What Nonlinear−IR Experiments Can Tell You about Water that the IR Spectrum Cannot

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Abstract
Frequently, the IR spectrum of water is used to characterize the structure and strength of the associated hydrogen bond network. Here, we use nonlinear−IR spectroscopy to investigate the dynamics of four aqueous systems that have very similar absorption spectra. We address the question: to what extent can the dynamics of water vary in systems with very similar absorption spectra? The results illustrate that the vibrational lifetimes and orientational relaxation time scales vary dramatically between the four samples and do not correlate with the amount of water relative to surfactant or solute in solution. Nonlinear−IR spectroscopies are therefore important for providing detailed information necessary to understand hydrogen bonded systems.

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