In this article, we present coarse-grained potentials of ethylbenzene developed at 298 K and of amorphous polystyrene developed at 500 K by the pressure-corrected iterative Boltzmann inversion method. The potentials are optimized against the fully atomistic simulations until the radial distribution functions generated from coarse-grained simulations are consistent with atomistic simulations. In the coarse-grained polystyrene melts of different chain lengths, the Flory exponent of 0.58 is obtained for chain statistics. Both potentials of polystyrene and ethylbenzene are transferable over a broad range of temperature. The thermal expansion coefficients of the fully atomistic simulations are well reproduced in the coarse-grained models for both systems. However, for the case of ethylbenzene, the coarse-grained potential is temperature-dependent. The potential needs to be modified by a temperature factor of T / T 0 when it is transferred to other temperatures; T 0 = 298 K is the temperature at which the coarse-grained potential has been developed. For the case of polystyrene, the coarse-grained potential is temperature-independent. An optimum geometrical combination rule is proposed with the combination constant x = 0.4 for mutual interactions between the polystyrene monomer and ethylbenzene molecules in their mixtures at different composition and different temperature.

A first principles study of a hydrated electron in water at ordinary and supercritical conditions is presented. In the first case, the electron cleaves a cavity in the hydrogen bond network in which six H2O molecules form the solvation shell. The electron distribution assumes an ellipsoidal shape, and the agreement of the computed and the experimental optical absorption seems to support this picture. At supercritical conditions, instead, the H-bond network is not continuous and allows us to predict that the electron localizes in preexisting cavities in a more isotropic way. Four water molecules form the solvation shell but the localization time shortens significantly.

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We present a first-principles molecular dynamics study of water near and above the critical point ( T = 647 K, rho = 0.32 g/cm(3)). We find that the systems undergo fast dynamics with continuous formation and breaking of H bonds. At low density, the system fragments mostly into trimers, dimers, and single molecules. At a higher density, more complex structures appear and an extended, albeit very dynamical, H-bond network can be identified. These structures have important consequences for the screening properties of the system. This offers a clue to understanding the peculiar chemical behavior of a supercritical system and allows thermodynamical tuning of its solvent properties.