Multiphoton dissociation of macromolecular ions at the single-molecule level

The laser-induced decay of ethylene oxide polymer ions of megadalton size has been studied in the multiphoton IR excitation regime, with fragmentation products of individual ions being monitored over long times by a trapping device. The experiment reveals several fragmentation pathways having distinct signatures at the single-molecule level that would not be accessible from studies based on statistically averaged reaction rates only. The observations are supported by dedicated molecular simulations based on a coarse-grained model, which further highlight the role played by continuous heating in such out-of-equilibrium conditions. In particular, both experiment and modeling indicate that the dissociation kinetics depends nonlinearly on heating rate.