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.

In exploiting the analytical capabilities of plasma-based spectroscopy method, the evaluation of plasma parameters, particularly the plasma temperature, is a crucial step. In this work, a modified Saha-Boltzmann plot, which uses the columnar densities of atomic and ionic ground levels, is utilized to calculate the plasma temperature in a laser-induced plasma from an aluminum alloy target. The columnar densities are here calculated by quantifying the self-absorption of resonance lines. It is demonstrated that this is a promising method for accurate determination of plasma temperature. To validate the capability of this technique, plasma emission is measured at different gate delay times. For each delay, excitation temperature is calculated both by the conventional Saha-Boltzmann plot (by using the excited states) and by exploiting the new Columnar Density Saha-Boltzmann (CD-SB) plot. The results suggest that at later times of the plasma evolution, the CD-SB plot can be more suitable for the determination of plasma temperature than conventional Saha-Boltzmann plot. These findings provide a new approach for physical characterization of plasmas and give access to a wealth of information about the state of plasma.