Simulation Studies of Liquids, Supercritical Fluids and Radiation Damage effects

Abstract

The work in this thesis aims to gain fundamental understanding of several important types of disordered systems, including liquids, supercritical fluids and amorphous solids on the basis of extensive molecular dynamics simulations. I begin with studying the diffusion in amorphous zirconolite, a potential waste form to encapsulate highly radioactive nuclear waste. I find that amorphization has a dramatic effect for diffusion. Interestingly and differently from previous understanding, diffusion increases as a result of amorphization at constant density. Another interesting insight is related to different response of diffusion of different atomic species to structural disorder. I calculate activation energies and diffusion pre-factors which can be used to predict long-term diffusion properties in this system. This improves our understanding of how waste forms operate and provides a quantitative tool to predict their performance. I subsequently study the effects of phase coexistence and phase decomposition in Y-stabilized zirconia, the system of interest in many industrial applications including in encapsulating nuclear waste due to its exceptional resistance to radiation damage. For the first time I show how the microstructure emerges and evolves in this system and demonstrate its importance for self-diffusion and other properties. This has not been observed before and is important for better understanding of existing experiments and planning the new ones. I subsequently address dynamical properties of subcritical liquids and supercritical fluids. I start with developing a new empirical potential for CO2 with improved performance. Using this and other potentials, I simulate the properties of supercritical H2O, CO2 and CH4 and map their Frenkel lines in the supercritical region of the phase diagram. I observe that the Frenkel line for CO2 coincides with experimentally found maxima of solubility and explain this finding by noting that the Frenkel line corresponds to the optimal combination of density and temperature where the density is maximal and the diffusion is still in the fast gas-like regime. This can serve as a guide in future applications of supercritical fluids and will result in their more efficient use in dissolving and extracting applications. I extend my study to collective modes in liquids. Here, my simulations provide first direct evidence that a gap emerges and evolves in the reciprocal space in transverse spectra of liquids. I show that the gap increases with temperature and is inversely proportional to liquid relaxation time. Interestingly, the gap emerges and evolves not only in subcritical liquids but also in supercritical fluids as long as they are below the Frenkel line. Given the importance of phonons in condensed matter physics and other areas of physics, I propose that the discovery of the gap represents a paradigm change. There is an active interest in the dynamics of liquids and supercritical fluids, and I therefore hope that my results will quickly stimulate high-temperature and high-pressure experiments aimed at detecting and studying the gap in several important systems.