Probing Ionic Complexes of Ethylene and Acetylene with Vacuum-Ultraviolet Radiation BandyopadhyayBiswajit SteinTamar FangYigang KostkoOleg WhiteAlec Head-GordonMartin AhmedMusahid 2016 Mixed complexes of acetylene–ethylene are studied using vacuum-ultraviolet (VUV) photoionization mass spectrometry and theoretical calculations. These complexes are produced and ionized at different distances from the exit of a continuous nozzle followed by reflectron time-of-flight mass spectrometry detection. Acetylene, with a higher ionization energy (11.4 eV) than ethylene (10.6 eV), allows for tuning the VUV energy and initializing reactions either from a C<sub>2</sub>H<sub>2</sub><sup>+</sup> or a C<sub>2</sub>H<sub>4</sub><sup>+</sup> cation. Pure acetylene and ethylene expansions are separately carried out to compare, contrast, and hence identify products from the mixed expansion: these are C<sub>3</sub>H<sub>3</sub><sup>+</sup> (<i>m</i>/<i>z</i> = 39), C<sub>4</sub>H<sub>5</sub><sup>+</sup> (<i>m</i>/<i>z</i> = 53), and C<sub>5</sub>H<sub>5</sub><sup>+</sup> (<i>m</i>/<i>z</i> = 65). Intensity distributions of C<sub>2</sub>H<sub>2</sub>, C<sub>2</sub>H<sub>4</sub>, their dimers and reactions products are plotted as a function of ionization distance. These distributions suggest that association mechanisms play a crucial role in product formation closer to the nozzle. Photoionization efficiency (PIE) curves of the mixed complexes demonstrate rising edges closer to both ethylene and acetylene ionization energies. We use density functional theory (ωB97X-V/aug-cc-pVTZ) to study the structures of the neutral and ionized dimers, calculate their adiabatic and vertical ionization energies, as well as the energetics of different isomers on the potential energy surface (PES). Upon ionization, vibrationally excited clusters can use the extra energy to access different isomers on the PES. At farther ionization distances from the nozzle, where the number densities are lower, unimolecular decay is expected to be the dominant mechanism. We discuss the possible decay pathways from the different isomers on the PES and examine the ones that are energetically accessible.