Accepted Manuscript

Page 7 of 12 Physical Chemistry Chemical Physics
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Published on 22 May 2012 on http://pubs.rsc.org | doi:10.1039/C2CP40962C
E/N (kcal.mol −1 )
−12
−12.2
−12.4
−12.6
−12.8
−13
−13.2
−13.4
0.0⋅10 0
266 K
2.5⋅10 6
5.0⋅10 6
7.5⋅10 6
Monte Carlo cycles
262 K
252 K
240 K
1.0⋅10 7
Fig. 2 Plot of the total energy (E) per particle from the liquid-Ih
direct coexistence simulations of the quantum system at p=1 bar.
pressure (bar)
12000
10000
8000
6000
4000
2000
VI
V
II III
Ih
0
140 160 180 200 220 240 260 280 300 320
temperature (K)
liquid
Fig. 3 Phase diagram of water from path integral simulations of the
TIP4PQ/2005 model. Experimental results (blue points) are also
shown 1,56
Δv (cm 3 Δv (cm /mol)
3 /mol)
4.5
4
3.5
3
2.5
2
1.5
1
0.5
II-Ih
VI-II
III-Ih
V-III
VI-V
V-II
w-Ih
V-w
III-w
VI-w
II-III
0
140 160 180 185 200 220 240 230 260 280 275 300 320 340 320
4.5
4
3.5
3
2.5
2
1.5
1
temperature (K)
II-Ih
III-Ih
w-Ih
V-w
V-III
V-II VI-V
VI-w
0.5
II-III
III-w
0
200 230 260 290 320
Fig. 4 Molar volume change (Δv=vB− vA) along the phase
boundaries from (Left) path integral simulations and (Right)
experimental results 1 . (w indicates the liquid phase).
pressure (bar)
12000
10000
8000
6000
4000
2000
0
140 160 180 200 220 240 260 280 300
temperature (K)
liquid
View Online
Fig. 5 Classical phase diagram of the TIP4PQ/2005 model (dashed
blue lines) compared to the diagram obtained from path integral
simulations (solid red lines).
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Physical Chemistry Chemical Physics Accepted Manuscript