Vibrational Spectroscopy of Bisulfate/Sulfuric Acid/Water Clusters: Structure, Stability, and Infrared Multiple-Photon Dissociation Intensities
The Journal of Physical Chemistry A2013Vol. 117(32), pp. 7081–7090
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Tara I. Yacovitch, Nadja Heine, Claudia Brieger, Torsten Wende, Christian Hock, Daniel M. Neumark, Knut R. Asmis
Abstract
The structure and stability of mass-selected bisulfate, sulfuric acid, and water cluster anions, HSO4(-)(H2SO4)m(H2O)n, are studied by infrared photodissociation spectroscopy aided by electronic structure calculations. The triply hydrogen-bound HSO4(-)(H2SO4) configuration appears as a recurring motif in the bare clusters, while incorporation of water disrupts this stable motif for clusters with m > 1. Infrared-active vibrations predominantly involving distortions of the hydrogen-bound network are notably missing from the infrared multiple-photon dissociation (IRMPD) spectra of these ions but are fully recovered by messenger-tagging the clusters with H2. A simple model is used to explain the observed "IRMPD transparency".
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