Gaussian excitations model for glass-former dynamics and thermodynamics

Abstract

We describe a model for the thermodynamics and dynamics of glass-forming liquids in terms of excitations from an ideal glass state to a Gaussian manifold of configurationally excited states. The quantitative fit of this three parameter model to the experimental data on excess entropy and heat capacity shows that "fragile" behavior, indicated by a sharply rising excess heat capacity as the glass transition is approached from above, occurs in anticipation of a first-order transition--usually hidden below the glass transition--to a "strong" liquid state of low excess entropy. The distinction between fragile and strong behavior of glass formers is traced back to an order of magnitude difference in the Gaussian width of their excitation energies. Simple relations connect the excess heat capacity to the Gaussian width parameter, and the liquid-liquid transition temperature, and strong, testable, predictions concerning the distinct properties of energy landscape for fragile liquids are made. The dynamic model relates relaxation to a hierarchical sequence of excitation events each involving the probability of accumulating sufficient kinetic energy on a separate excitable unit. Super-Arrhenius behavior of the relaxation rates, and the known correlation of kinetic with thermodynamic fragility, both follow from the way the rugged landscape induces fluctuations in the partitioning of energy between vibrational and configurational manifolds. A relation is derived in which the configurational heat capacity, rather than the configurational entropy of the Adam-Gibbs equation, controls the temperature dependence of the relaxation times, and this gives a comparable account of the experimental observations without postulating a divergent length scale. The familiar coincidence of zero mobility and Kauzmann temperatures is obtained as an approximate extrapolation of the theoretical equations. The comparison of the fits to excess thermodynamic properties of laboratory glass formers, and to configurational thermodynamics from simulations, reveals that the major portion of the excitation entropy responsible for fragile behavior resides in the low-frequency vibrational density of states. The thermodynamic transition predicted for fragile liquids emerges from beneath the glass transition in case of laboratory water and the unusual heat capacity behavior observed for this much studied liquid can be closely reproduced by the model.

Dynamical and orientational structural crossovers in low-temperature glycerol

“…5 and 6) all occur in the same range of temperatures. A possible scenario to explain this coincidence might include a structural transition resulting in a drop of the configurational entropy [53]. According to the general arguments based on the Adam-Gibbs relation [23], this would result in a much slower main relaxation process, which would sharply disappear from the observation window of our numerical experiment.…”

Glass formation and glass transition in supercooled liquids, with insights from study of related phenomena in crystals

“…More recently, it has been suggested [48] that the thermodynamics enters the relaxation time expression through the fluctuations in energy between potential (configurational) and kinetic (vibrational) manifolds which build up the configurationally "hot" domains via which relaxation occurs. This leads to an expression for the relaxation time of Eq.…”

Physical vapor deposition as a route to hidden amorphous states

“…Because this is impossible, it is generally assumed that the extrapolation that produces this crisis must be incorrect, and thus something interesting must occur when a supercooled liquid is cooled very slowly. Several theories suggest that a first-order thermodynamic phase transition occurs below the laboratory glass transition (13,14) but other resolutions, including second-order transitions (15,16) and continuous processes (17)(18)(19)(20)(21)(22), have been proposed. Because of the impractically long time scales associated with molecular motion below the conventional T g , these ideas are not easily tested by experiments in which bulk liquids are cooled.…”