Radiative cooling of carbon cluster anions C2n+1− (n = 3–5) is investigated using the cryogenic electrostatic ion storage ring DESIREE. Two different strategies are applied to infer infrared emission on slow (milliseconds to seconds) and ultraslow (seconds to minutes) timescales. Initial cooling of the ions over the millisecond timescale is probed indirectly by monitoring the decay in the yield of spontaneous neutralization by thermionic emission. The observed cooling rates are consistent with a statistical model of thermionic electron emission in competition with infrared photon emission due to vibrational de-excitation. Slower cooling over the seconds to minutes timescale associated with infrared emission from low-frequency vibrational modes is probed using time-dependent action spectroscopy. For C9− and C11−, cooling is evidenced by the time-evolution of the yield of photo-induced neutralization following resonant excitation of electronic transitions near the detachment threshold. The cross-section for resonant photo-excitation is at least two orders of magnitude greater than for direct photodetachment. In contrast, C7− lacks electronic transitions near the detachment threshold.

/pdf/radiative-cooling-of-carbon-cluster-anions-c2n-1-n-3-5-3agxp15ir6.pdf

Radiative cooling of carbon cluster anions C2n+1− (n = 3–5)

Electronic structure and spectroscopic properties of some low-lying electronic states of neutral and ionic species CN and CN −

We have used a Monte Carlo trajectory calculation to model the chemiionization reaction, HI+B→I−+HB+. B is, in our experiments, a polyatomic amine, but the model treats it as a single atom. The reaction occurs on two potential energy surfaces, one covalent dissociating to the reactants, and one ionic corresponding to the products. Several restrictions were included in the model to account for the fact that B is really a molecule. Classical trajectories were then run at a range of energies and for several variations of potential parameters. The model showed that the reactive cross section rises rapidly as a function of translational energy and that the dynamic threshold energy is 0.38 eV higher than the minimum energy required to form the products. Product angular distributions at low energies show a peak in the forward direction but give a large amount of scattering at and behind the center of mass, in qualitative agreement with the experiments. As the energy increases, the distribution shifts to smaller ...

Trajectory modeling of organic chemiionization reactions

Molecular beam study of reactions of hydrogen iodide and amines

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Molecular beam study of reactions of hydrogen iodide and amines