Abstract
A correlation-function-based scheme is proposed for calculating the osmotic second virial coefficient B for solutes that dissolve very little in a solvent. The short-distance contribution to B, a volume integral of the solute-solute pair correlation function h(r) from 0 to some finite distance rc, is evaluated with h(r) obtained by molecular simulation. The remaining contribution to B from rc to ∞ is calculated with an asymptotic form of h(r) (Evans, R.; et al. J. Chem. Phys. 1994, 100, 591). It is shown here that B for a model system of methane in water is obtained accurately in the temperature range between 238 and 373 K at 1 bar, with a result that B is a monotonically decreasing function of temperature, and the hydrophobic interaction between methane molecules measured by B is repulsive (B > 0) in supercooled water, virtually null (B ≲ 0) at around 0 C, and attractive (B <0) at higher temperatures. It is also remarked that a nearly linear relation holds between B and the first-peak height of the solute-solute radial distribution function.
| Original language | English |
|---|---|
| Pages (from-to) | 12619-12624 |
| Number of pages | 6 |
| Journal | Journal of Physical Chemistry B |
| Volume | 117 |
| Issue number | 41 |
| DOIs | |
| Publication status | Published - Oct 17 2013 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Materials Chemistry
- Surfaces, Coatings and Films
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Osmotic second virial coefficient of methane in water. / Koga, Kenichiro.
In: Journal of Physical Chemistry B, Vol. 117, No. 41, 17.10.2013, p. 12619-12624.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Osmotic second virial coefficient of methane in water
AU - Koga, Kenichiro
PY - 2013/10/17
Y1 - 2013/10/17
N2 - A correlation-function-based scheme is proposed for calculating the osmotic second virial coefficient B for solutes that dissolve very little in a solvent. The short-distance contribution to B, a volume integral of the solute-solute pair correlation function h(r) from 0 to some finite distance rc, is evaluated with h(r) obtained by molecular simulation. The remaining contribution to B from rc to ∞ is calculated with an asymptotic form of h(r) (Evans, R.; et al. J. Chem. Phys. 1994, 100, 591). It is shown here that B for a model system of methane in water is obtained accurately in the temperature range between 238 and 373 K at 1 bar, with a result that B is a monotonically decreasing function of temperature, and the hydrophobic interaction between methane molecules measured by B is repulsive (B > 0) in supercooled water, virtually null (B ≲ 0) at around 0 C, and attractive (B <0) at higher temperatures. It is also remarked that a nearly linear relation holds between B and the first-peak height of the solute-solute radial distribution function.
AB - A correlation-function-based scheme is proposed for calculating the osmotic second virial coefficient B for solutes that dissolve very little in a solvent. The short-distance contribution to B, a volume integral of the solute-solute pair correlation function h(r) from 0 to some finite distance rc, is evaluated with h(r) obtained by molecular simulation. The remaining contribution to B from rc to ∞ is calculated with an asymptotic form of h(r) (Evans, R.; et al. J. Chem. Phys. 1994, 100, 591). It is shown here that B for a model system of methane in water is obtained accurately in the temperature range between 238 and 373 K at 1 bar, with a result that B is a monotonically decreasing function of temperature, and the hydrophobic interaction between methane molecules measured by B is repulsive (B > 0) in supercooled water, virtually null (B ≲ 0) at around 0 C, and attractive (B <0) at higher temperatures. It is also remarked that a nearly linear relation holds between B and the first-peak height of the solute-solute radial distribution function.
UR - http://www.scopus.com/inward/record.url?scp=84886938627&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84886938627&partnerID=8YFLogxK
U2 - 10.1021/jp4085298
DO - 10.1021/jp4085298
M3 - Article
C2 - 24050222
AN - SCOPUS:84886938627
VL - 117
SP - 12619
EP - 12624
JO - Journal of Physical Chemistry B Materials
JF - Journal of Physical Chemistry B Materials
SN - 1520-6106
IS - 41
ER -