Phases, periphases, and interphases equilibrium by molecular modeling. I. Mass equilibrium by the semianalytical...

The SASP (semianalytical stochastic perturbations) method is an original mixed macro-nano-approach dedicated to the mass equilibrium of multispecies phases, periphases, and interphases. This general method, applied here to the reflexive relation C(k)<=>mu(k) between the concentrations C(k) and the chemical potentials mu(k) of k species within a fluid in equilibrium, leads to the distribution of the particles at the atomic scale. The macroaspects of the method, based on analytical Taylor's developments of chemical potentials, are intimately mixed with the nanoaspects of molecular mechanics computations on stochastically perturbed states. This numerical approach, directly linked to definitions, is universal by comparison with current approaches, DLVO Derjaguin-Landau-Verwey-Overbeek, grand canonical Monte Carlo, etc., without any restriction on the number of species, concentrations, or boundary conditions. The determination of the relation C(k)<=>mu(k) implies in fact two problems: a direct problem C(k)=>mu(k) and an inverse problem mu(k)=>C(k). Validation of the method is demonstrated in case studies A and B which treat, respectively, a direct problem and an inverse problem within a free saturated gypsum solution. The flexibility of the method is illustrated in case study C dealing with an inverse problem within a solution interphase, confined between two (120) gypsum faces, remaining in connection with a reference solution. This last inverse problem leads to the mass equilibrium of ions and water molecules within a 3 A thick gypsum interface. The major unexpected observation is the repulsion of SO(4) (2-) ions towards the reference solution and the attraction of Ca(2+) ions from the reference solution, the concentration being 50 times higher within the interphase as compared to the free solution. The SASP method is today the unique approach able to tackle the simulation of the number and distribution of ions plus water molecules in such extreme confined conditions. This result is of prime importance for all coupled chemical-mechanical problems dealing with interfaces, and more generally for a wide variety of applications such as phase changes, osmotic equilibrium, surface energy, etc., in complex chemical-physics situations.