis of electron multi-rescattering dynamics. (d) Exploration of the dynamical origin of resonance-enhanced near- and below-threshold harmonics. (e) Probing the high-order harmonics generation in disordered semiconductor. (f) Multiphoton ionization of one-electron relativistic diatomic quasi-molecules in strong laser fields. and, (g) New development of non-adiabatic density functional theory. The theoretical and simulation projects we have pursued are closely related to the ongoing experimental researches in several leading laboratories in the US and Europe, etc. It is expected that the outcome of this project will provide timely and significant new information and insight for the advancement of strong-field atomic and molecular physics and ultrafast science and technology.

74 ATOMIC AND MOLECULAR PHYSICS↗

Electron ionization of open/closed chain isocarbonic molecules relevant in plasma processing: Theoretical cross sections

In this paper, we report theoretical electron impact ionization cross sections from threshold to 2000 eV for isocarbonic open chain molecules C{sub 4}H{sub 6}, C{sub 4}H{sub 8}, C{sub 4}F{sub 6} including their isomers, and closed chain molecules c-C{sub 4}H{sub 8} and c-C{sub 4}F{sub 8}. Theoretical formalism employed presently, viz., Complex Scattering Potential-ionization contribution method has been used successfully for a variety of polyatomic molecules. The present ionization calculations are very important since results available for the studied targets are either scarce or none. Our work affords comparison of C{sub 4} containing hydrocarbon versus fluorocarbon molecules. Comparisons of the present ionization cross sections are made wherever possible, and new ionization data are also presented.

2-METHYLPROPENE↗

Imaging photoelectron circular dichroism of chiral molecules by femtosecond multiphoton coincidence detection

Here, we provide a detailed account of novel experiments employing electron-ion coincidence imaging to discriminate chiral molecules. The full three-dimensional angular scattering distribution of electrons is measured after photoexcitation with either left or right circular polarized light. The experiment is performed using a simplified photoelectron-photoion coincidence imaging setup employing only a single particle imaging detector. Results are reported applying this technique to enantiomers of the chiral molecule camphor after three-photon ionization by circularly polarized femtosecond laser pulses at 400 nm and 380 nm. The electron-ion coincidence imaging provides the photoelectron spectrum of mass-selected ions that are observed in the time-of-flight mass spectra. The coincident photoelectron spectra of the parent camphor ion and the various fragment ions are the same, so it can be concluded that fragmentation of camphor happens after ionization. We discuss the forward-backward asymmetry in the photoelectron angular distribution which is expressed in Legendre polynomials with moments up to order six. Furthermore, we present a method, similar to one-photon electron circular dichroism, to quantify the strength of the chiral electron asymmetry in a single parameter. The circular dichroism in the photoelectron angular distribution of camphor is measured to be 8% at 400 nm. The electron circular dichroism using femtosecond multiphoton excitation is of opposite sign and about 60% larger than the electron dichroism observed before in near-threshold one-photon ionization with synchrotron excitation. We interpret our multiphoton ionization as being resonant at the two-photon level with the 3s and 3p Rydberg states of camphor. Theoretical calculations are presented that model the photoelectron angular distribution from a prealigned camphor molecule using density functional theory and continuum multiple scattering X alpha photoelectron scattering calculations. Qualitative agreement is observed between the experimental results and the theoretical calculations of the Legendre moments representing the angular distribution for the two enantiomers. The electron-ion coincidence technique using multiphoton ionization opens new directions in table-top analytical mass-spectrometric applications of mixtures of chiral molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transient behavior of drift and ionization in atmospheric pressure nitrogen discharge

The fluid models are frequently used to describe a non-thermal plasma such as a streamer discharge. The required electron transport data and rate coefficients for the fluid model are parametrized using the local field approximation (LFA) in first order models and the local-mean-energy approximation (LMEA) in second order models. We performed Monte Carlo simulations in Nitrogen gas with step changes in the E/N (reduced electric field) to study the behavior of the transport properties in the transient phase. During the transient phase of the simulation, we extract the instantaneous electron mean energy, which is different from the steady state mean electron energy, and the corresponding transport parameters and rate coefficients. Our results indicate that the mean electron energy is not a suitable parameter for mobility/drift of electrons due to big difference in momentum relaxation and energy relaxation. Furthermore, the high energy threshold rates such as ionization show a strong correlation to mean electron energy. In second order models where the energy-balance equation is solved, we suggest that it would rather be appropriate to use the local electric field to find electron drift velocity in gases such as Nitrogen and the local mean electron energy to determine the ionization and excitation rates.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Electron-Stimulated Desorption of Cesium Atoms from Graphene-Covered Iridium

Electron-stimulated desorption (ESD) of cesium atoms from graphene on a metal (iridium) substrate has been directly observed for the first time using the time-of-flight technique with a surface-ionization detector. The appearance threshold of the yield of Cs atoms from the sample surface at 160 K was 20 eV. An additional ESD peak of Cs atoms was observed at an electron energy of 56 eV. The observed ESD of Cs atoms from graphene is related to the nonmetal nature of this carbon film on the metal substrate surface.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Photoionization from the Xe 4d orbitals of XeF 2

Here, we present a comparison of the photoionization dynamics of the 4d shell of XeF 2 from threshold to 250 eV to those of the prototypical 4d shell of atomic Xe. The new experimental data include spin–orbit and ligand-field-resolved partial cross sections, photoelectron angular distributions, branching fractions, and lifetime widths for the 4d-hole states. The spin–orbit branching fractions and angular distributions are remarkably similar to the corresponding distributions from atomic Xe across a broad energy interval that includes both the intense shape resonance in the f continuum and a Cooper minimum in the same channel. The angular distributions and branching fractions are also in reasonably good agreement with our first-principles theoretical calculations on XeF 2 . Data are also presented on the lifetime widths of the substate-resolved 4d-hole states of XeF 2 . While the trends in the widths are similar to those in the earlier experimental and theoretical work, the linewidths are considerably smaller than in the previous measurements, which may require some reinterpretation of the decay mechanism. Finally, we present new data and an analysis of the Auger electron spectra for ionization above the 4d thresholds and resonant Auger spectra for several pre-edge features.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗