Transferable Potentials for Phase Equilibria. 6. United-Atom Description for Ethers, Glycols, Ketones, and Aldehydes

The extension of the transferable potentials for phase equilibria−united atom (TraPPE−UA) force field to the ether, glycol, ketone, and aldehyde functionalities is presented. New parameters for the ether oxygen, the carbonyl carbon (ketones), the carbonyl methine (aldehydes), and a special intramolecular hydrogen-bond term were fitted to the vapor−liquid coexistence curves for selected one-component systems. Coupled−decoupled configurational bias Monte Carlo simulations in the Gibbs or grand canonical ensemble were used to compute the vapor−liquid coexistence curves for the neat systems of dimethyl ether, ethyl methyl ether, diethyl ether, dipropyl ether, diisopropyl ether, methyl tert-butyl ether, 1,2-ethanediol, 2-methoxyethan-1-ol, 1,2-dimethoxyethane, 1,3-propanediol, acetone, 2-pentanone, 2-octanone, acetaldehyde, pentanal, and octanal. Additional simulations were performed for the binary mixtures of diethyl ether + ethanol and acetone + hexane. Excellent agreement with experimental results was found...