A simple polarizable water model is developed and optimized for molecular dynamics simulations of the liquid phase under ambient conditions. The permanent charge distribution of the water molecule is represented by three point charges: two hydrogen sites and one additional M site positioned along the HOH bisector. Electronic induction is represented by introducing a classical charged Drude particle attached to the oxygen by a harmonic spring. The oxygen site carries an equal and opposite charge, and is the center of an intermolecular Lennard-Jones interaction. The HOH gas-phase experimental geometry is maintained rigidly and the dipole of the isolated molecule is 1.85 D, in accord with experiment. The model is simulated by considering the dynamics of an extended Lagrangian in which a small mass is attributed to the Drude particles. It is parametrized to reproduce the salient properties of liquid water under ambient conditions. The optimal model, refered to as SWM4-DP for “simple water model with four sites and Drude polarizability,” yields a vaporization enthalpy of 10.52 kcal/mol, a molecular volume of 29.93 Å3, a static dielectric constant of 79±5, a self-diffusion constant of (2.30±0.04)×10−5cm2/s, and an air/water surface tension of 66.9±0.9 dyn/cm, all in excellent accord with experiments. The energy of the water dimer is −5.18 kcal/mol, in good accord with estimates from experiments and high level ab initio calculations. The polarizability of the optimal model is 1.04 Å3, which is smaller than the experimental value of 1.44 Å3 in the gas phase. It is likely that such a reduced molecular polarizability, which is essential to reproduce the properties of the liquid, arises from the energy cost of overlapping electronic clouds in the condensed phase due to Pauli’s exclusion principle opposing induction.

1.
Computational Biochemistry and Biophysics, edited by O. M. Becker, A. D. MacKerell, Jr., B. Roux, and M. Watanabe (Marcel Dekker, New York, 2001).
2.
A. D. MacKerell, Jr., in Computational Biochemistry and Biophysics, edited by O. M. Becker, A. D. MacKerell, Jr., B. Roux, and M. Watanabe (Marcel Dekker, New York, 2001), Chap. 2.
3.
T. A.
Halgren
and
W.
Damm
,
Curr. Opin. Struct. Biol.
11
,
236
(
2001
).
4.
S. W. Rick and S. J. Stuart, in Reviews in Computational Chemistry, edited by K. B. Lipkowitz and D. B. Boyd (Wiley-VCH, Hoboken, NJ, 2002), Vol. 18, pp. 89–146.
5.
W. L.
Jorgensen
,
J.
Chandrasekhar
,
J. D.
Madura
,
R. W.
Impey
, and
M. L.
Klein
,
J. Chem. Phys.
79
,
926
(
1983
).
6.
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.
7.
T. R.
Dyke
and
J. S.
Muenter
,
J. Chem. Phys.
59
,
3125
(
1973
).
8.
J. K.
Gregory
,
D. C.
Clary
,
K.
Liu
,
M. G.
Brown
, and
R. J.
Saykally
,
Science
275
,
814
(
1997
).
9.
M.
Sprik
,
J. Chem. Phys.
95
,
6762
(
1991
).
10.
J.-C.
Soetens
,
M. T. C. M.
Costa
, and
C.
Millot
,
Mol. Phys.
94
,
577
(
1998
).
11.
A. Wallqvist and R. D. Mountain, in Molecular Models of Water: Derivation and Description, Vol. 13 of Reviews in Computational Chemistry, edited by K. B. Lipkowitz and D. B. Boyd (Wiley-VCH, New York, 1999), Chap. 4, pp. 183–247.
12.
P. L.
Silvestrelli
and
M.
Parrinello
,
Phys. Rev. Lett.
82
,
3308
(
1999
).
13.
P. L.
Silvestrelli
and
M.
Parrinello
,
J. Chem. Phys.
111
,
3572
(
1999
).
14.
Y. S.
Badyal
,
M.-L.
Saboungi
,
D. L.
Price
,
S. D.
Shastri
,
D. R.
Haeffner
, and
A. K.
Soper
,
J. Chem. Phys.
112
,
9206
(
2000
).
15.
A. V.
Gubskaya
and
P. G.
Kusalik
,
J. Chem. Phys.
117
,
5290
(
2002
).
16.
I.-F.
Kuo
and
D. J.
Tobias
,
J. Phys. Chem. B
105
,
5827
(
2001
).
17.
C. J.
Burnham
,
J.
Li
,
S. S.
Xantheas
, and
M.
Leslie
,
J. Chem. Phys.
110
,
4566
(
1999
).
18.
M. W.
Feyereisen
,
D.
Feller
, and
D. A.
Dixon
,
J. Phys. Chem.
100
,
2993
(
1996
).
19.
L. X.
Dang
and
T.-M.
Chang
,
J. Chem. Phys.
106
,
8149
(
1997
).
20.
S. W.
Rick
,
S. J.
Stuart
, and
B. J.
Berne
,
J. Chem. Phys.
101
,
6141
(
1994
).
21.
H.
Saint-Martin
,
J.
Hernández-Cobos
,
M. I.
Bernal-Uruchurtu
,
I.
Ortega-Blake
, and
H. J. C.
Berendesen
,
J. Chem. Phys.
113
,
10899
(
2000
).
22.
Y.-P.
Liu
,
K.
Kim
,
B. J.
Berne
,
R. A.
Friesner
, and
S. W.
Rick
,
J. Chem. Phys.
108
,
4739
(
1998
).
23.
T. P.
Lybrand
and
P. A.
Kollman
,
J. Chem. Phys.
83
,
2923
(
1985
).
24.
M.
Sprik
,
M. L.
Klein
, and
K.
Watanabe
,
J. Phys. Chem.
94
,
6483
(
1990
).
25.
L. X.
Dang
and
D. E.
Smith
,
J. Chem. Phys.
99
,
6950
(
1993
).
26.
S. J.
Stuart
and
B. J.
Berne
,
J. Phys. Chem.
100
,
11934
(
1996
).
27.
D. J.
Tobias
,
P.
Jungwirth
, and
M.
Parrinello
,
J. Chem. Phys.
114
,
7036
(
2001
).
28.
S. S.
Xantheas
and
L. X.
Dang
,
J. Phys. Chem.
100
,
3989
(
1996
).
29.
R. A.
Bryce
,
M. A.
Vincent
,
N. O. J.
Malcolm
,
I. H.
Hillier
, and
N. A.
Burton
,
J. Chem. Phys.
109
,
3077
(
1998
).
30.
O. M.
Cabarcos
,
C. J.
Weinheimer
,
J. M.
Lisy
, and
S. S.
Xantheas
,
J. Chem. Phys.
110
,
5
(
1999
).
31.
J.
Baik
,
J.
Kim
,
D.
Majumdar
, and
K. S.
Kim
,
J. Chem. Phys.
110
,
9116
(
1999
).
32.
W. H.
Robertson
,
E. G.
Diken
,
E. A.
Price
,
J.-W.
Shin
, and
M. A.
Johnson
,
Science
299
,
1367
(
2003
).
33.
F. C.
Lightstone
,
E.
Schwegler
,
R. Q.
Hood
,
F.
Gygi
, and
G.
Galli
,
Chem. Phys. Lett.
343
,
549
(
2001
).
34.
I.
Bakó
,
J.
Hutter
, and
G.
Pálinkás
,
J. Chem. Phys.
117
,
9838
(
2002
).
35.
A.
Wallqvist
,
Chem. Phys. Lett.
165
,
437
(
1990
).
36.
K. A.
Motakabbir
and
M. L.
Berkowitz
,
Chem. Phys. Lett.
176
,
61
(
1991
).
37.
A.
Kohlmeyer
,
W.
Witschel
, and
E.
Spohr
,
Chem. Phys.
213
,
211
(
1996
).
38.
I.-C.
Yeh
and
M. L.
Berkowitz
,
J. Chem. Phys.
112
,
10491
(
2000
).
39.
M. H.
New
and
B. J.
Berne
,
J. Am. Chem. Soc.
117
,
7172
(
1995
).
40.
S. W.
Rick
and
B. J.
Berne
,
J. Phys. Chem. B
101
,
10488
(
1997
).
41.
R. A.
Kuharski
and
P. J.
Rossky
,
Chem. Phys. Lett.
103
,
357
(
1984
).
42.
P. Drude, The Theory of Optics (Longmans, Green, and Co., New York, 1902), translation by C. Riborg Mann and Robert A. Millikan.
43.
L. X.
Dang
,
J. Chem. Phys.
97
,
2659
(
1992
).
44.
J.
Brodholt
,
M.
Sampoli
, and
R.
Vallauri
,
Mol. Phys.
86
,
149
(
1995
).
45.
I. M.
Svishchev
,
P. G.
Kusalik
,
J.
Wang
, and
R. J.
Boyd
,
J. Chem. Phys.
105
,
4742
(
1996
).
46.
P. J.
van Maaren
and
D.
van der Spoel
,
J. Phys. Chem. B
105
,
2618
(
2001
).
47.
H. A.
Stern
,
F.
Rittner
,
B. J.
Berne
, and
R. A.
Friesner
,
J. Chem. Phys.
115
,
2237
(
2001
).
48.
H.
Yu
,
T.
Hansson
, and
W. F.
van Gunsteren
,
J. Chem. Phys.
118
,
221
(
2003
).
49.
D. P.
Fernandez
,
Y.
Mulev
,
A. R. H.
Goodwin
, and
J. M. H. L.
Sengers
,
J. Phys. Chem. Ref. Data
24
,
33
(
1995
).
50.
W. F.
Murphy
,
J. Chem. Phys.
67
,
5877
(
1977
).
51.
G.
Lamoureux
and
B.
Roux
,
J. Chem. Phys.
119
,
3025
(
2003
).
52.
Water: A Comprehensive Treatise, edited by F. Franks (Plenum, New York, 1972), Vol. 1: The Physics and Physical Chemistry of Water.
53.
A. K.
Soper
,
F.
Bruni
, and
M. A.
Ricci
,
J. Chem. Phys.
106
,
247
(
1997
).
54.
G.
Hura
,
J. M.
Sorenson
,
R. M.
Glaeser
, and
T.
Head-Gordon
,
J. Chem. Phys.
113
,
9140
(
2000
).
55.
G. J.
Martyna
,
D. J.
Tobias
, and
M. L.
Klein
,
J. Chem. Phys.
101
,
4177
(
1994
).
56.
G. J.
Martyna
,
M. E.
Tuckerman
,
D. J.
Tobias
, and
M. L.
Klein
,
Mol. Phys.
87
,
1117
(
1996
).
57.
B. R.
Brooks
,
R. E.
Bruccoleri
,
B. D.
Olafson
,
D. J.
States
,
S.
Swaminathan
, and
M.
Karplus
,
J. Comput. Chem.
4
,
187
(
1983
).
58.
T.
Darden
,
D.
York
, and
L.
Pedersen
,
J. Chem. Phys.
98
,
10089
(
1993
).
59.
G.
Jancsó
and
W. A.
van Hook
,
Chem. Rev.
74
,
689
(
1974
).
60.
M.
Neumann
and
O.
Steinhauser
,
Chem. Phys. Lett.
106
,
563
(
1984
).
61.
A. D.
Buckingham
,
Proc. R. Soc. London, Ser. A
238
,
235
(
1956
).
62.
M.
Neumann
and
O.
Steinhauser
,
Chem. Phys. Lett.
102
,
508
(
1983
).
63.
M. P. Allen and D. J. Tildesley, Computer Simulation of Liquids (Clarendon, Oxford, 1987).
64.
J. G.
Kirkwood
and
F. P.
Buff
,
J. Chem. Phys.
17
,
338
(
1949
).
65.
K.
Ichikawa
,
Y.
Kameda
,
T.
Yamaguchi
,
H.
Wakita
, and
M.
Misawa
,
Mol. Phys.
73
,
79
(
1991
).
66.
M.
Karplus
,
Acc. Chem. Res.
35
,
321
(
2002
).
67.
T. R.
Dyke
,
K. M.
Mack
, and
J. S.
Muenter
,
J. Chem. Phys.
66
,
498
(
1977
).
68.
L. A.
Curtiss
,
D. J.
Frurip
, and
M.
Blander
,
J. Chem. Phys.
71
,
2703
(
1979
).
69.
A.
Morita
and
S.
Kato
,
J. Chem. Phys.
110
,
11987
(
1999
).
70.
M.
in het Panhuis
,
P. L. A.
Popelier
,
R. W.
Munn
, and
J.
Ángyán
,
J. Chem. Phys.
114
,
7951
(
2001
).
71.
Y.
Tu
and
A.
Laaksonen
,
Chem. Phys. Lett.
329
,
283
(
2000
).
72.
A.
Morita
,
J. Comput. Chem.
23
,
1466
(
2002
).
73.
K.
Krynicki
,
C. D.
Green
, and
D. W.
Sawyer
,
Discuss. Faraday Soc.
66
,
199
(
1978
).
74.
M. P.
Hodges
,
A. J.
Stone
, and
S. S.
Xantheas
,
J. Phys. Chem. A
101
,
9163
(
1997
).
75.
J. M.
Sorenson
,
G.
Hura
,
R. M.
Glaeser
, and
T.
Head-Gordon
,
J. Chem. Phys.
113
,
9149
(
2000
).
76.
A. A.
Chialvo
and
P. T.
Cummings
,
J. Chem. Phys.
105
,
8274
(
1996
).
77.
L. D.
Site
,
A.
Alavi
, and
R. M.
Lynden-Bell
,
Mol. Phys.
96
,
1683
(
1999
).
78.
S.
Chalmet
and
M. F.
Ruiz-López
,
J. Chem. Phys.
115
,
5220
(
2001
).
79.
T. D.
Poulsen
,
P. R.
Ogilby
, and
K. V.
Mikkelsen
,
J. Chem. Phys.
116
,
3730
(
2002
).
80.
M. W.
Mahoney
and
W. L.
Jorgensen
,
J. Chem. Phys.
112
,
8910
(
2000
).
81.
K.
Coutinho
,
R. C.
Guedes
,
B. J. C.
Cabral
, and
S.
Canuto
,
Chem. Phys. Lett.
369
,
345
(
2003
).
82.
D. E.
Smith
and
L. X.
Dang
,
J. Chem. Phys.
100
,
3757
(
1994
).
83.
P.
Höchtl
,
S.
Boresch
,
W.
Bitomsky
, and
O.
Steinhauser
,
J. Chem. Phys.
109
,
4927
(
1998
).
84.
B.
Guillot
,
J. Mol. Liq.
101
,
219
(
2002
).
85.
U.
Kaatze
,
J. Chem. Eng. Data
34
,
371
(
1989
).
86.
J.
Barthel
,
K.
Bachhuber
,
R.
Buchner
, and
H.
Hetzenauer
,
Chem. Phys. Lett.
165
,
369
(
1990
).
87.
J. T.
Kindt
and
C. A.
Schmuttenmaer
,
J. Phys. Chem.
100
,
10373
(
1996
).
88.
S. E.
Feller
,
R. W.
Pastor
,
A.
Rojnuckarin
,
S.
Bogusz
, and
B. R.
Brooks
,
J. Phys. Chem.
100
,
17011
(
1996
).
89.
M. C.
Goh
,
J. M.
Hicks
,
K.
Kemnitz
,
G. R.
Pinto
,
T. F.
Heinz
,
K. B.
Eisenthal
, and
K.
Bhattacharyya
,
J. Phys. Chem.
92
,
5074
(
1988
).
90.
M.
Paluch
,
Adv. Colloid Interface Sci.
84
,
27
(
2000
).
91.
L. X.
Dang
and
T.-M.
Chang
,
J. Phys. Chem. B
106
,
235
(
2002
).
92.
P.
Vassilev
,
C.
Hartnig
,
M. T. M.
Koper
,
F.
Frechard
, and
R. A.
van Santen
,
J. Chem. Phys.
115
,
9815
(
2001
).
93.
S. S.
Xantheas
,
C. J.
Burnham
, and
R. J.
Harrison
,
J. Chem. Phys.
116
,
1493
(
2002
).
94.
M.
Losada
and
S.
Leutwyler
,
J. Chem. Phys.
117
,
2003
(
2002
).
95.
J. K.
Gregory
and
D. C.
Clary
,
J. Phys. Chem. A
101
,
6813
(
1997
).
96.
J.
Verhoeven
and
A.
Dymanus
,
J. Chem. Phys.
52
,
3222
(
1970
).
97.
K.
Watanabe
and
M. L.
Klein
,
Chem. Phys.
131
,
157
(
1989
).
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