Article

pubs.acs.org/JPCB

Water−Methanol Mixtures: Simulations of Mixing Properties over the

Entire Range of Mole Fractions
Jean-Christophe Soetens* and Philippe A. Bopp
Institut des Sciences Moléculaires, UMR CNRS no. 5255, and Department of Chemistry, Université de Bordeaux, 351 Cours de la
Libération, 33405 Talence, France

ABSTRACT: Numerous experimental and theoretical investigations

have been devoted to the hydrogen bond in pure liquids and mixtures.
Among the different theoretical approaches, molecular dynamics (MD)
simulations are predominant in obtaining detailed information, on the
molecular level, simultaneously on the structure and the dynamics.
Water and methanol are the two most prominent hydrogen-bonded
liquids, and they and their mixtures have consequently been the subject
of many studies; we revisit here the problem of the mixtures. An
important first step is to check whether a classical potential model, the
components of which are deemed to be satisfactory for the pure liquids,
is able to reproduce the known thermodynamic excess properties of the
mixtures sufficiently well. We have used the available BJH (water) and
PHH (methanol) flexible models because they are by construction
mutually compatible and also well suited to study, in a second step, some
dynamic property characteristic of hydrogen-bonded liquids. In this article we show that these models, after a slight
reparametrization for use in NpT simulations, reproduce the essential features of the excess mixing and molar properties of
water−methanol mixtures. Furthermore, in the pure liquids, the agreement of the radial distribution functions with experiment
remains as satisfactory as before. Similarly, the translation self-diffusion coefficients D are modified by less than 10%. In the
mixtures, they evolve nonmonotonously as a function of mole fraction.

■ INTRODUCTION
Water (H2O) and methanol (CH3OH, MeOH) are completely
miscible liquids at room temperature and ambient pressure,
as is to be expected from the polar character of these two
molecules. The molecular dipole moments (in the gas phase
μH2O = 1.86 D, μMeOH = 1.69 D) are similar; however, the static
dielectric constant (relative permittivities) of the two neat
liquids (εH2O ≈ 80, εMeOH ≈ 33) are markedly different because
of the different structures.
The presence of a hydrophobic group CH3 nevertheless
contributes to peculiar properties such as the appearance of
a minimum in the partial molar volume of methanol. Thus,
alcohols are sometimes seen as soluble hydrocarbons, and
models to explain the properties of their mixtures with water
are still discussed.1−4 Molecular simulations are certainly the
methods of choice to elucidate the properties of these systems
on a microscopic level. Most theoretical efforts have used
molecular dynamics (MD) simulations to study the structure,
the dynamic properties, and the properties of mixing, separately
or together.5−12 A number of experimental investigations have
also been performed over the years, and most properties such as
the density,13−15 the diffusion,16 the properties of mixing,17−20
and the structure1,21,22 are well known.
Even though there is a wealth of studies on mixtures, not
many combined efforts to obtain thermodynamic, structural,
and dynamic properties in a consistent fashion have been
reported so far. This has, however, been accomplished for some
neat liquids, for which detailed analyses of the hydrogen bond
network have been carried out by combining MD simulations
and vibrational spectroscopy experiments23−25 Applied to
mixtures such as water−methanol, we expect that this strategy
will lead to an improved qualitative and quantitative microscopic
understanding of the peculiar properties of these systems. To
achieve this goal, an important first step is to check whether a
classical (flexible) potential model is able to reproduce the well-
known excess properties of these mixtures sufficiently well.
Interaction models for mixtures are usually constructed by
combining existing models developed and tested for the pure
liquids, in most cases by keeping the partial charges of the initial
models and applying empirical combination rules (Lorentz−
Berthelot,26 Kong,27 and others) for the Lennard-Jones 12−6
terms. In the present study we have started from the available
BJH28 and PHH29 flexible models for water and methanol,
respectively; they have already been used extensively. (See ref 30
and the references therein.) Having been devised to be mutually
compatible, they are also suited to study spectroscopic pro-
perties because they describe with good accuracy, in the
approximation of classical mechanics, the vibrational modes of
water and methanol and in particular the shifts in the OH
stretching region.5
Received: April 7, 2015
Revised: May 29, 2015

© XXXX American Chemical Society A DOI: 10.1021/acs.jpcb.5b03344

J. Phys. Chem. B XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry B Article

Most of the previous MD studies of water−methanol mixtures Table 1. Refitted Parameters for the BJH28 and PHH29
have, however, been performed at constant volume (NVE or Models (Equations 1−4)
NVT ensembles), mostly at the experimental density at room
old new
temperature and normal pressure. Because both models were not parameters28,29 parameters
devised to reproduce the experimental densities, their use in
p1 1.045 1.463 kJ/mol
NpT simulations is not satisfactory. In some cases (depending,
p2 418 10.45 kJ/mol
for example, on mixture compositions) this may prove to be
p3 3.47 3.61 Å, water−methanol interactions only
impossible as they then predict unrealistic pressures. For these
p4 3.86 3.52 Å
reasons we did not investigate the energy properties in any
depth. The mixing effects are small, and comparing NVE and
NpT simulations, at different average pressures and temperatures oxygen−oxygen (VOO), oxygen−hydrogen (VOH), and hydrogen−
and with different box sizes and truncation schemes, would hydrogen (VHH) contributions are identical for the water−
require extensive work. Suffice it to say that we obtain the correct water, water−methanol, and water−methanol interactions, and
qualitative behavior of the potential energies as a function of the any change in the parametrization should retain this homogeneity.
mole fractions. 111 889
VOO = − p1 [exp(−4(r − 3.5)2 ) + exp(−1.5(r − 4.5)2 )]
In this article we first introduce a new parametrization for the r 8.86
BJH and PHH models to allow their use in NpT simulations (1)
of both the pure liquids and the mixtures over the entire 26.07 41.79 16.74
miscibility range, i.e. χ = 0 to 1. We have attempted to keep the VOH = 9.2 −
1 + exp(40(r − 1.05))
−
1 + exp(5.439(r − 2.2))
r
modifications as small as possible. We show that we can in this
(2)
way reproduce the essential features of the density, excess
volume, and partial molar volumes of water and methanol over p2
VHH =
the whole range of molar fraction reasonably well. These 1 + exp(29.9(r − 1.968)) (3)
properties of the binary systems are found to be quite sensitive
⎡⎛ p ⎞12 ⎛ p ⎞6⎤
to details of the intermolecular interactions, so the results VMeO = 4 × 0.3713⎢⎜ 3 ⎟ − ⎜ 3 ⎟ ⎥
presented below can be said to be a quite stringent test of the ⎢⎣⎝ r ⎠ ⎝ r ⎠ ⎥⎦
models. Of course, we also want to preserve the features that ⎡⎛ p ⎞12 ⎛ p ⎞6⎤
made the original models successful. We therefore proceeded to VMeMe = 4 × 0.1883⎢⎜ 4 ⎟ − ⎜ 4 ⎟ ⎥
⎢⎣⎝ r ⎠ ⎝ r ⎠ ⎥⎦ (4)
reevaluate some structural and dynamics properties of the pure
liquids and mixtures in a consistent fashion. In the next sections We note that the main modification concerns parameter p2,
we present first the modified model used in this study and the which essentially controls the H−H repulsion (cf. the original
details of the MD simulations. Then we look at the properties CF models32,33). The original large value of this parameter,
that we considered to be important and that were consequently which had essentially been carried over in later developments,
used to parametrize the model. After comparing the radial dis- was one of the main causes of the unsatisfactory pressures
tributions functions (RDFs) for the modified and unmodified obtained originally. Earlier work34 aiming essentially at bringing
models in the pure liquids, we proceed to discuss the radial pair the H−H radial distribution into better agreement with
distribution functions and translational self-diffusion constants experimental data35 involved adjusting the distance (1.968 Å)
in the mixtures.

■
MODELS AND SIMULATION DETAILS
Interaction Model. All simulations presented in this article
make use of the BJH28 and PHH29 models for water and
methanol, respectively. In both models, the molecules are
represented by three interacting sites located on the oxygen and
hydrogen atoms of the hydroxyl group and on the methyl group
(which is thus a united atom, a drastic simplification). The total
potential energy is the sum of intra- and intermolecular con-
tributions. The intramolecular parts, the anharmonicity of
which has been adjusted31 in the water case to yield, roughly,
the observed vibrational frequency shifts between the gas and
liquid phases,31 were not modified. The modifications of the
intermolecular potentials were kept, as already stated, minimal
and are not expected to affect the vibrational frequencies,31
which just should not require any modification of the intra-
molecular part. More details can be found in ref 5.
The model for the intermolecular potential energy is derived
from the central force model.32,33 The electrostatic part consists
of Coulomb terms between partial charges (qO = −0.66e and
qH = 0.33e for water; qO = −0.60e, qH = 0.35e, and qMe = 0.25e
for methanol). We recall below the empirical parts of the
intermolecular pair potential (in kJ mol−1 and Å); p1−p4 are
the parameters that we selected to be refitted in this work, and
they are summarized in Table 1. It is important to note that the
B DOI: 10.1021/acs.jpcb.5b03344
where the repulsion sets in. It succeeded in improving the
structure but failed otherwise, among other things, because the
self-diffusion coefficient increased by almost 40% in the case
where the best agreement of the gOO values was achieved.
Simulation Runs. After a large number of trial runs to
determine which parameters in the original model to keep and
which ones to readjust (eqs 1−4) and determine the new values
(reported in Table 1), we have first carried out MD simulations
of the pure liquids in the NEV ensemble at ⟨T⟩ = 298 K and
experimental density.17 The electrostatic interactions were
treated here, as everywhere else, with the reaction (RF)
method36,37 (here for charge−charge interactions); the dielectric
constant of the surrounding continuum was set to εRF = ∞.
A molecular cutoff equal to half of the edge of the box was
applied. The other empirical potential terms were truncated
so that numerical problems (e.g., under/overflows in the
exponential functions) were avoided. These simulations were
carried out with N = 1000 molecules. The equations of motions
were integrated with the velocity Verlet algorithm38 with a time
step equal to 0.2 fs. The simulations were run with the MDpol39
program package, and each simulation consisted of two
independent calculations of 500 ps (2.5 M steps) each after
appropriate equilibration periods. During the simulations, a
small velocity rescaling has nevertheless been applied every
0.1 ps in order to reach the desired average temperature with a
deviation of less than 1 K. The NpT simulations (at 298.15 K
J. Phys. Chem. B XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry B Article

and 1 atm) were carried out in a similar manner; i.e., all of the
technical details were the same excepted for the thermodynamic
ensemble controlled using the Nosé−Andersen algorithm40−42
(with coupling constants of 5 and 1 ps−1 with a heat bath and
piston, respectively).
We studied nine mixtures with mole fractions varying from
0.1 to 0.9 as well as the two pure liquids in NpT-MD simula-
tions (details in Table 3). In all cases, as above, two runs starting
from different and uncorrelated initial conditions were first
equilibrated before starting the 500 ps productions runs. The
results reported below stem from these simulations.
Thermodynamics. Mixtures of liquids such as the water− Figure 1. Density of water−methanol mixtures at T = 298 K,
methanol binary system can be characterized by their excess p = 1 atm as a function of the mole fraction of methanol: results from
mixing functions. For the volume, for instance, one can express NpT-MD simulations (dashed line and circles) and experimental
the corresponding excess property VE as results17 (solid line). The ideal densities, shown for comparison
(dashed−dotted line), are obtained from a linear combination of the
mole volumes of the pure compounds.
V E = Vmix − ∑ nivi(0)
i (5)

where Vmix is the volume of the mixture, v(0)i is the molar

volumes of the pure compounds, and ni is the number of moles
of each component. In the present binary mixtures, the partial
molar volume of each component, vi, can be obtained from
the following relations

Table 2. Comparison of Some Properties of Liquid Water

and Liquid Methanol under Ambient Conditions Obtained
from NEV-MD Simulations Using the Original Models
(BJH28 and PHH,29Respectively) and NpT-MD Simulations
with the New Parametrization for These Models, as Figure 2. Excess molar volumes obtained from NpT-MD simulations
Described in the Text at T = 298 K, p = 1 atm (dashed line and circles), experimental
results17 (solid line), and results from previous simulation work9
NEV NpT (dashed−dotted line).
⟨T⟩ =298 K T = 298.15 K, p = 1 atm
Water BJH Model Modified Model Table 4. Parameters Obtained from a Fit Using Equation 7
ρ (g cm−3) 0.99717 0.997 on Experimental Data17 and Previous Work from Diego
⟨Epot⟩ (kJ mol−1) −41.9 −45.8 González-Salgado et al.9 and the Present Worka
D (10−9 m2 s−1) 1.5 1.5
⟨p⟩ (atm) 4015 1 Ak exp previous work this work
Methanol PHH Model Modified Model A0 −4.033 −3.209 −3.997
ρ (g cm−3) 0.78717 0.788 A1 −0.294 −0.291 1.043
⟨Epot⟩ (kJ mol−1) −26.6 −28.2 A2 0.478 0.224
D (10−9 m2 s−1) 4.0 4.4 A3 0.851 1.033
a
⟨p⟩ (atm) 1000 1 The corresponding curves are presented in Figure 2.

Table 3. Details of the NpT-MD Simulations of Water−Methanol Mixtures, Mole Fractions, Number of Molecules in the
Simulation Boxes, Experimental17 and Simulated Densities, and Excess Volumes of the Systemsa
density (g cm−3) VE (cm3 mol−1)

χMeOH NMeOH NH2O exp simulation exp simulation

0.0 0 1000 0.99710 0.9970 ± 0.0001 0.0000 0.000 ± 0.000
0.1 100 900 0.97015 0.9656 ± 0.0014 −0.3174 −0.221 ± 0.026
0.2 200 800 0.94719 0.9428 ± 0.0005 −0.6166 −0.510 ± 0.017
0.3 300 700 0.92523 0.9204 ± 0.0000 −0.8441 −0.708 ± 0.007
0.4 400 600 0.90339 0.9014 ± 0.0007 −0.9758 −0.904 ± 0.014
0.5 500 500 0.88175 0.8820 ± 0.0003 −1.0083 −1.001 ± 0.020
0.6 600 400 0.86073 0.8638 ± 0.0002 −0.9509 −1.040 ± 0.016
0.7 700 300 0.84075 0.8437 ± 0.0004 −0.8176 −0.910 ± 0.005
0.8 800 200 0.82195 0.8256 ± 0.0007 −0.6189 −0.749 ± 0.019
0.9 900 100 0.80417 0.8077 ± 0.0010 −0.3535 −0.490 ± 0.060
1.0 1000 0 0.78690 0.7876 ± 0.0003 0.0000 0.000 ± 0.000

a
The results and uncertainties were obtained from two sets of uncorrelated calculations, as discussed in the text.

C DOI: 10.1021/acs.jpcb.5b03344
J. Phys. Chem. B XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry B Article

Figure 3. Partial molar volumes of water and methanol in their

mixtures obtained from NpT-MD simulations at T = 298 K, p = 1 atm
(dashed line and circles), experimental results17 (solid line), and
results from previous simulation work9 (dashed−dotted line). The
lines are given by eq 7, and the parameters are listed in Table 4.

Figure 5. Radial distribution functions of liquid methanol. Comparison

of the results obtained from the original PHH water model29 under
NEV conditions (dashed lines) with the modified model under NpT
(T = 298 K) conditions (solid lines).

■ RESULTS AND DISCUSSION

Excess Properties. The simulated properties of the pure
liquids in the NVE and NpT ensembles are given in Table 2.
The goal of having the correct experimental pressure is achieved
in both cases while the average potential energies of both systems
are lowered. The self-diffusion constant of water remains the
same, i.e., a bit too low, while that of methanol, already too high
compared to experiment,16 is increased by about 10%.
We present in Table 3 the densities and the excess volumes
Figure 4. Radial distribution functions of liquid water. Comparison of of the water−methanol mixtures as a function of the methanol
the results obtained from the original BJH water model28 under mole fraction χMeOH. The variation of these properties is also
NEV conditions (dashed lines) with the modified model under NpT shown in Figures 1 and 2 and compared with experimental
(T = 298 K) conditions (solid lines). results. The densities and their associated error bars have been
⎛ ⎞ ⎛ ⎞ obtained from the two independent 500 ps productions runs
∂V ∂Δv ⎟
vi = ⎜⎜ mix ⎟⎟ = vi(0) + Δv − χj ⎜⎜ ⎟
(as described in a previous section). The statistical errors
⎝ ∂ni ⎠T , P , n ≠ n ⎝ ∂χj ⎠T , P appear to be negligible, and the agreement with experiment
j i (6)
is fairly good as the maximum deviation is about 0.5%. The
where χi = ni/(n1 + n2) is the mole fraction of component i and calculated excess volume VE also agrees well with experiment,
Δv = ((VE)/(n1 + n2)). The following equation17 can be used and the maximum deviation with respect to ideal mixtures is
to fit the simulated volumes: about −1 cm3 mol−1. The extremum is slightly shifted toward
3 larger mole fractions. Figure 2 also shows the curve resulting
V E = χ1 χ2 ∑ Ak (χ2 − χ1 )k from a fit of simulated data using eq 7, and the corresponding
k=0 (7) optimized parameters are given in Table 4.
D DOI: 10.1021/acs.jpcb.5b03344
J. Phys. Chem. B XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry B Article

Figure 6. Selected radial distribution functions (left ordinate) and corresponding integrals (right ordinate) for methanol−water mixtures as a
function of the mole fraction of methanol. (Left) Top: gOwOw(r). Middle: gOmOm(r). Bottom: gOwOm(r). (Right) Top: gOwHw(r). Middle: gOmHm(r).
Bottom: gOwHm(r). Subscripts w and m denote water and methanol, respectively. For clarity, only the results for the systems with the following mole
fractions of methanol have been plotted: 0.1, 0.3, 0.5, 0.7, and 0.9. Because the sequence of the curves is monotonous, only the lowest mole fraction
of each set is indicated.

Using these parameters one can calculate the partial molar
volumes of water and methanol; the results are presented in
Figure 3. As the densities of the pure liquids are very well re-
produced the calculated partial molar volumes of water (vH(0)2O =
18.07 cm3 mol−1) and methanol (v(0) 3
MeOH = 40.66 cm mol )
−1
virtually coincide with experimental results. For both species
the overall agreement is also good for intermediate mole
fractions. To the best of our knowledge the minimum in the
partial volume of methanol at low concentration has been
reproduced here for the first time. Because this feature depends
on the slope of the excess volume curve, the present model
seems to be able to describe the subtle changes occurring in the
structure of the mixture when only a few alcohol molecules are
mixed with water.
Structure. The structures of the pure liquids and of the
mixtures have been analyzed by computing radial distributions
functions (RDFs) together with the corresponding running
coordination numbers. In Figure 4 we present the three water−
water partial RDFs in pure water, namely, gOwOw(r), gOwHw(r),
and gHwHw(r), where subscript w denotes water (and later on
subscript m denotes methanol). Figure 5 shows the correspond-
ing three functions for pure methanol. Finally, Figure 6 shows
E DOI: 10.1021/acs.jpcb.5b03344
selected self and cross g functions in mixtures of various
compositions. We define as usual
Nβ r
nαβ (r ) = 4π ∫0 r′2 gαβ (r′) dr′
V (8)
where Nβ is the number of β particles in the system and ⟨V⟩ is
the average volume (in NpT simulations, otherwise the fixed
volume) of the simulation box. nαβ(r) is thus the total number of
β-type neighbors around a particle of type α.
The results presented in Figures 4 and 5 allow a comparison
with the original model, BJH and PHH, respectively, under
NEV conditions, with the present modified versions under NpT
conditions. In both systems gOO(r) and gOH(r) remain constant
and only very slight differences are observed in the gHwHw(r) and
gMeMe(r) functions. The new parametrization obviously does
not alter the interactions responsible for the hydrogen bonding
yet modifies other parts of the potential enough to maintain a
reasonable pressure in the systems.
The cross g functions in mixtures, presented in Figure 6,
show an increase in the height of the peaks as the mole fraction
of methanol increases. The positions of the first and second
peaks seem not to be affected by the change in composition in
J. Phys. Chem. B XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry B
Figure 7. Running coordination numbers (text and eq 8), nOwOw (solid
line and triangles), and nOwOm (dashed line and circles) as a function of
the mole fraction of methanol.
the system. The values of the integrals of the gOwOw(r) and
gOwOm(r) RDFs at the first minimum are shown in Figure 7.
The first peak in the gOwOw(r) functions becomes higher as
χMeOH increases, but the coordination number associated with
its integration decreases, which indicates the presence of
methanol molecules around water molecules even at very low
mole fractions. The “inversion” in the number of neighbors
occurs around χMeOH = 0.65, i.e., the number of methanol
molecules in the first solvation shell of water becomes larger
than the number of water molecules. These results show that
the correct evolution of the density of the system seen here
results from a progressive mixing of the two species and not
from a segregation process.
Dynamics. We have characterized the translational mobility
of the molecules by their self-diffusion constant D. This pro-
perty was obtained from the mean square displacements using
the Einstein relation.26 For the pure liquids under ambient con-
ditions, the experimental self-diffusion constants of water and
methanol are similar, namely, 2.3 × 10−9 and 2.4 × 10−9 m2 s−1,
respectively.16 In addition to other properties it is well known
that these values are difficult to reproduce by most potentials.
(For water, see ref 43.) This remark applies in particular to the
PHH model because it makes use of only three interacting sites.
It has already been observed that the reduced steric hindrance
resulting from this choice, compared to an all-atom six-site
model, leads to an increase in the diffusion processes.44
The results are presented in Figure 8. In the mixtures, D goes
through a minimum as a function of composition of both the
water and methanol molecules. This feature is moderately well
reproduced in our simulations for water; i.e., we see a minimum
but not at the mole fraction where it is found experimentally. For
methanol, the simulated self-diffusion increases monotonously
with increasing mole fraction of MeOH and rises to a value that
is too large for the pure system. The very slight minimum seen
experimentally around χMeOH ≈ 0.3 does not appear.
■
CONCLUDING REMARKS
The modified versions of the BJH and PHH models presented
in this article demonstrate that it is possible within the frame-
work of pair interactions to describe the pure liquids and to
reproduce the excess mixing and molar properties of mixtures.
To the best of our knowledge, one of these properties, the
minimum in the partial volume of methanol at low concentra-
tion in water, has been reproduced here for the first time. Only
minor changes in the model parameters were required to use
these models in NpT simulations, thus retaining their intrinsic
qualities such as the interactions responsible for the hydrogen
bonding and the adjusted intramolecular parts.
F DOI: 10.1021/acs.jpcb.5b03344
Article
Figure 8. Self-diffusion coefficient of water (top) and methanol
(bottom) in water−methanol mixtures obtained from NpT simulations
(dashed lines and circles) as a function of the mole fraction of
methanol. Experimental data are from ref 16 (solid lines and triangles).
Because these models have essentially been constructed to
study spectroscopic properties, they are particularly well suited to
study in detail the hydrogen bond networks and its evolution: the
shifts of the vibrational OH-streching frequencies induced by
the presence of hydrogen bonds (or other perturbations) can be
easily detected and correlated with structural features. We expect
that the combination of such studies with vibrational spectroscopy
experiments will lead to an improved qualitative and quantitative
understanding of the peculiar properties of these systems.
■
AUTHOR INFORMATION
Corresponding Author
*Phone: +33 (0)5 4000 2242. E-mail: jean-christophe.
soetens@u-bordeaux.fr.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
Computer time for this study was provided by MCIA
(Mésocentre de Calcul Intensif Aquitain), the public research
HPC center in Aquitany, France.
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