New quantitative structure-fragmentation relationship strategy for chemical structure identification using the calculated enthalpy of formation as a descriptor for the fragments produced in electron ionization mass spectrometry: a case study with tetrachlorinated biphenyls.

Differential mass spectrometry correlated with quantum chemical calculations (QCC-ΔMS) has been shown to be an efficient tool for the chemical structure identification (CSI) of isomers with similar mass spectra. For this type of analysis, we report here a new strategy based on ordering (ORD), linear correlation (LCOR) algorithms, and their coupling, to filter the most probable structures corresponding to similar mass spectra belonging to a group with dozens of isomers (e.g.