Isochronal Superposition Research Articles

Isochronal Superposition of the Structural α-Relaxation and Invariance of Its Relation to the β-Relaxation to Changes of Thermodynamic Conditions in Methyl m-Toluate.

The dielectric spectra of methyl m-toluate (MMT) in supercooled liquid and glassy states were measured over wide ranges of temperature T at ambient and elevated pressures P. We found that the frequency dispersion of the loss peak contributed by the structural α-relaxation is invariant to changes of P and T, while keeping the loss peak frequency fα(T,P) constant. This isochronal superposition property of the α-relaxation holds for different choices of fα(T,P). The invariant frequency dispersions for the same fα(T,P) are also indicated by the fractional exponent βKWW in the Fourier transform of the Kohlrausch-Williams-Watts (KWW) function. Similarly, the fragility m index of MMT keeps approximately constant on varying pressure, largely different from H-bonded glass formers. The secondary β-relaxation at a frequency higher than fα(T,P) is found to shift to lower frequencies by elevating pressure in concert with the α-relaxation. The ratio τα(T,P)/τβ(T,P) is approximately unchanged to variations of T and P while keeping τα(T,P) constant. These properties observed in MMT offer experimental evidence of the dynamic correlation between α- and β-relaxations in pure small-molecule glass-formers.

Isochronal superposition and density scaling of the α-relaxation from pico- to millisecond.

The relaxation dynamics in two van der Waals bonded liquids and one hydrogen-bonding molecular liquid are studied as a function of pressure and temperature by incoherent neutron scattering using simultaneous dielectric spectroscopy. The dynamics are studied in a range of alpha relaxation times from pico- to milliseconds, primarily in the equilibrium liquid state. In this range, we find that isochronal superposition and density scaling work not only for the two van der Waals liquids but also for the hydrogen-bonding liquid, though the density scaling exponent is much smaller for the latter. Density scaling and isochronal superposition are seen to break down for intra-molecular dynamics when it is separated in time from the alpha relaxation, in close agreement with previous observations from molecular dynamics simulations.

Confinement-Induced Changes in the Glassy Dynamics and Crystallization Behavior of Supercooled Fenofibrate

Here, we have studied the effect of spatial restrictions on the molecular dynamics and crystallization behavior of modeled lipophilic drug fenofibrate incorporated into nanoporous aluminum oxide membranes of different pore size. Our measurements demonstrate that, on subsequent cooling, dynamics of confined liquid split up into two distinct fractions, due to the presence of core and interfacial layers. At the temperature, at which vitrification of the interfacial layer takes place (Tg_interface), departure from the bulk-like behavior occurs, and molecules in the center of the pores enter quasi-isochoric conditions. Depending on the thermal protocol and pore size, the volume fixed at Tg_interface might be a bit different so as the core liquid’s dynamics. Interestingly, below that temperature, the nanoconfined liquid can still obey the fundamental density scaling relation (1/TVγ), just like in the bulk phase, while not necessarily isochronal superposition. This is in contrast to a common observation that the...

Communication: Effect of density on the physical aging of pressure-densified polymethylmethacrylate.

The rate of physical aging of glassy polymethylmethacrylate (PMMA), followed from the change in the secondary relaxation with aging, is found to be independent of the density, the latter controlled by the pressure during glass formation. Thus, the aging behavior of the secondary relaxation is the same whether the glass is more compacted or less dense than the corresponding equilibrium liquid. This equivalence in aging of glasses formed under different pressures indicates that local packing is the dominant variable governing the glassy dynamics. The fact that pressure densification yields different glass structures is at odds with a model for non-associated materials having dynamic properties exhibited by PMMA, such as density scaling of the relaxation time and isochronal superposition of the relaxation dispersion.

Communication: Pseudoisomorphs in liquids with intramolecular degrees of freedom.

Computer simulations show that liquids of molecules with harmonic intramolecular bonds may have "pseudoisomorphic" lines of approximately invariant dynamics in the thermodynamic phase diagram. We demonstrate that these lines can be identified by requiring scale invariance of the inherent-structure reduced-unit low-frequency vibrational spectrum evaluated for a single equilibrium configuration. This rationalizes why generalized excess-entropy scaling, density scaling, and isochronal superposition apply for many liquids with internal degrees of freedom.

Dielectric Relaxation Study at Ambient and Elevated Pressure of the Modeled Lipophilic Drug Fenofibrate.

We have investigated the molecular dynamics in supercooled liquid and glassy state of the pharmaceutical agent fenofibrate. To do that, dielectric relaxation studies at ambient and elevated pressure were performed. Data collected at atmospheric pressure were found to be in good agreement with that already reported in the literature. High-pressure studies enable us to distinguish the secondary relaxation processes of the different molecular origin. This includes (i) pressure insensitive γ-relaxation of the activation energy Ea = 28 kJ/mol and (ii) β-relaxation that senses the density increase and originates most probably from the intermolecular movements (Ea = 77 kJ/mol at 480 MPa). The results of high-pressure studies have also revealed the validity of isochronal superposition and decoupling between α-relaxation and translational motions of charged species reflected by dc conductivity. The latter one was found to intensify with increasing pressure. Finally, we also show that the presence of quite complex inter- and intramolecular hydrogen bonds might still exert some subtle effect on the molecular dynamics of supercooled fenofibrate.

Isochronal superposition and density scaling of the intermolecular dynamics in glass-forming liquids with varying hydrogen bonding propensity

We have tested the idea of thermodynamic scaling T−1ργ and isochronal superposition in glass-forming liquids with varying propensity to form hydrogen bonds.

Communication: Two measures of isochronal superposition

A liquid obeys isochronal superposition if its dynamics is invariant along the isochrones in the thermodynamic phase diagram (the curves of constant relaxation time). This paper introduces two quantitative measures of isochronal superposition. The measures are used to test the following six liquids for isochronal superposition: 1,2,6 hexanetriol, glycerol, polyphenyl ether, diethyl phthalate, tetramethyl tetraphenyl trisiloxane, and dibutyl phthalate. The latter four van der Waals liquids obey isochronal superposition to a higher degree than the two hydrogen-bonded liquids. This is a prediction of the isomorph theory, and it confirms findings by other groups.

Strongly correlating liquids and their isomorphs

This paper summarizes the properties of strongly correlating liquids, i.e., liquids for which the virial/potential energy correlation coefficient is above 0.9 for equilibrium fluctuations in the NVT ensemble. The definition and properties of strongly correlating liquids' isomorphs are given, and various isomorph invariants are discussed. The cause of strong virial/potential energy correlations is also discussed, and it is argued that strongly correlating liquids are not merely to be thought of as approximate inverse power-law liquids. The experimental predictions for strongly correlating glass-forming liquids include: i) density scaling; ii) isochronal superposition; iii) that there is a single function of frequency from which all frequency-dependent viscoelastic response functions may be calculated; iv) that strongly correlating liquids are approximately single-parameter liquids with close to unity Prigogine–Defay ratio; v) that the fictive temperature initially decreases for an isobaric temperature up jump. The paper also briefly discusses the “isomorph filter”, which provides a necessary condition for universality of theories for the non-Arrhenius temperature dependence of the relaxation time.

Pressure-energy correlations in liquids. IV. “Isomorphs” in liquid phase diagrams

This paper is the fourth in a series devoted to identifying and explaining the properties of strongly correlating liquids, i.e., liquids where virial and potential energy correlate better than 90% in their thermal equilibrium fluctuations in the NVT ensemble. For such liquids we here introduce the concept of "isomorphic" curves in the phase diagram. A number of thermodynamic, static, and dynamic isomorph invariants are identified. These include the excess entropy, the isochoric specific heat, reduced-unit static and dynamic correlation functions, as well as reduced-unit transport coefficients. The dynamic invariants apply for both Newtonian and Brownian dynamics. It is shown that after a jump between isomorphic state points the system is instantaneously in thermal equilibrium; consequences of this for generic aging experiments are discussed. Selected isomorph predictions are validated by computer simulations of the Kob-Andersen binary Lennard-Jones mixture, which is a strongly correlating liquid. The final section of the paper relates the isomorph concept to phenomenological melting rules, Rosenfeld's excess entropy scaling, Young and Andersen's approximate scaling principle, and the two-order parameter maps of Debenedetti and co-workers. This section also shows how the existence of isomorphs implies an "isomorph filter" for theories for the non-Arrhenius temperature dependence of viscous liquids' relaxation time, and it explains isochronal superposition for strongly correlating viscous liquids.