Experimental bond dissociation energies of benzylpyridinium thermometer ions determined by threshold-CID and RRKM modeling

[Display omitted] •BDE of benzylpyridinium ions were determined by TCID measurements and RRKM modeling.•Commercial QhQ enables relative measurements of critical energies.•Critical energy differences are in agreements with high-level theoretical values.•Fragmentation processes relate to kinetic rather than energetic bottleneck. Benzylpyridinium salts (BPs) have often been used as thermometer ions to obtain an energy calibration of mass spectrometric experiments (in particular to determine internal energy distributions of ions after the ionization process). Fragmentation of BP+ molecular ions is characterized by specific Bond Dissociation Energies (BDE) which depend on the substituent group and its location on the benzyl ring. Although those BDE values are regularly re-evaluated by quantum chemical calculations, their experimental determination is still missing from the literature. In this paper, a modified Quadrupole-hexapole-Quadrupole (QhQ) mass spectrometer is used to obtain such values on 4 BP+ molecular ions (characterized by a wide range of CN bond strengths) using Threshold Collision-Induced Dissociations (TCID) and Rice–Ramsperger–Kassel–Marcus (RRKM) kinetic modeling. It is found that experimental values are systematically 0.5eV lower than their most recent theoretical evaluations. Despite this shift, the absolute critical energy values are maintained in the same order (pOMe