Integrative data science in mass spectrometry: connecting molecular structures with diverse mass spectrometry fragmentation behaviours

We investigated how molecular structure influences ultraviolet photon dissociation (UVPD), at 266 nm and electron activated dissociation (EAD) of small molecules using a dataset of 178 pesticides. Logistic regression revealed distinct structure–fragmentation relationships and simple models can predict the likelihood of distinct UVPD fragmentation events based purely on molecular structure, while density functional theory (DFT)-based analysis showed that the appearance of [M+H]²⁺• radicals in EAD at energies above 10 eV correlates with their thermodynamic stability. These results support a partial electron removal mechanism in EAD and highlight the predictive value of simple models.