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J Phys Chem Lett
Department of Chemistry, University of Texas at Austin, 105 East 24th Street, Stop A5300, Austin, Texas 78712-1224, United States.
Published: March 2020
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 dimethylformamide (DMF). Picosecond H-bond dynamics are fastest in the intermediate concentration regime (20-50 mol % DMSO), because 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 time scales, 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.
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http://dx.doi.org/10.1021/acs.jpclett.0c00378 | DOI Listing |
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