title: Hydrated magnesium cations Mg+(H2O)n, n ≈ 20-60, exhibit chemistry of the hydrated electron in reactions with O2 and CO2.
abstract: Ion-molecule reactions of Mg(+)(H(2)O)(n), n ≈ 20-60, with O(2) and CO(2) are studied by Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry. O(2) and CO(2) are taken up by the clusters. Both reactions correspond to the chemistry of hydrated electrons (H(2)O)(n)(-). Density functional theory calculations predicted that the solvation structures of Mg(+)(H(2)O)(16) contain a hydrated electron that is solvated remotely from a hexa-coordinated Mg(2+). Ion-molecule reactions between Mg(+)(H(2)O)(16) and O(2) or CO(2) are calculated to be highly exothermic. Initially, a solvent-separated ion pair is formed, with the hexa-coordinated Mg(2+) ionic core being well separated from the O(2)(•-) or CO(2)(•-). Rearrangements of the solvation structure are possible and produce a contact-ion pair in which one water molecule in the first solvation shell of Mg(2+) is replaced by O(2)(•-) or CO(2)(•-).
authors.affiliation: Institut für Physikalische Chemie, Christian-Albrechts-Universität zu Kiel, Olshausenstrasse 40, 24098 Kiel, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: van der Linde
authors.forename: Amou
authors.initials: A
authors.lastname: Akhgarnusch
authors.forename: Chi-Kit
authors.initials: CK
authors.lastname: Siu
authors.forename: Martin K
authors.initials: MK
authors.lastname: Beyer