Gas-Phase Redox Dynamics in High-Energy Collisions

摘要: Mass analysed ion kinetic energy (MIKE) spectra following collisions have been recorded using a double focusing mass spectrometer with 5 kV acceleration voltage. Metal complexes studied were formed by pick-up of metal atoms in mixed argon/solvent clusters made supersonic expansion. DFT calculations used to rationalise experimental data. Complexes the form MLn+ where M = Mg, Ca, Mn, Cu, and Zn while L NH3, CO2, benzene, pyridine, acetonitrile, acetone collided O2 MgLn+ also N2O, benzene. Complexes few ligands are most prone oxidation due their high speed which facilitates electron transfer. Calculated affinities, Mulliken populations, natural bond orbitals collision gases transfer trends. Collision trap electrons more efficiently if they π-bonds or adjacent electronegative atoms. Metal complex molecular dications H2 determine stability reduced products. No systematic differences found between two at energies examined. The fate monocations depends on relaxation dissociation relaxed monocations. LZ theory was unable explain MIKE spectra. Metal MLn2+ propensity MXLn-m+ CH3X X F Cl. Reactivity is determined IE decrease increasing n. Dications much likely react as can enough internal overcome potential barriers.