Download - 5th Liquid Matter Conference
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Konstanz, 14-18 September 2002
Potential Energy Landscape Equation of State
Emilia La Nave, Francesco Sciortino, Piero Tartaglia (Roma)
Stefano Mossa (Boston/Paris)
5th Liquid Matter Conference
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IS
Pe
IS
Statistical description of the number, depth and shapeof the PEL basins
Potential Energy Landscape
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fbasin i(T)= -kBT ln[Zi(T)]
all basins i
fbasin(eIS,T)= eIS+
kBTln [hj(eIS)/kBT] +
fanharmonic(T)
normal modes j
Z(T)= Zi(T)
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Thermodynamics in the IS formalismStillinger-Weber
F(T)=-kBT ln[(<eIS>)]+fbasin(<eIS>,T)
with
fbasin(eIS,T)= eIS+fvib(eIS,T)
and
Sconf(T)=kBln[(<eIS>)]
Basin depth and shape
Number of explored basins
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Real Space
rN
Distribution of local minima (eIS)
Vibrations (evib)
+
eIS
e vib
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F(T)=-kBT ln[(<eIS>)]+fbasin(<eIS>,T)
From simulations…..• <eIS>(T) (steepest descent minimization)
• fbasin(eIS,T) (harmonic and anharmonic
contributions)
• F(T) (thermodynamic integration from ideal gas)
Data for two rigid-molecule models: LW-OTP, SPC/E-H20
In this talk…..
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Basin Free Energy
ln[i(eIS)]=a+b eIS
SPC/E LW-OTP
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The Random Energy Model for eIS
Hypothesis:
Predictions:
eIS)deIS=eN -----------------deIS
e-(eIS
-E0)2/22
22
ln[i(eIS)]=a+b eIS
<eIS(T)>=E0-b2 - 2/kT
Sconf(T)=N- (<eIS (T)>-E0)2/22
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eIS=eiIS
E0=<eNIS>=Ne1
IS
2= 2N=N 2
1
Gaussian Distribution ?
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T-dependence of <eIS> (SPC/E)
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T-dependence of <eIS> (LW-OTP)
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T-dependence of Sconf (SPC/E)(SPC/E)
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The V-dependence of , 2, E0
eIS)deIS=eN -----------------deISe-(e
IS -E
0)2/22
22
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Landscape Equation of State
P=-∂F/∂V|T
F(V,T)=-TSconf(T,V)+<eIS(T,V)>+fvib(T,V)
In Gaussian (and harmonic) approximationP(T,V)=Pconst(V)+PT(V) T + P1/T(V)/T
Pconst(V)= - d/dV [E0-b2]PT(V) =R d/dV [-a-bE0+b22/2]P1/T(V) = d/dV [2/2R]
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Developing an EOS based on PES properties
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SPC/E Water P(T,V)=Pconst(V)+PT(V) T + P1/T(V)/T
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Conclusion I
The V-dependence of the statistical properties of the PEL has been quantified for two models of molecular liquids
Accurate EOS can be constructed from these information
Interesting features of the liquid state (TMD line) can be correlated to features of the PEL statistical properties
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Aging in the PEL-IS framework
Starting Configuration
(Ti)
Short after the T-change
(Ti->Tf)
Long timeT
i
Tf
Tf
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Reconstructing P(T,V) P=-∂F/∂V
F(V,T)=-TSconf(T,V)+<eIS(T,V)>+fvib(T,V)
P(T,V)= Pconf(T,V) + Pvib(T,V)
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From Equilibrium to OOE….
P(T,V)= Pconf(T,V)+ Pvib(T,V)
If we know which equilibrium basin the system is exploring…
eIS acts as a fictive T !
eIS(V,Tf).VPconf
eIS(V,Tf),V,Tlog()Pvib
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Numerical TestsHeating a glass at constant P
T
P
time
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Numerical TestsCompressing at constant T
Pf
T
time
Pi
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Liquid-to-Liquid
T-jump at constant V
P-jump at constant T
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Conclusion IIThe hypothesis that the system samples in aging the same basins explored in equilibrium allows to develop an EOS for OOE-liquids depending on one additional parameter
Small aging times, small perturbations are consistent with such hipothesis. Work is requested to evaluate the limit of validity.
This parameter can be chosen as fictive T, fictive P or depth of the explored basin eIS
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Perspectives
An improved description of the statistical properties of the potential energy surface.
Role of the statistical properties of the PEL in liquid phenomena
A deeper understanding of the concept of Pconf and of EOS of a glass.
An estimate of the limit of validity of the assumption that a glass is a frozen liquid (number of parameters)
Connections between PEL properties and Dynamics
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References and Acknowledgements
We acknowledge important discussions, comments, criticisms from P. Debenedetti, S. Sastry, R. Speedy, A. Angell, T. Keyes, G. Ruocco and collaborators
Francesco Sciortino and Piero TartagliaExtension of the Fluctuation-Dissipation theoremto the physical aging of a model glass-forming liquidPhys. Rev. Lett. 86 107 (2001).Emilia La Nave, Stefano Mossa and Francesco Sciortino Potential Energy Landscape Equation of StatePhys. Rev. Lett., 88, 225701 (2002).Stefano Mossa, Emilia La Nave, Francesco Sciortino and Piero Tartaglia, Aging and Energy Landscape: Application to Liquids and Glasses., cond-mat/0205071
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Entering the supercooled region
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Same basins in Equilibrium and Aging ?