Turton, D. and Wynne, K. (2014) Stokes−Einstein−Debye failure in molecular orientational diffusion: exception or rule? Journal of Physical Chemistry B, 118(17), pp. 4600-4604. (doi: 10.1021/jp5012457)
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Abstract
The Stokes–Einstein–Debye (SED) expression is used routinely to relate orientational molecular diffusivity quantitatively to viscosity. However, it is well-known that Einstein’s equations are derived from hydrodynamic theory for the diffusion of a Brownian particle in a homogeneous fluid and examples of SED breakdown and failure for molecular diffusion are not unusual. Here, using optical Kerr-effect spectroscopy to measure orientational diffusion for solutions of guanidine hydrochloride in water and mixtures of carbon disulfide with hexadecane, we show that these two contrasting systems each show pronounced exception to the SED relation and ask if it is reasonable to expect molecular diffusion to be a simple function of viscosity.
| Item Type: | Articles |
|---|---|
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Turton, Dr David and Wynne, Professor Klaas |
| Authors: | Turton, D., and Wynne, K. |
| Subjects: | Q Science > QC Physics Q Science > QD Chemistry |
| College/School: | College of Science and Engineering > School of Chemistry |
| Research Group: | Ultrafast chemical physics |
| Journal Name: | Journal of Physical Chemistry B |
| Publisher: | American Chemical Society |
| ISSN: | 1520-6106 |
| ISSN (Online): | 1520-5207 |
| Copyright Holders: | Copyright © 2014 American Chemical Society |
| First Published: | First published in Journal of Physical Chemistry B 118(17):4600-4604 |
| Publisher Policy: | Reproduced in accordance with the copyright policy of the publisher |
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