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Article
Structure and thermodynamics of H3O+(H2O)8 clusters: A combined molecular dynamics and quantum mechanics approach
Faculty Journal Articles
  • Berhane Temelso
  • Thorsten Koddermann, SCAI
  • Karl K. Kirschner, SCAI
  • Katurah L. Klein, Bucknell University
  • George C. Shields, Bucknell University
Publication Date
1-1-2013
Description
We have studied the structure and stability of (H3O+)(H2O)8 clusters using a combination of molecular dynamics sampling and high-level ab initio calculations. 20 distinct oxygen frameworks are found within 2 kcal/mol of the electronic or standard Gibbs free energy minimum. The impact of quantum zero-point vibrational corrections on the relative stability of these isomers is quite significant. The box-like isomers are favored in terms of electronic energy, but with the inclusion of zero-point vibrational corrections and entropic effects tree-like isomers are favored at higher temperatures. Under conditions from 0 to 298.15 K, the global minimum is predicted to be a tree-like structure with one dangling singly coordinated water molecule. Above 298.15 K, higher entropy tree-like isomers with two or more singly coordinated water molecules are favored. These assignments are generally consistent with experimental IR spectra of (H3O+)(H2O)8 obtained at 150 K.
Disciplines
Journal
Computational and Theoretical Chemistry
Department
Chemistry
Citation Information
Berhane Temelso, Thorsten Koddermann, Karl K. Kirschner, Katurah L. Klein, et al.. "Structure and thermodynamics of H3O+(H2O)8 clusters: A combined molecular dynamics and quantum mechanics approach" Vol. 1021 (2013) p. 240 - 248
Available at: http://works.bepress.com/berhane_temelso/6/