Molecular dynamics phase diagram

Tycko, R. Molecular dynamics, phase diagrams and electronic properties of fuller-enes and alkali fullerides Insights from sohd-state nuclear magnetic resonance spectroscopy.. Solid State Nud. Masn. Reson. 1994 3 303-314. 

In summary, NMR studies can deal with a wide range of problems in surfactant science. These include, e.g., molecular transport, phase diagrams, phase structure, self-association, micelle size and shape, counterion binding and hydration, solubilization, and polymer-micelle interactions. NMR is fruitfully applied to isotropic or liquid crystalline bulk phases, to dispersions (vesicles, emulsions, etc.), to polymer-surfactant mixtures, and to surfactant molecules at solid surfaces. In all cases NMR can provide information on molecular interactions and dynamics as well as on microstructure. 

Phase transitions in two-dimensional layers often have very interesting and surprising features. The phase diagram of the multicomponent Widom-Rowhnson model with purely repulsive interactions contains a nontrivial phase where only one of the sublattices is preferentially occupied. Fluids and molecules adsorbed on substrate surfaces often have phase transitions at low temperatures where quantum effects have to be considered. Examples are molecular layers of H2, D2, N2 and CO molecules on graphite substrates. We review the path integral Monte Carlo (PIMC) approach to such phenomena, clarify certain experimentally observed anomalies in H2 and D2 layers, and give predictions for the order of the N2 herringbone transition. Dynamical quantum phenomena in fluids are analyzed via PIMC as well. Comparisons with the results of approximate analytical theories demonstrate the importance of the PIMC approach to phase transitions where quantum effects play a role. 

The principal tools have been density functional theory and computer simulation, especially grand canonical Monte Carlo and molecular dynamics [17-19]. Typical phase diagrams for a simple Lennard-Jones fluid and for a binary mixture of Lennard-Jones fluids confined within cylindrical pores of various diameters are shown in Figs. 9 and 10, respectively. Also shown in Fig. 10 is the vapor-liquid phase diagram for the bulk fluid (i.e., a pore of infinite radius). In these examples, the walls are inert and exert only weak forces on the molecules, which themselves interact weakly. Nevertheless,... 

Tinte et al.54 have carried out molecular dynamic simulations of first-principles based effective Hamiltonian for PSN under pressure and of PMN at ambient pressure that clearly exhibit a relaxor state in the paraelectric phase. Analysis of the short-to-medium range polar order allows them to locate Burns temperature Tb. Burns temperature is identified as the temperature below which dynamic nanoscale polar clusters form. Below TB, the relaxor state characterized by enhanced short-to-medium range polar order (PNR) pinned to nanoscale chemically ordered regions. The calculated temperature-pressure phase diagram of PSN demonstrates that the stability of the relaxor state depends on a delicate balance between the energetics that stabilize normal ferroelectricity and the average strength of quenched "random" local fields. 

B. B. Laird and A. D. J. Haymet, "Phase diagram for the inverse sixth power potential system from molecular dynamics computer simulation , Mol. Phys. 75 (1992) 71. 

The p-T phase diagram of sulfur is about the most complicated amongst the chemicd elements, and many open questions still exist with respect to phase boundaries, structures in detail, and kinetics of phase transitions in the solid as well as in the hquid state. Not only the molecular and crystalline variety of sulfur contributes to this complexity but also the metastabihty of high-pressure phases which is related to the application of different experi-mentd procedures. For example, early structural studies on the p-T phase diagram of sulfur could not be performed in-situ. Therefore, in these experiments the sulfur samples were quenched from a selected temperature-pressure point to STP conditions. The results obtained by such a procedure depend strongly on the variables AT and Ap as well as on their time derivatives (gradients), dT/dt and dp/dt, respectively. Especially, dynamic compression (shock wave) methods may introduce further complications since melting of... 

The study of colloidal crystals was initiated as part of research into the determination of phase diagrams for colloids, which itself was perceived as a means to model phase behaviour in molecular systems [22]. Extensive literature is available on the dynamics of colloidal crystal formation, as a function of several parameters, such as the nature of the solvent, surface charge, particle size and concentration. The results described here refer to the formation of colloidal crystals from dispersions of silica-coated gold nanoparticles in ethanol, after silica surface functionalization with 3-(trimethoxysilyl)propyl methacrylate (TPM). Earlier studies by Philipse and Vrij [23] showed that TPM adsorption leads to a reduction in surface charge, so that the particles are stable in organic solvents with low polarity, such as ethanol, toluene or DMF. This means that the particle be-... 

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