Glasses can be formed by many routes. In some cases, distinct polyamorphic forms are found. The normal mode of glass formation is cooling of a viscous liquid. Liquid behavior during cooling is classified between "strong" and "fragile," and the three canonical characteristics of relaxing liquids are correlated through the fragility. Strong liquids become fragile liquids on compression. In some cases, such conversions occur during cooling by a weak first-order transition. This behavior can be related to the polymorphism in a glass state through a recent simple modification of the van der Waals model for tetrahedrally bonded liquids. The sudden loss of some liquid degrees of freedom through such first-order transitions is suggestive of the polyamorphic transition between native and denatured hydrated proteins, which can be interpreted as single-chain glass-forming polymers plasticized by water and cross-linked by hydrogen bonds. The onset of a sharp change in d dT( is the Debye-Waller factor and T is temperature) in proteins, which is controversially indentified with the glass transition in liquids, is shown to be general for glass formers and observable in computer simulations of strong and fragile ionic liquids, where it proves to be close to the experimental glass transition temperature. The latter may originate in strong anharmonicity in modes ("bosons"), which permits the system to access multiple minima of its configuration space. These modes, the Kauzmann temperature T(K), and the fragility of the liquid, may thus be connected.

https://science.sciencemag.org/content/sci/267/5206/1924.full.pdf

Formation of glasses from liquids and biopolymers.

Glasses are disordered materials that lack the periodicity of crystals but behave mechanically like solids. The most common way of making a glass is by cooling a viscous liquid fast enough to avoid crystallization. Although this route to the vitreous state-supercooling-has been known for millennia, the molecular processes by which liquids acquire amorphous rigidity upon cooling are not fully understood. Here we discuss current theoretical knowledge of the manner in which intermolecular forces give rise to complex behaviour in supercooled liquids and glasses. An intriguing aspect of this behaviour is the apparent connection between dynamics and thermodynamics. The multidimensional potential energy surface as a function of particle coordinates (the energy landscape) offers a convenient viewpoint for the analysis and interpretation of supercooling and glass-formation phenomena. That much of this analysis is at present largely qualitative reflects the fact that precise computations of how viscous liquids sample their landscape have become possible only recently.

Supercooled liquids and the glass transition

N G van Kampen 1981 Amsterdam: North-Holland xiv + 419 pp price Dfl 180 This is a book which, at a lower price, could be expected to become an essential part of the library of every physical scientist concerned with problems involving fluctuations and stochastic processes, as well as those who just enjoy a beautifully written book. It provides an extensive graduate-level introduction which is clear, cautious, interesting and readable.

https://iopscience.iop.org/article/10.1088/0031-9112/34/4/040/pdf

Stochastic Processes in Physics and Chemistry

Although it has long been recognized that dynamics in supercooled liquids might be spatially heterogeneous, only in the past few years has clear evidence emerged to support this view. As a liquid is cooled far below its melting point, dynamics in some regions of the sample can be orders of magnitude faster than dynamics in other regions only a few nanometers away. In this review, the experimental work that characterizes this heterogeneity is described. In particular, the following questions are addressed: How large are the heterogeneities? How long do they last? How much do dynamics vary between the fastest and slowest regions? Why do these heterogeneities arise? The answers to these questions influence practical applications of glass-forming materials, including polymers, metallic glasses, and pharmaceuticals.

Spatially Heterogeneous Dynamics in Supercooled Liquids

The field of viscous liquid and glassy solid dynamics is reviewed by a process of posing the key questions that need to be answered, and then providing the best answers available to the authors and their advisors at this time. The subject is divided into four parts, three of them dealing with behavior in different domains of temperature with respect to the glass transition temperature, Tg , and a fourth dealing with ‘‘short time processes.’’ The first part tackles the high temperature regime T.Tg ,i n which the system is ergodic and the evolution of the viscous liquid toward the condition at Tg is in focus. The second part deals with the regime T;Tg , where the system is nonergodic except for very long annealing times, hence has time-dependent properties ~aging and annealing!. The third part discusses behavior when the system is completely frozen with respect to the primary relaxation process but in which secondary processes, particularly those responsible for ‘‘superionic’’ conductivity, and dopart mobility in amorphous silicon, remain active. In the fourth part we focus on the behavior of the system at the crossover between the low frequency vibrational components of the molecular motion and its high frequency relaxational components, paying particular attention to very recent developments in the short time dielectric response and the high Q mechanical response. © 2000 American Institute of Physics.@S0021-8979~00!02213-1#

https://lib.dr.iastate.edu/cgi/viewcontent.cgi?article=1065&context=mse_pubs

Relaxation in glassforming liquids and amorphous solids

Dynamics of supercooled liquids and glassy solids

Several experimental methods feature the potential to distinguish between slow and fast contributions to the non-exponential, ensemble averaged primary response in glass-forming materials. Some of these techniques are based on the selection of subensembles using multi-dimensional nuclear magnetic resonance, optical bleaching, and non-resonant spectral hole burning. Others, such as the time-dependent solvation spectroscopy, measure microscopic responses induced by local perturbations. Using several of these methods it could be demonstrated for various glass-forming materials that the non-exponential relaxation results from a superposition of dynamically distinguishable entities. The experimental observation that subensembles can be selected efficiently indicates a large degree of heterogeneity. The intrinsic response is compatible with single exponential relaxation.

Nature of the Non-exponential Primary Relaxation in Structural Glass-formers Probed by Dynamically Selective Experiments

Using deuteron NMR, we have studied molecular reorientation rates and rate exchange processes in supercooled ortho-terphenyl. We monitor the re-equilibration of differently selected subensembles through four-time stimulated echo experiments. A comparison of the two-time with the four-time echoes suggests that the characteristic time scales for reorientation and dynamical exchange are relatively similar. The four-time correlation functions were described using various multi-state rate exchange models.

https://iopscience.iop.org/article/10.1209/epl/i1996-00186-5/pdf

Dynamic heterogeneity in supercooled ortho-terphenyl studied by multidimensional deuteron NMR

We have studied details of the molecular origin of slow secondary relaxation near T(g) in a series of neat polyalcohols by means of dielectric spectroscopy and (2)H NMR. From glycerol to threitol, xylitol, and sorbitol the appearance of the secondary relaxation changes gradually from a wing-type scenario to a pronounced beta peak. It is found that in sorbitol the dynamics of the whole molecule contributes equally to the beta process, while in glycerol the hydrogen bond forming OH groups remain rather rigid compared to the hydrogens bonded to the carbon skeleton.

From strong to fragile glass formers: Secondary relaxation in polyalcohols

Multidimensional deuteron NMR provides powerful tools for studying molecular reorientation in supercooled liquids. We present results on selectively deuterated toluene-${d}_{5},$ which may be one of the molecularly most simple van der Waals glass formers. From two-time correlation functions the time scale of reorientation was obtained slightly above the calorimetric glass transition temperature. The applied stimulated echo method provides a geometry parameter that, in analogy to $q$-dependent scattering experiments, allows one to investigate the geometry of the elementary rotational process. Continuous time random walk computer simulations were used for the interpretation of the data. It is shown that an isotropic single jump angle model does not describe the toluene rotation, rather the existence of several jump angles is required. Assuming mainly small jump angles $l6\ifmmode^\circ\else\textdegree\fi{}$ but also some larger angles up to 30\ifmmode^\circ\else\textdegree\fi{} an acceptable fit to the experimental data was obtained. Using four-time correlation functions further properties of molecular reorientation are elucidated. Slow reorienting subensembles can be selected. Their return to the full ensemble occurs on the same time scale as the elementary rotational jump process. In accord with previous investigations in other supercooled liquids, a heterogeneous scenario is found for the rotational dynamics of toluene.

Gerald Hinze

Papers

Dynamics of supercooled liquids and glassy solids

Nature of the Non-exponential Primary Relaxation in Structural Glass-formers Probed by Dynamically Selective Experiments

Dynamic heterogeneity in supercooled ortho-terphenyl studied by multidimensional deuteron NMR

From strong to fragile glass formers: Secondary relaxation in polyalcohols

Geometry and time scale of the rotational dynamics in supercooled toluene