We investigate the influence of thermostatting methods on the electrical conductivity and structure of molten and supercritical sodium chloride obtained in nonequilibrium molecular dynamics simulations in strong constant (dc) electric fields. The strong dependence of the results on the type of thermostat employed in simulations becomes apparent only at extremely high fields (>0.5×109V/m). For this range of fields, quantitative differences of unexpected size can be seen in the melt. In the supercritical fluid, different thermostats predict qualitatively very different behavior and structure. While the kinetic-type thermostats predict increased association of ions in the field, configurational thermostat predicts enhanced dissociation.

1.
J. W. E.
Lewis
and
K.
Singer
, J. Chem. Faraday Trans. 71, 31 (1964).
2.
J. P.
Hansen
and
I. R.
McDonald
,
Phys. Rev. A
11
,
2111
(
1975
).
3.
G.
Cicotti
,
G.
Jacucci
, and
I. R.
McDonald
,
Phys. Rev. A
13
,
426
(
1976
).
4.
J. A.
Padró
,
J.
Trullàs
, and
G.
Sesé
,
Mol. Phys.
72
,
1035
(
1991
).
5.
J.
Trullàs
and
J. A.
Padró
,
Phys. Rev. B
55
,
12210
(
1997
).
6.
Y.
Guissani
and
B.
Guillot
,
J. Chem. Phys.
101
,
490
(
1994
).
7.
K. S.
Pitzer
,
J. Chem. Phys.
104
,
6724
(
1996
).
8.
I. M.
Svishchev
and
P. G.
Kusalik
,
Phys. Chem. Liq.
26
,
237
(
1994
).
9.
D. J. Evans and G. P. Morriss, Statistical Mechanics of Non-Equilibrium Liquids (Academic, London, 1990).
10.
W. G. Hoover, Computational Statistical Mechanics (Elsevier, New York, 1991).
11.
W. G. Hoover, K. Aoki, C. G. Hoover, and S. V. De Groot, Physica D, Proceedings of the International Workshop on Microscopic Chaos and Transport in Many-Particle Systems (CHAOTRAN), held in Dresden, Germany 5–25 August 2002 (to be published).
12.
H. H.
Rugh
,
Phys. Rev. Lett.
78
,
772
(
1997
);
H. H.
Rugh
,
J. Phys. A
31
,
7761
(
1998
).
13.
J.
Delhommelle
and
D. J.
Evans
,
J. Chem. Phys.
115
,
43
(
2001
).
14.
L.
Lue
,
O. G.
Jepps
,
J.
Delhommelle
, and
D. J.
Evans
,
Mol. Phys.
100
,
2387
(
2002
).
15.
M. P.
Tosi
and
F. G.
Fumi
,
J. Phys. Chem. Solids
25
,
31
(
1964
).
16.
D.
MacGowan
and
D. J.
Evans
,
Phys. Rev. A
34
,
2133
(
1986
).
17.
S. W.
de Leeuw
,
J. W.
Perram
, and
E. R.
Smith
,
Proc. R. Soc. London, Ser. A
373
,
27
(
1980
).
18.
S.
Nosé
and
M. L.
Klein
,
Mol. Phys.
50
,
1055
(
1983
).
19.
M. P. Allen and D. J. Tildesley, Computer Simulation of Liquids (Clarendon, Oxford, 1987).
20.
J. P. Hansen and I. R. McDonald, Theory of Simple Liquids (Academic, London, 1986).
21.
R.
Sundheim
,
J. Phys. Chem.
60
,
1381
(
1956
).
22.
J.
Delhommelle
and
J.
Petravic
,
J. Chem. Phys.
118
,
2783
(
2003
).
This content is only available via PDF.
You do not currently have access to this content.