Abstract
Perchlorate IR lineshapes in ionic solutions, polymeric membrane, and perchlorate coordinated onto manganese(III) porphyrin were investigated using various model systems. The lineshape of perchlorate ligand is very sensitive to the nanoscopic aqueous environment. The observed asymmetric mode of ligated perchlorate has a smaller bandwidth and faster dynamics than that of 1M perchlorate aqueous solution. When we used chemical exchange models of coherence, the IR lineshapes of 6M-concentrated anionic solutions have better fit. The IR lineshape of 6M-concentrated anionic solution in the polymer matrix was best fitted by assuming the chemical exchange of coherence with spectral diffusion.
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