Thermodynamic and structural properties of a coarse-grained model of methanol are examined by Monte Carlo simulations and reference interaction site model (RISM) integral equation theory. Methanol particles are described as dimers formed from an apolar Lennard-Jones sphere, mimicking the methyl group, and a sphere with a core-softened potential as the hydroxyl group. Different closure approximations of the RISM theory are compared and discussed. The liquid structure of methanol is investigated by calculating site-site radial distribution functions and static structure factors for a wide range of temperatures and densities. Results obtained show a good agreement between RISM and Monte Carlo simulations. The phase behavior of methanol is investigated by employing different thermodynamic routes for the calculation of the RISM free energy, drawing gas-liquid coexistence curves that match the simulation data. Preliminary indications for a putative second critical point between two different liquid phases of methanol are also discussed.

Topics
Coarse-grain model, Free energy, Numerical algorithms, Computer simulation, Integral equations, Monte Carlo methods, Crystallography, Organic compounds, Reference interaction site model, Classical statistical mechanics
1.
W. L.
 
Jorgensen
,
J. Phys. Chem.
 
90
,
1276
–
1284
(
1986
).
https://doi.org/10.1021/j100398a015
Google Scholar
Crossref
Search ADS
 
2.
M. E.
 
van Leeuwen
 and
B.
 
Smit
,
J. Phys. Chem.
 
99
,
1831
–
1833
(
1995
).
https://doi.org/10.1021/j100007a006
Google Scholar
Crossref
Search ADS
 
3.
M.
 
Haughney
,
M.
 
Ferrario
, and
I. R.
 
McDonald
,
Mol. Phys.
 
58
,
849
–
853
(
1986
).
https://doi.org/10.1080/00268978600101611
Google Scholar
Crossref
Search ADS
 
4.
M.
 
Haughney
,
M.
 
Ferrario
, and
I. R.
 
McDonald
,
J. Phys. Chem.
 
91
,
4934
–
4940
(
1987
).
https://doi.org/10.1021/j100303a011
Google Scholar
Crossref
Search ADS
 
5.
T.
 
Schnabel
,
A.
 
Srivastava
,
J.
 
Vrabec
, and
H.
 
Hasse
,
J. Phys. Chem. B
 
111
,
9871
–
9878
(
2007
).
https://doi.org/10.1021/jp0720338
Google Scholar
Crossref
Search ADS
PubMed
 
6.
G.
 
Guevara-Carrion
,
C.
 
Nieto-Draghi
,
J.
 
Vrabec
, and
H.
 
Hasse
,
J. Phys. Chem. B
 
112
,
16664
–
16674
(
2008
).
https://doi.org/10.1021/jp805584d
Google Scholar
Crossref
Search ADS
PubMed
 
7.
A.
 
Chaimovich
 and
M. S.
 
Shell
,
Phys. Rev. E
 
88
,
052313
(
2013
).
https://doi.org/10.1103/PhysRevE.88.052313
Google Scholar
Crossref
Search ADS
 
8.
J. R.
 
Dowdle
,
S. V.
 
Buldyrev
,
H. E.
 
Stanley
,
P. G.
 
Debenedeti
, and
P. J.
 
Rossky
,
J. Chem. Phys.
 
138
,
064506
(
2013
).
https://doi.org/10.1063/1.4789981
Google Scholar
Crossref
Search ADS
PubMed
 
9.
M.
 
Huš
 and
T.
 
Urbic
,
J. Chem. Phys.
 
139
,
114504
(
2013
).
https://doi.org/10.1063/1.4821226
Google Scholar
Crossref
Search ADS
PubMed
 
10.
M.
 
Huš
 and
T.
 
Urbic
,
J. Chem. Phys.
 
140
,
144904
(
2014
).
https://doi.org/10.1063/1.4870514
Google Scholar
Crossref
Search ADS
PubMed
 
11.
M. E.
 
Johnson
,
T.
 
Head-Gordon
, and
A. A.
 
Louis
,
J. Chem. Phys.
 
126
,
144509
(
2007
).
https://doi.org/10.1063/1.2715953
Google Scholar
Crossref
Search ADS
PubMed
 
12.
M.
 
Huš
 and
T.
 
Urbic
,
Phys. Rev. E
 
90
,
022115
(
2014
).
https://doi.org/10.1103/PhysRevE.90.022115
Google Scholar
Crossref
Search ADS
 
13.
Y. D.
 
Fomin
,
E. N.
 
Tisok
, and
V. N.
 
Ryzhov
,
J. Chem. Phys.
 
135
,
124512
(
2011
).
https://doi.org/10.1063/1.3643115
Google Scholar
Crossref
Search ADS
PubMed
 
14.
S.
 
Zhou
,
J. Chem. Phys.
 
133
,
134107
(
2010
).
https://doi.org/10.1063/1.3486570
Google Scholar
Crossref
Search ADS
PubMed
 
15.
A. B.
 
de Oliveira
,
P. A.
 
Netz
,
T.
 
Colla
, and
M. C.
 
Barbosa
,
J. Chem. Phys.
 
124
,
084505
(
2006
).
https://doi.org/10.1063/1.2168458
Google Scholar
Crossref
Search ADS
PubMed
 
16.
W. P.
 
Krekelberg
,
T.
 
Kumar
,
J.
 
Mittal
,
J. R.
 
Errington
, and
T. M.
 
Truskett
,
Phys. Rev. E
 
79
,
031203
(
2009
).
https://doi.org/10.1103/PhysRevE.79.031203
Google Scholar
Crossref
Search ADS
 
17.
S. V.
 
Buldyrev
,
P.
 
Kumar
,
P. G.
 
Debenedetti
,
P. J.
 
Rossky
, and
H. E.
 
Stanley
,
Proc. Natl. Acad. Sci. U.S.A.
 
104
,
20177
–
20182
(
2007
).
https://doi.org/10.1073/pnas.0708427104
Google Scholar
Crossref
Search ADS
PubMed
 
18.
E. A.
 
Jagla
,
J. Chem. Phys.
 
111
,
8980
(
1999
).
https://doi.org/10.1063/1.480241
Google Scholar
Crossref
Search ADS
 
19.
L.
 
Xu
,
S. V.
 
Buldyrev
,
C. A.
 
Angell
, and
H. E.
 
Stanley
,
Phys. Rev. E
 
74
,
031108
(
2006
).
https://doi.org/10.1103/PhysRevE.74.031108
Google Scholar
Crossref
Search ADS
 
20.
L.
 
Xu
,
N.
 
Giovambattista
,
S. V.
 
Buldyrev
,
P. G.
 
Debenedetti
, and
H. E.
 
Stanley
,
J. Chem. Phys.
 
134
,
064507
(
2011
).
https://doi.org/10.1063/1.3521486
Google Scholar
Crossref
Search ADS
PubMed
 
21.
G.
 
Franzese
,
J. Mol. Liq.
 
136
,
267
–
273
(
2007
).
https://doi.org/10.1016/j.molliq.2007.08.021
Google Scholar
Crossref
Search ADS
 
22.
Z.
 
Su
,
S. V.
 
Buldyrev
,
P. G.
 
Debenedetti
,
P. J.
 
Rossky
, and
H. E.
 
Stanley
,
J. Chem. Phys.
 
136
,
044511
(
2012
).
https://doi.org/10.1063/1.3677185
Google Scholar
Crossref
Search ADS
PubMed
 
23.
J. P.
 
Hansen
 and
I. R.
 
McDonald
,
Theory of Simple Liquids
, 3rd ed. (
Academic Press
,
New York
,
2006
).
Google Scholar
 
24.
C.
 
Caccamo
,
Phys. Rep.
 
274
,
1
–
105
(
1996
).
https://doi.org/10.1016/0370-1573(96)00011-7
Google Scholar
Crossref
Search ADS
 
25.
D.
 
Chandler
 and
H. C.
 
Andersen
,
J. Chem. Phys.
 
57
,
1930
–
1937
(
1972
).
https://doi.org/10.1063/1.1678513
Google Scholar
Crossref
Search ADS
 
26.
L. J.
 
Lowden
 and
D.
 
Chandler
,
J. Chem. Phys.
 
61
,
5228
–
5241
(
1974
).
https://doi.org/10.1063/1.1681868
Google Scholar
Crossref
Search ADS
 
27.
E.
 
Johnson
 and
R. P.
 
Hazoume
,
J. Chem. Phys.
 
70
,
1599
(
1979
).
https://doi.org/10.1063/1.437699
Google Scholar
Crossref
Search ADS
 
28.
L.
 
Lue
 and
D.
 
Blankschtein
,
J. Chem. Phys.
 
102
,
5427
–
5437
(
1995
).
https://doi.org/10.1063/1.469270
Google Scholar
Crossref
Search ADS
 
29.
A.
 
Kovalenko
 and
F.
 
Hirata
,
J. Theor. Comput. Chem.
 
1
,
381
–
406
(
2002
).
https://doi.org/10.1142/S0219633602000282
Google Scholar
Crossref
Search ADS
 
30.
B. M.
 
Pettitt
 and
P. J.
 
Rossky
,
J. Chem. Phys.
 
78
,
7296
–
7299
(
1983
).
https://doi.org/10.1063/1.444719
Google Scholar
Crossref
Search ADS
 
31.
B.
 
Kvamme
,
Phys. Chem. Chem. Phys.
 
4
,
942
–
948
(
2002
).
https://doi.org/10.1039/b108724j
Google Scholar
Crossref
Search ADS
 
32.
D.
 
Costa
,
G.
 
Munaò
,
F.
 
Saija
, and
C.
 
Caccamo
,
J. Chem. Phys.
 
127
,
224501
(
2007
).
https://doi.org/10.1063/1.2803059
Google Scholar
Crossref
Search ADS
PubMed
 
33.
F.
 
Hirata
,
Molecular Theory of Solvation
(
Kluwer Academic Publishers
,
Dordrecht
,
2003
).
Google Scholar
 
34.
G.
 
Munaò
,
D.
 
Costa
,
F.
 
Sciortino
, and
C.
 
Caccamo
,
J. Chem. Phys.
 
134
,
194502
(
2011
).
https://doi.org/10.1063/1.3582904
Google Scholar
Crossref
Search ADS
PubMed
 
35.
M.
 
Tripathy
 and
K. S.
 
Schweizer
,
J. Phys. Chem. B
 
117
,
373
(
2013
).
https://doi.org/10.1021/jp308991c
Google Scholar
Crossref
Search ADS
PubMed
 
36.
G.
 
Munaó
,
D.
 
Costa
,
A.
 
Giacometti
,
C.
 
Caccamo
, and
F.
 
Sciortino
,
Phys. Chem. Chem. Phys.
 
15
,
20590
(
2013
).
https://doi.org/10.1039/c3cp52425f
Google Scholar
Crossref
Search ADS
PubMed
 
37.
T.
 
Urbic
 and
C. L.
 
Dias
,
J. Chem. Phys.
 
140
,
094703
(
2014
).
https://doi.org/10.1063/1.4867289
Google Scholar
Crossref
Search ADS
PubMed
 
38.
A.
 
Kovalenko
 and
F.
 
Hirata
,
J. Chem. Phys.
 
110
,
10095
(
1999
).
https://doi.org/10.1063/1.478883
Google Scholar
Crossref
Search ADS
 
39.
A.
 
Kovalenko
 and
F.
 
Hirata
,
Chem. Phys. Lett.
 
349
,
496
(
2001
).
https://doi.org/10.1016/S0009-2614(01)01241-6
Google Scholar
Crossref
Search ADS
 
40.
T.
 
Urbic
,
J. Phys. Chem.
 
139
,
164515
(
2013
).
https://doi.org/10.1063/1.4827862
Google Scholar
Crossref
Search ADS
 
41.
T.
 
Morita
 and
K.
 
Hiroike
,
Progr. Theor. Phys. (Jpn)
 
23
,
1003
(
1960
).
https://doi.org/10.1143/PTP.23.1003
Google Scholar
Crossref
Search ADS
 
42.
S. J.
 
Singer
 and
D.
 
Chandler
,
Mol. Phys.
 
55
,
621
–
625
(
1985
).
https://doi.org/10.1080/00268978500101591
Google Scholar
Crossref
Search ADS
 
43.
M.
 
Huš
 and
T.
 
Urbic
, “
Existence of a liquid-liquid phase transition in methanol
,” Phys. Rev. E (to be published).
44.
G.
 
Malescio
,
G.
 
Franzese
,
G.
 
Pellicane
,
A.
 
Skibinsky
,
S. V.
 
Buldyrev
, and
H. E.
 
Stanley
,
J. Phys: Condens. Matter
 
14
,
2193
(
2002
).
https://doi.org/10.1088/0953-8984/14/9/308
Google Scholar
Crossref
Search ADS
 
45.
E.
 
Lomba
,
N. G.
 
Almarza
,
C.
 
Martín
, and
C. M.
 
Bride
,
J. Chem. Phys.
 
126
,
244510
(
2007
).
https://doi.org/10.1063/1.2748043
Google Scholar
Crossref
Search ADS
PubMed
 
46.
L. J.
 
Lowden
 and
D.
 
Chandler
,
J. Chem. Phys.
 
59
,
6587
(
1973
).
https://doi.org/10.1063/1.1680038
Google Scholar
Crossref
Search ADS
 
47.
G.
 
Munaò
,
D.
 
Costa
, and
C.
 
Caccamo
,
J. Chem. Phys.
 
130
,
144504
(
2009
).
https://doi.org/10.1063/1.3098551
Google Scholar
Crossref
Search ADS
PubMed
 
48.
G.
 
Munaò
,
D.
 
Costa
, and
C.
 
Caccamo
,
Chem. Phys. Lett.
 
470
,
240
(
2009
).
https://doi.org/10.1016/j.cplett.2009.01.064
Google Scholar
Crossref
Search ADS
 
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