Computational studies of the stability of the (H2O)100 nanodrop
2010 (English)In: Journal of Molecular Structure: THEOCHEM, ISSN 0166-1280, Vol. 944, no 1-3, 163-167 p.Article in journal (Refereed) Published
The stability of the (H2O)100 nanodrop, experimentally known from a polyoxomolybdatecrystal structure (Müller et al. Inorg. Chem. Commun., 2003, 6, 52) and other structuresinferred from clathrate structures, are studied by quantum-chemical B3LYP computations.The free energies are compared to the trends for smaller clusters with 15-30 molecules. Forthe small clusters both cage-based structures and denser structures with a larger number of Hbondsobtained by an evolutionary algorithm (Bandow and Hartke, J. Phys. Chem. A, 2006,110, 5809) are used. The dense structures are most often found to be lower in electronicenergy. The cage-based structures, to which the structure of the experimentally found(H2O)100 cluster can be categorized, become more stable when Gibbs free energy is calculatedat 298 K. Additional cage-based clusters in the 35-81 molecular range were constructed forcomparison. The experimental cluster with 100 molecules (C2h/Ci-symmetry for oxygens/allatoms) and the constructed cluster with 42 molecules are found to be lower in energy than aplausible overall trend. The (H2O)42 cluster has an extraordinary high symmetry (S6), evenwhen the hydrogens are considered. The (H2O)100 cluster is the only of the studied clusters forwhich ΔG is negative at 298 K.
Place, publisher, year, edition, pages
2010. Vol. 944, no 1-3, 163-167 p.
Water clusters, Quantum-chemical computations, Hydrogen bonding, B3LYP calculations, Gibbs free energy
National CategoryNatural Sciences
IdentifiersURN: urn:nbn:se:liu:diva-53176DOI: 10.1016/j.theochem.2009.12.033ISI: 000275688200022OAI: oai:DiVA.org:liu-53176DiVA: diva2:287413
Annika Lenz and Lars Ojamäe, Computational studies of the stability of the (H2O)100 nanodrop, 2010, Journal of Molecular Structure: THEOCHEM, (944), 1-3, 163-167.
Copyright: Elsevier Science B.V., Amsterdam