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American Chemical Society, The Journal of Physical Chemistry A, 9(112), p. 1851-1853, 2008

DOI: 10.1021/jp710624r

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On the Determination of Monomer Dissociation Energies of Small Water Clusters from Photoionization Experiments

Journal article published in 2008 by Shawn M. Kathmann, Gregory K. Schenter ORCID, Sotiris S. Xantheas ORCID
This paper is available in a repository.
This paper is available in a repository.

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Abstract

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-1H+ + OH* 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.