In this review, we report and critically discuss the application of LIBS for the determination of plasma-emission fundamental parameters, such as transition probabilities, oscillator strengths, Stark broadening and shifts, of the emission lines in the spectrum. The knowledge of these parameters is of paramount importance for plasma diagnostics or for quantitative analysis using calibration-free LIBS methods. In the first part, the theoretical basis of the analysis is laid down; in the second part, the main experimental and analytical approaches for the determination by LIBS of the spectral line spectroscopic parameters are presented. In the conclusion, the future perspectives of this kind of analysis are discussed.
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