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Citation: The Journal of Chemical Physics 72, 5935 (1980); doi: 10.1063/1.439092
View online: http://dx.doi.org/10.1063/1.439092
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/72/11?ver=pdfcov
Published by the AIP Publishing
Phase behavior of the restricted primitive model and square-well fluids from Monte Carlo simulations in the grand
canonical ensemble
J. Chem. Phys. 110, 1581 (1999); 10.1063/1.477798
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Primitive model electrolytes. I. Grand canonical Monte
Carlo computations
John P. Valleau and L. Kenneth Cohen
Lash Miller Chemical Laboratories. University of Toronto. Toronto. Ontario. Conada M5S IAI
(Received 20 December 1979; accepted 21 February 1980)
Monte Carlo calculations in the grand canonical ensemble are described for coulombic systems. and
carried out for 1:1. 2:2, 2:1. and 3:1 aqueous electrolytes in the primitive model with equal ion sizes.
Energies and activity coefficients are obtained, and the scope and reliability of the method is discussed.
J. Chem. Phys. 72(11). 1 June 1980 0021·9606/80/115935·07$01.00 © 1980 American Institute of Physics 5935
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5936 J. P. Valleau and L. K. Cohen: Primitive model electrolytes. I
E.uo:!!.L (1)
state. Combining Eqs. (1)-(5), we obtain (still with
Pjj 1T I N;=~+v., Nj=Nj-+vJ
and we seek such transition probabilities. As usual we
attempt, at each step of the chain, a "trial" change of (6)
state, and this trial move is then accepted or rejected
in such a way as to lead to (1). Suppose the probability where Il =:; V.(.1.. + v_f.1._ is the chemical potential of the elec-
of a trial step i to j is qlj' and the probability of ac- trolyte. Extending a definition due to Adams, 2 we in-
ceptance of that trial step isflj for i*j. Then troduce
Pi};' qjjfiJ> (ii-j) , (2) B'" !3«(.1. - Iltdeal) + lnyu+N-u.
V"
(7)
PH;' 1- LP jj
j~i
which leads to
There is of course wide latitude in the choice of I I qjJII ,
and then also of I I ftJl I, satisfying (1). We examine h , -N:'!'''''
_ N."! Ni! [
expB-!3Ui -Uj
( )] (8)
simple choices of I I qjjll 'and I I fjjll, of the sort pro- f Ji j.lV j '
4
TABLE I. Results for 1: 1 electrolyte with R = 4.25 A and e:T= 2.345 x 10 • The columns are as follows: L is the length of the
cubical periodic box; B the chemical potential input parameter [Eq. (7)]; No. Steps refers to the length of the Me run, while No.
Disc. shows how much of the run was regarded as aging and ignored in the averaging; 2P is the proportion of steps in which addi-
tions or deletions were attempted, and the next column gives the acceptance rate for such steps; the average number of particles
N and the resulting molarity M are followed by the data for the activity coefficients and the reduced configurational energies.
the diameter of each ion. The properties of the system Hoskins and Smith16 on two-component plasmas confirm
depend on R and on the product ET, as well as on the that for low r the methods agree well while for higher r
ionic charge types. Rand E T were chosen to match they give totally different results. Up to r - 10 the dis-
closely those used earlier in the CMC calculations 3 : for crepancy is comparable to the statistical uncertainty.
the 1: 1 case R=4.25 A and ET=2.345xl0· deg (cf. R For all of the calculations reported here r is substan-
=4.25 A and ET=2.339xl0· for CMC), and for the 2:2, tially less than 10 (e. g., for the 2: 2 system at 2 M, r
2:1, and 3:1 cases R=4.2 A and ET=2.342xl0· (cf. R = 4. 9), so the energy approximation should be trust-
=4. 2 A and E T =2. 336 X 10·). A t room temperature the worthy. For the more concentrated solutions this was
parameter ET corresponds to the dielectric constant of tested, however, by carrying out parallel runs with sys-
water. Of course the results can equally well be inter- tems of double the usual size. One expects the results
preted as corresponding to a lower E at a higher tem- to vary with the system's size if the energy approxima-
perature, for example, a plasma at about 2.34 x lOS OK. tion is becoming inadequate; the results are discussed
In a similar way the results we describe as those of 2: 2 below.
electrolyte may be interpreted as a 1 : 1 electrolyte at a
value of ET reduced by a factor of 4 (e.g., an E of 19.6 Two "experimental" parameters will affect the conver-
at 25°C). gence rate of the Markov chain. These are the "step
size" 6 allowed when a particle move is attempted, and
Periodic boundary conditions were used, and the re- the ratio 2P/(l- 2P) of attempted additions and deletions
peating box was cubical. The energy calculations were to attempted particle moves. The former was chosen to
done in the minimum image apprOXimation (MI): that is make the acceptance rate for moves well behaved; for
the potential energy of a particle is evaluated by sum- the denser systems it was adjusted to give an acceptance
ming the pair interactions with only one image of each rate close to 50%. Little is known about the best way to
of the other particles, the image closest to the particle choose P, and we made no systematic study of this. At
in question. This corresponds to a cubical cutoff having low densities the acceptance rates for addition and de-
the dimensions and orientation of the repeating box. It letion are substantial, and we chose P =0.1. A high
has been showni • 16 that a spherical cutoff is totally un- densities the acceptance rate becomes small, however,
acceptable for coulombic systems, and this is readily and it was necessary to increase P in order to get ade-
understood. 14 Many calculations on Coulombic systems quate variation of concentration during the runs. Data
have approximated the truly periodic boundary condi- on P and the addition/deletion acceptance rates are re-
tions by doing Ewald summations, although it seems ported. Since pair correlation function data for most of
that this will introduce very nonphysical forces and cor- these systems had been obtained in the earlier CMC
relations. 14 Fortunately at low ionic densities the calculations,3 it was not collected in the runs reported
Ewald and MI approximations are expected to agree with here. (For systems with unequal ion Sizes, reported in
each other and to be physically meaningful. Brush, Paper IV, CMC results were not available and pair cor-
Sahlin, and Teller 17 compared the two approximations relations were studied in the GCMC runs. )
for the one-component plasma and found that they agreed
as long as the dimensionless parameter
IV. RESULTS AND DISCUSSIONS
_/4rr1J'\1/3 Z2 e 2
r -\- 6Y) EkT (13) Tables I-IV refer to the 1: 1, 2: 2, 2: 1, and 3: 1 sys-
tems, in that order. In each table the last three columns
was below about 10. (Here N/V is the number density report the physical results: activity coefficients y,. and
and Ze the ionic charge.) Our own tests 1 ,14 and those of configurational energies U at various concentrations.
TABLE n. Results for 2: 2 electrolyte with R=4. 2 A and E:T=2. 342 x104. The columns are described in the legend of Table I.
TABLE m. Results for 2: 1 electrolyte with R=4. 2 A and E:T=2. 342 x 104• The columns are described in the legend of Table I.
TABLE IV. Results for 3: 1 electrolytes with R = 4. 2 A and E:T= 2. 342 x 104• The columns are described in the legend of Table I.
298.4 13.410 420 60 0.20 0.53 64.54 ± 0.31 0.001008 ± 0.000005 0.252 ± 0.005 0.298 ± 0.006
375.9 16.182 480 60 0.20 0.53 129.0 ± 1. 3 0.001008 ± O. 000010 0.252 ± 0.010 0.282 ± O. 005
138.5 11.770 420 60 0.20 0.30 64.00 ± O. 48 0.01000 ± O. 00007 0.654 ± 0.008 0.756 ± O. 012
80.99 9.890 420 60 0.20 O. 18 59.88 ± O. 34 0.0468 ± O. 0003 1. 058 ± 0.006 1. 202 ± O. 013
80.99 10.110 420 60 0.20 O. 18 65. 23 ± O. 48 0.0510 ± 0.0004 1. 088 ± O. 007 1. 236 ± 0.016
47.36 8.046 420 60 0.20 0.087 61.17±0.64 O. 2390 ± O. 0025 1. 540 ± 0.010 1. 759 ± 0.030
35.376 7.560 420 60 0.20 0.036 60. 80±0. 53 0.570 ± 0.005 1.655 ± O. 009 2.101 ± O. 030
29.835 8. 120 1440 120 0.20 0.011 62.38 ± 0.46 0.975 ± 0.007 1. 541 ± O. 007 2.344±0.028
34.62 10.466 1200 60 0.50 0.0079 106.32 ± O. 83 1. 06~ ± O. 008 1. 488 ± O. 008 2.378±0.031
27.48 9.080 1680 120 0.60 0.0035 65. 04± O. 49 1. 30J ± 0.010 1. 343 ± 0.008 2.489 ± 0.031
34.62 11.852 960 60 0.50 0.0029 131. 7 ± 1.1 1.317± O. 011 1.355±0.009 2. 489± 0.034
25.51 10.390 2400 240 0.80 0.00091 64.65 ± O. 46 1.617±0.012 1. 009 ± O. 007 2.605 ± 0.028
32.14 13.162 1800 200 0.80 0.00078 130.68 ± 0.94 1. 634± O. 012 1.020 ± 0.007 2.610 ± 0.032
\
q,
, ......0- __ - /
0
5)'
\
-1.0 ,\ a \ ~
I
I
,b \
,
)(
\ I
I
-0.5 ~\ \x\
\ , 3: 1 I~
I
1:1
\
b\ ' \
b
---_A .,--~-
-1.5 q, ',CSt /'
-1.0
\
\
, '0
\
, . . " -2-"
, X
I \ "
\
o, " '0, -2.0 \ °
\
\
" 'o"f!l \
\ x
x
0,
-1.5 \ .......~
\ . ..c.2:1
i \
~
'~
'a... -2.5
-2.0
2
o
'"'
"-
'"::;) 3:1 FIG. 2. Mean ionic activity coefficients (as l.rry • .J as a function
-2.5 of concentration. Open circles refer to GCMC results with
N ~ 64, open triangles to systems with N ~ 128. Crosses give
some apparent values obtained from CMC osmotic coefficients:
except for the 1 : 1 system they are dubious.
-3.0
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5940 J. P. Valleau and L. K. Cohen: Primitive model electrolytes.
It is well known that the nonideality !J lny" =/3(1J. - lJ.ideal) different ways, in fact, with perfect consistency. Most
of electrolytes goes through a minimum in the concentra- of the 3: 1 CMC results for lny. turn out to be fairly
tion ranges studied here. It follows (if the number of par- good, in spite of our misgivings about them. For the
ticles N is to be kept roughly constant) that the parame- 2: 2 case, however, the CMC results are quite wrong.
ter B will also go through a minimum as the concentra- This is undoubtedly due mostly to lack of success in ex-
tion is increased for approximately constant N, and this trapolating g._ (r) back to r:R. The extrapolation was
can be seen in the tables. One might imagine that this done by using a quadratic fit to the small-r values of
would lead to ambiguous MC results, two concentrations g._ (r); the errors correspond to too-high values of g._
corresponding to a single value of B. This is not the (R). It is possible to get lower (or higher) values of g._
case, however, since for fixed volume the two concen- (R) by extrapolating differently, but there is no a Priori
trations would have to be such that [cf. Eqs. (7) and (9)] way to choose the best extrapolation. These results
the difference in lny. was given by justify our reluctance to publish CMC results for the os-
motic coefficients of the higher-valence electrolytes.
~lny = -1. ~ln(N·"·N-"-) = - ~lnM
• !J ' The GCMC results appear totally satisfactory ex-
but lny. always decreases much less rapidly than -lnM; cept for the 2: 2 system at concentrations> 2 M. There
hence the results are single valued. the number dependence appears to be large and erratic.
In particular the result at 3.69 M (with N= 118) should
For most of the runs the volumes and the values of B coincide with that at 3.21 M (with N= 51), instead of
were chosen to give roughly N- 64 particles. The num- which they are totally discrepant in energy and density
ber dependence of the thermodynamic properties for di- and thus activity. The apparent number dependencies
lute solutions was studied previously, 1,3 and it is known at 1. 9 M and 2.9 M are just believable as random error,
that a system of this size gives adequate scientific re- but also look really to be discrepant. Although the
sults. For the denser systems studied here, where one small-system results (N- 64) fall on a credible curve for
might worry about the adequacy of the energy approxi- both energy and activity, the peculiar behaviour of the
mation, parallel runs were performed with double the large-system (N- 128) results puts all of the results into
volume and an appropriately adjusted B [cf. Eq. (7)]. question.
These results appear in the figures as open triangles to
distinguish them from the smaller systems. It is evi- It is natural to seek an explanation in terms of slow
dent that, except for the 2: 2 systems, the agreement is convergence due to low addition/deletion acceptance
entirely satisfactory, in most cases well within the sta- rates. In fact, however, these 2: 2 runs show accept-
tistical uncertainty of the results. In going to a larger ance rates very much higher than those which were easi-
system one expects to find a very slightly less negative ly handled for the other systems. Furthermore, control
energy (since the cancelling charge surrounding each charts of Nand U show neither long correlation times
ion is allowed to spread over a larger volume); in the nor any tendency to drift, so simple slow convergence seems
CMC work this was found to raise the energy by - 1% on to be ruled out. The other obvious explanation is an enhanced
doubling the size from N =64 (and by - 2% in extrapolat- number dependence due to breakdown of the minimum-
ing to an infinite system). The N dependence of the image energy approximation. All the evidence 14 ,16 sug-
GCMC results is not inconsistent with that, although it gests that in this case the larger system should have a
may be even weaker for the 2: 1 and 3: 1 systems. The less negative energy, however, while these results show
very large 2: 2 discrepancies are discussed separately. a lower energy. Furthermore, the fact that the density
discrepancies are in different directions seems puzzling
Comparison with the CMC results l - 3 on the same sys- on this hypotheSiS, while previous tests 3 ,16,17 indicate
tems provides a useful check on the GCMC results. One that the minimum image approximation remains quite ac-
expects the precision of the GCMC energy estimates to curate at the values of r in question here.
be less than those of the CMC, due to the density fluctu-
ations. This is borne out by the results, in which the So (always supposing that no error crept into the pro-
standard deviations of the energies are several times gramme!) the problem looks to be one of quasiergodic-
larger than in the CMC case, in spite of the longer runs. ity. In this connection it is of interest that there is be-
The accuracy is all one could hope for, however: in lieved to be a phase change in Coulombic systems with
Fig. 1 the solid lines show the very precise CMC results a critical point at a temperature somewhat lower than
for N=64, and the agreement of the GCMC results is ours and at a somewhat uncertain density. 18,19 [Some
everywhere complete. results of Vorontsov-Vel'yaminov and Chasovskikh,18
based on MC computations, suggest that there might be
In the case of the activity coefficients, on the other a critical point in a 2-2 "aqueous" electrolyte (i. e. ,
hand, it is the GCMC results which are expected to be with E = 78.4) near 200 A and 3.6 M.] It is natural to ask
more precise, as discussed above. Figure 2 shows (as whether the apparent quasiergodicity of the 2-2 results
crosses) some CMC results obtained by Gibbs-Duhem is associated with such a phase transition; that is the
integration of the osmotic coefficients. 3 For the 1: 1 subject of a separate study now underway. Meanwhile
case the extrapolations of g._ (r) to r= R were not diffi- it seems prudent not to use the results for the 2-2 sys-
cult, and the results were checked by using multistage tem at high concentrations.
sampling,4 so it is not surprising to find the total agree-
ment with the new GCMC results. The free energy re- The scientific implications of the results are discussed
sults for the 1 : 1 system have now been obtained in three in the following two papers 20 ,21 of the series.
mating osmotic coefficients from CMC data. imagine a process of fixing the labels to the particles in a
consistent way in spite of the additions and deletions: every
system with N+ cations and N- cations should involve a particu-
I D• N. Card and J. P. Valleau, J. Chern. Phys. 52, 6232 lar set of labels, e. g., integers from 1 to N+ for the cations
(1970). and from 1 to N- for the anions. One way of achieving this
2J. C. Rasaiah, D. N. Card, and J. P. Valleau, J. Chern. would be to assign those labels to the particles, at random,
Phys. 56, 248 (1972). after each attempted addition or deletion. We could then
3D. N. Card, thesis, University of Toronto, 1972. impute, for the labeled states [cf. Eqs. (3) and (4)]
4J. P. Valleau and D. N. Card, J. Chern. Phys. 57, 5457
(1972).
P 1
qlJ - V"II+IIIJ NjlNjl
sG. M. Torrie and J. P. Valleau, J. Comput. Phys. 23, 187
(1977). and
6J • P. Valleau and G. M. Torrie, "A Guide to Monte Carlo for
P 1
Statistical Mechanics. 2. Byways," in Modern Theoretical
qJ/ NjNjll+III_1 NjlNj!
Chemistry, Vol. 5A, Statistical Mechanics: Equilibrium
Techniques, edited by B. Berne (Plenum, New York, 1977), However, the probability lTl of a configuration i for labeled
p. 169. particles will be [ef. Eq. (5)]
7W. W. Wood, in Physics of Simple Liquids, edited by H. N.
V. Temperley, G. S. Rushbrooke, and J. S. Rowlinson lTI=~ Njl~j! A'!1\"!'1 expfJ3(J.I+Nj+J.I_Nj) -IW I ]
(North-Holland, Amsterdam, 1968), Chap. 5.
8G. E. Norman and V. S. Filinov, High Temp. (USSR) 7, 216 and thus the ratio of acceptance probabilities (6) would be un-
(1969). changed. This point of view seems, however, cumbersome
9D• J. Adams, Mol. Phys. 28, 1241 (1974). and artifiCial, since no such labeling in fact takes place.
Ion. J. Adams, Mol. Phys. 29, 307 (1975). 16C. S. Hoskins and E. R. Smith (private communication).
ilL. A. Rowley, D. Nicholson, and N. G. Parsonage, J. Com- I7S. G. Brush, H. L. Sahlin, and E. Teller, J. Chern. Phys.
put. Phys. 17, 401 (1975). 45, 2102 (1966).
12L. A. Rowley, D. Nicholson, and N. G. Parsonage, Mol. 18B. P. Chasovskikh and P. N. Vorontsov-Vel'iaminov, High
Phys. 31, 365, 389 (1976); see also J. Comput. Phys. 26, Temp. (USSR) 14, 174 (1976).
66 (1978). 19G. Stell, K. C. Wu, and B. Larsen, Phys. Rev. 37, 1369
13J. M. Hammersley and D. C. Handscomb, Monte Carlo (1976).