We have calculated the density of model water potentials—employing an effective pairwise additive potential (RER) and an abinitio‐derived many‐body potential including polarizabilities (NEMO)—as a function of temperature at constant pressure. It is found that neither model can quantitatively reproduce the density of liquid water between 250 and 373 K. More disturbingly, neither potential exhibits a density maximum. Modifying the effective potential to give the correct density at different temperatures reveals subtle changes in the importance of different water configurations. These configurational changes are shown as possible causes of the anomalous density behavior of liquid water.

1.
W.
Blokzijl
and
J. B. F. N.
Engberts
,
Angew. Chem. Int. Ed. Engl.
32
,
1545
(
1993
).
2.
Water and Biological Macromolecules, edited by E. Westhol (Chemical Rubber, Boca Raton, Florida, 1993).
3.
C.
Millot
and
A. J.
Stone
,
Mol. Phys.
77
,
439
(
1992
).
4.
A.
Wallqvist
and
G.
Karlstrom
,
Chem. Scr.
29A
,
131
(
1989
).
5.
P.-O.
Åstrand
,
A.
Wallqvist
, and
G.
Karlström
,
J. Chem. Phys.
100
,
1262
(
1994
).
6.
K.
Laasonen
,
M.
Sprik
, and
M.
Parrinello
,
J. Chem. Phys.
99
,
9080
(
1993
).
7.
A.
Wallqvist
and
B. J.
Berne
,
J. Phys. Chem.
97
,
13841
(
1993
).
8.
B. V.
Zheleznyi
,
Russ. J. Phys. Chem.
43
,
1311
(
1969
).
9.
CRC Handbook of Chemistry and Physics, edited by R. C. Weast (Chemical Rubber, Boca Raton, Florida, 1985), Vol. 66.
10.
A.
Egelstaff
and
J. H.
Root
,
Chem. Phys.
76
,
405
(
1983
).
11.
S.-H.
Chen
and
J.
Teixeira
,
Adv. Chem. Phys.
64
,
1
(
1986
).
12.
R.
Corban
and
M. D.
Zeidler
,
Ber. Bunsenges. Phys. Chem.
96
,
1463
(
1992
).
13.
A. K.
Soper
and
M. G.
Phillips
,
Chem. Phys.
107
,
47
(
1986
).
14.
U.
Buontempo
,
P.
Postorino
,
M. A.
Ricci
, and
A. K.
Soper
,
Eur. Phys. Lett.
19
,
385
(
1992
).
15.
A.
Holtzer
and
M. F.
Emerson
,
J. Phys. Chem.
73
,
26
(
1969
).
16.
A. V.
Okhulkov
,
Yu. N.
Demianets
, and
Yu. E.
Gorbaty
,
J. Chem. Phys.
100
,
1578
(
1994
).
17.
M.
Vedamuthu
,
S.
Singh
, and
G. W.
Robinson
,
J. Phys. Chem.
98
,
2222
(
1994
).
18.
M.
Vedamuthu
,
S.
Singh
, and
G. W.
Robinson
,
J. Phys. Chem.
98
,
8591
(
1994
).
19.
S. R.
Billeter
,
P. M.
King
, and
W. F.
van Gunsteren
,
J. Chem. Phys.
100
,
6692
(
1994
).
20.
F. H.
Stillinger
and
A.
Rahman
,
J. Chem. Phys.
60
,
1545
(
1974
).
21.
W. L.
Jorgensen
,
J. Chem. Phys.
77
,
4156
(
1982
).
22.
J. P. M. Postma, Ph.D. thesis, University of Groningen, 1985.
23.
H. L.
Lemberg
and
F.
Stillinger
,
J. Chem. Phys.
62
,
1677
(
1975
).
24.
A.
Rahman
,
F. H.
Stillinger
, and
H. L.
Lemberg
,
J. Chem. Phys.
63
,
5223
(
1975
).
25.
F. H.
Stillinger
and
A.
Rahman
,
J. Chem. Phys.
68
,
666
(
1978
).
26.
H. J. C.
Berendsen
,
J. R.
Grigera
, and
T. P.
Straatsma
,
J. Phys. Chem.
91
,
6269
(
1987
).
27.
K.
Watanabe
and
M. L.
Klein
,
Chem. Phys.
131
,
157
(
1989
).
28.
A. D. Buckingham, in Intermolecular Forces, edited by J. O. Hirschfelder [Adv. Chem. Phys. 12 (Wiley, New York, 1967)].
29.
A. D. Buckingham, in Intermolecular Interactions: From Diatomics to Biopolymers, edited by B. Pullman (Wiley, New York, 1978).
30.
P.-O.
Åstrand
,
P.
Linse
, and
G.
Karlström
,
Chem. Phys.
191
,
195
(
1995
).
31.
H. C.
Andersen
J. Comput. Phys.
52
,
24
(
1983
).
32.
W. C.
Swope
,
H. C.
Andersen
,
P. H.
Berens
, and
K. R.
Wilson
,
J. Chem. Phys.
76
,
637
(
1982
).
33.
P. Linse and A. Wallqvist, MOLSIM 1.2, Lund University, Sweden (1991).
34.
H. J. C.
Berendsen
et al.,
J. Chem. Phys.
81
,
3684
(
1984
).
35.
P.
Ahlstrom
,
A.
Wallqvist
,
S.
Engstrom
, and
B.
Jonsson
,
Mol. Phys.
68
,
563
(
1989
).
36.
M. P. Allen and D. J. Tildesley, Computer Simulation of Liquids (Clarendon, Oxford, 1987).
37.
A.
Wallqvist
and
O.
Teleman
,
Mol. Phys.
74
,
515
(
1991
).
38.
H. J. C. Berendsen, J. P. M. Postma, W. F. van Gunsteren, and J. Hermans, in Intermolecular Forces, edited by B. Pullman (Reidel, Dordrecht, 1981), pp. 331–342.
39.
F.
Sciortino
,
A.
Geiger
, and
H. E.
Stanley
,
J. Chem. Phys.
96
,
3857
(
1992
).
40.
R. A.
Kuharski
and
P. J.
Rossky
,
J. Chem. Phys.
82
,
5164
(
1985
).
41.
A.
Wallqvist
and
B. J.
Berne
,
Chem. Phys. Lett.
117
,
214
(
1985
).
42.
J. L.
Finney
,
Chem. Scr.
29A
,
123
(
1989
).
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