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Quantitative concentrations measurements using time-resolved laser-induced fluorescence have been demonstrated for nitric oxide (NO) in flame. Fluorescence lifetimes measured using a picosecond Nd:YAG laser and optical parametric amplifier system have been used to directly compensate the measured signal for collisional quenching and evaluate NO concentration. The full evaluation also includes the spectral overlap between the ∼15 cm⁻¹ broad laser pulse and multiple NO absorption lines as well as the populations of the probed energy levels. Effective fluorescence lifetimes of 1.2 and 1.5 ns were measured in prepared NO/N₂/O₂ mixtures at ambient pressure and temperature and in a premixed NH₃-seeded CH₄/N₂/O₂ flame, respectively. Concentrations evaluated from measurements in NO/N₂/O₂ mixtures with NO concentrations of 100–600 ppm were in agreement with set values within 3% at higher concentrations. An accuracy of 13% was estimated by analysis of experimental uncertainties. An NO profile measured in the flame showed concentrations of ∼1000 ppm in the post-flame region and is in good agreement with NO concentrations predicted by a chemical mechanism for NH₃ combustion. An accuracy of 16% was estimated for the flame measurements. The direct concentration evaluation from time-resolved fluorescence allows for quantitative measurements in flames where the composition of major species and their collisional quenching on the probed species is unknown. In particular, this is valid for non-stationary turbulent combustion and implementation of the presented approach for measurements under such conditions is discussed.

In recent years, efforts have been made in catalysis related surface science studies to explore the possibilities to perform experiments at conditions closer to those of a technical catalyst, in particular at increased pressures. Techniques such as high pressure scanning tunneling/atomic force microscopy (HPSTM/AFM), near ambient pressure x-ray photoemission spectroscopy (NAPXPS), surface x-ray diffraction (SXRD) and polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS) at semi-realistic conditions have been used to study the surface structure of model catalysts under reaction conditions, combined with simultaneous mass spectrometry (MS). These studies have provided an increased understanding of the surface dynamics and the structure of the active phase of surfaces and nano particles as a reaction occurs, providing novel information on the structure/activity relationship. However, the surface structure detected during the reaction is sensitive to the composition of the gas phase close to the catalyst surface. Therefore, the catalytic activity of the sample itself will act as a gas-source or gas-sink, and will affect the surface structure, which in turn may complicate the assignment of the active phase. For this reason, we have applied planar laser induced fluorescence (PLIF) to the gas phase in the vicinity of an active model catalysts. Our measurements demonstrate that the gas composition differs significantly close to the catalyst and at the position of the MS, which indeed should have a profound effect on the surface structure. However, PLIF applied to catalytic reactions presents several beneficial properties in addition to investigate the effect of the catalyst on the effective gas composition close to the model catalyst. The high spatial and temporal resolution of PLIF provides a unique tool to visualize the on-set of catalytic reactions and to compare different model catalysts in the same reactive environment. The technique can be applied to a large number of molecules thanks to the technical development of lasers and detectors over the last decades, and is a complementary and visual alternative to traditional MS to be used in environments difficult to asses with MS. In this article we will review general considerations when performing PLIF experiments, our experimental set-up for PLIF and discuss relevant examples of PLIF applied to catalysis.

Intensity fluctuations in lasers are commonly studied above threshold in some special configurations (especially when emission is fed back into the cavity or when two lasers are coupled) and related with their chaotic behaviour. Similar fluctuating instabilities are usually observed in random lasers, which are open systems with plenty of quasi-modes whose non orthogonality enables them to exchange energy and provides the sort of loss mechanism whose interplay with pumping leads to replica symmetry breaking. The latter however, had never been observed in plain cavity lasers where disorder is absent or not intentionally added. Here we show a fluctuating lasing behaviour at the lasing threshold both in solid and liquid dye lasers. Above and below a narrow range around the threshold the spectral line-shape is well correlated with the pump energy. At the threshold such correlation disappears, and the system enters a regime where emitted laser fluctuates between narrow, intense and broad, weak peaks. The immense number of modes and the reduced resonator quality favour the coupling of modes and prepares the system so that replica symmetry breaking occurs without added disorder.