An efficient method for computing excess free energy of liquid

We present a new theoretical method for efficient calculation of free energy of liquid. This interaction entropy method allows one to compute entropy and free energy of liquid from standard single step MD(molecular dynamics) simulation directly in liquid state without the need to perform MD simulations at many intermediate states as required in thermodynamic integration or free energy perturbation methods. In this new approach, one only needs to evaluate the interaction energy of a single(fixed) liquid molecule with the rest of liquid molecules as a function of time from a standard MD simulation of liquid and the fluctuation of distribution of this interaction energy is then used to calculate the interaction entropy of the liquid. Explicit theoretical derivation of this interaction entropy approach is provided and numerical calculations for the benchmark liquid water system were carried out using three different water models. Numerical analysis of the result was performed and comparison of the computational result with experimental data and other theoretical results were provided. Excellent agreement of calculated free energies with the experimental data using TIP4 P model is obtained for liquid water.

A Prediction of the Excess Partial Molar Free Energies of MgCl_2 in the KCI-MgCl_2-LiCl Molten Salt System Containing MgCl_2 below 0.5 from Thermodynamic Properties of Binary Systems

The thermodynamical properties of MgCl_2 in KCI-MgCl_2-LiCl molten electrolytes containing MgCl_2 below 0.5 (mole fraction, the same below) have been determined from the interchange energies of two binary systems KCI-MgCl_2 and LiCI-MgCl_2, by means of a model on the assumptions that the electrolytes in the solution are treated as independent particles instead of their ion forms and the interchange energy between the component pair KCI-LiCl is ignored when compared with those of component pairs KCl-MgCl_2 and MgCl_2-LiCl. The interchange energies, wKCl-MgCl_2 and wMgcCl_2-Licl, are obtained as-70000 and -13800 J.mol-1, from the corresponding binary solutions, respectively.

Effects of dispersion forces in the instability of polymer films

Spontaneous rupture of some polymer films upon heating is commonplace. The very criterion for this instability is the system free energy possessing a negative curvature. Within the framework of full frequency-dependent theory of dispersion forces, we have derived the excess free energy of a typical system--polystyrene film deposited on the silicon substrate. The excess free energy, wavelengths and growth rates are calculate and a comparison is made between the accurate results and the approximate results. It is found that the stability of the fihn can be tuned by the variation of the thickness of the coating and the retardation effects can be significant sometimes.