Super-cooled and glassy water
and
liquid-liquid phase transitions:
a computer simulation
perspective
H.E. Stanley
Department of Physics
Boston University, Boston
Peter H. Poole
Department of Physics
St. Francis Xavier University
Antigonish, Nova Scotia, Canada
Outline of the talk
•Brief Review of Anomalies and Interpretation
models
•The contribution of Simulation
•Liquid-Liquid Critical Point: A review of the last 15
years
•Slow Dynamics
•Connection to the glass-glass transitions
•Landscape Interpretation of the thermodynamic
anomalies and of the Liquid-Liquid CP
Water Anomalies:
Increasing anomalous on supercooling
Diverge ?
Connections between anomalies ?
Dynamic Anomalies
Dh/T=const.
D tD=const.
The Speedy-Angel proposal
1992:Computer
Simulation
Approach to the
Problem (ST2)
The ST2 scenario (1992)
TIP5P
SPC/E
ST2 revisited (P. Poole et al preprint)
Isotherms of pressure vs volume for ST2 water
Cavitation:
nucleation of gas
bubble in
stretched liquid
Liquid-liquid
phase
separation
Isochores of liquid ST2 water
HDL
LDL
New Feature
• HDL = high density liquid
• LDL = low density liquid
liquid + gas
liquid
TMD
LDL
HDL+LDL
HDL
The 2005 ST2 Phase Diagram
Two open problems:
•If there is no reentrant
spinodal, why dynamics is
anomalous ?
•If there are two liquids at low
T, which are the two
corresponding glasses ?
Simulation Study of the
Slow Dynamic
Main Results:
TMCT <-----> Ts
Activated processes for T<TMCT
Strong behavior
PRL 76 1996
F. Starr et al PRE 1999
Fragile-to-Strong Cross-Over
Landscape EOS for supercooled liquids
What can we expect from
simulations (in this context!)
Resolution of the pre-glassy
Behavior (Tg glass, Strong/Fragile). Help from
primitive models.
Study of the phase diagram of polarizable
potentials and (later on) CP calculations
Detailed comparisons with exp data in
confined geometries
Many thanks to….
BU: Nicolas Giovanbattista, Francis
Starr, Steve Harrington, Yamada Masako,
Stefano Mossa
MIT: Sow-Hsin Chen, Paola Gallo
Princeton: Pablo De Benedetti
Bangalore: Sri Sastry
Roma: Emilia La Nave, Piero Tartaglia
And, of course, to Giulia Galli for inviting me here !