Excess volumes related to the process of forming a spherical cavity in water were used to obtain the excess number of solvent molecules at the accessible surface. The expression presented in a previous work to describe the scaling of this property with the cavity radius has been revised. In particular, changes were introduced in order to agree with results from scaled particle theory in the limit of very small cavities. This expression enables one to obtain equimolar radii and, after free energy calculations, the surface tension at the equimolar surfaces. The effect of the excess volume errors on these properties is discussed.
REFERENCES
1.
F. M.
Floris
, J. Chem. Phys.
126
, 074505
(2007
).2.
F. M.
Floris
, J. Phys. Chem. B
109
, 24061
(2005
).3.
H. S.
Ashbaugh
and T. M.
Truskett
, J. Chem. Phys.
134
, 014507
(2011
).4.
F. M.
Floris
, J. Phys. Chem. B
108
, 16244
(2004
).5.
M. S.
Moghaddam
and H. S.
Chan
, J. Chem. Phys.
126
, 114507
(2007
).6.
H.
Reiss
, H.
Frish
, and J.
Lebowitz
, J. Chem. Phys.
31
, 369
(1959
).7.
H. S.
Ashbaugh
and L.
Pratt
, Rev. Mod. Phys.
78
, 159
(2006
).8.
A.
Jain
and H. S.
Ashbaugh
, J. Chem. Phys.
129
, 174505
(2008
).9.
10.
F.
Buff
, J. Chem. Phys.
25
, 146
(1956
).11.
In this case the reference surface is the accessible surface to the motion of oxygen center of water molecules.
12.
W.
Jorgensen
, J.
Chandrasekhar
, J.
Madura
, R.
Impey
, and M.
Klein
, J. Chem. Phys.
79
, 926
(1983
).13.
See supplementary material at http://dx.doi.org/10.1063/1.3693329 for information on the whole range of data and on surface tension at the equimolar surface.
14.
A.
Ben-Naim
, Statistical Thermodynamics for Chemists and Biochemists
(Plenum
, New York
, 1992
).15.
D.
Ben-Amotz
, J. Chem. Phys.
123
, 184504
(2005
).16.
It has been assumed that f1 holds only at intermediate radii because it does not give constant adsorption at infinity.
17.
Fitted data were in fact derived by subtracting kKBT from the volumes reported in Table I of Ref. 4, which were erroneously considered as molar volumes instead of excess volumes. A revision of the simulation results has shown that the solute was fixed because of the 0 values set for the range of the attempted movements, which is not exactly the same as 0 number of attempted movements. However, systematic errors resulting from the procedure used should not have a particular sign and should decrease with longer simulations. In the worse case such errors are supposed to be of the same order of statistical uncertainties. This was proven on test calculations carried out for some cavity radii.
18.
J.
Rowlinson
, J. Phys. Condens. Matter
6
, A1
(1994
).19.
F. H.
Stillinger
, J. Solution Chem.
2
, 141
(1973
).20.
D.
Huang
, P.
Geissler
, and D.
Chandler
, J. Phys. Chem. B
105
, 6704
(2001
).© 2012 American Institute of Physics.
2012
American Institute of Physics
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