Surface electrostatic immobilization of thin layers of water on silver halide. Experimental and calculated infrared spectrum of cyclic trimer of water and a ponderal isotope effect

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Abstract

Evaporation of water on a planar AgX surface leads to a strongly bound monolayer for which IR spectra display the marker peaks for modest numbers of oligomers. From 700-1800 spectra for each isotopomer, H2O 16 and H2O18, a pair was selected with moderate intensity at 1616 cm-1 (a peak reported for the cyclic trimer of water) from the monolayer portion of the experiment. Every selected spectrum had lesser peaks for other oligomers. The sum of a spectroscopic pair reveals the vibrational spectra of the cyclic trimers of H2O16 and H2O18. All fundamentals in the mid-IR are seen including the bending, OH stretching, and intramolecular H-bonding regions, the last never previously recognized. The relative prevalence of cyclic trimer can be attributed to the "low" water concentration on the surface. In addition, a ponderal effect leads to higher concentrations of cyclic trimer in the H2O18 spectra than in the H2O16 spectra and allows observation of combination bands in the H2O 18 spectra, representing a new type of isotope effect. The spectroscopic results for the two water isotopomers are much more extensive than those obtained through matrix isolation. Remarkably complete spectra of the cyclic trimer are obtained for the first time, especially for H 2O18. DFT calculations with the cyclic trimer on a simplified model for the AgCl surface yield spectra consistent with the experimental spectrum. The technique can be extended to other oligomers of water and many other OH compounds.

Original languageEnglish
Pages (from-to)13208-13217
Number of pages10
JournalLangmuir
Volume28
Issue number37
DOIs
StatePublished - 18 Sep 2012

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