Ion-molecule reactions of several ions with ethylene oxide and propenal in a selected ion flow tube.

The selected ion flow tube (SIFT) technique has been used to investigate the ion-molecule reactions of several ions with the neutral molecules ethylene oxide, CH(2)OCH(2)-c, and propenal, CH(2)CHCHO. Both molecules have been identified in hot-core star forming regions [] and have significance to astrochemical models of the interstellar (ISM) and circumstellar medium (CSM). Moreover, the molecules contain functional groups, such as the epoxide group (ethylene oxide) and an aldehyde group, which are part of a conjugated pi-electron system (propenal) whose reactivities have not been studied in detail in gas-phase ion-molecule reactions. The larger recombination energy ions, Ar(+) and N(2)(+), were reacted with the neutrals to give insight into general fragmentation tendencies. These reactions proceeded via dissociative charge-transfer yielding major fragmentation products of CH(3)(+) and HCO(+) for ethylene oxide and CH(2)CH(+) and HCO(+) for propenal. The amino acids glycine and alanine are of particular interest to astrobiology, especially if they can be synthesized in the gas phase. In an attempt to synthesize amino acid precursors, ethylene oxide and propenal were reacted with NH(n)(+) (n = 1-4) and HCNH(+). As might be expected from the proton detachment energies, NH(+), NH(2)(+), and HCNH(+) reacted via proton transfer. NH(3)(+) reacted with each molecule via H-atom abstraction to produce NH(4)(+), and NH(4)(+) reacted via a ternary association. All binary reactions proceeded near the gas kinetic rate. Several associated molecule switching reactions were performed and implications of these reactions to the structures of the association products are discussed Ikeda et al. and Hollis et al.

Electron molecular ion recombination: product excitation and fragmentation.

Electron-ion dissociative recombination is an important ionization loss process in any ionized gas containing molecular ions. This includes the interstellar medium, circumstellar shells, cometary comae, planetary ionospheres, fusion plasma boundaries, combustion flames, laser plasmas and chemical deposition and etching plasmas. In addition to controlling the ionization density, the process generates many radical species, which can contribute to a parallel neutral chemistry. Techniques used to obtain rate data and product information (flowing afterglows and storage rings) are discussed and recent data are reviewed including diatomic to polyatomic ions and cluster ions. The data are divided into rate coefficients and cross sections, including their temperature/energy dependencies, and quantitative identification of neutral reaction products. The latter involve both ground and electronically excited states and including vibrational excitation. The data from the different techniques are compared and trends in the data are examined. The reactions are considered in terms of the basic mechanisms (direct and indirect processes including tunneling) and recent theoretical developments are discussed. Finally, new techniques are mentioned (for product identification; electrostatic storage rings, including single and double rings; Coulomb explosion) and new ways forward are suggested.

C3H3+ isomers: temperature dependencies of production in the H3+ reaction with allene and loss by dissociative recombination with electrons.

A technique has been developed to simultaneously determine recombination rate coefficients, alpha e, and initial concentrations of ion types that coexist in a flowing afterglow plasma. This was tested using the H3(+) + allene reaction in which two different C3H3+ isomers are produced. Use of an electrostatic Langmuir probe enabled the C3H3+ isomer branching ratios for propargyl and cyclic C3H3+ from this allene reaction and their alpha e to be determined over the temperature range 172-489 K. The study showed that the cyclic C3H3+ to propargyl C3H3+ branching ratios from the allene reaction varied from 50/50 at 172 K to 18/82 at 489 K. Over this temperature range, the alpha e for both isomers change only slightly. The room temperature alpha e values for propargyl and cyclic C3H3+ are (1.15 +/- 0.2) x 10(-7) and (8.00 +/- 0.1) x 10(-7) cm3/s, respectively. The data are discussed relative to current theories and in relation to fuel-rich flame chemistry, interstellar molecular synthesis, and modeling of Titan's atmosphere.

Mechanisms of electron-ion recombination of N2H+/N2D+ and HCO+/DCO+ ions: temperature dependence and isotopic effect.

The temperature dependencies of the rate coefficients, alpha(e), for electron-ion dissociative recombination (DR) of N2H+/N2D+ and HCO+/DCO+ ions with electrons have been measured over the range 100-500 K. Also, optical emissions have been detected at approximately 100 K from the N2(B3(pi)g) electronically excited products of N2H+/N2D+ recombination. The measurements were carried out using the classic FALP technique combined with an optical monochromator. For N2H+, there was no variation of alpha(e) with temperature above 200 K, with an average value of alpha(e)(N2H+) = 2.8 x 10(-7) cm3 s(-1). The temperature variation for T approximately 100-300 K observed for alpha(e)(HCO+) is similar to that of N2H+ ions for T approximately 300-500 K. The smaller rate coefficient measured for DCO+ and N2D+ ions shows the influence of an isotope effect. The substantial enhancement of the vibrational level, upsilon' = 6, from the N2B state for N2H+ recombination over N2D+ recombination is consistent with previous result at 300 K and implies the influence of a tunneling mechanism of DR.