Neutral Density Attachment Mass Spectrometry Research Articles

Excited-State N Atoms Transform Aromatic Hydrocarbons into N-Heterocycles in Low-Temperature Plasmas.

The direct formation of N-heterocycles from aromatic hydrocarbons has been observed in nitrogen-based low-temperature plasmas; the mechanism of this unusual nitrogen-fixation reaction is the topic of this paper. We used homologous aromatic compounds to study their reaction with reactive nitrogen species (RNS) in a dielectric barrier discharge ionization (DBDI) source. Toluene (C7H8) served as a model compound to study the reaction in detail, which leads to the formation of two major products at "high" plasma voltage: a nitrogen-replacement product yielding protonated methylpyridine (C6H8N+) and a protonated nitrogen-addition (C7H8N+) product. We complemented those studies by a series of experiments probing the potential mechanism. Using a series of selected-ion flow tube experiments, we found that N+, N2+, and N4+ react with toluene to form a small abundance of the N-addition product, while N(4S) reacted with toluene cations to form a fragment ion. We created a model for the RNS in the plasma using variable electron and neutral density attachment mass spectrometry in a flowing afterglow Langmuir probe apparatus. These experiments suggested that excited-state nitrogen atoms could be responsible for the N-replacement product. Density functional theory calculations confirmed that the reaction of excited-state nitrogen N(2P) and N(2D) with toluene ions can directly form protonated methylpyridine, ejecting a carbon atom from the aromatic ring. N(2P) is responsible for this reaction in our DBDI source as it has a sufficient lifetime in the plasma and was detected by optical emission spectroscopy measurements, showing an increasing intensity of N(2P) with increasing voltage.

Mutual neutralization of H+ and D+ with the atomic halide anions Cl−,Br−, and I−

Mutual neutralization (MN) rate constants kMN for the reactions of H+ and D+ with the atomic halide anions Cl-, Br-, and I- were measured using the variable electron and neutral density attachment mass spectrometry technique in a flowing afterglow Langmuir probe apparatus. At 300 K, the rate constants for each reaction studied are on the order of 10-8 cm3 s-1. A trend for the rate constants of the systems in this work, kMNCl-<kMNBr-<kMN(I-), is consistent with prior studies of rare gas cation with atomic halide anion MN. A recent theoretical study involving ab initio quantum mechanical treatment of the H++Cl- and D++Cl- reactions reported rate constants significantly lower than the rates reported here. A previously proposed empirical model that predicts atom-atom kMN as a simple function of the total reaction exothermicity shows good agreement with the newly measured rate constants.

Kinetics of Cations with C2 Hydrofluorocarbon Radicals.

Reactions of the cations Ar+, O2+, CO2+, and CF3+ with the C2 radicals C2H5, H2C2F3, C2F3, and C2F5 were investigated using the variable electron and neutral density attachment mass spectrometry technique in a flowing afterglow-Langmuir probe apparatus at room temperature. Rate coefficients for observed product channels for these 16 reactions are reported as well as rate coefficients and product branching fractions for the 16 reactions of the same cations with each of the stable neutrals used as radical precursors (the species RI, where R is the radical studied). Reactions with the stable neutrals proceed by charge transfer at or near the collisional rate coefficient where energetically allowed; where charge transfer is endothermic, bond-breaking/bond-making chemistry occurs. While also efficient, reactions with the radicals are more likely to occur at a smaller fraction of the collisional rate coefficient, and bond-breaking/bond-making chemistry occurs even in some cases where charge transfer is exothermic. It is noted that unlike radical reactions with neutral species, which occur with rate coefficients that are generally elevated compared to those of stable species, ion-radical reactivity is generally decreased relative to that of reactions with stable species. In particular, long-range charge transfer appears more likely to be frustrated in the ion-radical systems.

Dissociative recombination of HCl+, H2Cl+, DCl+, and D2Cl+ in a flowing afterglow.

Dissociative recombination of electrons with HCl+, H2Cl+, DCl+, and D2Cl+ has been measured under thermal conditions at 300, 400, and 500 K using a flowing afterglow-Langmuir probe apparatus. Measurements for HCl+ and DCl+ employed the variable electron and neutral density attachment mass spectrometry (VENDAMS) method, while those for H2Cl+ and D2Cl+ employed both VENDAMS and the more traditional technique of monitoring electron density as a function of reaction time. At 300 K, HCl+ and H2Cl+ recombine with kDR = 7.7±2.14.5 × 10-8 cm3 s-1 and 2.6 ± 0.8 × 10-7 cm3 s-1, respectively, whereas D2Cl+ is roughly half as fast as H2Cl+ with kDR = 1.1 ± 0.3 × 10-7 cm3 s-1 (2σ confidence intervals). DCl+ recombines with a rate coefficient below the approximate detection limit of the method (≲5 × 10-8 cm3 s-1) at all temperatures. Relatively slow dissociative recombination rates have been speculated to be responsible for the large HCl+ and H2Cl+ abundances in interstellar clouds compared to current astrochemical models, but our results imply that the discrepancy must originate elsewhere.

Dissociative recombination and mutual neutralization of heavier molecular ions: C10H8(+), WF5(+), and C(n)F(m)(+).

Dissociative recombination (DR) rate coefficients for the naphthalene cation, C10H8(+), and WF5(+), and mutual neutralization (MN) rate coefficients for these species and five CnFm(+) ions, were determined at 300 K using variable electron and neutral density attachment mass spectrometry (VENDAMS). DR proceeds at 9 ± 3 × 10(-7) cm(3) s(-1) for C10H8(+) and at 6.1 ± 1.4 × 10(-7) cm(3) s(-1) for WF5(+). Consistent with previous results, MN for the polyatomic cations with the halide anions Cl(-), Br(-), and I(-) exhibits an approximate μ(-1/2) reduced mass dependence of the reactant partners, demonstrating that ion collision velocities influence the rate coefficients. This work is an extension of VENDAMS to systems, where low reactant concentrations are necessary to avoid significant reaction of product ions with the neutral precursor, i.e., conditions not suitable for traditional flowing afterglow measurements, as well as to ions of masses > ∼ 100 Da, which are not amenable to the study of DR in magnetic storage rings. Our results expand the sparse literature on DR and MN of heavier ions.

Kinetics and product branching fractions of reactions between a cation and a radical: Ar(+) + CH3 and O2(+) + CH3.

A novel technique is described for the measurement of rate constants and product branching fractions of thermal reactions between cation and radical species. The technique is a variant of the variable electron and neutral density attachment mass spectrometry (VENDAMS) method, employing a flowing afterglow-Langmuir probe apparatus. A radical species is produced in situ via dissociative electron attachment to a neutral precursor; this allows for a quantitative derivation of the radical concentration and, as a result, a quantitative determination of rate constants. The technique is applied to the reactions of Ar(+) and O2(+) with CH3 at 300 K. The Ar(+) + CH3 reaction proceeds near the collisional rate constant of 1.1 × 10(-9) cm(3) s(-1) and has three product channels: → CH3(+) + Ar (k = 5 ± 2 × 10(-10) cm(3) s(-1)), → CH2(+) + H + Ar (k = 7 ± 2 × 10(-10) cm(3) s(-1)), → CH(+) + H2 + Ar (k = 5 ± 3 × 10(-11) cm(3) s(-1)). The O2(+) + CH3 reaction is also efficient, with direct charge transfer yielding CH3(+) as the primary product channel. Several results needed to support these measurements are reported, including the kinetics of Ar(+) and O2(+) with CH3I, electron attachment to CH3I, and mutual neutralization of CH3(+) and CH2(+) with I(-).

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.

Kinetics of ion-ion mutual neutralization: halide anions with polyatomic cations.

The binary mutual neutralization (MN) of a series of 17 cations (O₂⁺, NO(+), NO₂⁺, CO(+), CO₂⁺, Cl(+), Cl₂⁺, SO₂⁺, CF₃⁺, C₂F₅⁺, NH₃⁺, H₃⁺, D₃⁺, H2O(+), H3O(+), ArH(+), ArD(+)) with 3 halide anions (Cl(-), Br(-), I(-)) has been investigated in a flowing afterglow-Langmuir probe apparatus using the variable electron and neutral density attachment mass spectrometry technique. The MN rate constants of atom-atom reactions are dominated by the chemical nature of the system (i.e., the specific locations of curve crossings). As the number of atoms in the system increases, the MN rate constants become dominated instead by the physical nature of the system (e.g., the relative velocity of the reactants). For systems involving 4 or more atoms, the 300 K MN rate constants are well described by 2.7 × 10(-7) μ(-0.5), where the reduced mass is in Da and the resulting rate constants in cm(3) s(-1). An upper limit to the MN rate constants appears well described by the complex potential model described by Hickman assuming a cross-section to neutralization of 11,000 Å(2) at 300 K, equivalent to 3.5 × 10(-7) μ(-0.5).

Mutual neutralization of atomic rare-gas cations (Ne+, Ar+, Kr+, Xe+) with atomic halide anions (Cl−, Br−, I−)

We report thermal rate coefficients for 12 reactions of rare gas cations (Ne(+), Ar(+), Kr(+), Xe(+)) with halide anions (Cl(-), Br(-), I(-)), comprising both mutual neutralization (MN) and transfer ionization. No rate coefficients have been previously reported for these reactions; however, the development of the Variable Electron and Neutral Density Attachment Mass Spectrometry technique makes it possible to measure the difference of the rate coefficients for pairs of parallel reactions in a Flowing Afterglow-Langmuir Probe apparatus. Measurements of 18 such combinations of competing reaction pairs yield an over-determined data set from which a consistent set of rate coefficients of the 12 MN reactions can be deduced. Unlike rate coefficients of MN reactions involving at least one polyatomic ion, which vary by at most a factor of ∼3, those of the atom-atom reactions vary by at least a factor 60 depending on the species. It is found that the rate coefficients involving light rare-gas ions are larger than those for the heavier rare-gas ions, but the opposite trend is observed in the progression from Cl(-) to I(-). The largest rate coefficient is 6.5 × 10(-8) cm(3) s(-1) for Ne(+) with I(-). Rate coefficients for Ar(+), Kr(+), and Xe(+) reacting with Br2 (-) are also reported.

Electron attachment to C2 fluorocarbon radicals at high temperature

Thermal electron attachment to the radical species C2F3 and C2F5 has been studied over the temperature range 300-890 K using the Variable Electron and Neutral Density Attachment Mass Spectrometry technique. Both radicals exclusively undergo dissociative attachment to yield F(-). The rate constant for C2F5 shows little dependence over the temperature range, remaining ~4 × 10(-9) cm(3) s(-1). The rate constant for C2F3 attachment rises steeply with temperature from 3 × 10(-11) cm(3) s(-1) at 300 K to 1 × 10(-9) cm(3) s(-1) at 890 K. The behaviors of both species at high temperature are in agreement with extrapolations previously made from data below 600 K using a recently developed kinetic modeling approach. Measurements were also made on C2F3Br and C2F5Br (used in this work as precursors to the radicals) over the same temperature range, and, for C2F5Br as a function of electron temperature. The attachment rate constants to both species rise with temperature following Arrhenius behavior. The attachment rate constant to C2F5Br falls with increasing electron temperature, in agreement with the kinetic modeling. The current data fall in line with past predictions of the kinetic modeling approach, again showing the utility of this simplified approach.

Communication: Transfer ionization in a thermal reaction of a cation and anion: Ar+ with Br− and I−

We present experimental evidence that reactions of argon cations Ar(+) with the halogen anions Br(-) and I(-) do not occur exclusively by mutual neutralization, but also produce the cations Br(+) or I(+) ions by transfer ionization (TI). The experiments were carried out in flowing-afterglow plasmas at gas temperatures between and 300 and 500 K, and employed a variant of the Variable Electron and Neutral Density Attachment Mass Spectrometry method. The measured TI rate coefficients are 1.9 ± 0.6 × 10(-9) cm(3) s(-1) and 1.1 ± (0.3)(0.8) × 10(-9) cm(3) s(-1) for the Br(-) and I(-) reactions, respectively. We find that the TI rate coefficients decline with temperature as T(-0.5) to T(-1). No indication of TI was found in the reaction with Cl(-), where it is endoergic.

Electron attachment to CF3 and CF3Br at temperatures up to 890 K: Experimental test of the kinetic modeling approach

Thermal rate constants and product branching fractions for electron attachment to CF3Br and the CF3 radical have been measured over the temperature range 300-890 K, the upper limit being restricted by thermal decomposition of CF3Br. Both measurements were made in Flowing Afterglow Langmuir Probe apparatuses; the CF3Br measurement was made using standard techniques, and the CF3 measurement using the Variable Electron and Neutral Density Attachment Mass Spectrometry technique. Attachment to CF3Br proceeds exclusively by the dissociative channel yielding Br(-), with a rate constant increasing from 1.1 × 10(-8) cm(3) s(-1) at 300 K to 5.3 × 10(-8) cm(3) s(-1) at 890 K, somewhat lower than previous data at temperatures up to 777 K. CF3 attachment proceeds through competition between associative attachment yielding CF3 (-) and dissociative attachment yielding F(-). Prior data up to 600 K showed the rate constant monotonically increasing, with the partial rate constant of the dissociative channel following Arrhenius behavior; however, extrapolation of the data using a recently proposed kinetic modeling approach predicted the rate constant to turn over at higher temperatures, despite being only ~5% of the collision rate. The current data agree well with the previous kinetic modeling extrapolation, providing a demonstration of the predictive capabilities of the approach.

Flowing afterglow measurements of the density dependence of gas-phase ion-ion mutual neutralization reactions

We have studied the dependence of several ion-ion mutual neutralization (MN) reactions on helium density in the range from 1.6 × 10(16) to 1.5 × 10(17) cm(-3) at 300 K, using the Variable Electron and Neutral Density Attachment Mass Spectrometry method. The rate coefficients of the reactions Ar(+) + Br2(-), Ar(+) + SF6(-), and Ar(+) + C7F14(-) were found to be independent of gas density over the range studied, in disagreement with earlier observations that similar MN reactions are strongly enhanced at the same gas densities. The cause of the previous enhancement with density is traced to the use of "orbital-motion-limit" theory to infer ion densities from the currents collected by ion-attracting Langmuir probes in a region where it is not applicable.

Electron attachment to fluorocarbon radicals

Thermal electron attachment rate constants for a series of small fluorocarbon radicals (CF(2), C(2)F(3), 1-C(3)F(7), 2-C(3)F(7), C(3)F(5), CF(3)O) were measured from 300 to 600 K using the variable electron and neutral density attachment mass spectrometry method. With the exception of CF(2), for which no attachment was observed, all species exclusively underwent dissociative attachment to yield F(-). The magnitude and temperature dependences of the rate constants varied significantly between species; however, attachment was in all cases inefficient, never exceeding 2% of the calculated collisional value. The data are interpreted and extrapolated to conditions inaccessible to the experiment using a kinetic modeling approach to the electron attachment process.

Electron Attachment to Fe(CO)n (n = 0–5)

The rate constants of thermal electron attachment at 300 and 400 K to Fe(CO)(n) (n = 0-5) have been measured using a flowing afterglow Langmuir probe apparatus. The stable species Fe(CO)(5) was studied using the traditional method of monitoring electron depletion as a function of reaction time, and the remaining short-lived species were studied using the variable electron and neutral density attachment mass spectrometry (VENDAMS) technique. Attachment to Fe(CO)(5) is purely dissociative and about 20% efficient with a rate constant of (7.9 ± 1.4) × 10(-8) cm(3) s(-1) at 300 K and (8.8 ± 2) × 10(-8) cm(3) s(-1) at 400 K. The attachment rate constants decrease significantly as each CO ligand is removed, with Fe(CO)(n) (n = 4 to 1) attaching with efficiencies on the order of 10%, 1%, 0.1%, and 0.01% respectively. Under the conditions here, attachment to Fe(CO)(4) and Fe(CO)(3) are likely entirely dissociative, whereas attachment to Fe(CO)(2) and Fe(CO) are almost entirely associative. A statistical kinetic modeling approach is used to explain the strong dependence of the attachment rate constant on the number of ligands present in the neutral species through a combination of increasing autodetachment rates and decreasing exothermicities to dissociative attachment. The VENDAMS data also define the 300 K mutual neutralization rate constant of Fe(CO)(4)(-) + Ar(+) to be (5.0 ± 0.8) × 10(-8) cm(3) s(-1) with an upper limit to branching fraction of 0.5 to yield Fe(CO)(4), indicating that significant fragmentation to smaller Fe(CO)(n) occurs.

Kinetics of electron attachment to OH and HNO3 and mutual neutralization of Ar+ with NO2− and NO3− at 300 and 500 K

The electron attachment rate constant to nitric acid (HNO(3)) has been measured in a flowing afterglow-Langmuir probe (FALP) apparatus at 300 and 500 K using three independent methods: the traditional FALP technique of monitoring electron depletion, "one-gas" VENDAMS (variable electron and neutral density attachment mass spectrometry), and "two-gas" VENDAMS. The three measurements are in agreement with a 300 K weighted average of 1.4 ± 0.3 × 10(-7) cm(3) s(-1), 2 to 10 times higher than previously reported values. Attachment is primarily dissociative yielding NO(2)(-) as previously reported, but for the first time a small endothermic channel to produce OH(-) was also observed at 500 K. From the one-gas VENDAMS data, associative attachment to the OH produced in the primary attachment was found to occur with an effective two body rate constant of 1.2±(0.7) (3)×10(-11) cm(3) s(-1) at 300 K, the first reported rate constant for this radical species. Finally, ion-ion neutralization rate constants of NO(2)(-) and NO(3)(-) with Ar(+) were determined to be 5.2±(2.5) (1.5) × 10(-8) and 4.5 ± 2.5 × 10(-8) cm(3) s(-1) at 300 K, respectively.

Pressure and temperature dependence of dissociative and non-dissociative electron attachment to CF3: Experiments and kinetic modeling

The kinetics of electron attachment to CF(3) as a function of temperature (300-600 K) and pressure (0.75-2.5 Torr) were studied by variable electron and neutral density attachment mass spectrometry exploiting dissociative electron attachment to CF(3)Br as a radical source. Attachment occurs through competing dissociative (CF(3) + e(-) → CF(2) + F(-)) and non-dissociative channels (CF(3) + e(-) → CF(3)(-)). The rate constant of the dissociative channel increases strongly with temperature, while that of the non-dissociative channel decreases. The rate constant of the non-dissociative channel increases strongly with pressure, while that of the dissociative channel shows little dependence. The total rate constant of electron attachment increases with temperature and with pressure. The system is analyzed by kinetic modeling in terms of statistical theory in order to understand its properties and to extrapolate to conditions beyond those accessible in the experiment.

A new technique to study plasma chemistry kinetics

Accurate kinetics of plasma processes are necessary for modeling of the chemistry occurring in the upper atmosphere, re-entry, combustion, and discharges. While a great deal of data exists in the literature for most types of plasma chemistry processes, there remain gaps for reactions less amenable to traditional measurements. In particular ion-ion mutual neutralization reactions have received relatively little study, and essentially no detailed product branching fractions are known. Similarly, while hundreds of electron attachment rate constants to stable species have been reported, only a handful of measurements of electron attachment rate constants to unstable radical species exist in the literature. We report several measurements involving these classes of reactions using a novel flowing afterglow technique: Variable Electron and Neutral Density Attachment Mass Spectrometry (VENDAMS). The technique takes advantage of these processes occurring as secondary and tertiary chemistry in high density plasmas, and uses excess electrons as chemical ionization agents to monitor neutral product concentrations. Systems starting with a variety of neutrals have been studied over a temperature range of 300 to 550 K. We report several novel measurements including: the first temperature dependences of electron attachment rate constants to radical species; the first complete neutral product distributions of ion-ion mutual neutralization reactions along with the associated temperature dependences; evidence of a novel plasma chemistry process (A+ + B− + e− neutrals + e−), which we term electron catalyzed mutual neutralization.

Temperature dependences of rate coefficients for electron catalyzed mutual neutralization

The flowing afterglow technique of variable electron and neutral density attachment mass spectrometry (VENDAMS) has recently yielded evidence for a novel plasma charge loss process, electron catalyzed mutual neutralization (ECMN), i.e., A(+) + B(-) + e(-) → A + B + e(-). Here, rate constants for ECMN of two polyatomic species (POCl(3)(-) and POCl(2)(-)) and one diatomic species (Br(2)(-)) each with two monatomic cations (Ar(+)and Kr(+)) are measured using VENDAMS over the temperature range 300 K-500 K. All rate constants show a steep negative temperature dependence, consistent with that expected for a three body process involving two ions and an electron. No variation in rate constants as a function of the cation type is observed outside of uncertainty; however, rate constants of the polyatomic anions (~1 × 10(-18) cm(6) s(-1) at 300 K) are measurably higher than that for Br(2)(-) [(5.5 ± 2) × 10(-19) cm(6) s(-1) at 300 K].

Electron-Catalyzed Mutual Neutralization of Various Anions withAr+: Evidence of a New Plasma Process

The mutual neutralization of anions with Ar+ has been studied by variable electron and neutral density attachment mass spectrometry. Evidence of a previously unobserved plasma loss process, electron-catalyzed mutual neutralization (ECMN), e.g., SF6-+Ar+ + e-→neutrals + e-, is reported. Results for 10 species suggest that ECMN occurs generally and significantly affects the total ion-loss rate in plasmas with electron densities exceeding 10(10) cm-3. ECMN is discussed in the context of other known three-body plasma processes, the mechanisms for which appear insufficient to explain the observed effect. A mechanism for ECMN involving an incident electron facilitating energy transfer to the internal modes of the anion is proposed.