Using effective infinite dilution ion-ion interaction potentials derived from explicit-water molecular dynamics (MD) computer simulations in the hypernetted-chain (HNC) integral equation theory we calculate the liquid structure and thermodynamic properties, namely, the activity and osmotic coefficients of various multicomponent aqueous electrolyte mixtures. The electrolyte structure expressed by the ion-ion radial distribution functions is for most ions in excellent agreement with MD and implicit solvent Monte Carlo (MC) simulation results. Calculated thermodynamic properties are also represented consistently among these three methods. Our versatile HNC/MD hybrid method allows for a quick prediction of the thermodynamics of multicomponent electrolyte solutions for a wide range of concentrations and an efficient assessment of the validity of the employed MD force-fields with possible implications in the development of thermodynamically consistent parameter sets.

1.
P.
Debye
and
E.
Hückel
,
Phys. Z.
24
,
185
(
1923
).
2.
K. S.
Pitzer
,
J. Am. Chem. Soc.
102
,
2902
(
1980
).
3.
E.
Waisman
and
J. C.
Lebowitz
,
J. Chem. Phys.
56
,
3086
(
1972
).
5.
J. -P.
Simonin
,
L.
Blum
, and
P.
Turq
,
J. Phys. Chem.
100
,
7704
(
1996
).
6.
N.
Papaiconomou
,
J. -P.
Simonin
,
O.
Bernard
, and
W.
Kunz
,
Phys. Chem. Chem. Phys.
4
,
4435
(
2002
).
7.
N.
Papaiconomou
,
J. -P.
Simonin
,
O.
Bernard
, and
W.
Kunz
,
J. Mol. Liq.
113
,
5
(
2004
).
8.
P. S.
Ramanathan
and
H. L.
Friedman
,
J. Chem. Phys.
54
,
1086
(
1971
).
9.
P. G.
Kusalik
and
G. N.
Patey
,
J. Chem. Phys.
92
,
1345
(
1990
).
10.
C. P.
Ursenbach
,
D.
Wei
, and
G. N.
Patey
,
J. Chem. Phys.
94
,
6782
(
1991
).
11.
J. -P.
Simonin
,
O.
Bernard
,
N.
Papaiconomou
, and
W.
Kunz
,
Fluid Phase Equilib.
264
,
211
(
2008
).
12.
C.
Held
,
L. F.
Cameretti
, and
G.
Sadowski
,
Fluid Phase Equilib.
270
,
87
(
2008
).
13.
C.
Held
and
G.
Sadowski
,
Fluid Phase Equilib.
279
,
141
(
2009
).
14.
G. I.
Szasz
,
W.
Dietz
,
K.
Heinzinger
,
G.
Pćlinkás
, and
T.
Radnai
,
Chem. Phys. Lett.
92
,
388
(
1982
).
15.
E.
Spohr
,
G.
Pćlinkás
,
K.
Heinzinger
,
P.
Bopp
, and
M. M.
Probst
,
J. Phys. Chem.
92
,
6754
(
1988
).
16.
M.
Lund
,
B.
Jönsson
, and
T.
Pedersen
,
Mar. Chem.
80
,
95
(
2003
).
17.
B.
Hess
,
C.
Holm
, and
N.
van der Vegt
,
J. Chem. Phys.
124
,
164509
(
2006
).
18.
B.
Hess
,
C.
Holm
, and
N.
van der Vegt
,
Phys. Rev. Lett.
96
,
147801
(
2006
).
19.
I.
Kalcher
and
J.
Dzubiella
,
J. Chem. Phys.
130
,
134507
(
2009
).
20.
W.
Kunz
,
P.
Turq
,
M. -C.
Bellissent-Funel
, and
P.
Calmettes
,
J. Chem. Phys.
95
,
6902
(
1991
).
21.
H.
Krienke
,
V.
Vlachy
,
G.
Ahn-Ercan
, and
I.
Bakć
,
J. Phys. Chem. B
113
,
4360
(
2009
).
22.
A. P.
Lyubartsev
and
S.
Marčelja
,
Phys. Rev. E
65
,
041202
(
2002
).
23.
Scientific tools for Python (
2009
) (http://www.scipy.org).
24.
L.
Vrbka
, OZ-solver in Python (
2009
) (http://www.pyoz.vrbka.net).
25.
W. G.
McMillan
and
J. E.
Mayer
,
J. Chem. Phys.
13
,
276
(
1945
).
26.
J. -P.
Hansen
and
I. R.
McDonald
,
Theory of Simple Liquids
(
Academic
,
New York
,
2005
).
27.
L. S.
Ornstein
and
F.
Zernike
,
Proc. R. Acad. Sci. Amsterdam
17
,
793
(
1914
).
28.
K. -C.
Ng
,
J. Chem. Phys.
61
,
2680
(
1974
).
29.
J. C.
Rasaiah
and
H. L.
Friedman
,
J. Chem. Phys.
48
,
2742
(
1968
).
30.
J. P.
Hansen
,
G. M.
Torrie
, and
P.
Vieillefosse
,
Phys. Rev. A
16
,
2153
(
1977
).
31.
R.
Kjellander
and
S.
Sarman
,
J. Chem. Phys.
90
,
2768
(
1989
).
32.
L.
Verlet
and
D.
Levesque
,
Physica
28
,
1124
(
1962
).
33.
R. A.
Robinson
and
R. H.
Stokes
,
Electrolyte Solutions
(
Butterworths
,
London
,
1959
).
34.
H. L.
Friedman
,
J. Solution Chem.
1
,
387
(
1972
).
35.
J. P.
Simonin
,
J. Chem. Soc., Faraday Trans.
92
,
3519
(
1996
).
36.
C. A.
Haynes
and
J.
Newman
,
Fluid Phase Equilibria
145
,
255
(
1998
).
37.
Z.
Abbas
,
E.
Ahlberg
, and
S.
Nordholm
,
Fluid Phase Equilib.
260
,
233
(
2007
).
38.
H. J. C.
Berendsen
,
D.
van der Spoel
, and
R.
van Drunen
,
Comput. Phys. Commun.
91
,
43
(
1995
).
39.
E.
Lindahl
,
B.
Hess
, and
D.
van der Spoel
,
J. Mol. Model.
7
,
306
(
2001
).
40.
H. J. C.
Berendsen
,
J. P. M.
Postma
,
W. F.
van Gunsteren
,
A.
DiNola
, and
J. R.
Haak
,
J. Chem. Phys.
81
,
3684
(
1984
).
41.
H. J. C.
Berendsen
,
J. R.
Grigera
, and
T. P.
Straatsma
,
J. Phys. Chem.
91
,
6269
(
1987
).
42.
U.
Essmann
,
L.
Perera
,
M. L.
Berkowitz
,
T.
Darden
,
H.
Lee
, and
L. G.
Pedersen
,
J. Chem. Phys.
103
,
8577
(
1995
).
43.
L. X.
Dang
,
J. Chem. Phys.
96
,
6970
(
1992
).
44.
L. X.
Dang
,
J. Am. Chem. Soc.
117
,
6954
(
1995
).
45.
L. X.
Dang
and
B. C. J.
Garrett
,
J. Chem. Phys.
99
,
2972
(
1993
).
46.
J.
Perkyns
and
B. M.
Pettitt
,
J. Chem. Phys.
97
,
7656
(
1992
).
47.
Y. -Z.
Wei
,
P.
Chiang
, and
S.
Sridhar
,
J. Chem. Phys.
96
,
4569
(
1992
).
48.
R.
Buchner
,
G. T.
Hefter
, and
J.
Barthel
,
J. Chem. Soc., Faraday Trans.
90
,
2475
(
1994
).
49.
J.
Barthel
,
R.
Buchner
, and
M.
Münsterer
,
Electrolyte Data Collection
(
DECHEMA
,
Frankfurt/Main
,
1995
), Vol.
12
, Part 2.
50.
K.
Nörtemann
,
J.
Hilland
, and
U.
Kaatze
,
J. Phys. Chem. A
101
,
6864
(
1997
).
51.
A. K.
Lyashchenko
and
A. Y.
Zasetsky
,
J. Mol. Liq.
77
,
61
(
1998
).
52.
W.
Wachter
,
W.
Kunz
,
R.
Buchner
, and
G. T.
Hefter
,
J. Phys. Chem. A
109
,
8675
(
2005
).
53.
D. V.
Loginova
,
A. S.
Lileev
, and
A. K.
Lyashchenko
,
Russ. J. Phys. Chem.
80
,
1626
(
2006
).
54.
N. A.
Metropolis
,
A. W.
Rosenbluth
,
M. N.
Rosenbluth
,
A.
Teller
, and
E.
Teller
,
J. Chem. Phys.
21
,
1087
(
1953
).
55.
B.
Widom
,
J. Chem. Phys.
39
,
2808
(
1963
).
56.
D.
Frenkel
and
B.
Smit
,
Understanding Molecular Simulation
, 2nd ed. (
Academic
,
New York
,
2001
).
57.
D. A.
McQuarrie
,
Statistical Mechanics
, 2nd ed. (
University Science Books
,
Sausalito, CA
,
2000
).
58.
M.
Lund
,
M.
Trulsson
, and
B.
Persson
,
Source Code Biol. Med.
3
,
1
(
2008
).
59.
A.
Heydweiller
,
Ann. Phys.
335
,
873
(
1909
).
60.
W. J.
Hamer
and
Y. -C.
Wu
,
J. Phys. Chem. Ref. Data
1
,
1047
(
1972
).
61.
See EPAPS supplementary material at http://dx.doi.org/10.1063/1.3248218 for further discussion of errorbars associated with the calculations.
62.
B. M.
Pettitt
and
P. J.
Rossky
,
J. Chem. Phys.
84
,
5836
(
1986
).
63.
T.
Åkesson
,
C.
Woodward
, and
B.
Jönsson
,
J. Chem. Phys.
91
,
2461
(
1989
).
64.
R. A.
Robinson
and
C. K.
Lim
,
Trans. Faraday Soc.
49
,
1144
(
1953
).
65.
M. A.
Flesia
,
M. R. G.
de Chialvo
, and
A. C.
Chialvo
,
Fluid Phase Equilib.
131
,
189
(
1997
).
66.
H. F.
Holmes
,
J. C. F.
Baes
, and
R. E.
Mesmer
,
J. Chem. Thermodyn.
11
,
1035
(
1979
).
67.
H. F.
Holmes
and
R. E.
Mesmer
,
J. Chem. Thermodyn.
20
,
1049
(
1988
).
68.
A.
Dinane
,
M. E.
Guendouzi
, and
A.
Mounir
,
J. Chem. Thermodyn.
34
,
423
(
2002
).
69.
D.
Horinek
,
S. I.
Mamatkulov
, and
R. R.
Netz
,
J. Chem. Phys.
130
,
124507
(
2009
).

Supplementary Material

You do not currently have access to this content.