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Title:Electronic Structure And Vibrational Signatures Of The Delocalized Radical In Hydrated Clusters Of Copper (Ïi") Hydroxide, Cuoh+(h2o)0-2
Author(s):Christensen, Elizabeth G.
Contributor(s):Steele, Ryan P; Lutz, Kevin T
Abstract:The copper hydroxide ion, CuOH+ , serves as the catalytic core in several recently developed water-splitting catalysts, and an understanding of its chemistry is critical to determining viable catalytic mechanisms. In spite of its importance, the electronic structure of this open-shell ion has remained ambiguous in the literature. The source of this ambiguity is demonstrated to be the propensity of this ion to exist between traditional Cu(I) and Cu(II) oxidation-state limits. The spin density of the radical is shown to delocalize between the metal center and surrounding ligands, and increasing hydration serves to exacerbate this behavior. Equation-of-motion coupled-cluster methods were needed for spectral simulations, as well as direct simulation of the role of the deuterium “tag” molecules that are used in modern predissociation spectroscopy experiments. This nominally benign tag molecule underwent direct complexation with the open-valence metal ion, thereby forming a species akin to known metal- complexes and strongly impacting the resulting spectrum. Thermal populations of this configuration and other more traditional non-covalently bound isomers led to considerable broadening of the spectral lineshapes. Therefore, at least for the hydrates, these ions serve as a cautionary tale for the spectroscopy community, wherein the role of the tag is far from benign.
Issue Date:2021-06-23
Publisher:International Symposium on Molecular Spectroscopy
Genre:Conference Paper / Presentation
Date Available in IDEALS:2021-09-24

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