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Femtosecond midinfrared study of aggregation behavior in aqueous solutions of amphiphilic molecules

Petersen, C., Bakulin, A. A., Pavelyev, V. G., Pshenichnikov, M. S. & Bakker, H. J., 28-Oct-2010, In : Journal of Chemical Physics. 133, 16, p. 164514-1-164514-8 8 p., 164514.

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We study the spectral and orientational dynamics of HDO molecules in aqueous solutions of different concentrations of tertiary butyl alcohol (TBA) and trimethylamine-N-oxide (TMAO). The spectral dynamics is investigated with femtosecond two-dimensional infrared spectroscopy of the O-H stretch vibration of HDO: D(2)O, and the orientational dynamics is studied with femtosecond polarization-resolved pump-probe spectroscopy of the O-D stretch vibration of HDO: H(2)O. Both the spectral and orientational dynamics are observed to show bimodal behavior: part of the water molecules shows spectral and orientational dynamics similar to bulk liquid water and part of the water molecules displays a much slower dynamics. For low solute concentrations, the latter fraction of slow water increases linearly as a function of solute molality, indicating that the slow water is contained in the solvation shells of TBA and TMAO. At higher concentrations, the fraction of slow water saturates. The saturation behavior is much stronger for TBA solutions than for TMAO solutions, indicating the aggregation of the TBA molecules. (C) 2010 American Institute of Physics. [doi:10.1063/1.3493461]

Original languageEnglish
Article number164514
Pages (from-to)164514-1-164514-8
Number of pages8
JournalJournal of Chemical Physics
Volume133
Issue number16
Publication statusPublished - 28-Oct-2010

    Keywords

  • TERT-BUTYL ALCOHOL, TRIMETHYLAMINE-N-OXIDE, HYDROGEN-BOND DYNAMICS, LIQUID WATER, HYDROPHOBIC HYDRATION, INFRARED-SPECTROSCOPY, METHANOL, BUTANOL, REORIENTATION, ASSOCIATION

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