Photodetached Electrons Research Articles

Charge transfer reaction at gas-liquid interface of aqueous tetrabutylammonium iodide solution: influence of ions on dynamical response of solvent

Abstract Tetrabutylammonium iodide (TBAI) is known to create an electric double layer at the air-water interface. In the present study, we investigated the charge-transfer-to-solvent reaction from iodide ions to liquid water near the gas-liquid interface of an aqueous TBAI solution using extreme UV (EUV) time-resolved photoelectron spectroscopy. Use of EUV radiation ensured accurate measurements of electron kinetic energy distributions by minimizing spectral distortions caused by electron inelastic scattering in the liquid and the influence of the electron transmission efficiency through the gas-liquid interface. The spectra observed for photodetached electrons exhibited a rapid energy shift and a variation of the bandwidth in subpicoseconds, and the rates of these changes clearly depended on the TBAI concentration. The results indicate that the dynamical response of solvent water changes in the presence of a high density of ions.

Molecular Anions Perspective.

This Perspective attempts to shed light on developments in the theoretical and experimental study of molecular anions highlighting more recent workers in the field. The species I discuss include (i) valence-bound (singly and multiply charged) anions including atmospheric, catalytic, superhalogen, interfacial, and more; (ii) dipole- and correlation-bound anions including their role as doorways to other states and their appearance "in space", and (iii) metastable anions focusing on tools needed for their theoretical treatment. I also briefly discuss angular distributions of photodetached electrons and their growing utilization in experiments and theory. A recurring theme is the dependence of electron binding energies (EBEs) on the surrounding environment. Some anions that are nonexistent as isolated species evolve to be stable but with small EBEs when weakly solvated (e.g., as in a cluster or at an air-solvent interface). Others existing in isolation only as metastable species become stable when the underlying molecular framework contains one or more positively charged group (e.g., protonated side chains in a peptide) that generates a stabilizing Coulomb potential. On the other hand, a destabilizing Coulomb potential between/among negative sites in a multiply charged anion decreases the EBEs of each such site and generates a repulsive Coulomb barrier that can affect stability.

Laser-induced photodetachment of negative oxygen ions in the spatial afterglow of an atmospheric pressure plasma jet

Negative ions are an important constituent of the spatial afterglow of atmospheric pressure plasmas, where the fundamental plasma-substrate interactions take place that are vital for applications such as biomedicine, material synthesis, and ambient air treatment. In this work, we use laser-induced photodetachment to liberate electrons from negative ions in the afterglow region of an atmospheric pressure plasma jet interacting with an argon-oxygen mixture, and microwave cavity resonance spectroscopy to detect the photodetached electrons. This diagnostic technique allows for the determination of the electron density and the effective collision frequency before, during and after the laser pulse was shot through the measurement volume with nanosecond time resolution. From a laser saturation study, it is concluded that O− is the dominant negative ion in the afterglow. Moreover, the decay of the photodetached electron density is found to be dominantly driven by the (re)formation of O− by dissociative attachment of electrons with O2. As a consequence, we identified the species and process responsible for the formation of negative ions in the spatial afterglow in our experiment.

Manipulating the photodetachment dynamics of the H2− ion by a Gaussian laser field

The photodetachment of the ion in a time-dependent electric field is investigated for the first time. On the basis of time-dependent closed orbit theory, we calculate the photodetachment cross section (PCS) of a ion manipulated by a Gaussian laser field. We use the superposition principle and consider the interaction between two atomic centers in the ion to construct the electron wave function after photodetachment from the ion. Three different types of closed orbits for the photodetached electron in the Gaussian laser field are found. The PCS of the ion can be controlled by varying the Gaussian laser field strength, pulse duration, and final time where the electron moves in the laser field through numerical calculation. The oscillating cross section of the ion is approximately twice that of the H− ion by comparing their PCS in the same Gaussian laser field, thereby suggesting that the interference effect of the two centers in the ion is extremely significant. This study provides a semiclassical method for exploring the photodetachment dynamics of the negative molecular ion in the Gaussian laser field. Furthermore, it serves as guide for future molecular photodetachment microscopy experiments in the time-dependent electric field.

Mass-resolved electronic circular dichroism ion spectroscopy.

DNA and proteins are chiral: Their three-dimensional structures cannot be superimposed with their mirror images. Circular dichroism spectroscopy is widely used to characterize chiral compounds, but data interpretation is difficult in the case of mixtures. We recorded the electronic circular dichroism spectra of DNA helices separated in a mass spectrometer. We studied guanine-rich strands having various secondary structures, electrosprayed them as negative ions, irradiated them with an ultraviolet nanosecond optical parametric oscillator laser, and measured the difference in electron photodetachment efficiency between left and right circularly polarized light. The reconstructed circular dichroism ion spectra resembled those of their solution-phase counterparts, thereby allowing us to assign the DNA helical topology. The ability to measure circular dichroism directly on biomolecular ions expands the capabilities of mass spectrometry for structural analysis.

DNA circular dichroism in gas phase

Spectroscopy Circular dichroism spectroscopy is widely used to distinguish between nonidentical mirror-image molecules. The technique relies on differential absorption of left versus right circularly polarized light and therefore tends to require solution-phase samples for adequate sensitivity. Daly et al. now report gas-phase circular dichroism spectra of DNA oligonucleotides based on detection of photodetached electrons rather than transmitted light (see the Perspective by Barran). The salient spectral features matched those in solution. Pairing the technique with mass spectrometry enables prior mass selection of particular molecules for analysis. Science , this issue p. [1465][1]; see also p. [1426][2] [1]: /lookup/doi/10.1126/science.abb1822 [2]: /lookup/doi/10.1126/science.abc1294

Single-center approach for photodetachment and radiative electron attachment: Comparison with other theoretical approaches and with experimental photodetachment data

A single-center method for calculating photodetachment cross section for anions and radiative electron attachment cross section for neutral molecules by microreversibility is presented. It uses the integral equation method to calculate the ejected electron's continuum wave function while the single-electron bound function of the anion is described by the Dyson orbital. It is compared with related theoretical approaches and benchmarked to the experimental photodetachment cross sections of ${{\mathrm{O}}_{2}}^{\ensuremath{-}}$, ${\mathrm{OH}}^{\ensuremath{-}}$, and ${\mathrm{CN}}^{\ensuremath{-}}$. The use of the plane-wave approximation of the ejected electron wave function combined with the Hartree-Fock frozen-core approximation of the Dyson orbital is also considered and its results are compared with those of our methods and with experiment. A good agreement between the calculated photodetachment cross sections and the experimental data is obtained for ${{\mathrm{O}}_{2}}^{\ensuremath{-}}$ and ${\mathrm{CN}}^{\ensuremath{-}}$ when using the three methods. For ${\mathrm{OH}}^{\ensuremath{-}}$, the calculated scattering-wave electron photodetachment cross sections agree well with two most recent sets of experimental data among the three available while the plane-wave results disagree with all the experimental and theoretical data. The different approaches to calculate the Dyson orbital are also discussed as well as the convergence of the calculations with respect to the choice of the one-electron basis set. The approximation of Dyson orbitals by Kohn-Sham orbitals appears to overestimate the photodetachment cross section.

Extreme Correlation and Repulsive Interactions in Highly Excited Atomic Alkali Anions.

At high energies, single-photon photodetachment of alkali negative ions populates final states where both the ejected electron and the residual valence electron possess high angular momenta. The photodetached electron interacts strongly with the anisotropic core, and thus the partial cross sections for these channels display non-Wigner threshold behavior reflecting these large, and occasionally repulsive, interactions. Our fully quantum-mechanical theoretical study enables a deeper interpretation of these partial cross sections. Comparisons of the behavior in different channels and between different atomic species-sodium, potassium, and cesium-show the critical role of near degeneracies in the energy spectrum and demonstrate that much of the behavior of the partial photodetachment cross sections stems from the permanent, rather than induced, electric dipole moments of these nearly degenerate channels. This provides a concrete example of a system where negative dispersion forces play a decisive role.

The influence of the Ar/O2 ratio on the electron density and electron temperature in microwave discharges

The aim of this work is to study the properties of Ar–O2 microwave driven surfatron plasmas as a function of the Ar/O2 ratio in the gas mixture. The key parameters are the plasma electron density and electron temperature, which are estimated with Thomson scattering (TS) for O2 contents up to 50% of the total gas flow. A sharp drop in the electron density from to approximately is estimated as the O2 content in the gas mixture is increased up to 15%. For percentages of O2 lower than 10%, the electron temperature is estimated to be about 2–3 times higher than in the case of a pure argon discharge in the same conditions ( eV) and gradually decreases as the O2 percentage is raised to 50%. However, for O2 percentages above 30%, the scattering spectra become Raman dominated, resulting in large uncertainties in the estimated electron densities and temperatures. The influence of photo-detached electrons from negative ions caused by the typical TS laser fluences is also likely to contribute to the uncertainty in the measured electron densities for high O2 percentages. Moreover, the detection limit of the system is reached for percentages of O2 higher than 25%. Additionally, both the electron density and temperature of microwave discharges with large Ar/O2 ratios are more sensitive to gas pressure variations.

Time-dependent electric field effect on the photodetachment dynamics of negative ions

This paper addresses the photodetachment dynamics of a negative ion in a time-dependent electric field based on the semiclassical open-orbit theory. The photodetached electron probability density in a real time domain is studied in a gradient electric field for the first time. It is found that because of the influence of the gradient electric field, two or more electron trajectories can arrive at a given point on the detector, and the interference effect between these electron trajectories causes oscillatory structures in the electron probability density. Our calculation results suggest that when the external electric field changes very slowly with time, only two electron trajectories can arrive at a given point on the detector and the electron probability density exhibits a regular two-term oscillatory pattern. However, when the electric field changes quickly with time, four electron trajectories can reach the detector, which makes the oscillatory structures in the electron probability density become much more complicated. In addition, the electric field strength, photon energy, and the position of the detector can affect the electron probability density of this system sensitively. Our study provides a clear and intuitive picture for the photodetachment dynamics of the negative ion in the external electric field from a time-dependent viewpoint and may guide the future experimental researches on the photodetachment microscopy of negative ions in the time-dependent electric field.

Accurate electron affinity of Pb and isotope shifts of binding energies of Pb(.).

Lead (Pb) was the last element of the group IVA whose electron affinity had a low accuracy around 10 meV before the present work. This was due to the generic threshold photodetachment measurement that cannot extent well below 0.5 eV due to the light source limitation. In the present work, the electron affinity of Pb was determined to be 2877.33(13) cm(-1) or 0.356 743(16) eV for the isotope m = 208. The accuracy was improved by a factor of 500 with respect to the previous laser photodetachment electron spectroscopy. Moreover, remarkable isotope shifts of the binding energy of Pb(-) 6p(3) (4)S3/2 - Pb 6p(2) (3)P2 were observed for m = 206, 207, and 208.

Photodetachment Spectrum of Hydrogen Negative Ion Near a Partially Reflecting Spherical Surface

Photodetachment of negative ions near surfaces is of great interest in view of its fundamental significance and technological applications. We reinvestigate the dynamics of photoelectrons in H− photodetachment near a partially reflecting spherical surface by the semiclassical closed-orbit theory. Reflection parameter R and curvature K is used to observe inelastic and spherical effects of the surface, respectively. The classical action is evaluated from the photodetached electron trajectories incident normally at the surface, arising simultaneously from the source and its image. The derived analytical formula of photodetachment cross section correctly recovers the results of reflective spherical surface published recently based on theoretical imaging method.

Measurement of electronegativity at different laser wavelengths: accuracy of Langmuir probe assisted laser photo-detachment

Langmuir probe (LP) assisted pulsed laser photo-detachment (LPD) of negative ions is one of the frequently used diagnostic techniques in electronegative plasmas. The technique is based on measuring the rise in electron saturation current following photo-detachment. During the photo-detachment process it is assumed that the background electron parameters (temperature and density) remain unchanged in the laser channel and the photo-detached electrons thermalize instantaneously with the background electrons (same temperature). Therefore, the measured electronegativity should be independent of laser wavelengths. However, our recent simulation results (2015 Phys. Plasmas 22 073509) demonstrates a failure of these assumptions and suggests that the measured rise in electron saturation current has a dependence on the laser wavelength. This letter presents experimental evidence in support of these simulation results. In this work, photo-detachment is performed at two different laser wavelengths in an oxygen inductively coupled plasma discharge. Electronegativity measured by LP assisted LPD is compared with those obtained by the hairpin probe (HPP) assisted LPD which is based on quasi-neutrality assumption. The experimental results reveal that the electronegativities measured by LP assisted LPD are affected by the laser wavelength, whereas, electronegativities measured by HPP assisted LPD are almost independent. The discrepancy between the measurements is higher at high electronegativities. In conclusion, the experimental results validate the weakness of assumptions to estimate electronegativity from LPD combined with LP and therefore emphasizes the need of a more realistic model to analyze raw data or an alternate solution is to utilize HPP.

Numerical experiment to estimate the validity of negative ion diagnostic using photo-detachment combined with Langmuir probing

This paper presents a critical assessment of the theory of photo-detachment diagnostic method used to probe the negative ion density and electronegativity α = n-/ne. In this method, a laser pulse is used to photo-detach all negative ions located within the electropositive channel (laser spot region). The negative ion density is estimated based on the assumption that the increase of the current collected by an electrostatic probe biased positively to the plasma is a result of only the creation of photo-detached electrons. In parallel, the background electron density and temperature are considered as constants during this diagnostics. While the numerical experiments performed here show that the background electron density and temperature increase due to the formation of an electrostatic potential barrier around the electropositive channel. The time scale of potential barrier rise is about 2 ns, which is comparable to the time required to completely photo-detach the negative ions in the electropositive channel (∼3 ns). We find that neglecting the effect of the potential barrier on the background plasma leads to an erroneous determination of the negative ion density. Moreover, the background electron velocity distribution function within the electropositive channel is not Maxwellian. This is due to the acceleration of these electrons through the electrostatic potential barrier. In this work, the validity of the photo-detachment diagnostic assumptions is questioned and our results illustrate the weakness of these assumptions.

Photo-Detached Electron Flux Distribution in a Gradient Electric Field* *Supported by the National Natural Science Foundation of China under Grant Nos. 11374133 and 11074104, and a Project of Shandong Province Higher Educational Science and Technology Program of China under Grant No. J13LJ04

This paper investigates the flux distributions of the electron photo-detached from H− ion localized in a gradient electric field. In contrast with the photodetachment in the uniform electric field [Phys. Rev. A 40 (1989) 4983], where only two electron trajectories interfere at each given point on a detector, for the photodetachment in a gradient electric field, the electrons waves can travel along multiple paths from the negative ion to a given point on the detector plane, which makes the electron flux distributions on the detector plane become much complex. Using the semi-classical theory, we put forward a formula for calculating the electron flux. Our calculation results suggest that the electron flux distributions on a given detector plane is not only related to the propagation time of the detached electron, but also related to the detached electron's energy. With the increase of the detached electron's energy, the oscillating region in the electron flux distributions becomes enlarged and the oscillating structure in the flux distributions becomes much more complicated. This study will guide future experiment research on the photodetachment microscopy of the negative ions in the presence of non-uniform external fields.

Escape of photo-detached electron from an annular nanomicrocavity

The escaped probability density of the photo-detached electron in an annular nanomicrocavity shows strong oscillations as a function of the length of the escape orbits. We present a semiclassical theory that describes theses oscillations in terms of bundles of escape orbits. Due to the interference effects of the electron waves travelling along different escaped orbits, oscillatory structures appear in the escaped probability density. In addition, the calculation results suggest that the escaped probability density of the photo-detached electron is not only related to the inner radius of the annular microcavity, but also related to the laser polarization. In order to show the correspondence between the escaped probability density and the detached electron’s escaped orbits clearly, we calculate the Fourier transformed semiclassical wave function and find that the peak positions agree well with the length of the detached electron’s orbits. We hope that our results will be useful in understanding the escape and propagation process of particles through semiconductor microjunctions or ballistic microstructure.

Interferences in photo-detached electron spectra from a non-collinear tri-atomic anion

The electron flux oscillations in photo-detachment of a non-collinear tri-atomic anion have been studied by taking each atom of the system as a coherent source of detached-electron wave. These electron waves traversing along three different trajectories result in a quantum interference. An analytical expression of detached-electron flux is evaluated for various detached-electron energies and for different geometrical shapes of the system. The results show that the electron flux distributions exhibit molecular shape-induced oscillatory structures. These oscillations are explained using the semi-classical closed-orbit theory; the outgoing electron waves produced from one center are propagated in the vicinity of the sources at other centers. It is also observed that in a particular case our non-collinear tri-atomic system reduces to the collinear tri-atomic system recently published.

Chemical Reactions Triggered Using Electrons Photodetached from "Clean" Distributions of Anions Deposited in Cryogenic Matrices via Counterion Codeposition.

Application of matrix isolation spectroscopy to ionic species is typically complicated by the presence of neutral contaminants during matrix deposition. Herein we demonstrate that simultaneous deposition of balanced currents of counterions with mass-selected ions of interest generates "clean" distributions of matrix-isolated metal carbonyl anions, where the only bands appearing in the CO-stretching region of the vibrational spectrum arise from ions. (Neutrals are initially absent.) Photodetachment by mild irradiation with visible light leads to complete conversion of the anions into their corresponding neutral species. The photodetached electrons, in turn, initiate covalent chemistry, inducing C-C bond formation following electron-capture by CO van der Waals dimers to produce trans-OCCO(-). The initial clean distribution of ions enables clear connections to be drawn between the spectral changes occurring at each experimental step, thus demonstrating the potential of the counterion codeposition technique to facilitate detailed studies of chemistry involving ions and electron transfer in cryogenic matrices.

Charge balance for the mesosphere with meteoric dust particles

An aerosol particle charging model initially developed for noctilucent cloud ice particles has been extended in several steps in order to better explain the data for charged meteoric smoke particles (MSPs) obtained by the nighttime and daytime CHAMPS rockets launched from Andøya, Norway, in October 2011. Addition of photodetachment to the model shows that this process reduces the number density of positively charged MSPs as well as the number density of negatively charged MSPs as a consequence of the photodetached electrons neutralizing the positively charged MSPs. In addition, the model shows that the ionization rate can be deduced from the electron number density and the electron–ion recombination rate only at the highest altitudes (those with ionization rates above 20cm−3s−1) as a consequence of recombination on the MSPs being dominant at lower altitudes. The differences between the daytime and the nighttime rocket data suggest a photodetachment rate between 0.1 and 0.01s−1. A further extension of the model to include the formation of negative ions and their destruction helps explain the ledge seen in the number density of the lightest negatively charged particles. The MSP number densities that are the inputs to the charging model are taken from the CARMA/CHEM2D model. The CHAMPS data are more consistent with number densities generated with an assumed input flux from ablation of 4td−1 than with 44td−1 assumed previously.

Numerical simulations used for a validity check on the laser induced photo-detachment diagnostic method in electronegative plasmas

Laser photo-detachment is used as a method to measure or determine the negative ion density and temperature in electronegative plasmas. In essence, the method consists of producing an electropositive channel (negative ion free region) via pulsed laser photo-detachment within an electronegative plasma bulk. Electrostatic probes placed in this channel measure the change in the electron density. A second pulse might be used to track the negative ion recovery. From this, the negative ion density and temperature can be determined. We study the formation and relaxation of the electropositive channel via a two-dimensional Particle-In-Cell/Mote Carlo collision model. The simulation is mainly carried out in a Hydrogen plasma with an electronegativity of α = 1, with a parametric study for α up to 20. The temporal and spatial evolution of the plasma potential and the electron densities shows the formation of a double layer (DL) confining the photo-detached electrons within the electropositive channel. This DL evolves into two fronts that move in the opposite directions inside and outside of the laser spot region. As a consequence, within the laser spot region, the background and photo-detached electron energy distribution function relaxes/thermalizes via collisionless effects such as Fermi acceleration and Landau damping. Moreover, the simulations show that collisional effects and the DL electric field strength might play a non-negligible role in the negative ion recovery within the laser spot region, leading to a two-temperature negative ion distribution. The latter result might have important effects in the determination of the negative ion density and temperature from laser photo detachment diagnostic.