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Z. Phys. Chem. 223 (2009) 939–956 . DOI 10.1524.zpch.2009.6064
© by Oldenbourg Wissenschaftsverlag, München
Review paper
Understanding Static and Dynamic
Heterogeneities in Confined Water
By H. Eugene Stanley
*
Center for Polymer Studies and Department of Physics, 590 Commonwealth Avenue, Boston
University, 02215 Boston, MA, USA
Dedicated to Prof. Dr. Alfons Geiger on the occasion of his 65
th
birthday
(Received July 24, 2009; accepted July 26, 2009)
Confined Water . Widom Line
We report recent efforts to understand the new MIT-Messina experimental discovery of a dy-
namic crossover at low temperatures in confined water. Preliminary calculations are not incon-
sistent with one tentative interpretation of this dynamic crossover as resulting from the system
passing from the high-temperature high-pressure "HDL" side of the Widom line (where the
liquid might display fragile behavior) to the low-temperature low-pressure "LDL" side of the
Widom line (where the liquid might display strong behavior). The Widom line - defined to be
the line in the pressure-temperature plane where the correlation length has its maximum - arises
only if there is a critical point. Hence interpreting the MIT experiments in terms of a Widom
line is of potential relevance to testing experimentally, for confined water, the liquid-liquid
critical point hypothesis.
1. Introduction
This author's water research began 30 years ago - when, under the auspices of a
Guggenheim Fellowship, he learned "the facts of water" under the tutelage of
three mentors, J. Teixeira, A. Geiger, and C. A. Angell. The most puzzling facts
dealt with understanding what are the various experimentally-observed cross-
overs and non-monotonic behavior telling us about the underlying physics and
chemistry of water. How can we understand the observed facts that as one cools
below 46
°
C and 35
°
C, respectively, the volume and entropy fluctuations (com-
*
Corresponding author. E-mail: hes@bu.edu