Comparison of thermodynamic properties of coarse-grained and atomic-level simulation models.
Thermodynamic data are often used to calibrate or test amomic-level (AL) force fields for molecular dynamics (MD) simulations. In contrast, the majority of coarse-grained (CG) force fields do not rely extensively on thermodynamic quantities. Recently, a CG force field for lipids, hydrocarbons, ions, and water, in which approximately four non-hydrogen atoms are mapped onto one interaction site, has been proposed and applied to study various aspects of lipid systems. To date, no extensive investigation of its capability to describe salvation thermodynamics has been undertaken. In the present study, a detailed picture of vaporization, solvation, and phase-partitioning thermodynamics for liquid hydrocarbons and water was obtained at CG and AL resolutions, in order to compare the two types or models and evaluate their ability to describe thermodynamic properties in the temperature range between 263 and 343 K. Both CG and AL models capture the experimental dependence of the thermodynamic properties on the temperature, albeit a systematically weaker dependence is found for the CG model. Moreover, deviations are found for solvation thermodynamics and for the corresponding enthalpy-entropy compensation for the CG model. Particularly water/oil repulsion seems to be overestimated. However, the results suggest that the thermodynamic properties considered should be reproducible by a CG model provided it is reparametrized on the basis of these liquid-phase properties.
Baron
Riccardo
R
Laboratorium für Physikalische Chemie, ETH, Swiss Federal Institute of Technology Zürich, 8093 Zürich, Switzerland.
Trzesniak
Daniel
D
de Vries
Alex H
AH
Elsener
Andreas
A
Marrink
Siewert J
SJ
van Gunsteren
Wilfred F
WF
D000473:Alkanes / Q000737:chemistry; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D003198:Computer Simulation; D008956:Models, Chemical; D009821:Oils / Q000737:chemistry; D012997:Solvents; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
D000473:Alkanes; D009821:Oils; D012997:Solvents; D014867:Water