Coulomb Explosion Dynamics of Multiply Charged para-Nitrotoluene Cations

This work explores Coulomb explosion (CE) dissociation pathways in multiply charged cations of para-nitrotoluene (PNT), a model compound for nitroaromatic energetic molecules. Experiments using strong-field ionization and mass spectrometry indicate that metastable cations PNT²⁺ and PNT³⁺ undergo CE to produce NO₂⁺ and NO⁺. The experimentally measured kinetic energy release from CE upon formation of NO₂⁺ and NO⁺ agrees qualitatively with the kinetic energy release predicted by computations of the reaction pathways in PNT²⁺ and PNT³⁺ using density functional theory (DFT). Both DFT computations and mass spectrometry identified additional products from CE of highly charged PNT cations with q > 3. The dynamical timescales required for direct CE of PNT²⁺ and PNT³⁺ to produce NO₂⁺ were estimated to be 200 and 90 fs, respectively, using ultrafast disruptive probing measurements.