Molecular formation dynamics of 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one, 1,3,5-trinitroperhydro-1,3,5-triazine, and 2,4,6-trinitrotoluene in air, nitrogen, and argon atmospheres studied using femtosecond laser induced breakdown spectroscopy

• LIBS studies of NTO, RDX, and TNT in nitrogen, air, and argon were performed using fs pulses.
• Decay constants of C, CN in three atmospheres were recorded systematically.
• Different molecular to elemental ratios were investigated in detail.
• CN/C and CN/N ratios were observed to be prominent in nitrogen and air atmospheres.

Femtosecond laser induced breakdown spectroscopic (LIBS) studies were performed on three high energy materials namely 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (NTO), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), and 2,4,6-trinitrotoluene (TNT). LIBS spectral features were obtained for these samples in three different atmospheres i.e. air, nitrogen, and argon. Different molecular to elemental ratios in these three atmospheres were investigated in detail. CN/C and CN/N ratios were observed to be prominent in nitrogen and air atmospheres. We attempt to elucidate the role of several reactions involving CN molecular formation in connection with discrepancies obtained in the measured ratios. The complete temporal dynamics of atomic C (247.82 nm) and CN (388.20 nm) molecular species in three different atmospheres are elaborated. The decay rates of C peak were found to be longest (96 ns–121 ns) in argon atmosphere for all the samples. The decay rates of CN peak (388.2 nm) were longer (161 ns–364 ns) in nitrogen compared to air and argon atmospheres. We also attempt to explicate the decay mechanisms with respect to the molecular species formation dynamics in different atmospheres.