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Issue 18, 2012

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

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Abstract

Two dimensional vibrational echo spectra of oxalate in the carboxylate asymmetric stretch region in D2O 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.

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

Supplementary files

Article information


Submitted
05 Dec 2011
Accepted
13 Jan 2012
First published
13 Jan 2012

Phys. Chem. Chem. Phys., 2012,14, 6219-6224
Article type
Paper

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

D. G. Kuroda and R. M. Hochstrasser, Phys. Chem. Chem. Phys., 2012, 14, 6219 DOI: 10.1039/C2CP23892F

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