Molecular dynamics simulations have been performed on the aqueous solutions of poly(vinyl methyl ether) (PVME) at various concentrations. Both radial and spatial distribution functions are used to investigate the detailed hydration structures. The structures of water are found to get increasingly concentrated when polymers are introduced and the water motions are severely hindered by the polymer matrix. At low concentrations, larger populations of tt conformers in meso dyads than those at higher concentrationsare found and this phenomenon is believed to be due to the increasing in bonding of water molecule to two ether oxygens in meso dyad. At higher concentrations, the size and conformations of polymers are quite similar to those in bulk. A transition of hydrogen bond fractions between PVME and water at around the concentration of 0.3 is observed and this value is perfectly in agreement with the results of conformational analysis and Raman spectra. Second neighbor hydrogen bond statistics revealed the domination of complicated hydrogen bond networks at low concentrations, but single hydrogen bonds as well as isolated clusters composed of 2-4 water molecules are usual around each polymer repeat unit.

The most atomistic molecular details of polymer glass transition were analyzed through the frozen torsions in our molecular dynamics simulations. Different observation times were used to determine the frozen fractions and frozen chain lengths. The glass transition temperature was found to coincide well with the temperature at which the frozen fractions were reduced to 1/e. The frozen chain segments grow as the temperature decreases in a similar way with that of linear polymerization, and the inverse number-average frozen chain length leads to the formulation of configuration entropy during glass transition. The ideal glass transition temperature extrapolated to zero configuration entropy corresponds well with those reported in the literature, and the relation between the relaxation time and the configuration entropy shows perfect agreement with the Adam–Gibbs theory around the glass transition temperature. Volume spanning clusters are formed at the low temperature end, which might serve as a premature prototype for the formation of the “ideal glassy state” with limited accessible configurations.