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

Powdered potassium ammonium iodide mixed crystals with ammonium concentrations of 20% and 70% have been studied using deuteron NMR techniques. For the less doped sample the deuteron line starts to broaden and the spin-lattice relaxation time ${T}_{1}$ becomes nonexponential below about 20 K. These observations indicate the breakdown of ergodicity and the onset of orientational glass freezing. At the lowest temperatures ${T}_{1}$ reaches a plateau value. For the 70% sample a relatively abrupt onset of two-phase behavior at $Tl35\mathrm{K}$ is inferred from measurements of the spin-spin and spin-lattice relaxation times. These observations are taken to indicate an order-disorder transition to a crystalline phase which exhibits dynamically distinguishable lattice sites.

Deuteron NMR investigations of glass and phase transitions in (KI)1-x(ND4I)x mixed crystals

Single crystals of the orientational glass have been studied using iodine NMR for temperatures 1.8 K < T < 300 K. Two-dimensional spectroscopy has shown that the quadrupole-perturbed central transitions are predominantly inhomogeneously broadened. The orientational glass transition is already accompanied by a considerable increase of that broadening in the regime of fast motion. Evidence for a random-field smearing of the random-bond-induced freezing process is obtained. Measurements of the spin - lattice relaxation time reveal the existence of a broad distribution of orientational correlation times at low temperatures.

https://iopscience.iop.org/article/10.1088/0953-8984/9/1/013/pdf

The orientational glass studied by nuclear magnetic resonance

Erratum: Orientational Dynamics in Supercooled Liquids near T c and Comparison with Ideal Mode-Coupling Theory [Phys. Rev. Lett. 84, 2437 (2000)]

Dynamic heterogeneity has often been modeled by assuming that a single-particle observable, fluctuating at a molecular scale, is influenced by its coupling to environmental variables fluctuating on a second, perhaps slower, time scale. Starting from the most simple Gaussian Markov process we model the exchange between `slow' and `fast' environments by treating the fluctuating single-particle variable as a projection from a higher-dimensional Markov process. The moments of the resulting stochastic process are calculated from the corresponding master equations or Langevin equations, depending on the model. The calculations show the importance of the way to treat exchange processes. The resulting stochastic process is non-Markovian for all models. However, the deviations from a Gaussian behavior depend on the details of the models. A comparison of our results with other model treatments and experiments should provide further insight into the concept of dynamic heterogeneity.

Stochastic models for heterogeneous relaxation: application to inhomogeneous optical lineshapes

Time resolved data from single molecule experiments often suffer from contamination with noise due to a low signal level. Identifying a proper model to describe the data thus requires an approach with sufficient model parameters without misinterpreting the noise as relevant data. Here, we report on a generalized data evaluation process to extract states with piecewise constant signal level from simultaneously recorded multivariate data, typical for multichannel single molecule experiments. The method employs the minimum description length principle to avoid overfitting the data by using an objective function, which is based on a tradeoff between fitting accuracy and model complexity. We validate our method with synthetic data from Monte Carlo simulations modeling fluorescence resonance energy transfer and rotational jumps, respectively. The method is applied to quantify rotational jump dynamics of single terrylene diimide (TDI) molecules deposited on a solid substrate. Depending on the substitution pattern of the TDI molecules and the chosen substrate materials, we find significant differences in time scale and geometry of molecular reorientation. From an additional application of our state transition identification in multivariate time series approach, a significant correlation between shifts of emission spectra and the occurrence of rotational jumps was found.

Gerald Hinze

Papers

Deuteron NMR investigations of glass and phase transitions in (KI)1-x(ND4I)x mixed crystals

The orientational glass studied by nuclear magnetic resonance

Erratum: Orientational Dynamics in Supercooled Liquids near T c and Comparison with Ideal Mode-Coupling Theory [Phys. Rev. Lett. 84, 2437 (2000)]

Stochastic models for heterogeneous relaxation: application to inhomogeneous optical lineshapes

State transition identification in multivariate time series (STIMTS) applied to rotational jump trajectories from single molecules.