Ion-molecule Chemistry Research Articles

Calcium Chemistry in Carbon-rich Circumstellar Environments: The Laboratory and Astronomical Discovery of Calcium Dicarbide, CaC2 * * This work is based on observations done using the 100 m Green Bank Telescope (GBT), the Yebes 40 m telescope (projects 19A010, 20A017, 20B014, and 21A019), and the IRAM 30 m telescope. The 100 m GBT is an instrument of the Green Bank

Calcium dicarbide, CaC2, has been characterized at high resolution in the laboratory, and its main isotopologue, 40CaC2, has been assigned to 14 rotational emission lines between 14 and 115 GHz, including 12 previously unassigned lines, in the expanding molecular envelope of the evolved carbon star IRC+10216. Aided by high-level quantum calculations and measurements of multiple isotopologues, CaC2 is determined to be a T-shaped molecule with a highly ionic bond linking the metal atom to the C2 unit, very similar in structure to isovalent magnesium dicarbide (MgC2). The excitation of CaC2 is characterized by a very low rotational temperature of 5.8 ± 0.6 K and a kinetic temperature of 36 ± 16 K, similar to values derived for MgC2. On the assumption that the emission originates from a 30″ shell in IRC+10216, the column density of CaC2 is (5.6 ± 1.7) × 1011 cm−2. CaC2 is only the second Ca-bearing molecule besides CaNC and only the second metal dicarbide besides MgC2 identified in space. Owing to the similarity between the predicted ion–molecule chemistry of Ca and Mg, a comparison of the CaC2 abundance with that of MgC2 and related species permits empirical inferences about the radiative association–dissociative recombination processes postulated to yield metal-bearing molecules in IRC+10216 and similar objects.

Integrating density functional theory and chemical ionization mass spectrometry techniques to assess benzophenone derivatives in food packaging: implications for enhancing food quality and safety.

Benzophenone and related derivatives are widely used as photoinitiators for food packaging to cure inks or lacquers with ultraviolet (UV) light on cardboard and paper. However, there are concerns about the potential health risks of their migration into food. Knowing the physical and chemical properties of benzophenone and its derivatives could play a significant role in their quantification and analysis using chemical ionization mass spectrometry (CI-MS) methods. These parameters are evaluated using B3LYP/6-311++** density functional theory (DFT) implemented on Gaussian code. Ion-molecule chemistry through the selection of reagent ions, reaction energetics and kinetics, thermodynamic stability, and reactivity of molecules deemed to foster VOC identification and quantification via CI-MS techniques. The VOCs under study are expected to undergo exothermic reactions from H3 O+ , NH4 + , NO+ , and O2 + ions, except endothermic proton transfer from NH4 + to 2-hydroxy-4-methoxybenzophenone and 2,3,4-trihydroxy benzophenone. These compounds possess less proton affinities than NH3 and are least stable in their protonated forms. The DFT computed properties provide the basis for developing reliable and accurate methods to detect and measure the presence of benzophenone and its derivatives in packaging materials and food products.

Synthesis of organo-uranium(II) species in the gas-phase using reactions between [UH]+ and nitriles.

One challenge in the quest to map the intrinsic reactivity of model actinide species has been the controlled synthesis of organo-actinide ions in the gas phase. We report here evidence that a series of gas-phase, σ-bonded [U-R]+ species (where R = CH3, C2H3, C2H5, C3H7, or C5H6) can be generated for subsequent study of ion-molecule chemistry by using preparative tandem mass spectrometry (PTMSn) via ion-molecule reactions between [UH]+ and a series of nitriles. Density functional theory calculations support the hypothesis that the [U-R]+ ions are created in a pathway that involves intramolecular hydride attack and the elimination of neutral HCN. Subsequent reactivity experiments revealed that the [UCH3]+ readily undergoes hydrolysis, yielding cationic uranium hydroxide ([UOH]+) and methane (CH4). Other possible reaction pathways, such as the spontaneous rearrangement to [HUCH2]+, are shown by theoretical calculations to have energy barriers, strengthening the evidence for the formation of a σ-bonded [U-CH3]+ complex in the gas-phase.

First detection of deuterated methylidyne (CD) in the interstellar medium

While the abundance of elemental deuterium is relatively low (D/H ~ a few ×10−5), orders of magnitude higher D/H abundance ratios have been found for many interstellar molecules, enhanced by deuterium fractionation. In cold molecular clouds (T < 20 K), deuterium fractionation is driven by the H2D+ ion, whereas at higher temperatures (T ≥ 20–30 K) gas-phase deuteration is controlled by reactions with CH2D+ and C2HD+. While the role of H2D+ in driving cold interstellar deuterium chemistry is well understood, thanks to observational constraints from direct measurements of H2D+, deuteration stemming from CH2D+ is far less understood as a result of the absence of direct observational constraints of its key ions. Therefore, making use of chemical surrogates is imperative in order to explore deuterium chemistry at intermediate temperatures. Formed at an early stage of ion-molecule chemistry directly from the dissociative recombination of CH3+ (CH2D+), CH (CD) is an ideal tracer for investigating deuterium substitution initiated by reactions with CH2D+. This paper reports the first detection of CD in the interstellar medium (ISM), carried out using the APEX 12 m telescope toward the widely studied low-mass protostellar system IRAS 16293–2422. Observed in absorption towards the envelope of the central protostar, the D/H ratio derived from the column densities of CD and CH is found to be 0.016 ± 0.003. This is an order of magnitude lower than the values found for other small molecules like C2H and H2CO observed in emission but whose formation, which is similar to that of CH, is also initiated via pathways involving warm deuterium chemistry. Gas-phase chemical models reproducing the CD/CH abundance ratio suggest that it reflects ‘warm deuterium chemistry’ (which ensues in moderately warm conditions of the ISM) and illustrates the potential use of the CD/CH ratio in constraining the gas temperatures of the envelope gas clouds it probes.

Cold Ion-Molecule Chemistry: The Very Different Reactions of He⁺ with CO and NO.

The ion-molecule reactions He+ + CO → He + C+ + O and He+ + NO → He + N+ + O have been measured at collision energies between 0 and kB · 10 K. Strong variations of the rate coefficients are observed below kB · 5 K. The rate of the He+ + CO reaction decreases by ~30% whereas that of the He+ + NO reaction increases by a factor of ~1.5. These observations are interpreted in the realm of an adiabatic-channel capture model as arising from interactions between the ion charge and the dipole and quadrupole moments of CO and NO. We show that the different low-energy behavior of these reactions originates from the closed- vs. open-shell electronic structures of CO and NO.

High kinetic energy-ion mobility spectrometry-mass spectrometry investigations of several volatiles and their fully deuterated analogues

The first High Kinetic Energy-Ion Mobility Spectrometry-Mass Spectrometry (HiKE-IMS-MS) studies involving six volatiles (acetone, acetonitrile, methanol, ethanol, 2-propanol, and 1-butanol) and their fully deuterated analogues are reported. The goal is to further our understanding of the ion–molecule chemistry occurring in the HiKE-IMS. This is needed for its full analytical potential to be reached. Product ions are identified as a function of the reduced electric field (30–115 Td) and the influence of sample air humidity in the reaction region on deuterium/hydrogen (D/H) exchange reactions is discussed. Reagent ions include H3O+(H2O)m (n = 0, 1, 2 or 3), NO+(H2O)n (m = 0 or 1) and O2+·. Reactions with H3O+(H2O)m lead to protonated monomers (through either proton transfer or ligand switching). Reactions with NO+ involve association with acetone and acetonitrile, hydride anion abstraction from ethanol, 2-propanol, and 1-butanol, and hydroxide abstraction from 2-propanol and 1-butanol. With the exception of acetonitrile, O2+· predominantly reacts with the volatiles via dissociative charge transfer. A number of sequential secondary ion-volatile processes occur leading to the formation of dimer and trimer-containing ion species, whose intensities depend on a volatile’s concentration and the reduced electric field in the reaction region. Deuterium/hydrogen (D/H) exchange does not occur for product ions from acetone-d6 and acetonitrile-d3, owing to their inert methyl functional groups. For the deuterated alcohols, rapid D/H-exchange reaction at the hydroxy group is observed, the amount of which increased with the increasing humidity of the sample air and/or lowering of the reduced electric field.Graphical abstract

Dynamics and reactivity of thermalized ions in a radiofrequency quadrupole gas-reaction cell used for the production of radioactive molecular ions

Two-dimensional radiofrequency quadrupole (RFQ) ion guides are versatile tools that are used over a wide range of ion energies. Properly tuned, they can provide an ideal environment for ion-molecule chemistry to proceed by allowing thermalized ions to react on-line with gaseous reactants. We exploit this capability in the Ion Reaction Cell (IRC), an RFQ-based system designed to form radioactive molecules (RM) from radioactive ion beams (RIB). Functionally, the IRC accepts RIB produced upstream by the isotope separation on-line (ISOL) method, decelerates it to eV energies for production of the RM and then re-accelerates RM to their incident energy. This system promises to form a highly versatile source of complex inorganic or organic RM that can be used in fundamental symmetry studies or as precursors to new radiopharmaceuticals. We discuss the challenges of transferring ions from a RIB into a gas cell at room temperature while constraining ions within the RFQ energy well, and of reforming a beam from synthesized RM. Various factors influencing ion dynamics and reactivity in thermal and non-thermal zones inside the IRC are considered, using results obtained recently with the Isobar Separator for Anions, an analogous RFQ technique used in Accelerator Mass Spectrometry, to illustrate key points.

Self-consistent global transport of metallic ions with WACCM-X

Abstract. The NCAR Whole Atmosphere Community Climate Model with thermosphere and ionosphere eXtension (WACCM-X) v2.1 has been extended to include the neutral and ion–molecule chemistry and dynamics of three metals (Mg, Na, and Fe), which are injected into the upper mesosphere–lower thermosphere by meteoric ablation. Here we focus on the self-consistent electrodynamical transport of metallic ions in both the E and F regions. The model with full ion transport significantly improves the simulation of global distribution and seasonal variations of Mg+, although the peak density is slightly lower (about 35 % lower in peak density) compared with the SCIAMACHY measurements. Near the magnetic equator, the diurnal variation in upward and downward transport of Mg+ is generally consistent with the “ionosphere fountain effect”. The thermospheric distribution of Fe is shown to be closely coupled to the transport of Fe+. The effect of ion mass on ion transport is also examined: the lighter ions (Mg+ and Na+) are transported above 150 km more easily than the heavy Fe+. We also examine the impact of the transport of major molecular ions, NO+ and O2+, on the distribution of metallic ions.

Determination of Total Silicon and SiO2 Particles Using an ICP-MS Based Analytical Platform for Toxicokinetic Studies of Synthetic Amorphous Silica.

Synthetic amorphous silica (SAS), manufactured in pyrogenic or precipitated form, is a nanomaterial with a widespread use as food additive (E 551). Oral exposure to SAS results from its use in food and dietary supplements, pharmaceuticals and toothpaste. Recent evidence suggests that oral exposure to SAS may pose health risks and highlights the need to address the toxic potential of SAS as affected by the physicochemical characteristics of the different forms of SAS. For this aim, investigating SAS toxicokinetics is of crucial importance and an analytical strategy for such an undertaking is presented. The minimization of silicon background in tissues, control of contamination (including silicon release from equipment), high-throughput sample treatment, elimination of spectral interferences affecting inductively coupled plasma mass spectrometry (ICP-MS) silicon detection, and development of analytical quality control tools are the cornerstones of this strategy. A validated method combining sample digestion with silicon determination by reaction cell ICP-MS is presented. Silica particles are converted to soluble silicon by microwave dissolution with mixtures of HNO3, H2O2 and hydrofluoric acid (HF), whereas interference-free ICP-MS detection of total silicon is achieved by ion-molecule chemistry with limits of detection (LoDs) in the range 0.2–0.5 µg Si g−1 for most tissues. Deposition of particulate SiO2 in tissues is assessed by single particle ICP-MS.

Shuji Kato

Shuji Kato, 62, died on Jan. 21 in Tokyo. “From his many handwritten notes to his outstanding publications in ion-molecule chemistry, Shuji’s integrity, distinction, and scholarship stand out over his remarkably productive life. He touched many of us as an extraordinarily generous and hardworking colleague, with wit and wisdom. His great dedication, support, and attention to his family shone through. Most of all, Shuji was thrilled by opportunities to do excellent science. As a professor at Toho University, his natural inclination to be an educator was fulfilled. Shuji was the irreplaceable colleague everyone would like to have.”—Stephen R. Leone, friend and colleague Most recent title: Professor of chemistry, Toho University Education: BS, chemistry, 1980, MS, chemistry, 1982, and PhD, chemistry, 1985, Tokyo University Survivors: Wife, Yoko; daughter, Rieko; son, Satofumi; two grandchildren To recognize your late loved one or colleague, submit obituary information at cenm.ag/obits.

The intensification of metallic layered phenomena above thunderstorms through the modulation of atmospheric tides

We present a multi-instrument experiment to study the effects of tropospheric thunderstorms on the mesopause region and the lower ionosphere. Sodium (Na) lidar and ionospheric observations by two digital ionospheric sounders are used to study the variation in the neutral metal atoms and metallic ions above thunderstorms. An enhanced ionospheric sporadic E layer with a downward tidal phase is observed followed by a subsequent intensification of neutral Na number density with an increase of 600 cm−3 in the mesosphere. In addition, the Na neutral chemistry and ion-molecule chemistry are considered in a Na chemistry model to simulate the dynamical and chemical coupling processes in the mesosphere and ionosphere above thunderstorms. The enhanced Na layer in the simulation obtained by using the ionospheric observation as input is in agreement with the Na lidar observation. We find that the intensification of metallic layered phenomena above thunderstorms is associated with the atmospheric tides, as a result of the troposphere-mesosphere-ionosphere coupling.

Electrostatic Switching and Selection of H3O+, NO+, and O2+• Reagent Ions for Selected Ion Flow-Drift Tube Mass Spectrometric Analyses of Air and Breath.

Soft chemical ionization mass spectrometry techniques, particularly the well-established proton transfer reactionmass spectrometry, PTR-MS, and selected ion flow tube mass spectrometry, SIFT-MS, are widely used for real-time quantification of volatile organic compounds in ambient air and exhaled breath with applications ranging from environmental science to medicine. The most common reagent ions H3O+, NO+, or O2+• can be selected either by quadrupole mass filtering from a discharge ion source, which is relatively inefficient, or by switching the gas/vapor in the ion source, which is relatively slow. The chosen reagent ions are introduced into a flow tube or flow-drift tube reactor where they react with analyte molecules in sample gas. This article describes a new electrostatic reagent ion switching, ERIS, technique by which H3O+, NO+, and O2+• reagent ions, produced simultaneously in three separate gas discharges, can be purified in post-discharge source drift tubes, switched rapidly, and selected for transport into a flow-drift tube reactor. The construction of the device and the ion-molecule chemistry exploited to purify the individual reagent ions are described. The speed and sensitivity of ERIS coupled to a selected ion flow-drift tube mass spectrometry, SIFDT-MS, is demonstrated by the simultaneous quantification of methanol with H3O+, acetone with NO+, and dimethyl sulfide with O2+• reagent ions in single breath exhalations. The present ERIS approach is shown to be preferable to the previously used quadrupole filtering, as it increases analytical sensitivity of the SIFDT-MS instrument while reducing its size and the required number of vacuum pumps.

Ion mobility studies on the negative ion-molecule chemistry of pentachloroethane

In this study we present an investigation of the negative ion-molecule chemistry of pentachloroethane (PCE) in air based ion mobility spectrometry and ion mobility spectrometry–mass spectrometry systems. The observed product ions are Cl−, produced by dissociative electron attachment, and Cl−·HOO resulting from a reaction with O2−. Based upon the moisture content of the system, these ions can be observed as a doublet in a ‘dry’ system or as a singlet in a ‘wet’ system. The nature of the Cl−·HOO product ion was investigated by using isoflurane (ISOF) as a probe to monitor the changing ratios of Cl− and Cl−·HOO as the PCE concentration decreased. This confirmed the origins of the two product anions. Electronic structure calculations are provided. These have aided the understanding of the reaction processes observed.

Ion Mobility Studies on the Negative Ion-Molecule Chemistry of Isoflurane and Enflurane

In the present work we present an investigation of the negative ion-molecule chemistry of the anaesthetics isoflurane, ISOF, and enflurane, ENF, in an ion mobility spectrometry/mass spectrometry (IMS/MS), in both air and nitrogen. Hexachloroethane (HCE) was introduced in both air and nitrogen to produce Cl– as a reactant ion. This study was undertaken owing to uncertainties in the chemical processes, which lead to the cluster ions reported in other work (Eiceman et al. Anal. Chem. 61, 1093–1099, 1). In particular for ISOF the product ion observed was ISOF.Cl–, and it was suggested that the Cl– was formed by dissociative electron attachment (DEA) although there was mention of a chlorine containing contaminant. We show in this study that ISOF and ENF do not produce Cl– in an IMS system either by capture of free electrons or reaction with O2–. This demonstrates that the Cl– containing ions, reported in the earlier study, must have been the result of a chlorine containing contaminant as suggested. The failure of ISOF and ENF to undergo DEA was initially surprising given the high calculated electron affinities, but further calculations showed that this was a result of the large positive vertical attachment energies (VAEs). This experimental work has been supported by electronic structure calculations at the B3LYP level, and is consistent with those obtained in a crossed electron-molecular beam two sector field mass spectrometer. An unusual observation is that the monomer complexes of ISOF and ENF with O2– are relatively unstable compared with the dimer complexes.Graphical ᅟ

Enhancement of Compound Selectivity Using a Radio Frequency Ion-Funnel Proton Transfer Reaction Mass Spectrometer: Improved Specificity for Explosive Compounds.

A key issue with any analytical system based on mass spectrometry with no initial separation of compounds is to have a high level of confidence in chemical assignment. This is particularly true for areas of security, such as airports, and recent terrorist attacks have highlighted the need for reliable analytical instrumentation. Proton transfer reaction mass spectrometry is a useful technology for these purposes because the chances of false positives are small owing to the use of a mass spectrometric analysis. However, the detection of an ion at a given m/z for an explosive does not guarantee that that explosive is present. There is still some ambiguity associated with any chemical assignment owing to the presence of isobaric compounds and, depending on mass resolution, ions with the same nominal m/z. In this article we describe how for the first time the use of a radio frequency ion-funnel (RFIF) in the reaction region (drift tube) of a proton transfer reaction-time-of-flight-mass spectrometer (PTR-ToF-MS) can be used to enhance specificity by manipulating the ion-molecule chemistry through collisional induced processes. Results for trinitrotoluene, dinitrotoluenes, and nitrotoluenes are presented to demonstrate the advantages of this new RFIF-PTR-ToF-MS for analytical chemical purposes.

Selected Ion Flow-Drift Tube Mass Spectrometry: Quantification of Volatile Compounds in Air and Breath

A selected ion flow-drift tube mass spectrometric analytical technique, SIFDT-MS, is described that extends the established selected ion flow tube mass spectrometry, SIFT-MS, by the inclusion of a static but variable E-field along the axis of the flow tube reactor in which the analytical ion-molecule chemistry occurs. The ion axial speed is increased in proportion to the reduced field strength E/N (N is the carrier gas number density), and the residence/reaction time, t, which is measured by Hadamard transform multiplexing, is correspondingly reduced. To ensure a proper understanding of the physics and ion chemistry underlying SIFDT-MS, ion diffusive loss to the walls of the flow-drift tube and the mobility of injected H3O(+) ions have been studied as a function of E/N. It is seen that the derived diffusion coefficient and mobility of H3O(+) ions are consistent with those previously reported. The rate coefficient has been determined at elevated E/N for the association reaction of the H3O(+) reagent ions with H2O molecules, which is the first step in the production of H3O(+)(H2O)1,2,3 reagent hydrate ions. The production of hydrated analyte ion was also experimentally investigated. The analytical performance of SIFDT-MS is demonstrated by the quantification of acetone and isoprene in exhaled breath. Finally, the essential features of SIFDT-MS and SIFT-MS are compared, notably pointing out that a much lower speed of the flow-drive pump is required for SIFDT-MS, which facilitates the development of smaller cost-effective analytical instruments for real time breath and fluid headspace analyses.

The molecular composition of the planet-forming regions of protoplanetary disks across the luminosity regime

(Abridged) Near- to mid-IR observations of protoplanetary disks show that the inner regions (<10AU) are rich in small organic volatiles (e.g., C2H2 and HCN). Trends in the data suggest that disks around cooler stars (~3000K) are potentially more carbon- and molecule-rich than their hotter counterparts. Our aims are to explore the composition of the planet-forming region of disks around stars from M dwarf to Herbig Ae and compare with the observed trends. Models of the disk physical structure are coupled with a gas-grain chemical network to map the abundances in the planet-forming zone. N2 self shielding, X-ray-induced chemistry, and initial abundances, are investigated. The composition in the 'observable' atmosphere is compared with that in the midplane where the planet-building reservoir resides. M dwarf disk atmospheres are relatively more molecule rich than those for T Tauri or Herbig Ae disks. The weak far-UV flux helps retain this complexity which is enhanced by X-ray-induced ion-molecule chemistry. N2 self shielding has only a small effect and does not explain the higher C2H2/HCN ratios observed towards cooler stars. The models underproduce the OH/H2O column density ratios constrained in Herbig Ae disks, despite reproducing the absolute value for OH: H2O self shielding only increases this discrepency. The disk midplane content is sensitive to the initial main elemental reservoirs. The gas in the inner disk is generally more carbon rich than the midplane ices and is most significant for disks around cooler stars. The atmospheric C/O ratio appears larger than it actually is when calculated using observable tracers only because gas-phase O2 is predicted to be a significant oxygen reservoir. The models suggest that the gas in the inner regions of disks around cooler stars is more carbon rich; however, calculations of the molecular emission are necessary to confirm the observed trends.

Dependence of mesospheric Na and Fe distributions on electron density at Arecibo

We present case studies of the mesospheric alkali and non-alkali metals, Na and Fe, along with electron concentrations [Ne] obtained from measurements made at Arecibo on nights of 17–18 and 18–19 March 2004. The background mesospheric conditions as recorded by an airglow all-sky imager displayed ripple- and band-type structures on these nights. Both of the metals display detailed structures within their neutral sporadic layer but are more pronounced in Na than for Fe. A sporadic-E (Es) with electron concentrations [Ne] exceeding 3000 electrons cm−3 is accompanied by a strong Na enhancement and a weak sporadic Fe (Fes) layer around 95-km altitude. The concentration of Fe+ and Na+ is estimated to be close to 600 and 30 ions.cm−3, respectively, within the sporadic-E layer. In order to investigate ion-neutral coupling, a correlative analysis was performed in two altitude regions. Similar features are seen between neutrals and electrons in the 96–100-km altitude range, while within the altitude range of 80–90 km, an opposite behavior is seen. A comparative study between neutral layers below 90 km often referred to as the main or permanent layer and sporadic activity above 90 km reveals different characteristics for alkali and non-alkali metal. Fe concentrations in the main layer are higher than in Fes resulting in a density ratio of less than 1 determined from two layers of 3 km thickness centered at 97 and 87 km. For the case of Na, the ratio exceeds 1 during Es activity on both the nights. The case studies discussed in this work facilitate our understanding of different factors that can influence the sporadic activity in alkali and non-alkali metals. In a region dominated by ion-molecule chemistry, temperature fluctuations that can be induced by wave activity will have more impact on Na than for Fe within their layers depending on altitude.

CO/H2, C/CO, OH/CO, and OH/O2 in dense interstellar gas: from high ionization to low metallicity

We present numerical computations and analytic scaling relations for interstellar ion-molecule gas phase chemistry down to very low metallicities ($ 10^{-3} \times$ solar), and/or up to high driving ionization rates. Relevant environments include the cool interstellar medium (ISM) in low-metallicity dwarf galaxies, early enriched clouds at the reionization and Pop-II star formation era, and in dense cold gas exposed to intense X-ray or cosmic-ray sources. We focus on the behavior for H$_2$, CO, CH, OH, H$_2$O and O$_2$, at gas temperatures $\sim 100$ K, characteristic of a cooled ISM at low metallicities. We consider shielded or partially shielded one-zone gas parcels, and solve the gas phase chemical rate equations for the steady-state "metal-molecule" abundances for a wide range of ionization parameters, $\zeta/n$, and metallicties, $Z'$. We find that the OH abundances are always maximal near the H-to-H$_2$ conversion points, and that large OH abundances persist at very low metallicities even when the hydrogen is predominantly atomic. We study the OH/O$_2$, C/CO and OH/CO abundance ratios, from large to small, as functions of $\zeta/n$ and $Z'$. Much of the cold dense ISM for the Pop-II generation may have been OH-dominated and atomic rather than CO-dominated and molecular.

Production of and Dissociative Electron Attachment to the Simplest Criegee Intermediate in an Afterglow.

The simplest Criegee intermediate, CH2OO, has been produced in a flowing afterglow using a novel technique. CH2I is produced by dissociative electron attachment to CH2I2, leading to the established reaction CH2I + O2 → CH2OO + I. The presence of CH2OO is established by observation of dissociative electron attachment to yield O(-) using the variable electron and neutral density attachment mass spectrometry (VENDAMS) technique. The measurements establish the electron attachment rate coefficient of thermal electrons at 300 K to CH2OO as 1.2 ± 0.3 × 10(-8) cm(3) s(-1). Thermal electron attachment is solely dissociative and is not a promising route to producing stable CH2OO(-). The results open the possibility of measuring ion-molecule chemistry involving Criegee intermediates, as well as the reactivity of other unstable radicals produced in an analogous manner.