Penning Ionization Research Articles

Developing a penning ionization gauge ion source with a filament for a compact ion microbeam system

We present the development of a penning ionization gauge ion source with a filament (F-PIG) for producing submicron ion beams in a compact ion microbeam system. The conventional penning ionization gauge ion source (PIG) represents a viable choice for microbeam system due to its compact size and low power consumption. However, directly utilizing a PIG for generating submicron ion beam poses challenges, primarily from significant energy spread, causing substantial aberrations. Considering this, this study proposes a solving the generation of low-voltage discharge plasma, achieved using low-energy electrons from a filament by focusing on the development of F-PIG for this purpose. Experimental results demonstrate that the F-PIG exhibits considerable promise an ion source to forming submicron beam within a compact ion microbeams system. These findings indicate that F-PIG can effectively reduce the width of the beam energy spread, making it a valuable asset for microbeam applications.

Pressure-Driven Switching of Photoelectron Impact Ionization-Chemical Ionization/Penning Ionization in Vacuum Ultraviolet Photoionization Mass Spectrometry.

Vacuum ultraviolet photoionization (VUV-PI) is a soft ionization technique that operates under pressures ranging from vacuum to ambient pressure. VUV-PI has played an essential role in direct sampling mass spectrometry. In this study, new ionization processes initiated by photoelectrons have been studied through the inclusion of a radio frequency (RF) electric field at different pressures. After deducting the contribution of single photoionization (SPI), the signal intensity of 1 ppmv toluene (C7H8+) in Ar was approximately 5-fold higher than that in N2. Mixed gases with different ionization energies (IEs) and excitation energies (EEs) were further investigated to reveal that metastable species were involved in the enhancement process. Reactant ions were produced by photoelectron impact ionization (PEI), which further triggered ion-molecule reactions, i.e., chemical ionization (CI). Metastable species were produced by photoelectron impact excitation (PEE), which further triggered Penning ionization (PenI). Analytes with IEs above 10.6 eV, such as CO2 (IE = 13.78 eV) and CHCl3 (IE = 11.37 eV), could be sensitively ionized by PenI with a sensitivity comparable to SPI. Except for the contribution of SPI, the dominant ionization process was switched from PEI-CI to PenI when the pressure was elevated from 50 to 500 Pa, as the electron energy gradually decreased and was only able to produce metastable states based on the kinetic energy balance equation of electrons. The conversion processes and conditions from PEI-CI to PenI will provide novel insights to develop new selective and sensitive VUV-PI sources and understand the ionization mechanism in other discharge ionization sources.

Mixed Cluster Ions of Magnesium and C60.

Magnesium clusters exhibit a pronounced nonmetal-to-metal transition, and the neutral dimer is exceptionally weakly bound. In the present study, we formed pristine Mgnz+ (n = 1-100, z = 1-3) clusters and mixed (C60)mMgnz+ clusters (m = 1-7, z = 1, 2) upon electron irradiation of neutral helium nanodroplets doped with magnesium or a combination of C60 and magnesium. The mass spectra obtained for pristine magnesium cluster ions exhibit anomalies, consistent with previous reports in the literature. The anomalies observed for C60Mgn+ strongly suggest that Mg atoms tend to wet the surface of the single fullerene positioning itself above the center of a pentagonal or hexagonal face, while, for (C60)mMgnz+, the preference for Mg to position itself within the dimples formed by fullerene cages becomes apparent. Besides doubly charged cluster ions, with the smallest member Mg22+, we also observed the formation of triply charged ions Mgn3+ with n > 24. The ion efficiency curves of singly and multiply charged ions exhibit pronounced differences compared to singly charged ions at higher electron energies. These findings indicate that sequential Penning ionization is essential in the formation of doubly and triply charged ions inside doped helium nanodroplets.

Trumpet-shaped diffuse plasma jet in a semi-confined environment

Abstract This paper reports a unique trumpet-shaped diffuse plasma jet (TDPJ) with a caliber exceeding 30 mm in a semi-confined environment, which is larger than the diameter of existing atmospheric pressure plasma jets (APPJs) in an open environment. The morphology of the TDPJ is attributed to the influence of the electric field on the development characteristics of ionization waves in the ambient environment. High-speed ICCD camera images show that the plasma bullets in the TDPJ have a completely different propagation trajectory compared to the APPJ. Different shapes of diffuse plasma jets can also be formed by adjusting the doping gas, which is due to the Penning ionization and consistent with the impact of the electric field. This research reveals the long-neglected effect of the electric field on ionization waves and provides a way to manipulate the morphology of plasma jets efficiently. The generation mechanism of the TDPJ can provide preliminary guidance for the effective medical treatment of plasma jets in semi-confined environments, such as human internal organs.

A time-dependent quantum approach to dissociative recombination, associative ionization, and Penning ionization.

A time-dependent wave packet method is introduced for calculating the integral and differential cross sections for the dissociative recombination (DR), associative ionization (AI), and Penning ionization (PI) processes. This method is demonstrated for DR/AI of the N + O ↔ NO+ + e- system and PI for the He* + Ar → He + Ar+ + e- system. Good agreement with previous theoretical and experimental results is obtained for these DR, AI, and PI processes. This method has the potential to provide a quantitative characterization of polyatomic ionization-involved processes on multidimensional potential energy surfaces.

Tomography of Feshbach resonance states

Feshbach resonances are fundamental to interparticle interactions and become particularly important in cold collisions with atoms, ions, and molecules. In this work, we present the detection of Feshbach resonances in a benchmark system for strongly interacting and highly anisotropic collisions: molecular hydrogen ions colliding with noble gas atoms. The collisions are launched by cold Penning ionization, which exclusively populates Feshbach resonances that span both short- and long-range parts of the interaction potential. We resolved all final molecular channels in a tomographic manner using ion-electron coincidence detection. We demonstrate the nonstatistical nature of the final-state distribution. By performing quantum scattering calculations on ab initio potential energy surfaces, we show that the isolation of the Feshbach resonance pathways reveals their distinctive fingerprints in the collision outcome.

Controlling Energy Transfer in Plasma-Driven Ammonia Synthesis by Adding Helium Gas

Plasma-driven ammonia (NH3) synthesis is regarded as a green complementary to the conventional Haber–Bosch process, especially for decentralized and on-demand production. However, a major challenge remains in reducing its energy cost because a huge amount of energy is consumed but not specifically for exciting, ionizing, and dissociating the feedstock. Therefore, controlling the energy transfer to predominantly generate more reactive species instead of gas heating is crucial to enhancing energy yields in the plasma synthesis of ammonia. Helium (He) is commonly used in atmospheric-pressure gas discharges to assist the generation of stable nonthermal plasmas with reduced breakdown voltages and gas temperatures while enhancing thermal conductivity and diffusion rate. In this work, a simple process based on adding He, which can be recycled and returned to the reactor along with unreacted N2 and H2, has been developed for enhancing NH3 synthesis. Optical emission spectra (OES) show an increased electron density with a significantly enhanced N2+ emission centered at 391.5 nm. With the addition of He, the energy transfer in the plasma is modified, with electron impact leading to the formation of metastable He and He2+ species, which collide with N2 molecules to generate N2+ through Penning ionization and charge transfer, contributing to more efficient N2 activation and NH3 production.

The effect of Penning ionization reactions on the evolution of He with O2 admixtures plasma jets

In this study, the effect of the O2 and N2 Penning ionization reactions on the evolution a capillary helium atmospheric pressure plasma jet (APPJ) with and without the presence of oxygen admixtures is investigated numerically using a two dimensional axi-symmetric model. In order to better understand potential applications of plasma surface interaction, the He and He + O2 (1000 ppm) APPJ is launched into a dielectric target. Moreover, the numerical model is compared with experimental measurements showing that the model captures the right physics and can elucidate the discharge dynamics. The comparison is realized for axial and radial measurements in order to have a complete picture of the plasma jet evolution. In this paper, the velocity and the shape of the plasma guided streamer were chosen as indicators of plasma jet evolution. In particular, the investigation is accomplished experimentally by tracking the spatio-temporal resolved emission of 706.5 nm (3s3S → 2p3P) line and numerically by calculating the reaction rate for the same transition. The O2 and N2 Penning reactions are then independently considered in the numerical model in order to isolate their contribution to the plasma evolution. It is shown that for the pure helium plasma, the N2 Penning reactions are more important to the plasma evolution. However, when oxygen admixtures are added to the plasma gas, the O2 Penning reactions become more important than the N2 ones.

Vibrational kinetics in repetitively pulsed atmospheric pressure nitrogen discharges: average-power-dependent switching behaviour

Characterisation of the vibrational kinetics in nitrogen-based plasmas at atmospheric pressure is crucial for understanding the wider plasma chemistry, which is important for a variety of biomedical, agricultural and chemical processing applications. In this study, a 0-dimensional plasma chemical-kinetics model has been used to investigate vibrational kinetics in repetitively pulsed, atmospheric pressure plasmas operating in pure nitrogen, under application-relevant conditions (average plasma powers of 0.23–4.50 W, frequencies of 1–10 kHz, and peak pulse powers of 23–450 W). Simulations predict that vibrationally excited state production is dominated by electron-impact processes at lower average plasma powers. When the average plasma power increases beyond a certain limit, due to increased pulse frequency or peak pulse power, there is a switch in behaviour, and production of vibrationally excited states becomes dominated by vibrational energy transfer processes (vibration–vibration (V–V) and vibration–translation (V–T) reactions). At this point, the population of vibrational levels up to increases significantly, as a result of V–V reactions causing vibrational up-pumping. At average plasma powers close to where the switching behaviour occurs, there is potential to control the energy efficiency of vibrational state production, as small increases in energy deposition result in large increases in vibrational state densities. Subsequent pathways analysis reveals that energy in the vibrational states can also influence the wider reaction chemistry through vibrational–electronic (V–E) linking reactions (N + N N + N and N + N N + N), which result in increased Penning ionisation and an increased average electron density. Overall, this study investigates the potential for delineating the processes by which electronically and vibrationally excited species are produced in nitrogen plasmas. Therefore, potential routes by which nitrogen-containing plasma sources could be tailored, both in terms of chemical composition and energy efficiency, are highlighted.

Reaction chain used to describe the process and mechanism of helium breakdown under high pressure

In this study, we establish a two-dimensional axisymmetric fluid model and verify its efficacy via experiments. We analyze the reaction rates to introduce a concept that we have termed “reaction chain” to describe the process and mechanism of helium discharge at high pressure. We observe that the entire process of discharge can be perfectly described by the reaction chains, which indicates that the breakdown process of helium involves a series of chain reactions, just like the nuclear fission. The results revealed that ground-state ionization reaction predominates the early discharge stage, whereas with the quick accumulation of He2*, penning ionization reaction will eventually play a dominant role. Our study confirms that metastable atoms play an important role in helium discharge. We demonstrated that He* is converted into He2* as an intermediate and that the number density of He2* eventually influences the breakdown of helium.

Surface effects in a capacitive argon discharge in the intermediate pressure regime

One-dimensional particle-in-cell/Monte Carlo collisional simulations are performed on a capacitive 2.54 cm gap, 1.6 Torr argon discharge driven by a sinusoidal rf current density amplitude of 50 A m−2 at 13.56 MHz. The excited argon states (metastable levels, resonance levels, and the 4p manifold) are modeled self-consistently with the particle dynamics as space- and time-varying fluids. Four cases are examined, including and neglecting excited states, and using either a fixed or energy-dependent secondary electron emission yield due to ion and/or neutral impact on the electrodes. The results for all cases show that most of the ionization occurs near the plasma-sheath interfaces, with little ionization within the plasma bulk region. Without excited states, secondary electrons emitted from the electrodes are found to play a strong role in the ionization process. When the excited states, and secondary electron emission due to neutral and ion impact on the electrodes are included in the discharge model, the discharge operation transitions from α-mode to γ-mode, in which nearly all the ionization is due to secondary electrons. Secondary electron production due to the bombardment of excited argon atoms was approximately14.7 times greater than that due to ion bombardment. Electron impact of ground state argon atoms by secondary electrons contributes about 76% of the total ionization; primary electrons, about 11%; metastable Penning ionization, about 13%; and multi-step ionization, about 0.3%.

Study of He*/Ne*+Ar, Kr, N2, H2, D2 Chemi-Ionization Reactions by Electron Velocity-Map Imaging.

The chemi-ionization of Ar, Kr, N2, H2, and D2 by Ne(3P2) and of Ar, Kr, and N2 by He(3S1) was studied by electron velocity map imaging (e-VMI) in a crossed molecular beam experiment. A curved magnetic hexapole was used to state-select the metastable species. Collision energies of 60 meV were obtained by individually controlling the beam velocities of both reactants. The chemi-ionization of atoms and molecules can proceed along different channels, among them Penning ionization and associative ionization. The evolution of the reaction is influenced by the internal redistribution of energy, which happens at the first reaction step that involves the emission of an electron. We designed and built an e-VMI spectrometer in order to investigate the electron kinetic energy distribution, which is related to the internal state distribution of the ionic reaction products. The analysis of the electron kinetic energy distributions allows an estimation of the ratio between the two-reaction channel Penning and associative ionization. In the molecular cases the vibrational or electronic excitation enhanced the conversion of internal energy into the translational energy of the forming ions, thus influencing the reaction outcome.

Unveiling the formation and control of unique swirling discharge pattern in helium plasma candle device

The generation of a large cold plasma jet while maintaining the reproducibility and homogeneity of the discharge is one of the major challenges encountered by the plasma community to efficiently apply this technology in the industry. Here, we report on the discharge in a recently developed device called the plasma candle (PC), wherein a stable plasma jet with a diameter of 20 mm can be generated at atmospheric pressure and temperature. Unlike the discharge morphology previously reported for conventional plasma jet devices, the unique configuration of PC device resulted in distinctive discharge patterns. Homogenous discharge was generated in the electrode gap and followed by a swirling discharge toward the tube nozzle. Fast photography and electrical measurements revealed that filament propagation and its morphology form the visually observable swirl discharge. Detailed analysis indicated that residual helium metastable species (Hem) and their penning ionization play an essential role in the discharge mode and its transition, which was verified by changing the feeding gas and the frequency of the applied voltage. For instance, it is found that only filamentary discharge was observed along the entire tube at frequencies less than 3 kHz, at which the time between consecutive discharges was long enough for Hem decay. Consequently, the homogenous discharge pattern was recovered by increasing the pre-ionization levels by adding a trace of impurities (N2, O2 or H2O) to the feeding gas. However, the level of these impurities must be carefully adjusted to achieve a homogenous discharge without negatively affecting the jet properties. A trivial change in the gas impurity, in the range of adsorption and desorption of water from the gas tubing, is sufficient to cause a noticeable change and instability in the discharge mode. This finding is critical to predicting the production of reactive species and plasma-surface interaction for different applications.

Study of ionization and ion transfer rates in flowing N2 DC discharges and post-discharges

In this work, we studied the ionization and ion transfer rates in flowing nitrogen DC discharges and post-discharges. Two different experimental set-ups and conditions for the flowing nitrogen discharges were analyzed. The first experimental set-up includes a post-discharge tube where the pink afterglow phenomenon was detected. Two well-established discharge and post-discharge kinetic numerical models we had previously developed to study the nitrogen flowing DC discharges and post-discharges were employed to calculate the rates for our experimental conditions. We analyzed 18 ionization and nine ion transfer mechanisms for N+, N2 +, N3 +, and N4 + ions in the discharges and post-discharges. We observed that the electron density of the discharges, which varies by one order of magnitude, plays a major role in the rates behavior for the two experimental set-ups. Moreover, we observed that the rates found in the pink afterglow phenomenon are relevant when compared to rates found in the discharges. The important role of molecular metastable Penning ionization and atoms and molecules associative ionization appear in the ionization rates of the discharges. It is also shown that ion transfer mechanisms play a crucial role in the ions densities distribution found in the discharges and post-discharges. This work brings an original comparative study of ionization and ion transfer rates for experimental flowing nitrogen DC positive columns and pink afterglow post-discharge. This is the first time that a detailed combined experimental and theoretical analysis on the ionization and ion transfer rates is carried out for nitrogen flowing DC positive columns and pink afterglow plasma.

A novel crossed-molecular-beam experiment for investigating reactions of state- and conformationally selected strong-field-seeking molecules

ABSTRACT The structure and quantum state of the reactants have a profound impact on the kinetics and dynamics of chemical reactions. Over the past years, significant advances have been achieved in the control and manipulation of molecules with external electric and magnetic fields in molecular-beam experiments for investigations of their state-, structure- and energy-specific chemical reactivity. Whereas studies for neutrals have so far mainly focused on weak-field-seeking species, we report here progress towards investigating reactions of strong-field-seeking molecules by introducing a novel crossed-molecular-beam experiment featuring an electrostatic deflector. The new setup enables the characterisation of state- and geometry-specific effects in reactions under single-collision conditions. As a proof of principle, we present results on the chemi-ionisation reaction of metastable neon atoms with rotationally state-selected carbonyl sulfide (OCS) molecules and show that the branching ratio between the Penning and dissociative ionisation pathways strongly depends on the initial rotational state of OCS.

Coherent-control mechanisms of Penning and associative ionization in cold He*(2 3S)−He*(2 3S) reactive scattering

We explore coherent control of Penning and associative ionization in cold collisions of metastable He$^*({2}^3\text{S})$ atoms via the quantum interference between different states of the He$_2^*$ collision complex. By tuning the preparation coefficients of the initial atomic spin states, we can benefit from the quantum interference between molecular channels to maximize or minimize the cross sections for Penning and associative ionization. In particular, we find that we can enhance the ionization ratio by 30% in the cold regime. This work is significant for the coherent control of chemical reactions in the cold and ultracold regime.

Optical characterization of miniature flexible micro-tube plasma (FμTP) ionization source: A dielectric guided discharge

Miniature DBD has been obtaining more and more attention. A recently developed miniature flexible micro-tube plasma (FμTP) has proved to be an excellent soft ionization source for mass spectrometry and ion mobility spectrometry. In this paper, the optical characterization of the novel FμTP ionization source was carried out, aiming to cast light on the plasma propagation mechanism in one discharge cycle. To provide a clean environment for investigating the plasma propagation, the plasma was totally sustained in a capillary tube. It was found that in one discharge cycle, three discharge developments, namely two dielectric guided discharges in both positive and negative half cycle, and a negative glow discharge in the negative half cycle. Compared with the conventional dielectric barrier discharge, there is no formation of a dissociative plasma, which improves the soft ionization capacity of the present source. In addition to the whole light emission from 200 nm to 1100 nm, the lines related to the reactive species including He 706 nm, N2+ 391 nm, and O 777 nm were investigated spatially and temporally. Due to the effect of the attached charges, the plasma of the negative half cycle propagates faster than that of the positive half cycle. It was also found that the plasma in the positive half cycle propagates more discretely than that of the negative one, while the negative one has a larger emission intensity due to the overlap of the signal in both temporal and spatial scales. Further on, the electric field distribution was proved to be in Gaussian shape along the diameter of the capillary, while the negative one has a flat shape. By changing the concentration of N2 in He, the electron collision and penning ionization for generating N2+ were experimentally proved and identified. This study identifies the typical discharge process of the FμTP in one discharge cycle, indicating the plasma is indeed a dielectric guided discharge.

Strong enhancement of Penning ionisation in cold Rydberg gases II: Tom and Jerry pairs for alkali-metal atoms

Penning ionisation (PI) processes involving pairs of Rydberg alkali-metal atoms, excited to different quantum states and experiencing dipole–dipole interactions, have a wide range of important properties in atomic physics. Within the framework of the semiclassical approximation, we have used both numerical and analytical approaches to examine the Penning autoionisation width dependence on the state quantum numbers in a quasi-molecule formed by the interacting partner atoms. We described the characteristics of optimal quantum numbers that lead to enhanced PI widths for the interacting Rydberg atom pairs of all alkali-metal atoms. The excited states of atoms in these pairs are asymmetric, resulting in a large atomic shell size difference: inspired by Efimov et al (2016 J. Phys. B: At. Mol. Opt. Phys. 49 125302), we call such a pair ‘Tom’ and ‘Jerry’ (for ‘big’ and ‘small’). Compared to symmetric pairs, the optimal asymmetric pairs display a significant (by several orders of magnitude) increase in the PI rate. This property makes PI a relevant source for producing charged particles in cold Rydberg systems that spontaneously evolve into cold plasma. Contrary to hydrogen atoms examined in (Efimov et al 2016 J. Phys. B: At. Mol. Opt. Phys. 49 125302), the difference in quantum defects in alkali-metal atoms results in a strong Penning width dependence on the orbital quantum numbers l of the quasi-molecule. In particular, alkali-metal atoms exhibit two PI channels associated with bound–bound optical transitions showing Δl = ±1—individual and closely spaced (doublet-like) configurations of optimal pairs. Furthermore, we demonstrate that the presence of Förster resonances can lead to a notable (up to five times) increase in the PI efficiency.

Atmospheric dielectric barrier discharge containing helium–air mixtures: the effect of dry air impurities on the spatial discharge behavior

Air is a typical and arguably unavoidable impurity in atmospheric pressure dielectric barrier discharges (DBDs). The introduction of air may bring rich plasma chemical effects on DBDs and lead to a significant change of discharge characteristics. Here we implement a two-dimensional fluid model to study the spatial discharge behavior in a helium–dry-air DBD under the air impurity level (N air) of 10–200 ppm. The simulation results reveal that under low impurity content (less than 30 ppm), the gas gap cannot be ignited due to the feeble Penning ionization during the breakdown. However, with an elevation in the impurity level, the progressively enhanced Penning ionization makes the DBD experience three different spatial modes, namely uniform, columnar, and complementary quasi-uniform modes. Of particular note is that the improvement of discharge uniformity observed after the second mode transition is not directly controlled by seed electron level—a previously reported qualitative indicator of the discharge uniformity concluded by helium DBDs with only nitrogen traces. And the main contributor to this phenomenon is the complementary spatial structure appearing in successive two discharges induced by the further reinforced Penning ionization with extra oxygen doped. The result suggests the necessity of considering oxygen in helium–air DBDs when the impurity effect of air is concerned.

Radio frequency field-induced electron mobility in an ultracold plasma state of arrested relaxation

Penning ionization releases electrons in a state-selected Rydberg gas of nitric oxide entrained in a supersonic molecular beam. Subsequent processes of electron impact avalanche, bifurcation, and quench form a strongly coupled, spatially correlated ultracold plasma of NO$^+$ ions and electrons that exhibits characteristics of self-organized criticality. This plasma contains a residue of nitric oxide Rydberg molecules. A conventional fluid dynamics of ion-electron-Rydberg quasi-equilibrium predicts rapid decay to neutral atoms. Instead, the NO plasma endures for a millisecond or more, suggesting that quenched disorder creates a state of suppressed electron mobility. Supporting this proposition, a 60 MHz radiofrequency field with a peak-to-peak amplitude less than 1 V cm$^{-1}$ acts dramatically to mobilize electrons, causing the plasma to dissipate by dissociative recombination and Rydberg predissociation. An evident density dependence shows that this effect relies on collisions, giving weight to the idea of arrested relaxation as a cooperative property of the ensemble.