Thermochemical studies of hydrated manganese dications, Mn2+(H2O)x (x = 4–9), using guided ion beam tandem mass spectrometry

Abstract

The experimental hydration energies of Mn2+(H2O)x complexes, where x = 4–9, are determined by threshold collision-induced dissociation (TCID) with Xe using a guided ion beam tandem mass spectrometer, coupled with an electrospray ionization (ESI) source. The ESI source naturally produces intense beams of the x = 7–9 complexes, but smaller complexes, x = 4–6, can be formed using an in-source fragmentation technique. For all systems, the dominant fragmentation processes observed are sequential loss of water ligands, but at x = 4 and 5, charge separation (CS) reactions are observed where formation of singularly charged species becomes competitive. Kinetic energy-dependent cross sections are obtained and analyzed to yield 0 K bond dissociation energies (BDEs) for the losses of one and two water ligands, which are then converted to 298 K binding enthalpies and Gibbs energies. Barrier heights for three different CS reactions are also determined. These thermodynamic results are compared with values obtained theoretically, with reasonable agreement being achieved. Theoretical geometry and single-point energy calculations are performed at B3LYP, B3P86, M06, and MP2(full) levels of theory.