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Water dynamics in large and small reverse micelles: From two ensembles to collective behavior
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10.1063/1.3159779
/content/aip/journal/jcp/131/1/10.1063/1.3159779
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/1/10.1063/1.3159779
View: Figures

Figures

Image of FIG. 1.
FIG. 1.

The structure of AOT.

Image of FIG. 2.
FIG. 2.

Infrared absorption spectra of the OD stretch of dilute HOD in in bulk water and in AOT reverse micelles. The spectrum shifts to higher frequencies as the reverse micelle size decreases.

Image of FIG. 3.
FIG. 3.

Two component fit to the spectrum of the reverse micelle. The core spectrum is the spectrum of bulk water and the interfacial spectrum is the spectrum of the reverse micelle.

Image of FIG. 4.
FIG. 4.

Semilog plot of the vibrational population relaxation of the OD stretch at for a range of reverse micelle sizes. As the reverse micelle size decreases, the vibrational relaxation becomes slower. All decays are biexponential, as shown by the deviation from the straight dashed lines for the data.

Image of FIG. 5.
FIG. 5.

Anisotropy decays at for the large reverse micelles. The solid lines are the results of simultaneous fits of the vibrational population relaxation and anisotropy decays for a range of frequencies for each reverse micelle based on a two component model consisting of a bulk water core and interfacial water.

Image of FIG. 6.
FIG. 6.

Vibrational population relaxation of the OD stretch at several frequencies for the reverse micelle. There is a frequency dependence to the vibrational lifetime demonstrating that the HOD molecules experience slightly different environments in spite of the fact that nearly all of them are interacting directly with the interface.

Image of FIG. 7.
FIG. 7.

Anisotropy decays for bulk water and three frequencies for the reverse micelle. After an initial fast decay that has a frequency dependent amplitude, the long time anisotropy decay in the reverse micelle is frequency independent, demonstrating that the long time orientational dynamics of all the water in the reverse micelle are the same.

Image of FIG. 8.
FIG. 8.

Anisotropy decays at three frequencies for the reverse micelle. After an initial fast decay that has a frequency dependent amplitude, the long time anisotropy decay in the reverse micelle is frequency independent, demonstrating that the long time orientational dynamics of all water in the reverse micelle are the same.

Image of FIG. 9.
FIG. 9.

Anisotropy decay at for the and reverse micelles. The has a fast decay to a plateau similar to the larger reverse micelles (see Fig. 5) while the has a fast decay that leads into a slower long time decay. This indicates that the dynamics of water in the reverse micelle are not collective like the dynamics but may be described using a two component model like the larger reverse micelles.

Image of FIG. 10.
FIG. 10.

Anisotropy decay at for the reverse micelle. The red solid line is the result of a simultaneous fit of the anisotropy and lifetime decays for a range of frequencies assuming the same time constants as the large reverse micelles. The fit misses the data at both short and long times. The black solid line is the result of a simultaneous fit of the anisotropy and lifetime decays for a range of frequencies allowing the lifetimes and orientational times to vary but restricting them to be slower than bulk water and the interfacial water found in the large reverse micelles.

Image of FIG. 11.
FIG. 11.

Surface area per AOT reproduced from Ref. 3. The surface area increases rapidly up to . The change in area shows that dramatic changes occur in the reverse micelle interface with size for small reverse micelles. The surface area per AOT is essentially constant above , showing the similarity of the interface for all of the large reverse micelles.

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/content/aip/journal/jcp/131/1/10.1063/1.3159779
2009-07-07
2014-04-19
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Water dynamics in large and small reverse micelles: From two ensembles to collective behavior
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/1/10.1063/1.3159779
10.1063/1.3159779
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