Abstract.This paper offers an outline of Laser Induced Fluorescence (LIF) diagnostics and practical recommendations for its use in atmospheric pressure discharges. LIF principles, technical requirements and rationalization of experimental outcomes by modelling are addressed. Important issues that are particularly relevant to small scale, spatially inhomogeneous discharges, like plasma-jets, are emphasized. For the first time, all collision processes and the spatial non-homogeneity of the laser beam are together accounted for in the LIF model. Saturation characteristics are discussed and used for the assessment of model parameters. A calibration procedure is discussed and implemented. Gas temperature measurements by LIF are also addressed. The whole description of the technique is given, without loss of generality, through the example of its application to the OH radical. Notes on other diatomic radicals, CH, NO and CN, are given along the paper. Some results in a RF plasma-jet are presented as an example of application in a discharge system where all the concepts developed in the paper are applied.

This work represents the first experimental demonstration that planar molecules tend to travel as a "frisbee" when a gaseous mixture with lighter carriers expands into a vacuum, the orientation being due to collisions. The molecule is benzene, the prototype of aromatic chemistry. The demonstration is via two complementary experiments: interrogating benzene by IR-laser light and controlling its orientation by selective scattering on rare gas targets. The results cast new light on the microscopic mechanisms of collisional alignment and suggest a useful way to produce intense beams of aligned molecules, permitting studies of steric effects in gas-phase processes and in surface catalysis.

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The large number of elastic and inelastic collisions which take place during supersonic gaseous expansions produce not only acceleration and internal cooling of molecules, but also their alignment or orientation. The collisional alignment of the rotational angular momentum, corresponding to the orientation of the benzene molecular plane, in supersonic seeded expansions with lighter carrier gases is demonstrated via two complementary experiments: one interrogating benzene via polarized laser light IR absorption the other one probing its orientation via molecular beam scattering on rare gas targets. Typical seeding gases are helium, neon and their mixtures, and molecular hydrogen. Total stagnation pressures are of the order of ∼1 bar and ∼0.1 mm nozzle. A propensity is demonstrated for benzene molecules in seeded molecular beams to fly with the molecular plane preferentially oriented parallel to the molecular beam propagation direction. The analysis of the experimental results has been carried out using a phenomenological model which provides the fraction of molecules traveling in such a “frisbee” mode. A frisbee propensity function is defined and found to range between 0.71 and 0.85, corresponding to IR and to scattering experiments, respectively. These values are significantly higher than the value 2/3, expected for a random distribution of molecular plane orientations. The trend in the measured values is discussed in terms of different angular cones of the supersonic expansion sampled in the two experiments and evidence is provided that the orientation is higher the narrower is the sampled cone aperture.

A CO 2 nanosecond repetitively pulsed discharge (NRP) is a harsh environment for laser induced fluorescence (LIF) diagnostics. The difficulties arise from it being a strongly collisional system in which the gas composition, pressure and temperature, have quick and strong variations. The relevant diagnostic problems are described and illustrated through the application of LIF to the measurement of the OH radical in three different discharge configurations, with gas mixtures containing CO 2 +H 2 O. These range from a dielectric barrier NRP with He buffer gas, a less hostile case in which absolute OH density measurement are possible, to an NRP in CO 2 +H 2 O, where the full set of drawbacks is at work. In the last case, the OH density measurement is not possible with laser pulses and detector time resolution in the ns time scale. Nevertheless, it is shown that with a proper knowledge of the collisional rate constants involved in the LIF process, a Collisional Energy Transfer (CET)-LIF methodology is still applicable to deduce the gas composition from the analysis of LIF spectra.