- Previous Article
- Next Article
- Table of Contents
Journal of Physical Chemistry A, Vol.112, No.9, 1851-1853, 2008
On the determination of monomer dissociation energies of small water clusters from photoionization experiments
Recently, monomer dissociation energies of neutral water clusters were estimated via a thermodynamic cycle that utilized the measured appearance energies of vacuum ultraviolet (VUV) photoionized water clusters and the previously reported dissociation energies of protonated water clusters. The thermodynamic cycle incorrectly assumed that the energy difference between the (H2O)(n)(+) -> (H2O)(n-1)H+ + OH center dot asymptotes (the relaxation energy) was zero. We show that these relaxation energies are large and cannot be neglected in the analysis. Thus, the neutral water cluster monomer dissociation energies cannot be directly determined from the measured ionization potentials because they are themselves involved in the appropriate thermodynamic cycle.