super-cooled and glassy water and liquid-liquid phase transitions: a computer simulation perspective...

Super-cooled and glassy water and

liquid-liquid phase transitions: a computer simulation

perspectivePeter H. PoolePeter H. Poole

Department of PhysicsDepartment of PhysicsSt. Francis Xavier UniversitySt. Francis Xavier University

Antigonish, Nova Scotia, CanadaAntigonish, Nova Scotia, Canada

H.E. StanleyH.E. StanleyDepartment of PhysicsDepartment of Physics

Boston University, BostonBoston University, Boston

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 supercoolingDiverge ?Connections between anomalies ?

Dynamic Anomalies

D/T=const.

D D=const.

The Speedy-Angel proposal

1992:Computer

Simulation

Approach to the

Problem (ST2)

The ST2 scenario (1992)

SPC/E

TIP5P

Isotherms of pressure vs volume for ST2 water Cavitation: nucleation of gas bubble in stretched liquid

Liquid-liquid phase separation

ST2 revisited (P. Poole et al preprint)

Isochores of liquid ST2 water

New Feature

LDL

HDL

TMD

liqui

d +

gas

liquid

LDLHDLHDL+LDL

• HDL = high density liquid • LDL = low density liquid

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

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

What can we expect from simulations (in this context!)

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 !