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Microwave Study of Triflic Acid Hydrates: Evidence for the Transition from Hydrogen-Bonded Clusters to a
Anna K Huff1, Nathan Love1, Kenneth R Leopold1
1Department of Chemistry, University of Minnesota, 207 Pleasant Street, SE, Minneapolis, Minnesota 55455, United States.
Abstract:
Rotational spectra of the mono-, di-, and trihydrates of triflic acid, CF3SO3H···(H2O), have been recorded by pulsed nozzle Fourier transform microwave spectroscopy and spectroscopic constants obtained have been compared with values calculated at several levels of theory. The experimental results are consistent with the theoretical predictions presented here and elsewhere, indicating that with only one or two water molecules, triflic acid remains un-ionized in a cold molecular complex. The experiments further concur with theoretical predictions that the addition of a third water molecule transforms the system into what is best regarded as a hydrated hydronium triflate ion pair. Thus, only three water molecules are needed to induce ionization of triflic acid in a cold molecular cluster. This number is somewhat low compared with that for other simple protic acids and likely reflects the superacidity of triflic acid. Simple energetic arguments can be used to rationalize this result.
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