Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 6, Issue 10, Pages 1989-1995Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.5b00786
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Funding
- National Science Foundation [CHE-1213289, CHE-1213449]
- JSPS
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1213449, 1213289] Funding Source: National Science Foundation
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The water hexamer and heptamer are the smallest sized water clusters that support three-dimensional hydrogen-bonded networks, with several competing structures that could be altered by interactions with a solute. Using infrared-ultraviolet double resonance spectroscopy, we record isomer-specific OH stretch infrared spectra of gas-phase benzene-(H2O)(6,7) clusters that demonstrate benzene's surprising role in reshaping (H2O)(6,7). The single observed isomer of benzene-(H2O)(6) incorporates an inverted book structure rather than the cage or prism. The main conformer of benzene-(H2O)(7) is an inserted-cubic structure in which benzene replaces one water molecule in the S-4-symmetry cube of the water octamer, inserting itself into the water cluster by engaging as a pi H-bond acceptor with one water and via C-H center dot center dot center dot O donor interactions with two others. The corresponding D-2d-symmetry inserted-cube structure is not observed, consistent with the calculated energetic preference for the S-4 over the D-2d inserted cube. A reduced-dimension model that incorporates stretch-bend Fermi resonance accounts for the spectra in detail and sheds light on the hydrogen-bonding networks themselves and on the perturbations imposed on them by benzene.
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