Radiative cooling of cationic carbon clusters, CN+, N = 8, 10, 13-16.

The radiative cooling of highly excited carbon cluster cations of sizes N = 8, 10, 13-16 has been studied in an electrostatic storage ring. The cooling rate constants vary with cluster size from a maximum at N = 8 of 2.6 × 104 s-1 and a minimum at N = 13 of 4.4 × 103 s-1. The high rates indicate that photon emission takes place from electronically excited ions, providing a strong stabilizing cooling of the molecules.

Role of a Neighbor Ion in the Fragmentation Dynamics of Covalent Molecules.

Fragmentation of molecular nitrogen dimers (N_{2})_{2} induced by collision with low energy 90 keV Ar^{9+} ions is studied to evidence the influence of a molecular environment on the fragmentation dynamics of N_{2} cations. Following the capture of three or four electrons from the dimer, the three-body N_{2}^{+}+N^{m+}+N^{n+} [with (m,n)=(1,1) or (1, 2)] fragmentation channels provide clean experimental cases where molecular fragmentation may occur in the presence of a neighbor molecular cation. The effect of the environment on the fragmentation dynamics within the dimer is investigated through the comparison of the kinetic energy release (KER) spectra for these three-body channels and for isolated N_{2}^{(m+n)+} monomer cations. The corresponding KER spectra exhibit energy shifts of the order of 10 eV, attributed to the deformation of the N^{m+}+N^{n+} potential energy curves in the presence of the neighboring N_{2}^{+} cation. The KER structures remain unchanged, indicating that the primary collision process is not significantly affected by the presence of a neighbor molecule.

Interatomic Coulombic decay as a new source of low energy electrons in slow ion-dimer collisions.

We provide the experimental evidence that the single electron capture process in slow collisions between O^{3+} ions and neon dimer targets leads to an unexpected production of low-energy electrons. This production results from the interatomic Coulombic decay process, subsequent to inner-shell single electron capture from one site of the neon dimer. Although pure one-electron capture from the inner shell is expected to be negligible in the low collision energy regime investigated here, the electron production due to this process overtakes by 1 order of magnitude the emission of Auger electrons by the scattered projectiles after double-electron capture. This feature is specific to low charge states of the projectile: similar studies with Xe^{20+} and Ar^{9+} projectiles show no evidence of inner-shell single-electron capture. The dependence of the process on the projectile charge state is interpreted using simple calculations based on the classical over the barrier model.

Atomic site-sensitive processes in low energy ion-dimer collisions.

Electron capture processes for low energy Ar(9+) ions colliding with Ar(2) dimer targets are investigated, focusing attention on charge sharing between the two Ar atoms as a function of the molecular orientation and the impact parameter. A preference for charge-asymmetric dissociation channels is observed, with a strong correlation between the projectile scattering angle and the molecular ion orientation. The measurements here provide clear evidence that projectiles distinguish each atom in the target and that electron capture from near-site atoms is favored. Monte Carlo calculations based on the classical over-the-barrier model, with dimer targets represented as two independent atoms, are compared to the data. They give new insight into the dynamics of the collision by providing, for the different electron capture channels, the two-dimensional probability maps p(b), where b is the impact parameter vector in the molecular frame.

Note: Absolute detection efficiency of a tapered microchannel plate for Ne⁺ ions.

The absolute detection efficiency of a tapered microchannel plate with an open-area ratio of 90% was measured for Ne(+) with energies up to 5 keV, and comparison with the results for Xe(+) was made. As in the case of Xe(+), the maximum detection efficiency was 90%. The energy dependence of the efficiency curves normalized with respect to the open-area ratios was examined based on the scaling law proposed previously.

Cooling dynamics of photoexcited C6(-) and C6H(-).

We report conclusive evidence of an efficient cooling mechanism via the electronic radiative transitions of hot small molecular anions isolated in vacuum. We stored C6(-) and C6H(-) in an ion storage ring and observed laser-induced electron detachment with delays up to several milliseconds. The terminal hydrogen atom caused a drastic change in the decay profiles. The decay of photoexcited C6H(-) is slow and nonexponential, which can be explained by depletion cooling, whereas that for C6(-) occurs extremely fast, on a time scale below 0.1 ms and can only be explained by electronic radiative cooling via low-lying electronic excited states.

Radiative cooling of C7⁻.

The spontaneous and photo-induced neutralization of C7⁻ produced in a laser ablation source was measured in an electrostatic storage ring. The measurements provide three independent determinations of the radiative cooling of the ions, based on the short time spontaneous decay and on the integrated amplitude and the shape of the photo-induced neutralization signal. The amplitude of the photo-induced signal was measured between 0.5 ms and 35 ms and found to depend on photon wavelength and ion storage time. All three signals can be reproduced with identical thermal IR radiative cooling rates with oscillator strengths equal to theoretical predictions. In addition, the measurements provide the excitation energy distribution.

Mobilities of Li(+)-attached butanol isomers in He gas.

Mobilities of Li(+)-attached butanol isomers, (n-BuOH)Li(+), (s-BuOH)Li(+), (i-BuOH)Li(+), and (t-BuOH)Li(+), in helium gas were measured over a range of reduced electric fields (E/N = 25-96 Td) at room temperature. Arrival time measurements accurately identified small differences in the measured mobilities of the isomer ions. At low E/N (≤30 Td, corresponding to a mean collision energy ε≤0.05 eV), (n-BuOH)Li(+) showed a mobility about 1.5% greater than that of the other ions, but at high E/N (≥75 Td, ε≥0.1 eV) its mobility was about 1.1% less.

Direct observation of internal energy distributions of C5(-).

Photon induced decay of C5(-) has been measured in an electrostatic storage ring. The time dependence of the photo-enhanced decay is close to a 1∕t decay which indicates a thermal process. The deviation from the expected power of -1 is quantitatively explained by the small heat capacity of the anion. Measurements of the photo-enhanced decay at different storage times and photon energies allow a determination of the radiative cooling rate and the energy distribution of the ions. The average energy content between 15 and 70 ms is found to vary as time to the power -0.72, and at 50 ms the ions contain an average excitation energy of 0.5 eV. The time dependent energy distribution is consistent with cooling by infrared photon emission if published oscillator strengths are reduced by a factor 2.5, in contrast to cooling of larger molecular carbon-based ions where electronic transitions cause a much stronger cooling.

Asymmetry in multiple-electron capture revealed by radiative charge transfer in Ar dimers.

We measured kinetic energies of the fragment ions of argon dimers multiply ionized by low-energy Ar(9+) collisions. For (Ar2)(4+) dissociation, the asymmetric channel (Ar(3+) + Ar(+)) yield is found unexpectedly higher than the symmetric channel (Ar(2+) + Ar(2+)) yield in contrast with previous observation for covalent molecules or clusters. For the dissociation channel (Ar2)(2+)→Ar(+) + Ar(+), two well-separated peaks were observed, clearly evidencing that the direct Coulombic dissociation and the radiative charge transfer followed by ionic dissociation alternatively occur for the dicationic dimers. The respective intensity of these two peaks provides a direct mean to unravel the respective proportion of one-site and two-site double-electron capture, which are found equal for this collision system.

Absolute cooling rates of freely decaying fullerenes.

The cooling rates of C60- have been measured in an electrostatic storage ring between several hundred mus and several tens of ms with one-photon laser excitation. The absolute energy scale is established by the photon energy, and the cooling time interval is derived from the nonexponential decay of the ensemble of hot molecules. The energy decreases due to the combined action of depletion and thermal emission of IR photons with a total energy loss rate that varies inversely proportional to time, 0.9 eV/t. The radiative component decreases from a few hundred eV/s at submillisecond time scales to several tens of eV/s at 20 ms and confirms that the crossover from depletion to predominantly radiative cooling occurs around 5 ms. The method is applicable to any large molecule or cluster which decays spontaneously, irrespective of the specific decay channel.