We demonstrate a method for isolating the vibrational predissociation spectra of different structural isomers of mass-selected cluster ions based on a population-labeling double resonance scheme. This involves a variation on the “ion dip” approach and is carried out with three stages of mass selection in order to separate the fragment ion signals arising from a fixed-frequency population-monitoring laser and those generated by a scanned laser that removes population of species resonant in the course of the scan. We demonstrate the method on the Ar-tagged cluster, where we identify the spectral patterns arising from two isomers. One of these structures features accommodation of the water molecule in a double H-bond arrangement, while in the other, attaches in a single ionic H-bond motif where the nominally free OH group is oriented toward the N atom of . Transitions derived from both the and constituents are observed for both isomers, allowing us to gauge the distortions suffered by both the ion and solvent molecules in the different hydration arrangements.
Isolating the spectra of cluster ion isomers using Ar-“tag” -mediated IR-IR double resonance within the vibrational manifolds: Application to
Ben M. Elliott, Rachael A. Relph, Joseph R. Roscioli, Joseph C. Bopp, George H. Gardenier, Timothy L. Guasco, Mark A. Johnson; Isolating the spectra of cluster ion isomers using Ar-“tag” -mediated IR-IR double resonance within the vibrational manifolds: Application to . J. Chem. Phys. 7 September 2008; 129 (9): 094303. https://doi.org/10.1063/1.2966002
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