Associative Ionization Research Articles

Formation of antihydrogen molecular ions by associative ionization

Formation of antihydrogen molecular ions by associative ionization

Dissociative recombination and resonant ion-pair formation in electron collisions with HD+

We have developed a method for which a variety of reactive scattering processes involving the H2 reaction complex can be studied using the same set of potential curves and couplings. The method is based on a close-coupling approach in a strict diabatic representation. By rigorously incorporating nonadiabatic couplings among bound states, we enable the computation of final-state distributions. Loss into the ionization continuum is accounted for with a nonlocal complex potential matrix. The method has successfully been applied in studies of H++H− mutual neutralization and H(1s)+H(ns) associative ionization. In this paper, we investigate the applicability of this method to dissociative recombination and resonant ion-pair formation in electron collisions with HD+. The importance of a nonlocal description of autoionization is demonstrated. Calculated cross sections and final-state distributions are compared with results from experiments and previous theoretical studies. Published by the American Physical Society 2024

Zero-dimensional analysis of the effect of water vapor on reducing electrons in the plasma sheath

In this study, an air-water vapor ionization reaction model is developed within the quantum-kinetic (Q–K) model of the direct simulation Monte Carlo method to investigate the detailed mechanism of how water vapor reduces electrons. The zero-dimensional simulations of a typical non-equilibrium flow field downstream of a normal shock are designed, where the electron number density decreases by two orders of magnitude due to water vapor. We conclude that the introduction of water vapor reduces the mole fractions of oxygen atoms and nitrogen atoms through five pairs of reactions and enhances the reverse nitric oxide associative ionization reaction, leading to electron consumption. The phenomena and corresponding mechanisms under varying mole fractions of water vapor, air temperatures, and water vapor temperatures are investigated. Based on the mechanisms, we propose that the addition of hydrogen ions could improve the water's mitigation effect, which is then proven to be able to reduce the electron number density by another two orders of magnitude, not only at high air temperatures but also at lower air temperatures or lower mass injection rates.

Sensitivity Analysis of Ionization in Two-Temperature Models of Hypersonic Air Flows

Plasma generation in hypersonic flows is analyzed using a two-temperature model of nonequilibrium air. The uncertainties in electron number density predictions are assessed for flow scenarios that correspond to both strongly shocked and strongly expanded flows, and the dependencies of the calculated uncertainties on individual input parameters are quantified. Ionization levels behind 5 and 7 km/s normal shocks are found to be most sensitive to the associative ionization reactions producing O2+ and NO+ in the region of peak electron number density, with nitric oxide kinetics dominating the uncertainty downstream. The higher levels of ionization behind a 9 km/s shock are found to strongly depend on the electron impact ionization of atomic nitrogen as well as the charge exchange between N2+ and N. Recombining flow scenarios depend on many of the same processes that influence the shocked flows, with the notable addition of the reassociation reaction O++N2↔NO++N, which is responsible for large uncertainties in electron number density in net recombining flows. The results provide valuable insight into the typical magnitude of uncertainty associated with plasma formation predictions in hypersonic flows and identify the parameters that should be targeted in efforts to reduce those uncertainties.

Ultra-sensitive analysis of exhaled biomarkers in ozone-exposed mice via PAI-TOFMS assisted with machine learning algorithms

Ground-level ozone ranks sixth among common air pollutants. It worsens lung diseases like asthma, emphysema, and chronic bronchitis. Despite recent attention from researchers, the link between exhaled breath and ozone-induced injury remains poorly understood. This study aimed to identify novel exhaled biomarkers in ozone-exposed mice using ultra-sensitive photoinduced associative ionization time-of-flight mass spectrometry and machine learning. Distinct ion peaks for acetonitrile (m/z 42, 60, and 78), butyronitrile (m/z 70, 88, and 106), and hydrogen sulfide (m/z 35) were detected. Integration of tissue characteristics, oxidative stress-related mRNA expression, and exhaled breath condensate free-radical analysis enabled a comprehensive exploration of the relationship between ozone-induced biological responses and potential biomarkers. Under similar exposure levels, C57BL/6 mice exhibited pulmonary injury characterized by significant inflammation, oxidative stress, and cardiac damage. Notably, C57BL/6 mice showed free radical signals, indicating a distinct susceptibility profile. Immunodeficient non-obese diabetic Prkdc-/-/Il2rg-/- (NPI) mice exhibited minimal biological responses to pulmonary injury, with little impact on the heart. These findings suggest a divergence in ozone-induced damage pathways in the two mouse types, leading to alterations in exhaled biomarkers. Integrating biomarker discovery with comprehensive biopathological analysis forms a robust foundation for targeted interventions to manage health risks posed by ozone exposure.

The associative ionization of N(2P) + O(3P).

The rate constant of the associative ionization reaction N(2P) + O(3P) → NO+ + e- was measured using a flow tube apparatus. A flowing afterglow source was used to produce an ion/electron plasma containing a mixture of ions, including N2+, N3+, and N4+. Dissociative recombination of these species produced a population of nitrogen atoms, including N(2P). Charged species were rejected from the flow tube using an electrostatic grid, subsequent to which oxygen atoms were introduced, produced either using a discharge of helium and oxygen or via the titration of nitrogen atoms with NO. Only the title reaction can produce the NO+ observed after the introduction of O atoms. The resulting rate constant (8 ± 5 ×10-11cm3s-1) is larger than previously reported N(2P) + O disappearance rate constants (∼2 × 10-11cm3s-1). The possible errors in this or previous experiments are discussed. It is concluded that the N(2P) + O(3P) reaction proceeds almost entirely by associative ionization, with quenching to the 2D or 4S states as only minor processes.

Resonant and Anomalous Structures of Associative Ionization Spectra Involving Rydberg Atoms

Resonant and Anomalous Structures of Associative Ionization Spectra Involving Rydberg Atoms

Insight into the crucial reason causing the difference in secondary organic aerosol yields of monocyclic aromatic hydrocarbons with different methyl substituent numbers

The secondary organic aerosol (SOA) yield of toluene photooxidation was reported to substantially higher than that of trimethylbenzene due to the effect of the number of methyl substituents. However, the intrinsic mechanism for this disparity is not clear enough. In this study, a highly-sensitive thermal-desorption photoinduced associative ionization mass spectrometer (TD-PAI-MS) was used to real-time characterize the molecular composition and its evolution of the SOA generated from the photooxidation of toluene and 1,2,3-trimethylbenzene (1,2,3-TMB) in a smog chamber. In the new particle formation (NPF) stage, toluene generated more variety of nucleation precursors, such as benzaldehyde (MW 106) and benzoic acid (MW 122), resulting in a much higher nucleation rate and SOA number concentration. In the SOA growth/aging stage, the key SOA components of toluene were mainly dialdehydes, e.g., 2-oxopropanedial (MW 86) and 4-oxopent-2-enedial (MW 112), which played an important role in the formation of highly oxidized species (HOS) through oligomerization or cyclization reactions. In contrast, due to the presence of more methyl groups, 1,2,3-TMB was inclined to produce ketones, e.g., 2,3-butanedione (MW 86) and 3-methyl-4-oxopent-2-enal (MW 112), which would be cleaved into high-volatility low molecular compounds, e.g., acetic acid, through fragmentation. Taken together, relative to 1,2,3-TMB, the higher nucleation rate during NPF and the significant oligomerization/functionalization process during SOA growth are thought to be the major reasons resulting in the higher SOA yield of toluene. This work provides a reference for the insight into the different SOA yields of monocyclic aromatic hydrocarbons (MAHs) through further revealing the SOA formation mechanism during toluene and 1,2,3-TMB photooxidation.

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.

A Simple High-Flux Switchable VUV Lamp Based on an Electrodeless Fluorescent Lamp for SPI/PAI Mass Spectrometry.

Single-photon ionization (SPI) is a unique soft ionization technique for organic analysis. A convenient high-flux vacuum ultraviolet (VUV) light source is a key precondition for wide application of SPI techniques. In this study, we present a novel VUV lamp by simply modifying an ordinary electrodeless fluorescent lamp. By replacing the glass bulb with a stainless steel bulb and introducing 5% Kr/He (v/v) as the excitation gas, an excellent VUV photon flux over 4.0 × 1014 photons s-1 was obtained. Due to its rapid glow characteristics, the VUV lamp can be switched on and off instantly as required by detection, ensuring the stability and service life of the lamp. To demonstrate the performance of the new lamp, the switchable VUV lamp was coupled with an SPI-mass spectrometer, which could be changed to photoinduced associative ionization (PAI) mode by doping gaseous CH2Cl2 to initiate an associative ionization reaction. Two types of volatile organic compounds sensitive to SPI and PAI, typically benzene series and oxygenated organics, respectively, were selected as samples. The instrument exhibited a high detection sensitivity for the tested compounds. With a measurement time of 11 s, the 3σ limits of detection ranged from 0.33 to 0.75 pptv in SPI mode and from 0.03 to 0.12 pptv in PAI mode. This study provides an extremely simple method to assemble a VUV lamp with many merits, e.g., portability, robustness, durability, low cost, and high flux. The VUV lamp may contribute to the development of SPI-related highly sensitive detection technologies.

Exploring the mechanisms leading to diffuse and filamentary modes in dielectric barrier discharges in N_2 with N_2O admixtures

The effects of nitrous oxide (N_2O) in nitrogen (N_2) on the development and morphology of sine-driven dielectric barrier discharges in a single-filament arrangement were studied. Detailed insight in the characteristics of the discharge and its development were obtained from electrical measurements combined with ICCD and streak camera recordings as well as numerical modelling. A miniaturised atmospheric pressure Townsend discharge (APTD) could be generated for admixtures up to 5 vol% N_2O in N_2 although N_2O is an efficient collisional quencher of metastable nitrogen molecules. Increasing the high voltage amplitude led to a transition into a hybrid mode with the generation of an intermediate filament in addition to the diffuse, non-constricted APTD. A time-dependent, spatially one-dimensional fluid model was applied in order to study the underlying mechanisms causing the diffuse discharge characteristics. It was found that even for small N_2O admixtures, the associative ionisation of atomic nitrogen and oxygen (O + N(^2P) rightarrow NO^+ + e) is the major electron source sustaining the volume memory effect and is therefore the reason for the formation of a diffuse APTD.Graphical abstract

Direct detection of acetonitrile at the pptv level with photoinduced associative ionization time-of-flight mass spectrometry.

Photoionization mass spectrometry (PI-MS) has become a versatile tool in the real-time analysis of volatile organic compounds (VOCs) from the atmosphere or exhaled breath. However, some key species, e.g., acetonitrile, are hard to measure due to their higher ionization energies than photon energy. In this study, the direct and sensitive detection of gaseous acetonitrile based on a photoinduced associative ionization (PAI) reaction was investigated with a laboratory-built PAI time-of-flight mass spectrometer (PAI-TOFMS). By doping CH2Cl2 in the photoionization ion source, the mass signal of acetonitrile that cannot be effectively obtained by photoionization appeared with an extremely high intensity through the PAI reaction between acetonitrile, CH2Cl2, and residual H2O in the system. Though the moisture in the sample gas has an evident impact on the detection efficiency of acetonitrile, with a relative signal intensity decreasing from 100% under dry conditions to 60% at saturated relative humidity, excellent detection sensitivity was still obtained for gaseous acetonitrile in different matrixes. The sensitivity calibration experiment showed that the detection sensitivities of acetonitrile in N2 buffer gas, exhaled gas, and outdoor air were 682.4 ± 5.2, 17.0 ± 0.7, and 23.9 ± 0.2 counts pptv-1, respectively, with an analysis time of 10 s. The corresponding 3σ LODs reached 0.22, 8.82, and 6.28 pptv, which are equivalent to 0.40, 16.0, and 11.4 ng m-3. The performance of the PAI-TOFMS was first demonstrated by analyzing exhaled acetonitrile from healthy non-smokers and smokers and continuous monitoring of acetonitrile in outdoor air. In summary, this study provides a new and highly sensitive method for the real-time detection of acetonitrile through mass spectrometry.

Electronic Spectroscopy of SmO in the 645 to 670 nm Range.

The associative ionization reaction Sm + O → SmO+ + e- is being investigated as an electron source that could transiently modify high-altitude electron densities via Sm vapor release. Electronic spectra have been obtained from tests where sounding rockets released Sm vapor, but the interpretation of these results has been hampered by the limited laboratory spectral data available for both SmO and SmO+. The present study extends the spectroscopic characterization of SmO in the 645-670 nm range, where the field data show the most prominent molecular emission features. Rotationally resolved excitation spectra, dispersed laser-induced fluorescence spectra, and fluorescence decay lifetimes are reported. The results are consistent with the assignment of a subset of the red-region bands to configurational transitions of the form Sm2+(4f56s)O2- ↔ Sm2+(4f55d)O2-. Analysis of the excited state hyperfine structure supports this configurational description.

Numerical analysis of structural change process in millimeter-wave discharge at subcritical intensity

Plasma-front propagation processes of 170 GHz millimeter-wave discharge were investigated under subcritical incident electric field intensity by using a one-dimensional model. The discharge structure was numerically reproduced at more than 0.2 MV/m by introducing the detailed chemical reaction and radiation transport processes into the conventional model. The results revealed that the propagation mechanism of the plasma front in the millimeter-wave discharge changes depending on the incident electric field intensity. At intensities greater than 1.4 MV/m, the plasma front propagated at supersonic speed, while forming a discrete structure, which has intervals of 1/4 wavelength of the millimeter wave. This structure was generated by electron-impact ionization and photoionization processes. At the intermediate intensities, the plasma front propagated continuously rather than discretely because the gas expansion increased the reduced electric field and induced electron-impact ionization. The dominant heating process at the plasma front was fast gas heating. At intensities less than 0.3 MV/m, the plasma front propagated continuously, but the dominant heating process changed to vibrational–translational relaxation. The discharge was maintained by thermal ionization and associative ionization. The simulation results were in good agreement with the past millimeter discharge experiments at this intensity.

An ultrasensitive SPI/PAI ion source based on a high-flux VUV lamp and its applications for the online mass spectrometric detection of sub-pptv sulfur ethers

Single-photon ionization mass spectrometry (SPI-MS) is an attractive analytical technique for the online detection of volatile organic compounds; however, the low photon flux of the vacuum ultraviolet (VUV) lamp commonly used in the SPI ion source and the corresponding low detection sensitivity remain a constraint to its wide field applications. In this study, a new VUV lamp-based SPI ion source was developed. By increasing the discharging volume and optimizing the configuration of the lens and ionizer, the photon flux of the VUV lamp and the sensitivity of the ion source were significantly improved. The VUV lamp output was 2.8 × 1015 photons s−1, which was focused into the small ionization zone, and the ion intensity of gaseous benzene under SPI achieved 1.7 × 104 counts per second per pptv (cps pptv−1). This ion source can also function in photoinduced associative ionization (PAI) mode by introducing gaseous CH2Cl2 to initiate an associative ionization reaction. Because of the high efficiency of the ion source, the amount of doped CH2Cl2 needed for PAI was greatly reduced (∼2.5% of that used in previous experiments). PAI exhibited an outstanding protonation effect on monosulfur ethers (CnH2n+1S). The signal intensities of the protonated molecular ions (MH+) were 46–128 times higher than those of the molecular ions (M+) produced by SPI. Since monosulfur ethers generally have lower SPI cross-sections than polysulfur ethers (CnH2n+1S2 or CnH2n+1S3), the PAI and SPI modes were selected for the online measurement of a series of mono- and polysulfur ethers, respectively. The obtained detection sensitivity of the mono- and polysulfur ethers reached 476.5 ± 1.72–2835.1 ± 99.5 and 47.9 ± 0.4–105.1 ± 2.3 counts pptv−1, respectively, in 10 s of sampling time. The corresponding 3σ limits of detection (LODs) were 0.12–0.71 and 0.06–0.14 pptv, respectively. This study provides advances in the development of a high-flux VUV lamp and a highly efficient SPI/PAI ion source, as well as an ultrasensitive analytical method for detecting sulfur ethers.

Charged particle kinetics and gas heating in CO2 microwave plasma contraction: comparisons of simulations and experiments

This work investigates kinetics and transport of CO2 microwave plasmas through simulation results from a 1D radial fluid model and experiments. Simulation results are validated against spatially resolved measurements of neutral species mole fractions, gas temperature, electron number density and temperature obtained by means of Thomson and Raman scattering diagnostics, yielding good agreement. As such, the model is used to complement experiments and assess the main chemical reactions, mass and energy transport in diffuse and contracted plasma regimes. From model results, it is found that, as pressure is raised, the inhomogeneous gas heating induces significant gradients in neutral and charged species mole fractions profiles. Moreover, the transition from diffuse to contracted plasma is accompanied by a change in the dominant charged species, which favours electron–ion recombination over dissociative attachment. Associative ionization rates increase in the plasma core from diffuse to contracted regime. These processes contribute to the increase in the peak electron number density with pressure, that determines radial plasma contraction.

Photoinduced Associative Ionization Time-of-Flight Mass Spectrometry for the Sensitive Determination of Monoterpenes

Recently, photoinduced associative ionization (PAI) has been demonstrated to be extremely efficient for the determination of oxygenated volatile organic compounds. However, its application for the determination hydrocarbons has not yet been reported. In this study, associative ionization of nine typical monoterpenes induced by dichloromethane (CH2Cl2) under vacuum ultraviolet (VUV) light was investigated using a laboratory-constructed PAI time-of-flight mass spectrometer (PAI-TOFMS). Without doping CH2Cl2, VUV light generated ordinary photoionization mass spectra of monoterpenes that were dominated by fragment ions, while the molecular ions were inconspicuous. In contrast, doping with CH2Cl2 resulted in the appearance of mass peaks of the characteristic protonated molecular ions of the monoterpenes. The PAI method significantly enhanced the signals for the monoterpenes. The intensities of protonated molecular ions derived from PAI were amplified by 52 to 108 fold compared with those of molecular ions produced by VUV photoionization (VUV PI). With the high ionization efficiency of PAI toward monoterpenes, the sensitivities of PAI-TOFMS toward limonene, β-ocimene, β-myrcene, β-pinene, and α-pinene were from 291 ± 6 to 1338 ± 20 counts pptv−1 using an acquisition time of 30 s. The limits of detection were from 0.32 to 1.45 pptv, equivalent to between 1.92 and 8.83 ng m−3. The applicability of this ionization mode was further characterized by the determination of monoterpenes from potted Sabina chinensis. This study provides a new and highly efficient ionization method for the determination of plant monoterpenes using mass spectrometry.

The Chemical Origins of Plasma Contraction and Thermalization in CO2 Microwave Discharges.

Thermalization of electron and gas temperature in CO2 microwave plasma is unveiled with the first Thomson scattering measurements. The results contradict the prevalent picture of an increasing electron temperature that causes discharge contraction. It is known that as pressure increases, the radial extension of the plasma reduces from ∼7 mm diameter at 100 mbar to ∼2 mm at 400 mbar. We find that, simultaneously, the initial nonequilibrium between ∼2 eV electron and ∼0.5 eV gas temperature reduces until thermalization occurs at 0.6 eV. 1D fluid modeling, with excellent agreement with measurements, demonstrates that associative ionization of radicals, a mechanism previously proposed for air plasma, causes the thermalization. In effect, heavy particle and heat transport and thermal chemistry govern electron dynamics, a conclusion that provides a basis for ab initio prediction of power concentration in plasma reactors.

Exploring breath biomarkers in BLM-induced pulmonary fibrosis mice with associative ionization time-of-flight mass spectrometry

Pulmonary fibrosis (PF) is a common but fatal disease that threatens human health worldwide. Developing effective diagnostic methods is of great importance for the early detection of PF in patients. In this study, bleomycin (BLM) was used in mice to mimic idiopathic pulmonary fibrosis (IPF). The exhaled breath of BLM-induced PF, PF plus DDAH1 overexpression, and healthy control mice were analyzed in real-time using a newly developed associative ionization time-of-flight mass spectrometry method (AI-TOFMS), which is uniquely sensitive, especially to oxygenated volatile organic compounds (VOCs). Multivariate data analyses and discriminant modeling analyses revealed that four exhaled compounds, i.e., acrolein, ethanol, nitric oxide, and ammonia, had a strong correlation with PF symptoms. An Orthogonal Partial Least Square Discriminant Analysis (OPLS-DA) score plot showed an excellent separation between these three groups. The area under the receiver operating characteristic (ROC) curve for these four compounds distinguished PF mice from healthy controls at 0.989. In addition, the degrees of acute inflammation and fibrosis were assessed with Hematoxylin and Eosin (H&E) staining and Masson's Trichrome staining. Finally, combined with pathological characteristics and mRNA expression levels, the formation of the above-mentioned volatile compounds was explored. The obtained experimental results indicated that these four breath compounds, acrolein, ethanol, nitric oxide, and ammonia, were potential exhaled biomarkers for pulmonary fibrosis.

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.