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Darya Kisuryna

Publications and source records attributed to Darya Kisuryna.

2 recordsLinked to original sources

Charge transfer from ammonia neutralizes propylene oxide cations: Implications for the astrochemistry of chiral molecules

To date only one chiral species, propylene oxide, has been observed in the interstellar medium but little is known about the chemistry that leads to a detectable abundance of this molecule in Sagittarius B2. We used a glow-discharge ion source and a room-temperature ion trap to study the neutralization reactions necessary to convert propylene oxide cation (PO$^+$) -- the assumed precursor for propylene oxide in space -- into the observed astrochemical. We found that the charge-transfer reaction between PO$^+$ and ammonia (NH$_3$) proceeds with a pressure-independent rate coefficient of $(1.39\pm0.03)\times10^{-12}$ cm$^{3}$ s$^{-1}$ to neutralize PO$^+$ and form the radical cation NH$_3$. Although this measured rate coefficient is much slower than that predicted by capture theories, the high abundance of NH$_3$ in Sagittarius B2 motivates the inclusion of this reaction in astrochemical models. We hypothesize that the low ionization energies of many chiral molecules important to origin-of-life theories means these species may exist as cations in the interstellar medium.

physics.chem-ph

Development of a glow-discharge ion-trap instrument for measuring effective radiative-association rate coefficients

The ability to directly measure radiative-association rate coefficients for reactions between ions and neutral molecules has long challenged chemical physics laboratories, yet radiative association is one of the most important processes occurring in cold, diffuse regions of space. A reaction kinetics instrument has been developed for the investigation of ion--molecule radiative-association reactions, aimed at measuring slow, effective reaction rate coefficients for species relevant to astrophysical objects. The instrument consists of a glow-discharge ion source for production of bright and stable ion currents, a quadrupole mass filter for mass selection and detection, and a quadrupole ion trap capable of trapping reactants and products for the long times needed to measure slow kinetics. The performance and adaptability of the glow-discharge ion source has been evaluated using several configurations. To assess the feasibility of measuring reaction rate coefficients, the reaction of Ag$^{+}$ and O$_{2}$ was studied under pseudo-first-order conditions in the ion trap at room temperature. We present the first pressure-dependent study of this reaction and extract a lower limit of $1 \times 10^{-15}$ cm$^3$ molecule$^{-1}$ s$^{-1}$ for the Ag$^{+}$ + O$_{2}$ effective radiative-association rate coefficient. Measurements of effective radiative-association rate coefficients are possible for diverse atomic and molecular ions that react with neutral molecules over a range of rates in this versatile new instrument.

physics.chem-ph