Over the last four years we have illustrated the potential of a novel wavelength-dependent approach in determining molecular processes at work in the photodesorption of interstellar ice analogs. This method, utilizing the unique beam characteristics of the vacuum UV beamline DESIRS at the French synchrotron facility SOLEIL has revealed an efficient indirect desorption mechanism that scales with the electronic excitations in molecular solids. This process, known as DIET--desorption induced by electronic transition--occurs efficiently in ices composed of very volatile species (CO, N2), for which photochemical processes can be neglected. In the present study, we investigate the photodesorption energy dependence of pure and pre-irradiated CO2 ices at 10-40 K and between 7 and 14 eV. The photodesorption from pure CO2 is limited to photon energies above 10.5 eV and is clearly initiated by CO2 excitation and by the contribution of dissociative and recombination channels. The photodesorption from "pre-irradiated" ices is shown to present an efficient additional desorption pathway below 10 eV, dominating the desorption depending on the UV-processing history of the ice film. This effect is identified as an indirect DIET process mediated by photoproduced CO, observed for the first time in the case of less volatile species. The results presented here pinpoint the importance of the interconnection between photodesorption and photochemical processes in interstellar ices driven by UV photons having different energies.
A recent breakthrough in the analysis of Nd IV resulted in the establishment of 37 energy levels of the ground configuration 4f3. We report here the completion to all 41 levels of this configuration. Wavelength measurements extended to 2800 Å and in higher excitation conditions lead to the classification of 1426 lines involving the excited configurations 4f25d, 4f26p, 4f26s. Owing to configuration mixing between 5p64f26p and the core-excited 5p54f4, numerous 5p64f25d–5p54f4 transitions, normally dipole-forbidden, are observed. Altogether 111 odd parity levels and 121 even parity ones have been established. Their parametric least-squares fits have rms deviations of 91 cm−1 and 37 cm−1, respectively. The interaction 5p64f25d–5p54f35d has an impact on the 4f3–4f25d transition probabilities computed by means of the Cowan codes. Theoretical values of lifetimes are reported for all the even parity levels.
The spectrum of neodymium excited by a sliding spark source was photographed on two vacuum ultraviolet normal-incidence spectrographs. About 250 lines attributed to Nd V, hitherto unknown, have been identified. The analysis of this spectrum established all the energy levels of the configurations 4f2, 4f5d, 4f6s and 4f6p (except for 4f2 1S0). Altogether, 48 known levels classify about 160 lines. Their theoretical calculation includes a least-squares fit with an rms error of 28 cm−1 for the even-parity levels and 26 cm−1 for the odd-parity ones, as well as the best values for relevant radial interaction parameters. In particular, interactions with the core-excited configurations 5p54f3 and 5p54f25d are discussed. Intensities derived from phosphor image plates are used to estimate an effective temperature in the spark of Teff=3.6 eV.
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