Nonergodicity in electron capture dissociation investigated using hydrated ion nanocalorimetry.

Hydrated divalent magnesium and calcium clusters are used as nanocalorimeters to measure the internal energy deposited into size-selected clusters upon capture of a thermally generated electron. The infrared radiation emitted from the cell and vacuum chamber surfaces as well as from the heated cathode results in some activation of these clusters, but this activation is minimal. No measurable excitation due to inelastic collisions occurs with the low-energy electrons used under these conditions. Two different dissociation pathways are observed for the divalent clusters that capture an electron: loss of water molecules (Pathway I) and loss of an H atom and water molecules (Pathway II). For Ca(H(2)O)(n)(2+), Pathway I occurs exclusively for n >or= 30 whereas Pathway II occurs exclusively for n <or= 22 with a sharp transition in the branching ratio for these two processes that occurs for n approximately 24. The number of water molecules lost by both pathways increases with increasing cluster size reaching a broad maximum between n = 23 and 32, and then decreases for larger clusters. From the number of water molecules that are lost from the reduced cluster, the average and maximum possible internal energy is determined to be approximately 4.4 and 5.2 eV, respectively, for Ca(H(2)O)(30)(2+). This value is approximately the same as the calculated ionization energies of M(H(2)O)(n)(+), M = Mg and Ca, for large n indicating that the vast majority of the recombination energy is partitioned into internal modes of the ion and that the dissociation of these ions is statistical. For smaller clusters, estimates of the dissociation energies for the loss of H and of water molecules are obtained from theory. For Mg(H(2)O)(n)(2+), n = 4-6, the average internal energy deposition is estimated to be 4.2-4.6 eV. The maximum possible energy deposited into the n = 5 cluster is <7.1 eV, which is significantly less than the calculated recombination energy for this cluster. There does not appear to be a significant trend in the internal energy deposition with cluster size whereas the recombination energy is calculated to increase significantly for clusters with fewer than 10 water molecules. These, and other results, indicate that the dissociation of these smaller clusters is nonergodic.