Title

Dynamic structures of aqueous oxalate and the effects of counterions seen by 2D IR

Document Type

Article

Publication Date

5-14-2012

Abstract

Two dimensional vibrational echo spectra of oxalate in the carboxylate asymmetric stretch region in D 2O show two transitions having anomalously slow spectral diffusion and a third transition having relaxation properties typical of the free carboxylate ion. Quantitative analysis of the frequency shifts of the carboxylate asymmetric stretch modes caused by a singly charged cation in the oxalate hydration shell supports that ion pairs can be responsible for these new transitions. Experimental evidence and DFT calculations are consistent with oxalate forming a mixture of "side-on" and "end on" contact ion pairs wherein the carboxylate groups are protected from mobile heavy water molecules. © the Owner Societies 2012.

Publication Source (Journal or Book title)

Physical Chemistry Chemical Physics

First Page

6219

Last Page

6224

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