Adsorption of water molecules on selected charged sodium-chloride clusters

James A. Bradshaw, Sidney L. Gordon, Andrew J. Leavitt, Robert L. Whetten

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

The adsorption of water molecules (H 2O) on sodium chloride cluster cations and anions was studied at 298 K over a mass range of 100-1200 amu using a custom-built laser desorption ionization reactor and mass spectrometer. Under the conditions used, the cations Na 3Cl 2 + and Na 4Cl 3 + bind up to three water molecules, whereas the larger cations, Na 5Cl 4 + to Na 19Cl 18 +, formed hydrates with one or two only. The overall trend is a decrease in hydration with increasing cluster size, with an abrupt drop occurring at the closed-shell Na 14Cl 13 +. As compared to the cluster cations, the cluster anions showed almost no adsorption. Among smaller clusters, a weak adsorption of one water molecule was observed for the cluster anions Na 6Cl 7 - and Na 7Cl 8 -. In the higher mass region, a substantial adsorption of one water molecule was observed for Na 14Cl 15 -. Density functional theory (DFT) computations were carried out for the adsorption of one molecule of H 2O on the cations Na nCl n-1 +, for n = 2-8, and the anions Na nCl n+1 -, for n = 1-7. For each ion, the structure of the hydrate, the hydration energy, and the standard-state enthalpy, entropy, and Gibbs energy of hydration at 298 K were computed. In addition, it was useful to compute the distortion energy, defined as the electronic energy lost due to weakening of the Na-Cl bonds upon adsorption of H 2O. The results show that strong adsorption of a H 2O molecule occurs for the linear cations only at an end Na ion and for the nonlinear cations only at a corner Na ion bonded to two Cl ions. An unexpected result of the theoretical investigation for the anions is that certain low-energy isomers of Na 6Cl 7 - and Na 7Cl 8 - bind H 2O strongly enough to produce the observed weak adsorption. The possible implications of these results for the initial hydration of extended NaCl surfaces are discussed.

Original languageEnglish (US)
Pages (from-to)27-36
Number of pages10
JournalJournal of Physical Chemistry A
Volume116
Issue number1
DOIs
StatePublished - Jan 12 2012
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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