Charge dependence of solvent-mediated intermolecular Coster-Kronig decay dynamics of aqueous ions.
The 2s and 2p photoelectron spectra have been measured for Na(+), Mg(2+), and Al(3+) ions in aqueous solution. In all cases, the 2s lines are significantly broader than the 2p features, which is attributed to a shorter lifetime of the respective 2s hole. Since intraionic Coster-Kronig decay channels from the (2s)(-1) state are closed for free Na(+), Mg(2+), and Al(3+) ions, this is evidence for an intermolecular Coster-Kronig-like process, reminiscent of intermolecular Coulombic decay (ICD), involving neighboring water solvent molecules. The observed 2s Lorentzian line widths correspond to lifetimes of the (2s)(-1) state of 3.1, 1.5, and 0.98 fs for the solvated Na, Mg, and Al ions, respectively.
MAX-lab, Lund University, P.O. Box 118, SE-221 00 Lund, Sweden. gunnar.ohrwall@maxlab.lu.se
G
G
Ohrwall
N
N
Ottosson
W
W
Pokapanich
S
S
Legendre
S
S
Svensson
O
O
Björneholm