Comparison of the thermodynamic and correlation criteria for internal standard selection in laser-induced breakdown spectrometry

• Novel criterion for internal standard selection, based on the correlation of analytical line and reference one
• Comparison of correlation and thermodynamic criteria
• Correlation analysis of the spectrum can be useful for atomic line identification.
• Correlation approach can be used in LTE and non-LTE conditions.

The use of the reference line of an internal standard in LIBS is a usual way to eliminate or reduce the fluctuations of plasma parameters from pulse to pulse as well as from sample to sample. Thermodynamic criterion, i.e. closeness of excitation potentials of the analytical line and the reference one, is often used to select an appropriate reference line. In this work, we propose an alternative criterion based on searching the best correlated pairs of lines under the variations of laser energy. Two criteria were compared for high-alloy steels and soils of different origins. The discrepancy among the values of plasma temperature calculated from Fe I, Mn I and Cr I transitions was found under the conditions of slightly changed laser fluence on steel samples. On the other hand, the agreement between plasma temperatures, obtained for Fe I and Mn I transitions, was demonstrated in plasma on soil samples. Calibration results obtained for manganese in steels and lead in soils show that thermodynamic criterion can be an appropriate way for choosing an internal standard only under LTE conditions. Two lines of Mn I at 403.07 nm and 404.14 nm and Pb I at 405.78 nm were the analytical lines for the quantification of manganese in steels and lead in soils, respectively. The use of the correlative criterion seems to be suitable for internal standardization under LTE or non-LTE conditions. Probable limitations of the correlative criterion and its possibilities to identify weak lines are discussed in the article.