Theoretical study of charge exchange dynamics in He+^+ + NO collisions

We investigate the charge transfer mechanism in the collisions of helium ions on nitric oxide using a molecular description framework with consideration of the orientation of the projectile toward the target. The anisotropy of the collision process has been analysed in detail in connection with the non-adiabatic interactions around avoided crossings. Potential energy curves, radial and rotational coupling matrix elements have been determined by means of ab initio quantum chemical methods. The collision dynamics is performed in the [1.-25.] keV collision energy range using a semiclassical approach, and the total electron transfer cross sections are analysed with regard to available experimental data.Comment: 16 pages, 3 tables, 6 figure

Electron transfer driven decomposition of adenine and selected analogs as probed by experimental and theoretical methods

We report on a combined experimental and theoretical study of electron transfer induced decomposition of adenine and a selection of analogue molecules in collisions with potassium atoms (K). Time-of-flight negative ion mass spectra have been obtained in a wide collision energy range (6–68 eV in the centre-of-mass frame), providing a comprehensive investigation of the fragmentation patterns of purine, adenine, 9-methyl adenine, 6-dimethyl adenine and 2-D adenine. Following our recent communication about selective hydrogen loss from the transient negative ions (TNI) produced in these collisions [T. Dunha et al. J. Chem. Phys. 148, 021101 (2018)], this work focuses on the production of smaller fragment anions. In the low-energy part of the present range, several dissociation channels that are accessible in free electron attachment experiments are absent from the present mass spectra, notably NH2 loss from adenine and 9-methyl adenine. This can be understood in terms of a relatively long transit time of the K+ cation in the vicinity of the TNI tending to enhance the likelihood of intramolecular electron transfer. In this case, the excess energy can be redistributed through the available degrees of freedom inhibiting fragmentation pathways. Ab initio theoretical calculations were performed for 9-methyl adenine (9-mAd) and adenine (Ad) in the presence of a potassium atom and provided a strong basis for the assignment the lowest unoccupied molecular orbitals accessed in the collision process

Potassium-uracil/thymine ring cleavage enhancement as studied in electron transfer experiments and theoretical calculations

We report experimental and theoretical studies on ring cleavage enhancement in collisions of potassium atoms with uracil/thymine in order to further increase the understanding of the complex mechanisms yielding such fragmentation pathways. In these electron transfer processes time-of-flight (TOF) negative ion mass spectra were obtained in the collision energy range 13.5 – 23.0 eV. We note that CNO– is the major ring breaking anion formed and its threshold formation is discussed within the collision energy range studied. Such decomposition process is supported by the first theoretical calculations in order to clarify how DNA/RNA pyrimidine bases fragmentation is enhanced in electron transfer processes yielding ion-pair formation

Fragmentation processes of ionized 5-fluorouracil in the gas phase and within clusters

We have measured mass spectra for positive ions produced from neutral 5-fluorouracil by electron impact at energies from 0 to 100 eV. Fragment ion appearance energies of this (radio-)chemotherapy agent have been determined for the first time and we have identified several new fragment ions of low abundance. The main fragmentations are similar to uracil, involving HNCO loss and subsequent HCN loss, CO loss, or FCCO loss. The features adjacent to these prominent peaks in the mass spectra are attributed to tautomerization preceding the fragmentation and/or the loss of one or two additional hydrogen atoms. A few fragmentions are distinct for 5-fluorouracil compared to uracil, most notably the production of the reactive moiety CF+. Finally, multiphoton ionization mass spectra are compared for 5-fluorouracil from a laser thermal desorption source and from a supersonic expansion source. The detection of a new fragment ion at 114 u in the supersonic expansion experiments provides the first evidence for a clustering effect on the radiation response of 5-fluorouracil. By analogy with previous experiments and calculations on protonated uracil, this is assigned to NH3 loss from protonated 5-fluorouracil

A Kinetic Database For Astrochemistry (KIDA)

We present a novel chemical database for gas-phase astrochemistry. Named the KInetic Database for Astrochemistry (KIDA), this database consists of gas-phase reactions with rate coefficients and uncertainties that will be vetted to the greatest extent possible. Submissions of measured and calculated rate coefficients are welcome, and will be studied by experts before inclusion into the database. Besides providing kinetic information for the interstellar medium, KIDA is planned to contain such data for planetary atmospheres and for circumstellar envelopes. Each year, a subset of the reactions in the database (kida.uva) will be provided as a network for the simulation of the chemistry of dense interstellar clouds with temperatures between 10 K and 300 K. We also provide a code, named Nahoon, to study the time-dependent gas-phase chemistry of zero-dimensional and one-dimensional interstellar sources

Recombination by Electron Capture in the Interstellar Medium

Rate constants for charge transfer processes in the interstellar medium are calculated using ab-initio molecular calculations. Two important reactions are presented: the recombination of Si2+ and Si3+ ions with atomic hydrogen and helium which is critical in determining the fractional abundances of silicon ions, and the C+ + S -> C+ S+ reaction, fundamental in both carbon and sulphur chemistry

TRAPPING OF NOBLE GASES BY RADIATIVE ASSOCIATION WITH H3+{{\rm{H}}}_{3}^{+} IN THE PROTOSOLAR NEBULA

International audienceThe heavy noble gas deficiencies observed in Titan's atmosphere and in comets have been proposed to be related to a sequestration process by H-3(+) in the gas phase at the early protosolar nebula. Chemical thermodynamics and astrophysics modeling are favorable to this hypothesis, as presented in preceding papers. However, there is a point still to be raised, i.e., that no dynamical study of the efficiency of the collisional processes had been performed so far. Here, we show that, apart from the expected exception of Ne, the rate constants obtained, i.e., 0.7 x 10(-18), 0.5 x 10(-16), and 10(-16) (cm(3) s(-1)) for Ar, Kr, and Xe, respectively, are reasonably high for such processes, particularly in the case of Kr and Xe. The temperature dependence is also considered, showing a similar behavior for all noble gases with a peak efficiency in the range 50-60 K. Globally, we can conclude that the scenario of sequestration by H-3(+) is definitively comforted by the results of our quantum dynamical treatment. This process may also be responsible of the Ar impoverishment just measured in comet 67P/Churyumov-Gerasimenko by the ROSINA mass spectrometer on board the Rosetta spacecraft