Realistic simulation of molecular emission spectra: an advancement in direct calibration-free isotopic analysis

This study employs Calibration-Free Laser Ablation Molecular Isotopic Spectrometry (CF-LAMIS), enhanced by the Molecular spectrA simulator under Born–OppenHeimer Approximation anD Boltzmann Equilibrium enVironment (MAHADEV) algorithm and its AWGN (Additive White Gaussian Noise) incorporated variant to directly analyse boron isotopes in natural boric acid samples and nuclear-grade boron carbide (B4C) samples. The boric acid samples yielded accuracy and precision consistent with previous studies. Initial analyses of B4C samples were challenged by the atomic and ionic interference lines. However, the BO:B-X (0–1) ro-vibrational band (RVB) was found to have fewer interferences, providing a clearer analytical window at longer acquisition delay times (td = 22 μs). This approach achieved reasonable accuracy and precision levels comparable to those obtained from pure boric acid samples, demonstrating the effectiveness of the CF-LAMIS method in handling complex matrices. The application of the AWGN–MAHADEV algorithm provided isotopic composition with significant (~ 50%) improvement in precision while maintaining comparable accuracy. Boric acid samples achieved an accuracy and precision of 0.3% and 0.8% respectively, while natural and 10B-enriched B4C samples achieved an accuracy of 0.7% and 0.2% and a precision of 0.9% and 0.6% respectively. This study highlights the potential of noise integration in calibration-free methods to achieve more precise and accurate results.