Liquid-liquid phase separation is common in complex mixtures, but the behavior of nanoconfined liquids is poorly understood from a physical perspective. Dimethyl sulfoxide (DMSO) is an amphiphilic molecule with unique concentration-dependent bulk properties in mixtures with water. Here, we use ultrafast two-dimensional infrared (2D IR) spectroscopy to measure the H-bond dynamics of two probe molecules with different polarities: formamide (FA) and dimethyl formamide (DMF). Picosecond H-bond dynamics are fastest in the intermediate concentration regime (20-50 mol% DMSO); as such confined water exhibits bulk-like dynamics. Each vibrational probe experiences a unique microscopic environment as a result of nanoscale phase separation. Molecular dynamics simulations show that the dynamics span multiple timescales from femtoseconds to nanoseconds. Our studies suggest a previously unknown liquid environment, which we label "local bulk", in which despite the local heterogeneity, the ultrafast H-bond dynamics are similar to bulk water.
Liquid-Liquid Phase Separation Produces Fast H-Bond Dynamics in DMSO-Water Mixtures.
Kwang-Im Oh,Xiao You,Jennifer C Flanagan,Carlos R. Baiz
Published 2020 in Journal of Physical Chemistry Letters
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- Publication year
2020
- Venue
Journal of Physical Chemistry Letters
- Publication date
2020-02-18
- Fields of study
Medicine, Materials Science, Chemistry
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- Source metadata
Semantic Scholar, PubMed
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