Abstract
Molecular ions are key species in the chemistry of the interstellar medium (ISM). Given the low temperatures and number densities typically occurring in the ISM, one of the few available mechanisms to form more complex molecules is through barrierless exothermic reactions, as it is the case for many ion-molecule reactions. Ions are highly reactive species but they can be formed efficiently in the ISM by cosmic-ray or ultraviolet ionization and can survive for relatively long times due to the few collisions they suffer. On earth, molecular ions are “exotic” species much more difficult to produce in appreciable quantities. Electrical discharges in low pressure gases form cold plasmas which can be used to produce molecular ions in abundances high enough to enable their spectroscopic study.
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- 1.
There is nothing magical about these particular frequencies. They are within bands assigned by the International Telecommunication Union for Industrial, Scientific and Medical (ISM!) purposes, other than radiocommunications.
- 2.
Other authors had made significant contributions before and should also be mentioned: Wing et al. (1976) and Carrington and Softley (1983) developed the Doppler-tuned ion-beam infrared spectroscopy technique, in which the transitions of the ions were brought into resonance with a fixed-frequency laser using electric fields and the Doppler effect. Saykally and Evenson (1979) used the Laser Magnetic Resonance technique (LMR), in which far-IR transitions of paramagnetic species (such as HBr+ in that work) were brought into resonance by tuning the transitions with an electric field using the Zeeman effect. In both types of experiments CO2 and CO lasers were used. These are fixed frequency lasers, emitting in the IR, that can only be tuned line-by-line, thus making the techniques applicable only to a few molecules with resonances close to the laser lines. The success of Oka in recording the IR spectrum of the ν 2 band of \(\mathrm {H}_3^+\) was partly due to a high resolution broadly tunable IR source, a difference frequency spectrometer (Pine 1974, 1976) continuously tunable from 2400 to 4500 cm−1.
- 3.
I have already mentioned the problem of detecting small fluctuations in the photon flux received by a detector, especially if the background is strong. Moreover, the quantum efficiency of detectors for low energy photons (like those in the IR or microwave energy range) is rather low. On the contrary, ion-counting techniques are extremely well developed, and even a single ion can be counted.
- 4.
Known to ∼0.1 MHz accuracy (Quinn 2003).
- 5.
Some years later, the rotational transition was accurately measured in Cologne, obtaining a value 262816.904 with σ = 15 kHz (Stoffels et al. 2016).
- 6.
Expected to be in operation in 2019.
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Acknowledgements
The work carried out at the laboratories of the Molecular Physics Department of IEM- CSIC has been partially funded by Spanish MINECO through grants CSD2009-00038 (Consolider Astromol project), FIS2012-38175, FIS2013-408087-C2-1P and FIS2016-77726-C3-1P. Additional partial support has been received from the European Research Council through the Synergy Grant ERC-2013-SyG-610256 NANOCOSMOS. Dr. O. Asvany and the support for a research stay at the University of Cologne by the Deutsche Forschungsgemeinschaft via SFB 956 project B2 are most gratefully acknowledged.
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Doménech, JL. (2018). Infrared Spectroscopy of Ions of Astrophysical Interest. In: Muñoz Caro, G., Escribano, R. (eds) Laboratory Astrophysics . Astrophysics and Space Science Library, vol 451. Springer, Cham. https://doi.org/10.1007/978-3-319-90020-9_13
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