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Title:Isolating site-specific spectral signatures of individual water molecules in H-bonded networks with isotopomer-selective, IR-IR double resonance vibrational predissociation spectroscopy
Author(s):Johnson, Mark
Contributor(s):Wolke, Conrad T.
Subject(s):Spectroscopy in Traps
Abstract:We will discuss an experimental method that directly yields the embedded correlations between the two OH stretches and the intramolecular bending modes associated with a single H$_{2}$O water molecule embedded in an otherwise all-D isotopologue. This is accomplished using isotopomer-selective IR-IR hole-burning on the Cs$^{+}$(D$_{2}$O)$_{5}$(H$_{2}$O) clusters formed by gas-phase exchange of a single, intact H$_{2}$O molecule for D$_{2}$O in the Cs$^{+}$(D$_{2}$O)$_{6}$ ion. The OH stretching pattern of the Cs$^{+}$(H$_{2}$O)$_{6}$ isotopologue is accurately recovered by superposition of the isotopomer spectra, thus establishing that the H$_{2}$O incorporation is random and that the OH stretching manifold is largely due to contributions from decoupled water molecules. This behavior enables a powerful new way to extract structural information from vibrational spectra of size-selected clusters by explicitly identifying the local environments responsible for specific infrared features. Extension of this method to address the degree to which OH stretches are decoupled in the protonated water clusters will also be discussed.
Issue Date:2016-06-22
Publisher:International Symposium on Molecular Spectroscopy
Genre:Conference Paper/Presentation
Rights Information:Copyright 2016 by the authors
Date Available in IDEALS:2017-01-26

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