Abstract: Electron scattering cross sections for pyridine in the energy range 0–100 eV, which we previously measured or calculated, have been critically compiled and complemented here with new measurements of electron energy loss spectra and double differential ionization cross sections. Experimental techniques employed in this study include a linear transmission apparatus and a reaction microscope system. To fulfill the transport model requirements, theoretical data have been recalculated within our independent atom model with screening corrected additivity rule and interference effects (IAM-SCAR) method for energies above 10 eV. In addition, results from the R-matrix and Schwinger multichannel with pseudopotential methods, for energies below 15 eV and 20 eV, respectively, are presented here. The reliability of this complete data set has been evaluated by comparing the simulated energy distribution of electrons transmitted through pyridine, with that observed in an electron-gas transmission experiment under magnetic confinement conditions. In addition, our representation of the angular distribution of the inelastically scattered electrons is discussed on the basis of the present double differential cross section experimental results.

Abstract: Escalating global water scarcity necessitates high-performance desalination membranes, for which fundamental understanding of structure–property–performance relationships is required. In this study, we comprehensively assess the ionization behavior of nanoporous polyamide selective layers in state-of-the-art nanofiltration (NF) membranes. In these films, residual carboxylic acids and amines influence permeability and selectivity by imparting hydrophilicity and ionizable moieties that can exclude coions. We utilize layered interfacial polymerization to prepare physically and chemically similar selective layers of controlled thickness. We then demonstrate location-dependent ionization of carboxyl groups in NF polyamide films. Specifically, only surface carboxyl groups ionize under neutral pH, whereas interior carboxyl ionization requires pH >9. Conversely, amine ionization behaves invariably across the film. First-principles simulations reveal that the low permittivity of nanoconfined water drives the anomalous carboxyl ionization behavior. Furthermore, we report that interior carboxyl ionization could improve the water–salt permselectivity of NF membranes over fourfold, suggesting that interior charge density could be an important tool to enhance the selectivity of polyamide membranes. Our findings highlight the influence of nanoconfinement on membrane transport properties and provide enhanced fundamental understanding of ionization that could enable novel membrane design.

Abstract: As dark matter searches push into the sub-GeV mass range, they look for electrons ionized by direct scattering with dark particles. However, dark matter scattering off nuclei can also produce electrons through the Migdal effect. In this paper the authors show that the Migdal effect can contribute significantly to signal rates and has to be included when interpreting experimental results.

Abstract: Orbital optimization is crucial when using a non-Aufbau Slater determinant that involves promotion of an electron from a (nominally) occupied molecular orbital to an unoccupied one, or else ionization from a molecular orbital that lies below the highest occupied frontier molecular orbital. However, orbital relaxation of a non-Aufbau determinant risks "variational collapse" back to the Aufbau solution of the self-consistent field (SCF) equations. Algorithms such as the maximum overlap method (MOM) that are designed to avoid this collapse are not guaranteed to work, and more robust alternatives increase the cost per SCF iteration. Here, we introduce an alternative procedure called state-targeted energy projection (STEP) that is based on level shifting and is identical in cost to a normal SCF procedure, yet converges in numerous cases where MOM suffers variational collapse. Benchmark calculations on small-molecule reference data suggest that ΔSCF calculations based on STEP are an accurate way to compute both ionization and excitation energies, including core-level ionization and excited states with significant double-excitation character. For the molecule 2,4,6-trifluoroborazine, ΔSCF calculations based on STEP afford excellent agreement with experiment for both vertical and adiabatic ionization energies, the latter requiring geometry optimization of a non-Aufbau valence hole. Semiquantitative agreement with experiment is obtained for the absorption spectrum of chlorophyll a. Finally, the importance of asymptotic exchange and correlation is illustrated by application to Rydberg states using spin-scaled Moller-Plesset perturbation theory with a non-Aufbau reference determinant. Together, these results suggest that STEP offers a reliable and affordable alternative to the MOM procedure for determining non-Aufbau solutions of the SCF equations.

Abstract: The chemical abundances of spiral galaxies, as probed by HII regions across their disks, are key to understanding the evolution of galaxies over a wide range of environments. We present LBT/MODS spectra of 52 HII regions in NGC3184 as part of the CHemical Abundances Of Spirals (CHAOS) project. We explore the direct-method gas-phase abundance trends for the first four CHAOS galaxies, using temperature measurements from one or more auroral line detections in 190 individual HII regions. We find the dispersion in Te-Te relationships is dependent on ionization, as characterized by F_5007/F_3727, and so recommend ionization-based temperature priorities for abundance calculations. We confirm our previous results that [NII] and [SIII] provide the most robust measures of electron temperature in low-ionization zones, while [OIII] provides reliable electron temperatures in high-ionization nebula. We measure relative and absolute abundances for O, N, S, Ar, and Ne. The four CHAOS galaxies marginally conform with a universal O/H gradient, as found by empirical IFU studies when plotted relative to effective radius. However, after adjusting for vertical offsets, we find a tight universal N/O gradient of alpha_N/O = -0.33 dex/Re with sigma_tot. = 0.08 for Rg/Re < 2.0, where N is dominated by secondary production. Despite this tight universal N/O gradient, the scatter in the N/O-O/H relationship is significant. Interestingly, the scatter is similar when N/O is plotted relative to O/H or S/H. The observable ionic states of S probe lower ionization and excitation energies than O, which might be more appropriate for characterizing abundances in metal-rich HII regions.

Abstract: We present a new public python package, darkhistory, for computing the effects of dark matter annihilation and decay on the temperature and ionization history of the early universe. darkhistory simultaneously solves for the evolution of the free electron fraction and gas temperature, and for the cooling of annihilation/decay products and the secondary particles produced in the process. Consequently, we can self-consistently include the effects of both astrophysical and exotic sources of heating and ionization, and automatically take into account backreaction, where modifications to the ionization/temperature history in turn modify the energy-loss processes for injected particles. We present a number of worked examples, demonstrating how to use the code in a range of different configurations, in particular for arbitrary dark matter masses and annihilation/decay final states. Possible applications of darkhistory include mapping out the effects of dark matter annihilation/decay on the global 21 cm signal and the epoch of reionization, as well as the effects of exotic energy injections other than dark matter annihilation/decay. The code is available at https://github.com/hongwanliu/DarkHistory with documentation at https://darkhistory.readthedocs.io. Data files required to run the code can be downloaded at https://doi.org/10.7910/DVN/DUOUWA.

Abstract: Surface assisted laser desorption ionization mass spectrometry (SALDI-MS) has been recognized as one of the prominent techniques in mass analysis of small molecules as well as large nonvolatile mol...

Abstract: We present and analyze characteristics of the runaway electron flow in a high-voltage (the voltage rise rate of up to 1.5 MV/ns) air-filled electrode gap with a strongly nonuniform electric field. It is demonstrated that such a flow contains a high-energy electron component of duration not more than 10 ps. According to numerical simulations, runaway electron generation/termination is governed by impact ionization of the gas near the cathode and switching on/off a critical (sufficient for electrons to run away) electric field at the boundary of the expanding cathode plasma. The corresponding characteristic time estimated to be 2–3 ps is defined by the ionization rate at a critical field.

Abstract: The formation and decay of the thermal spark generated by a single nanosecond high-voltage pulse between pin electrodes are characterized in this study. The influence of air pressure in the range 50-1000 mbar is investigated at 300 K. By performing short-gate imaging and Optical Emission Spectroscopy (OES), we find that the thermal sparks exhibit an intense emission from excited electronic states of N+, in contrast with non-thermal sparks for which the emission is dominated by electronic transitions of N2. Spark thermalization consists of the following steps: (i) partial ionization of the plasma channel accompanied by N2 emission, (ii) creation of a fully ionized filament at the cathode characterized by N+ emission, (iii) formation of a fully ionized filament at the anode, (iv) propagation of these filaments toward the middle of the interelectrode gap, and (v) merging of the filaments. The formation of the filaments, steps (ii) and (iii), occurs at sub-nanosecond timescales. The propagation speed of the filaments is on the order of 104 m/s during step (iv). For the 1-bar condition, the electron number densities are measured from the Stark broadening of N+ and Hα lines, with spatial and temporal resolution. The electron temperature is also determined, from the relative emission intensity of N+ excited states, attaining a peak value of 48,000 K. In the post-discharge, the electron number density decays from 4x1019 to 2x1018 cm-3 in 100 ns due to an isentropic expansion. During this decay phase, the plasma is found to be in chemical equilibrium. Comparisons are given with previous experiments from the literature. Expressions for the Van der Waals and resonant broadenings of H, Hβ, and several lines of O, O+, N and, N+ are derived in the appendix.

Abstract: Interaction of a strong laser pulse with matter transfers not only energy but also linear momentum of the photons. Recent experimental advances have made it possible to detect the small amount of linear momentum delivered to the photoelectrons in strong-field ionization of atoms. We present numerical simulations as well as an analytical description of the subcycle phase (or time) resolved momentum transfer to an atom accessible by an attoclock protocol. We show that the light-field-induced momentum transfer is remarkably sensitive to properties of the ultrashort laser pulse such as its carrier-envelope phase and ellipticity. Moreover, we show that the subcycle-resolved linear momentum transfer can provide novel insights into the interplay between nonadiabatic and nondipole effects in strong-field ionization. This work paves the way towards the investigation of the so-far unexplored time-resolved nondipole nonadiabatic tunneling dynamics.

Abstract: Quantum electrodynamics coupled-cluster (QED-CC) theory is used to model vacuum-field-induced changes to ground-state properties of a series of sodium halide compounds (NaX, X = F, Cl, Br, I) strongly coupled to an optical cavity. Ionization potentials (IPs) and electron affinities (EAs) are presented, and it is demonstrated that EAs are easily modulated by cavity interactions, while IPs for these compounds are far less sensitive to the presence of the cavity. EAs predicted by QED-CC can be reduced by as much 0.22 eV (or ~50%) when considering experimentally-accessible coupling parameters.

Abstract: We developed a new method for coarse-grained simulations of acid–base equilibria in a system coupled to a reservoir at a given pH and concentration of added salt, that we term the Grand-reaction me...

Abstract: The search for dark matter weakly interacting massive particles with noble liquids has probed masses down and below a GeV/c2. The ultimate limit is represented by the experimental threshold on the energy transfer to the nuclear recoil. Currently, the experimental sensitivity has reached a threshold equivalent to a few ionization electrons. In these conditions, the contribution of a Bremsstrahlung photon or a so-called Migdal electron due to the sudden acceleration of a nucleus after a collision might be sizable. In the present work, we use a Bayesian approach to study how these effects can be exploited in experiments based on liquid argon detectors. In particular, taking inspiration from the DarkSide-50 public spectra, we develop a simulated experiment to show how the Migdal electron and the Bremsstrahlung photon allow to push the experimental sensitivity down to masses of 0.1 GeV/c2, extending the search region for dark matter particles of previous results. For these masses we estimate the effect of the Earth shielding that, for strongly interacting dark matter, makes any detector blind. Finally, we show how the sensitivity scales for higher exposure.

Abstract: In standard lasers, light amplification requires population inversion between an upper and a lower state to break the reciprocity between absorption and stimulated emission. However, in a medium prepared in a specific superposition state, quantum interference may fully suppress absorption while leaving stimulated emission intact, opening the possibility of lasing without inversion. Here we show that lasing without inversion arises naturally during propagation of intense femtosecond laser pulses in air. It is triggered by the combination of molecular ionization and molecular alignment, both unavoidable in intense light fields. The effect could enable inversionless amplification of broadband radiation in many molecular gases, opening unusual opportunities for remote sensing.

Abstract: The enhanced probability of water dissociation at the aqueous electrode interfaces is predicted by path-integral ab initio molecular dynamics. The ionization process is observed at the aqueous platinum interface when nuclear quantum effects are introduced in the statistical sampling, while minor effects have been observed at the gold interface. We characterize the dissociation mechanism of the formed water ions. In spite of the fact that the concentration and lifetime of the ions might be challenging to experimentally detect, they may serve as a guide to future experiments. Our observation might have a significant impact on the understanding of electrochemical processes occurring at the metal electrode surface.

Abstract: The development of single charge resolving, macroscopic silicon detectors has opened a window into rare processes at the $\mathcal{O}(\mathrm{eV})$ scale. In order to reconstruct the energy of a given event, or model the charge signal obtained for a given amount of energy absorbed by the electrons in a detector, an accurate charge yield model is needed. In this paper we review existing measurements of charge yield in silicon, focusing in particular on the region below 1 keV. We highlight a calibration gap between 12--50 eV (referred to as the ``UV-gap'') and employ a phenomenological model of impact ionization to explore the likely charge yield in this energy regime. Finally, we explore the impact of variations in this model on a test case, that of dark matter scattering off electrons, to illustrate the scientific impact of uncertainties in charge yield.

Abstract: Electrospray ionization (ESI) operating in negative mode coupled to high resolution mass spectrometry is the most popular technique for the characterization of dissolved organic matter (DOM). The v...

Abstract: Large liquid argon time projection chambers (LArTPCs), especially those operating near the surface, are susceptible to space charge effects. In the context of LArTPCs, the space charge effect is the build-up of slow-moving positive ions in the detector primarily due to ionization from cosmic rays, leading to a distortion of the electric field within the detector. This effect leads to a displacement in the reconstructed position of signal ionization electrons in LArTPC detectors ("spatial distortions"), as well as to variations in the amount of electron-ion recombination experienced by ionization throughout the volume of the TPC. We present techniques that can be used to measure and correct for space charge effects in large LArTPCs by making use of cosmic muons, including the use of track pairs to unambiguously pin down spatial distortions in three dimensions. The performance of these calibration techniques are studied using both Monte Carlo simulation and MicroBooNE data, utilizing a UV laser system as a means to estimate the systematic bias associated with the calibration methodology.

Abstract: The solar wind (SW) and the extreme ultraviolet (EUV) radiation modulate fluxes of interstellar and heliospheric particles inside the heliosphere both in time and in space. Understanding this modulation is necessary to correctly interpret measurements of particles of interstellar origin inside the heliosphere. We present a revision of heliospheric ionization rates and provide the Sun-Heliosphere Observation-based Ionization Rates (SHOIR) model based on the currently available data. We calculate the total ionization rates using revised SW and solar EUV data. We study the in-ecliptic variation of the SW parameters, the latitudinal structure of the SW speed and density, and the reconstruction of the photoionization rates. The revision most affects the SW out of the ecliptic plane during solar maximum and the estimation of the photoionization rates, the latter due to a change of the reference data. The revised polar SW is slower and denser during the solar maximum of solar cycle (SC) 24. The current estimated total ionization rates are higher than the previous ones for H, O, and Ne, and lower for He. The changes for the in-ecliptic total ionization rates are less than 10% for H and He, up to 20% for O, and up to 35% for Ne. Additionally, the changes are not constant in time and vary as a function of time and latitude.

Abstract: Stripping heavy atoms in solid matter of most of their electrons requires the extreme conditions that exist in astrophysical plasmas, but are difficult to create in the laboratory1–3. Here we demonstrate solid-density gold plasmas with atoms stripped of up to 72 electrons (N-like Au72+) over large target depths. This record ionization is achieved by irradiating solid foils and near-solid-density nanowire arrays with highly relativistic (3 × 1021 W cm−2) second-harmonic femtosecond laser pulses of 8 µm) by energetic electrons generated near the nanowire tips. Larger laser spots could result in solid Au plasmas ionized up to He-like. Gold atoms were stripped of up to 72 electrons by irradiating gold foils and nanowire arrays with a relativistic 400 nm laser pulse. This work will open the door to the study of the atomic physics of highly charged atoms in very-high-density plasmas.

Abstract: Ionization of atoms by strong laser fields produces photoelectron momentum distributions that exhibit modulations due to the interference of outgoing electron trajectories. For a faithful modeling, it is essential to include previously overlooked phase shifts occurring when trajectories pass through focal points. Such phase shifts are known as Gouy's phase anomaly in optics or as Maslov phases in semiclassical theory. Because of Coulomb focusing in three dimensions, one out of two trajectories in photoelectron holography goes through a focal point as it crosses the symmetry axis in momentum space. In addition, there exist observable Maslov phases already in two dimensions. Clustering algorithms enable us to implement a semiclassical model with the correct preexponential factor that affects both the weight and the phase of each trajectory. We also derive a simple rule to relate two-dimensional and three-dimensional models for linear polarization. It explains the shifted interference fringes and weaker high-energy yield in three dimensions. The results are in excellent agreement with solutions of the time-dependent Schr\"odinger equation.

Abstract: More than 100 years after its discovery and its explanation in the energy domain, the duration of the photoelectric effect is still heavily studied. The emission time of a photoelectron can be quantified by the Wigner time delay. Experiments addressing this time delay for single-photon ionization became feasible during the last 10 years. A missing piece, which has not been studied, so far, is the Wigner time delay for strong-field ionization of molecules. Here we show experimental data on the Wigner time delay for tunnel ionization of $H_{2}$ molecules and demonstrate its dependence on the emission direction of the electron with respect to the molecular axis. We find, that the observed changes in the Wigner time delay can be quantitatively explained by elongated/shortened travel paths of the electrons that are due to spatial shifts of the electron's birth position after tunneling. This introduces an intuitive perspective towards the Wigner time delay in strong-field ionization.