Dynamics of liquid silica as explained by properties of the potential energy landscape.

The dynamics of silica displays an Arrhenius temperature dependence, classifying silica as a strong glass-former. Using recently developed concepts to analyze the potential energy landscape, one can get a far-reaching understanding of the long-range transport of silica. It can be expressed in terms of properties of the thermodynamics as well as local relaxation processes, thereby extending the phenomenological standard picture of a strong glass-former. The local relaxation processes are characterized by complex correlated sequences of bond breaking and reformation processes.

Origin of the decoupling of oxygen and silicon dynamics in liquid silica as expressed by its potential energy landscape.

The oxygen and silicon dynamics in silica are compared via computer simulations. In agreement with experimental data and previous simulations a decoupling of oxygen and silicon dynamics is observed upon cooling. The origin of this decoupling is studied in the framework of the potential energy landscape. From analysis of the transition features between neighboring superstructures of minima, denoted metabasins, the differences between the oxygen and silicon dynamics can be quantified. The decoupling can be explicitly related to the presence of generalized rotational processes, giving rise to oxygen but not to silicon displacement. Closer analysis of these processes yields important insight into the nature of the potential energy landscape of silica. The physical picture of relaxation processes in silica, obtained in previous work for oxygen dynamics, is consistent with decoupling effects, elucidated here.

Potential-energy landscape of a supercooled liquid and its resemblance to a collection of traps.

It is analyzed whether the potential energy landscape of a glass-forming system can be effectively mapped on a random model which is described in statistical terms. For this purpose we generalize the simple trap model of Monthus and Bouchaud [J. Phys. A 29, 3847 (1996)] by dividing the total system into M weakly interacting identical subsystems, each being described in terms of a trap model. The distribution of traps in this extended trap model (ETM) is fully determined by the thermodynamics of the glass former. The dynamics is described by two adjustable parameters, one characterizing the common energy level of the barriers, the other the strength of the interaction. The comparison is performed for the standard binary mixture Lennard-Jones system with 65 particles. The metabasins, identified in our previous work, are chosen as traps. Comparing molecular dynamics simulations of the Lennard-Jones system with Monte Carlo calculations of the ETM allows one to determine the adjustable parameters. Analysis of the first moment of the waiting distribution yields an optimum agreement when choosing M approximately 3 subsystems. Comparison with the second moment of the waiting time distribution, reflecting dynamic heterogeneities, indicates that the sizes of the subsystems may fluctuate.

Origin of the fragile-to-strong crossover in liquid silica as expressed by its potential-energy landscape.

The origin of the fragile-to-strong crossover in liquid silica is characterized in terms of properties of the potential-energy landscape (PEL). Using the standard BKS model [B. W. H. van Beest, G. J. Kramer, and R. A. van Santen, Phys. Rev. Lett. 64, 1955 (1990)] of silica we observe a low-energy cutoff of the PEL. It is shown that this feature of the PEL is responsible for the occurrence of the fragile-to-strong crossover and may also explain the avoidance of the Kauzmann paradox. The number of defects, i.e., deviations from the ideal tetrahedral structure, vanishes for configurations with energies close to this cutoff. This suggests a structural reason for this cutoff.