Scaling of hydrophobic solvation free energies

Journal Article · Tue Apr 03 04:00:00 EDT 2001 · Journal of Physical Chemistry, B

DOI:https://doi.org/10.1021/jp0104029· OSTI ID:785320

Huang, David M ^[1]; Geissler, Phillip L; Chandler, David

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1. LBNL Library

We have calculated the free energy of solvation for hard sphere solutes, as large as 20 Angstroms in diameter, in two simple-point-charge models of water. These results were obtained using umbrella sampling of ensembles with fixed, ambient temperature and pressure. For the same water models, we have also calculated the surface tension of a liquid-vapor interface at room temperature. Analogous calculations were carried out for three thermodynamic states of the Lennard-Jones (LJ) fluid near liquid-vapor coexistence. For both water and the LJ fluid at the conditions we have simulated, extrapolation of our results suggests that the planar interface between coexisting liquid and vapor phases has the same surface tension as the planar limit of hard sphere solvation. We expect this correspondence to be a general result for fluids at thermodynamic states close to phase coexistence, as measured by the difference in chemical potential between bulk liquid and vapor phases, and far from the critical point. The solvation free energies we have computed for water and the LJ fluid crossover at microscopic solute sizes from a dependence on solute volume to an approximate dependence on solute surface area, as predicted by Lum et al. [J. Phys. Chem. B 1999, 103, 4570].

• Research Organization: Lawrence Berkeley National Lab., CA (US)
• Sponsoring Organization: USDOE Director, Office of Science (US)
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 785320
• Report Number(s): LBNL--48773
• Journal Information: Journal of Physical Chemistry, B, Journal Name: Journal of Physical Chemistry, B Journal Issue: 28 Vol. 105
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
AMBIENT TEMPERATURE
EXTRAPOLATION
FREE ENERGY
HYDROPHOBIC SOLVATION HARD SPHERE SOLUTES FREE ENERGY
SAMPLING
SOLUTES
SOLVATION
SURFACE AREA
SURFACE TENSION
THERMODYNAMICS
WATER