Mark Pond1, Gaurav Goel1, William P. Krekelberg1, Vincent K. Shen2, Jeffrey R. Errington3, and Thomas M. Truskett4. (1) Department of Chemical Engineering, The University of Texas at Austin, 1 University Station, C0400, Austin, TX 78712, (2) Physical and Chemical Properties Division, NIST, 100 Bureau Dr. MS 8380, Gaithersburg, MD 20899-8380, (3) Chemical and Biological Engineering, University at Buffalo, 303 Furnas Hall, Buffalo, NY 14260, (4) Department of Chemical Engineering and Institute for Theoretical Chemistry, The University of Texas at Austin, 1 University Station, C0400, Austin, TX 78712
The transport properties of a variety of bulk and confined equilibrium fluids show a simple, quasi-universal correlation to their structure [1,3]. However, recent studies have shown that diffusivity and viscosity of supercooled bulk fluids develop different couplings to structure [2]. Interestingly, this provides a structural interpretation for the breakdown of the Stokes-Einstein relationship. It has been shown that confinement shifts the onset of supercooled dynamics [4]. This leads to a number of open questions in regards to supercooled confined fluids. First, how does confinement affect the coupling between structure and dynamics? Second, does the Stokes-Einstein relationship break down, and if so can this be interpreted in terms of structure? In this work, we address these questions via molecular simulation and theory.
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[2] - W. P. Krekelberg, J. Mittal, V.Ganesan and T. M. Truskett, The Journal of Chemical Physics 127, 044502 (2007).
[3] - J. Mittal, V. K.Shen, J. R. Errington and T. M. Truskett, The Journal of Chemical Physics 127, 154513 (2007).
[4] - C. R. Nugent, K. V. Edmond, H. N. Patel and E. R. Weeks, Physical Review Letters 99, 025702 (2007).