Justin P. Wiens

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).

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(-).

Collisions of sodium atoms with liquid glycerol: Insights into solvation and ionization

The reactive uptake and ionization of sodium atoms in glycerol were investigated by gas-liquid scattering experiments and ab initio molecular dynamics (AIMD) simulations. A nearly effusive beam of Na atoms at 670 K was directed at liquid glycerol in vacuum, and the scattered Na atoms were detected by a rotatable mass spectrometer. The Na velocity and angular distributions imply that all impinging Na atoms that thermally equilibrate on the surface remain behind, likely ionizing to e(-) and Na(+). The reactive uptake of Na atoms into glycerol was determined to be greater than 75%. Complementary AIMD simulations of Na striking a 17-molecule glycerol cluster indicate that the glycerol hydroxyl groups reorient around the Na atom as it makes contact with the cluster and begins to ionize. Although complete ionization did not occur during the 10 ps simulation, distinct correlations among the extent of ionization, separation between Na(+) and e(-), solvent coordination, and binding energies of the Na atom and electron were observed. The combination of experiments and simulations indicates that Na-atom deposition provides a low-energy pathway for generating solvated electrons in the near-interfacial region of protic liquids.

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.

Reaction of the CF3 Radical with Various Cations (Ar+, Xe+, O2+, NO+, CO2+, C2F5+)

Abstract The kinetics of reactions of the trifluoromethyl radical (CF3) with several simple cations (Ar+, Xe+, O2+, NO+, CO2+, C2F5+) are studied via the variable electron and neutral density attachment mass spectrometry (VENDAMS) technique. CF3 is produced via dissociative electron attachment to CF3I, resulting in radical concentrations that are smaller than produced using pyrolysis methods, but better quantified. Rate constants and product branching fractions are reported, with typical uncertainties of ∼ 30%. Three of the reactions, Ar+, O2+, and C2F5+ proceed near the calculated collisional rate constant, while the other reactions are between 10% – 30% efficient. The inefficiency of the reactions of Xe+ and CO2+ can be explained by the reactions strictly obeying spin-conservation. The reaction of Ar+ yields predominantly (90%) CF2+ via dissociative charge transfer, with a minor channel to CF3+. The reaction of C2F5+ yields predominantly CF3+ with a second channel (∼ 25%) yielding C2F4+ and CF4, the only example here of a bond-breaking and bond-making reaction. For the other four reactions, only charge transfer to yield CF3+ is observed. Rate constants for these same ions with CF3I are also reported and found to be rapid with a variety of products formed.

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.

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.